DISPERSION RESIN, PREPARATION METHOD THEREFOR AND PHOTORESIST COMPOSITION

Abstract

The present invention provides a dispersion resin and a preparation method therefor, and a low-temperature cured photoresist composition. The dispersion resin is represented by a formula (2): (Z-A).sub.nR.sub.m (2), n=1-5, m=1-5, and n+m<=6; Z represents H, or an acrylic copolymer containing an amino group, an epoxy group, an alkyl group having 1-14 carbon atoms, a cycloalkyl group having 3-14 carbon atoms or an aryl substituent; R represents C, N, CH groups,

##STR00001##

or at least one of linear alkyl, aliphatic cycloalkyl, aryl and heteroaryl containing 6-14 carbon atoms; A is represented by formula (3):

##STR00002##

In formula (3), W is linked to Z, the carboxyl group is linked to R, and W represents at least one of an H atom, a substituted or unsubstituted alkyl group having 1-14 carbon atoms, an alkylene oxide group having 2-6 carbon atoms, a substituted or unsubstituted aryl group and a substituted or unsubstituted heteroaryl group having 3-14 carbon atoms.

Claims

1. A dispersion resin is characterized in that the dispersion resin is expressed by formula (2):
(Z-A).sub.nR.sub.m(2), in formula (2), n=1-5, m=1-5, and n+m6; Z represents H, or an acrylic copolymer containing an amino group, an epoxy group, an alkyl group having 1-14 carbon atoms, a cycloalkyl group having 3-14 carbon atoms or an aryl substituent; R represents C, N, CH groups, ##STR00027## or at least one of linear alkyl containing 2-14 carbon atoms, aliphatic cycloalkyl containing 2-14 carbon atoms, aryl group and heteroaryl group containing 3-14 carbon atoms; A is represented by formula (3): ##STR00028## and in formula (3), W is connected to Z, the carboxyl group is linked to R, and W represents at least one of an H atom, a substituted or unsubstituted alkyl group having 1-14 carbon atoms, an alkylene oxide group having 2-6 carbon atoms, a substituted or unsubstituted aryl group and a substituted or unsubstituted heteroaryl group having 3-14 carbon atoms.

2. The dispersion resins described in claim 1 are characterized by, n=1-3, m=1-3, and n+m4, and/or Z represents a copolymer formed by more than one compound selected from the group consisting of methacrylic acid, acrylic acid, benzyl acrylate, styrene, methyl methacrylate, butyl methacrylate, isobornyl methacrylate, glycidyl methacrylate, dicyclopentanyl methacrylate, hydroxyethyl methylacrylate, hydroxybutyl acrylate, N-phenyl maleimide, maleic anhydride, 2-acrylic acid-2 hydroxy-3-phenoxypropyl acrylate or pentaerythritol acrylate, and/or W represents at least one of H, methyl, ethyl, and hydroxy substituted alkyl, epoxy alkyl, phenyl, benzyl, and phenolic groups; and Z represents an acrylic copolymer with an Mw of 5000-10000, a Pd value of less than 2.5, and a viscosity of less than 5000 cps.

3. The dispersion resins referred to in claim 1 are characterized by the fact that A represents at least one of the compounds represented by the following: ##STR00029##

4. An intermediate used for preparing the dispersion resin according to claim 1 is represented by formula (4):
(X-A).sub.nR.sub.m(4), in formula (4), X represents halogen; n=1-5, m=1-5, and n+m6; R represents C, N, CH groups, ##STR00030## or at least one of linear alkyl containing 2-14 carbon atoms, aliphatic cycloalkyl containing 2-14 carbon atoms, aryl group and heteroaryl group containing 3-14 carbon atoms; A is represented by formula (3): ##STR00031## and in Formula (3), W is connected to X, and carboxyl group is connected to R, where W represents H atom, saturated or unsaturated alkyl group with 1 to 14 carbon atoms, epoxy group with 2 to 6 carbon atoms, substituted or unsubstituted aryl group with 3 to 14 carbon atoms, and at least one of substituted or unsubstituted heteraryl group.

5. According to claim 4, the dispersion resin is characterized by, X is Cl, Br or I, n=1-3, m=1-3, and n+m4, and/or W represents at least one of H, methyl, ethyl, hydroxy substituted alkyl, epoxy alkyl, phenyl, benzyl, and phenolic groups.

6. The intermediate according to claim 4 is one of the compounds represented by the following: ##STR00032## ##STR00033## ##STR00034##

7. A method for preparing the dispersion resin according to claim 1, comprises the following steps: under the action of a radical initiator, acrylic compounds containing amino groups, epoxy groups, alkyl groups having 1-14 carbon atoms, and cycloalkyl group or aryl substituents having 3-14 carbon atoms are added to a first solvent containing a chain transfer agent, and an acrylic copolymer Z is generated through radical solution polymerization under an inert atmosphere; and the obtained acrylic copolymer Z is reacted with the intermediate according to any one of claims 4 to 6 in the presence of a catalyst in a second solvent to generate the dispersion resin.

