CN117586161A - Sulfur ester compound and preparation method thereof, alkali-soluble resin, photosensitive resin composition and application thereof - Google Patents

Sulfur ester compound and preparation method thereof, alkali-soluble resin, photosensitive resin composition and application thereof Download PDF

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Publication number
CN117586161A
CN117586161A CN202210983448.4A CN202210983448A CN117586161A CN 117586161 A CN117586161 A CN 117586161A CN 202210983448 A CN202210983448 A CN 202210983448A CN 117586161 A CN117586161 A CN 117586161A
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alkali
groups
soluble resin
methyl
resin composition
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葛庆余
钱彬
张学龙
尹志兴
鲍文畅
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Changzhou Tronly New Electronic Materials Co Ltd
Changzhou Tronly Advanced Electronic Materials Co Ltd
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Changzhou Tronly New Electronic Materials Co Ltd
Changzhou Tronly Advanced Electronic Materials Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C327/00—Thiocarboxylic acids
    • C07C327/20—Esters of monothiocarboxylic acids
    • C07C327/28—Esters of monothiocarboxylic acids having sulfur atoms of esterified thiocarboxyl groups bound to carbon atoms of hydrocarbon radicals substituted by singly-bound oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1807—C7-(meth)acrylate, e.g. heptyl (meth)acrylate or benzyl (meth)acrylate
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • 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
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/02—Systems containing only non-condensed rings with a three-membered ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Optics & Photonics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention provides a thioester compound and a preparation method thereof, alkali-soluble resin, photosensitive resin composition and application thereof. The thioester compound has the following general formula I:wherein m is 1 or 2, q is any one integer from 0 to 2, p is any one integer from 0 to 10, R 1 Selected from C 6 ～C 30 Substituted or unsubstituted aryl, C 4 ～C 30 Any one of substituted or unsubstituted heteroaryl groups; r is R 2 Selected from H, C 1 ～C 10 Straight chain alkyl, C 3 ～C 15 Branched alkyl, C 1 ～C 10 Any one of the alkoxy groups of (a); r is R 3 Selected from H, C 1 ～C 10 Straight chain alkyl, C 3 ～C 10 Branched alkyl, C 1 ～C 10 Any one of the alkoxy groups of (a); r is R 4 Selected from H, C 1 ～C 10 Any one of the alkyl groups of (a). The thioester compound can better adapt to the lower process temperature requirement of the flexible display device.

Description

Sulfur ester compound and preparation method thereof, alkali-soluble resin, photosensitive resin composition and application thereof
Technical Field
The invention relates to the technical field of photosensitive materials, in particular to a thioester compound and a preparation method thereof, alkali-soluble resin, photosensitive resin composition and application thereof.
Background
In the process of producing display elements such as optical filters, it is often necessary to perform a post-baking process at a high temperature to sufficiently cure the optical filter in order to provide the optical filter with better adhesion and solvent resistance. With the advent and development of flexible touch screens, higher requirements are put on the application performance of related materials. The substrates used in flexible display devices are generally not resistant to high temperature baking and require materials with good flexibility, adhesion and mechanical strength. For application to flexible display devices that are not resistant to high temperatures, development of photosensitive resin compositions that can be sufficiently cured under post-baking conditions at low temperatures (at least 200 ℃ or less) and that exhibit good adhesion and solvent resistance is required.
In order to improve the low-temperature curing performance of the photosensitive resin composition, the prior art mostly adopts the addition of a thiol compound into the photosensitive resin composition to promote the double bond of the acrylic substance to polymerize at a lower temperature, thereby meeting the low-temperature processing requirement. The thiol compound is a highly effective chain transfer agent, and can effectively promote the polymerization of the polymerizable additive in the resin composition under the condition of low temperature, thereby effectively improving the crosslinking density of the cured film. In addition, the mercaptan can effectively reduce the polymerization inhibition effect of oxygen in the curing process and effectively improve the curing degree of the composition, thereby improving the adhesive force, solvent resistance and other properties of the cured film. However, the thiol compound generally has a large odor, and when thiol and a polymerizable double bond coexist, the storage condition is required to be high, which is disadvantageous for stable storage and use of the photocurable resin composition.
Disclosure of Invention
The invention mainly aims to provide a thioester compound and a preparation method thereof, alkali-soluble resin, photosensitive resin composition and application thereof, so as to solve the problems of high odor and poor preservation of a low-temperature curing type photosensitive resin composition in the prior art.
In order to achieve the above object, according to one aspect of the present invention, there is provided a thioester compound having the following general formula I:
wherein m is 1 or 2, q is any integer from 0 to 2, and p is any integer from 0 to 10; r is R 1 Selected from C 6 ～C 30 Substituted or unsubstituted aryl, C 4 ～C 30 Any one of substituted or unsubstituted heteroaryl groups; r is R 2 Selected from H, C 1 ～C 10 Straight chain alkyl, C 3 ～C 15 Branched alkyl, C 1 ～C 10 Any one of the alkoxy groups of (a); r is R 3 Selected from H, C 1 ～C 10 Straight chain alkyl, C 3 ～C 10 Branched alkyl, C 1 ～C 10 Any one of the alkoxy groups of (a); r is R 4 Selected from H, C 1 ～C 10 Any one of the alkyl groups of (a).
Further, R is as described above 1 Selected from C 6 ～C 18 Is taken from (a)Substituted or unsubstituted aryl, C 4 ～C 18 Any of the substituted or unsubstituted heteroaryl groups, preferably R 1 Selected from C 6 ～C 18 Substituted or unsubstituted phenyl, C 10 ～C 18 Substituted or unsubstituted naphthyl, C 4 ～C 10 Any of the substituted or unsubstituted heteroaryl groups, preferably R 1 Selected from the group consisting of Wherein "×" is R 1 And a position to which the thioester compound is bonded.
Further, R is as described above 2 Selected from H, C 1 ～C 5 Straight chain alkyl, C 3 ～C 6 Branched alkyl, C 1 ～C 5 Preferably R 2 Any one selected from H, methyl, ethyl, propyl, isopropyl, isobutyl, isopentyl, methoxy, ethoxy, and propoxy, and further, R is preferably selected 2 Selected from any one of H, methyl, propyl and isobutyl.
Further, R is as described above 3 Selected from H, C 1 ～C 5 Straight chain alkyl, C 3 ～C 5 Branched alkyl, C 1 ～C 5 Preferably R 3 Any one selected from H, methyl, ethyl, propyl, isopropyl, isobutyl, isopentyl, methoxy, ethoxy, and propoxy, and further, R is preferably selected 3 Is methyl.
Further, R is as described above 4 Selected from H, C 1 ～C 10 Any of the alkyl groups of (2), preferably R 4 Selected from H, C 1 ～C 5 Any of the alkyl groups of (2), preferably R 4 Any one selected from H, methyl, ethyl and propyl, and further, R is preferable 4 Is H or ethyl.
