CN115057962A - Dispersion resin, process for producing the same, and photoresist composition - Google Patents
Dispersion resin, process for producing the same, and photoresist composition Download PDFInfo
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- CN115057962A CN115057962A CN202210729269.8A CN202210729269A CN115057962A CN 115057962 A CN115057962 A CN 115057962A CN 202210729269 A CN202210729269 A CN 202210729269A CN 115057962 A CN115057962 A CN 115057962A
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
- C08F220/302—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and two or more oxygen atoms in the alcohol moiety
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D17/00—Pigment pastes, e.g. for mixing in paints
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- G02B5/20—Filters
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
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Abstract
The invention provides a scatter treeA resin, a method for preparing the same, and a low-temperature-curable photoresist composition, the dispersion resin being represented by formula (2): (Z-A) n ‑R m (2) N is 1-5, m is 1-5, and n + m is less than or equal to 6; z represents H, or an acrylic copolymer containing amino, epoxy, alkyl with 1-14 carbon atoms, cycloalkyl with 3-14 carbon atoms or aryl substituent; r represents a group C, N, CH,
Or at least one of a linear alkyl group, an aliphatic cycloalkyl group, an aryl group and a heteroaryl group having 6 to 14 carbon atoms; a is represented by formula (3):
and in formula (3), W is bonded to Z, a carboxyl group is bonded to R, and W represents at least one of an H atom, a substituted or unsubstituted alkyl group having 1 to 14 carbon atoms, an epoxyalkyl group having 2 to 6 carbon atoms, a substituted or unsubstituted aryl group having 3 to 14 carbon atoms, and a substituted or unsubstituted heteroaryl group.
Description
Technical Field
The invention relates to the technical field of dispersion resin and photoresist materials, in particular to dispersion resin, a preparation method thereof and a photoresist composition.
Background
The method for processing the device by using the color photoresist is various, such as: dyeing methods, pigment dispersion methods, printing methods, electrodeposition methods, inkjet methods, and the like. Wherein, the pigment dispersing method is that organic/inorganic pigment is dispersed in resin solution, and then photoresist with color is coated on a glass/PET/CPI/metal substrate; and the color layer of the color filter can be prepared by photoetching processes such as exposure, development and the like, and the color filter has the advantages of fine process, high light resistance, high contrast, high color saturation, stable performance and the like.
The color filter is a critical component of the lcd capable of colorizing, and the manufacturing technique and quality of the color photoresist have a crucial influence on the display performance of the lcd. At present, liquid crystal devices of color filters are more used in notebook computers, smart phones, vehicle-mounted displays, large-sized liquid crystal televisions, and the like. These liquid crystal devices require high chroma and high contrast.
The polaroid is a polarizer, is a device which must be relied on for imaging of a liquid crystal display and an OLED display, and is provided with a front polarizer and a rear polarizer which are tightly attached to the upper surface and the lower surface of a display screen. The basic structure of the conventional polarizer includes: the most central PVA (polyvinyl alcohol), two layers of TAC (cellulose triacetate), PSA film (pressure sensitive adhesive), Release film (Release film) and Protective film (Protective film).
In addition, as the temperature of the manufacturing process of the flexible display screen is reduced or the high-temperature operation time is shortened, namely, the low-temperature coating and the related technologies are more and more applied, and the requirement on the low-temperature curing photoresist material is higher and higher. The most core is the low temperature curing type negative photoresist, and the low temperature curing type product of the color photoresist can be prepared by adding the pigment liquid on the basis.
The polarized light emitting technology of the flexible OLED display greatly reduces the light emitting efficiency of the flexible OLED if a traditional polarizer is adopted, so that a color filter method is adopted by display device manufacturers such as samsung display in korea to correspondingly manufacture a layer of color pixels on red, green and blue three-primary-color pixels of the OLED to solve the polarized light problem. Such color resists are required to be low temperature curing type lithographic materials.
JP2005-380016 discloses that a method of color filters of three colors of red, green and blue plus a black matrix is the most representative conventional filter structure, and the pixel width is in the range of 20 um. However, the patent document CN201210070934 solves some leveling and coupling problems, but because the dispersed resin and the grinding resin inside the used pigment paste cannot be completely matched and unified with the polarity of the developing resin in the photoresist and the like all the time when the photoresist is blended, the pixel accuracy, especially the resolution of the pixel edge, cannot be improved.
In order to meet the performance requirement of the color upgrading of the liquid crystal display, besides the need of fine pigment dispersion, the preparation of high polymers in a pigment photoresist is optimized so as to prepare patterns with the size of less than 10 mu m and prepare red, yellow, blue and green or red, transparent, blue and green four-color filters.
In addition, some new devices also require special patterns of less than 10 μm and contain red, green, blue, yellow, magenta, cyan, black or white as a mark. And it is required that these colored fine patterns of 10 μm or less can be made on various kinds of PET or metal sheets.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a dispersion resin suitable for a low-temperature curing (85-100 ℃) condition, a preparation method thereof and a photoresist composition, and also provides an intermediate for preparing the dispersion resin, a nano pigment color paste composition and a method for preparing a pattern on a substrate by using a photoetching low-temperature post-baking process for preparing a low-temperature color photoresist prepared from the nano pigment color paste composition.
In order to solve the problems, the technical scheme adopted by the invention is as follows:
a dispersion resin represented by formula (2):
(Z-A) n -R m (2)，
wherein, in formula (2), n is 1 to 5, m is 1 to 5, and n + m is less than or equal to 6;
z represents H, or an acrylic copolymer containing amino, epoxy, alkyl with 1-14 carbon atoms, cycloalkyl with 3-14 carbon atoms or aryl substituent;
r represents a group C, N, CH,
Or at least one of a linear alkyl group having 2 to 14 carbon atoms, an aliphatic cycloalkyl group having 2 to 14 carbon atoms, an aryl group and a heteroaryl group having 3 to 14 carbon atoms;
a is represented by formula (3):
and in formula (3), W is bonded to Z, a carboxyl group is bonded to R, and W represents at least one of an H atom, a substituted or unsubstituted alkyl group having 1 to 14 carbon atoms, an epoxyalkyl group having 2 to 6 carbon atoms, a substituted or unsubstituted aryl group having 3 to 14 carbon atoms, and a substituted or unsubstituted heteroaryl group.
In some alternative embodiments, n-1-3, m-1-3, and n + m ≦ 4, and/or
Z represents a copolymer of at least one compound selected from the group consisting of methacrylic acid, acrylic acid, benzyl acrylate, styrene, methyl methacrylate, butyl methacrylate, isobornyl methacrylate, glycidyl methacrylate, tricyclo [5.2.1.02,6] decan-8-yl methacrylate, hydroxyethyl methacrylate, hydroxybutyl acrylate, aminophenylmaleimide, maleic anhydride, 2-hydroxy-3-phenoxypropyl 2-acrylate or pentaerythritol acrylate, and/or
W represents at least one of H, methyl, ethyl, hydroxyl-substituted alkyl, epoxyalkyl, phenyl, benzyl and phenolic group;
z represents Mw of 5000-10000, Pd value is below 2.5 and viscosity is less than 5000cps of the acrylic copolymer.
