CN114644740A - Fluorine-containing phenolic resin, preparation method thereof and photoresist composition adopting fluorine-containing phenolic resin - Google Patents

Fluorine-containing phenolic resin, preparation method thereof and photoresist composition adopting fluorine-containing phenolic resin Download PDF

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CN114644740A
CN114644740A CN202011495554.5A CN202011495554A CN114644740A CN 114644740 A CN114644740 A CN 114644740A CN 202011495554 A CN202011495554 A CN 202011495554A CN 114644740 A CN114644740 A CN 114644740A
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fluorine
substituted
phenolic resin
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containing phenolic
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李青松
刘永祥
王旭
韩红彦
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Hefei Dingcai Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
    • C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
    • C08G8/14—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with halogenated phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
    • C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • 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
    • G03F7/004—Photosensitive materials

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Abstract

The invention relates to phenolic resin and application thereof in the technical field of liquid crystal and organic electroluminescence display, in particular to fluorine-containing phenolic resin, a preparation method thereof and a photoresist composition adopting the fluorine-containing phenolic resin. The invention provides a fluorine-containing phenolic resin, the molecular weight of which is 3000-15000, the fluorine-containing phenolic resin has a structure shown as a structural formula (A), and any position on a non-hydroxyl group in the structural formula (A) is provided with at least one fluorine substituent. The fluorine-containing phenolic resin has high alkali dissolution rate, and the existence of C-F bonds improves the rigidity of molecular chains and has certain hydrophobicity, so that the dissolution inhibition of a photoresist containing the fluorine-containing phenolic resin in a non-exposure area is enhanced, and the residual film rate and the image resolution are favorably improved.
Figure DDA0002842046710000011

Description

Fluorine-containing phenolic resin, preparation method thereof and photoresist composition adopting fluorine-containing phenolic resin
Technical Field
The invention relates to phenolic resin and application thereof in the technical field of liquid crystal and organic electroluminescence display, in particular to fluorine-containing phenolic resin, a preparation method thereof and a photoresist composition adopting the fluorine-containing phenolic resin.
Background
The positive photoresist is used for protecting an etched circuit in a TFT (thin film transistor) manufacturing process of a liquid crystal panel and an OLED (organic light emitting diode) panel, and the TFT photoresist is developed towards a high-sensitivity and high-resolution technology along with the development of a panel technology. High sensitivity photoresists typically have a lower molecular weight, a higher hydrophilic group density, and perform poorly in residual film rate performance. Insufficient residual film rate of the photoresist can cause the image resolution and the pattern appearance of the etching process to be deteriorated, and the product yield is influenced.
Disclosure of Invention
The present invention is to solve the problem that in order to further satisfy the requirements of high sensitivity, high resolution, high film retention rate, etc. for a Thin Film Transistor (TFT) photoresist, it is necessary to develop a new photoresist composition to obtain a TFT liquid crystal panel or an OLED panel with good performance.
In order to solve the above problems in the prior art, the inventors have made intensive studies and found that the addition of a fluorine-containing phenol resin as an essential component to a photoresist composition can ensure a high film-remaining rate while ensuring a high sensitivity and a high resolution.
Specifically, the invention provides a fluorine-containing phenolic resin, the molecular weight of which is 3000-15000, the fluorine-containing phenolic resin is a random copolymer which is composed of structural monomers shown in formulas (I), (II) and (III) and has a structure shown in formula (A), and any position on a non-hydroxyl group in the formula (A) carries at least one fluorine substituent:
Figure BDA0002842046690000011
in the formula (A), M is a structure shown in the formula (I) below, and Q is a structure shown in the formula (II) below:
Figure BDA0002842046690000012
in the formula A, R13Selected from hydrogen, substituted orUnsubstituted C1-C18 aliphatic radical; n1 and n2 are respectively and independently integers which are more than 1 and less than 100, and the value of n1/(n1+ n2) is between 0.1 and 0.5;
in the formula (I), R1-R5Ra-Re are respectively and independently selected from hydrogen, hydroxyl, substituted or unsubstituted aliphatic radical of C1-C30, halogen atom, R6、R7Each independently selected from hydrogen, substituted or unsubstituted aliphatic hydrocarbon groups of C1-C30, substituted or unsubstituted aromatic hydrocarbon groups of C6-C60 and halogen atoms, R8Is a single bond, substituted or unsubstituted aliphatic hydrocarbon group of C1-C30, substituted or unsubstituted aromatic hydrocarbon group of C6-C60, R9、R10Each independently selected from hydrogen, substituted or unsubstituted aliphatic hydrocarbon group with C1-C30, substituted or unsubstituted aromatic hydrocarbon group with C6-C60 and halogen atom;
and R is1-R5At least 1 of them being hydroxyl, or at least 1 of Ra-Re being hydroxyl, R6And R7Not simultaneously being a substituted or unsubstituted C6-C60 aromatic hydrocarbon radical, R9And R10Is not substituted or unsubstituted C6-C60 aromatic hydrocarbon group at the same time;
in the formula (II), R11、R12Each independently selected from hydrogen, substituted or unsubstituted aliphatic radical of C1-C30, hydroxyl;
the substituted groups on the substituted aliphatic hydrocarbon group and the substituted aromatic hydrocarbon group are respectively and independently selected from one of halogen, chain alkyl of C1-C10, cycloalkyl of C3-C10, aryl of C6-C30 and heteroaryl of C3-C30.