Further, the structural formula of the thioester compound is
Any one or more of the following.
In another exemplary embodiment of the present application, there is provided a method for preparing a thioester compound, the method comprising: esterification reaction is carried out on reaction raw materials comprising thioacrylate compounds and acrylate monomers to generate thioester compounds; wherein, the structural formulas of the thioacrylate compound and the acrylate monomer are as follows in sequence:
R 5 Selected from C 2 ～C 20 And C is any one of hydrocarbon groups of 2 ～C 20 Comprises at least one C in the hydrocarbon group 2 ～C 10 Epoxy group R of (2) 1 、R 2 And R is 3 R is as in the above 1 、R 2 And R is 3 。
Further, R is as described above 5 Selected from C 2 ～C 10 Is preferably any one of the hydrocarbon groups of R 5 Selected from C 2 ～C 10 Any of the alkyl groups of (2), preferably R 5 Selected from C 2 ～C 5 Any of the alkyl groups of (2), preferably R 5 Selected from the group consisting of Wherein "×" is R 5 And the position connected with the acrylic monomer.
Further, the above C 2 ～C 20 Comprises at least one C in the hydrocarbon group 2 ～C 5 Epoxy groups of (C) are preferred 2 ～C 20 Comprises at least one cyclopropoxy or cyclobutoxy group, preferably the acrylic monomer is selected from the group consisting of glycidyl acrylate, glycidyl methacrylate, oxetane methacrylate,N represents any one of integers from 1 to 10, preferably n represents any one of integers from 1 to 5, preferably n is 1 or 3; preferably R 6 、R 7 Each independently is H or methyl; preferably R 8 Selected from C 1 ～C 10 Straight chain alkyl, C 3 ～C 10 Branched alkyl, C 3 ～C 12 Is preferably R 8 Selected from C 1 ～C 5 Straight chain alkyl, C 3 ～C 6 Branched alkyl, C 3 ～C 6 Is preferably R 8 Any one selected from methyl, ethyl, propyl, isopropyl, isobutyl, isopentyl, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl, and further, R is preferably selected from 8 Is methyl.
In yet another exemplary embodiment of the present application, an alkali-soluble resin obtained by polymerizing the aforementioned thioester compound with a monomer having a carbon-carbon double bond is provided.
Further, the weight average molecular weight of the alkali-soluble resin is within a range of 8000 to 20000, preferably 14000 to 18000.
Further, the acid value of the alkali-soluble resin is 70 to 200mgKOH/g, preferably 80 to 150mgKOH/g, and further preferably 100 to 120mgKOH/g.
Further, the monomer containing a carbon-carbon double bond is selected from any one or more of acrylic monomers, acrylic ester monomers, substituted or unsubstituted styrene monomers, unsaturated organic acids, unsaturated organic acid anhydrides, unsaturated imine monomers and acrylamide monomers.
In yet another exemplary embodiment of the present application, there is provided a photosensitive resin composition including an alkali-soluble resin, which is the alkali-soluble resin described above.
In yet another exemplary embodiment of the present application, there is provided a use of the aforementioned photosensitive resin composition, including use of the photosensitive resin composition for color filters.
By applying the technical scheme of the invention, the thioester compound with the general formula I can be subjected to copolymerization reaction with other compounds with unsaturated double bonds to obtain the corresponding alkali-soluble resin with thioester groups. Under UV radiation, the thioester groups undergo cis-trans isomerism rearrangement to decompose and produce compounds with thiol groups, so that double bond polymerization of the active polymerizable compounds is promoted to cure, and the curing temperature of the photosensitive resin composition is greatly reduced. In addition, the thioester group does not directly decompose a thiol group under the influence of external factors such as no light, that is, does not promote the polymerization of the related active polymerizable compound, and thus the storage stability of the photosensitive resin composition is good. Compared with a formula in which the thiol compound is directly added, the problems of poor storage stability, unpleasant odor and the like of the photosensitive resin composition caused by the addition of the thiol compound (exposed thiol group) are effectively avoided. Furthermore, the thioester compound can effectively promote high-density crosslinking of unsaturated double bonds at a lower temperature, so that the comprehensive properties of strength, adhesive force and the like of a cured film are effectively improved, and the low-temperature flexible display device can be better adapted to the lower process temperature requirement.
Detailed Description
It should be noted that, in the case of no conflict, the embodiments and features in the embodiments may be combined with each other. The present invention will be described in detail with reference to examples.
As analyzed by the background art, the low-temperature curing type photosensitive resin composition in the prior art has the problems of large odor and poor preservation, and in order to solve the problems, the invention provides a thioester compound and a preparation method thereof, an alkali-soluble resin, a photosensitive resin composition and application thereof.
In one exemplary embodiment of the present application, a thioester compound is provided having the following formula I:
wherein m is 1 or 2, q is any one integer from 0 to 2, p is any one integer from 0 to 10, R 1 Selected from C 6 ～C 30 Substituted or unsubstituted aryl, C 4 ～C 30 Any one of substituted or unsubstituted heteroaryl groups; r is R 2 Selected from H, C 1 ～C 10 Straight chain alkyl, C 3 ～C 15 Branched alkyl, C 1 ～C 10 Any one of the alkoxy groups of (a); r is R 3 Selected from H, C 1 ～C 10 Straight chain alkyl, C 3 ～C 10 Branched alkyl, C 1 ～C 10 Any one of the alkoxy groups of (a); r is R 4 Selected from H, C 1 ～C 10 Any one of the alkyl groups of (a).
The thioester compound having the above general formula I can be copolymerized with other compounds having an unsaturated double bond to obtain the corresponding alkali-soluble resin having a thioester group. Under UV radiation, the thioester groups undergo cis-trans isomerism rearrangement to decompose and produce compounds with thiol groups, so that double bond polymerization of the active polymerizable compounds is promoted to cure, and the curing temperature of the photosensitive resin composition is greatly reduced. In addition, the thioester group does not directly decompose a thiol group under the influence of external factors such as no light, that is, does not promote the polymerization of the related active polymerizable compound, and thus the storage stability of the photosensitive resin composition is good. Compared with a formula in which the thiol compound is directly added, the problems of poor storage stability, unpleasant odor and the like of the photosensitive resin composition caused by the addition of the thiol compound (exposed thiol group) are effectively avoided. Furthermore, the thioester compound can effectively promote high-density crosslinking of unsaturated double bonds at a lower temperature, so that the comprehensive properties of strength, adhesive force and the like of a cured film are effectively improved, and the low-temperature flexible display device can be better adapted to the lower process temperature requirement.
