CN101162364B - Photosensitive resin composition and method of making the same and film build method - Google Patents
Photosensitive resin composition and method of making the same and film build method Download PDFInfo
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Abstract
The invention relates to a sensitive resin composite which is made of paint, light-cured resin, organic solvent, photoinitiator and dispersant, wherein, the weight percentage of the paint is from 4 to 15 percent, the weight percentage of the light-cured resin is from 8 to 40 percent, the weight percentage of the organic solvent is from 40 to 80 percent, the weight percentage of the photoinitiator is from 0.02 to 2.5 percent, and the weight percentage of the dispersant is from 0.5 to 15 percent. Based on this, the invention also provides the preparing method and film forming method of the sensitive resin composite. The sensitive resin composite of the invention has the advantages of high light sensitivity and high curing speed; a film made of the sensitive resin composite has the advantages of high thermal endurance and high alkali resistance, thereby enabling the sensitive resin composite of the invention to be directly used for preparing color screens used in the fields such as liquid crystal display, organic light emitting display (OLED) and etc.
Description
Technical field
The present invention relates to a kind of photosensitive resin composition and method of making the same and film build method, particularly relate to a kind of optical filter photosensitive resin composition and method of making the same and film build method.
Background technology
Colour liquid crystal display device is popularized rapidly in recent years, and people also improve constantly the requirement that the LCD color shows.Usually the structure of LCD is at colored filter substrate and thin film transistor (TFT) (ThinFilm Transistor, TFT) filling liquid crystal material in the gap of the 1-10 μ m of the opposed formation of substrate is sealed to form its periphery with encapsulants such as epoxy resin then.Wherein, colored filter is that LCD realizes one of critical component of full-color demonstration.The performance of colored filter is to the color display quality important influence of LCD.
Photosensitive resin is to utilize organic compound or polymkeric substance under light action, the chemical change (photolysis, photopolymerization or photo-crosslinking) of molecular structure takes place, cause that physical propertys such as its dissolving power in solvent, painted, sclerosis, adhesion change, thereby produce the photosensitive non-silver material of image.As a current class novel high polymer material of greatly developing and developing, photosensitive resin is a kind of important source material of preparation LCD colored filter.How to obtain that colorimetric performance is good, storage stability good, thermotolerance, photostability, resistance to chemical attack is strong and transmitance is high colored filter photosensitive resin composition are to prepare vital problem in the high performance color filter technology simultaneously.
Summary of the invention
The present invention's first purpose is to provide a kind of optical filter photosensitive resin composition, in order to colorimetric performance and the storage stability that improves this photosensitive resin composition.
The present invention's second purpose is to provide a kind of optical filter with photosensitive resin preparation of compositions method, makes that this preparation method of employing prepares photosensitive resin composition light sensitivity height, polymerization speed is fast, has good colorimetric performance and storage stability simultaneously.
The present invention's the 3rd purpose is to provide a kind of film build method of photosensitive resin composition, and in order to strengthen flatness, light transmission rate, thermotolerance and the chemical resistance of photosensitive resin rete, this film build method can directly apply among the preparation technology of colored filter.
In order to realize first purpose, first aspect present invention provides a kind of photosensitive resin composition, is formed by pigment, light-cured resin, organic solvent, light trigger and dispersant at least, and wherein, the percentage by weight of described pigment is 4%-15%; The percentage by weight of described light-cured resin is 8%-40%; The percentage by weight of described organic solvent is 40%-80%; The percentage by weight of described light trigger is 0.02-2.5%; The percentage by weight of described spreading agent is 0.5%-15%.Described light-cured resin is formed by oligomer, monomer, initiator and solvent, and wherein, the percentage by weight of described oligomer is 30%-90%; The percentage by weight of described monomer is 4%-65%; The percentage by weight of described initiator is 0.1%-6.5%; The percentage by weight of described solvent is 2%-45%.
The photosensitive resin composition that first aspect present invention provides has comprised the various ingredients of different proportionings, has improved the performance such as colorimetric performance, storage stability of this photosensitive resin preferably.