8. According to the method described in claim 7, it is characterized by, the obtained acrylic copolymer Z and the intermediates are heated in the presence of a catalyst, dissolved in a second solvent for 2-5 Hr, and stirred for 5-12 hr at 70120 C. to react to generate the dispersion resin, and/or the mass ratio of the acrylic copolymer Z to the intermediate is 1:1 to 1.5:1.

9. According to the method described in claim 8, it is characterized by, the obtained acrylic copolymer Z is reacted with the intermediate in the presence of a catalyst, after heated dissolution reflux of 3.5 Hr in a second solvent, and stirred 8 Hr at 90 C. to generate the dispersion resin, and/or the mass ratio of the acrylic copolymer Z to the intermediate is 1.2:1.

10. The method described in claim 7 is characterized by, the acrylic compound is more than one compound selected from the group consisting of methacrylic acid, acrylic acid, benzyl acrylate, styrene, methyl methacrylate, butyl methacrylate, isobornyl methacrylate, glycidyl methacrylate, dicyclopentanyl methacrylate, hydroxyethyl methylacrylate, hydroxybutyl acrylate, N-phenyl maleimide, maleic anhydride, 2-acrylic acid-2 hydroxy-3-phenoxypropyl 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 tetramethyl guanidine, TMG, KI, NaI, triethylamine, and metformin.

11. A nano pigment paste composition comprises the following components by weight parts: 5-30 parts of nano pigment; 0.5-5 parts of hyperdispersant; 0.5-5 parts of the dispersion resin according to claim 1; and 15-75 parts of organic solvent.

12. The nano pigment paste composition according to claim 11 has an average particle size D.sub.50 of 20-200 nm, a bulk density of 0.7-1.8 g/cm.sup.3, and a specific surface area of 100-200 m.sup.2/g.

13. The nano pigment paste composition according to claim 11, characterized in that, 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 monomethyl ether, propylene glycol methyl ether acetate, ethyl 3-ethoxypropionate, and butyl acetate.

14. A photoresist composition, comprises the following components by weight parts: claim 11 of the nano-pigment pigment paste compositions 1-50 copies; TABLE-US-00004 alkali-soluble resin 1-20 parts; resin oligomer 1-20 parts; photoinitiator 0.2-2 parts; active aid 0.02-2 parts; light-cured resin 1-15 parts; and polar organic solvent 20-200 parts.

15. The photoresist composition according to claim 14, characterized in that, the alkali-soluble resin is at least one selected from the group consisting of a methacrylic acidmethyl methacrylate copolymer, a methacrylic acidcyclohexyl methacrylate copolymer, a methacrylic acidepoxypropyl methacrylate copolymer, a methacrylic acid-2-hydroxyethyl methacrylate copolymer, a methacrylic acidcyclohexyl methacrylate copolymer, and a styrene-2-hydroxyethyl methacrylate copolymer, and/or the light-cured resin is at least one selected from the group consisting of acrylated epoxidized soybean oil, modified epoxy acrylate, polyester acrylate, active amine, HDDA, TMPTA, DPGDA, PETA, IOBA, EB114, EB145, EB160, ODA, TCDA and OTA480; ##STR00035## ##STR00036## the photoinitiator is at least one selected from the group consisting of diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, 1-hydroxycyclohexylphenyl ketone, 2-benzyl-2-(dimethylamino)-4-morpholinobutyryl benzene, 2-methyl-1-[4-methylthiophenyl]-2-morpholinopropan-2-one, 2-hydroxy-2-methyl-1-phenyl-1-acetone, 2-isopropylthioxanthone, 4-dimethylaminobenzoate, 4-dimethylaminobenzoate 2-ethylhexyl acrylate, methyl o-benzoylbenzoate, 4-methylbenzophenone; ##STR00037## the active aid is at least one of a flatting agent and a coupling agent, wherein the flatting 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 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--aminoethyl-N--aminoethyl--aminopropylmethyldimethoxysilane, N--aminoethyl-N--aminoethyl--aminopropylmethyldimethoxysilane, N--aminoethyl-N--aminoethyl--aminopropylmethyldiethoxysilane, N--aminoethyl-N--aminoethyl--aminopropyltrimethoxysilane, N--aminoethyl-N--aminoethyl--aminopropyltriethoxysilane and N--aminoethyl-N--aminoethyl--aminomethyl triethoxysilane, -cyclohexylaminopropyltriethoxysilane and methyl, -cyclohexylaminopropyldimethoxysilane and -chloropropyltriethoxysilane, and/or the polar organic solvent is at least one selected from the group consisting of methyl ethyl ketone, ethyl cellosolve, 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 diethyl ether acetate, and butyl acetate, and/or the resin oligomer is represented by formulae (1-1), (1-2) or (1-3): ##STR00038## and in formulae (1-1), (1-2) and (1-3), R.sup.1 and R.sup.3 each represent linear hydrocarbyl group or grafted copolymer groups having 2-8 carbon atoms, and R.sup.2 and R.sup.4 each represent C, benzene ring ##STR00039##

16. A method for manufacturing graphics on a substrate, characterized by comprising the following steps: a photoresist layer is formed on the substrate by using the photoresist composition according to claim 14, and the photoresist layer is dried to form a color film; and on a color film, graphics are formed on a substrate using a mask after exposure, development, and low temperature curing, the low temperature curing temperature being 85-100 C.