In some alternative embodiments, a represents at least one of the compounds represented by the following formulae:
an intermediate for use in the preparation of the dispersion resin according to any one of the above, said intermediate being represented by formula (4):
(X-A) n -R m (4)，
wherein, in formula (4), X represents halogen;
n is 1-5, m is 1-5, and n + m is less than or equal to 6;
r represents a group C, N, CH,
Or at least one of a linear alkyl group having 2 to 14 carbon atoms, an aliphatic cycloalkyl group having 2 to 14 carbon atoms, an aryl group and a heteroaryl group having 3 to 14 carbon atoms;
a is represented by formula (3):
and in formula (3), W is connected with X, carboxyl is connected with R, W represents at least one of H atom, saturated or unsaturated alkyl with 1-14 carbon atoms, epoxy with 2-6 carbon atoms, substituted or unsubstituted aryl with 3-14 carbon atoms and substituted or unsubstituted heteroaryl.
In some alternative embodiments, X is Cl, Br or I,
n is 1-3, m is 1-3, and n + m is less than or equal to 4, and/or
W represents at least one of H, methyl, ethyl, hydroxyl-substituted alkyl, epoxyalkyl, phenyl, benzyl and phenolic group.
In some alternative embodiments, the intermediate is one of the compounds represented by the following formulae:
as described above, in the formulae (4-1) to (4-12), X represents a halogen, preferably Cl, Br or I, more preferably Br.
A process for preparing the dispersion resin of any one of the above, comprising the steps of:
under the action of a free radical initiator, adding an acrylic compound containing amino, epoxy, alkyl with 1-14 carbon atoms, cycloalkyl with 3-14 carbon atoms or aryl substituent groups into a first solvent containing a chain transfer agent, and carrying out free radical solution polymerization reaction under an inert atmosphere to generate an acrylic copolymer Z;
the obtained acrylic copolymer Z is reacted with the intermediate described in any one of the above in a second solvent in the presence of a catalyst to produce a dispersion resin.
According to the method for producing a dispersion resin of the present invention, the dispersion resin of the present invention can be efficiently produced.
In some optional embodiments, in the preparation method of the dispersion resin of the present invention, the obtained acrylic copolymer Z and the intermediate are heated in a second solvent in the presence of a catalyst for dissolution and reflux for 2 to 5Hr, and then reacted at 70 to 120 ℃ with stirring for 5 to 12Hr to form the dispersion resin, and/or
The mass ratio of the acrylic copolymer Z to the intermediate is 1: 1-1.5: 1.
In some alternative embodiments, in the method for producing a dispersion resin of the present invention, the obtained acrylic copolymer Z and the intermediate are heated in a second solvent in the presence of a catalyst to be dissolved under reflux for 3.5Hr, and then reacted at 90 ℃ with stirring for 8Hr to produce the dispersion resin, and/or the mass ratio of the acrylic copolymer Z to the intermediate is 1.2: 1.
In some alternative embodiments, in the method for preparing a dispersion resin according to the present invention, the acrylic compound is one or more compounds selected from the group consisting of methacrylic acid, acrylic acid, benzyl acrylate, styrene, methyl methacrylate, butyl methacrylate, isobornyl methacrylate, glycidyl methacrylate, tricyclo [5.2.1.02,6] decan-8-yl methacrylate, hydroxyethyl methacrylate, hydroxybutyl acrylate, aminophenylmaleimide, maleic anhydride, 2-hydroxy-3-phenoxypropyl 2-acrylate or pentaerythritol acrylate, and/or
The first solvent and the second solvent are each at least one selected from the group consisting of toluene, ethyl acetate, DMF, NMP, DMSO, and acetonitrile, and/or
The catalyst is at least one selected from the group consisting of tetramethylguanidine, TMG, KI, NaI, triethylamine, and metformin.
In some alternative embodiments, after the reaction is finished, the solvent is evaporated by rotation, for example, n-butanol of 1.5 times of the volume of the original reaction solvent may be added again, for example, stirred at 55 ℃ for example at 1Hr, added into petroleum ether of 3 times, and the precipitate is suction-filtered and dried to obtain the dispersion resin.
A nanometer pigment color paste composition comprises the following components in parts by weight:
5-30 parts of a nano pigment;
0.5-5 parts of hyperdispersant;
0.5 to 5 parts of any one of the dispersion resins; and
15-75 parts of organic solvent.
The weight parts of the nano pigment are 10 parts, 15 parts, 20 parts and 25 parts; the weight parts of the hyperdispersant are 1 part, 2 parts, 3 parts and 4 parts; the weight parts of the dispersion resin are, for example, 1 part, 2 parts, 3 parts, 4 parts; the organic solvent is, for example, 20 parts, 30 parts, 40 parts, 50 parts, 60 parts, 65 parts, or 70 parts by weight.
The method for preparing the pigment color paste according to the chromaticity requirement generally comprises the following steps: one is to mix and grind two or more pigment crystals in a dispersion slurry, for example: the red color can be obtained by directly mixing and grinding PR177 and PR254 or directly mixing and grinding PR254 and PY 138; green is direct mixed grinding of PG36 and PY150, or direct mixed grinding of PG58 and PY 150; blue PB 15: 4 direct blend milling with PV19, or PB 15: 6 direct blend milling with PV 23; the black color is the direct mixing and grinding of C black and titanium black; white is the direct milling of titanium oxide.
In some alternative embodiments, the nanopigment mill base composition has an average particle size D 50 In the range of 10-200nm, the bulk density is 0.5-4.8g/cm 3 Specific surface area of 100-400m 2 /g。
In some alternative embodiments, the nanopigment mill base composition has an average particle size D 50 In the range of 20-200nm, the bulk density is 0.7-1.8g/cm 3 The specific surface area is 100-200m 2 /g。
In some alternative embodiments, the nanopigment is at least one of red, yellow, blue, green, black, white, six-color organic and/or inorganic nanopigments. The nano-pigment may be an organic pigment or an inorganic pigment: the organic pigments that can be selected have a primary red color of PR177, PR 254; green is PG36, PG 58; blue PB 15: 4, PB 15: 6; yellow is PY138, PY 150; purple color is PV19, PV 23. And inorganic metals and their oxides, carbon black particles: white is TiO 2 ，SiO 2 (ii) a The black color is C black 7, C black 11, titanium black and iron oxide.
The mill base composition of the present invention is subjected to wetting and dispersing in addition to the selected pigment. The hyperdispersant is at least one of a copolymer of methacrylic acid and styrene, a polyester copolymer, a polyurethane copolymer and an epoxy resin copolymer. Commercially available products which may be exemplified have mainly the following trade names: EFKA-4060, EFKA-4080, EFKA-4043, EFKA-4047, Disperbyk-2000, Disperbyk-2001, Disperbyk-161-167, Disperbyk-2050, Disperbyk-2100, Disperbyk-2020, Disperbyk-333, Solsperse28000, Solsperse24000, Solsperse5000, Solsperse22000, Solsperse32500, Solsperse 38500.