In order to realize second purpose, second aspect present invention provides a kind of photosensitive resin preparation of compositions method, comprising:
With percentage by weight is that the light-cured resin of 8%-40% and light trigger that percentage by weight is 0.02-2.5% mix the back to add 2/7ths percentage by weight be that the organic solvent of 40%-80% evenly mixes, and forms Photocurable composition;
With percentage by weight is after the spreading agent of 0.5%-15% and organic solvent that 5/7ths percentage by weight is 40%-80% mix, the adding percentage by weight is that the pigment of 4%-15% carries out dispersion treatment, forms the pigment dispersion of granularity less than 100nm;
Described pigment dispersion and Photocurable composition through stirring or shaking even mixing, are made described photosensitive resin composition.
The photosensitive resin preparation of compositions method that second aspect present invention provides, at first make light-cured resin by the prepolymerization operation, again by light modulated hardening composition and pigment dispersion, and the two is fully mixed, make light sensitivity height, the fast photosensitive resin composition of polymerization speed, the photosensitive resin composition that makes simultaneously has good colorimetric performance and storage stability.
In order to realize the 3rd purpose, third aspect present invention provides a kind of film build method of photosensitive resin composition, comprising:
Spin coating photosensitive resin composition on glass substrate forms the photosensitive resin rete;
With described photosensitive resin rete thermal treatment 3-5min under 50-120 ℃ of temperature;
With the photosensitive resin rete illumination after the thermal treatment is that the ultraviolet light of 100-250mJ/cm2 carries out exposure-processed 2-15s;
Adopt alkaline-based developer to carry out development treatment the photosensitive resin rete after the exposure-processed;
Photosensitive resin rete after the development treatment is toasted 30-60min under 200-250 ℃ of temperature, make optical filter photosensitive resin rete.
The film build method of the photosensitive resin composition that third aspect present invention provides, help improving the quality of forming film of photosensitive resin composition, to have strong, the anti-inflorescence corrosivity of thermotolerance strong for photosensitive resin rete by the preparation of this film build method simultaneously, particularly alkali resistance is strong, flatness good, the light transmission rate advantages of higher, by this film build method, this photosensitive resin composition can directly apply to the preparation of LCD, organic light emitting display field colored filters such as (OLED).
Description of drawings
Fig. 1 is the implementing procedure figure of photosensitive resin preparation method of composition of the present invention;
Fig. 2 is light-cured resin preparation method's of the present invention implementing procedure figure;
Fig. 3 is the implementing procedure figure of photosensitive resin composition film build method of the present invention.
Embodiment
Below by drawings and Examples, technical scheme of the present invention is described in further detail.
Photosensitive resin composition provided by the invention, its key component comprises pigment, light-cured resin, organic solvent, light trigger and spreading agent, is formed by said components mixing under certain preparation condition, reaction according to a certain ratio.The percentage by weight that each component accounts for the photosensitive resin composition respectively is: pigment 4%-15%; Light-cured resin 8%-40%; Organic solvent 40%-80%; Light trigger 0.02-2.5%; Spreading agent 0.5%-15%.In addition, also can add the adjuvant that percentage by weight is 0.01%-3%, in order to improve performances such as levelability of the present invention, stability, tack.
The pigment that the present invention selects for use can be the potpourri of a kind of red pigment or multiple red pigment, or the composition of red pigment and other coloured pigment, or the composition of other pigment such as yellow uitramarine and orange pigment.When only selecting for use red to prepare red photosensitive resin composition, the percentage by weight of the red photosensitive resin composition of each ingredients constitute is respectively in the red photosensitive resin composition: red 5%-15%; Light-cured resin 10%-35%; Organic solvent 55%-80%; Light trigger 0.05-2.0%; Spreading agent 1%-10%; Adjuvant 0.02%-2%.
The light-cured resin that the present invention adopts is fully being made after the reaction under the uniform temperature condition by oligomer, monomer, initiator and solvent, and wherein, the percentage by weight of each ingredients constitute light-cured resin is respectively: oligomer 30%-90%, monomer 4%-65%; Initiator 0.1%-6.5%; The percentage by weight of solvent is 2%-45%.
Above-mentioned pigment dispersing connects in the material at the macromolecular compound of different performance type, in the presence of solvent, will show specific colorability, glossiness, flowability and flocculating properties, these characteristics are not only relevant with molecular structure, the particle state of pigment, also relevant with organic solvent, the organic solvent of therefore should suit (acid, alkalescence or neutral) according to the characteristics selection polarity of pigment itself.