17. A use of the dispersion resin according to claim 1 in the preparation of the nano pigment paste composition or photoresist.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0073] FIGS. 1A-1D are schematic diagrams of the photolithography process using the photoresist composition of the present invention.

[0074] FIG. 2 shows a color photoresist line made on a glass substrate according to the photolithography process illustrated in FIGS. 1A-1D.

[0075] FIG. 3 shows a color photoresist line made on an ITO metal substrate according to the photolithography process illustrated in FIGS. 1A-1D.

[0076] FIG. 4 shows a color photoresist line made on a PET substrate according to the photolithography process illustrated in FIGS. 1A-1D.

[0077] FIGS. 5-7 show colored photoresist graphics made on a PET substrate according to the photolithography process illustrated in FIGS. 1A-1D.

[0078] FIG. 8 is a picture of the comparative example 1 not using a filter made of a photoresist composition of resin oligomer in the present invention.

[0079] FIG. 9 is the infrared signature spectrum of the disperse resin 2-1 of embodiment 2.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0080] Formula (4) Examples of intermediate preparation.

[0081] Taking the structural formula (X is Br) shown in intermediate 4 and 5 as an example, the intermediate of equation (4) is prepared by the following method.

##STR00016##

[0082] Specifically, starting from a known starting substance, the starting substance is prepared into a Grignard reagent by a known method, and then reacts with 2-bromooxirane (CAS No. 37497-56-6) to obtain an intermediate product, which reacts with pentaerythritol (CAS No. 115-77-5) to produce intermediate 4-5.

[0083] Among them, the reaction between the intermediate product and Pentaerythritol is a known method. For details, refer to the preparation method of the compound (CAS No. 31775-89-0) disclosed in Japanese patent JP2011084479A, or refer to the preparation method in known patents CN110647010A and CN111868626A.

[0084] The following is a specific embodiment of the present invention, wherein Embodiment 1 is a preparation method of the oligomer resin in the present invention; Embodiment 2 to Embodiment 5 are the preparation methods of the dispersion resin described in the present invention. The reagents involved in the following embodiments are available in the market.

Embodiment 1

[0085] Preparation of Oligomer Resin:

##STR00017##

[0086] The preparation method for the compound in the above general formula (1) can be obtained by the following synthesis route:

[0087] Route:

##STR00018## ##STR00019##

[0088] Among them, the initial reactant

##STR00020##

is commissioned by a chemical company to customize the purchase, obtained from the raw material

##STR00021##

with a molar ratio of 1:3 to D-sorbitol to produce compound 1. Next, the compound 1 and the intermediate containing R4 continue to react in a molar ratio of 1:2 to obtain the general formula (1), for aftertreatment and purification.

[0089] In the general formula (1), R1 and R3 can be designed to link a linear hydrocarbon with 2-8 carbon atoms or grafted copolymer groups through a reaction; R2, R4 can be designed as C atom, benzene ring,

##STR00022##

The oligomer (1-1) is obtained.

[0090] According to this route, the following can also be obtained:

##STR00023##

[0091] In oligomers (1-1), (1-2) and (1-3), R.sup.1 and R.sup.3 each represent linear hydrocarbyl groups or grafted copolymer groups having 2 to 8 carbon atoms; R.sup.2 and R.sup.4 each represent C, benzene ring

##STR00024##

The Mw value of the oligomers (1-1), (1-2) and (1-3) may be 10000-20000; Pd value may be 1.8-2.0.

[0092] In this embodiment 1, in the oligomers (1-1), (1-2) and (1-3), R1 is CH.sub.2CH.sub.2CH.sub.3, R.sup.2 is

