CN102854742A - Black resin composition, black matrix and light shielding layer - Google Patents

Black resin composition, black matrix and light shielding layer Download PDF

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Publication number
CN102854742A
CN102854742A CN2012101163721A CN201210116372A CN102854742A CN 102854742 A CN102854742 A CN 102854742A CN 2012101163721 A CN2012101163721 A CN 2012101163721A CN 201210116372 A CN201210116372 A CN 201210116372A CN 102854742 A CN102854742 A CN 102854742A
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black
resin composition
colored resin
benchmark
take
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Inventor
林凡森
赵志翰
李静安
黄新义
张志毅
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Everlight Chemical Industrial Corp
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Everlight Chemical Industrial Corp
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Abstract

The present invention provides a black resin composition comprising: the alkali-soluble resin is a copolymer formed by polymerizing styrene, tricyclodecanyl methacrylate, unsaturated carboxylic acid, isobornyl acrylate, N-phenyl maleimide and other monomers; a black pigment; a photopolymerization initiator; a polyfunctional compound; and a solvent. The invention also provides a black matrix formed by the black resin composition.

Description

Black-colored resin composition, black matix and light shield layer
Technical field
The present invention relates to a kind of resin combination, relate in particular to a kind of black-colored resin composition.
Background technology
In the liquid crystal indicator, form black matix as light shield layer/film at transparency carrier.As light shield layer, must contain screening optical activity material (dyestuff or pigment) in the material of this black matix to reach shaded effect.TaiWan, China patent TW432245 has disclosed the black matix coating (black matrix coating) that contains dye well pigment.The black pigment that uses in the black matix can be inorganic pigment or organic pigment.The inoranic membrane that contains chrome black (chromium and/or chromium oxide) with usual use is made light shield layer, yet this cost of manufacture that contains chrome black light shield layer/film is high, and the problem of environmental pollution is arranged.Therefore, further develop the inorganic particulate such as, carbon black black with graphite, iron oxide black, titanium as the resin combination of light screening material, in order to prepare the employed light shield layer/film of liquid crystal indicator.
But, with respect to employed inoranic membrane in the past, use the formed light shield layer/film of resin combination, the optical concentration of its unit thickness (OD value) lower (shading rate is relatively poor), therefore, for the contrast that improves liquid crystal indicator and keep its high image quality, need to increase thickness to reach the requirement of high optical concentration.Yet, in order to meet the development trend of filming, high performance, improve optical concentration when reducing thickness, to keep good screening optical activity, then become main research and development problem.Increasing the content of light screening material in the resin, is the feasible pattern that improves optical concentration, and still, the increase of light screening material content will be so that the content of resinous principle, thereby affects its sensing optical activity, and this will cause adverse influence to the patterning of resin.Jap.P. JP2006-163233 has disclosed the composition that contains organo-silicon compound or organofluorine compound, but through overexposure, when development forms black matix with the patterning said composition, on the substrate surface of black matix opening, can have the residual situation of organic silicon compound or organofluorine compound.Jap.P. JP2004-93656 has disclosed and has used the resin that contains graphite to form light shield layer/film (black matix), and thickness is less than 0.9 μ m, and has the optical concentration of 4.4/ μ m.Yet, can increase reflectivity with graphite as the black pigment in the resin, thereby may reduce the contrast of display device.
In the inorganic black pigment, the colouring power that carbon black and titanium are black is better.And from improving the viewpoint of optical concentration and resistance value, titanium is black to be better selection.Jap.P. JP2004-004651 and Jap.P. JP2000-143985 have disclosed and have used the resin that contains titanium oxynitrides to form light shield layer/film, and its optical concentration is more than 3.0.Taiwan patent TW200834231 has disclosed with the black black-colored resin composition as black pigment of titanium, but the black matix of its formation does not have gratifying resistance value.Jap.P. JP9-166869 has then disclosed with the black matix of carbon black as black pigment, reaches excellent screening optical activity.Yet, during as black pigment, when improving optical concentration, have the problem (the electric conductivity increase will cause the interference to device) that reduces the black matix resistance value with carbon black.Moreover in the manufacturing process of liquid crystal indicator, manufacturing process's temperature will further reduce the resistance value of this black matix up under 250 ℃ the situation.In addition, the visualization capabilities of this host material is poor, and also easily residual situation occurs at substrate.Therefore, for meeting industry demand, still need badly can satisfy the demand, the visualization capabilities that improve optical concentration and keep the pyrometric scale surface resistance good, can residual condition not occur at substrate, and have good moisture resistance and etch-resistance to possess the black-colored resin composition of excellent adhesive attraction.