The light trigger that the present invention adopts can be radical photoinitiator or cationic photoinitiator, or the composition of above-mentioned light trigger, is used to make respective components of the present invention under the irradiation of ultraviolet light free radical polymerization and/or cationic polymerization can take place.
That the spreading agent that the present invention adopts is mainly used in is wetting, dispersion, deflocculation and stable dispersion, reduction viscosity etc.
Table 1: the composition and the reaction conditions table of 5 preferred embodiments of light-cured resin of the present invention
Table 1 is the composition and the reaction conditions table of 5 preferred embodiments of light-cured resin of the present invention.TMPTA is trimethylolpropane triacrylate in the table 1; SR 399 is two (gathering) pentaerythrite five acrylate; DPHA is the mixture of two (gathering) pentaerythrite six acrylate and two (gathering) pentaerythrite five acrylate; AMBN is AMBN; PM is propylene glycol monomethyl ether.The percentage by weight of each component is the percentage by weight of each ingredients constitute light-cured resin in the table 1.
Light-cured resin first embodiment
In the present embodiment, the key component of light-cured resin sees Table shown in embodiment in 1 " " row, and light-cured resin comprises that percentage by weight is that to be respectively 3.47% DPHA and percentage by weight be that 17.36% benzyl methacrylate potpourri (monomer), percentage by weight are that 1.05% AMBN (initiator) and percentage by weight are that 4 3.4% PM (solvent) mixes for 34.72% styrene and copolymer-maleic anhydride (oligomer), percentage by weight.
Light-cured resin second embodiment
In the present embodiment, the key component of light-cured resin sees Table shown in embodiment in 1 " two " row, and light-cured resin comprises that percentage by weight is that 30.03% styrene and copolymer-maleic anhydride, percentage by weight are that 3% TMPTA and percentage by weight are that to be respectively 4.5% DPHA and percentage by weight be that 15.02% benzyl methacrylate potpourri (monomer), percentage by weight are that 0.9% AMBN (initiator) and percentage by weight are that 37.5 4% PM (solvent) mixes for 9.01% SR399 potpourri (oligomer), percentage by weight.
Light-cured resin the 3rd embodiment
In the present embodiment, the key component of light-cured resin sees Table shown in embodiment in 1 " three " row, and light-cured resin comprises that percentage by weight is that 29.94% styrene and copolymer-maleic anhydride, percentage by weight are that 3.89% TMPTA and percentage by weight are that to be respectively 5.38% DPHA and percentage by weight be that 14.97% benzyl methacrylate potpourri (monomer), percentage by weight are that 0.9% AMBN (initiator) and percentage by weight are that 37.43% PM (solvent) mixes for 7.49% SR399 potpourri (oligomer), percentage by weight.
Light-cured resin the 4th embodiment
In the present embodiment, the key component of light-cured resin sees Table shown in embodiment in 1 " four " row, and light-cured resin comprises that percentage by weight is that 32.47% styrene and copolymer-maleic anhydride and percentage by weight are that to be respectively 1.62% DPHA and percentage by weight be that 16.23% benzyl methacrylate potpourri (monomer), percentage by weight are that 0.98% AMBN (initiator) and percentage by weight are that 40.58% PM (solvent) mixes for 8.12% SR 399 potpourris (oligomer), percentage by weight.
Light-cured resin the 5th embodiment
In the present embodiment, the key component of light-cured resin sees Table shown in embodiment in 1 " five " row, and light-cured resin comprises that percentage by weight is that 30.96% styrene and copolymer-maleic anhydride and percentage by weight are that to be respectively 1.55% DPHA and percentage by weight be that 15.48% benzyl methacrylate potpourri (monomer), percentage by weight are that 0.93% AMBN (initiator) and percentage by weight are that 38.7% PM (solvent) mixes for 12.38% SR399 potpourri (oligomer), percentage by weight.
