CN109839802A - Photosensitive resin composition containing polymerizable type photoinitiator - Google Patents
Photosensitive resin composition containing polymerizable type photoinitiator Download PDFInfo
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Abstract
The present invention relates to a kind of photosensitive resin compositions, and it includes the polymerizable type photoinitiators selected from structure shown in lower note general formula (1) or general formula (2):Wherein, R is selected from C1~C8Alkyl.The solubility of photoinitiator in the composition can be improved in the acrylate group of the polymerizable type photoinitiator, and improves the compatibility of itself and resin, monomer etc.；Unsaturated double-bond in polymerizable type photoinitiator may participate in photocuring, and multiple double bonds on single molecule participate in polymerization, can be improved color glue crosslink density, improve hardness.
Description
Technical Field
The present disclosure relates to the field of liquid crystal display, and in particular, to a photosensitive resin composition and a color filter containing a polymerizable photoinitiator.
Background
The photoresist is also called as photoresist, and is a photosensitive mixture composed of photosensitive resin, photoinitiator, solvent and the like. Which can undergo a cross-linking curing or degradation reaction (known as photolithography) under the irradiation of a beam of ultraviolet light. A color photoresist (or color photosensitive resin composition) is formed by adding colorants (red, green, and blue) to the photoresist. The color photoresist is coated on a glass substrate to form a film, and the film is photoetched by ultraviolet light to form a color pattern, so that the color filter is manufactured. Color filters used for color liquid crystal display devices, image pickup elements, and the like are generally manufactured using a pigment dispersion method: a single color resist of red, blue or green is uniformly applied on a glass substrate on which a black matrix pattern is formed, and then the resultant is heated, dried and formed into a film (referred to as a prebake), and the formed film is subjected to ultraviolet exposure, development, and heat curing (referred to as a postbake), thereby obtaining a color filter of a single color. The above operations are repeated according to different colors as required to form a color filter with three-color pixels, and the color filter is applied to the field of thin film transistor liquid crystal displays (TFT-LCDs).
The photoinitiator is a core component in the color photosensitive resin composition and is an essential material for the composition to be cured under ultraviolet irradiation. Although there are many kinds of photoinitiators, the photoinitiator is required to meet the requirements of production and application processes of color filters, such as heat resistance, acid resistance, alkali resistance, illumination resistance, color influence of color glue, color chromaticity influence of color glue and the like, so that the number of the selected photoinitiators is small. The existing photoinitiator for the color glue mostly uses a solid micromolecule photoinitiator, which has the defects of color, poor compatibility with color paste, resin, monomers and the like, easy agglomeration and easy precipitation; the defects of low solubility, poor thermal stability, easy migration or precipitation from the colored glue after photocuring and the like affect the quality of the colored glue and the health of workers on a production line.
In view of the above disadvantages of the conventional color photosensitive resin composition, it is an urgent need to develop a photoinitiator that can overcome the above disadvantages, and design a color photosensitive resin composition with higher stability and higher film hardness around the photoinitiator.
Disclosure of Invention
The invention solves the technical problems of low solubility of photoinitiator in the existing color adhesive, poor thermal stability, easy migration or precipitation from the color adhesive after photocuring and the like
The invention provides a photosensitive resin composition, which at least comprises a polymerizable photoinitiator selected from the following structures represented by general formula (1) or general formula (2):
wherein R is independently selected from C1～C8Alkyl group of (1).
The photosensitive resin composition containing the polymerizable photoinitiator not only has higher system stability, but also has higher film hardness, and reduces the precipitation and migration of small molecules caused by postbaking high temperature or extreme conditions.
The present disclosure also provides a color filter including a glass substrate and a color photosensitive resin composition coated on the substrate and cured.
Detailed Description
The technical solution of the present invention is explained in further detail below.
The photosensitive resin composition is also referred to as a photoresist.