##STR00025##

R.sup.3 is CH.sub.3, R.sup.4 is

##STR00026##

Embodiment 2

[0093] Preparation of Dispersion Resin 2-1: [0094] 1) Oligomer synthesis: 15 g of 2-hydroxy-3-phenoxypropyl acrylate, 3.74 g of acrylic acid, 5.41 g of styrene, 5.2 g of methyl methacrylate; 0.58 g of radical initiator 2,2-azobis(2-methylbutyronitrile); 1.05 g of chain transfer agent -methylstyrene linear dimer; adding to 50 g of solvent toluene; under nitrogen atmosphere, heating to 90 C., stirring at 300 rpm for 4 Hr, and conducting radical reaction synthesis to obtain oligomer intermediate Z-2; upon characterization, the oligomer intermediate Z-2 has an Mw of 5000-10000, a Pd value of less than 2.5, and viscosity of less than 5000 cps; [0095] 2) Product synthesis: putting 36 g of compound 4-5 of general formula (4) (wherein X is Br) and the oligomer intermediate Z-2 obtained in step 1) into four-neck bottle; then adding 60 g of acetonitrile solvent, dissolving 0.08 g of KI catalyst into 20 g of acetonitrile, putting in a constant pressure funnel, connecting it to a four-neck bottle, and dripping it in 30 minutes; at the same time, after magnetic stirring, heating, dissolving and refluxing for 4-5 Hr, maintaining the reaction heating temperature of 95 C., stirring at 350 rpm for 8 Hr, and after the reaction is completed, transferring to a rotary evaporator for rotary evaporation of the solvent; then, adding 180 g of n-butanol again, stir at 55 C. for 1 Hr, and putting it into 540 g of petroleum ether conical flask; after filtering and drying the precipitate, obtaining the dispersion resin 2-1 of the general formula (2). Upon characterization, the dispersion resin 2-1 has an Mw of 16801, and a Pd value of 2.4.

[0096] FIG. 9 is the infrared characteristic spectrum of disperse resin 2-1 of the embodiment 2. From the infrared characteristic spectrum, it can be seen that the characteristic absorption peaks of hydroxyl group and sulfhydryl group appear in the infrared characteristic spectrum of disperse resin 2-1, which proves that when compound 4 and 5 (where X is Br) reacts with oligomers, The reaction site of compound 4-5 is Br. According to the infrared characteristic spectrum and the detection results of its properties in the photolithography process, the desired dispersion resin can be obtained by the above-mentioned preparation method.

Embodiment 3

[0097] Preparation of Dispersion Resin 2-2: [0098] 1) Oligomer synthesis: 15 g of 2-hydroxy-3-phenoxypropyl acrylate, 4.47 g of methacrylic acid, 5.2 g of methyl methacrylate, 7.4 g of benzyl acrylate; 0.6 g of radical initiator azodiisobutyronitrile; 1.05 g of chain transfer agent -methyl styrene linear dimer; adding to 60 g of solvent ethyl acetate; under nitrogen atmosphere, heating to 80 C., stirring for 4 Hr at 300 rpm, and conducting radical reaction synthesis to obtain the oligomer intermediate Z-3; upon characterization, the oligomer intermediate Z-3 has an MW of 3000-10000, a Pd value of less than 2.5, and viscosity of less than 5000 cps. [0099] 2) Product synthesis: putting 40 g of compound 4-6 of general formula (4) (wherein X is Br) and the oligomer intermediate Z-3 obtained in step 1) into four-neck bottle; then adding 80 g of acetonitrile solvent, dissolving 0.08 g of KI catalyst into 20 g of acetonitrile, putting in a constant pressure funnel, connecting it to a four-neck bottle, and dripping it in 30 minutes; at the same time, after magnetic stirring, heating, dissolving and refluxing for 4-5 Hr, maintaining the reaction heating temperature of 90 C., stirring at 350 rpm for 8 Hr, and after the reaction is completed, transferring to a rotary evaporator for rotary evaporation of the solvent; then, adding 180 g of n-butanol again, stirring at 55 C. for 1 Hr, and putting it into 540 g of petroleum ether conical flask; after filtering and drying the precipitate, obtaining the dispersion resin 2-2 of the general formula (2). Upon characterization, the dispersion resin 2-2 has an Mw of 20350, and a Pd value of 2.3.

Embodiment 4

[0100] Preparation of Dispersion Resin 2-3: [0101] 1) Oligomer synthesis: 15 g of 2-hydroxy-3-phenoxypropyl acrylate, 3.74 g of acrylic acid, 5.41 g of styrene, 5.2 g of methyl methacrylate, 7.4 g of benzyl acrylate; adding to 80 g of solvent ethyl acetate; adding 0.8 g of radical initiator azodiisobutyronitrile and 1.05 g of chain transfer agent -methylstyrene linear dimer into 1.05 g of constant pressure funnel, and then dripping 10 g of ethyl acetate in 30 min; under nitrogen atmosphere, heating to 90 C., stirring for 4 Hr at 300 rpm, and conducting radical reaction synthesis to obtain the oligomer intermediate Z-4; upon characterization, the oligomer intermediate Z-4 has an MW of 3000-10000, a Pd of less than 2.5, and viscosity of less than 5000 cps. [0102] 2) Product synthesis: putting 42 g of compound 4-9 of general formula (4) (wherein X is I) and the oligomer intermediate Z-4 obtained in step 1) into four-neck bottle; then adding 80 g of DMF solvent, dissolving 0.08 g of triethylamine catalyst into 20 g of DMF, putting in a constant pressure funnel, connecting it to a four-neck bottle, and dripping it in 30 minutes; at the same time, after magnetic stirring, heating, dissolving and refluxing for 4-5 Hr, maintaining the reaction heating temperature of 90 C., stirring at 350 rpm for 8 Hr, and after the reaction is completed, transferring to a rotary evaporator for rotary evaporation of the solvent; then, adding 200 g of n-butanol again, stir at 55 C. for 1 Hr, and putting it into 600 g of petroleum ether conical flask; after filtering and drying the precipitate, obtaining the resin 2-3 of the general formula (2). Upon characterization, the dispersion resin 2-3 has an Mw of 17168, and a Pd value of 1.8.