In one embodiment of the present application, R is as described above 1 Selected from C 6 ～C 18 Substituted or unsubstituted aryl, C 4 ～C 18 Any of the substituted or unsubstituted heteroaryl groups, preferably R 1 Selected from C 6 ～C 18 Substituted or unsubstituted phenyl, C 10 ～C 18 Substituted or unsubstituted naphthyl, C 4 ～C 10 Any of the substituted or unsubstituted heteroaryl groups, preferably R 1 Selected from the group consisting of Wherein "×" is R 1 And a position to which the thioester compound is bonded.
R of the above thioester compound 1 When selected from the above substituents, these aryl groups may undergo p-pi conjugation with adjacent carbon-carbon double bonds and thioester bonds, thereby making the thioester bonds more reactive and thus rapidly converting the thioester bonds to thiols upon subsequent photocuring.
Further, R is preferably as described above 2 Selected from H, C 1 ～C 5 Straight chain alkyl, C 3 ～C 6 Branched alkyl, C 1 ～C 5 Preferably R 2 Any one selected from H, methyl, ethyl, propyl, isopropyl, isobutyl, isopentyl, methoxy, ethoxy, and propoxy, and further, R is preferably selected 2 Selected from any one of H, methyl, propyl and isobutyl.
In order to improve the efficiency and effect of polymerization of the thioester compound and the monomer having a carbon-carbon double bond, the R is preferably 3 Selected from H, C 1 ～C 5 Straight chain alkyl, C 3 ～C 5 Branched alkyl of (2)、C 1 ～C 5 Preferably R 3 Any one selected from H, methyl, ethyl, propyl, isopropyl, isobutyl, isopentyl, methoxy, ethoxy, and propoxy, and further, R is preferably selected 3 Is methyl.
In one embodiment of the present application, R is preferably as defined above 4 Selected from H, C 1 ～C 10 Any of the alkyl groups of (2), preferably R 4 Selected from H, C 1 ～C 5 Any of the alkyl groups of (2), preferably R 4 Any one selected from H, methyl, ethyl and propyl, and further, R is preferable 4 Is H or ethyl.
In some embodiments of the present application, the above thioester compound is preferably of the formula
Can be polymerized with monomers containing carbon-carbon double bonds better to obtain the photo-curing alkali-soluble resin with excellent comprehensive performance.
In another exemplary embodiment of the present application, there is provided a method for preparing a thioester compound, the method comprising: esterification reaction is carried out on reaction raw materials comprising thioacrylate compounds and acrylate monomers to generate thioester compounds; wherein, the structural formulas of the thioacrylate compound and the acrylate monomer are as follows in sequence:
R 5 Selected from C 2 ～C 20 And C is any one of hydrocarbon groups of 2 ～C 20 Comprises at least one C in the hydrocarbon group 2 ～C 10 Epoxy group R of (2) 1 、R 2 And R is 3 R in the same claim 1 1 、R 2 And R is 3 。
The thioacrylate compound and acrylate monomer are dissolved in a certain amount of solvent, and then catalyst (such as tetraethylammonium chloride, etc., the catalyst dosage is 0.1-3.0% of thioacrylate compound dosage), polymerization inhibitor (such as 4-methoxyphenol, 2, 6-di-tert-butyl-4-methylphenol, etc., the polymerization inhibitor dosage is 0.1% of acrylate monomer dosage) are added, preferably under the condition of bubbling in dry air, the temperature is gradually raised to 70-100 ℃, the reaction is kept for 4-8 h, and the temperature is reduced to room temperature. The solution is washed by water, and the organic layer is distilled and concentrated under reduced pressure to obtain light yellow oily liquid, namely the thioester compound.
Solvents that can effectively dissolve the above-mentioned thioacrylate compounds and acrylate monomers and that do not react with the epoxy group may be used. In the present invention, an exemplary list is as follows: benzene, toluene, xylene, dichloroethane, N-dimethylformamide, N-diethylformamide, dimethylsulfoxide, and the like, and toluene and/or xylene are more preferable as the reaction solvent.
The catalyst is not particularly limited as long as it can promote the esterification reaction between the epoxy group of the acrylic monomer and the thioester group in the thioacrylate compound. Preferred quaternary ammonium catalysts in the present invention are exemplified by: catalysts such as tetrabutylammonium bromide, tetraethylammonium bromide, tetramethylammonium chloride, benzyltrimethylammonium chloride, and benzyltriethylammonium chloride, and more preferably tetramethylammonium chloride and/or tetraethylammonium chloride.
In order to promote the ring opening of the epoxy group in the acrylic monomer and thereby improve the efficiency and effect of the esterification reaction, a sulfur ester compound having excellent properties is obtained, preferably R 5 Selected from C 2 ～C 10 Is preferably any one of the hydrocarbon groups of R 5 Selected from C 2 ～C 10 Any of the alkyl groups of (2), preferably R 5 Selected from C 2 ～C 5 Any of the alkyl groups of (2), preferably R 5 Selected from the group consisting of Wherein "×" is R 5 And the position connected with the acrylic monomer.
The above C 2 ～C 20 Comprises at least one C in the hydrocarbon group 2 ～C 5 Epoxy groups of (C) are preferred 2 ～C 20 Comprises at least one cyclopropoxy or cyclobutoxy group, preferably the acrylic monomer is selected from the group consisting of glycidyl acrylate, glycidyl methacrylate, oxetane methacrylate, N represents any one of integers from 1 to 10, preferably n represents any one of integers from 1 to 5, preferably n is 1 or 3; preferably R 6 、R 7 Each independently is H or methyl; preferably R 8 Selected from C 1 ～C 10 Straight chain alkyl, C 3 ～C 10 Branched alkyl, C 3 ～C 12 Is preferably R 8 Selected from C 1 ～C 5 Straight chain alkyl, C 3 ～C 6 Branched alkyl, C 3 ～C 6 Is preferably R 8 Any one selected from methyl, ethyl, propyl, isopropyl, isobutyl, isopentyl, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl, and further, R is preferably selected from 8 Is methyl.
In yet another exemplary embodiment of the present application, an alkali-soluble resin obtained by polymerizing the above-described thioester compound with a monomer having a carbon-carbon double bond is provided.
The alkali-soluble resin can be obtained through simple polymerization reaction, specifically, according to a designed formula, the optimized thioester compound and the monomer containing carbon-carbon double bond are uniformly mixed according to a certain proportion for standby, and then quantitative initiator solution is prepared for standby. Adding quantitative solvent into a container with stirring and reflux condensing pipes, such as a four-neck flask, heating to a certain reaction temperature, such as 70-80 ℃, dropwise adding a monomer mixed solution and an initiator solution at the same time for 2-3 h, performing heat preservation reaction for 4-8 h, cooling to room temperature, and discharging to obtain alkali soluble resin solution.