The photosensitive resin composition of the present invention contains at least a polymerizable photoinitiator selected from the group consisting of the following structures represented by the general formula (1) or the general formula (2):
in the general formula (1) and the general formula (2), R is independently selected from C1～C8Alkyl group of (1).
In the general formula (1) and the general formula (2), it is preferable that an acrylate group is bonded to the para-position of the phenyl group, that is, the photoinitiator is preferably a compound having a structure represented by the following general formula (3) or general formula (4),
in the general formula (3) and the general formula (4), R is independently selected from C1～C8Alkyl group of (1).
In the above general formulae (1) to (4), R is preferably C1～C4Alkyl groups of (a); as C1～C4Specific examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl.
In the general formula (2) or the general formula (4), two R groups may be the same or different; preferably both R are the same.
The photoinitiator preferably has the following specific structure:
the acrylate group is introduced into the photoinitiator molecule, so that the solubility of the photoinitiator in a color photoresist system can be improved, and the compatibility with resin, monomers and the like can be improved; the molecular precipitation and migration of the small-molecular photoinitiator can be reduced, and the harm to a human body is reduced; the molecular weight is increased, the boiling point of the photoinitiator is favorably improved, and the loss of the photoinitiator in the pre-baking process is reduced. Unsaturated double bonds in the photoinitiator can participate in photocuring, and multiple double bonds on a single molecule participate in polymerization, so that the crosslinking density of the colored rubber can be improved, and the hardness can be improved.
The photosensitive resin composition of the present invention further comprises ingredients well known in the art, such as an alkali-soluble resin, a colorant, a polyfunctional monomer, a co-initiator, a solvent, and additives.
The alkali soluble resin may be selected from at least one of acrylic resin and/or acrylate resin.
The colorant may be a pigment and/or a dye, specifically, a red pigment/dye, a green pigment/dye, a blue pigment/dye, a yellow pigment/dye, an orange pigment/dye, a violet pigment/dye or a mixture of two or more of the above pigments/dyes, and preferably, the colorant may be a color paste in which the above pigments/dyes are dispersed in a solvent, and the solid content of the color paste may be 5 to 50 wt%.
The polyfunctional monomer (or photosensitive monomer) is a monomer having a plurality of reactive functional groups such as an unsaturated double bond, a hydroxyl group, a carboxyl group, and a carbonyl group in a molecule, and the addition of the polyfunctional monomer can achieve technical effects such as formation of a clear pixel pattern in an exposed portion and prevention of mold release during development, and an appropriate polyfunctional monomer can be selected. One or more compounds known in the art to participate in the crosslinking reaction are generally used in combination, and representative examples thereof include at least one selected from the group consisting of 1, 6-ethylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, 3-propoxylated glycerol triacrylate, trimethylolpropane triacrylate, ethoxylated pentaerythritol tetraacrylate, propoxylated pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, 3- (trimethoxy silane) propyl acrylate, glycidyl methacrylate and benzyl methacrylate, but are not limited to the above polyfunctional monomers.
The co-initiator may be at least one selected from the group consisting of an aliphatic tertiary amine, an ethanolamine tertiary amine, a tertiary amine benzoate, and an active amine.
The photosensitive resin composition may contain a solvent for easy coating, and any solvent known in the art may be used. The solvent preferably includes a high boiling point solvent having a boiling point of 150 to 200 ℃ and a low boiling point solvent having a boiling point of less than 150 ℃ from the viewpoint of environmental requirements, flatness of the film surface, and handling property of the process operation, and the high boiling point solvent and the low boiling point solvent are preferably contained in a weight ratio of 10:90 to 50: 50. Wherein the high boiling point solvent is at least one selected from dipropylene glycol methyl ether, diethylene glycol butyl ether acetate, diethylene glycol diethyl ether acetate, 3-ethoxyethyl propionate, 3-methoxybutyl acetate and ethyl lactate; the low boiling point solvent is at least one selected from the group consisting of ethylene glycol methyl ether, ethylene glycol ethyl ether, propylene glycol methyl ether acetate, cyclohexane, and isopropyl alcohol.