Embodiment 5

[0103] Preparation of Dispersion Resin 2-4:

[0104] 1) Oligomer synthesis: 15 g of 2-hydroxy-3-phenoxypropyl acrylate, 4.47 g of methacrylic acid, 5.41 g of styrene, 11.55 g of isobornyl methacrylate; 0.8 g of radical initiator azodiisobutyronitrile; 1.05 g of chain transfer agent -methylstyrene linear dimer; adding to 65 g of solvent ethyl acetate; under nitrogen atmosphere, heating to 90 C., stirring for 4 Hr at 300 rpm, and conducting radical reaction synthesis to obtain the oligomer intermediate Z-5; upon characterization, the oligomer intermediate Z-5 has an MW of 3000-10000, a Pd value of less than 2.5, and viscosity of less than 5000 cps.

[0105] 2) Product synthesis: putting 40 g of compound 4-11 of general formula (4) (wherein X is I) and the oligomer intermediate Z-5 obtained in step 1) into four-neck bottle; then adding 80 g of DMF solvent, dissolving 0.08 g of KI catalyst into 20 g of acetonitrile, putting in a constant pressure funnel, connecting it to a four-neck bottle, and dripping it in 30 minutes; at the same time, after magnetic stirring, heating, dissolving and refluxing for 4-5 Hr, maintaining the reaction heating temperature of 95 C., stirring at 350 rpm for 8 Hr, and after the reaction is completed, transferring to a rotary evaporator for rotary evaporation of the solvent; then, adding 200 g of n-butanol again, stir at 55 C. for 1 Hr, and putting it into 600 g of petroleum ether conical flask; after filtering and drying the precipitate, obtaining the resin 2-4 of the general formula (2). Upon characterization, the dispersion resin 2-3 has an Mw of 16115, and a Pd value of 2.2.

Embodiment 6

[0106] Preparation of Dispersion Resin 2-5:

[0107] 1) Oligomer synthesis: 15 g of 2-hydroxy-3-phenoxypropyl acrylate, 3.74 g of acrylic acid, 5.8 g of cyclohexyl methacrylate copolymer, 9.4 g of benzyl methacrylate; 0.6 g of radical initiator azodiisobutyronitrile; 1.05 g of chain transfer agent -methylstyrene linear dimer; adding to 60 g of solvent ethyl acetate; under nitrogen atmosphere, heating to 80 C., stirring for 4 Hr at 300 rpm, and conducting radical reaction synthesis to obtain oligomer intermediate Z-6; upon characterization, the oligomer intermediate Z-6 has an Mw of 3000-10000, a Pd value of less than 3.5, and viscosity of less than 5000 cps.

[0108] 2) Product synthesis: putting 40 g of compound 4-8 of general formula (4) (wherein X is Br) and the oligomer intermediate Z-6 obtained in step 1 into four-neck bottle; then adding 80 g of acetonitrile solvent, dissolving 0.08 g of KI catalyst into 20 g of acetonitrile, putting in a constant pressure funnel, connecting it to a four-neck bottle, and dripping it in 30 minutes; at the same time, after magnetic stirring, heating, dissolving and refluxing for 4-5 Hr, maintaining the reaction heating temperature of 90 C., stirring at 350 rpm for 8 Hr, and after the reaction is completed, transferring to a rotary evaporator for rotary evaporation of the solvent; then, adding 180 g of n-butanol again, stir at 55 C. for 1 Hr, and putting it into 540 g of petroleum ether conical flask; after filtering and drying the precipitate, obtaining the dispersion resin 2-5 of the general formula (2). Upon characterization, the dispersion resin 2-5 has an Mw of 21507, and a Pd value of 1.9.

Embodiment 7

[0109] Preparation of Dispersion Resin 2-6:

[0110] 1) Oligomer synthesis: 158 of 2-hydroxy-3-phenoxypropyl acrylate, 4.47 g of methacrylic acid, 11.2 g of methyl methacrylate, 4.4 g of epoxypropyl methacrylate; 0.6 g of radical initiator azodiisobutyronitrile; 1.05 g of chain transfer agent -methylstyrene linear dimer; adding to 60 g of solvent ethyl acetate; under nitrogen atmosphere, heating to 90 C., stirring for 4 Hr at 300 rpm, and conducting radical reaction synthesis to obtain the oligomer intermediate Z-7; upon characterization, the oligomer intermediate Z-7 has an MW of 3000-10000, a Pd value of less than 2.5, and viscosity of less than 5000 cps.

