CN104238269A - Photosensitive resin composition and application thereof - Google Patents
Photosensitive resin composition and application thereof Download PDFInfo
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- CN104238269A CN104238269A CN201410484588.2A CN201410484588A CN104238269A CN 104238269 A CN104238269 A CN 104238269A CN 201410484588 A CN201410484588 A CN 201410484588A CN 104238269 A CN104238269 A CN 104238269A
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Abstract
The invention discloses a photosensitive resin composition. The photosensitive resin composition is prepared by matching opacifier with a specific structure, resin and an initiator. The photosensitive resin composition can be used for preparing a black matrix, a spacer, a color filter and a BCS (black column spacer) on a TFT (thin film transistor), and has the advantages of low dielectric constant, nonconductivity, and high in toughness and low contamination to liquid crystal when being used as the spacer, and the like; in application of the photosensitive resin composition, the manufacturing process of a liquid crystal display can be simplified and the performance of the liquid crystal display is enhanced.
Description
[technical field]
The invention belongs to photosensitivity chemical material field, be specifically related to a kind of photosensitive polymer combination and preparing the application in black matrix", colored filter, photoresistance separation material (Photo Spacer), black photoresistance (Black Resist), black cylindrical gap thing (Black column spacer) and liquid crystal display.
[background technology]
Traditional color liquid crystal display arrangement injects liquid crystal after being pasted by the glass substrate containing colored filter and the thin film semiconductor's glass substrate being called as TFT to be made.Needing to carry out checking of location of pixels when two pieces of glass substrates are pasted, in order to ensure that calibration accuracy needs to leave certain space and has more than needed, therefore needing within the pixel black matrix" part to be done slightly, reduce overall opening degree.In recent years, the research and development of color liquid crystal display arrangement start to lay particular stress on the technology not needing to carry out positional precision and check, and wherein, the function of colored filter being transferred in TFT substrate is very important technology branch.This technology does not need the excess room in conventional machining process, can increase opening degree, more can improve the brightness of display screen.And want to realize this structure, just need on TFT, form black matrix" and RGB.
On the other hand, for Simplified flowsheet and the object guaranteeing gap of liquid crystal cell, the technology being called as black cylindrical gap thing (Black column spacer is called for short BCS) having photoresistance separation material (Photo Spacer) and black photoresistance (Black Resist) performance concurrently obtains more concern recently.But in normally used black photoresist, what be used as opacifier is carbon, and it has electric conductivity, be applied in the problem that TFT can occur leak electricity.And because the photoresistance separation material of liquid crystal display directly contacts with liquid crystal, if containing pigment, the ion component in pigment can pollute liquid crystal, thus may cause the decline of display performance.
Development and the application of above-mentioned technology propose very high requirement to material property, such as low permittivity, the obdurability without electric conductivity, separation material, the low stain etc. to liquid crystal, and prior art is difficult to meet these requirements simultaneously.
[summary of the invention]
For the deficiencies in the prior art, the object of the present invention is to provide a kind of photosensitive polymer combination.By the opacifier of ad hoc structure, resin and initiating agent being combined, the performance of products obtained therefrom can reach above-mentioned requirements, can simplify the manufacturing process of liquid crystal display simultaneously, strengthens the performance of liquid crystal display.
A kind of photosensitive polymer combination, comprises: (A) opacifier, (B) alkali soluble resin, (C) photopolymerizable compound, (D) Photoepolymerizationinitiater initiater; Wherein
Black pigment shown in described (A) opacifier contains [change 1]
[changing 1],
Wherein, R represents H independently of one another, the alkyl of C1-C12, alkenyl or alkoxy, or containing optional substituent phenyl;
Polymkeric substance shown in described (B) alkali soluble resin contains [change 2]
[changing 2],
Wherein, X is group shown in [changing 3], and Y is the residue after dicarboxylic anhydride removes anhydride group (-CO-O-CO-), and Z is the residue after tetracarboxylic dianhydride removes 2 anhydride group,
[changing 3];
Described (D) Photoepolymerizationinitiater initiater contains oxime system light trigger.
Photosensitive polymer combination of the present invention employs the component of above-mentioned ad hoc structure, by the cooperation between component, said composition can be used for the preparation of black matrix" on TFT, separation material, colored filter, BCS, have permittivity low, without electric conductivity, strong as toughness during separation material, to advantages such as liquid crystal pollution are low, and the manufacturing process of liquid crystal display can be simplified in application, strengthen the performance of liquid crystal display.
