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
This disclosure relates to field of liquid crystal display, and in particular, to a kind of photosensitive resin containing polymerizable type photoinitiator
Composition and colored filter.
Background technique
Photoresist is also known as photoresist, the photaesthesia mixture being made of photosensitive resin, photoinitiator and solvent etc..
It can crosslink solidification or degradation reaction (referred to as photoetching) under ultraviolet light beams irradiation.It is added into photoresist
Colored photoresist (or color sensitive/photosensitive resin composition) has just been made in toner (red, green and blue).It will be colored
Photoresist is applied to film forming on glass substrate and forms multicolour pattern through ultraviolet light photoetching and colored filter has just been made.For colour
The colored filter of liquid crystal display device or capturing element etc. is manufactured usually using pigment dispersion method: being formed with black matrix" figure
Red, the blue or green monochromatic photoresist of even spread on the glass substrate of case, then heat drying forms a film (referred to as front baking),
To be formed by film through uv-exposure, develop, be heating and curing and (dried after referred to as), just obtain the colored filter of solid color.
Repeat aforesaid operations by different colours as needed, the colored filter containing three-color pixel can be formed, is applied to thin
The field film transistor liquid crystal display (TFT-LCD).
Photoinitiator is the core component in color photosensitive resin compositions, is that composition can be consolidated under ultraviolet light
The necessary material of change.Although the type of photoinitiator has the production for being much limited by colored filter and technique for applying requirement,
Heat-resisting, acidproof, alkaline-resisting, light shine is had to comply with, not by color glue Color influences and the requirement that does not influence color glue coloration etc., therefore
Optional type is fewer.It is existing coloured silk glue solid small molecule photoinitiator is used with photoinitiator more, be commonly present it is coloured, with mill base,
The poor compatibilities such as resin, monomer, easy to reunite, easily precipitation；Solubility is low, thermal stability is poor, migrates in Yi Congcai glue after photocuring
Or the disadvantages of being precipitated, color glue quality is influenced, the health of worker on production line is also influenced.
Have disadvantage as above in view of the photoinitiator that current color photosensitive resin composition uses, thus develop one kind can gram
The photoinitiator of disadvantages mentioned above is taken, and designs the colour with more high stability and more high film hardness around this photoinitiator
Photosensitive resin composition is current real problems that need to be solved urgently.
Summary of the invention
Present invention solves the technical problem that being that photoinitiator solubility is low, thermal stability is poor in existing color glue, after photocuring
The disadvantages of migrating or be precipitated in Yi Congcai glue, thus
The present invention provides a kind of photosensitive resin composition, includes at least selected from knot shown in lower note general formula (1) or general formula (2)
The polymerizable type photoinitiator of structure:
Wherein, R is independently selected from C1~C8Alkyl.
Photosensitive resin composition containing above-mentioned polymerizable type photoinitiator, not only system stability with higher, together
When membrane body hardness also with higher, and dry small molecule caused by high temperature or extreme condition after reducing and be precipitated and migration.
The disclosure also provides a kind of colored filter, which includes glass substrate and be coated on substrate and consolidate
The color photosensitive resin compositions of change.
Specific embodiment
Technical solution of the present invention is described in further detail below.
Photosensitive resin composition is also referred to as photoresist.
Photosensitive resin composition of the invention includes at least gathering selected from structure shown in lower note general formula (1) or general formula (2)
Mould assembly photoinitiator:
In the general formula (1) and general formula (2), R is independently selected from C1~C8Alkyl.
In above-mentioned general formula (1), general formula (2), the preferably preferred acrylate group contraposition that is connected to phenyl, i.e., the described light draws
The compound of structure shown in preferably lower note general formula (3) of agent or general formula (4) is sent out,
In the general formula (3) and general formula (4), R is independently selected from C1~C8Alkyl.
In above-mentioned general formula (1)~(4), the preferred C of R1~C4Alkyl；As C1~C4Alkyl concrete example, first can be enumerated
Base, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, tert-butyl etc..
It should be noted that two R can be the same or different in general formula (2) or general formula (4)；Preferably two R phases
Together.