In order to allow better application and subsequent work in the preparation of the photocurable composition, the solvents chosen in the preparation of the polymer remain identical to the solvents used in the photocurable composition, examples of solvents being: any one or more of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol N-propyl ether, ethylene glycol mono-N-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol mono-N-butyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-N-propyl ether, propylene glycol mono-N-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-N-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propylene glycol methyl ether acetate, N-methylpyrrolidone, γ -butyrolactone, and further, preferably any one or more of diethylene glycol methyl ether, N-methylpyrrolidone, propylene glycol methyl ether acetate.
The initiator used in the above polymerization process is not particularly limited, and may be used as long as it can provide sufficient radicals to promote polymerization of the double bond. Exemplary lists are as follows: azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisbutyrate, azobisisoheptonitrile, benzoyl peroxide, t-butyl peroxy (2-ethylhexanoate). Preferably, one or more of the above initiators are used in combination, so that a better reaction effect can be achieved.
In one embodiment of the present application, the weight average molecular weight of the alkali-soluble resin is within a range of 8000 to 20000, preferably 14000 to 18000.
The alkali-soluble resin having a too large weight average molecular weight is disadvantageous in that it is better dissolved in an organic solvent, thereby having a certain influence on the development effect, and the alkali-soluble resin having a too small weight average molecular weight is reduced in adhesion and even the cured film including the same is liable to peel off from the substrate, and therefore, the alkali-soluble resin having the above number average molecular weight range is preferable in order to satisfy both the curing property and flexibility of the photosensitive resin composition.
In order to maintain good alkali solubility, the acid value of the alkali-soluble resin is preferably 70 to 200mgKOH/g, more preferably 80 to 150mgKOH/g, still more preferably 100 to 120mgKOH/g.
The above polymerization reaction is not particularly limited as long as the polymerizable monomer is a monomer having a radically polymerizable double bond. In order to improve the overall properties of the alkali-soluble resin obtained by polymerization, it is preferable that the monomer having a carbon-carbon double bond is selected from any one or more of an acrylic monomer, a substituted or unsubstituted styrene monomer, an unsaturated organic acid anhydride, an unsaturated imine monomer, and an acrylamide monomer. Further, the following can be exemplified: alkyl (meth) acrylates such as (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate, and mono-2- (2-acryloyloxy) oxyethanol succinate; acrylic esters such as benzyl (meth) acrylate, dicyclopentyl methacrylate, cyclohexyl methacrylate, isooctyl (meth) acrylate, and n-octyl (meth) acrylate; styrenes such as styrene and hydroxystyrene; unsaturated organic acids such as maleic acid and anhydrides thereof; substituted imines such as N-phenylmaleimide and N-cyclohexylmaleimide; acrylamides such as N-methacrylamide, N-ethylacrylamide, N-isopropylacrylamide, N-methylolacrylamide, N-methylacrylamide, N-ethylmethacrylamide, N-isopropylmethacrylamide, N-methylolmethacrylamide, N-dimethylacrylamide, N-diethylacrylamide, N-dimethylacrylamide, N-diethylacrylamide; polyethylene glycol di (meth) acrylate (ethylene number 2 to 14), and the like.
In yet another exemplary embodiment of the present application, there is provided a photosensitive resin composition including an alkali-soluble resin, which is the alkali-soluble resin described above.
In the photosensitive resin composition comprising the alkali-soluble resin, under the irradiation of UV, the thioester groups undergo cis-trans isomerism rearrangement to decompose to generate a compound with a thiol group, so that the double bond polymerization of the active polymerizable compound is promoted to be cured, and the curing temperature of the photosensitive resin composition is greatly reduced. In addition, the thioester group does not directly decompose a thiol group under the influence of external factors such as no light, that is, does not promote the polymerization of the related active polymerizable compound, and thus the storage stability of the photosensitive resin composition is good. Compared with a formula in which the thiol compound is directly added, the problems of poor storage stability, unpleasant odor and the like of the photosensitive resin composition caused by the addition of the thiol compound (exposed thiol group) are effectively avoided. Furthermore, the thioester compound can effectively promote high-density crosslinking of unsaturated double bonds at a lower temperature, so that the comprehensive properties of strength, adhesive force and the like of a cured film are effectively improved, and the low-temperature flexible display device can be better adapted to the lower process temperature requirement.
In order to enhance the synergistic interaction between the components in the photosensitive resin composition, it is preferable that the photosensitive resin composition comprises, by weight, 20 to 50 parts of an alkali-soluble resin, 0.1 to 10 parts of a photoinitiator, 1 to 25 parts of a photopolymerizable compound, 10 to 60 parts of a colorant, 20 to 50 parts of a solvent, and 0 to 3 parts of an auxiliary agent, and further, it is preferable that the photosensitive resin composition comprises 20 to 35 parts of an alkali-soluble resin, 0.5 to 5 parts of a photoinitiator, 10 to 20 parts of a photopolymerizable compound, 20 to 40 parts of a colorant, 20 to 30 parts of a solvent, and 0 to 1 part of an auxiliary agent.
The photoinitiator is not particularly limited, and may be any one or more selected from oxime ester photoinitiators, benzophenone initiators, triazine initiators, dialkoxyacetophenone initiators, acylphosphine oxide initiators, benzophenone initiators, benzoin initiators, benzil initiators, heterocyclic aromatic ketone initiators, alpha-aminoalkyl ketone initiators, and alpha-hydroxyalkyl ketone initiators. Exemplary examples are: benzophenone, 4-phenylbenzophenone, 4-benzoyl-4 ' -methyldiphenylsulfide, diethoxyacetophenone, 2, 4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6-piperonyl-1, 3, 5-triazine, benzoin methyl ether, benzoin isobutyl ether, 2-ethyl-9, 10-dimethoxyanthracene, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9, 10-phenanthrenequinone, O-ethoxycarbonyl-a-oxyimino-1-phenylpropanone, 1, 2-octanedione 1- (4-phenylthio) phenyl-2 (O-benzoyloxime), 1- (9-ethyl) -6- (2-methylbenzoyl) carbazol-3-yl-1- (O-acetyloxime), 1- [ 9-ethyl-6- (2-methylbenzoyl) -9-hydro-carbazol-3-yl ] -1- (oxo-29-acetyloxime), GGI-124, GGI-224, OXE-01, NCI-831, 2,4, 5-triarylimidazole dimer, 4' -bis-diethylaminobenzophenone, 4' -dichlorobenzene ketone, 2-methyl thioxanthone, 2-isopropyl thioxanthone, dibenzocycloheptone, trichloroacetophenone, amyl-4-dimethylaminobenzoate, 9-phenylacridine, 1, 7-bis (9-acridinyl) heptane, 1, 3-bis (9-acridinyl) propane, 2-methyl-4, 6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) vinyl ] -4, 5-bis (trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2 methylphenyl) vinyl ] -4, 6-bis (trichloromethyl) -s-triazine, 2, 4-bis (trichloromethyl) -6- (2-bromo-4-methoxy) phenyl-s-triazine, 2, 4-bis (trichloromethyl) -6- (3-bromo-4-methoxy) styrylphenyl-s-triazine, 2, 4-bis (trichloromethyl) -6- (2-bromo-4-methoxy) styrylphenyl-s-triazine, 4-benzoyl-4' -methyldimethyl sulfide, 4-dimethylaminoethyl benzoate, 4-dimethylaminomethyl benzoate, benzyl-beta-ethyl-methoxy-phenyl-s-triazine, benzyl-1-dimethyl ketal, 2-oxo-1-dimethyl ketal, 2-o-propyl-1-carbonyl-1-butanone, particularly preferred are any one or more of 1- (9-ethyl) -6- (2-methylbenzoyl) carbazol-3-yl-1- (O-acetyl oxime), 1- [ 9-ethyl-6- (2-methylbenzoyl) -9-hydro-carbazole-3-substituent ] -1- (oxo-29-acetyl oxime).