[detailed Description Of The Invention]
As mentioned above, the invention provides a kind of photosensitive polymer combination, comprise: (A) opacifier, (B) alkali soluble resin, (C) photopolymerizable compound, (D) Photoepolymerizationinitiater initiater; Wherein, the black pigment shown in described (A) opacifier contains [change 1], described (B) alkali soluble resin the contains polymkeric substance shown in [changing 2], described (D) Photoepolymerizationinitiater initiater contains oxime system light trigger.
< (A) opacifier >
As the light-proofness component used in photosensitive polymer combination of the present invention, containing the specific black organic pigment of pigment in (A) opacifier, represent with [changing 1]
[changing 1],
Wherein, R represents H independently of one another, the alkyl of C1-C12, alkenyl or alkoxy, or containing optional substituent phenyl.
Preferably, in [change 1], R represents H independently of one another, the alkyl of C1-C6, alkenyl or alkoxy, or phenyl.
Further preferably, R is selected from following groups independently of one another: hydrogen base, methyl, ethyl, propyl group, isopropyl, normal-butyl, methoxyl, ethoxy, vinyl, phenyl.
Except the black organic pigment shown in above-mentioned [change 1], described (A) opacifier can also containing other the pigment such as black, red, blue, green, yellow, purple to carry out the adjustment of tone.These other pigments can be conventional those pigments (such as carbon element), and this easily determines to those skilled in the art.
In (A) opacifier, shown in [changing 1], the content of pigment is more than 60wt%, now, photosensitive polymer combination of the present invention not only can obtain good sensitivity when film forming (more than 2 μm of thickness), and gained photomask has good shading rate.Preferably, shown in [changing 1], the content of pigment is more than 80wt%, more preferably 100wt%.
When using carbon element as other pigment, if carbon element is less than the 15wt% of opacifier total amount, then when not reducing the sensitivity of above-mentioned photosensitive resin composition, its shading rate can be improved.
In photosensitive polymer combination of the present invention, when the consumption of (B) alkali soluble resin is 100 weight portion, then the perfect match amount of (A) opacifier is 10-100 weight portion, preferred 20-60 weight portion, more preferably 30-40 weight portion.
< (B) alkali soluble resin >
(B) alkali soluble resin contains the polymkeric substance shown in [changing 2]
[changing 2],
Wherein, X is group shown in [changing 3], and Y is the residue after dicarboxylic anhydride removes anhydride group (-CO-O-CO-), and Z is the residue after tetracarboxylic dianhydride removes 2 anhydride group,
[changing 3].
Polymkeric substance itself shown in above-mentioned [changing 2] has optical polymerism (photo-curable), by increasing ultraviolet transmitance to improve the sensitivity of the photosensitive polymer combination containing this polymkeric substance.
As the dicarboxylic anhydride corresponding with Y group, object lesson has: in maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrabydrophthalic anhydride, HHPA, methyl-and methylene-tetrabydrophthalic anhydride, chlorendic anhydride, methylcyclohexene dicarboxylic anhydride, penta 2 (acid) acid anhydride etc.
As the tetracarboxylic dianhydride corresponding with Z group, object lesson has: pyromellitic dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic dianhydrides, bibenzene tetracarboxylic dianhydride, Biphenyl Ether tetracarboxylic dianhydride etc.
Shown in [changing 2], the weight-average molecular weight (Mw) (the polystyrene conversion benchmark according to gel permeation chromatography) of polymkeric substance is not though there is particular requirement, but wish within the scope of 1000-200000, preferably within the scope of 3000-100000, more preferably within the scope of 5000-15000.When the Mw of polymkeric substance is less than 200000, photosensitive polymer combination has sufficient dissolubility in a solvent; When being greater than 1000, the shaping section configuration of photosensitive polymer combination will be very well.
Based on the developability of adjustment black photoresistance and the object of mouldability thereof, at least one in following polymers in (B) alkali soluble resin, also additionally can be added:
Monomer (as (methyl) acrylic acid) with unsaturated chain thiazolinyl and carboxyl be selected from methyl acrylate, methyl methacrylate, ethyl acrylate, β-dimethyl-aminoethylmethacrylate, 2-hydroxy-ethyl acrylate, 2-hydroxyethyl methylacrylate, 2-hydroxy propyl methacrylate, N-n-butyl acrylate, N-Vinalac 5920, isobutyl acrylate, isobutyl methacrylate, benzyl acrylate, benzyl methacrylate, phenyl acrylate, phenyl methacrylate, isobornyl acrylate, isobornyl methacrylate, glycidyl methacrylate, styrene, the multipolymer that one or more unsaturated monomers of acrylamide and vinyl cyanide generate through copolyreaction,
The resins such as phenol novolak type epoxy acrylate, phenol novolak type epoxy methacrylates, cresol novolak type epoxy acrylate, cresol novolak type epoxy methacrylate, bisphenol-A type Epocryl, bisphenol S type epoxy acrylate resin.