The organic solvent is at least one of propylene glycol methyl ether, propylene glycol methyl ether acetate, 3-ethoxy ethyl propionate and butyl acetate.
A photoresist composition comprising the following components in parts by weight:
the weight portions of the nano pigment color paste composition are 5 portions, 10 portions, 20 portions, 30 portions, 40 portions, 45 portions; the parts by weight of the alkali-soluble resin are, for example, 3 parts, 5 parts, 7 parts, 10 parts, 12 parts, 14 parts, 16 parts, 18 parts; the parts by weight of the oligomeric resin are, for example, 3 parts, 5 parts, 7 parts, 10 parts, 12 parts, 14 parts, 16 parts, 18 parts; the weight parts of the photoinitiator are, for example, 0.4 part, 0.7 part, 1 part, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts; the parts by weight of the coagent are, for example, 0.05 part, 0.1 part, 0.15 part, 0.2 part, 0.4 part, 0.6 part, 0.8 part, 1 part, 1.2 part, 1.5 part, 1.8 part; the parts by weight of the photocurable resin are, for example, 3 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, and 12 parts; the polar organic solvent is, for example, 30 parts, 40 parts, 50 parts, 80 parts, 100 parts, 120 parts, 140 parts, 160 parts, or 180 parts by weight.
In the above embodiment, the "alkali-soluble resin" refers to a polymer resin containing an alkyl methacrylate group, and the alkali-soluble resin has an average acid value of 60KOH/g to 200KOH/g, preferably 90KOH/g to 150 KOH/g. In some alternative embodiments, the alkali soluble resin is at least one selected from the group consisting of methacrylic acid and methyl methacrylate copolymer, methacrylic acid and cyclohexyl methacrylate copolymer, methacrylic acid and glycidyl methacrylate copolymer, methacrylic acid and 2-hydroxyethyl methacrylate copolymer, methacrylic acid and cyclohexyl methacrylate and styrene and 2-hydroxyethyl methacrylate copolymer, and/or
The light-cured resin adopts light-cured resin with vinyl double bonds, and is selected from epoxy soybean oil acrylate, modified epoxy acrylate, polyester acrylate, active amine, HDDA, TMPTA, DPGDA, PETA, IOBA, EB114, EB145, EB160, ODA, TCDA, OTA480, and epoxy acrylate,
At least one of the group consisting of, and/or
The photoinitiator is selected from diphenyl oxide (2,4, 6-trimethylbenzoyl) phosphine, 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2- (dimethylamino) -4' -morpholinobutyrophenone, 2-methyl-1- [ 4-methylthiophenyl ] -2-morpholinopropan-2-one, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2-isopropyl thioxanthone, ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, methyl o-benzoylbenzoate, 4-methylbenzophenone, methyl o-benzoylbenzoate, methyl-N-methyl-phenyl-1-propanone, methyl-N-methyl-2-methyl-1-one, methyl-N-ethyl-2-methyl-2-one, methyl-N-ethyl-4-dimethylaminobenzoate, methyl-ethyl-methyl-2-ethyl-methyl-4-methyl-phenyl-methyl-2-ethyl-methyl-benzoylbenzoate, methyl-phenyl-2-ethyl-methyl-2-ethyl-one, methyl-N-ethyl-methyl-benzoylbenzoate, and ethyl-methyl-ethyl-2-ethyl-2-methyl-ethyl-2-ethyl-one,
At least one of the group consisting of, and/or
The active assistant is at least one of a leveling agent and a coupling agent, wherein the leveling agent is at least one selected from the group consisting of a polyether-modified polydimethylsiloxane solution, a polyester-modified polydimethylsiloxane solution, a polyether-modified polysiloxane solution, a polyester-modified polymethylalkylsiloxane solution, a polyether-modified polydimethylsiloxane solution, a polyacrylate solution, and a fluorocarbon copolymer solution, and the coupling agent is at least one selected from the group consisting of N '-beta' -aminoethyl-N-beta-aminoethyl-gamma-aminopropylmethyldimethoxysilane, N '-beta' -aminoethyl-N-beta-aminoethyl-gamma-aminopropylmethyldiethoxysilane, and N '-beta' -aminoethyl-N-beta-aminoethyl-gamma-aminopropylmethyldiethoxysilane Silane, N '-beta' -aminoethyl-N-beta-aminoethyl-gamma-aminopropyltrimethoxysilane, N '-beta' -aminoethyl-N-beta-aminoethyl-gamma-aminopropyltriethoxysilane and N '-beta' -aminoethyl-N-beta-aminoethyl-alpha-aminomethyl triethoxysilane, gamma-cyclohexylaminopropyltriethoxysilane and at least one member of the group consisting of methyl, gamma-cyclohexylaminopropyldimethoxysilane and gamma-chloropropyltriethoxysilane (gamma 2), and/or
The polar organic solvent is preferably a low-polar organic solvent or a medium-polar organic solvent, and the organic solvent is at least one selected from the group consisting of methyl ethyl ketone, ethyl cellosolve, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, 2-ethoxypropanol, 2-methoxypropanol, 3-methoxybutanol, cyclohexanone, cyclopentanone, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate and butyl acetate, and/or
The oligomeric resin is represented by formula (1-1), (1-2) or (1-3):
wherein, in the formulae (1-1), (1-2) and (1-3), R 1 And R 3 Each represents a linear hydrocarbon group having 2 to 8 carbon atoms or a graft copolymer group, and R 2 And R 4 Each represents C, a benzene ring,
In some alternative embodiments, the Ms value of the oligomeric resin is 3000-8000; the weight average molecular weight (Mw value) is 6000-; the Pd value is around 1.8.
As an example, the photoresist composition of the invention can be prepared by the following method, according to the proportion of the photoresist composition, the method comprises the following steps:
(1) preparing a nano pigment color paste composition: adding organic solvent into nano pigment particles and a hyper-dispersant in a sand mill of a zirconium ball with the diameter of 0.1mm for wet grinding, and adding dispersion resin represented by the formula (2) as stable resin in the grinding process to prepare pigment dispersion color paste;
(2) preparing a photosensitive solution: mixing and dispersing alkali-soluble resin, light-cured resin with vinyl double bonds, an electrically asymmetric active photoinitiator, an active auxiliary agent, oligomeric resin with a formula (1) and a polar organic solvent into a solution, and filtering to obtain a photosensitive solution;
(3) and (3) mixing the pigment dispersion color paste in the step (1) with the photosensitive solution in the step (2), adding a polar organic solvent to adjust the viscosity, dispersing in a dispersion machine, and filtering to prepare the photoresist composition.
In the above steps, the polarity and the pH value of the oligomeric resin of formula (1) in step (1) and step (2) may be adjusted. The pore size of the filter adopted by the filtration mentioned in the step (2) is between 400 and 1000 nm.