Summary of the invention
The invention provides a kind of black-colored resin composition, the demand of utilizing to meet industry, this black-colored resin composition comprises: alkali soluble resins, it is the multipolymer that is formed by monomer polymerizations such as styrene, methacrylic acid three ring decyl ester, unsaturated carboxylic acid, the different camphane ester of acrylic acid (Isobornyl acrylate, isobornyl acrylate) and N-phenylmaleimides, wherein, take the gross weight of this black-colored resin composition as benchmark, the content of this alkali soluble resins is 3 % by weight to 20 % by weight (wt%); Black pigment, its content is 20wt% to 60wt% take the gross weight of this black-colored resin composition as benchmark; Photoepolymerizationinitiater initiater, its content is 0.3wt% to 5wt% take the gross weight of this black-colored resin composition as benchmark; Polyfunctional compound, its content is 1wt% to 5wt% take the gross weight of this black-colored resin composition as benchmark; And, the solvent of surplus.
One specific embodiment according to the present invention, this unsaturated carboxylic acid is methacrylic acid.
One specific embodiment according to the present invention, this black pigment is carbon black.
One specific embodiment according to the present invention, the weight-average molecular weight of this alkali soluble resins are 4000 to 8000.
One specific embodiment according to the present invention, black-colored resin composition can optionally comprise adhesion promoter and/or adjuvant.
The present invention also provides a kind of black matix, is formed by black-colored resin composition of the present invention.
The present invention also provides a kind of light shield layer, is formed by black-colored resin composition of the present invention.
The formed black matix of black-colored resin composition provided by the invention can when improving optical concentration, represent excellent high temperature sheet resistance value.In addition, the visualization capabilities of black-colored resin composition provided by the invention is good, when forming black matix, can reach the requirement of noresidue and high adhesion force (moisture-proof that tool is good and anti-etching) on the base material at patterning, and the utmost point meets the demand of industry.
Embodiment
Below by particular specific embodiment explanation embodiments of the present invention, those skilled in the art can understand other advantage of the present invention and effect by content disclosed in the present specification.The present invention also can be implemented or be used by other different specific embodiment, and the every details in this instructions also can based on different viewpoints and application, not carried out various modifications and change under the spirit departing from this creation.
Term as used herein " weight-average molecular weight " is the value of utilizing the weight average molecular weight that is converted into polystyrene (Mw) of gel permeation chromatography (GPC) mensuration, and solvent is tetrahydrofuran (THF).
Term as used herein " acrylic acid series " comprises acrylic acid series and metha crylic.Term as used herein " (methyl) acrylic acid ... " expression comprises or does not comprise the literal in the bracket.For example, " (methyl) acrylic acid " comprises acrylic acid and methacrylic acid, by that analogy.
The invention provides a kind of black-colored resin composition, the demand of utilizing to meet industry, this black-colored resin composition comprises: alkali soluble resins, it is the multipolymer that is formed by monomer polymerizations such as styrene, methacrylic acid three ring decyl ester, unsaturated carboxylic acid, the different camphane ester of acrylic acid and N-phenylmaleimides, wherein, take the gross weight of this black-colored resin composition as benchmark, the content of this alkali soluble resins is 3wt% to 20wt%; Black pigment, its content is 20wt% to 60wt% take the gross weight of this black-colored resin composition as benchmark; Photoepolymerizationinitiater initiater, its content is 0.3wt% to 5wt% take the gross weight of this black-colored resin composition as benchmark; Polyfunctional compound, its content is 1wt% to 5wt% take the gross weight of this black-colored resin composition as benchmark; And, the solvent of surplus.
According to black-colored resin composition of the present invention, the weight-average molecular weight of alkali soluble resins is 4000 to 8000.
One specific embodiment according to the present invention, take the gross weight of this black-colored resin composition as benchmark, the content of alkali soluble resins is 3wt% to 15wt%.In one specific embodiment, take the gross weight of this black-colored resin composition as benchmark, the content of alkali soluble resins is 3wt% to 8wt%
The alkali soluble resins of black-colored resin composition of the present invention is the multipolymer that is formed by monomer polymerizations such as styrene, methacrylic acid three ring decyl ester, unsaturated carboxylic acid, the different camphane ester of acrylic acid and N-phenylmaleimides.One specific embodiment according to the present invention, when forming multipolymer, take the total amount of all monomers as benchmark, the consumption of styrene monomer is 5wt% to 20wt%.One specific embodiment according to the present invention, take the total amount of all monomers as benchmark, the consumption of methacrylic acid three ring decyl ester monomers is 15wt% to 45wt%.One specific embodiment according to the present invention, take the total amount of all monomers as benchmark, the consumption of the different camphane ester of acrylic acid monomer is 10wt% to 25wt%.One specific embodiment according to the present invention, take the total amount of all monomers as benchmark, the consumption of N-phenylmaleimide monomer is 15wt% to 25wt%.