If import acryloyl group or methacryl in this resinoid, cross-linking efficiency can be improved further, thus photostability and the resistance to chemical reagents of its film can be improved further.
< (C) photopolymerizable compound >
In photosensitive polymer combination of the present invention, (C) photopolymerizable compound can be those photopolymerization monomers conventional in this area, includes but not limited to: methyl acrylate, methyl methacrylate, 2-hydroxy-ethyl acrylate, 2-hydroxyethyl methylacrylate, 2-hydroxy propyl methacrylate, 2-acrylic acid 1,2-second two base ester, methacrylic acid glycol ester, triethylene glycol diacrylate, double methyl methacrylate triethylene glycol ester, tetraethylene glycol diacrylate, dimethacrylate tetraethylene-glycol ester, propylene glycol diacrylate, dimethacrylate, trimethylolpropane triacrylate, trimethylol-propane trimethacrylate, four (trimethylolpropane) tetrapropylene fat, four (trimethylolpropane) tetramethyl propylene fat, pentaerythrite mono acrylic ester, pentaerythrite monomethacrylates, tetramethylol methane tetraacrylate, pentaerythritol tetramethylacrylate, dipentaerythrite five acrylate, dipentaerythrite pentamethacrylates, dipentaerythrite six acrylate, dipentaerythrite hexamethacrylate, 1,6-hexanediyl ester, benzyl acrylate, benzyl methacrylate, acrylic acid, methacrylic acid etc.
Photopolymerizable compound can be independent a kind of material, also can be that two or more material is used in combination.
When the consumption of (B) alkali soluble resin is 100 weight portion, the perfect match weight range of (C) photopolymerizable compound is 5-500 weight portion, preferred 20-300 weight portion, more preferably 40-80 weight portion.The use amount of (C) photopolymerizable compound is remained on more than 5 weight portions, solidification when exposing can be prevented bad, and can make it that there is sufficient thermotolerance, drug resistance; Remain on below 500 weight portions, then can guarantee good filming performance, and can prevent the film after developing from remaining.
< (D) Photoepolymerizationinitiater initiater >
Oxime system light trigger shown in photosensitive polymer combination of the present invention, (D) Photoepolymerizationinitiater initiater contains [change 4]
[changing 4],
In [changing 4], X ' is selected from [changing 5] or the group shown in [changing 6], R
11phenyl, the alkyl of C1-C20 ,-CN ,-NO
2or the haloalkyl of C1-C4, R
12the alkyl of C2-C12 or the acyl group of C4-C8;
[changing 5]
In [changing 5], R
13-R
17represent the alkyl of H, halogen atom, C1-C12, phenyl, C independently of one another
6h
5s-;
[changing 6]
In [changing 6], R
18-R
19represent the alkyl of H, halogen atom, C1-C12, phenyl independently of one another.
In oxime system light trigger shown in above-mentioned [changing 4], R
11preferred phenyl, C1-C10 alkyl ,-CN; R
12preferred C2-C4 alkyl, C4-C7 acyl group; R
13-R
17preferred H, methyl, ethyl, phenyl, C independently of one another
6h
5s-; R
18-R
19preferable methyl, ethyl, phenyl independently of one another.