A method of fabricating a pattern on a substrate, comprising the steps of:
forming a photoresist layer on a substrate using the photoresist composition as described above, the photoresist layer being dried to form a color thin film;
on the color film, a mask plate is utilized to form a pattern on a substrate through exposure, development and low-temperature curing, wherein the low-temperature curing temperature is 85-100 ℃.
Compared with the prior art, the invention has the beneficial effects that at least:
the dispersion resin can stabilize rheology and resist agglomeration and flocculation, and when the dispersion resin is used in a photoresist composition, the nano pigment can exist in a dispersion state of fine particles, so that pigment particles can not agglomerate and flocculate, and the photoresist composition can be used for manufacturing fine patterns and has high etching precision.
Drawings
FIGS. 1A-1D are schematic illustrations of a photolithographic process using photoresist compositions of the invention.
FIG. 2 is a color photoresist line fabricated on a glass substrate according to the photolithography process illustrated in FIGS. 1A-1D.
FIG. 3 is a schematic illustration of a photolithographic process illustrated in FIGS. 1A-1D to produce colored photoresist lines on an ITO metal substrate.
FIG. 4 is a color photoresist line made on a PET substrate according to the photolithographic process illustrated in FIGS. 1A-1D.
FIGS. 5, 6 and 7 are color photoresist patterns formed on a PET substrate according to the photolithography process illustrated in FIGS. 1A-1D.
FIG. 8 is a picture of a filter fabricated by using a photoresist composition of comparative example 1 without using the oligomer resin of the present invention.
Detailed Description
Specific embodiments of the present invention are described below, but it should be noted that, without conflict, new embodiments/examples may be formed by any combination between the various embodiments/examples or technical features described below.
The following are specific examples of the present invention, wherein example 1 is a process for the preparation of oligomeric resins according to the present invention; examples 2 to 5 are the preparation method of the dispersion resin according to the present invention; the reagents referred to in the following examples are all commercially available.
Example 1
Preparation of oligomeric resin:
the process for the preparation of the compound of the above general formula (1) can be obtained by the following synthetic route:
route:
wherein, starting reactants
Is a custom purchase made by a entrusted chemical company from raw materials
Thus, the feeding molar ratio of the D-sorbitol to the D-sorbitol is 1:3, and the compound 1 is prepared. Next, compound 1 was further reacted with an intermediate containing R4 in a molar ratio of 1:2 to produce general formula (1). And (5) post-treatment and purification.
In the general formula (1), R1 and R3 can be designed to be reacted and connected with straight-chain hydrocarbon or graft copolymer groups with 2-8 carbon atoms; r2, R4 may be C atom, benzene ring,
To obtain an oligomer (1-1).
From this route, the following can also be obtained:
in the oligomers (1-1), (1-2) and (1-3), R 1 ，R 3 May each represent a linear hydrocarbon group having 2 to 8 carbon atoms or a graft copolymer group; r 2 ，R 4 May each represent C, a benzene ring,
The Mw values of the oligomers (1-1), (1-2) and (1-3) may be 10000-; the Pd value may be 1.8-2.0.
In example 1, in the oligomers (1-1), (1-2) and (1-3), R 1 is-CH 2 CH 2 CH 3 ，R 2 Is composed of
R 3 is-CH 3 ，R 4 Are respectively as
Example 2
Preparation of Dispersion resin 2-1:
1) oligomer synthesis: 15g of 2-acrylic acid-2 hydroxy-3-phenoxypropyl ester, 3.74g of acrylic acid, 5.41g of styrene and 5.2g of methyl methacrylate; 0.58g of azobisisovaleronitrile serving as a free radical initiator; 1.05g of chain transfer agent alpha-methyl styrene linear dimer; adding the mixture into 50g of solvent toluene; heating to 90 ℃ under the nitrogen atmosphere, stirring at 300rpm for 4Hr, and performing free radical reaction synthesis to obtain an oligomer intermediate Z-2, wherein the Mw of the oligomer intermediate Z-2 is 5000-10000, the Pd value is below 2.5, and the viscosity is less than 5000cps by characterization;
2) product synthesis: 36g of a compound 4-5 of the general formula (4) (wherein X is Br) was put into a four-necked flask together with the oligomer intermediate Z-2 obtained in step 1); then 60g of acetonitrile solvent is added, 0.08gKI of catalyst is dissolved into 20g of acetonitrile, a constant pressure funnel is put into the acetonitrile, the mixture is connected to a four-mouth bottle, and the dropping is completed in 30 min; and simultaneously stirring, heating, dissolving and refluxing the magnetic particles for 4-5Hr, keeping the reaction heating temperature at 95 ℃, stirring at 350rpm for 8Hr, after the reaction is finished, transferring the reaction product into a rotary evaporator to evaporate the solvent in a rotating manner, adding 180g of n-butyl alcohol again, stirring at 55 ℃ for 1Hr, putting the mixture into a 540g petroleum ether conical flask, and performing suction filtration and drying on the precipitate to obtain the dispersion resin 2-1 of the general formula (2), wherein the Mw of the dispersion resin 2-1 is 16801 and the Pd value is 2.4.
Example 3
Preparation of Dispersion resin 2-2:
1) oligomer synthesis: 15g of 2-acrylic acid-2 hydroxy-3-phenoxypropyl ester, 4.47g of methacrylic acid, 5.2g of methyl methacrylate and 7.4g of benzyl methacrylate; 0.6g of azobisisobutyronitrile as a radical initiator; 1.05g of chain transfer agent alpha-methyl styrene linear dimer; adding into 60g of ethyl acetate solvent; heating to 80 ℃ in nitrogen atmosphere, stirring at 300rpm for 4Hr, and performing free radical reaction synthesis to obtain an oligomer intermediate Z-3; the molecular weight of the oligomer intermediate Z-3 is 3000-10000, the Pd value is below 2.5 and the viscosity is less than 5000 cps.
2) Product synthesis: putting 40g of a compound 4-6 of the general formula (4) (wherein X is Br) together with the oligomer intermediate Z-3 obtained in the step 1) into a four-necked flask; adding 80g of acetonitrile solvent, dissolving 0.08gKI of catalyst into 20g of acetonitrile, putting the mixture into a constant pressure funnel, connecting the funnel to a four-mouth bottle, and dripping the mixture for 30 min; and simultaneously stirring, heating, dissolving and refluxing the magnetic particles for 4-5Hr, keeping the reaction heating temperature at 90 ℃, stirring at 350rpm for 8Hr, after the reaction is finished, transferring the reaction product into a rotary evaporator to evaporate the solvent in a rotating manner, adding 180g of n-butyl alcohol again, stirring at 55 ℃ for 1Hr, putting the mixture into a 540g petroleum ether conical flask, and performing suction filtration and drying on the precipitate to obtain the dispersion resin 2-2 of the general formula (2), wherein the Mw of the dispersion resin 2-2 is 20350 and the Pd value is 2.3.