Further, in above-mentioned each enforcement, oligomer also can be: the fragrant same clan or aliphatic category have the epoxy resin that contains a plurality of methylbenzene epoxide groups on the acid anhydrides of acid, hydroxyl of polyester acrylate, the hydroxyl of acrylate, styrene and copolymer-maleic anhydride, urethane acrylate, the hydroxyl of polyfunctionality or the main chain, or the composition of above-mentioned oligomer.Wherein above acrylate can be two (gathering) pentaerythrite five acrylate, the ethoxy-basic triacrylate of (15)-trihydroxy methyl third (alkane), propoxyl group suffering penta (alkane) ethyl glycol diacrylate or polyether acrylate, or the composition of aforesaid propylene acid esters.In addition, styrene and copolymer-maleic anhydride has a following general formula:
Wherein: R is alkyl aromatic ether, acrylate, methacrylate, allyl or hydroxyl; R1 is an aromatic radical, and the value of n1 is 1-5; The value of n2 is 1-20.The light-cured resin that employing has the styrene of this general formula and a copolymer-maleic anhydride preparation can obviously shorten the exposure imaging time of light-cured resin, improves the surface smoothness of light-cured resin film.The epoxy resin that adopts also can specifically comprise the phenol aldehyde type epoxy resin of following functional group:
Wherein, n represents the quantity of functional group's repetitive, and the span of n can be 0.1-6.The light-cured resin that employing has a phenol aldehyde type epoxy resin preparation of this functional group can obviously reduce the shrinkage ratio of light-cured resin film, improves the surface smoothness of light-cured resin film.
Monomer also can be: contain vinyl compound, maleimide, phthalimide or 2-hydroxyl-4-phthalimide, or above-mentioned monomer combination.
In above-mentioned each enforcement, initiator also can be: azoisobutyronitrile, ABVN, peroxidating two (2, the 4-dichloro-benzoyl), AMBN, diacetyl peroxide, dioctanoyl peroxide, dilauroyl peroxide, dicumyl peroxide, di-tert-butyl peroxide or di-isopropyl peroxydicarbonate, or the composition of above-mentioned initiator.
In above-mentioned each enforcement, available solvent also has acid flux material, as: formic acid, acetate or chloroform etc.; Basic solvent, as: ketone, ester, ether or some aromatic hydrocarbon solvent etc.; Neutral flux, as: aliphatic hydrocarbon, cycloalkane compound or some aromatic hydrocarbon solvent etc. specifically can be fatty alcohol, glycol ether, ethyl acetate, MEK, methyl isobutyl ketone, monomethyl ether glycol ester, gamma-butyrolacton, propionic acid-3-ether ethyl ester, butyl carbitol, butyl carbitol acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexane, dimethylbenzene, isopropyl alcohol.Wherein be preferably propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexane, butyl carbitol, butyl carbitol acetate or gamma-butyrolacton, or the potpourri of above-mentioned neutral flux.
Table 2 is the composition and the evaluation result table of 5 preferred embodiments of photosensitive resin composition of the present invention.The light-cured resin that comprises among the photosensitive resin composition embodiment one to five in the table 2, corresponding with above-mentioned light-cured resin embodiment one to five in the table 1 respectively.P.R.254 is the red that the product call number is P.R.254 in the table 2: two (rubigan)-1.4-diketone are coughed up and are coughed up; P.Y.147 is the yellow pigment that the product call number is P.Y.147: amino grace quinone Huang; EFKA4047 is the modified polyurethane polymeric dispersant that product type is EFKA4047; BYK-161 is the high molecular weight block copolymer solution spreading agent that contains the affine group of pigment that product type is BYK-161; PMA is propylene glycol methyl ether acetate; Ciba369 is 2-phenyl benzyl-2-dimethyl amine-1-(4-morpholine benzyl phenyl) butanone-1.The percentage by weight of each component is the percentage by weight of each ingredients constitute photosensitive resin composition in the table 2.
Table 2: the component and the evaluation result table of 5 preferred embodiments of photosensitive resin composition of the present invention
Photosensitive resin composition first embodiment
Present embodiment photosensitive resin composition key component sees Table shown in 2 " embodiment one " row, and the photosensitive resin composition is that 15.43% light-cured resin, percentage by weight are that 7.5% P.R.254 pigment, percentage by weight are that 1.93% EFKA4047 spreading agent, percentage by weight are that 75.01% PMA solvent, percentage by weight are that 0.1% Ciba 369 light triggers and percentage by weight are that 0.03% adjuvants such as wetting agent evenly mix by percentage by weight; Wherein, the light-cured resin in the present embodiment is first embodiment of above-mentioned light-cured resin.