In the structure of the fluorinated phenol resin of the present invention, the position of the bonding site of the two structural units of the formula (I) and the formula (II) on the polymer chain of the structure of the formula (A) is not particularly limited, that is, the fluorinated phenol resin of the present invention is a random copolymer, as long as R is1-R13Ra-Re, and n1-n2 satisfy the above-mentioned limits, and the object and technical effects of the present invention can be achieved.
The fluorine-containing phenolic resin adopts a structure of a formula (A), any position on a non-hydroxyl group in the formula (A) is provided with at least one fluorine substituent, and the existence of a C-F bond improves the rigidity of a molecular chain and has certain hydrophobicity, so that the fluorine-containing phenolic resin has high alkali dissolution rate, the dissolution inhibition of a photoresist prepared by the fluorine-containing phenolic resin in a non-exposure area can be enhanced, and the improvement of the residual film rate and the image resolution is facilitated.
Wherein "alkali dissolution rate" refers to the dissolution rate of the photoresist composition in an alkaline developer; the residual film rate refers to the ratio of the film thickness of a non-exposure area after development to the film thickness before development, and the higher the residual film rate is, the higher the washing resistance of the photoresist composition is; "image resolution" refers to the size of the smallest pattern that can be obtained by the photoresist.
In the present invention, the expression of chemical elements includes the concept of chemically identical isotopes, such as the expression of "hydrogen", and also includes the concept of chemically identical "deuterium" and "tritium".
The hydrocarbon compound is a generic term for hydrocarbon, and is a compound composed of carbon and hydrogen atoms, and mainly includes alkane, cycloalkane, alkene, alkyne, and aromatic hydrocarbon. Hydrocarbyl refers to a group containing only carbon and hydrogen atoms, and generally refers to a group remaining after a hydrogen atom (H) has been lost from a corresponding hydrocarbon compound, and different types of hydrocarbyl groups can be obtained from different hydrocarbons. The hydrocarbon group can be classified into monovalent, divalent and trivalent groups, for example, monovalent groups: CH3CH2- (ethyl), (isopropyl), CH ≡ C-CH2- (2-propynyl); a divalent group: CH3CH ═ ethylene, -CH ═ CH- (1, 2-ethenylene); a trivalent group: CH3C ≡ (ethenyl).
In the present specification, the hydrocarbon group includes aliphatic hydrocarbon groups and aromatic hydrocarbon groups. Specifically, a hydrocarbon group having one or more hydrogen atoms in the aliphatic hydrocarbon molecule is called an aliphatic hydrocarbon group. The aliphatic group may be further subdivided into alkyl, alkenyl, alkynyl groups, and the like. For example: CH 3-methyl (alkyl), CH2 ═ CH-vinyl (alkenyl), CH ≡ C-ethynyl (alkynyl). Methyl, ethyl, n-propyl and isopropyl are the most common of several hydrocarbyl groups. Hydrocarbyl groups which have one or more hydrogen atoms removed from the aromatic hydrocarbon nucleus are referred to as aromatic hydrocarbyl groups, for example phenyl C6H 5-.