The preferably following specific structure of the photoinitiator:
Acrylate group is introduced into photoinitiator molecules, and it is molten in colored photoresist system that photoinitiator can be improved
Xie Du improves the compatibility with resin, monomer etc.；The molecule that can reduce small molecule photoinitiator is precipitated and migration, reduction pair
Human injury；Increase molecular weight, is conducive to the boiling point for improving photoinitiator, reduces the loss of photoinitiator during front baking.Light
Unsaturated double-bond may participate in photocuring in initiator, and multiple double bonds on single molecule participate in polymerization, can be improved color glue crosslinking
Density improves hardness.
Photosensitive resin composition of the invention also includes alkali soluble resins, colorant, polyfunctional monomer, aided initiating, molten
The ingredient as known in the art such as agent and additive.
The alkali soluble resins can be selected from least one of acrylic resin and/or acrylate.
As colorant, pigment and/or dyestuff can be, can be red pigment/dyestuff, viridine green/dye specifically
Material, blue pigment/dyestuff, yellow uitramarine/dyestuff, orange pigment/dyestuff, violet pigment/dyestuff or above two and a variety of
The mixture of pigment/dye, it is preferable that the colorant can disperse the mill base to be formed for above-mentioned pigment/dye in a solvent,
The solid content of mill base can be 5-50wt%.
As polyfunctional monomer (or photo-sensitive monomer), refer in molecule comprising unsaturated double-bond, hydroxyl, carboxyl, carbonyl
Etc. multiple monomers with reactive functional group, addition multifunctional monomer, which can be realized, forms clearly pixel in exposed portion
Pattern prevents the technical effects such as development demoulding, and suitable polyfunctional monomer may be selected.It may participate in usually using well known in the art
The one or more of cross-linking reaction are used in mixed way, representative to enumerate as selected from 1,6- glycol diacrylate, two contractings third
Omega-diol diacrylate, tripropylene glycol diacrylate, 3- glycerol propoxylate triacrylate, trimethylolpropane tris propylene
Acid esters, ethoxyquin pentaerythritol tetraacrylate, third oxidation pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate,
Dipentaerythritol Pentaacrylate, dipentaerythritol hexaacrylate, 3- (trimethoxy silane) propyl acrylate, methyl-prop
At least one of olefin(e) acid ethylene oxidic ester and benzyl methacrylate, but it is not limited to above-mentioned multi-functional monomer.
It, can be in aliphatic tertiary amine, ethanolamines tertiary amine, tertiary amine benzoic ether and reactive amines as aided initiating
At least one.
In order to be easy to be coated, solvent, solvent well known in the art may include in photosensitive resin composition.From
From the aspect of environmental requirement, film surface planarization, technological operation treatability, it is 150~200 that boiling point is preferably included in the solvent
DEG C high boiling solvent and boiling point be lower than 150 DEG C of low boiling point solvent, preferably include described with the weight ratio of 10:90~50:50
High boiling solvent and the low boiling point solvent.Wherein, the high boiling solvent is selected from dipropylene glycol methyl ether, butyl
Acetate, diethylene glycol diethyl ether acetate, 3- ethoxyl ethyl propionate, 3- methoxyacetic acid butyl ester, in ethyl lactate extremely
Few one kind；It is selected from ethylene glycol monomethyl ether, ethylene glycol ethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether vinegar as the low boiling point solvent
At least one of acid esters, hexamethylene, isopropanol.
In addition, photosensitive resin composition of the invention can also include additive, the additive can be sensitizer, disappear
At least one of infusion, levelling agent, polymerization inhibitor, wetting dispersing agent and adhesion promoter.
More specifically, photosensitive resin composition of the invention draws comprising alkali soluble resins, colorant, polyfunctional monomer, light
Send out agent, aided initiating, solvent and additive.Relative to the alkali soluble resins polymer of 100 parts by weight, the colorant
Content be 200~500 parts by weight, the content of the polyfunctional monomer is 50~100 parts by weight, and the photoinitiator is (containing helping
Initiator) content be 0.1~10 parts by weight, the content of the solvent is 100~800 parts by weight and additive 0.1~10
Parts by weight.
Photosensitive polymer combination is coated on substrate, then passes through the processing steps such as preliminary drying, exposure, development and rear baking,
The pattern of specific shape can be obtained, to form pixel etc..