Photosensitive resin composition second embodiment
Present embodiment photosensitive resin composition key component sees Table shown in 2 " embodiment two " row, and the photosensitive resin composition is that 17.3% light-cured resin, percentage by weight are that 4.67% P.R.254 and percentage by weight are that 2.6% P.Y.147 potpourri (pigment), percentage by weight are that 2.6% BYK-161 (spreading agent), percentage by weight are that 72.71% PMA solvent, percentage by weight are that 0.1% Ciba 369 and percentage by weight are that two dodecyl benzene salt compounded of iodine (light trigger) of 0.02% mix by percentage by weight; Wherein, the light-cured resin in the present embodiment is second embodiment of above-mentioned light-cured resin.Photosensitive resin composition the 3rd embodiment
Present embodiment photosensitive resin composition key component sees Table shown in 2 " embodiment three " row, and the photosensitive resin composition is that 17.2% light-cured resin, percentage by weight are that 7.73% P.R.254 (pigment), percentage by weight are that 2.83% EFKA4047 (spreading agent), percentage by weight are that 72.09% PMA solvent, percentage by weight are that 0.08% Ciba 369 and percentage by weight are that 0.02% two dodecyl benzene salt compounded of iodine (light trigger) potpourris and percentage by weight are that 0.05% adjuvants such as wetting agent evenly mix by percentage by weight; Wherein, the light-cured resin in the present embodiment is the 3rd embodiment of above-mentioned light-cured resin.
Photosensitive resin composition the 4th embodiment
Present embodiment photosensitive resin composition key component sees Table shown in 2 " embodiment four " row, and the photosensitive resin composition is that 16.36% light-cured resin, percentage by weight are that 7.44% P.Y.147 (pigment), percentage by weight are that 1.7% BYK-161 (spreading agent), percentage by weight are that 74.35% PMA solvent, percentage by weight are that 0.06% Ciba 369 and percentage by weight are that 0.06% two dodecyl benzene salt compounded of iodine (light trigger) potpourris and percentage by weight are that 0.0 3% adjuvants such as wetting agent evenly mix by percentage by weight; Wherein, the light-cured resin in the present embodiment is the 4th embodiment of above-mentioned light-cured resin.
Photosensitive resin composition the 5th embodiment
Present embodiment photosensitive resin composition key component sees Table shown in 2 " embodiment five " row, and the photosensitive resin composition is that 16.88% light-cured resin, percentage by weight are that 3.66% P.R.254 and percentage by weight are that 3.66% P.R.147 potpourri (pigment), percentage by weight are that 2.52% EFKA4047 (spreading agent), percentage by weight are that 73.18% PMA solvent, percentage by weight are that 0.08% Ciba 369 and percentage by weight are that two dodecyl benzene salt compounded of iodine (light trigger) of 0.02% evenly mix by percentage by weight.
Further, in above-mentioned each enforcement, the pigment that the present invention selects for use can be the potpourri of a kind of red pigment or multiple red pigment, or the composition of red pigment and other coloured pigment, or the composition of other pigment such as yellow uitramarine and orange pigment.
Red pigment also can be perylene pigment, quinacridine ketone pigment or pyrrolopyrrole class pigment, as: the product call number is reds such as P.R.122, P.R.123, P.R.177, P.R.179, P.R.190, P.R.202, P.R.210, P.R.224, P.R.254, P.R.255, P.R.264, P.R.270 or P.R.272.
Yellow uitramarine also can be azo type pigment, azo condensed type pigment or heterocyclic pigment, as: the product call number is yellow pigments such as P.Y.12, P.Y.1, P.Y.3, P.Y.13, P.Y.83, P.Y.93, P.Y.94, P.Y.95, P.Y.109, P.Y.126, P.Y.127, P.Y.138, P.Y.139, P.Y.147, P.Y.150 or P.Y.174.