The example of unsaturated carboxylic acid monomer that is used for the alkali soluble resins of black-colored resin composition of the present invention includes, but are not limited to: (methyl) acrylic acid, butenoic acid, maleic acid, fumaric acid, methyl-maleic acid, mesaconic acid, itaconic acid, hexadienoic acid and combination thereof etc.Wherein, preferred (methyl) acrylic acid, more preferably methacrylic acid.One specific embodiment according to the present invention, alkali soluble resins contains at least a unsaturated carboxylic acid.In these specific embodiments of part, alkali soluble resins contains methacrylic acid at least.
During the alkali soluble resins of preparation black-colored resin composition of the present invention, take the total amount of all monomers as benchmark, the consumption of unsaturated carboxylic acid monomer is 10wt% to 25wt%.
The alkali soluble resins that is used for black-colored resin composition of the present invention, can encircle the multipolymer that the monomer polymerizations such as decyl ester, unsaturated carboxylic acid, the different camphane ester of acrylic acid and N-phenylmaleimide form by styrene, methacrylic acid three at least by the whole bag of tricks preparation, the preparation method includes, but are not limited to the method that this paper embodiment narrates.
The preparation of this multipolymer can utilize polyreaction to carry out, and polyreaction is carried out in the presence of polymerization initiator usually.There is no particular restriction for polymerization initiator, can use general employed polymerization initiator in this technical field.Can use one or more polymerization initiator.There is no particular restriction for the consumption of polymerization initiator.When using the potpourri of two or more polymerization initiators, blending ratio is not particularly limited.The temperature of polymerization is generally 65 ℃ to 85 ℃, preferred 70 ℃ to 80 ℃.
Can optionally add chain-transferring agent when utilizing polyreaction to prepare alkali soluble resins.There is no particular restriction for chain-transferring agent, can use normally used chain-transferring agent in this technical field, for example 2,4-diphenyl-4-methyl-1-pentene, 1-dithiobenzoic acid phenethyl ester (1-phenylethyl dithiobenzoate) and dithiobenzoic acid cumenyl ester (cumyl dithiobenzoate).Can use one or more chain-transferring agent.There is no particular restriction for the consumption of chain-transferring agent.When using the potpourri of two or more chain-transferring agents, blending ratio is not particularly limited.
Polyreaction is carried out in the presence of solvent usually, the preferred solvent that is enough to dissolve each composition, polymerization initiator etc. and obtained resin in the alkali soluble resins that uses.There is no particular restriction for solvent, can use normally used solvent in this technical field.Can use one or more solvent.There is no particular restriction for the amount of solvent.When using the potpourri of two or more solvents, blending ratio is not particularly limited.
One specific embodiment according to the present invention, the alkali soluble resins with preparation is finished with black pigment, Photoepolymerizationinitiater initiater, polyfunctional compound and solvent combination, obtains black-colored resin composition.
The black pigment (Pigment) that is used for black-colored resin composition of the present invention can be inorganic pigment, organic pigment (for example, azo pigment, C.I. pigment black 1, C.I. pigment black 7 etc.) and combination thereof, is preferably inorganic pigment.The example of inorganic black pigment includes, but are not limited to that graphite, manganese dioxide, synthetic iron oxide black, carbon black, copper ferrimanganic are that oxide, copper chromium manganese series oxides, titanium are deceived, titanium carbon and analog thereof.Can use one or more black pigment.When using the potpourri of two or more black pigments, blending ratio is not particularly limited.One specific embodiment according to the present invention, the preferred carbon black of black pigment, titanium are deceived and combination.One specific embodiment according to the present invention, black-colored resin composition of the present invention use carbon black as black pigment.Carbon black can optionally be used in combination with other black pigment.The carbon black that black-colored resin composition of the present invention uses preferably has electrical insulation property, can use commercially available carbon black as black pigment.