In the present invention, the aliphatic hydrocarbon group having C1-C30 preferably includes: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, neopentyl, n-hexyl, neohexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-dodecyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, ethenyl, propenyl, butenyl; the aromatic hydrocarbon group having C6-C60 includes preferably: phenyl, naphthyl, anthracenyl, benzanthracenyl, phenanthryl, benzophenanthryl, pyrenyl, perylenyl, fluoranthenyl, biphenyl, anthryl, terphenyl, fluorenyl, dihydrophenanthryl, dihydropyrenyl, tetrahydropyrenyl, 2-biphenyl, 3-biphenyl and 4-biphenyl, p-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl, m-terphenyl-2-yl, 1-naphthyl, 2-naphthyl, 1-anthracenyl, 2-anthracenyl, 9-anthracenyl, 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl, fluorenyl, 9-fluorenyl, 1-pyrenyl, 2-pyrenyl, 4-pyrenyl and the like.
The molecular weight of the fluorine-containing phenolic resin represented by the general formula (A) in the invention is 3000-15000, if the molecular weight of the fluorine-containing phenolic resin is too high, the alkali dissolution rate is reduced, the light sensitivity of the photoresist composition is reduced, and if the molecular weight is too low, the effects of heat resistance and developing performance are difficult to achieve.
In the structure (I) of the present invention, R1-R5The number of the medium hydroxyl groups is preferably 1 to 3, most preferably 1, wherein the positions of the hydroxyl groups are preferably located in the ortho-and para-positions with respect to the C in which R6 and R7 are located, preferably, R1、R3And R4At least one of which is a hydroxyl group. R1-R5The number of medium aliphatic groups is preferably 1 to 2, and the aliphatic group is preferably a methyl group. R6、R7Preferably a hydrogen, methyl or halogen atom, R8Preferably a single bond or a C6-C60 aromatic hydrocarbon group, preferably phenyl, naphthyl, anthracenyl, benzanthracenyl, phenanthrenyl, benzophenanthrenyl, pyrenyl, perylenyl, fluoranthenyl, biphenyl, idophenyl, terphenyl, and the like. Ra-ReThe number of medium hydroxyl groups is preferably 1 to 3, most preferably 1, wherein the position of the aliphatic radical is preferably located at R9、R10Ortho and para to C, preferably, Ra、RcAnd ReAt least one of which is a hydroxyl group.Ra-ReThe number of medium aliphatic groups is preferably 1 to 2, and the aliphatic group is preferably a methyl group. R9、R10Preferably hydrogen, methyl or halogen atoms.
Structure (I) is preferably a structure containing a fluorine substituent, which may be located at R1-R10、Ra-ReAt any position on the non-hydroxyl group in (1).
The structure (I) of the present invention may be selected from the following structures but is not limited thereto:
Figure BDA0002842046690000031
Figure BDA0002842046690000041
Figure BDA0002842046690000051
in the structural formula (II) of the present invention, R11And R12Preferably hydrogen, the formula (II) is 2, 5-xylenol or 3, 5-xylenol or a mixture of both.
R in the structural formula (III) of the invention13The compound is hydrogen or substituted or unsubstituted alkyl, the structural formula (III) can be selected from one of formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, hexanal, trichloroacetaldehyde, furfural, glyoxal, allyl aldehyde, benzaldehyde, crotonaldehyde, o-tolualdehyde, salicylaldehyde and the like, and formaldehyde is preferred.
The invention also aims to provide a photoresist composition taking fluorine-containing phenolic resin as one of the essential components, which is characterized by comprising the fluorine-containing phenolic resin A, fluorine-free phenolic resin, a photosensitizer, a solvent and an auxiliary agent;
further preferably, the composition may further include a sensitivity adjuster and a crosslinking agent.
The proportion of each component in the photoresist composition can be adjusted by those skilled in the art according to the needs, and the total weight of the photoresist composition is 100%, and the weight content of each component in the photoresist composition is as follows: 1-5% of photosensitizer; 6-11% of fluorine-free phenolic resin; 75-93% of a solvent; 0.01 to 0.5 percent of auxiliary agent; fluorine-containing phenolic resin A: 2.5 to 7 percent.
Furthermore, the proportion of each component in the photoresist composition can be prepared according to the requirement, and the photoresist composition further comprises 0.1-1% of sensitivity regulator and 0.1-2% of cross-linking agent on the basis of the components.
In the above photoresist composition of the present invention, the photosensitizer is a diazonaphthoquinone photosensitizer well known to those skilled in the art, and may be, for example, a di-substituted ester compound of diazonaphthoquinone sulfonyl chloride and trihydroxybenzophenone, a tri-substituted ester compound of diazonaphthoquinone sulfonyl chloride and tetrahydroxybenzophenone, or the like.