[0111] 2) Product synthesis: putting 40 g of compound 4-11 of general formula (4) (wherein X is I) and the oligomer intermediate Z-7 obtained in step 1 into four-neck bottle; then adding 80 g of acetonitrile solvent, dissolving 0.08 g of triethylamine catalyst into 20 g of acetonitrile, putting in a constant pressure funnel, connecting it to a four-neck bottle, and dripping it in 30 minutes; at the same time, after magnetic stirring, heating, dissolving and refluxing for 4-5 Hr, maintaining the reaction heating temperature of 90 C., stirring at 350 rpm for 8 Hr, and after the reaction is completed, transferring to a rotary evaporator for rotary evaporation of the solvent; then, adding 180 g of n-butanol again, stirring at 55 C. for 1 Hr, and putting it into 540 g of petroleum ether conical flask; after filtering and drying the precipitate, obtaining the dispersion resin 2-6 of the general formula (2). Upon characterization, the dispersion resin 2-6 has an Mw of 22340, and a Pd value of 2.3.

Embodiment 8

[0112] Preparation of Dispersion Resin 2-7:

[0113] 1) Oligomer synthesis: 15 g of 2-hydroxy-3-phenoxypropyl acrylate, 3.74 g of acrylic acid, 7.6 g of styrene, 6.4 g of 2-hydroxyethyl methacrylate; 0.6 g of radical initiator azodiisobutyronitrile; 1.05 g of chain transfer agent -methyl styrene linear dimer; adding to 60 g of solvent ethyl acetate; under nitrogen atmosphere, heating to 80 C., stirring for 4 Hr at 300 rpm, and conducting radical reaction synthesis to obtain the oligomer intermediate Z-8; upon characterization, the oligomer intermediate Z-8 has an MW of 3000-10000, a Pd value of less than 2.5, and viscosity of less than 5000 cps.

[0114] 2) Product synthesis: putting 40 g of compound 4-3 of general formula (4) (wherein X is Br) and the oligomer intermediate Z-8 obtained in step 1 into four-neck bottle; then adding 80 g of acetonitrile solvent, dissolving 0.08 g of K1 catalyst into 20 g of acetonitrile, putting in a constant pressure funnel, connecting it to a four-neck bottle, and dripping it in 30 minutes; at the same time, after magnetic stirring, heating, dissolving and refluxing for 4-5 Hr, maintaining the reaction heating temperature of 90 C., stirring at 350 rpm for 8 Hr, and after the reaction is completed, transferring to a rotary evaporator for rotary evaporation of the solvent; then, adding 180 g of n-butanol again, stirring at 55 C. for 1 Hr, and putting it into 540 g of petroleum ether conical flask; after filtering and drying the precipitate, obtaining the dispersion resin 2-7 of the general formula (2); Upon characterization, the dispersion resin 2-7 has an Mw of 16579, and a Pd value of 2.1.

Embodiment 9

[0115] Preparation of Dispersion Resin 2-8:

[0116] 1) Oligomer synthesis: 15 g of 2-hydroxy-3-phenoxypropyl acrylate, 4.47 g of methacrylic acid, 4.7 g of methyl methacrylate, 8.8 g of benzyl methacrylate; 0.6 g of radical initiator azodiisobutyronitrile; 1.05 g of chain transfer agent -methylstyrene linear dimer; adding to 60 g of solvent ethyl acetate; under nitrogen atmosphere, heating to 80 C., stirring for 4 Hr at 300 rpm, and conducting radical reaction synthesis to obtain the oligomer intermediate Z-9; upon characterization, the oligomer intermediate Z-9 has an MW of 3000-10000, a Pd value of less than 2.5, and viscosity of less than 5000 cps.

[0117] 2) Product synthesis: putting 40 g of compound 4-5 of general formula (4) (wherein X is I) and the oligomer intermediate Z-9 obtained in step 1 into four-neck bottle; then adding 80 g of acetonitrile solvent, dissolving 0.08 g of triethylamine catalyst into 20 g of acetonitrile, putting in a constant pressure funnel, connecting it to a four-neck bottle, and dripping it in 30 minutes; at the same time, after magnetic stirring, heating, dissolving and refluxing for 4-5 Hr, maintaining the reaction heating temperature of 90 C., stirring at 350 rpm for 8 Hr, and after the reaction is completed, transferring to a rotary evaporator for rotary evaporation of the solvent; then, adding 180 g of n-butanol again, stirring at 55 C. for 1 Hr, and putting it into 540 g of petroleum ether conical flask; after filtering and drying the precipitate, obtaining the dispersion resin 2-8 of the general formula (2). Upon characterization, the dispersion resin 2-8 has an Mw of 22790, and a Pd value of 2.5.