Further preferably, the oxime system light trigger shown in above-mentioned [changing 4] is selected from the compound of following structure:
,
。
Optionally, except the oxime system light trigger shown in above-mentioned [changing 4], (D) Photoepolymerizationinitiater initiater can also containing other extra light trigger, such as: 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenyl-1-ketone, 1-[4-(2-hydroxyl-oxethyl) phenyl]-2-hydroxy-2-methyl-1-propane-1-ketone, 1-(4-cumenyl-phenyl)-2-hydroxy-2-methyl-1-ketone, 1-(4-dodecylphenyl)-2-hydroxy-2-methyl-1-ketone, 2, 2-dimethoxy-1, 2-diphenylethane-1-ketone, two (4-dimethylamino phenyl) ketone, 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholine propane-1-ketone, 2-benzyl-2-dimethyl-1-(4-morpholinyl phenyl)-butane-1-ketone, 2, 4, 6-trimethyl benzoyl diphenyl base phosphine oxide, 4-benzoyl-4'-methyl dimethoxy base sulphur, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzoic acid methyl esters, EDMAB, 4-dimethylaminobenzoic acid butyl ester, 4-dimethylamino-2-ethylhexyl Benzoic acid, 4-dimethylamino-2-isopentyl ester benzoic acid, benzyl-'beta '-methoxy ethyl acetal, benzyl dimethyl ketal, 1-phenyl-1, 2-propanedione-2-(o-carbethoxyl group) oxime, o-benzoyl benzoic acid methyl, 2,4-diethyl thiazolone, CTX, 2,4-diformazan thioxanthones, the chloro-4-propoxythioxanthone of 1-, thiazolone, 2-diuril oxazolone, 2,4-diethyl thiazolone, 2-methyl thioxanthones, ITX, 2-EAQ, prestox ring anthraquinone, 1,2-benzanthrone, 2,3-biphenyl anthrone, azoisobutyronitrile, benzoyl peroxide, dicumyl peroxide, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-(o-chlorphenyl)-4,5-bis-(m-methoxyphenyl)-imidazole radicals dimer, benzophenone, 2-chlorobenzophenone, the two dimethylamino benzopheone of p, p'-, the two dimethylamino benzopheone of 4,4'-, 3,3-dimethyl-4-methoxy benzophenone, benzyl, styrax, styrax methyl ether, benzoin ethyl ether, benzoin isopropyl ether, styrax-n-isobutyl ether, benzoin isobutyl butyl ether, styrax butyl ether, acetophenone, 2,2-diethoxy acetophenone, p-dimethyl acetophenone, p-is to amido Propafenone, dichloroacetophenone, trichloroacetophenone, p-tert-butyl benzene ethyl ketone, p-dimethylamino benzoylformaldoxime, p-tert-butyl group trichloroacetophenone, p-tert-butyl group dichloroacetophenone, α, α-two chloro-4-benzene oxygen acetophenone, thioxanthones, 2-methyl thioxanthones, ITX, dihydro-dibenzo, amyl group-4-dimethylaminobenzoic acid ester, 9-phenylacridine, 1,7-pair-(9-acridinyl) heptane, 1,5-pair-(9-acridinyl) pentane, 1,3-pair-(9-acridinyl) propane, p-methoxyl triazine, 2,4,6-tri-(trichloromethyl)-s-triazine, two (the trichloromethyl)-s-triazine of 2-methyl-4,6-, two (the trichloromethyl)-s-triazine of 2-[2-(5-methylfuran-2-base) vinyl]-4,6-, 2-2-furans-2-base) and vinyl]-4,6-two (trichloromethyl)-s-triazines, two (the trichloromethyl)-s-triazine of 2-［ 2-(4-lignocaine-2-aminomethyl phenyl) vinyl ］-4,6-, two (the trichloromethyl)-s-triazine of 2-［ 2-(3,4-Dimethoxyphenyl) vinyl ］-4,6-, two (the trichloromethyl)-s-triazine of 2-(4-methoxyphenyl)-4,6-, two (the trichloromethyl)-s-triazine of 2-(4-ethoxystyrene)-4,6-, two (the trichloromethyl)-s-triazine of 2-(4-n-butoxy phenyl)-4,6-, 2,4-pair-trichloromethyl-6-(the bromo-4-methoxyl of 3-) phenyl-s-triazine, 2,4-pair-trichloromethyl-6-(the bromo-4-methoxyl of 2-) phenyl-s-triazine, 2,4-pair-trichloromethyl-6-(the bromo-4-methoxyl of 3-) styryl phenyl-s-triazine, 2,4-pair-trichloromethyl-6-(the bromo-4-methoxyl of 2-) styryl phenyl-s-triazine etc.
Wherein, triazines, as p-methoxyl triazine etc., containing halomethyl triaizine compounds class, as 2, 4, 6-tri-(trichloromethyl)-s-triazine, 2-methyl-4, two (the trichloromethyl)-s-triazine of 6-, 2-[2-(5-methylfuran-2-base) vinyl]-4, two (the trichloromethyl)-s-triazine of 6-, 2-2-furans-2-base) and vinyl]-4, two (the trichloromethyl)-s-triazine of 6-, 2-［ 2-(4-lignocaine-2-aminomethyl phenyl) vinyl ］-4, two (the trichloromethyl)-s-triazine of 6-, 2-［ 2-(3, 4-Dimethoxyphenyl) vinyl ］-4, two (the trichloromethyl)-s-triazine of 6-, 2-(4-methoxyphenyl)-4, two (the trichloromethyl)-s-triazine of 6-, 2-(4-ethoxystyrene)-4, two (the trichloromethyl)-s-triazine of 6-, 2-(4-n-butoxy phenyl)-4, two (the trichloromethyl)-s-triazine of 6-, imidazole-based compounds class, as 2-(o-chlorphenyl)-4,5-bis-(m-methoxyphenyl)-imidazole radicals dimer, aminoketone compounds class, as 2-benzyl-2-dimethyl-1-(4 morphlinophenyl)-butane-1 ketone etc., preferred.