Embodiment
The polymerizable type light of photosensitive resin composition provided by the invention is described in further detail below by example
The preparation embodiment of initiator.Embodiment is not used to limit the scope of the present invention, any those skilled in the art,
Made modification and variation under without prejudice to spirit of the invention, all belong to the scope of the present invention.Used chemical reagent is for the first time
Model is marked in bracket below when appearance and manufacturer, the reagent occurred later are identical as source when first appearing.
Embodiment 1.2- (benzophenone base) methyl acrylateSynthesis
It is stirred after 250mL three-necked flask is added in 48g methanol (1.5mol), is warming up to reflux, it is bis- to be slowly added to 42g
5h is reacted in ketenes (0.5mol), continuation at a reflux temperature, and vacuum distillation obtains methyl acetoacetate 89.4g (0.77mol).
The NaH (60% that 200mL THF and 15.6g are dispersed with stirring is added in the 500mL there-necked flask protected to argon gas
Dispersion in mineral oil, 0.39mol), 34.8g methyl acetoacetate (0.3mol) is added dropwise at room temperature
Into flask and it is sufficiently stirred.It after liquid becomes clarification in flask, is added dropwise 46.8g iodomethane (0.33mmol), mixes
Object stirs 10h at 40 DEG C, and reaction solution is quenched with saturated aqueous ammonium chloride and is extracted with ethyl acetate 3 times.Merge organic
It is spin-dried for solvent after layer anhydrous sodium sulfate drying, with Flash chromatography post separation (petroleum ether: ethyl acetate 30:1), obtains 27.3g
2- oxo -3- metliyl-butyric acid methyl esters (0.21mol).
6.51g 2- oxo -3- metliyl-butyric acid methyl esters (50mmol) and 19.2g are added into 500mL there-necked flask to acetyl
Amino phenyl sulfonyl acyl azide (p-ABSA, 80mmol) is sufficiently stirred after the dissolution of 150mL acetonitrile is added, 22mL1,8- is added at 0 DEG C
11 carbon -7- alkene (DBU, 150mmol) of diazabicylo is then slowly increased to room temperature, stirs 12h, and reaction is quenched with 1N HCl,
Three times with n-hexane extraction, merge organic layer saturation NaHCO3Solution and saturated common salt are washed to neutrality, use anhydrous sodium sulfate
It is dry, Flash chromatography post separation (petroleum ether: ethyl acetate=20:1) is used after being spin-dried for solvent, obtains 3.99gα-nitrine-propionic acid first Ester [B-1](35mmol)。
Under nitrogen protection, 40mL toluene, 100mg chlorination Allylpalladium ([PdCl are added into 100mL three-necked flask
(C3H5)]2, 0.25mmol), 0.48g 2- dicyclohexyl phosphorus -2 ', 4 ', 6 '-tri isopropyl biphenyls ([Xphos], 1mmol), often
Temperature stirring after ten minutes, is added 3.02g diisopropylamine (30mmol), the bromo- benzophenone of 2.61g 4- (10mmol) and 1.71g
[B-1](15mmol).Mixture stirs at 80 DEG C, and TLC detection is until the bromo- benzophenone end of reaction of 4-.After being spin-dried for solvent
With Flash chromatography post separation (petroleum ether: ethyl acetate=5:1), 2.31g is obtained2- (benzophenone base) methyl acrylate [C-1]
(8.3mmol)。
Wherein, ketene dimer: analysis is pure, is purchased from Suzhou Haobo Technology Holdings Co., Ltd.；
P-ABSA: purity 98%, purchased from the resistance to Jilin Chemical of peace；
[PdCl(C3H5)]2: purity is greater than 97%, is purchased from Sigma-Adrich；
NaH, 60%dispersion in mineral oil are purchased from the smooth science and technology of upper Haitai；
HCl:38% is purchased from Beijing chemical industry；
[Xphos]: purity 98%, purchased from the resistance to Jilin Chemical of peace；
DBU: purity 98%, purchased from the resistance to Jilin Chemical of peace；
The bromo- benzophenone of 4-: purity 98%, purchased from the resistance to Jilin Chemical of peace；
4,4 '-two bromo- benzophenone: purity 98%, purchased from the resistance to Jilin Chemical of peace；
Acetonitrile, methanol, anhydrous sodium sulfate, toluene, sodium bicarbonate, petroleum ether, ethyl acetate, ammonium chloride etc. are purchased from western Gansu Province
Chemical industry.