[0118] Embodiments 10 to 15 and comparative examples 1-2 are photoresist compositions prepared using the resin oligomer and dispersion resin obtained from Embodiments 1-9 above. The consumption of components and raw materials in Embodiments 10 to 15 and comparative examples 1 and 2 is as shown in Table 2. The preparation method of the photoresist composition is as follows: [0119] (1) preparation of nano pigments paste composition: the nano pigments particle and hyperdispersant are added into 0.1 mm zirconium ball grinder with an organic solvent for wet grinding, and the resin oligomer with the structural unit represented by formula (1) is added as a stabilizing resin during the grinding process to prepare a pigment dispersion paste; [0120] (2) Preparation of photosensitive liquid: the alkali-soluble resin, light-cured resin with vinyl double bonds, electrically asymmetric photoinitiator, active aid, resin oligomer of formula (1), and polar organic solvent are mixed and dispersed into solution, and filtered by a filter with pore size of 400-1000 nm to obtain a photosensitive liquid; [0121] (3) the pigment dispersion paste in step (1) is mixed with the photosensitive liquid in step (2), and finally a polar organic solvent is added to adjust the viscosity, dispersed in a dispersion machine and filtered to obtain the photoresist composition.

[0122] Referring to FIGS. 1A to 1D, the photoresist compositions of Embodiments 6 to 11 and comparative examples land 2 are developed into graphics according to the following methods: [0123] (1) treatment of a substrate 10: vacuum attachment and fixation on a substrate; or load rolls by means of a Roll-to-Roll device the substrate 10 may be glass/PET/PI/metal substrate; [0124] (2) making a photoresist layer: rotating/Slit coating/printing or spraying the photoresist composition as described in the present invention on the substrate 10, and then successively undergoing vacuum and prebaking (70-100 C./2-5 min) to form the first layer 2-5 m color film 20; [0125] (3) making pixel graphics: using a mask 30 on the color film 20 in step (2) above to mask, UV exposure, development, and low temperature curing to form graphics on the mask.

[0126] Referring to FIGS. 2 to 7, FIG. 2 (Embodiment 10) shows that, according to the photolithography technique illustrated in FIGS. 1A-1D, the color photoresist lines made on a glass substrate are magnified 5000 times under a metallographic microscope and CCD, and the measured width is 3.3 m. FIG. 3 (Embodiment 11) shows that, according to the photolithography technique illustrated in FIGS. 1A-1D, the color photoresist lines made on an ITO metal substrate are magnified 5000 times under a metallographic microscope and CCD, and the measured width is 3.9 m. FIG. 4 (Embodiment 12) shows that, according to the photolithography technique illustrated in FIGS. 1A-1D, the color photoresist lines made on a PET substrate are magnified 5000 times under a metallographic microscope and CCD, and the measured width is 20.0 m. FIGS. 5-7 (corresponding to Embodiments 13-15) show that, according to the photolithography technique illustrated in FIGS. 1A-1D, the color photoresist graphics made on an ITO metal substrate are magnified 5000 times under a metallographic microscope and CCD, and the measured minimum spacing is 1.2-3.3 m. From FIG. 2 to FIG. 7, the photoresist composition of the present invention can be used for making fine graphics with high photolithography accuracy.

[0127] In order to reflect the effect of the photoresist composition of the present invention, nano pigments PR254 and C Black 7 are also directly used as two groups of comparative embodiments.

TABLE-US-00002 TABLE 1 Photolithography Development lines in Embodiments 10to 15 and Comparative Examples 1 and 2 Comparative Comparative Raw Embodi- Embodi- Embodi- Embodi- Embodi- Embodi- example example materials ment 10 ment 11 ment 12 ment 13 ment 14 ment 15 1 2 Nano PR254 PY150 PB15:6 PG58 TiO2 C black 7 PR254 C black 7 pigment 3 parts 3 parts 3 parts 3 parts 3 parts 3 parts 3 parts 3 parts Hyperdispersant Byk-2001 Byk-163 Byk-161 Byk-2001 EFKA-4047 EFKA-4047 Byk-2001 EFKA-4047 0.2 parts 0.2 parts 0.2 parts 0.2 parts 0.2 parts 0.2 parts 0.2 parts 0.2 parts Dispersion 2-1 2-2 2-3 2-2 2-4 2-5 2-2 resin 0.5 parts 0.5 parts 0.5 parts 0.5 parts 0.5 parts 0.5 parts 0.5 parts Organic EEP EEP EEP EEP EEP EEP EEP EEP solvent 6 parts 6 parts 6 parts 6 parts 6 parts 6 parts 6 parts 6 parts MMA MMA-ST MMA-ST MMA-ST MMA-ST MMA-ST MMA-ST MMA-ST MMA-ST alkyl copolymer copolymer copolymer copolymer copolymer copolymer copolymer copolymer resin 2.2 parts 2 parts 1 part 1 part 1 part 1 part 2.5 parts 2.5 parts Light-cu DPPA DPPA DPPA DPPA DPPA DPPA DPPA DPPA red resin 2.5 parts 2.5 parts 2.5 parts 2.5 parts 2.5 parts 2.5 parts 2.5 parts 2.5 parts Photoinitiator 369/907 369/907 369/907 369/907 369/907 369/907 369/907 369/907 0.1/0.1 0.1/0.1 0.1/0.1 0.1/0.1 0.1/0.1 0.1/0.1 0.1/0.1 0.1/0.1 parts parts parts parts parts parts parts parts Active EFKA3883/ EFKA3883/ EFKA3883/ EFKA3883/ EFKA3883/ EFKA3883/ EFKA3883/ EFKA3883/ aid KH570 KH570 KH570 KH570 KH570 KH570 KH570 KH570 0.01/0.01 0.01/0.01 0.01/0.01 0.01/0.01 0.01/0.01 0.01/0.01 0.01/0.01 0.01/0.01 parts parts parts parts parts parts parts parts Resin Copolymer Copolymer Copolymer Copolymer Copolymer Copolymer oligomer 1-1 1-2 1-3 1-2 1-3 1-2 0.3 parts 0.5 parts 1.5 parts 1.5 parts 1.5 parts 1.5 parts Polar PMA PMA PMA PMA PMA PMA PMA PMA solvent 15 parts 15 parts 15 parts 15 parts 15 parts 15 parts 15 parts 15 parts Accuracy 3 m 4 m 1.8 m 3 m 2 m 3 m 15 m 3 m of photolithography development lines Pixel OK OK OK OK OK OK OK NG shedding