When (D) Photoepolymerizationinitiater initiater is simultaneously containing the oxime system light trigger shown in [changing 4] and other extra light trigger, mass ratio is between the two preferably 10:90-90:10, preferred 20:80-80:20.Both can interact effectively, improve photosensitive property and the developing performance of photosensitive polymer combination further.
When the consumption of (B) alkali soluble resin is 100 weight portion, the perfect match weight range of (D) Photoepolymerizationinitiater initiater is 0.1-30 weight portion, preferred 1-20 weight portion, more preferably 5-15 weight portion.
For improving coating and adjustment viscosity, photosensitive polymer combination of the present invention can contain (E) organic solvent.
Described (E) organic solvent can be selected from: benzene, toluene, dimethylbenzene, methyl ethyl ketone, acetone, methyl isobutyl ketone, cyclohexanone, methyl alcohol, ethanol, propyl alcohol, butanols, hexanol, cyclohexanol, ethylene glycol, diglycol, glycerine, glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, 3-methoxybutyl acetic acid esters, 3-methyl-3-methoxybutyl acetic acid esters, propylene glycol methyl ether acetate (PGMEA), propylene glycol propylene glycol monomethyl ether propionic ester, propylene glycol monomethyl ether propionate, methyl carbonic, ethyl carbonate, propyl carbonate, butyl carbonate etc.Wherein, 3-methoxybutyl acetic acid esters and propylene glycol methyl ether acetate (PGMEA) not only show higher dissolubility relative to the soluble ingredient in photosensitive polymer combination, also can improve the dispersiveness of the insoluble compositions such as pigment, so be preferred.
(E) use amount of organic solvent does not have special provision, can coating concentration, coating film thickness suitably set according to substrate.
The viscosity of photosensitive polymer combination of the present invention can be 5-100cp, is preferably 10-50cp, and the best is 20-30cp.In addition, each component of composition before combination solid component concentration can be 5-100wt%, is preferably 20-50wt%.
Optionally, photosensitive polymer combination of the present invention also can contain the auxiliary agents such as thermal polymerization inhibitor, defoamer, surfactant.Described thermal polymerization inhibitor can use known material, as quinhydrones, Hydroquinone monoethylether etc.; Described defoamer can use known silicon system, fluorine based compound etc.; Described surfactant can use known cationic, anionic, non-ionics.
The allotment > of < photosensitive polymer combination
Photosensitive polymer combination of the present invention can be allocated according to following methods: (A) opacifier, (B) alkali soluble resin, (C) photopolymerizable compound, (D) Photoepolymerizationinitiater initiater and other optional component are mixed in the stirrers such as three-high mill, bowl mill, sand mill, then by after the membrane filter filtration of 5 μm, photosensitive polymer combination is obtained.
Photosensitive polymer combination of the present invention is applicable to form the light shield layer of thickness more than 2 μm.There is no particular restriction for the upper limit of this light shield layer thickness, but more thick better within the bounds of possibility.This light shield layer film thickness range can be about 3 ~ 10 μm, is preferably about 3 ~ 8 μm, and the best is 4 ~ 6 μm.
The light shield layer mentioned in the present invention is black matrix", and the display device with black matrix" has liquid crystal display, plasma display etc.
The formation method > of < light shield layer
Be made as example with black matrix", use photosensitive polymer combination of the present invention to prepare light shield layer.
First, the glass substrate with light transmission uses the non-contact type apparatus for coating photosensitive resin coating composition such as contact transfer printing type apparatus for coating or rotary coating machine, curtain coater etc. such as coating roller, oppositely coating machine, line rod coating machine.Substrate thickness is preferably 0.5-1.1mm.In order to improve the adherence between glass substrate and photosensitive polymer combination, can silane-coating coupling agent on the glass substrate in advance, or add silane coupling agent when preparing photosensitive polymer combination.
After coating, dry to remove solvent.Drying means is not particularly limited, can be: (1) at the temperature of 80-120 DEG C of preferred 90-100 DEG C dry 60 seconds-120 seconds, (2) ambient temperatare puts a few hours to a few days, and (3) put into storage heater or infrared heater several tens minutes to a few hours.
Then, through covering tabula rasa (as negativity covers tabula rasa), irradiating expose with ultraviolet, excimer laser beam isoreactivity energy-ray.Irradiate the size of energy with 30-2000mJ/cm
2be advisable.
After exposure, use developer solution to develop, form black matrix" figure.Developing method does not have special provision, such as, can use the method such as infusion process, spray-on process.Developer solution, concrete example has: the organic systems such as monoethanolamine, diethanolamine, triethanolamine, the aqueous solution etc. such as NaOH, potassium hydroxide, sodium carbonate, ammonia, quaternary ammonium salt.