Example 4
Preparation of Dispersion resins 2-3:
1) oligomer synthesis: 15g of 2-hydroxy-3-phenoxypropyl 2-acrylate, 3.74g of acrylic acid, 5.41g of styrene, 5.2g of methyl methacrylate and 7.4g of benzyl methacrylate; adding into 80g of ethyl acetate solvent; 0.8g of free radical initiator azobisisovaleronitrile and 1.05g of chain transfer agent alpha-methyl styrene linear dimer, 10g of ethyl acetate are added dropwise from a constant pressure funnel for 30 min; heating to 90 ℃ in nitrogen atmosphere, stirring at 300rpm for 4Hr, and performing free radical reaction synthesis to obtain an oligomer intermediate Z-4; the low polymer intermediate Z-4 is characterized by Mw of 3000-10000, Pd below 2.5 and viscosity less than 5000 cps.
2) Product synthesis: 42g of the compound 4-9 of the general formula (4) wherein X is I are charged into a four-necked flask together with the oligomer intermediate Z-4 obtained in step 1); then 80g of DMF solvent is added, 0.08g of triethylamine catalyst is dissolved into 20g of DMF, the mixture is put into a constant pressure funnel and connected to a four-mouth bottle, and the dripping is finished within 30 min; and simultaneously stirring, heating, dissolving and refluxing the magnetic particles for 4-5Hr, keeping the reaction heating temperature at 90 ℃, stirring at 350rpm for 8Hr, after the reaction is finished, transferring the reaction product into a rotary evaporator to evaporate the solvent in a rotating manner, adding 200g of n-butyl alcohol again, stirring at 55 ℃ for 1Hr, putting the reaction product into a 600g petroleum ether conical flask, and performing suction filtration and drying on precipitates to obtain the resin 2-3 of the general formula (2), wherein the Mw of the dispersed resin 2-3 is 17168, and the Pd value is 1.8.
Example 5
Preparation of Dispersion resins 2 to 4:
1) oligomer synthesis: 15g of 2-acrylic acid-2 hydroxy-3-phenoxypropyl ester, 4.47g of methacrylic acid, 5.41g of styrene and 11.55g of isobornyl methacrylate; 0.8g of azobisisobutyronitrile as a radical initiator; 1.05g of chain transfer agent alpha-methyl styrene linear dimer; adding into 65g of ethyl acetate solvent; heating to 90 ℃ in nitrogen atmosphere, stirring at 300rpm for 4Hr, and performing free radical reaction synthesis to obtain an oligomer intermediate Z-5; the molecular weight of the oligomer intermediate Z-5 is 3000-10000, the Pd value is below 2.5 and the viscosity is less than 5000 cps.
2) Product synthesis: charging 40g of compound 4-11 of general formula (4) wherein X is I together with the oligomer intermediate Z-5 obtained in step 1) into a four-necked flask; then 80g of DMF solvent is added, 0.08gKI catalyst is dissolved into 20g of acetonitrile, a constant pressure funnel is put into the acetonitrile and connected to a four-mouth bottle, and the dropping is finished within 30 min; and simultaneously stirring, heating, dissolving and refluxing the magnetic particles for 4-5Hr, keeping the reaction heating temperature at 95 ℃, stirring at 350rpm for 8Hr, after the reaction is finished, transferring the reaction product into a rotary evaporator to evaporate the solvent in a rotating manner, adding 200g of n-butyl alcohol again, stirring at 55 ℃ for 1Hr, putting the reaction product into a 600g petroleum ether conical flask, and performing suction filtration and drying on precipitates to obtain the resin 2-4 with the general formula (2), wherein the Mw of the dispersed resin 2-4 is 16115, and the Pd value is 2.2.
Example 6
Preparation of Dispersion resins 2-5:
1) oligomer synthesis: 15g of 2-acrylic acid-2 hydroxy-3-phenoxypropyl ester, 3.74g of acrylic acid, 5.8g of cyclohexyl methacrylate copolymer and 9.4g of benzyl methacrylate; 0.6g of azobisisobutyronitrile as a radical initiator; 1.05g of chain transfer agent alpha-methyl styrene linear dimer; adding into solvent ethyl acetate 60 g; heating to 80 ℃ in nitrogen atmosphere, stirring at 300rpm for 4Hr, and performing free radical reaction synthesis to obtain an oligomer intermediate Z-6, wherein the Mw of the oligomer intermediate Z-6 is 3000-10000, the Pd value is below 3.5, and the viscosity is less than 5000 cps.
2) Product synthesis: charging 40g of compound 4-8 of general formula (4) (wherein X is Br) and oligomer intermediate Z-6 obtained in step 1) into a four-necked flask; then 80g of acetonitrile solvent is added, 0.08gKI catalyst is dissolved into 20g of acetonitrile, a constant pressure funnel is put into the acetonitrile and connected to a four-mouth bottle, and the dropping is finished within 30 min; and simultaneously stirring, heating, dissolving and refluxing the magnetic particles for 4-5Hr, keeping the reaction heating temperature at 90 ℃, stirring at 350rpm for 8Hr, after the reaction is finished, transferring the reaction product into a rotary evaporator to evaporate the solvent in a rotating manner, adding 180g of n-butyl alcohol again, stirring at 55 ℃ for 1Hr, putting the mixture into a 540g petroleum ether conical flask, and performing suction filtration and drying on precipitates to obtain the dispersion resin 2-5 of the general formula (2), wherein the Mw of the dispersion resin 2-5 is 21507 and the Pd value is 1.9.
Example 7
Preparation of Dispersion resins 2 to 6:
1) oligomer synthesis: 15g of 2-acrylic acid-2 hydroxy-3-phenoxypropyl ester, 4.47g of methacrylic acid, 11.2g of methyl methacrylate and 4.4g of glycidyl methacrylate; 0.6g of azobisisobutyronitrile as a radical initiator; 1.05g of chain transfer agent alpha-methyl styrene linear dimer; adding into solvent ethyl acetate 60 g; heating to 90 ℃ in nitrogen atmosphere, stirring at 300rpm for 4Hr, and performing free radical reaction synthesis to obtain an oligomer intermediate Z-7; as a result, the oligomer intermediate Z-7 has Mw of 3000-10000, a Pd value of 2.5 or less, and a viscosity of less than 5000 cps.
2) Product synthesis: charging 40g of compound 4-11 of general formula (4) (wherein X is I) together with oligomer intermediate Z-7 obtained in step 1) into a four-necked flask; then 80g of acetonitrile solvent is added, 0.08g of triethylamine catalyst is dissolved into 20g of acetonitrile, a constant pressure funnel is put into the acetonitrile and connected to a four-mouth bottle, and the dropping is finished within 30 min; and simultaneously stirring, heating, dissolving and refluxing the magnetic particles for 4-5Hr, keeping the reaction heating temperature at 90 ℃, stirring at 350rpm for 8Hr, after the reaction is finished, transferring the reaction product into a rotary evaporator to evaporate the solvent in a rotating manner, adding 180g of n-butyl alcohol again, stirring at 55 ℃ for 1Hr, putting the mixture into a 540g petroleum ether conical flask, and performing suction filtration and drying on precipitates to obtain the dispersion resin 2-6 of the general formula (2), wherein the Mw of the dispersion resin 2-6 is 22340, and the Pd value is 2.3.