In the photoresist composition of the present invention, the fluorine-free phenol resin is well known to those skilled in the art and is obtained by polymerizing a phenol compound and an aldehyde compound as raw materials. For example, the phenolic hydroxyl compound may be one or more selected from phenol, cresol, xylenol, ethylphenol, propylphenol, butylphenol, t-butylphenol, di-t-butylphenol, octylphenol, fluorophenol, chlorophenol, bromophenol, iodophenol, naphthol, anthralin, dihydroxybenzene, dihydroxynaphthalene, biphenol, bisphenol, aminophenol, nitrophenol, and phloroglucinol. The aldehyde compound can be one or more selected from formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, hexanal, chloral, furfural, glyoxal, allyl aldehyde, benzaldehyde, crotonaldehyde, o-tolualdehyde, salicylaldehyde, etc. More specifically, there may be mentioned a novolak resin obtained by polymerizing cresol and formaldehyde, a novolak resin obtained by polymerizing xylenol and formaldehyde, a novolak resin obtained by polymerizing di-t-butylphenol and formaldehyde, a novolak resin obtained by polymerizing dihydroxynaphthalene and formaldehyde, a novolak resin obtained by polymerizing phloroglucinol and formaldehyde, a novolak resin obtained by polymerizing xylenol and formaldehyde and salicylaldehyde, and the like.
In the above-mentioned photoresist composition of the present invention, the solvent is well known to those skilled in the art, and may be selected from one or more of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol butyl methyl ether, diethylene glycol butyl ethyl ether, diethylene glycol diethyl ether ethyl acetate, propylene glycol monomethyl ether acetate, dipropylene glycol butyl methyl ether, dipropylene glycol ethylhexyl ether, triethylene glycol dimethyl ether, triethylene glycol tert-butyl ether, chloroform, xylene, ethyl lactate, γ -butyrolactone, N-methylpyrrolidone, benzyl alcohol, and dimethyl sulfoxide, for example.
In the photoresist composition of the present invention, in order to improve the coating performance of the photoresist composition, some auxiliary agents may be selected, for example, one or more selected from leveling agents, defoaming agents, coupling agents, and ultraviolet absorbers. In particular, the kind and amount of the auxiliary agents known to those skilled in the art can be selected, and for example, the leveling agent can be selected from acrylic leveling agents, silane leveling agents, fluorine-containing leveling agents. The defoaming agent can be selected from organic silicon defoaming agent, polyether defoaming agent and polyether modified polysiloxane defoaming agent. The coupling agent can be selected from trimethoxysilylbenzoic acid, vinyltrimethoxysilane, vinyltriacetoxysilane, gamma-methacryloxypropyltrimethoxysilane, gamma-isocyanatopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, etc. The ultraviolet absorbent can be selected from 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole, phenyl o-hydroxybenzoate, 2, 4-dihydroxybenzophenone, 4-benzoyloxy-2, 2,6, 6-tetramethylpiperidine, etc.
Further, the photoresist composition of the present invention may further include a sensitivity modifier, which is a small molecule compound known to those skilled in the art to improve sensitivity, and specifically, may be a small molecule phenolic resin, phenol, naphthol, methyl phenol, dimethyl phenol, trihydroxybenzophenone, tetrahydroxybenzophenone, or the like.
Further, the photoresist composition of the present invention may further include a crosslinking agent, which is well known to those skilled in the art, including amino-based crosslinking agents, epoxy-based crosslinking agents, ether-based crosslinking agents, urea-based crosslinking agents, and the like. Specifically, hexamethylenetetramine, 3- (2, 3-glycidoxy) propyltrimethoxysilane, 1, 4-butanediol diglycidyl ether, hexamethoxymethylmelamine, trialkoxycarbonylaminotriazine 1, 3-bis (methoxymethyl) -4, 5-dimethoxy-2-imidazolidinone, and the like can be mentioned.
The invention also provides a method for preparing the fluorine-containing phenolic resin, which comprises the following steps: copolymerizing structural monomers represented by the following formulae (I), (II) and (III) by contacting them with each other under reaction conditions using an organic acid as a catalyst to obtain the fluorine-containing phenol resin according to any one of claims 1 to 5:
Figure BDA0002842046690000071
preferably, the copolymerization reaction comprises: heating in water bath, stirring, refluxing the reaction mixture for 1-5 hr (1 hr, 2 hr, 3 hr, 4 hr, 5 hr), cooling to room temperature after stirring, separating water layer, distilling the reaction solution under reduced pressure, slowly heating to 120-170 deg.C (120 deg.C, 125 deg.C, 130 deg.C, 135 deg.C, 140 deg.C, 150 deg.C, 155 deg.C, 160 deg.C, 165 deg.C, 170 deg.C), maintaining for 0.5-3 hr (0.5 hr, 1 hr, 1.5 hr, 2 hr, 2.5 hr, 3 hr), and removing residual water;
still preferably, the copolymerization reaction comprises: after heating in a water bath and stirring, the reaction mixture refluxes for 3h, after stirring uniformly, the reaction mixture is cooled to room temperature and the water layer is separated, the reaction liquid is decompressed and distilled, and the temperature is slowly raised to 150 ℃, and the reaction liquid is kept for 1h to remove residual water.