One specific embodiment according to the present invention, take the gross weight of this black-colored resin composition as benchmark, the content of black pigment is 20wt% to 60wt%.Wherein, when using carbon black as black pigment, in order to reach suitable optical concentration and to keep simultaneously suitable resistance value, take the gross weight of this black-colored resin composition as benchmark, the content of black pigment is preferably 25wt% to 55wt%.In one specific embodiment, take the gross weight of this black-colored resin composition as benchmark, the content of black pigment is 35wt% to 55wt%.
There is no particular restriction to be used for the Photoepolymerizationinitiater initiater of black-colored resin composition of the present invention, can use to absorb the Photoepolymerizationinitiater initiater that can cause Raolical polymerizable after the luminous energy.
The example of Photoepolymerizationinitiater initiater includes, but are not limited to: benzoin and alkyl ether thereof, for example, benzoin, benzoin methylether, benzoin ethyl ether, benzoin iso-propylether, benzoin phenyl ether (benzoin phenyl ether), acetyl benzoin; Acetophenone, for example, acetophenone, 2,2-dimethoxy-2-phenyl acetophenone, 2,2-diethoxy-2-phenyl acetophenone, 1,1-dichloroacetophenone; Aminoacetophenone, for example, 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholinyl third-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl) fourth-1-ketone; Anthraquinone, for example, 2-methylanthraquinone, 2-EAQ, 2-tert-butyl group anthraquinone, 1-chloroanthraquinone, 2-amyl anthraquinone (2-amylanthraquinone); Thioxanthones (thioxanthone) and xanthone (xanthone), for example, 2,4-dimethyl thioxanthones, 2,4-diethyl thioxanthone, CTX, 2,4-diisopropyl thioxanthones; Ketal, for example, acetophenone dimethyl ketal, benzyl dimethyl ketone; Benzophenone, for example, benzophenone, 4,4 '-two (N, N '-dimethylamino) benzophenone (4,4 '-bis (N, the benzophenone of N '-di-methyl-amino)), 4,4 '-two (N, N '-diethylamino) benzophenone; Acridine derivatives (acridine derivative); Azophenlyene derivant (phenazine derivative); Triphenylphosphine; Phosphine oxide; for example; (2,6-dimethoxy benzoyl)-2,4; 4-amyl group phosphine oxide ((2; 6-dimethoxybenzoyl)-2,4,4-pentyl phosphine oxide); two (2; 4; the 6-trimethylbenzoyl) phenylphosphine oxide (bis (2,4,6-trimethylbenzoyl)-phenyl phosphine oxide); 2; 4; 6-trimethylbenzoyl-diphenyl phosphine oxide (2,4,6-trimethylbenzoyl-diphenyl phosphine oxide); 2; 4,6-trimethylbenzoyl-phenyl-phosphonite ethyl ester
(ethyl-2,4,6-trimethylbenzoyl-phenyl phosphinate); 1-phenyl-1,2-propanedione-2-O-benzoyl oxime (1-phenyl-1,2-propanedione 2-O-benzoyl oxime); 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl] ethyl ketone 1-(O-acetyl oxime)
(1-[9-Ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl] ethanone 1-(O-acetyloxime)); 4-(2-hydroxyl-oxethyl) phenyl-(2-propyl group) ketone
(4-(2-hydroxyethoxy) Phenyl-(2-propyl) ketone); 1-aminophenyl ketone (1-aminophenyl ketone) and 1-photoinitiator (1-hydroxy phenyl ketone), for example, 1-hydroxycyclohexylphenylketone, 2-hydroxyl isopropyl phenyl ketone, phenyl 1-hydroxyl nezukone (phenyl 1-hydroxyisopropyl ketone), 4-isopropyl phenyl 1-hydroxyl nezukone (4-isopropylphenyl 1-hydroxyisopropyl ketone); 2,2 '-azobis isobutyronitrile; Various superoxide (peroxide); Mercaptan compound; And combination.
One specific embodiment according to the present invention, take the gross weight of this black-colored resin composition as benchmark, the content of Photoepolymerizationinitiater initiater is 0.3wt% to 3wt%.
The polyfunctional compound that is used for black-colored resin composition of the present invention can carry out polymerized/cross-linked with alkali soluble resins after the absorption luminous energy.There is no particular restriction to be used for polyfunctional compound of the present invention, as long as can carry out polymerization with alkali soluble resins after absorbing luminous energy.One specific embodiment according to the present invention, multi-functional compound are selected from polyfunctional monomer and/or the oligomer with ethylene type unsaturated link.