Example 8
Preparation of Dispersion resins 2 to 7:
1) oligomer synthesis: 15g of 2-acrylic acid-2-hydroxy-3-phenoxypropyl ester, 3.74g of acrylic acid, 7.6g of styrene and 6.4g of 2-hydroxyethyl methacrylate; 0.6g of azobisisobutyronitrile as a radical initiator; 1.05g of chain transfer agent alpha-methyl styrene linear dimer; adding into solvent ethyl acetate 60 g; heating to 80 ℃ in nitrogen atmosphere, stirring at 300rpm for 4Hr, and performing free radical reaction synthesis to obtain an oligomer intermediate Z-8; the molecular weight of the oligomer intermediate Z-8 is 3000-10000, the Pd value is below 2.5 and the viscosity is less than 5000 cps.
2) Product synthesis: charging 40g of a compound 4-3 of the general formula (4) (wherein X is Br) and the oligomer intermediate Z-8 obtained in step 1) into a four-necked flask; then 80g of acetonitrile solvent is added, 0.08gKI catalyst is dissolved into 20g of acetonitrile, a constant pressure funnel is put into the acetonitrile and connected to a four-mouth bottle, and the dropping is finished within 30 min; simultaneously stirring, heating, dissolving and refluxing by magnetons for 4-5Hr, keeping the reaction heating temperature at 90 ℃, stirring at 350rpm for 8Hr, after the reaction is finished, transferring into a rotary evaporator to evaporate the solvent in a rotating way, adding 180g of n-butyl alcohol again, stirring at 55 ℃ for 1Hr, putting into a 540g of petroleum ether conical flask, and performing suction filtration and drying on the precipitate to obtain the dispersing resin 2-7 of the general formula (2); the Mw of dispersion resins 2-7 was characterized as 16579 and the Pd value was 2.1.
Example 9
Preparation of dispersing resin 2-8:
1) oligomer synthesis: 15g of 2-acrylic acid-2 hydroxy-3-phenoxypropyl ester, 4.47g of methacrylic acid, 4.7g of methyl methacrylate and 8.8g of benzyl methacrylate; 0.6g of azobisisobutyronitrile as a radical initiator; 1.05g of chain transfer agent alpha-methyl styrene linear dimer; adding into 60g of ethyl acetate solvent; heating to 80 ℃ in nitrogen atmosphere, stirring at 300rpm for 4Hr, and performing free radical reaction synthesis to obtain an oligomer intermediate Z-9; as a result, the oligomer intermediate Z-9 has Mw of 3000-10000, a Pd value of 2.5 or less, and a viscosity of less than 5000 cps.
2) Product synthesis: charging 40g of a compound 4-5 of the general formula (4) (wherein X is I) together with the oligomer intermediate Z-9 obtained in step 1) into a four-necked flask; then 80g of acetonitrile solvent is added, 0.08g of triethylamine catalyst is dissolved into 20g of acetonitrile, a constant pressure funnel is put into the acetonitrile and connected to a four-mouth bottle, and the dropping is finished within 30 min; and simultaneously stirring, heating, dissolving and refluxing the magnetic particles for 4-5Hr, keeping the reaction heating temperature at 90 ℃, stirring at 350rpm for 8Hr, after the reaction is finished, transferring the reaction product into a rotary evaporator to evaporate the solvent in a rotating manner, adding 180g of n-butyl alcohol again, stirring at 55 ℃ for 1Hr, putting the mixture into a 540g petroleum ether conical flask, and performing suction filtration and drying on precipitates to obtain the dispersion resin 2-8 of the general formula (2), wherein the Mw of the dispersion resin 2-8 is 22790, and the Pd value is 2.5.
Examples 10 to 15 and comparative examples 1 to 2 are photoresist compositions prepared using the oligomeric resins and the dispersed resins obtained in the above examples 1 to 9, wherein the amounts of the respective components and raw materials used in examples 10 to 15 and comparative examples 1 to 2 are shown in Table 2, and the photoresist compositions are prepared as follows:
(1) preparing a nano pigment color paste composition: adding organic solvent into nano pigment particles and a hyper-dispersant in a sand mill of a zirconium ball with the diameter of 0.1mm for wet grinding, and adding oligomeric resin of a structural unit represented by the formula (1) as stable resin in the grinding process to prepare pigment dispersion color paste;
(2) preparing a photosensitive solution: mixing and dispersing alkali-soluble resin, light-cured resin with vinyl double bonds, an electrically asymmetric photoinitiator, a coagent, oligomeric resin with the formula (1) and a polar organic solvent into a solution, and filtering the solution by using a filter with the aperture of 400-plus 1000nm to obtain a photosensitive solution;
(3) and (3) mixing the pigment dispersion color paste in the step (1) with the photosensitive liquid in the step (2), adding a polar organic solvent to adjust the viscosity, dispersing in a dispersion machine, and filtering to prepare the photoresist composition.
Referring to FIGS. 1A to 1D, the photoresist compositions of examples 6 to 11 and comparative examples 1 to 2 were developed to prepare patterns according to the following methods,
(1) processing of the substrate 10: vacuum adhering and fixing on the substrate; or Roll to Roll equipment is utilized for feeding the coiled materials; the substrate 10 may be a glass/PET/PI/metal substrate.
(2) Manufacturing a photoresist layer: the photoresist composition of the present invention is coated/printed/sprayed on the substrate 10 by spin/Slit coating, and then sequentially subjected to vacuum and pre-baking (70-100 deg.C/2-5 min) to form a first 2-5 μm color film 20.
(3) Manufacturing a pixel pattern: and (3) forming a pattern on a mask plate on the color film 20 in the step (2) by using the steps of masking by a mask plate 30, UV exposure, development and low-temperature curing.
Referring to fig. 2 to 7, in which fig. 2 (example 10) shows a width of a color photoresist line fabricated on a glass substrate according to the photolithography process illustrated in fig. 1A to 1D, measured at 5000 times combined magnification under a metallographic microscope and a CCD, as 3.3 μm. FIG. 3 (example 11) shows that the width of a color resist line fabricated on an ITO metal substrate according to the photolithography process illustrated in FIGS. 1A to 1D was 3.9 μm as measured under a metallographic microscope and a CCD at 5000 times combined magnification. FIG. 4 (example 12) shows that the width of a color resist line formed on a PET substrate by the photolithography process shown in FIGS. 1A to 1D was 20.0 μm as measured by a metallographic microscope and a CCD under a combined magnification of 5000 times. FIGS. 5-7 (corresponding to examples 13-15, respectively) show that the minimum pitch, measured under a metallographic microscope and a CCD at 5000 times combined magnification, of color resist patterns fabricated on ITO metal substrates according to the photolithography process illustrated in FIGS. 1A-1D, is in the range of 1.2-3.3 μm in width. From FIG. 2 to FIG. 7, the photoresist composition of the present invention can be used for making fine patterns with high photolithography precision.