The invention also aims to provide the application of the fluorine-containing phenolic resin and the photoresist composition in the preparation of a Thin Film Transistor (TFT).
The invention has the beneficial effects that: the fluorine-containing phenolic resin has high alkali dissolution rate, and the existence of C-F bonds improves the rigidity of molecular chains and has certain hydrophobicity, so that the dissolution inhibition of a photoresist consisting of the resin in a non-exposure area is enhanced, and the improvement of the residual film rate and the image resolution is facilitated.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) photograph of a bevel angle (taper) profile of a photoresist composition prepared in example 1 of the present invention after development and baking;
FIG. 2 is an SEM photograph of the bevel angle (taper) profile of the photoresist composition prepared in comparative example 1 of the present invention after development and baking.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention. In the following examples and comparative examples, temperatures are given in degrees centigrade, parts and percentages are by weight, unless otherwise indicated.
Preparation example 1
The preparation of the phenolic resin A takes acid as a catalyst and adopts a one-step synthesis method. A three-necked flask equipped with a mechanical stirrer, reflux condenser and thermometer was charged with 36.24g of the compound of formula (12), 18.3g of 2, 5-dimethylphenol, 13.8g of a 37% aqueous formaldehyde solution, 2.5ml of deionized water and 0.8g of oxalic acid hydrate. Heating in water bath, stirring, refluxing the reaction mixture for 3 hr, adding 90ml deionized water, stirring, cooling to room temperature, and separating water layer. The reaction solution was distilled under reduced pressure and slowly warmed to 150 ℃ for 1 hour to remove residual water. The product was cooled to room temperature to give a brittle solid with a weight average molecular weight of 5000 as determined by gel permeation chromatography.
Preparation example 2
To a three-necked flask equipped with a mechanical stirrer, a reflux condenser and a thermometer were charged 17.16g of the compound of formula (3), 18.3g of 2, 5-dimethylphenol, 13.8g of a 37% aqueous formaldehyde solution, 2.5ml of deionized water and 0.5g of oxalic acid hydrate. Heating in water bath, stirring, refluxing the reaction mixture for 3 hr, adding 90ml deionized water, stirring, cooling to room temperature, and separating water layer. The reaction solution was distilled under reduced pressure and slowly warmed to 150 ℃ for 1 hour to remove residual water. The product was cooled to room temperature to give a brittle solid with a weight average molecular weight of 4000 as determined by gel permeation chromatography.
Preparation example 3
Into a three-necked flask equipped with a mechanical stirrer, a reflux condenser and a thermometer were charged 23.4g of the compound of the structural formula (4), 18.3g of 2, 5-dimethylphenol, 13.8g of a 37% aqueous formaldehyde solution, 2.5ml of deionized water and 0.6g of oxalic acid hydrate. Heating in water bath, stirring, refluxing the reaction mixture for 3 hr, adding 90ml deionized water, stirring, cooling to room temperature, and separating water layer. The reaction solution was distilled under reduced pressure and slowly warmed to 150 ℃ for 1 hour to remove residual water. The product was cooled to room temperature to give a brittle solid with a weight average molecular weight of 4500, molecular weight determined by gel permeation chromatography.
Preparation example 4
41.04g of the compound of the structural formula (13), 18.3g of 2, 5-dimethylphenol, 13.8g of a 37% aqueous formaldehyde solution, 2.5ml of deionized water, and 0.9g of oxalic acid hydrate were charged into a three-necked flask equipped with a mechanical stirrer, a reflux condenser and a thermometer. Heating in water bath, stirring, refluxing the reaction mixture for 3 hr, adding 90ml deionized water, stirring, cooling to room temperature, and separating water layer. The reaction solution was distilled under reduced pressure and slowly warmed to 150 ℃ for 1h to remove residual water. The product was cooled to room temperature to give a brittle solid with a weight average molecular weight of 5300, molecular weight determined by gel permeation chromatography.