The photopolymerizable compound is used for improving the photosensitivity, mechanical strength and other application properties of the photosensitive resin composition. The photopolymerizable compound is not particularly limited, and one or a combination of several monomers may be selected as needed as long as one or more monomers capable of double bond polymerization having an unsaturated bond in the molecule are present. Preferred photopolymerizable compounds selected in the present invention are exemplified by: alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate; styrenes such as styrene and hydroxystyrene; unsaturated organic acids such as maleic acid and anhydrides thereof; acrylamides such as N-methacrylamide, N-ethylacrylamide, N-isopropylacrylamide, N-methylolacrylamide, N-methylacrylamide, N-ethylmethacrylamide, N-isopropylmethacrylamide, N-methylolmethacrylamide, N-dimethylacrylamide, N-diethylacrylamide, N-dimethylacrylamide, N-diethylacrylamide; polyethylene glycol di (meth) acrylate (ethylene number 2 to 14); trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxytri (meth) acrylate, trimethylolpropane propoxytri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, polypropylene glycol di (meth) acrylate (propylene number 2 to 14); dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol a polyoxyethylene di (meth) acrylate, bisphenol a dioxyethylene di (meth) acrylate, bisphenol a trioxyethylene di (meth) acrylate, bisphenol a oxyethylene di (meth) acrylate, esters of polycarboxylic acids (e.g., phthalic anhydride, etc.) with compounds having hydroxyl groups and ethylenically unsaturated groups (e.g., β -hydroxyethyl (meth) acrylate, etc.); one or more of N-vinyl pyrrolidone, N-vinyl formamide, N-vinyl acetamide and N-vinyl imidazole are mixed for use. In order to further improve the photosensitivity, mechanical strength and other properties of the photosensitive resin composition, the polymerizable compound is more preferably diethylene glycol diglycidyl ether and/or hydroxystyrene.
In order to enhance the dispersing effect of the photosensitive resin composition of the present invention for convenience of use, it is preferable to add some common solvent, and it is possible to select (poly) alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, etc.; aromatic hydrocarbons such as: toluene, xylene, trimethylbenzene, etc.; amide compounds such as: n-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide and the like; carboxylic acid ester compounds such as: ethyl 2-oxobutyrate, methyl acetoacetate, ethyl acetate, n-propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, n-pentyl formate, isopentyl acetate, butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl acetone, methyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl glycolate, methyl 2-hydroxy-3-methylbutyrate, 3-methyl-3-methoxybutylacetate, 3-methyl-3-methoxybutylpropionate, and the like; ketones such as: methyl ethyl ketone, cyclohexanone, heptanone, 3-heptanone, and the like; cyclic ethers such as tetrahydrofuran, pyran and the like; cyclic esters such as gamma butyrolactone and the like. These solvents may be used alone or in combination of two or more, and preferably one or more of propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether, and diethylene glycol methylether are used in combination; it is further preferable to use propylene glycol methyl ether acetate and/or diethylene glycol methyl ether in combination to obtain better solubility and dispersibility.
The photosensitive resin composition may optionally contain a colorant commonly used in the art to form a color filter, if necessary. Any of organic pigments and inorganic pigments commonly used in the art may be selectively used as the colorant of the present application. The pigment can be used singly or after being mixed, and is determined according to the specific application requirements of the product.
The pigments used in the present invention are exemplified by, but not limited to, the following pigments. Specific examples of compounds having color index (staining worker association (c.i.) number are: C.I. pigment orange 1, 3, 11, 13, 14, 15, 16, 17, 20, 24, 3, 53, 55, 60, 65, 71, 73, 74, 81, 83, 86, 93, 95, 97, 98, 100, 101, 106, 109, 120, 125, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 167, 175, 180, 183, 185; C.I. pigment yellow 1, 2, 3, 5, 13, 31, 32, 34, 36, 37, 42, 43, 46, 53, 65; C.I. pigment violet 1, 14, 19, 23, 29, 30, 36, 37, 38, 39, 40; C.I. pigment red 1, 2' 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 18, 19, 21, 23, 30, 31, 37, 38, 40, 42, 48, 53:1, 57, 57:2, 60:1, 83, 97, 105, 122, 144, 166, 176, 180, 192, 202, 206, 207, 208, 215, 224, 242, 254, 255, 264, 265; c.i. pigment blue 1, 2, 15, 15:3, 15:6, 16, 21, 22, 60, 64, 66; c.i. pigment green 7, 10, 15, 25, 36, 47, 48; c.i. pigment brown 23, 25, 26, 28; c.i. pigment black 1 and 7, etc.
One or more of the above pigments are selected for use as needed. More preferably in the present invention: pigment red 8, 10, 11, 12, etc. The content of the colorant is selected according to the application requirements of the photosensitive resin composition, and in the photosensitive resin composition provided by the invention, if the total amount of the composition is 100 parts by weight, the colorant is 10 to 60 parts by weight, more preferably 20 to 40 parts by weight. In order to uniformly disperse the colorant in the photosensitive resin composition, a dispersing agent may also be used. As such a dispersant, a polyethyleneimine-based, polyurethane-based, acrylic resin-based polymer dispersant, in particular, an oleic acid acrylic resin-based dispersant is preferably used.
The photosensitive resin composition may further contain additives such as fillers, leveling agents, adhesion promoters, antioxidants, ultraviolet absorbers, etc., but is not limited thereto.