This polyfunctional compound can use commercially available polyfunctional compound, such as, but not limited to Nikalac MX-302 (by Sanwa Chemical Co., Ltd. makes); Aronix M-400, M-402, M-403, M-404, M-408, M-450, M-305, M-309, M-310, M-313, M-315, M-320, M-325, M-326, M-327, M-350, M-360, M-208, M-210, M-215, M-220, M-225, M-233, M-240, M-245, M-260, M-270, M-1100, M-1200, M-1210, M-1310, M-1600, M-221, M-203, TO-924, TO-1270, TO-1231, TO-595, TO-756, TO-1343, TO-1382, TO-902, TO-904, TO-905, TO-1330 (by Toagosei Co., Ltd. makes); Kayarad D-310, D-330, DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-120, DN-0075, DN-2475, SR-295, SR-355, SR-399E, SR-494, SR-9041, SR-368, R-415, SR-444, SR-454, SR-492, SR-499, SR-502, SR-9020, SR-9035, SR-111, SR-212, SR-213, SR-230, SR-259, SR-268, SR-272, SR-344, SR-349, SR-368, SR-601, SR-602, SR-610, SR-9003, PET-30, T-1420, GPO-303, TC-120S, HDDA, NPGDA, TPGDA, PEG400DA, MANDA, HX-220, HX-620, R-551, R-712, R-167, R-526, R-551, R-712, R-604, R-684, TMPTA, THE-330, TPA-320, TPA-330, KS-HDDA, KS-TPGDA, KS-TMPTA (by Nippon Kayaku Co., Ltd. makes); Light Acrylate PE-4A, DPE-6A, DTMP-4A (by Kyoeisha Chemical Co., Ltd. makes) etc., and combination.
One specific embodiment according to the present invention, take the gross weight of this black-colored resin composition as benchmark, the content of this multi-functional compound is 2wt% to 4wt%.
One specific embodiment according to the present invention, black-colored resin composition comprises: alkali soluble resins, black pigment, Photoepolymerizationinitiater initiater, polyfunctional compound, and, balance solvent.
There is no particular restriction to be used for the solvent of black-colored resin composition of the present invention, can use normally used solvent in this technical field.The example of solvent includes, but are not limited to: ketone such as cyclohexanone, MEK, diethyl ketone, methyl isobutyl ketone, ethyl isobutyl ketone etc.; Ester class such as ethyl acetate, butyl acetate, isoamyl acetate, butyl propionate, isopropyl isobutyrate, ethyl butyrate, butyl butyrate, amyl formate, methyl lactate, ethyl lactate, hydroxy methyl acetate, hydroxyl ethyl acetate, Butyl Glycolate, methoxy menthyl acetate, the methoxyacetic acid ethyl ester, the methoxyacetic acid butyl ester, ethoxy acetate, ethoxy ethyl acetate, the 2 hydroxy propanoic acid methyl esters, the 2 hydroxy propanoic acid ethyl ester, the 2 hydroxy propanoic acid propyl ester, the 3-hydroxy methyl propionate, 3-hydracrylic acid ethyl ester, the 2-methoxy methyl propionate, 2-methoxy propyl acetoacetic ester, 2-methoxy propyl propyl propionate, 2-ethoxy-propionic acid methyl esters, the 2-ethoxyl ethyl propionate, the 3-methoxy methyl propionate, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, the 3-ethoxyl ethyl propionate, 3-ethoxyethyl propionic ester etc.; Ethers such as glycol monoethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol methyl ether acetate, propylene-glycol ethyl ether acetic acid esters, propylene glycol propyl ether acetic acid esters etc.Can use one or more solvents.When using the potpourri of two or more solvents, blending ratio is not particularly limited.
Take the gross weight of this black-colored resin composition as benchmark, the consumption of solvent is 30wt% to 70wt%.In one specific embodiment, take the gross weight of black-colored resin composition as benchmark, the consumption of solvent is 30wt% to 50wt%.
One specific embodiment according to the present invention, black-colored resin composition can optionally comprise adhesion promoter (adhesion promoter).The employed adhesion promoter of black-colored resin composition is not particularly limited, can use silane (silane) class adhesion promoter, for example, but be not limited to: vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three (2-methoxy ethoxy) silane, γ-methacryloxypropyl trimethoxy silane, APTES, the 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl group methyl dimethoxysilane, 2-(3,4-epoxy radicals cyclohexyl) ethyl trimethoxy silane, 3-sulfydryl propyl trimethoxy silicane, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, N-(2-amino-ethyl)-3-TSL 8330, the 3-chloropropylmethyldimethoxysilane, 3-r-chloropropyl trimethoxyl silane etc.Can use one or more adhesion promoters.When using the potpourri of two or more adhesion promoters, its blending ratio is not particularly limited.