In addition, the photosensitive resin composition of the present invention may further include an additive, which may be at least one of a sensitizer, an antifoaming agent, a leveling agent, a polymerization inhibitor, a wetting dispersant, and an adhesion promoter.
More specifically, the photosensitive resin composition of the present invention comprises an alkali-soluble resin, a colorant, a multifunctional monomer, a photoinitiator, a co-initiator, a solvent, and additives. The alkali-soluble resin composition comprises, relative to 100 parts by weight of the alkali-soluble resin polymer, 200-500 parts by weight of a colorant, 50-100 parts by weight of a multifunctional monomer, 0.1-10 parts by weight of a photoinitiator (including a co-initiator), 100-800 parts by weight of a solvent, and 0.1-10 parts by weight of an additive.
The photosensitive resin composition is coated on a substrate, and then a pattern with a specific shape can be obtained through the process steps of pre-baking, exposure, development, post-baking and the like, so that pixels and the like are formed.
Examples
The following examples further specifically illustrate embodiments of the polymerizable photoinitiator for the photosensitive resin composition provided by the present invention. The examples are not intended to limit the scope of the present invention, and any modifications and variations made by those skilled in the art without departing from the spirit of the present invention are intended to be included within the scope of the present invention. The chemical reagents used are indicated in the following brackets with the type and manufacturer when they first appear, and the reagents appearing later are of the same origin as when they first appear.
Example 1.2- (Diphenylmethyl keto) acrylic acid methyl esterSynthesis of (2)
After 48g of methanol (1.5mol) was charged into a 250mL three-necked flask, the mixture was stirred, the temperature was raised to reflux, 42g of diketene (0.5mol) was slowly added thereto, the reaction was continued at the reflux temperature for 5 hours, and the mixture was distilled under reduced pressure to obtain 89.4g (0.77mol) of methyl acetoacetate.
To a 500mL three-necked flask under argon atmosphere was added 200mL of THF and 15.6g of NaH (60% dispersion in minor oil, 0.39mol) dispersed with stirring, and 34.8g of methyl acetoacetate (0.3mol) was added dropwise to the flask at room temperature and stirred well. When the liquid in the flask became clear, 46.8g of methyl iodide (0.33mmol) was added dropwise, the mixture was stirred at 40 ℃ for 10h, and the reaction was quenched with saturated aqueous ammonium chloride solution and extracted 3 times with ethyl acetate. The combined organic layers were dried over anhydrous sodium sulfate, the solvent was dried, and flash column chromatography (petroleum ether: ethyl acetate 30:1) was performed to obtain 27.3g of 2-oxo-3-methyl-butyric acid methyl ester (0.21 mol).