The pigment of selecting for use also can be orange pigment, as: azo class pigment, pyrazolone pigment or diphenyl amine pigment, as: P.0.5, P.0.13, P.0.16, P.0.34, P.0.36, P.0.48, P.0.49, P.0.71 or P.0.73 the product call number for waiting orange pigment.
In the various embodiments described above, also can be according to selecting for use the available solvent of pigment own characteristic to also have:
Acid flux material, as: formic acid, acetate or chloroform etc.;
Basic solvent, as: ketone, ester, ether or some aromatic hydrocarbon solvent etc.;
Neutral flux, as: aliphatic hydrocarbon, cycloalkane compound or some aromatic hydrocarbon solvent etc. specifically can be fatty alcohol, glycol ether, ethyl acetate, MEK, methyl isobutyl ketone, monomethyl ether glycol ester, gamma-butyrolacton, propionic acid-3-ether ethyl ester, butyl carbitol, butyl carbitol acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexane, dimethylbenzene, isopropyl alcohol.Wherein be preferably propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexane, butyl carbitol, butyl carbitol acetate or gamma-butyrolacton, or the potpourri of above-mentioned neutral flux.
In the various embodiments described above, spreading agent also can be acylamide polymer, modification polyurethane polymkeric substance, contains the high-molecular block copolymer of close pigment group, polyether-modified dimethyl polysiloxane multipolymer, organic silicon surfactant, modified polyurethane or modified polyacrylate, or the composition of above-mentioned spreading agent.
In the various embodiments described above, film surface property when improving photosensitive resin composition film forming also can add a spot of wetting agent levelling agent and defoamer as required, as: organosiloxane wetting agent, fluorine-carbon modified polyacrylate or acrylic compounds levelling agent etc.; In addition, can also use as required and select for use one of them and combination in any thereof such as adhesion promoter, antioxidant, ultraviolet light absorber, anti flocculant, stabilizing agent as adjuvant, as:
Polymerization taking place when depositing for minimizing, improve the storage stability of resin, can select stabilizing agent for use, as p-dihydroxy-benzene, methoxyl p-cresol, 1,4-benzoquinone, p-tert-butyl catechol, 2,5-di-tert-butyl hydroquinone or 2,5-are to the dimethyl 1,4-benzoquinone, or the composition of aforementioned stable agent.
For the anchorage that increases film and glass surface can be selected adhesion promoter for use, as γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane, β-(3, the 4-7-oxa-bicyclo[4.1.0) ethyl trimethoxy silane, gamma-aminopropyl-triethoxy-silane, the chain alkyl trimethoxy silane, vinyltriethoxysilane, vinyltrimethoxy silane, γ-chloropropyl triethoxysilane, two-(the silica-based propyl group of γ-triethoxy) tetrasulfide, anilinomethyl triethoxysilane, N-β (aminoethyl)-γ-An Bingjisanjiayangjiguiwan, N-(β-aminoethyl)-gamma-aminopropyl-triethoxy-silane, N-β (aminoethyl)-γ-aminopropyl methyl dimethoxysilane, γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane, γ-(methacryloxypropyl) oxypropyl trimethyl silane, γ-Qiu Jibingjisanjiayangjiguiwan or γ-sulfydryl propyl-triethoxysilicane etc.
Commonly used in coloured system to the dialkylamino benzoic ether, the different monooctyl ester of (dimethylamino)-ethyl benzoate and p-(dimethylamino)-benzoic acid, they cooperate with BP (benzophenone) or ITX (2-isopropyl thioxanthone), not only can improve solidification rate greatly, can also remove oxygen effectively, thereby reduce the inhibition that overcomes oxygen, can improve the performance of photosensitive resin composition.