Take the gross weight of this black-colored resin composition as benchmark, the consumption of adhesion promoter is 0.1wt% to 3wt%.In one specific embodiment, take the gross weight of this black-colored resin composition as benchmark, the consumption of adhesion promoter is 0.1wt% to 1wt%.
One specific embodiment according to the present invention, black-colored resin composition can optionally comprise adjuvant.The example of adjuvant comprises, but be not limited to: modifier (modifier), toughner (toughener), stabilizing agent (stabilizer), defoamer, spreading agent (dispersant), levelling agent (leveling agent), thickening agent (thickening agent), reinforcing agent (reinforcing agent), coupling agent (coupling agent), increase and scratch agent (flexibility-imparting agent), antioxidant, pigment, dyestuff, antisettling agent etc., and combination.Take the gross weight of this black-colored resin composition as benchmark, the content of adjuvant is no more than 10wt% usually.
One specific embodiment according to the present invention, black-colored resin composition can be used for making the light shield layer/film of colored filter in the display device.In these specific embodiments of part, black-colored resin composition can be used for making the dividing wall between each pixel in the display device.In these specific embodiments of part, put on black-colored resin composition on the base material patterned and after forming black matix, can further form thereon the assemblies such as diaphragm, transparency electrode, oriented film.
The formed black matix of black-colored resin composition provided by the invention can when improving optical concentration, represent excellent high temperature (250 ℃) sheet resistance value.Therefore, the formed black matix of black-colored resin composition provided by the invention can have abundant screening optical activity and tool high surface resistance under high brightness backlights, meets the demand that industry is utilized.In addition, the visualization capabilities of black-colored resin composition provided by the invention is good, when forming black matix, can reach the requirement of noresidue and high adhesion force (moisture-proof that tool is good and anti-etching) on the base material at patterning.
Black-colored resin composition provided by the invention can in order to form black matix, be made the light shield layer/film with excellent specific property (having abundant screening optical activity and high surface resistance).Black-colored resin composition provided by the invention has good visualization capabilities and high adhesion force, also provides good screening optical activity and high resistance simultaneously, and the utmost point meets the industry demand of display device.
The present invention will be described more specifically by embodiment, but these embodiment are not for restriction category of the present invention.Unless specialize, it is as benchmark take weight that " % " that is used for representing the content of any composition and any amount of substance in the following example and the comparing embodiment reaches " weight portion ".
Embodiment
The preparation of alkali soluble resins
Synthesis example 1:
Synthesizing of resin 1
Condenser pipe is being housed, in the flask of stirrer, drop into 15 grams 2,2 '-azobis isobutyronitrile (polymerization initiator), 4 grams 2,4-diphenyl-4-methyl-1-pentene (chain-transferring agent) and 310 gram diethylene glycol monomethyl ethylethers (Methyl Ethyl Di Glycol) (solvent), then add 11 gram styrene, 44 gram methacrylic acids, three ring decyl ester (Tricyclodecanyl methacrylate), 21 gram methacrylic acids, the 27 gram different camphane esters of acrylic acid (Isobornyl acrylate) and 24 gram N-phenylmaleimides (N-Phenylmaleimide), stirring at room made its dissolving in 30 minutes, behind nitrogen replacement, make temperature maintain 75 ℃, stirred 6 hours, obtain resin 1, molecular weight is 4700, and solids content is 31.3%.
Synthesis example 2 to 10:
Resin 2 is synthetic to resin 10
Same way as with synthesis example 1, in the flask that condenser pipe, stirrer are housed, drop into 15 grams 2,2 '-azobis isobutyronitrile, 4 grams 2,4-diphenyl-4-methyl-1-pentene and 310 gram diethylene glycol monomethyl ethylethers then add according to composition shown in the following table 1 and consumption, prepare respectively resin 2 to resin 10.Stirring at room made its dissolving in 30 minutes, behind nitrogen replacement, made temperature maintain 75 ℃, stirred 6 hours, obtained respectively resin 2 to resin 10.Each molecular weight and solids content are as shown in table 1.