Preparation example 5
Preparation example 5 differs from preparation example 1 in that the heating reflux time of preparation example 5 was 2 hours, and finally a brittle solid with a weight average molecular weight of 3900 was obtained, the molecular weight being determined by gel permeation chromatography.
Preparation example 6
Preparation example 6 differs from preparation example 1 in that preparation example 5 was heated under reflux for 4 hours, and finally yielded a brittle solid with a weight average molecular weight of 7000, which was determined by gel permeation chromatography.
Example 1
The photoresist composition was prepared by combining the fluorinated phenol-formaldehyde resin a obtained in preparation example 1 with propylene glycol monomethyl ether acetate (PMA as a solvent), a non-fluorinated phenol-formaldehyde resin (novolac, shengquan 8850), a photosensitizer (toyoyo PAC350), a silane coupling agent (γ -glycidyl ether propyl trimethoxysilane), and a fluorinated leveling agent (dow corning DC-7), and the specific composition and content thereof are shown in table 1.
Example 2
Example 2 differs from example 1 in that example 2 is a photoresist composition made from the phenolic resin prepared in preparation 2.
Example 3
Example 3 differs from example 1 in that example 3 is a photoresist composition made using the phenolic resin prepared in preparation 3.
Example 4
Example 4 differs from example 1 in that example 4 is a photoresist composition formulated using the phenolic resin prepared in preparation example 4.
Example 5
Example 5 differs from example 1 in that example 5 is a photoresist composition made using the phenolic resin prepared in preparation 5.
Example 6
Example 6 differs from example 1 in that example 6 is a photoresist composition made using the phenolic resin prepared in preparation 6.
Comparative example 1
Comparative example 1 is similar to example 1 except that comparative example 1 replaces the fluorochemical phenolic resin of preparation example 1 with a non-fluorinated phenolic resin of similar molecular weight (asahi organic 40B 40G).
Comparative example 2
Comparative example 2 is similar to example 1 except that comparative example 2 replaces the fluorine-containing phenolic resin of preparation example 1 with a similar molecular weight phenolic resin (asahi organic 6050G) that does not contain fluorine and structural units of structure (II).
Test example
The photoresist compositions prepared in examples 1-6 and comparative examples 1-2 were respectively subjected to photolithography experiments under the same conditions, and specifically included the following steps:
first, a glass substrate was prepared, irradiated with a UV cleaner for 1 minute and the surface of the glass substrate was cleaned with deionized water. Then, the photoresist composition is uniformly coated on the surface of the glass substrate in a spin coating mode. Prebaking at 110 ℃ for 140s to obtain a film layer with the thickness of 1.5 microns, exposing by adopting 365nm ultraviolet light, developing by using a mask plate and a coating film at the distance of 0 micron and 2.38% TMAH (tetramethylammonium hydroxide) developing solution at 23 ℃ for 40s, washing by using water, drying, baking at 130 ℃/120s after developing, and respectively testing the exposure and the residual film rate.
The exposure is an index for evaluating the sensitivity of the photoresist, and means that the exposure of a 1:1 pattern is resolved under an optical mask with the L/S being 1:1, the exposure can be correspondingly adjusted according to requirements, and the quality of the performance of the photoresist composition cannot be judged according to the exposure; the residual film rate is an index for evaluating the washing resistance of the photoresist, the thickness of the film before and after development can be tested by an ellipsometer, and the ratio of the film thickness after development to the film thickness before development is calculated to be the residual film rate, wherein the quality of the performance of the photoresist composition is judged by the residual film rate. The specific experimental results of examples 1-6, comparative examples 1 and 2 are detailed in table 1 below.
Table 1:
Figure BDA0002842046690000091
Figure BDA0002842046690000101
as can be seen from Table 1, the photoresist compositions prepared in examples 1-6 of the present invention all exhibited a relatively higher residual film ratio than the photoresist compositions prepared in comparative examples 1-2, and thus were found to have better practical properties.
Specifically, example 1 differs from comparative example 1 only in that the fluorine-containing phenol resin provided by the present invention is added to example 1, whereas comparative example 1 is a fluorine-free phenol resin. As can be seen, the photoresist composition prepared in example 1 has a significantly improved film residue rate compared to comparative example 1; in addition, as can be seen from fig. 1 and 2, example 1 has a better pattern profile and shows an improved resolution as compared with comparative example 1. Thus, it is shown that the photoresist composition of the present invention is advantageous in improving the residual film rate and the degree of image formation.
