CN109839802B - Photosensitive resin composition containing polymerizable photoinitiator - Google Patents
Photosensitive resin composition containing polymerizable photoinitiator Download PDFInfo
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Abstract
The present invention relates to a photosensitive resin composition comprising a polymerizable photoinitiator selected from the group consisting of a structure represented by the following general formula (1) or general formula (2):
wherein R is selected from C 1 ～C 8 Alkyl group of (1). The acrylate group of the polymerizable photoinitiator can improve the solubility of the photoinitiator in the composition and improve the compatibility with resin, monomer and the like; unsaturated double bonds in the polymerizable photoinitiator can participate in photocuring, and multiple double bonds on a single molecule participate in polymerization, so that the crosslinking density of the colored adhesive can be improved, and the hardness can be improved.
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 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 present invention provides a photosensitive resin composition comprising at least a polymerizable photoinitiator selected from the group consisting of a structure represented by the following general formula (1) or general formula (2):
wherein R is independently selected from C 1 ～C 8 Alkyl 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 micromolecule precipitation and migration 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 C 1 ～C 8 The alkyl 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 C 1 ～C 8 Alkyl group of (1).
In the above general formulae (1) to (4), R is preferably C 1 ～C 4 Alkyl groups of (a); as C 1 ～C 4 Specific 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 cross-linking density of the colored adhesive can be improved, and the hardness is 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 at least one selected from an acrylic resin and/or an 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 colorant obtained by dispersing the above pigments/dyes in a solvent, and the solid content of the colorant may be 5 to 50wt%.
The polyfunctional monomer (or photosensitive monomer) is a monomer having a plurality of reactive functional groups such as unsaturated double bonds, hydroxyl groups, carboxyl groups, and carbonyl groups in the 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 a suitable 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- (trimethoxysilane) 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 tertiary aliphatic amines, tertiary ethanolamine amines, tertiary amine benzoates, and active amines.
The photosensitive resin composition may contain a solvent for easy coating, and any solvent known in the art may be used. From the viewpoint of environmental requirements, flatness of the film surface, and handling properties of process operations, 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 ℃, and the solvent preferably contains the high boiling point solvent and the low boiling point solvent in a weight ratio of 10. 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 ethylene glycol methyl ether, ethylene glycol ethyl ether, propylene glycol methyl ether acetate, cyclohexane and isopropanol.
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 colorant is contained in an amount of 200 to 500 parts by weight, the multifunctional monomer is contained in an amount of 50 to 100 parts by weight, the photoinitiator (including a co-initiator) is contained in an amount of 0.1 to 10 parts by weight, the solvent is contained in an amount of 100 to 800 parts by weight, and the additive is contained in an amount of 0.1 to 10 parts by weight, with respect to 100 parts by weight of the alkali-soluble resin polymer.
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, thereby forming pixels and the like.
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 which would occur to 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 first appearance of the chemical reagent used is indicated by the type and manufacturer in the following brackets, and later appearance of the reagent is from the same source as the first appearance.
Example 1.2- (Diphenyl-keto) acrylic acid methyl esterSynthesis of (2)
After 48g of methanol (1.5 mol) was charged into a 250mL three-necked flask, the mixture was stirred, the temperature was raised to reflux, 42g of diketene (0.5 mol) 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 (0.77 mol) of methyl acetoacetate.
To a 500mL three-necked flask under argon atmosphere, 200mL of THF and 15.6g of NaH dispersed with stirring (60% dispersion in minor oil, 0.39mol) were added, and 34.8g of methyl acetoacetate (0.3 mol) was added dropwise to the flask at room temperature with stirring. When the liquid in the flask became clear, 46.8g of methyl iodide (0.33 mmol) 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 the residue was separated by flash chromatography (petroleum ether: ethyl acetate 30.