Into a 500mL three-necked flask was added 6.51g of 2-oxo-3-methyl-Methyl butyrate (50mmol), and 19.2g p-acetamido-benzenesulfonyl azide (p-ABSA, 80mmol), dissolved in 150mL acetonitrile and stirred well, 22mL1, 8-diazabicycloundecen-7-ene (DBU, 150mmol) was added at 0 deg.C and then slowly warmed to room temperature, stirred for 12h, the reaction was quenched with 1N HCl, extracted three times with N-hexane, the combined organic layers were saturated NaHCO3The solution was washed with saturated brine to neutrality, dried over anhydrous sodium sulfate, and the solvent was evaporated and separated by flash column chromatography (petroleum ether: ethyl acetate 20:1) to obtain 3.99g of a mixtureα Azide-propionic acid methyl ester Ester [ B-1]](35mmol)。
To a 100mL three-necked flask, 40mL of toluene, 100mg of allylpalladium chloride ([ PdCl (C)) was added under nitrogen atmosphere3H5)]20.25mmol), 0.48g of 2-dicyclohexylphosphonium-2 ', 4 ', 6 ' -triisopropylbiphenyl ([ Xphos)]1mmol), stirred at room temperature for 10 minutes, 3.02g of diisopropylamine (30mmol), 2.61g of 4-bromo-benzophenone (10mmol) and 1.71g of [ B-1]](15 mmol). The mixture was stirred at 80 ℃ and checked by TLC until the 4-bromo-benzophenone reaction was complete. The solvent was dried by evaporation and separated by flash column chromatography (petroleum ether: ethyl acetate: 5:1) to give 2.31g2- (Diphenylketonyl) acrylic acid methyl ester [ C-1]](8.3mmol)。
Wherein, diketene: analytically pure, purchased from Suzhou Haobao science and technology GmbH;
p-ABSA: purity 98%, purchased from annaiji chemistry;
[PdCl(C3H5)]2: purity greater than 97% purchased from Sigma-Adrich;
NaH, 60% dispersion in minor oil, available from shanghai taitan science;
HCl: 38% of the total alcohol, purchased from Beijing chemical engineering;
[ Xphos ]: purity 98%, purchased from annaiji chemistry;
DBU: purity 98%, purchased from annaiji chemistry;
4-bromo-benzophenone: purity 98%, purchased from annaiji chemistry;
4, 4' -dibromo-benzophenone: purity 98%, purchased from annaiji chemistry;
acetonitrile, methanol, anhydrous sodium sulfate, toluene, sodium bicarbonate, petroleum ether, ethyl acetate, ammonium chloride, and the like are all purchased from Shigaku chemical industry.
Nuclear magnetic spectral data of compound C-1:1H NMR(300Hz)in DMSO：δ3.69ppm(s，3H)，6.24ppm(d，J＝1.3，1H)，6.39ppm(d，J＝1.3，1H)，7.41-7.84ppm(m，9H)。
example 2 Synthesis of ethyl 2- (benzophenone-based) acrylate [ C-2]
[ C-2] Synthesis Process reference is made to the synthesis of [ C-1] except that methanol used in [ A-1] is replaced with ethanol.
[C-2]Nuclear magnetic spectrum data of (a):1H NMR(300Hz)in DMSO：δ1.07ppm(t，J＝8.0，3H)，4.00ppm(m，2H)，6.19ppm(d，J＝1.3，1H)，6.37ppm(d，J＝1.3，1H)，7.41-7.84ppm(m，9H)。
EXAMPLE 3 Synthesis of 2- (Diphenylketo) acrylic acid propyl ester [ C-3]
[ C-3] Synthesis Process reference is made to the synthesis of [ C-1] except that the methanol used in [ A-1] is replaced by propanol.
[C-3]Nuclear magnetic spectrum data of (a):1H NMR(300Hz)in DMSO：δ1.01ppm(t，J＝8.0，3H)，1.73ppm(m，2H)，4.12ppm(t，J＝7.1，2H)，6.19(d，J＝1.3，1H)，6.40ppm(d，J＝1.3，1H)，7.41-7.84ppm(m，9H)。
EXAMPLE 4 Synthesis of tert-butyl 2- (Benzophenoyl) acrylate [ C-4]
[ C-4] Synthesis Process reference is made to the synthesis of [ C-1] except that methanol used in [ A-1] is replaced with tert-butanol.
[C-4]Nuclear magnetic spectrum data of (a):1H NMR(300Hz)in DMSO：δ1.42ppm(s，9H)，6.22(d，J＝1.3，1H)，6.40ppm(d，J＝1.3，1H)，7.41-7.84ppm(m，9H)。
example 5 Synthesis of 2, 2' - (Benzophenoyl) Dimethylacrylate [ D-1]
In this example, the synthesis of [ B-1] is described in the synthesis of [ C-1 ].