The magnetic resonance spectroscopy data of compound C-1:1H NMR (300Hz) in DMSO: δ 3.69ppm (s, 3H), 6.24ppm
(d, J=1.3,1H), 6.39ppm (d, J=1.3,1H), 7.41-7.84ppm (m, 9H).
The synthesis of 2. 2- of embodiment (benzophenone base) ethyl acrylate [C-2]
The synthesis of the synthesis process reference [C-1] of [C-2], the difference is that methanol used in [A-1] is replaced with ethyl alcohol.
The magnetic resonance spectroscopy data of [C-2]:1DMSO: δ 1.07ppm (t, J=8.0,3H) of H NMR (300Hz) in,
4.00ppm (m, 2H), 6.19ppm (d, J=1.3,1H), 6.37ppm (d, J=1.3,1H), 7.41-7.84ppm (m, 9H).
The synthesis of 3. 2- of embodiment (benzophenone base) propyl acrylate [C-3]
The synthesis of the synthesis process reference [C-1] of [C-3], the difference is that methanol used in [A-1] is replaced with propyl alcohol.
The magnetic resonance spectroscopy data of [C-3]:1DMSO: δ 1.01ppm (t, J=8.0,3H) of H NMR (300Hz) in,
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).
The synthesis of 4. 2- of embodiment (benzophenone base) tert-butyl acrylate [C-4]
The synthesis of the synthesis process reference [C-1] of [C-4], the difference is that methanol used in [A-1] is replaced with the tert-butyl alcohol
It changes.
The magnetic resonance spectroscopy data of [C-4]:1H NMR (300Hz) in DMSO: δ 1.42ppm (s, 9H), 6.22 (d, J=
1.3,1H), 6.40ppm (d, J=1.3,1H), 7.41-7.84ppm (m, 9H).
The synthesis of embodiment 5. 2,2 '-(benzophenone base) diacrylate dimethyl ester [D-1]
The synthesis process of [C-1] is shown in the synthesis of [B-1] in this example.
Under nitrogen protection, 40mL toluene, 200mg [PdCl (C are added into 100mL three-necked flask3H5)]2
(0.5mmol), 0.96g [Xphos] (2mmol), stirring at normal temperature after ten minutes, are added 6.07g diisopropylamine (60mmol),
4,4 '-two bromo- benzophenone (10mmol) of 3.04g and 3.42g [B-1] (30mmol).Mixture stirs at 80 DEG C, TLC inspection
It surveys until 4,4 '-two bromo- benzophenone end of reaction.Be spin-dried for after solvent with Flash chromatography post separation (petroleum ether: ethyl acetate=
5:1), 2.49g 2- (benzophenone base) methyl acrylate [D-1] (7.1mmol) is obtained.
The magnetic resonance spectroscopy data of [D-1]:1H NMR (300Hz) in DMSO: δ 3.69ppm (s, 3H), 6.24ppm (d, J=
1.3,2H), 6.39ppm (d, J=1.3,2H), 7.40-7.68ppm (m, 8H).
The synthesis of embodiment 6. 2,2 '-(benzophenone base) diacrylate diethylester [D-2]
The synthesis of the synthesis process reference [D-1] of [D-2], the difference is that methanol used in [A-1] is replaced with ethyl alcohol.
The magnetic resonance spectroscopy data of [D-2]:1DMSO: δ 1.07ppm (t, J=8.0,6H) of H NMR (300Hz) in,
4.00ppm (m, 4H), 6.19ppm (d, J=1.3,2H), 6.37ppm (d, J=1.3,2H), 7.44-7.64ppm (m, 8H).
The synthesis of embodiment 7. 2,2 '-(benzophenone base) diacrylate dipropyl [D-3]
The synthesis of the synthesis process reference [D-1] of [D-3], the difference is that methanol used in [A-1] is replaced with propyl alcohol.