Use the photosensitive polymer combination in the present invention, photoetching method also can be used to form good figure even if thickness surpasses 2 μm, that is can obtain the black matrix" of thick film.
< separation material >
Use photosensitive polymer combination of the present invention can form the light shield layer of certain thickness.
In a liquid crystal display, between two plate bases, accommodating liquid crystal, in order to make to keep certain intervals between substrate, separation material must be set between the substrates.
In existing liquid crystal display, between two plate bases, configure separation material that is spherical or column.But when using spherical spacer particle, vibration or impact can cause spacer particle to move, thus the alignment film that scratch substrate inside is arranged; Use during column separation material and then need to arrange extra black matrix".In addition, existing separation material easily forms white scarce phenomenon under Transmission light state.
The light shield layer that photosensitive polymer combination of the present invention is formed can have the function of separation material concurrently simultaneously, it can not move and need not arrange extra black matrix", that is, there is no the defect of the separation material of existing spherical or column, also can simplify the manufacturing process of liquid crystal display; Further, owing to having light-proofness, the separation material that the present invention is formed can not form white scarce phenomenon under Transmission light state.
Though the thickness of the light shield layer that photosensitive polymer combination of the present invention is formed is not particularly limited, should more than 2 μm.
< colored filter >
Use photosensitive polymer combination of the present invention can form the black matrix" of thick film, therefore the present invention is particularly suitable for forming dyed layer with ink-jetting style in the peristome of black matrix", thus forming the manufacturing process of colored filter, the black matrix" of thick film plays the effect of partition wall at this.
In the present invention, formed with ink-jetting style in the manufacturing process of dyed layer, though have the thickness not specially provided for of the black matrix" of partition wall effect, 2 μm should be greater than.
Photosensitive polymer combination of the present invention is used to form the method with the black matrix" of partition wall effect identical with the formation method of above-mentioned light shield layer.Further, after forming black matrix", after carrying out colored ink coating, repeat solidify this colored ink and form dyed layer in this black matrix" peristome with ink-jetting style, necessary words can form transparent protective film and manufacture colored filter.Form dyed layer by ink-jetting style and can adopt known method of the prior art, this easily knows to those skilled in the art.
According to the present invention, the black matrix" with partition wall effect is thick film, so can prevent the colored ink in black matrix" peristome from exceeding partition wall and making to produce colour mixture between pixel.Further, compared with the situation of thin with black matrix film (partition wall is low), low viscous colored ink can be used.
In addition, current photoetching method also can be used to manufacture colored filter.
[Brief Description Of Drawings]
Fig. 1 is the IR collection of illustrative plates of the compound 1 obtained by the synthesis example of alkali soluble resin.
[embodiment]
Below by way of specific embodiment to be described in further detail the present invention, but limiting the scope of the invention should not be understood as.
the synthesis example of alkali soluble resin
Described in Japanese patent application publication No. 2001-354735, in 500ml four-hole boiling flask, add bisphenol fluorene type epoxy resin 235g(epoxide equivalent 235) and tetramethyl ammonium chloride 110 ㎎, 2,6-dual-tert-butyl-4-methylphenol 100 ㎎ and acrylic acid 72.0g, air is blown into, simultaneously heating for dissolving at 90-100 DEG C with the speed of 25ml/min.
Then, keep solution gonorrhoea state slowly to heat up, be heated to 120 DEG C and make it to dissolve completely.Now solution becomes clear viscous gradually, continues to stir.
During this period, measure acid number, before reaching 1.0 ㎎ KOH/g, continuous heating stirs.After acid number reaches target call, at room temperature cool.
Obtain water white transparency solid shape, can by the bisphenol fluorene type epoxy acrylate of following chemical formulation.
Then, in above-mentioned bisphenol fluorene type epoxy acrylate 307.0g, add propylene glycol methyl ether acetate 600g, after dissolving, mix with bibenzene tetracarboxylic dianhydride 78g and bromination tetraethyl ammonia 1g, be slowly warming up to 110 DEG C and make it reaction 4 hours.
In course of reaction, by anhydride content in IR spectrum monitoring system.After confirming that anhydride group disappears, mix with 1,2,3,6-tetrabydrophthalic anhydride (THPA) 38.0, react 6 hours at 90 DEG C.
Obtain the alkali soluble resin compound 1 that Mw is about 4500, structure is as follows:
Wherein, X is
, Y is the residue after 1,2,3,6-tetrabydrophthalic anhydride removes anhydride group, and Z is the residue after bibenzene tetracarboxylic dianhydride removes 2 anhydride group.