Table 1
Figure BSA00000704360600101
Composition 1: styrene
Composition 2: methacrylic acid three ring decyl ester
Composition 3: methacrylic acid
Composition 4: the different camphane ester of acrylic acid
Composition 5:N-phenyl maleimide
Composition 6: benzyl methacrylate
Composition 7: hydroxyethyl methylacrylate
Composition 8:3,4-epoxycyclohexyl methyl acrylate
Composition 9: Tetrahydrofurfuryl Methacrylate
The preparation of black-colored resin composition
Embodiment 1
Evenly mix by solution 13.50 grams of synthesis example 1 resulting resin 1 (4.23 gram), carbon black pigment 47.00 grams,
Figure BSA00000704360600102
I-242 (Photoepolymerizationinitiater initiater) (being made by BASF (BASF) company) 0.47 gram, tetraethyl michaelis ketone (Photoepolymerizationinitiater initiater) 0.17 gram, Aronix M 400 (polyfunctional compound) 3.06 grams, A-174 (adhesion promoter) (being made by general electronic corporation (GE) company) 0.57 gram and propylene glycol monomethyl ether (solvent) 35.23 grams, be configured to 100 gram black-colored resin compositions, then filter this solution with 10 μ m (micron) filtrators, obtain black-colored resin composition.
Embodiment 2 to 3
The resin 1 that replaces among the embodiment 1 with resin 2 and resin 3 respectively according to the step of embodiment 1, prepares respectively black-colored resin composition.
Comparative example 1 to 7
The resin 1 that replaces among the embodiment 1 with resin 4, resin 5, resin 6, resin 7, resin 8, resin 9 and resin 10 respectively according to the step of embodiment 1, prepares respectively black-colored resin composition.
Test
Measure respectively optical concentration and the surface resistance of the black-colored resin composition that above-described embodiment and comparative example obtain, and carry out the test of visualization capabilities (pattern formation), residual situation, moisture-proof, elching resistant etc.
The black-colored resin composition that respectively above-described embodiment and comparative example is obtained is uniformly coated on the electro-conductive glass base material that is coated with ITO (tin indium oxide) (trade name: 1737, healthy and free from worry (Corning) company system) in the mode of rotary coating.With 100 ℃ of dryings 5 minutes.See through the figuratum light shield of tool (photomask), with extra-high-pressure mercury vapour lamp (exposure energy: 200mJ (millijoule)/cm 2(square centimeter)) resin combination is exposed.Then, develop with the aqueous sodium carbonate of 0.5 quality %, then in 250 ℃ of thermmohardenings of carrying out 30 minutes, form and have pattern and thickness is the black matix of 1.0 μ m.According to following method, the black matix that black-colored resin composition is formed on the base material is tested, with the characteristic of assessment black-colored resin composition.The results are shown in following table 2.
(1) optical concentration:
Use penetron (Densitometer, Ai Seli (X-Rite) company system, trade name " 361T "), measure the optical concentration of the black matix of above-mentioned formation.
Following table 2 is depicted as the measured optical concentration of thickness 1m.As shown in Table 2, use the formed light shield layer/film of embodiment of the invention black-colored resin composition, have excellent optical concentration performance.
(2) surface resistance:
Prepare black matix with preceding method, but when exposure do not used light shield.And after 250 ℃ of thermmohardenings, then, use insulation resistance tester (trade name: R8340A, Advantest (Advantest) company system), apply 500V voltage, measure the sheet resistance value (Ω/cm of formed black matix 2).
As shown in table 2 below, the formed black matix of black-colored resin composition of the use embodiment of the invention has excellent high temperature sheet resistance value.
(3) visualization capabilities:
Observe formed black matix with the 500X optical microscope.
(a) face: observe whether the face of black matix has unusual or coarse after developing.
(b) rectilinearity: observe whether the pattern of black matix has overdevelop (over development) or the problem of expand (swelling) after developing.
As shown in table 2 below, represent in the following manner observations: zero: face is good without coarse/pattern edge rectilinearity, *: face is coarse/and overdevelop or expansion, P appear in pattern edge: can't film forming.The black-colored resin composition of the embodiment of the invention has good visualization capabilities.
(4) residual situation:
Whether observe with the 500X optical microscope has photoresistance residual on the base material.Represent in the following manner observations: zero: noresidue, △: slightly residual, but can accept, *: seriously residual.
As shown in table 2 below, the black-colored resin composition of the embodiment of the invention, after exposure, developing, residual situation can not occur in substrate in the place beyond pattern.
(5) moisture-proof:
(a) water-bath: soaked 60 minutes in 80 ℃ of deionized waters, then with hundred lattice scrapers and the 3M adhesive tape test photoresistance adhesion (ASTM D3359 method of testing) to base material.
(b) P.C.T (pressure cook test, autoclave pressure test): sample applies 2 atmospheric pressure after 24 hours in 120 ℃, then with hundred lattice scrapers and the 3M adhesive tape test photoresistance adhesion (ASTM D3359 method of testing) to base material.