The magnetic resonance spectroscopy data of [D-3]:1DMSO: δ 1.01ppm (t, J=8.0,6H) of H NMR (300Hz) in,
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).
The synthesis of embodiment 8. 2,2 '-(benzophenone base) diacrylate di tert butyl carbonate [D-4]
The synthesis of the synthesis process reference [D-1] of [D-4], the difference is that methanol used in [A-1] is replaced with the tert-butyl alcohol
It changes.
The magnetic resonance spectroscopy data of [D-4]:1H NMR (300Hz) in DMSO: δ 1.42ppm (s, 18H), 6.22 (d, J=
1.3,2H), 6.40ppm (d, J=1.3,2H), 7.44-7.64ppm (m, 8H).
Initiator precipitation property test
Photoinitiator C-1~C-4, D-1~D-4 and BP (benzophenone, pacifies resistance to Jilin Chemical, 99%) are separately added into
It is configured to the solution of 1wt% in TPGDA (tri (propylene glycol) diacrylate, Sartomer analyze pure), is applied using rotation
2.0 μm of uniform film layer is made on glass, is exposed using 365nm ultraviolet light, light exposure 5000mJ/ for glue machine gluing
cm2.It after film layer sufficiently solidifies, is scraped from glass, 100mg sample 10mL chloroform is taken to impregnate 96h.Chloroformic solution is through filtering
Afterwards with the ultraviolet maximum absorption wavelength λ in ultraviolet-visible spectrophotometer detection 200nm~400nm wave-length coveragemax, by extinction
Degree A and molar extinction coefficient ε, which substitutes into following formula, can obtain photoinitiator concentration c in chloroformic solution:
C=A/ (ε l)
In formula, c is photoinitiator concentration, and l is that cuvette width (is herein 1cm), the initiator quality of precipitation is as the following formula
It calculates:
M=M × c × 10-2
In formula, M is the relative molecular mass of photoinitiator, and then calculates the mass percent of initiator precipitation.
Photoinitiator is precipitated performance test and is shown in Table 1
| λmax(nm) | ε(L·mol-1·cm-1) | Mass percent is precipitated1)(%) | |
| 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: using same method, fails the precipitation quality for detecting D-1~D-4.
As shown in Table 1, the precipitation mass percent of polymerizable type photoinitiator C-1~C-4 an order of magnitude about lower than BP,
And the precipitation quality of D-1~D-4 fails to detect by equipment, can determine that polymerizable type photoinitiator not only takes part in ultraviolet light
Solidification, and can be effectively reduced the solution modeling and molecular migration of photoinitiator.
Embodiment 9~16
Photoinitiator [C-1]~[C-4], [D-1]~[D-4] further prepared using above-described embodiment 1~8, point
It is not configured to green photosensitive resin composition Q1~Q8.And they are subjected to photoetching development, to compare photosensitive resin composition
Correlated performance.Specifically apply the well-known photolithography method of those skilled in the art.
Formula: 3 parts by weight photoinitiators, 3 parts by weight aided initiating K, 200 parts by weight colorant L, the more officials of 50 parts by weight are taken
It can base monomer M1,50 parts by weight polyfunctional monomer M2,100 parts by weight alkali soluble resin N, 0.2 parts by weight additive O1,0.3
Parts by weight O 2 is added about 100 parts by weight solvent P1 and about 50 parts by weight solvent P2 and sufficiently dissolves mixing, controls solid content 20%
Left and right, obtains green photosensitive resin composition.Wherein,
Aided initiating K: trade name Photomer 4771 (analysis is pure), is purchased from Corning chemical industry；
Colorant L: viridine green dispersion liquid, trade name G58 are purchased from Dainippon Ink Chemicals；
Multiple functional radical monomer M1: dipentaerythritol hexaacrylate (analysis is pure) is purchased from Sartomer；
Multiple functional radical monomer M2: the third aoxidizes trimethylol-propane trimethacrylate (analysis is pure), is purchased from Taiwan double bond
Chemical industry；
Alkali soluble resin N: trade name Sarbox SB400 (analysis is pure), is purchased from Sartomer；
Additive O1:F-556 (trade name is purchased from Dainippon Ink Chemicals)；
Additive O2:KH570 (γ-methacryloxypropyl trimethoxy silane) is purchased from lark prestige；
Solvent P1:PGMEA (propylene glycol methyl ether acetate) is purchased from DOW Chemical；
Solvent P2:PM (propylene glycol monomethyl ether) is purchased from DOW Chemical.