The leveling agent may be a commercially available surfactant, and specifically may include an organosilicon surfactant, an ester surfactant, an ionic surfactant, a nonionic surfactant, an amphoteric surfactant, and the like, and these surfactants may be used alone or in combination of two or more. As the adhesion promoter, a silane-based compound can be used, and exemplified by: vinyl trimethoxy silane, vinyl triethoxy silane, N- (2-aminoethyl) -30 aminopropyl trimethoxy silane, 3-aminopropyl triethoxy silane, 3-chloropropyl methyl dimethoxy silane, 3-mercaptopropyl trimethoxy silane, 3-isocyanatopropyl triethoxy silane, and the like. The adhesion promoter may be used alone or in combination of two or more. Specific examples of antioxidants include: 4,4 '-butylidenebis (6-tert-butyl-3-methylphenol), 2, 6-di-tert-butyl-4-methylphenol, 2,3' -thiobis (4-methyl-6-tert-butylphenol), p-methoxyphenol and the like. The ultraviolet absorbent can be selected from 2- (3-tert-butyl-2 hydroxy-5-methylphenyl) -5-chlorobenzotriazole, alkoxy benzophenone, etc.
In yet another exemplary embodiment of the present application, there is provided a use of the above photosensitive resin composition, which comprises using the above photosensitive resin composition for a color filter.
The color filter comprising the photosensitive resin composition can effectively promote high-density crosslinking of unsaturated double bonds at a lower temperature, so that the strength and adhesive force of a cured film are effectively improved, the heat resistance and solvent resistance are good, a low-temperature baking paint film is smooth, the leveling property is good, the developing precision is high, and the obtained color filter has good application performance, so that the color filter can better meet the lower process temperature requirement of a flexible display device.
Furthermore, the thioester compound of the invention can be applied to paint, coating, printing ink, forming materials and the like, and can be particularly applied to coating materials for coating on plastic, metal, glass, ceramic, wood, wall and other substrates; protective film materials such as hard coating agents, antifouling films, antireflection films, impact-resistant films, and the like; photo-curing adhesives, photo-decomposing coatings, coating films, molded articles; optical recording media such as holographic image materials; optical molding resins such as 3D printing inks (resins), photoresists for electronic circuit and semiconductor manufacturing, photoresists for electronic materials such as color filters, black matrices, dry films, and the like in displays; an interlayer insulating film, a light extraction film, a brightness enhancement film, and a sealing material; printing inks for screen printing, offset printing, gravure printing, etc., photo-curable inks for inkjet printing; optical components such as a lens, a lens array, a light guide plate, a light diffusion plate, and a diffraction element; photo spacers, rib walls, nanoimprint material, quantum dots, OLEDs, etc.
The beneficial effects of the present application will be described below with reference to specific examples.
Preparation of thioester compounds:
example 1
Adding accurately weighed thioacrylate compound a into a four-neck flask with a reflux device 1 Dissolved in a thioacrylate compound a 1 Is prepared by adding 5 times of solvent (toluene) for standby, fully stirring, and then adding the thioacrylate compound a 1 Catalyst (tetraethylammonium chloride) with the dosage of 0.1-3.0%, and acrylate monomer b with the dosage of measurement 1 (epoxy group-containing (meth) acrylate in an amount of 1.01 times the molar amount of the thiol compound), and a polymerization inhibitor (4-methoxyphenol) in an amount of 0.1% of the amount of the epoxy group-containing (meth) acrylate monomer. Under the condition of bubbling dry air, the temperature is gradually increased to 70-100And (3) carrying out heat preservation reaction for 4 hours at the temperature, and cooling to the room temperature. The solution was washed 3 times with deionized water and the organic layer was collected. Concentrating the organic layer by distillation under reduced pressure to obtain pale yellow oily liquid, namely thioester compound c 1 。
Reference example 1 shows a preparation method using a thioacrylate compound a 1 ～a 10 (a 1 、a 2 Represents the same thioacrylate compounds, a 5 、a 6 Represents the same thioacrylate compound) and acrylate monomer b) 1 ～b 10 (b 1 、b 3 、b 5 、b 7 、b 8 、b 10 Represents the same acrylic monomer, b 2 、b 4 、b 9 Representing the same acrylic monomer) to prepare the thioester compound c with different structures 1 ～c 10 The specific preparation raw materials are shown in Table 1, and the prepared thioester compounds and the data nuclear magnetic characterization conditions are shown in Table 2.
TABLE 1
TABLE 2
Alkali-soluble resin preparation:
example 2
310.08g of Propylene Glycol Methyl Ether Acetate (PGMEA) as a solvent is added into a 1L flask and put into a four-neck flask with a reflux condenser, and the temperature is gradually increased to 70 ℃; simultaneously, 55.81g of methacrylic acid, 93.02g of benzyl methacrylate, 46.51g of n-butyl methacrylate, 77.52g of dicyclopentyl methacrylate and 37.21g of the thioester compound are prepared into a monomer mixed solution; further, 155.04g of PGMEA solvent was dissolved in 24.81g of dimethyl azodiisobutyrate to prepare an initiator solution. And when the temperature of the solution in the flask reaches 70 ℃, simultaneously dropwise adding the monomer and the initiator for 2 hours. After the dripping is finished, carrying out heat preservation reaction for 2 hours, heating to 85 ℃, carrying out heat preservation reaction for 1 hour, cooling and discharging to obtain alkali-soluble resin solution d 1 。
Referring to the preparation process of the above example 2 and comparative examples 1 and 2, other acrylic monomers were fixed and the thioester compounds provided in Table 2 were replaced to prepare alkali-soluble resin solutions d of different structures 2 ～d 10 The detection conditions of the specifically prepared alkali-soluble resin solution are shown in Table 3 below.
Comparative example 1
Adding 310.08g of Propylene Glycol Methyl Ether Acetate (PGMEA) solvent into a 1L flask, putting into a four-neck flask with a reflux condenser, and gradually heating to 70 ℃; simultaneously, 55.81g of methacrylic acid, 93.02g of benzyl methacrylate, 46.51g of n-butyl methacrylate, 77.52g of dicyclopentyl methacrylate and 37.21g of isooctyl methacrylate are prepared into a monomer mixed solution; further, 155.04g of PGMEA solvent was dissolved in 24.81g of dimethyl azodiisobutyrate to prepare an initiator solution. And when the temperature of the solution in the flask reaches 70 ℃, simultaneously dropwise adding the monomer and the initiator for 2 hours. After the dripping is completed, the reaction is carried out for 2 hours with heat preservation, the temperature is raised to 85 ℃ for heat preservation and reaction for 1 hour, and the alkali-soluble resin solution is obtained after cooling and discharging.
Comparative example 2
Adding 310.08g of Propylene Glycol Methyl Ether Acetate (PGMEA) solvent into a 1L flask, putting into a four-neck flask with a reflux condenser, and gradually heating to 70 ℃; simultaneously, 55.81g of methacrylic acid, 93.02g of benzyl methacrylate, 46.51g of n-butyl methacrylate, 77.52g of dicyclopentyl methacrylate and 37.21g of cyclohexyl methacrylate are prepared into a monomer mixed solution; further, 155.04g of PGMEA solvent was dissolved in 24.81g of dimethyl azodiisobutyrate to prepare an initiator solution. And when the temperature of the solution in the flask reaches 70 ℃, simultaneously dropwise adding the monomer and the initiator for 2 hours. After the dripping is completed, the reaction is carried out for 2 hours with heat preservation, the temperature is raised to 85 ℃ for heat preservation and reaction for 1 hour, and the alkali-soluble resin solution is obtained after cooling and discharging.