6.51g of methyl 2-oxo-3-methyl-butanoate (50 mmol) and 19.2g of p-acetamidophenylsulfonyl azide (p-ABSA, 80 mmol) were added to a 500mL three-necked flask, 150mL of acetonitrile was added to dissolve and stirring was carried out thoroughly, 22mL1, 8-diazabicycloundec-7-ene (DBU, 150 mmol) was added at 0 deg.C, followed by slowly raising to room temperature, stirring for 12h, quenching the reaction with 1N HCl, extraction with N-hexane three times, combining the organic layers and saturated NaHCO 3 The solution and a saturated saline solution were washed to neutrality, dried with anhydrous sodium sulfate, and after the solvent was dried by spinning, separated by a flash column (petroleum ether: ethyl acetate =20Alpha-azido-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 atmosphere 3 H 5 )] 2 0.25 mmol), 0.48g of 2-dicyclohexylphosphonium-2 ',4',6' -triisopropylbiphenyl ([ XPhos)]1 mmol) was added thereto, and after stirring at ordinary temperature for 10 minutes, 3.02g of diisopropylamine (30 mmol), 2.61g of 4-bromo-benzophenone (10 mmol) and 1.71g of [ 2.B-1 ]](15 mmol). The mixture was stirred at 80 ℃ and checked by TLC until the 4-bromo-benzophenone reaction was complete. After the solvent was dried by spinning, the mixture was separated by a flash column (petroleum ether: ethyl acetate =52- (Diphenylketonyl) acrylic acid methyl ester [ C-1]](8.3mmol)。
Wherein, diketene: the analysis is pure, purchased from Suzhou Haobo science and technology GmbH;
p-ABSA: purity 98%, purchased from annaiji chemistry;
[PdCl(C 3 H 5 )] 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: 1 H 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]
Synthesis of [ C-2] the synthesis of [ C-1] was referred to, except that methanol used in [ A-1] was replaced with ethanol.
[C-2]Nuclear magnetic spectrum data of (a): 1 H 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]
Synthesis procedure of [ C-3] reference is made to the synthesis of [ C-1] except that methanol used in [ A-1] is replaced with propanol.
[C-3]Nuclear magnetic spectrum data of (a): 1 H 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]
Synthesis of [ C-4] the synthesis of [ C-1] was referred to, except that methanol used in [ A-1] was replaced with t-butanol.
[C-4]Nuclear magnetic spectrum data of (c): 1 H 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 5.2 Synthesis of dimethyl 2' - (Benzophenoyl) diacrylate [ D-1]
In this example, the synthesis of [ B-1] is described in the synthesis of [ C-1 ].
40mL of toluene, 200 [ mg ] of PdCl (C) was added to a 100mL three-necked flask under the protection of nitrogen gas 3 H 5 )] 2 (0.5mmol)，0.96g[Xphos](2 mmol), after stirring at ordinary temperature for 10 minutes, 6.07g of diisopropylamine (60 mmol), 3.04g of 4,4' -dibromo-benzophenone (10 mmol) and 3.42g of [ 2.5 ] B-1](30 mmol). The mixture was stirred at 80 ℃ and checked by TLC until the 4,4' -dibromo-benzophenone reaction was complete. After the solvent was dried by spinning, separation was performed by flash chromatography (petroleum ether: ethyl acetate =5: 1) to obtain 2.49g of methyl 2- (benzophenone-yl) acrylate [ D-1](7.1mmol)。
[D-1]Nuclear magnetic spectrum data of (a): 1 H 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 6.2 Synthesis of diethyl 2' - (benzophenone) diacrylate [ 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 (c): 1 H 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 7.2 Synthesis of 2' - (Benzophenoyl) dipropyl diacrylate [ D-3]
Synthesis procedure of [ D-3] reference was made to the synthesis of [ D-1] except that methanol used in [ A-1] was replaced with propanol.
[D-3]Nuclear magnetic spectrum data of (a): 1 H 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 8.2 Synthesis of di-tert-butyl 2' - (benzophenone) 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): 1 H 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, annaiji chemical, 99%) into TPGDA (tripropylene glycol diacrylate, saedoma, analyzed) to prepare 1wt% solution, coating with a rotary coater to obtain 2.0 μm uniform film on glass, exposing with 365nm ultraviolet light, and exposing at 5000mJ/cm 2 . 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 96h. Filtering chloroform solution, and detecting the maximum ultraviolet absorption wavelength lambda in the wavelength range of 200-400 nm by using an ultraviolet-visible spectrophotometer max Substituting 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 1 cm), 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
| λ max (nm) | ε(L·mol -1 ·cm -1 ) | Mass percent of precipitation 1) (％) | |
| 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 are not detected by equipment, so that the polymerizable photoinitiators not only participate in ultraviolet curing, but also can effectively reduce the dissolution precipitation and molecular migration of the photoinitiators.