In order to show the effect of the photoresist composition of the present invention, nanopigments PR254, C black 7 were also directly used as two comparative examples.
Table 1: photolithographic developed lines of examples 10-15 and comparative examples 1 and 2
The photoresist compositions of examples 10-15 above were used for low temperature curing (90 ℃) to make monochromatic filters, which can be achieved by the following processes:
1) coating: 1-2 μm thick coating, vacuum-1 atm/30 s;
2) pre-baking: drying the coated substrate at 85 ℃ for 160 s;
3) exposure: the exposure energy is 100-;
4) and (3) developing: developing the corresponding pattern on the Mask plate by using 0.238% TMAH alkaline developing solution for 60-100S;
5) post-baking: baking at 90 deg.C for 60 min.
After the dispersion resin of the present invention was used in examples 10 to 15 and comparative example 2, the photolithographic development line accuracy could reach 4 μm or less; comparative example 1 line precision could only reach 15 μm without the photolithographic development of the dispersion resin of the present invention. The polarities of other components such as the dispersing resin and the developing resin in the photoresist are matched and unified, so that the pixel precision, particularly the resolution of the pixel edge is improved after UV photoetching and low-temperature post-baking. In addition, the oligomer resin of the present invention was not used in both comparative example 1 and comparative example 2, so that the pixel adherence after the low-temperature post-baking process was reduced, and the pixel of 4 μm or less had a peeling phenomenon; the pixel adherence of the photoresist formulation using the oligomeric resin of the present invention after the post-baking process at a low temperature of 90 ℃ does not have the peeling phenomenon, as shown in fig. 8.
The performance of the filters was measured and the results are shown in table 2.
Table 2: results of testing of monochromatic filters of examples 10 to 15 and comparative examples 1 and 2
Note: ● indicates pixel lines are missing; delta indicates that the pixel line is not fallen off, but the alignment patch mark (Marker) is fallen off; o indicates that neither the pixel nor the Marker is peeled off; the Slope, film thickness and CD Loss values are in units of μm.
As shown in Table 2, the monochromatic filters of examples 12-15 were good in terms of solvent resistance, acid and alkali resistance, CD loss, and adhesion of 10 μm line double 85 after post-baking treatment at 90 ℃ in the photolithography process.
Examples 10-11 added a small amount of the oligomeric resin of the present invention and the single color filters made therefrom were improved in solvent resistance, acid and alkali resistance, CD loss, and adhesion of 10 μm lines to double 85 after post-baking treatment at 90 ℃.
Comparative examples 1 and 2, which did not use the oligomeric resin of the present invention, were good at solvent resistance, acid and alkali resistance, CD loss, and 10 μm line double 85 adhesion after single color filters made therefrom were subjected to a 90 ℃ post-baking process.
The above embodiments are only preferred embodiments of the present invention, and the protection scope of the present invention is not limited thereby, and any insubstantial changes and substitutions made by those skilled in the art based on the present invention are within the protection scope of the present invention.
Claims (17)
1. A dispersion resin, characterized in that the dispersion resin is represented by formula (2):
(Z-A) n -R m (2)，
wherein, in formula (2), n is 1-5, m is 1-5, and n + m is less than or equal to 6;
z represents H, or an acrylic copolymer containing amino, epoxy, alkyl with 1-14 carbon atoms, cycloalkyl with 3-14 carbon atoms or aryl substituent;
r represents a group C, N, CH,
Or at least one of a straight-chain alkyl group having 2 to 14 carbon atoms, an aliphatic cycloalkyl group having 2 to 14 carbon atoms, an aryl group having 3 to 14 carbon atoms and a heteroaryl group;
a is represented by formula (3):
and in formula (3), W is bonded to Z, a carboxyl group is bonded to R, and W represents at least one of H atom, a substituted or unsubstituted alkyl group having 1 to 14 carbon atoms, an alkylene oxide group having 2 to 6 carbon atoms, a substituted or unsubstituted aryl group having 3 to 14 carbon atoms, and a substituted or unsubstituted heteroaryl group.
2. A dispersion resin according to claim 1,
n is 1-3, m is 1-3, and n + m is less than or equal to 4, and/or
Z represents a copolymer of at least one compound selected from the group consisting of methacrylic acid, acrylic acid, benzyl acrylate, styrene, methyl methacrylate, butyl methacrylate, isobornyl methacrylate, glycidyl methacrylate, tricyclo [5.2.1.02,6] decan-8-yl methacrylate, hydroxyethyl methacrylate, hydroxybutyl acrylate, aminophenylmaleimide, maleic anhydride, 2-hydroxy-3-phenoxypropyl 2-acrylate or pentaerythritol acrylate, and/or
W represents at least one of H, methyl, ethyl, hydroxyl-substituted alkyl, epoxyalkyl, phenyl, benzyl and phenolic group;
z represents that the acrylic copolymer has Mw of 5000-10000, a Pd value of below 2.5 and a viscosity of less than 5000 cps.
3. A dispersion resin according to claim 1 or 2, wherein a represents at least one of compounds represented by the following formulae:
4. an intermediate for preparing the dispersion resin according to any one of claims 1 to 3, wherein the intermediate is represented by formula (4):
(X-A) n -R m (4)，
wherein, in formula (4), X represents halogen;
n is 1-5, m is 1-5, and n + m is less than or equal to 6;
r represents a group C, N, CH,
Or a straight chain alkyl group having 2 to 14 carbon atoms, an aliphatic cycloalkyl group having 2 to 14 carbon atoms, an aryl group having 3 to 14 carbon atoms andat least one of heteroaryl;
a is represented by formula (3):
and in formula (3), W is connected with X, carboxyl is connected with R, W represents at least one of H atom, saturated or unsaturated alkyl with 1-14 carbon atoms, epoxy with 2-6 carbon atoms, substituted or unsubstituted aryl with 3-14 carbon atoms and substituted or unsubstituted heteroaryl.
5. The intermediate of claim 4,
x is Cl, Br or I,
n is 1-3, m is 1-3, and n + m is less than or equal to 4, and/or
W represents at least one of H, methyl, ethyl, hydroxyl-substituted alkyl, epoxyalkyl, phenyl, benzyl and phenolic group.
6. The intermediate of claim 4 or 5, wherein the intermediate is one of the compounds represented by the following formulae:
7. a process for preparing a dispersion resin according to any one of claims 1 to 3, characterized in that it comprises the following steps:
under the action of a free radical initiator, adding an acrylic compound containing amino, epoxy, alkyl with 1-14 carbon atoms, cycloalkyl with 3-14 carbon atoms or aryl substituent groups into a first solvent containing a chain transfer agent, and carrying out free radical solution polymerization reaction under an inert atmosphere to generate an acrylic copolymer Z;
reacting the obtained acrylic copolymer Z with an intermediate of any one of claims 4 to 6 in a second solvent in the presence of a catalyst to produce a dispersion resin.