TABLE 3 Table 3
Preparation of photosensitive resin composition
The alkali-soluble resin provided by the invention is adopted to prepare a photosensitive resin composition, and the composition comprises the following components in parts by weight:
the specific preparation process is described as follows:
30 parts by weight of an alkali-soluble resin d 1 15 parts by weight of the photopolymerizable monomer trimethylolpropane di (meth) propaneAlkenoate, 3 parts by weight of a photopolymerization initiator 1- [ 9-ethyl-6- (2-methylbenzoyl) -9-hydro-carbazole-3-substituent]Placing 1- (oxygen-29 acetyl oxime), 32 parts by weight of colorant pigment red 8 and 20 parts by weight of solvent (propylene glycol methyl ether acetate) into a clean four-mouth bottle, and stirring uniformly by a shaking stirrer at room temperature to obtain a photosensitive resin composition e 1 。
According to the above formulation, the following photosensitive resin composition e was prepared by selecting the components of the alkali-soluble resin, the selectively modified curing accelerator, the photopolymerizable monomer, the photopolymerization initiator, the solvent, the colorant, etc. as shown in Table 3 1 ～e 17 Further, a photosensitive resin composition e was prepared in a proportion of 40 parts of an alkali-soluble resin, 10 parts of a photopolymerizable monomer, 2 parts of a photopolymerization initiator, 28 parts of a colorant, and 20 parts of a solvent 18 The formulation of the specific examples is shown in Table 4.
TABLE 4 Table 4
Performance testing
1) Solution stability test of photosensitive resin composition
Taking the prepared photosensitive resin composition solutions, respectively sealing and storing, placing in a constant temperature box at 25 ℃, and observing the change condition. And judging whether the sample is settled or not by gel.
The judgment standard is as follows:
standing for more than 7 days without sedimentation or gel;
delta standing for 7 days, sedimentation or gelation occurs;
standing for less than 3 days, and settling or gelling;
2) Odor detection of photosensitive resin composition
Taking the photosensitive resin composition solution, respectively sealing and storing, placing in a constant temperature and humidity box at 23 ℃ for 24 hours, taking out a sample, opening a sealing cover, and smelling the smell of the sample.
The discrimination criteria are:
slightly odorous;
delta has a slight odor;
x has a pungent odor;
3) Evaluation of developing Effect
The photosensitive resin composition solutions were applied onto glass substrates (100 mm. Times.100 mm) using a spin coater, and prebaked at 90℃for 100 seconds to form coating films having a film thickness of 10.0. Mu.m. Then, the exposure gap was set to 50 μm by using a mirror projection alignment exposure apparatus, and exposure was performed through a negative mask having a line pattern of 20 μm formed thereon. The exposure was set to 60mJ/cm 2 . The exposed sample coating film was developed in a 0.04 mass% KOH aqueous solution at 26℃for 40s. Post baking at 90 ℃ for 60 minutes to form a pattern. The adhesion of the pattern to the substrate at a line width of 10 μm was tested, and the pattern integrity, solvent resistance, and the like were tested.
Evaluation criteria:
A. testing adhesion: the test was performed using the hundred grid method.
O: the test result is 4B-3B;
delta: the test result is 3B-2B;
x: the test result is below 2B;
B. pattern integrity: the pattern integrity was observed by scanning electron microscopy. The specific criteria are as follows:
o: the pattern is complete, and the edge is straight and clear;
delta: the pattern is complete, and the edge is serrated;
x: incomplete pattern and unclear edge;
4) Evaluation of solvent resistance
The developed substrate was baked at 90℃for 60 minutes, the thickness of the pattern was measured using a film thickness measuring instrument, immersed in an organic solvent (PGMEA) at 60℃for 2 minutes, dried again, and then the film thickness was measured again, and the solvent resistance was evaluated according to the following criteria.
Evaluation criteria:
o: the film thickness change is less than 1% before and after soaking;
delta: film thickness changes by 1% -3% before and after soaking;
x: film thickness variation is more than 3% before and after soaking;
the specific evaluation results are shown in Table 5:
TABLE 5
The photosensitive resin composition prepared by adopting the alkali-soluble resin containing the thioester group as the base resin can effectively improve the low-temperature curing effect of the photosensitive resin composition in the illumination process, and can still keep better curing effect even at lower baking temperature. The thioester group is stable when no illumination is carried out, so that the storage stability of the photosensitive resin composition solution is greatly improved, and no obvious pungent odor is generated. After exposure, the thioester group is decomposed to release mercaptan, so that double bond components in the photosensitive resin composition can be effectively promoted to polymerize, and the photosensitive resin composition can be rapidly cured at a lower post-baking temperature (90 ℃), and the curing effect is better. E in the above table 1 、e 3 、e 5 、e 6 、e 9 、e 11 、e 12 、e 14 、e 18 The photosensitive resin composition has better storage stability and lower odor, and the cured pattern of the photosensitive resin composition has better integrity, good adhesiveness and solvent resistance. E (E) 2 、e 4 、e 7 、e 8 、e 10 、e 13 、e 12 、e 14 、e 18 The photosensitive resin composition is slightly inferior in all of storage stability, odor, adhesion, pattern integrity, solvent resistance and the like.
And a photosensitive resin composition e composed of a polymer A, B having no thioester group 15 、e 16 The curing effect, the integrity of the developed pattern, the solvent resistance, the adhesion and the like are not good. Likewise, a composition e in which a polymer having no sulfate side chains and a thiol curing accelerator are present 17 The odor is heavy, the storage stability is poor, the solvent resistance and the pattern integrity are relatively poor.
From the above test results, it can be seen that the alkali-soluble resin composition provided by the invention releases thiol groups through ultraviolet irradiation at a lower temperature (less than 100 ℃), can effectively promote the curing of the photosensitive resin composition, and the obtained cured film has good adhesion to a substrate, good developing effect and good solvent resistance. And the polymer with thioester group has good stability in normal storage, and the photosensitive resin composition has smaller odor and good storage stability, thus having better application prospect.