40mL of toluene, 200mg of [ PdCl (C) were added to a 100mL three-necked flask under nitrogen atmosphere3H5)]2(0.5mmol)，0.96g[Xphos](2mmol), after stirring at room temperature for 10 minutes, 6.07g of diisopropylamine (60mmol), 3.04g of 4, 4' -dibromo-benzophenone (10mmol) and 3.42g of [ B-1]](30 mmol). The mixture was stirred at 80 ℃ and checked by TLC until the reaction of 4, 4' -dibromo-benzophenone was complete. The solvent was dried by evaporation and separated by flash column chromatography (petroleum ether: ethyl acetate: 5:1) to give 2.49g of 2- (benzophenone)Yl) methyl acrylate [ D-1]](7.1mmol)。
[D-1]Nuclear magnetic spectrum data of (a):1H NMR(300Hz)in DMSO：δ3.69ppm(s，3H)，6.24ppm(d，J＝1.3，2H)，6.39ppm(d，J＝1.3，2H)，7.40-7.68ppm(m，8H)。
example 6 Synthesis of 2, 2' - (Benzophenoyl) Diethyldiacrylate [ D-2]
Synthesis of [ D-2] the synthesis of [ D-1] was referred to, except that methanol used in [ A-1] was replaced with ethanol.
[D-2]Nuclear magnetic spectrum data of (a):1H NMR(300Hz)in DMSO：δ1.07ppm(t，J＝8.0，6H)，4.00ppm(m，4H)，6.19ppm(d，J＝1.3，2H)，6.37ppm(d，J＝1.3，2H)，7.44-7.64ppm(m，8H)。
example 7 Synthesis of 2, 2' - (Benzophenoyl) dipropylacrylate [ D-3]
Synthesis of [ D-3] the synthesis of [ D-1] was referred to, except that methanol used in [ A-1] was replaced with propanol.
[D-3]Nuclear magnetic spectrum data of (a):1H NMR(300Hz)in DMSO：δ1.01ppm(t，J＝8.0，6H)，1.73ppm(4H，m)，4.12ppm(t，J＝7.1，4H)，6.19(d，J＝1.3，2H)，6.40ppm(d，J＝1.3，2H)，7.44-7.64ppm(m，8H)。
EXAMPLE 8 Synthesis of 2, 2' - (Benzophenoyl) di-tert-butyl diacrylate [ D-4]
Synthesis of [ D-4] the synthesis of [ D-1] was followed except that methanol used in [ A-1] was replaced with tert-butanol.
[D-4]Nuclear magnetic spectrum data of (a):1H NMR(300Hz)in DMSO：δ1.42ppm(s，18H)，6.22(d，J＝1.3，2H)，6.40ppm(d，J＝1.3，2H)，7.44-7.64ppm(m，8H)。
initiator evolution test
Respectively adding photoinitiators C-1-C-4, D-1-D-4 and BP (benzophenone, Annagi Ching chemical, 99%) into TPGDA (tripropylene glycol diacrylate, Saedoma, analytical pure) to prepare 1 wt% solution, coating with a rotary coater to obtain a 2.0 μm uniform film on glass, exposing with 365nm ultraviolet light, and exposing to light at an exposure of 5000mJ/cm2. After the film layer was fully cured, the film was scraped off the glass and 100mg of the sample was soaked in 10mL of chloroform for 96 h. Filtering chloroform solution, and detecting the maximum ultraviolet absorption wavelength lambda within the wavelength range of 200 nm-400 nm by using an ultraviolet-visible spectrophotometermaxSubstituting the absorbance A and the molar extinction coefficient epsilon into the following formula to obtain the photoinitiator concentration c in the chloroform solution:
c＝A/(εl)
where c is the photoinitiator concentration and l is the cuvette width (here 1cm), the mass of initiator deposited is calculated as follows:
m＝M×c×10-2
in the formula, M is the relative molecular mass of the photoinitiator, and the mass percentage of the precipitated initiator is further calculated.