The preparation of the green photosensitive composition Q1 of embodiment 9.
By the polymerizable type photoinitiator [C-1] of 3 parts by weight, 3 parts by weight aided initiating K, 200 parts by weight colorant L, 50 weights
Measure part multiple functional radical monomer M1,50 parts by weight polyfunctional monomer M2,100 parts by weight alkali soluble resin N, the addition of 0.2 parts by weight
Agent O1,0.3 parts by weight O 2 are added about 100 parts by weight solvent P1 and about 50 parts by weight solvent P2 and sufficiently dissolve mixing, and control contains admittedly
Amount obtains green photosensitive resin composition Q1 20% or so.
Embodiment 10~16
It is replaced in embodiment 9 with compound [C-2], [C-3] [C-4], [D-1], [D-2], [D-3] and [D-4] respectively
Compound [C-1] is added in above-mentioned formula as photoinitiator, respectively obtains color photosensitive resin combination Q1~Q8 (respectively
Corresponding embodiment 9~16)；
Comparative example 1
Replace polymerizable type photoinitiator of the invention that above-mentioned formula is added benzophenone (pacify resistance to Jilin Chemical, 99%)
In, obtain green photosensitive resin composition Q9.
It is tested for the property using photosensitive resin composition Q1~Q9.The lithographic carried out using ultraviolet curable resin constituent
Imaging method includes the following steps:
Sheet glass is cleaned and dried, using photoresist spinner gluing, 1.3-2.0 μm of uniform film layer is made.At 90 DEG C
Front baking 120s is exposed using 365nm ultraviolet light, light exposure 40mJ/cm2, mask plate with 180 μm of film distance, at 23 DEG C
Develop 50s, dries 20min after 230 DEG C, tests subsequent correlated performance, the results are shown in Table 1.
Performance test and evaluation method:
1) surface hardness is tested: according to GB/T 6739-2006/ISO 15184:1998 standard, being drawn using advanced China
Pencil and the measurement of 1301 750g pencil hardometer of BEVS.Before test, sample panel is that (23 ± 2) DEG C are with relative humidity in temperature
16h is adjusted under conditions of (50 ± 5) %.
2) Miscibility: photosensitive polymer combination is placed under 0-10 DEG C of environment and is kept in dark place, its viscosity is tested
Change (at least six moon), and according to process conditions photoetching, color film surface is investigated at x500 times of OM, and whether there is or not Particle to go out
It is existing.
Evaluation criterion is as follows:
O: viscosity changing value < surface ± 5%mPa.s and x500 is without Particle；
Δ: viscosity changing value < surface ± 10%mPa.s and x500 is without Particle；
×: there is Particle on viscosity changing value > surface ± 10%mPa.s or x500；
2) heat resistance is tested: the heat resistance of resin, rear baking 20min at 230 DEG C, after repeating are verified by film lapse rate and color difference
It dries twice, film thickness is measured by XP-2 step instrument；
Film lapse rate=(drying film thickness after drying second of film thickness-after first time) dries film thickness after/first time, if S < 3%, shows
There is preferable heat resistance；
Color difference dries the value of chromatism of baking print after print and first time after being second, measured by Minolta CM-5, if △
Eab< 3%, then show there is preferable heat resistance；
3) solvent resistance is evaluated:
Sample after rear baking is put in isopropanol, impregnates 5min at room temperature, is put in baking oven after 150 DEG C of baking 30min,
Measurement front and back color difference, if △ Eab< 3, then show the solvent resistance having had.
4) line width, sideline uniformity and developing process allowance:
Line width and sideline uniformity are tested by x500 times of OM, 140 μm of mask plate line width.
When technique allowance is evaluated and tested, fixed other process conditions investigate developing time gained image between 40s-100s
Sideline uniformity and margin residual or edge remove situation, wherein fissility judges the measurement referring to adhesive force in the art
Method determines.