Example 1 differs from comparative example 2 only in that the fluorine-containing phenolic resin provided by the present invention is added to example 1, whereas comparative example 2 is a fluorine-free phenolic resin and does not contain the unit of formula (II). It can be seen that the residual film rate of the photoresist composition prepared in example 1 is significantly increased compared to comparative example 2, which indicates that the structural unit of dimethylphenol in structure (II) in the fluorine-containing phenolic resin structure of the present invention also has a beneficial effect on improving the residual film rate.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.

Claims (10)

1. A fluorine-containing phenolic resin is a random copolymer which is composed of structural monomers shown in formulas (I), (II) and (III) and has a structure shown in formula (A), the molecular weight of the fluorine-containing phenolic resin is 3000-15000, and any position on a non-hydroxyl group in the formula (A) is provided with at least one fluorine substituent:
Figure FDA0002842046680000011
in the formula (A), M is a structure shown in the formula (I), Q is a structure shown in the formula (II),
Figure FDA0002842046680000012
in the formula A, R13Selected from hydrogen, substituted or unsubstituted C1-C18 aliphatic radicals; n1 and n2 are respectively and independently integers more than 1 and less than 100And n1/(n1+ n2) has a value of 0.1-0.5;
in the formula (I), R1-R5Ra-Re are respectively and independently selected from hydrogen, hydroxyl, substituted or unsubstituted aliphatic radical of C1-C30, halogen atom, R6、R7Each independently selected from hydrogen, substituted or unsubstituted aliphatic hydrocarbon groups of C1-C30, substituted or unsubstituted aromatic hydrocarbon groups of C6-C60 and halogen atoms, R8Is a single bond, substituted or unsubstituted C1-C30 aliphatic hydrocarbon group, substituted or unsubstituted C6-C60 aromatic hydrocarbon group, R9、R10Each independently selected from hydrogen, substituted or unsubstituted aliphatic hydrocarbon groups of C1-C30, substituted or unsubstituted aromatic hydrocarbon groups of C6-C60 and halogen atoms;
and R is1-R5At least 1 of them being hydroxyl, or at least 1 of Ra-Re being hydroxyl, R6And R7Not simultaneously being a substituted or unsubstituted C6-C60 aromatic hydrocarbon radical, R9And R10Is not substituted or unsubstituted C6-C60 aromatic hydrocarbon group at the same time;
in the formula (II), R11、R12Each independently selected from hydrogen, substituted or unsubstituted aliphatic radical of C1-C30, hydroxyl;
the substituted groups on the substituted aliphatic hydrocarbon group and the substituted aromatic hydrocarbon group are respectively and independently selected from one of halogen, chain alkyl of C1-C10, cycloalkyl of C3-C10, aryl of C6-C30 and heteroaryl of C3-C30.
2. The fluorine-containing phenol resin according to claim 1, wherein in the formula (I), R is1-R5Wherein 1-3 are hydroxy, and R1-R51-2 of the above are substituted or unsubstituted C1-C20 aliphatic radicals;
1-3 of the Ra-Re are hydroxyl, and 1-2 of the Ra-Re are substituted or unsubstituted C1-C20 aliphatic radical;
the substituent group on the substituted aliphatic hydrocarbon group is selected from halogen, chain alkyl of C1-C10, cycloalkyl of C3-C10, aryl of C6-C30 or heteroaryl of C3-C30;
preferably, R1-R51-2 of them are methyl; ra-Re1-2 in the formula are methyl;
preferably, R1-R5Wherein 1 is hydroxyl; r isa-ReWherein 1 is hydroxyl;
preferably, R1、R3And R4At least one of which is a hydroxyl group; r isa、RcAnd ReAt least one of which is a hydroxyl group.
3. The fluorine-containing phenol resin according to claim 2, wherein R in the formula (I)6、R7Each independently selected from hydrogen, methyl or halogen atom, said R8Is a single bond, phenyl, naphthyl, anthryl, benzanthryl, phenanthryl, benzophenanthryl, pyrenyl, perylenyl, fluoranthenyl, biphenyl, idophenyl or terphenyl.