From the above description, it can be seen that the above embodiments of the present invention achieve the following technical effects:
the thioester compound having the above general formula I can be copolymerized with other compounds having an unsaturated double bond to obtain the corresponding alkali-soluble resin having a thioester group. Under UV radiation, the thioester groups undergo cis-trans isomerism rearrangement to decompose and produce compounds with thiol groups, so that double bond polymerization of the active polymerizable compounds is promoted to cure, and the curing temperature of the photosensitive resin composition is greatly reduced. In addition, the thioester group does not directly decompose a thiol group under the influence of external factors such as no light, that is, does not promote the polymerization of the related active polymerizable compound, and thus the storage stability of the photosensitive resin composition is good. Compared with a formula in which the thiol compound is directly added, the problems of poor storage stability, unpleasant odor and the like of the photosensitive resin composition caused by the addition of the thiol compound (exposed thiol group) are effectively avoided. Furthermore, the thioester compound can effectively promote high-density crosslinking of unsaturated double bonds at a lower temperature, so that the comprehensive properties of strength, adhesive force and the like of a cured film are effectively improved, and the low-temperature flexible display device can be better adapted to the lower process temperature requirement.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (15)

1. A thioester compound characterized in that the thioester compound has the following general formula I:
wherein m is 1 or 2, q is any integer from 0 to 2, and p is any integer from 0 to 10;
R 1 selected from C 6 ～C 30 Substituted or unsubstituted aryl, C 4 ～C 30 Any one of substituted or unsubstituted heteroaryl groups;
R 2 selected from H, C 1 ～C 10 Straight chain alkyl, C 3 ～C 15 Branched alkyl, C 1 ～C 10 Any one of the alkoxy groups of (a);
R 3 selected from H, C 1 ～C 10 Straight chain alkyl, C 3 ～C 10 Branched alkyl, C 1 ～C 10 Any one of the alkoxy groups of (a);
R 4 selected from H, C 1 ～C 10 Any one of the alkyl groups of (a).
2. The thioester compound according to claim 1, wherein the R 1 Selected from C 6 ～C 18 Substituted or unsubstituted aryl, C 4 ～C 18 Any one of the substituted or unsubstituted heteroaryl groups of (2), preferably R 1 Selected from C 6 ～C 18 Substituted or unsubstituted phenyl, C 10 ～C 18 Substituted or unsubstituted naphthyl, C 4 ～C 10 Any one of the substituted or unsubstituted heteroaryl groups of (2), preferably R 1 Selected from the group consisting of Wherein "×" is any one of the above R 1 And a position connected with the thioester compound.
3. The thioester compound according to claim 1 or 2, characterized in that R 2 Selected from H, C 1 ～C 5 Straight chain alkyl, C 3 ～C 6 Branched alkyl, C 1 ～C 5 Preferably any one of the alkoxy groups of (C), R is 2 Any one selected from H, methyl, ethyl, propyl, isopropyl, isobutyl, isopentyl, methoxy, ethoxy, and propoxy, and further, preferably, the R 2 Selected from any one of H, methyl, propyl and isobutyl.
4. A thioester compound according to any of claims 1 to 3, characterised in that R 3 Selected from H, C 1 ～C 5 Straight chain alkyl, C 3 ～C 5 Branched alkyl, C 1 ～C 5 Preferably any one of the alkoxy groups of (C), R is 3 Any one selected from H, methyl, ethyl, propyl, isopropyl, isobutyl, isopentyl, methoxy, ethoxy, and propoxy, and further, preferably, theR 3 Is methyl.
5. The thioester compound according to any one of claims 1 to 4, characterized in that the R 4 Selected from H, C 1 ～C 10 Any of the alkyl groups of (2), preferably R 4 Selected from H, C 1 ～C 5 Any of the alkyl groups of (2), preferably R 4 Any one selected from H, methyl, ethyl and propyl, and further, preferably, R 4 Is H or ethyl.
6. The thioester compound according to any one of claims 1 to 5, wherein the thioester compound has a structural formula of
Any one or more of the following.
7. A method for preparing a thioester compound, comprising:
esterification reaction is carried out on reaction raw materials comprising thioacrylate compounds and acrylate monomers to generate thioester compounds;
wherein, the structural formulas of the thioacrylate compound and the acrylate monomer are as follows in sequence:
R 5 selected from C 2 ～C 20 Any one of hydrocarbon groups of (C) 2 ～C 20 Comprises at least one C in the hydrocarbon group 2 ～C 10 Epoxy group R of (2) 1 、R 2 And R is 3 R as defined in claim 1 1 Said R is 2 And said R 3 。
8. The method of claim 7, wherein R is 5 Selected from C 2 ～C 10 Preferably any one of the hydrocarbon groups of (C), R is 5 Selected from C 2 ～C 10 Any of the alkyl groups of (2), preferably R 5 Selected from C 2 ～C 5 Any of the alkyl groups of (2), preferably R 5 Selected from the group consisting ofWherein "×" is any one of the above R 5 And a position connected with the acrylic monomer.
9. The method of claim 7 or 8, wherein C 2 ～C 20 Comprises at least one C in the hydrocarbon group 2 ～C 5 Preferably said C 2 ～C 20 Preferably the acrylic monomer is selected from the group consisting of glycidyl acrylate, glycidyl methacrylate, oxetane methacrylate,Any one of the above-mentioned materials,
n represents any one integer of 1 to 10, preferably n represents any one integer of 1 to 5, preferably n is 1 or 3;
preferably R 6 、R 7 Each independently is H or methyl;
preferably R 8 Selected from C 1 ～C 10 Straight chain alkyl, C 3 ～C 10 Is of (2)Chain alkyl, C 3 ～C 12 Preferably any one of the cycloalkyl groups of (2), R is 8 Selected from C 1 ～C 5 Straight chain alkyl, C 3 ～C 6 Branched alkyl, C 3 ～C 6 Preferably any one of the cycloalkyl groups of (2), R is 8 Any one selected from methyl, ethyl, propyl, isopropyl, isobutyl, isopentyl, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl, and further, preferably, R 8 Is methyl.
10. An alkali-soluble resin obtained by polymerizing the sulfur ester compound according to any one of claims 1 to 6 with a monomer having a carbon-carbon double bond.
11. The alkali-soluble resin according to claim 10, characterized in that the weight average molecular weight of the alkali-soluble resin is in the range of 8000 to 20000, preferably 14000 to 18000.
12. The alkali-soluble resin according to claim 10 or 11, wherein the acid value of the alkali-soluble resin is 70 to 200mgKOH/g, preferably 80 to 150mgKOH/g, further preferably 100 to 120mgKOH/g.
13. The alkali-soluble resin according to any one of claims 10 to 12, wherein the monomer containing a carbon-carbon double bond is selected from any one or more of an acrylic monomer, a substituted or unsubstituted styrene monomer, an unsaturated organic acid anhydride, an unsaturated imine monomer, an acrylamide monomer.
14. A photosensitive resin composition comprising an alkali-soluble resin, characterized in that the alkali-soluble resin is the alkali-soluble resin according to any one of claims 10 to 13.
15. Use of the photosensitive resin composition according to claim 14, wherein the use comprises using the photosensitive resin composition for a color filter.
CN202210983448.4A 2022-08-16 2022-08-16 Sulfur ester compound and preparation method thereof, alkali-soluble resin, photosensitive resin composition and application thereof Pending CN117586161A (en)

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