The photoinitiator precipitation performance is tested and shown in Table 1
| λmax(nm) | ε(L·mol-1·cm-1) | Mass percent of precipitate1)(％) | |
| C-1 | 273 | 59500 | 0.015 |
| C-2 | 272 | 61200 | 0.013 |
| C-3 | 271 | 60600 | 0.017 |
| C-4 | 265 | 59400 | 0.010 |
| D-1 | 283 | 62300 | —— |
| D-2 | 279 | 62500 | —— |
| D-3 | 278 | 61100 | —— |
| D-4 | 274 | 61600 | —— |
| BP | 254 | 56500 | 0.11 |
Note 1: the precipitation quality of D-1 to D-4 could not be detected by the same method.
As can be seen from Table 1, the precipitation mass percentages of the polymerizable photoinitiators C-1-C-4 are about one order of magnitude lower than BP, and the precipitation masses of D-1-D-4 cannot be detected by equipment, so that the polymerizable photoinitiators are determined to participate in ultraviolet curing, and the dissolution precipitation and molecular migration of the photoinitiators can be effectively reduced.
Examples 9 to 16
Further, the photoinitiators [ C-1] to [ C-4] and [ D-1] to [ D-4] prepared in examples 1 to 8 were used to prepare green photosensitive resin compositions Q1 to Q8, respectively. And they were subjected to photolithography development to compare the relevant properties of the photosensitive resin compositions. In particular, lithographic methods well known to those skilled in the art are applied.
The formula is as follows: taking 3 parts by weight of photoinitiator, 3 parts by weight of auxiliary initiator K, 200 parts by weight of colorant L, 50 parts by weight of polyfunctional monomer M1, 50 parts by weight of polyfunctional monomer M2, 100 parts by weight of alkali-soluble resin N, 0.2 part by weight of additive O1, 0.3 part by weight of O2, adding about 100 parts by weight of solvent P1 and about 50 parts by weight of solvent P2, fully dissolving and mixing, and controlling the solid content to be about 20%, thereby obtaining the green photosensitive resin composition. Wherein,
auxiliary initiator K: photomer 4771 (analytically pure) available from corning chemical;
colorant L: a green pigment dispersion, trade name G58, available from DIC;
polyfunctional monomer M1: dipentaerythritol hexaacrylate (analytically pure), available from sartomer;
polyfunctional monomer M2: trimethylolpropane trimethacrylate propoxylate (analytical grade), purchased from taiwan chemical double bond;
alkali-soluble resin N: trade name Sarbox SB400 (analytical grade), available from sartomer;
additive O1: f-556 (trade name, available from DIC corporation);
additive O2: KH570 (gamma-methacryloxypropyltrimethoxysilane), available from carbofuran;
solvent P1: PGMEA (propylene glycol methyl ether acetate), available from dow chemical;
solvent P2: PM (propylene glycol methyl ether), available from dow chemical.
EXAMPLE 9 preparation of Green photosensitive composition Q1
3 parts by weight of a polymerizable photoinitiator [ C-1], 3 parts by weight of a co-initiator K, 200 parts by weight of a colorant L, 50 parts by weight of a polyfunctional monomer M1, 50 parts by weight of a polyfunctional monomer M2, 100 parts by weight of an alkali-soluble resin N, 0.2 part by weight of an additive O1, 0.3 part by weight of O2, about 100 parts by weight of a solvent P1 and about 50 parts by weight of a solvent P2 were added and sufficiently dissolved and mixed to control the solid content to about 20%, thereby obtaining a green photosensitive resin composition Q1.
Examples 10 to 16
Compounds [ C-2], [ C-3] [ C-4], [ D-1], [ D-2], [ D-3] and [ D-4] were added to the above formulation as photoinitiators in place of the compound [ C-1] in example 9, to obtain colored photosensitive resin compositions Q1 to Q8 (corresponding to examples 9 to 16, respectively);
comparative example 1
Benzophenone (Annagar chemical, 99%) was added to the above formulation in place of the polymerizable photoinitiator of the present invention to obtain a green photosensitive resin composition Q9.