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 co-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 and 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 percent to obtain the green photosensitive resin composition. Wherein, the first and the second end of the pipe are connected with each other,
auxiliary initiator K: photomer 4771 (analytically pure) available from corning chemical;
colorant L: green pigment dispersion, trade name G58, available from DIC corporation;
polyfunctional monomer M1: dipentaerythritol hexaacrylate (analytically pure), available from sartomer;
polyfunctional monomer M2: trimethylolpropane trimethacrylate propoxylate (analytically pure), purchased from taiwan double bond chemical;
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 color photosensitive resin compositions Q1 to Q8 (corresponding to examples 9 to 16, respectively);
comparative example 1
Benzophenone (annagiki 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/cm 2 The distance between the mask plate and the coating film is 180 mu m, the film is developed at the temperature of 23 ℃ for 50s, and is baked at the temperature of 230 ℃ for 20min, and 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/T6739-2006/ISO 15184 1998 standard using an advanced Chinese drawing pencil and a BEVS 1301 750g pencil hardness meter. 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 < + > -5% mpa.s with no particles on the x500 surface;
Δ: viscosity change value < + -. 10% mPa.s and no particles on x500 surface;
x: viscosity change > +/-10% by volume of particles on the mPa.s or x500 surface;
2) And (3) testing heat resistance: verifying the heat resistance of the resin through the film reduction rate and the color difference, carrying out postbaking for 20min at 230 ℃, repeating the postbaking for two times, and determining the film thickness through an XP-2 step instrument;
the film reduction rate = (first postbaking film thickness-second postbaking film thickness)/first postbaking film thickness, if S <3%, the better heat resistance is shown;
the color difference is the color difference value between the second post-baking sample wafer and the first post-baking sample wafer, and is measured by Meinenda CM-5, if Delta E ab <3 percent, the product shows better heat resistance;
3) Evaluation of solvent resistance:
placing the post-baked sample in isopropanol, soaking at room temperature for 5min, baking in oven at 150 deg.C for 30min, and measuring the color difference between the front and back, if delta E ab <3, it shows good solvent resistance.
4) Line width, side line uniformity 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 may be aqueous solution of alkaline compound such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, calcium carbonate, ammonia water, 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 to 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 (12)
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 C 1 ～C 8 Alkyl 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 C 1 ～C 8 The alkyl group of (1).
3. The photosensitive resin composition according to claim 1 or 2, wherein: r is selected from C 1 ～C 4 The alkyl group of (1).
4. The photosensitive resin composition according to claim 1, wherein: in the general formula (2), both R's are the same.
5. The photosensitive resin composition according to claim 2, wherein: in the general formula (4), both R's are the same.
6. 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.
7. The photosensitive resin composition according to claim 6, wherein: the alkali soluble resin is selected from at least one of acrylic resin and/or acrylate resin.
8. The photosensitive resin composition according to claim 6, wherein: the multifunctional monomer is selected from at least one 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- (methoxysilane) propyl acrylate, glycidyl methacrylate, and benzyl methacrylate.
9. The photosensitive resin composition according to claim 6, 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.
10. The photosensitive resin composition according to claim 6, 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.
11. The photosensitive resin composition according to any one of claims 6 to 10, wherein: the content of each component is 100 parts by weight of the alkali soluble resin;
the content of the colorant is 200 to 500 parts by weight;
the content of the multifunctional monomer is 50 to 100 parts by weight;
the total content of the photoinitiator and the co-initiator is 0.1 to 10 weight parts;
the content of the solvent is 100 to 800 parts by weight;
0.1 to 10 parts by weight of the additive.
12. 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 11.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5900472A (en) * | 1996-12-23 | 1999-05-04 | Sartomer Technology | Copolymerizable benzophenone photoinitiators |
| CN102203048A (en) * | 2008-12-15 | 2011-09-28 | 赢创罗姆有限公司 | Method for producing methacrylated benzophenones |
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW200809398A (en) * | 2006-08-11 | 2008-02-16 | Eternal Chemical Co Ltd | Photosensitive resin composition |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5900472A (en) * | 1996-12-23 | 1999-05-04 | Sartomer Technology | Copolymerizable benzophenone photoinitiators |
| 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 |
| 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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