8. The method of claim 7,
heating the obtained acrylic copolymer Z and the intermediate in a second solvent in the presence of a catalyst, dissolving and refluxing for 2-5Hr, stirring for 5-12 Hr at 70-120 ℃ to react to generate the dispersion resin, and/or
The mass ratio of the acrylic copolymer Z to the intermediate is 1: 1-1.5: 1.
9. The method of claim 8,
heating the obtained acrylic copolymer Z and the intermediate in a second solvent in the presence of a catalyst, dissolving and refluxing for 3.5Hr, and then stirring for 8Hr at 90 ℃ to react to produce the dispersion resin, and/or
The mass ratio of the acrylic copolymer Z to the intermediate was 1.2: 1.
10. The method according to any one of claims 7 to 9,
the acrylic compound is at least one compound selected from the group consisting of methacrylic acid, acrylic acid, benzyl acrylate, styrene, methyl methacrylate, butyl methacrylate, isobornyl methacrylate, glycidyl methacrylate, tricyclo [5.2.1.02,6] decan-8-yl methacrylate, hydroxyethyl methacrylate, hydroxybutyl acrylate, aminophenylmaleimide, maleic anhydride, 2-hydroxy-3-phenoxypropyl 2-acrylate or pentaerythritol acrylate, and/or
The first solvent and the second solvent are each at least one selected from the group consisting of toluene, ethyl acetate, DMF, NMP, DMSO, and acetonitrile, and/or
The catalyst is at least one selected from the group consisting of tetramethylguanidine, TMG, KI, NaI, triethylamine, and metformin.
11. The nano pigment color paste composition is characterized by comprising the following components in parts by weight:
5-30 parts of a nano pigment;
0.5-5 parts of hyperdispersant;
0.5 to 5 parts of the dispersion resin according to any one of claims 1 to 3; and
15-75 parts of organic solvent.
12. The nanopigment mill base composition of claim 11 wherein the average particle size D of the nanopigment mill base composition 50 In the range of 20-200nm, the bulk density is 0.7-1.8g/cm 3 The specific surface area is 100-200m 2 /g。
13. The nanopigment color paste composition according to claim 11 or 12, wherein,
the nano pigment is at least one of red, yellow, blue, green, black and white organic and/or inorganic nano pigments, and/or
The hyperdispersant is at least one of a copolymer of methacrylic acid and styrene, a polyester copolymer, a polyurethane copolymer and an epoxy resin copolymer, and/or
The organic solvent is at least one of propylene glycol methyl ether, propylene glycol methyl ether acetate, 3-ethoxy ethyl propionate and butyl acetate.
14. A photoresist composition is characterized by comprising the following components in parts by weight:
15. the photoresist composition of claim 14,
the alkali soluble resin is at least one selected from the group consisting of methacrylic acid and methyl methacrylate copolymer, methacrylic acid and cyclohexyl methacrylate copolymer, methacrylic acid and glycidyl methacrylate copolymer, methacrylic acid and 2-hydroxyethyl methacrylate copolymer, methacrylic acid and cyclohexyl methacrylate and styrene and 2-hydroxyethyl methacrylate copolymer, and/or
The light-cured resin is selected from epoxy soybean oil acrylate, modified epoxy acrylate, polyester acrylate, active amine, HDDA, TMPTA, DPGDA, PETA, IOBA, EB114, EB145, EB160, ODA, TCDA, OTA480, and epoxy acrylate,
At least one of the group consisting of, and/or
The photoinitiator is selected from diphenyl oxide (2,4, 6-trimethylbenzoyl) phosphine, 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2- (dimethylamino) -4' -morpholinobutyrophenone, 2-methyl-1- [ 4-methylthiophenyl ] -2-morpholinopropan-2-one, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2-isopropyl thioxanthone, ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, methyl o-benzoylbenzoate, 4-methylbenzophenone, methyl o-benzoylbenzoate, methyl-N-methyl-phenyl-1-propanone, methyl-N-methyl-2-methyl-1-one, methyl-N-ethyl-2-methyl-2-one, methyl-N-ethyl-4-dimethylaminobenzoate, methyl-ethyl-methyl-2-ethyl-methyl-4-methyl-phenyl-methyl-2-ethyl-methyl-benzoylbenzoate, methyl-phenyl-2-ethyl-methyl-2-ethyl-one, methyl-N-ethyl-methyl-benzoylbenzoate, and ethyl-methyl-ethyl-2-ethyl-2-methyl-ethyl-2-ethyl-one,
At least one of the group consisting of, and/or
The active assistant is at least one of a leveling agent and a coupling agent, wherein the leveling agent is at least one selected from the group consisting of a polyether-modified polydimethylsiloxane solution, a polyester-modified polydimethylsiloxane solution, a polyether-modified polysiloxane solution, a polyester-modified polymethylalkylsiloxane solution, a polyether-modified polydimethylsiloxane solution, a polyacrylate solution, and a fluorocarbon copolymer solution, and the coupling agent is at least one selected from the group consisting of N '-beta' -aminoethyl-N-beta-aminoethyl-gamma-aminopropylmethyldimethoxysilane, N '-beta' -aminoethyl-N-beta-aminoethyl-gamma-aminopropylmethyldiethoxysilane, and N '-beta' -aminoethyl-N-beta-aminoethyl-gamma-aminopropylmethyldiethoxysilane Silane, N '-beta' -aminoethyl-N-beta-aminoethyl-gamma-aminopropyltrimethoxysilane, N '-beta' -aminoethyl-N-beta-aminoethyl-gamma-aminopropyltriethoxysilane and N '-beta' -aminoethyl-N-beta-aminoethyl-alpha-aminomethyl triethoxysilane, gamma-cyclohexylaminopropyltriethoxysilane and at least one member of the group consisting of methyl, gamma-cyclohexylaminopropyldimethoxysilane and gamma-chloropropyltriethoxysilane, and/or
The polar organic solvent is at least one selected from the group consisting of methyl ethyl ketone, ethyl cellosolve, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, 2-ethoxypropanol, 2-methoxypropanol, 3-methoxybutanol, cyclohexanone, cyclopentanone, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate and butyl acetate, and/or
The oligomeric resin is represented by formula (1-1), (1-2) or (1-3):
wherein, in the formulae (1-1), (1-2) and (1-3), R 1 And R 3 Each represents a linear hydrocarbon group having 2 to 8 carbon atoms or a graft copolymer group, and R 2 And R 4 Each represents C, a benzene ring,
16. A method of fabricating a pattern on a substrate, comprising the steps of:
forming a photoresist layer on a substrate using the photoresist composition of claim 14 or 15, the photoresist layer being dried to form a color thin film;
on the color film, a mask plate is utilized to form a pattern on a substrate through exposure, development and low-temperature curing, wherein the low-temperature curing temperature is 85-100 ℃.
17. Use of the dispersion resin according to any one of claims 1 to 3 for the preparation of a nanopigment paste composition or a photoresist.
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