Performance tests were conducted using the photosensitive resin compositions Q1 to Q9. A method of photolithography using a photosensitive resin composition, comprising the steps of:
cleaning and drying the glass sheet, and gluing by a rotary gluing machine to obtain a uniform film layer with the thickness of 1.3-2.0 microns. Pre-baking at 90 deg.C for 120s, exposing with 365nm ultraviolet light at exposure of 40mJ/cm2The distance between the mask plate and the coating film is 180 mu m, the development is carried out for 50s at 23 ℃, the postbaking is carried out for 20min at 230 ℃, and the subsequent related performances are tested, and the results are shown in Table 1.
Performance test and evaluation methods:
1) surface hardness test: measured according to GB/T6739-. Before the test, the sample plate was conditioned for 16h at a temperature of (23. + -. 2) ° C and a relative humidity of (50. + -. 5)%.
2) System compatibility: the photosensitive resin composition is placed in an environment of 0-10 ℃ and is kept in a dark place, the change of the viscosity of the photosensitive resin composition is tested (at least 6 months), photoetching is carried out according to the process conditions, and the existence of particles on the surface of a color film is inspected under an OM (open field memory) of x500 times.
The evaluation criteria are as follows:
o: viscosity change value is less than +/-5% mPa.s, and the surface of x500 has no Particle;
Δ: viscosity change value is less than +/-10% mPa.s, and the surface of x500 has no Particle;
x: viscosity change value > +/-10% mPa.s or Particle on the x500 surface;
2) and (3) testing heat resistance: the heat resistance of the resin is verified through the film reduction rate and the color difference, the postbaking is repeated twice at 230 ℃ for 20min, and the film thickness is measured through an XP-2 step instrument;
the film reduction rate is (first postbaking film thickness-second postbaking film thickness)/first postbaking film thickness, and if S < 3%, the film has better heat resistance;
color difference is the color difference between the second post-baking sample and the first post-baking sample, and is determined by Meinenda CM-5, if △ Eab<3 percent, the product shows better heat resistance;
3) evaluation of solvent resistance:
soaking the post-baked sample in isopropanol at room temperature for 5min, baking in oven at 150 deg.C for 30min, and determining the color difference between the front and the back, if △ Eab<3, it shows good solvent resistance.
4) Line width, sideline regularity and development process latitude:
and testing the line width and the side line uniformity by x500 times OM, wherein the line width of the mask plate is 140 mu m.
During process tolerance evaluation, other process conditions are fixed, the edge line uniformity and the edge residue or edge peeling condition of the image obtained within the development time of 40-100s are considered, and the peeling judgment refers to the determination method of the adhesive force in the field.
The evaluation criteria for the edge line uniformity are as follows:
o: the developing 50s sideline is neat and no residue is left at the edge;
Δ: burrs exist on the edge lines of the developed 50s image, and the burrs are irregular or residues exist at the edges;
x: image deletion
The evaluation criteria of the development process latitude are as follows:
o: the lines of the developing process are regular for 40-100s, and no residue or stripping exists at the edges;
Δ: the developing lines are neat in 50-80s, and no residue or stripping exists at the edges;
x: development for 50-80s, irregular edge, residual edge, or peeling edge
The alkaline developer used above is, for example, an aqueous solution of an alkaline compound such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, calcium carbonate, aqueous ammonia, diethylamine or tetramethylammonium hydroxide, OH-The concentration is 0.2-1.0%, preferably 0.4-0.6%.
TABLE 2
As can be seen from table 2, compared with the photoinitiator BP in the comparative example Q9, the photosensitive resin compositions in examples Q1-Q8, which contain the polymerizable photoinitiator of the present invention, have higher surface hardness, better system compatibility, better solvent resistance, better edge line uniformity and wider developing process margin under the same test conditions.
Claims (11)
1. A photosensitive resin composition characterized by: which comprises a polymerizable photoinitiator selected from the group consisting of the following structures represented by the general formula (1) or the general formula (2):
wherein R is independently selected from C1～C8Alkyl group of (1).