Product structure is confirmed by the IR collection of illustrative plates shown in accompanying drawing 1.
?
embodiment 1
By following each component mixing, modulation photosensitive polymer combination:
(A) opacifier of 30 weight portions, is made up of SOLSPERSE 24000 spreading agent of pigment III, 10wt% shown in the following structural formula of 15wt% and the solvent PGMEA of 75wt%;
(B) the alkali soluble resin compound 1 obtained by above-mentioned synthesis example of 100 weight portions;
(C) tetramethylol methane tetraacrylate of 50 weight portions;
(D) the Photoepolymerizationinitiater initiater OXE-02 (BASF AG's product) of 10 weight portions;
(E) organic solvent, is mixed with the mass ratio of 1:3 by PGMEA and 3-methoxybutyl acetic acid esters, and the solid component concentration before its use amount makes composition mix reaches 30wt%.
Use spin coater (1H-360S: three large bamboo hats with a conical crown and broad brim produce) by above-mentioned photosensitive polymer combination coating on the glass substrate, at 90 DEG C, within dry 2 minutes, form film on hot plate.Then, utilize exposure machine (USHIO product) with exposure 20mJ/cm
2expose.After exposure, 0.04% potassium hydroxide developer solution is carried out development in 60 seconds with spray pattern.Then, at 200 DEG C after dry 30 minutes, formed thickness be 3.5 μm web, point-like figure, isolation pattern black matrix".
To the black matrix" formed, 361 type OD measuring instruments of X-rite company are used to measure its Transmission light density (OD) value; The UX MCP-HT800 type high impedance analyzer of Mitsubishi Chemical Ind is used to measure its conductivity; The micro-nano hardness tester of HM2000 type of FISCHER company is used to measure its elastic recovery rate; Made simple liquid crystal original paper, measured its voltage retention (VHR); Estimate its exterior appearance.
Result shows, and the OD value of above-mentioned obtained black matrix" is 3.0, and conductivity is 10
14Ω/cm
2, elastic recovery rate is more than 90%, VHR is 95%, and shape is good.
comparative example 1
Produce, containing 24% carbon element with carbon element dispersion liquid #387(TOKUSHIKI) replace in embodiment 1 opacifier, modulation photosensitive polymer combination, and test on an equal basis with reference to the method for embodiment 1.
Wish the black matrix" that the web of the thickness 3.5 μm that can be formed in the same manner as in Example 1, point-like figure, isolation pattern form, but finally all peel off and cannot be shaped.
embodiment 2
By SOLSPERSE 24000 dispersant of the pigment III of 20 weight portions and 20 weight portions, and then mix by the mass ratio of 90:10 with carbon element dispersion liquid #387, use final mixed liquor 40 weight portion to replace the component (A) in embodiment 1, modulation photosensitive polymer combination.
Use the photosensitive polymer combination obtained, the method with reference to embodiment 1 forms film, 30mJ/cm
2expose under condition.After exposure, 0.04% potassium hydroxide developer solution carries out development 60 seconds with spray pattern.Then dry 30 minutes after at 200 DEG C, form the black matrix" of the web of thickness 3 μm, point-like figure, isolation pattern.
The OD value of the black matrix" formed is 4.5, and conductivity is 10
14Ω/cm
2, elastic recovery rate is more than 90%, VHR is 95%, and shape is good.
embodiment 3 separation material
By pigment III with the dispersion liquid of perylene pigment (C.I. pigment red 149) (pigment 31.35wt%, SOLSPERSE 24000 spreading agent 10wt%, solvent PGMEA surplus, wherein, two kinds of pigment ratio 1:1), Red Pigment Dispersion liquid (C.I. paratonere 177, content 23.4%) and Blue pigment dispersion liquid (C.I. pigment blue 15: 6, content 23.4%) be mixed to get pigment mixed liquor 40 weight portion by the part by weight of 88:5:7, the component (A) in embodiment 1 is replaced, modulation photosensitive polymer combination with it.
Use above-mentioned photosensitive polymer combination, the method with reference to embodiment 1 forms film, 200mJ/cm
2expose under condition.After exposure, 0.1% TMAH developer solution is carried out development 60 seconds with spray pattern.Then dry 30 minutes after at 250 DEG C, forming thickness is the separation material that 5 μm of point-like figures are formed.
The OD value of gained separation material is 4.0, and conductivity is 10
14Ω/cm
2, elastic recovery rate is more than 90%, VHR is 95%, and shape is good.
comparative example 2
Replace the pigment mixed liquor in embodiment 3 with the carbon element dispersion liquid #387 of 40 weight portions, modulation photosensitive polymer combination, and test on an equal basis with reference to the method for embodiment 3, form the separation material of thickness 5 μm of point-like figures, its OD value is 4.0.But the separation material surface obtained produces gauffer, cannot use as separation material.