Second aspect present invention also provides a kind of photosensitive resin preparation of compositions method.Fig. 1 is the implementing procedure figure of photosensitive resin preparation method of composition of the present invention.As shown in Figure 1, photosensitive resin preparation method of composition of the present invention comprises:
Before step 11, also can comprise the step for preparing light-cured resin.Fig. 2 is light-cured resin preparation method's of the present invention implementing procedure figure.As shown in Figure 2, the preparation method of light-cured resin specifically can be:
In the technique scheme, step 102 also can be: with percentage by weight is that 30%-90% oligomer and percentage by weight are that the monomer of 4%-65% evenly mixes, the percentage by weight of adding 1/5th is the solvent of 2%-25%, preparation oligomer monomer mixture solution; Step 103 should be mutually: the percentage by weight with remaining 3/5ths is that the solvent of 2%-45% is positioned over refrigeration under 5 ℃ of-10 ℃ of environment; Oligomer epoxy resin mixed solution is placed thermostatic container and fully stirring; evenly be added dropwise to initiator solution at interval with Preset Time simultaneously; 20 ℃-120 ℃ temperature and be filled with nitrogen as the protection gas reaction conditions under; after 1.5h-16h fully reacted, disposable adding made light-cured resin through 8/10ths solvent of refrigeration.
Among the above-mentioned preparation method, with partial solvent after refrigerating in the disposable adding oligomer monomer mixture solution, help constant temperature of reaction is reduced to normal temperature rapidly, be convenient to control the reaction conditions of light-cured resin preparation, thereby improve the performance of light-cured resin.
Below, adopt above-mentioned preparation method, each weight percentages of components shown in each weight percentages of components shown in the associative list 1, corresponding preparation condition and the table 2 specifies the concrete preparation method of light-cured resin first embodiment of the present invention and photosensitive resin composition first embodiment of the present invention.Light-cured resin preparation method embodiment
The key component of light-cured resin first embodiment and reaction conditions see Table shown in embodiment in 1 " " row, and the preparation method is as follows:
With percentage by weight be 1.05% AIBN (initiator) to be dissolved in 1/5th percentage by weight be 43.4% propylene glycol monomethyl ether (solvent), preparation initiator solution; Be 34.72% styrene with percentage by weight with copolymer-maleic anhydride (oligomer) and percentage by weight be that 3.47% DPHA (monomer) evenly mixes, the percentage by weight of adding 1/5th is 43.4% propylene glycol monomethyl ether (solvent), preparation oligomer monomer mixture solution; Percentage by weight with remaining 3/5ths is that 43.4% propylene glycol monomethyl ether (solvent) places refrigeration under 5 ℃ of-10 ℃ of environment; Disposable interpolation oligomer monomer mixture solution in four-hole bottle, and four-hole bottle is placed on the magnetic stirring apparatus that steady temperature is 40 ℃ (temperature of reaction), adjust stirring rate oligomer monomer mixture and solvent are stirred; When stirring, evenly be added dropwise in the four-hole bottle initiator solution at a certain time interval; Keeping the temperature of magnetic stirring apparatus is 40 ℃, and after stirring 6 hours (reaction time), disposable adding is 43.4% propylene glycol monomethyl ether (solvent) through 3/5ths percentage by weight of refrigeration, makes light-cured resin first embodiment of the present invention after mixing.
Photosensitive resin preparation method of composition embodiment
After preparing light-cured resin first embodiment of the present invention, begin to prepare the photosensitive resin composition.The photosensitive resin composition first embodiment key component sees Table shown in 2 " embodiment one " row, and the preparation method is as follows:
With percentage by weight is that 15.43% light-cured resin and percentage by weight are that 0.1% Ciba 369 (light trigger) mixes the back to add 2/7ths percentage by weight be that 75.01% PMA (organic solvent) evenly mixes, and forms Photocurable composition; With percentage by weight is that 1.93% EFKA4047 (spreading agent) and 5/7ths percentage by weight is after 75.01% organic solvent mixes, add percentage by weight and be 7.5% P.R.254 (pigment) and carry out dispersion treatment, form the pigment dispersion of granularity less than 100nm; The photoresistance composition for preparing and pigment dispersion through stirring or shaking even mixing, are made first embodiment of photosensitive resin composition.
The preparation method of light-cured resin second to the 5th embodiment of the present invention is identical with the light-cured resin of the present invention and first embodiment, the preparation method of photosensitive resin composition second to the 5th embodiment of the present invention is identical with photosensitive resin composition first embodiment of the present invention, the corresponding weight percentages of components of each embodiment, temperature of reaction and reaction time can join shown in table 1 and the table 2, repeat no more.