2. The photosensitive resin composition according to claim 1, wherein: the polymerizable photoinitiator is selected from compounds with structures shown in general formula (3) or general formula (4)
In the general formula (3) and the general formula (4), R is independently selected from C1～C8Alkyl group of (1).
3. The photosensitive resin composition according to claim 1 or 2, wherein: r is selected from C1～C4Alkyl group of (1).
4. The photosensitive resin composition according to claim 1 or 2, wherein: in the general formula (2) or the general formula (4), both R's are the same.
5. The photosensitive resin composition according to claim 1, wherein: it further comprises an alkali soluble resin, a colorant, a polyfunctional monomer, a co-initiator, a solvent, and an additive.
6. The photosensitive resin composition according to claim 5, wherein: the alkali soluble resin is selected from at least one of acrylic resin and/or acrylate resin.
7. The photosensitive resin composition according to claim 5, wherein: the multifunctional monomer is at least one selected from 1, 6-ethylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, 3-propoxylated glycerol triacrylate, trimethylolpropane triacrylate, ethoxylated pentaerythritol tetraacrylate, propoxylated pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, 3- (methoxy 1 silane) propyl acrylate, glycidyl methacrylate and benzyl methacrylate.
8. The photosensitive resin composition according to claim 5, wherein the co-initiator is at least one selected from the group consisting of aliphatic tertiary amines, ethanolamine-based tertiary amines, tertiary amine benzoates and reactive amines.
9. The photosensitive resin composition according to claim 5, wherein: the solvent is at least one selected from dipropylene glycol methyl ether, diethylene glycol butyl ether acetate, ethylene glycol methyl ether, ethylene glycol ethyl ether, propylene glycol methyl ether, 3-ethyl propionate, propylene glycol methyl ether acetate, 3-methoxybutyl acetate, diethylene glycol ethyl diethyl ether ethyl acetate, cyclohexane, ethyl lactate and isopropanol.
10. The photosensitive resin composition according to any one of claims 5 to 9, wherein: the content of each component is
100 parts by weight of the alkali-soluble resin;
the content of the colorant is 200-500 parts by weight;
the content of the multifunctional monomer is 50-100 parts by weight;
the content of the photoinitiator and the co-initiator is 0.1-10 parts by weight;
the content of the solvent is 100-800 parts by weight;
0.1-10 parts by weight of the additive.
11. A color filter comprising a substrate and a photosensitive resin composition coated on the substrate and cured, characterized in that: the photosensitive resin composition according to any one of claims 1 to 10.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112683828A (en) * | 2021-01-14 | 2021-04-20 | 陕西彩虹新材料有限公司 | Method for testing alkali dissolution rate of resin for photoresist by using absorbance of developing solution |
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| US20080039544A1 (en) * | 2006-08-11 | 2008-02-14 | Daxin Materials Corporation | Photosensitive resin composition |
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| CN102854749A (en) * | 2011-06-29 | 2013-01-02 | 第一毛织株式会社 | Photosensitive resin composition for color filter and color filter using same |
| CN103270452A (en) * | 2010-12-29 | 2013-08-28 | 第一毛织株式会社 | Photosensitive resin composition for color filter and color filter using same |
| CN105467754A (en) * | 2014-09-25 | 2016-04-06 | 三星Sdi株式会社 | Photosensitive Resin Composition and Color Filter Using the Same |
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| US20080039544A1 (en) * | 2006-08-11 | 2008-02-14 | Daxin Materials Corporation | Photosensitive resin composition |
| CN102203048A (en) * | 2008-12-15 | 2011-09-28 | 赢创罗姆有限公司 | Method for producing methacrylated benzophenones |
| CN103270452A (en) * | 2010-12-29 | 2013-08-28 | 第一毛织株式会社 | Photosensitive resin composition for color filter and color filter using same |
| CN102854749A (en) * | 2011-06-29 | 2013-01-02 | 第一毛织株式会社 | Photosensitive resin composition for color filter and color filter using same |
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