Sideline uniformity evaluation criterion is as follows:
O: develop the sideline 50s neatly and edge noresidue；
Δ: development 50s image sideline is jagged, and there is residual in irregular or edge；
×: image missing
Developing process allowance evaluation criterion is as follows:
O: the development sideline 40-100s is neat and the equal noresidue in edge, without removing；
Δ: the development sideline 50-80s is neat and the equal noresidue in edge, without removing；
×: the development sideline 50-80s is irregular or edge has residual or edge to have removing
The above-mentioned alkaline-based developer used, as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, calcium carbonate, ammonium hydroxide,
The aqueous solution of the alkali compounds such as diethylamine or tetramethylammonium hydroxide, OH-Concentration is 0.2-1.0%, preferably 0.4-0.6%.
Table 2
As shown in Table 2, the light-sensitive resin composition compared with the photoinitiator b P in comparative example Q9, in embodiment Q1-Q8
Because containing polymerizable type photoinitiator of the invention in object, under the same testing conditions, surface hardness is higher, Miscibility
More preferably, solvent resistance is more preferable, while having better sideline uniformity and developing process allowance.
Claims (11)
1. a kind of photosensitive resin composition, it is characterised in that: it includes selected from structure shown in lower note general formula (1) or general formula (2)
Polymerizable type photoinitiator:
Wherein, R is independently selected from C1~C8Alkyl.
2. photosensitive resin composition according to claim 1, it is characterised in that: the polymerizable type photoinitiator is selected from logical
The compound of structure shown in formula (3) or general formula (4)
In the general formula (3) and general formula (4), R is independently selected from C1~C8Alkyl.
3. photosensitive resin composition according to claim 1 or 2, it is characterised in that: R is selected from C1~C4Alkyl.
4. photosensitive resin composition according to claim 1 or 2, it is characterised in that: in general formula (2) or general formula (4), two
R is identical.
5. photosensitive resin composition according to claim 1, it is characterised in that: its also include alkali soluble resins, colorant,
Polyfunctional monomer, aided initiating, solvent and additive.
6. photosensitive resin composition according to claim 5, it is characterised in that: the alkali soluble resins is selected from acrylic acid tree
At least one of rouge and/or acrylate.
7. photosensitive resin composition according to claim 5, it is characterised in that: the polyfunctional monomer is selected from 1,6- second two
Alcohol diacrylate, two diacrylates of Poly-propylene glycol, tripropylene glycol diacrylate, three acrylic acid of 3- glycerol propoxylate
Ester, trimethylolpropane trimethacrylate, ethoxyquin pentaerythritol tetraacrylate, third oxidation pentaerythritol tetraacrylate,
Dipentaerythritol tetraacrylate, Dipentaerythritol Pentaacrylate, dipentaerythritol hexaacrylate, 3- (1 base silicon of methoxy
At least one of alkane) propyl acrylate, glycidyl methacrylate and benzyl methacrylate.
8. photosensitive resin composition according to claim 5, which is characterized in that the aided initiating is selected from aliphatic uncle
At least one of amine, ethanolamines tertiary amine, tertiary amine benzoic ether and reactive amines.
9. photosensitive resin composition according to claim 5, it is characterised in that: the solvent be selected from dipropylene glycol methyl ether,
Butyl acetate, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, propylene glycol monomethyl ether, propionic acid -3- ether ethyl ester, propylene glycol first
Ether acetate, 3- methoxybutyl acetic acid esters, diethylene glycol diethyl ether ethyl acetate, hexamethylene, ethyl lactate, in isopropanol
It is at least one.
10. according to any photosensitive resin composition of claim 5~9, it is characterised in that: each component content is
100 parts by weight of alkali soluble resins；
The content of the colorant is 200~500 parts by weight；
The content of the polyfunctional monomer is 50~100 parts by weight；
The content of the photoinitiator and aided initiating 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 additive.
11. a kind of colored filter, including substrate and it is coated on the substrate and cured photosensitive resin composition, feature
Be: the photosensitive resin composition is photosensitive resin composition described in any one of claim 1~10.
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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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| 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 |
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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 |
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