As shown in table 2 below, the black-colored resin composition of the embodiment of the invention shows excellent adhesion to base material, shows that it has good moisture-proof, thereby has good adhesion.
(6) elching resistant:
Sample is immersed in (HCl:215ml, 37wt% in the iron chloride acid etching liquid; H 2O:69.2ml; FeCl 3: 16.8ml, 15wt%), under 40 ℃, kept 3 minutes.Then with hundred lattice scrapers and the 3M adhesive tape test photoresistance adhesion (ASTM D3359 method of testing) to base material.As shown in table 2 below, the black-colored resin composition of the embodiment of the invention has good resistance to etching solution, and after etching base material is showed excellent adhesion.
Table 2
Figure BSA00000704360600131
The formed black matix of black-colored resin composition provided by the invention not only has the optical concentration greater than 3.5, and represents excellent high temperature (250 ℃) sheet resistance value.Therefore, the formed black matix of black-colored resin composition provided by the invention can have abundant screening optical activity and tool high surface resistance under high brightness backlights, meets the demand that industry is utilized.In addition, the visualization capabilities of black-colored resin composition provided by the invention is good, when forming black matix, can reach the requirement of noresidue and high adhesion force (having good moisture-proof and anti-etching) on the base material at patterning.
Black-colored resin composition provided by the invention can have in order to form black matix the light shield layer/film of excellent specific property with making.Black-colored resin composition provided by the invention has good visualization capabilities and high adhesion force, also provides good screening optical activity and high resistance simultaneously, and the utmost point meets the industry demand of display device.
Above-described embodiment is illustrative composition of the present invention and preparation method only, but not is used for restriction the present invention.Any those skilled in the art all can be under spirit of the present invention and category, and above-described embodiment is modified and changed.Therefore, the scope of the present invention should be put down in writing such as claims scope.

Claims (12)

1. a black-colored resin composition is characterized in that, comprising:
Alkali soluble resins, it is the multipolymer that is formed by styrene, methacrylic acid three ring decyl ester, unsaturated carboxylic acid, the different camphane ester of acrylic acid and N-phenylmaleimide monomer polymerization, wherein, take the gross weight of this black-colored resin composition as benchmark, the content of this alkali soluble resins is 3wt% to 20wt%;
Black pigment, its content is 20wt% to 60wt% take the gross weight of this black-colored resin composition as benchmark;
Photoepolymerizationinitiater initiater, its content is 0.3wt% to 5wt% take the gross weight of this black-colored resin composition as benchmark;
Polyfunctional compound, its content is 1wt% to 5wt% take the gross weight of this black-colored resin composition as benchmark; And,
The solvent of surplus.
2. black-colored resin composition as claimed in claim 1 is characterized in that, the unsaturated carboxylic acid monomer in this alkali soluble resins is methacrylic acid.
3. black-colored resin composition as claimed in claim 1 is characterized in that, this black pigment is carbon black.
4. black-colored resin composition as claimed in claim 1 is characterized in that, the weight-average molecular weight of this alkali soluble resins is 4000 to 8000.
5. black-colored resin composition as claimed in claim 1 is characterized in that, take the gross weight of this black-colored resin composition as benchmark, the content of this alkali soluble resins is 3wt% to 15wt%.
6. black-colored resin composition as claimed in claim 1 is characterized in that, take the gross weight of this black-colored resin composition as benchmark, the content of this black pigment is 25wt% to 55wt%.
7. black-colored resin composition as claimed in claim 1 is characterized in that, take the gross weight of this black-colored resin composition as benchmark, the content of this polyfunctional compound is 2wt% to 4wt%.
8. black-colored resin composition as claimed in claim 1 is characterized in that, this polyfunctional compound is the polyfunctional compound with ethene unsaturated link.
9. black-colored resin composition as claimed in claim 8 is characterized in that, this polyfunctional compound can carry out polymerization with this alkali soluble resins.
10. black-colored resin composition as claimed in claim 1 is characterized in that, take the gross weight of this black-colored resin composition as benchmark, the content of this Photoepolymerizationinitiater initiater is 0.3wt% to 3wt%.
11. a black matix is formed by each described black-colored resin composition in the claim 1 to 10.
12. a light shield layer is formed by each described black-colored resin composition in the claim 1 to 10.
CN2012101163721A 2011-06-30 2012-04-17 Black resin composition, black matrix and light shielding layer Pending CN102854742A (en)

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