[0128] The photoresist composition of Embodiments 10 to 15 above is used for low temperature curing (90 C.) to produce monochromatic filters, which can be achieved through the following process: [0129] 1) Coating: 1-2 m thick coating, with vacuum of 1 atm/30 s; [0130] 2) Prebaker: baking the coated substrate for 160 s at 85 C.; [0131] 3) Exposure: The exposure energy is 100-200 mj/cm.sup.2, and the Gap value of the mask is [0132] 4) Developing: using 0.238% TMAH alkaline developing solution to develop for 60-100 S into the corresponding graphics on the mask; and [0133] 5) Postbaker: baking at 90 C. for 60 min.

[0134] After using the dispersion resin of the present invention in Embodiments 10 to 15 and Comparative Example 2, the accuracy of the photolithography development line can reach below 4 m; The accuracy of the photolithography development line without using the dispersion resin of the present invention in Comparative Example 1 can only reach 15 m. This indicates that the dispersion resin of the present invention matches the polarity of other components such as the developing resin in the photoresist, resulting in improved pixel accuracy, especially the resolution of pixel edges, after UV lithography and low temperature postbaking. In addition, the resin oligomer of the present invention is not used in both Comparative Example 1 and Comparative Example 2, resulting in reduced pixel adhesion after the low temperature postbaking process and shedding of pixels below 4 m; However, the pixel adhesion of the photoresist formulation using the resin oligomer of the present invention after the baking process at a low temperature of 90 C. does not exhibit any shedding, as shown in FIG. 8.

[0135] The performances of the filter is detected, with the results as shown in Table 2.

TABLE-US-00003 TABLE 2 Detection Results of Monochromatic Filters in Embodiments 10to 15 and Comparative Examples 1 and 2 10 m 10 m 10 m 10 m line line acid line dual line dual Contrast solvent & alkali CD Film 8524H 85240H sample resistance resistance Loss/m thickness Slope adhesion adhesion Embodiment 0.3 1.5 5.36 10 Embodiment 0.3 1.4 5.28 11 Embodiment 0.2 1.3 3.97 12 Embodiment 0.3 1.6 4.83 13 Embodiment 0.3 1.5 5.51 14 Embodiment 0.2 1.5 4.99 15 Comparative .circle-solid. .circle-solid. 1.2 1.4 5.32 .circle-solid. .circle-solid. example 1 Comparative .circle-solid. .circle-solid. 0.2 1.5 5.62 .circle-solid. .circle-solid. example 2 Note: .circle-solid. indicates shedding of pixel lines; indicates no shedding of pixel lines, but the para-position patch marker has shedding; indicates that pixels and markers do not have shedding; Slope value, film thickness and CD Loss are in m.

[0136] As shown in Table 2, after the monochromatic filter used in Embodiments 12 to 15 is subjected to postbaking of 90 C. photolithography process, solvent resistance, acid and alkali resistance, CD loss, and 10 m line dual 85 adhesion and other properties are good.

[0137] After a small amount of resin oligomer of the present invention is added in Embodiments 10 and 11, and the monochromatic color filter made therefrom is subjected to postbaking of 90 C. photolithography process, the solvent resistance, acid and alkali resistance, CD loss, and 10 m line dual 85 adhesion and other properties are improved.

[0138] The oligomer resin of the present invention is not used in Comparative Examples 1 and 2, and after the monochromatic color filter made therefrom is subjected to postbaking of 90 C. photolithography process, the solvent resistance, acid and alkali resistance, CD loss, and 10 m line dual 85 adhesion and other properties are NG.

[0139] The above embodiments are only preferred embodiments of the present invention and cannot be used to define the scope of protection of the present invention. Any insubstantial changes and replacements made by those skilled in the art based on the present invention fall within the scope of protection required by the present invention.