4. The fluorine-containing phenolic resin according to claim 1, wherein the formula (I) is selected from the following structures:
Figure FDA0002842046680000021
Figure FDA0002842046680000031
5. the fluorine-containing phenol resin according to claim 1, wherein in the formula (II), R is11、R12Are all hydrogen, formula (II) is 2, 5-xylenol, 3, 5-xylenol or a mixture of 2, 5-xylenol and 3, 5-xylenol;
the formula (III) is one selected from formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, hexanal, chloral, furfural, glyoxal, allyl aldehyde, benzaldehyde, crotonaldehyde, o-tolualdehyde and salicylaldehyde, and preferably the formula (III) is formaldehyde.
6. A preparation method of fluorine-containing phenolic resin comprises the following steps:
copolymerizing structural monomers represented by the following formulae (I), (II) and (III) by contacting them with each other under reaction conditions using an organic acid as a catalyst to obtain the fluorine-containing phenol resin according to any one of claims 1 to 5:
Figure FDA0002842046680000041
preferably, the copolymerization reaction comprises: heating in water bath and stirring, refluxing the reaction mixture for 1-5 hr, stirring, cooling to room temperature, separating water layer, distilling the reaction liquid under reduced pressure, slowly heating to 120-170 deg.c, maintaining for 0.5-3 hr to eliminate residual water;
still preferably, the copolymerization reaction comprises: after heating in a water bath and stirring, the reaction mixture was refluxed for 3 hours, stirred uniformly, cooled to room temperature and separated from the water layer, the reaction solution was distilled under reduced pressure and slowly warmed to 150 ℃ for 1 hour to remove residual water.
7. A photoresist composition, comprising the fluorine-containing phenolic resin, the non-fluorine-containing phenolic resin, a photosensitizer, a solvent and an auxiliary agent, wherein the components are as follows by weight percent:
photosensitizer: 1 to 5 percent; fluorine-free phenol resin: 6 to 11 percent; solvent: 75-93%; auxiliary agent: 0.01 to 0.5 percent; fluorine-containing phenolic resin: 2.5 to 7 percent.
8. The photoresist composition of claim 7, wherein the photosensitizer is selected from di-substituted ester compounds of diazonaphthoquinone sulfonyl chloride and trihydroxybenzophenone, tri-substituted ester compounds of diazonaphthoquinone sulfonyl chloride and tetrahydroxybenzophenone;
the non-fluorine-containing phenolic resin is selected from resin polymerized by phenolic compounds and aldehyde compounds, the phenolic compounds are selected from one or more of phenol, cresol, xylenol, ethylphenol, propylphenol, butylphenol, tert-butylphenol, di-tert-butylphenol, octylphenol, fluorophenol, chlorophenol, bromophenol, iodophenol, naphthol, anthraphenol, dihydroxybenzene, dihydroxynaphthalene, biphenol, bisphenol, aminophenol, nitrophenol and phloroglucinol, and the aldehyde compounds are selected from one or more of formaldehyde, acetaldehyde, propionaldehyde, n-butyl aldehyde, hexanal, trichloroacetaldehyde, furfural, glyoxal, allyl aldehyde, benzaldehyde, crotonaldehyde, o-tolualdehyde and salicylaldehyde; preferably, the non-fluorine containing phenolic resin is selected from: novolac resins polymerized from cresol and formaldehyde, novolac resins polymerized from xylenol and formaldehyde, novolac resins polymerized from di-tert-butylphenol and formaldehyde, novolac resins polymerized from dihydroxynaphthalene and formaldehyde, novolac resins polymerized from phloroglucinol and formaldehyde, and novolac resins polymerized from xylenol, formaldehyde and salicylaldehyde;
the solvent is one or a combination of two or more of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol butyl methyl ether, diethylene glycol butyl ethyl ether, diethylene glycol diethyl ether ethyl acetate, propylene glycol monomethyl ether acetate, dipropylene glycol butyl methyl ether, dipropylene glycol ethylhexyl ether, triethylene glycol dimethyl ether, triethylene glycol tert-butyl ether, chloroform, xylene, ethyl lactate, gamma-butyrolactone, N-methylpyrrolidone, benzyl alcohol and dimethyl sulfoxide;
the auxiliary agent is one or a combination of two or more of a leveling agent, a defoaming agent, a coupling agent and an ultraviolet absorbent.
9. Use of the photoresist composition of claim 7 in the preparation of a thin film transistor.
10. Use of a fluorine-containing phenol resin according to any one of claims 1 to 5 for producing a thin film transistor.
CN202011495554.5A 2020-12-17 2020-12-17 Fluorine-containing phenolic resin, preparation method thereof and photoresist composition adopting fluorine-containing phenolic resin Pending CN114644740A (en)

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