Claims (10)
1. a photosensitive polymer combination, comprises: (A) opacifier, (B) alkali soluble resin, (C) photopolymerizable compound, (D) Photoepolymerizationinitiater initiater; Wherein
Black pigment shown in described (A) opacifier contains [change 1]
[changing 1],
Wherein, R represents H independently of one another, the alkyl of C1-C12, alkenyl or alkoxy, or containing optional substituent phenyl;
Polymkeric substance shown in described (B) alkali soluble resin contains [change 2]
[changing 2],
Wherein, X is group shown in [changing 3], and Y is the residue after dicarboxylic anhydride removes anhydride group (-CO-O-CO-), and Z is the residue after tetracarboxylic dianhydride removes 2 anhydride group,
[changing 3];
Described (D) Photoepolymerizationinitiater initiater contains oxime system light trigger.
2. photosensitive polymer combination according to claim 1, is characterized in that, in [change 1], R is selected from H independently of one another, the alkyl of C1-C6, alkenyl or alkoxy, or phenyl; Preferred following groups: hydrogen base, methyl, ethyl, propyl group, isopropyl, normal-butyl, methoxyl, ethoxy, vinyl, phenyl.
3. photosensitive polymer combination according to claim 1, it is characterized in that, when the consumption of (B) alkali soluble resin is 100 weight portion, the consumption of (A) opacifier is 10-100 weight portion, preferred 20-60 weight portion, more preferably 30-40 weight portion.
4. photosensitive polymer combination according to claim 1, it is characterized in that, the dicarboxylic anhydride corresponding with Y group to be selected from maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrabydrophthalic anhydride, HHPA, methyl-methylene-tetrabydrophthalic anhydride, chlorendic anhydride, methylcyclohexene dicarboxylic anhydride, penta 2 (acid) acid anhydride.
5. photosensitive polymer combination according to claim 1, is characterized in that, the tetracarboxylic dianhydride corresponding with Z group is selected from pyromellitic dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic dianhydrides, bibenzene tetracarboxylic dianhydride, Biphenyl Ether tetracarboxylic dianhydride.
6. photosensitive polymer combination according to claim 1, it is characterized in that, when the consumption of (B) alkali soluble resin is 100 weight portion, the consumption of (C) photopolymerizable compound is 5-500 weight portion, preferred 20-300 weight portion, more preferably 40-80 weight portion.
7. photosensitive polymer combination according to claim 1, is characterized in that, the oxime system light trigger shown in (D) Photoepolymerizationinitiater initiater contains [change 4]
[changing 4],
In [changing 4], X ' is selected from [changing 5] or the group shown in [changing 6], R
11phenyl, the alkyl of C1-C20 ,-CN ,-NO
2or the haloalkyl of C1-C4, R
12the alkyl of C2-C12 or the acyl group of C4-C8;
[changing 5]
In [changing 5], R
13-R
17represent the alkyl of H, halogen atom, C1-C12, phenyl, C independently of one another
6h
5s-;
[changing 6]
In [changing 6], R
18-R
19represent the alkyl of H, halogen atom, C1-C12, phenyl independently of one another.
8. photosensitive polymer combination according to claim 7, is characterized in that, in the oxime system light trigger shown in [changing 4], and R
11be selected from phenyl, C1-C10 alkyl ,-CN; R
12be selected from C2-C4 alkyl, C4-C7 acyl group; R
13-R
17be selected from H, methyl, ethyl, phenyl, C independently of one another
6h
5s-; R
18-R
19be selected from methyl, ethyl, phenyl independently of one another.
9. the photosensitive polymer combination according to any one of claim 1-8 is preparing the application in black matrix", colored filter, photoresistance separation material, black photoresistance, black cylindrical gap thing and liquid crystal display.
10. application according to claim 9, is characterized in that, black matrix", colored filter, photoresistance separation material, black photoresistance, black cylindrical gap thing are positioned on TFT.
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| CN108885399A (en) * | 2016-03-18 | 2018-11-23 | 东丽株式会社 | Negative light-sensitive resin combination, cured film, the display device and its manufacturing method for having cured film |
| CN109212901A (en) * | 2018-11-05 | 2019-01-15 | 江苏博砚电子科技有限公司 | A kind of colored filter novel photoresist and preparation method thereof |
| CN109343308A (en) * | 2018-08-21 | 2019-02-15 | 江苏博砚电子科技有限公司 | Organosilicon modified crylic acid resin composition |
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