Photosensitive resin composition of the present invention has colorimetric performance and storage stability preferably.Its preparation method at first makes light-cured resin by the prepolymerization operation, again by light modulated hardening composition and pigment dispersion, and the two is fully mixed, make light sensitivity height, the fast photosensitive resin composition of polymerization speed, the photosensitive resin composition that makes simultaneously has good colorimetric performance and storage stability.
Third aspect present invention also provides a kind of film build method of photosensitive resin composition.Fig. 3 is the implementing procedure figure of photosensitive resin composition film build method of the present invention.After preparing photosensitive resin composition first to the 5th embodiment of the present invention, estimate the film forming characteristics of photosensitive resin composition by preparing the photosensitive resin composition film, its film build method is specially as shown in Figure 3:
Step 25, the photosensitive resin rete after will developing toast 30-60min under 200-250 ℃ of temperature, make optical filter photosensitive resin rete.
The above-mentioned film build method of foundation prepares the photosensitive resin rete of above-mentioned first to the 5th photosensitive resin composition embodiment of the present invention respectively, and estimates 5 corresponding film forming characteristicss of embodiment of the present invention from 4 aspects such as thermotolerance, alkali resistance, the neat degree in edge and surface smoothness.Represent opinion rating with A, B and C Three Estate respectively in the table 2.
Evaluation of result 1, thermotolerance
To under the wave band of 380nm-680nm, test corresponding transmitance based on the photosensitive resin rete of 5 preferred embodiments of the present invention, after the test with the thermal treatment 60 minutes in 250 ℃ constant temperature oven of these photosensitive resin retes, under same wave band 380nm-680nm, test its transmitance again after the taking-up, the transmitance of contrast photosensitive resin rete before and after bakingout process.In the thermotolerance evaluation result, heat resistance rating is divided into A, B and C Three Estate, wherein, thermotolerance A, B and C level represent respectively the transmitance of photosensitive resin rete before and after the thermal treatment change be not more than 5%, transmitance changes and changes greater than 10% in 5%-10%, transmitance.
Be the A level from the photosensitive resin rete thermotolerance of 5 preferred embodiments of the present invention shown in the table 2, that is: the transmitance variation is less than or equal to 5% before and after its thermal treatment, shows that the embodiment of the invention has very high thermotolerance.
Evaluation of result 2, alkali resistance
To under the wave band of 380nm-680nm, test corresponding transmitance based on the photosensitive resin rete of 5 preferred embodiments of the present invention, alkali treatment is 30 minutes in after the test these photosensitive resin retes being immersed concentration and be in 1% the NaOH solution, its transmitance of test under same wave band again after the taking-up.In the alkali resistance evaluation result, the alkali resistance grade is divided into A, B and C Three Estate, wherein, alkali resistance A, B and C level represent respectively the transmitance of photosensitive resin rete before and after the alkali treatment change be not more than 5%, transmitance changes and changes greater than 10% in 5%-10%, transmitance.
Be the A level from the photosensitive resin rete alkali resistance of the present invention shown in the table 2 second and third and four embodiment, the photosensitive resin rete alkali resistance of the present invention first and five embodiment is the B level, shows embodiment of the invention alkali resistance height.
Evaluation of result 3, the neat degree in edge
Whether will examine under a microscope based on the photosensitive resin rete of 5 preferred embodiments of the present invention, it is neat to observe the edge.In the neat degree evaluation result in edge, the neat degree grade in edge is divided into A, B and C Three Estate, and wherein, edge neat degree A, B and C level are represented neat in edge, a little residue of marginal existence, the more residue of marginal existence respectively.
Be the A level from the neat degree in photosensitive resin rete edge of the present invention shown in the table 2 second and third and four embodiment, the neat degree in photosensitive resin rete edge of first embodiment of the invention is the B level, shows that the neat degree in edge is better in the embodiment of the invention film forming characteristics.
Evaluation of result 4, surface smoothness
Whether will examine under a microscope based on the photosensitive resin rete of 5 preferred embodiments of the present invention, it is smooth to observe the surface.In the surface smoothness evaluation result, the surface smoothness grade is divided into A, B and C Three Estate, and wherein, presentation surface is smooth respectively, the surface is more smooth but local out-of-flatness, surface exist texture or bubble for surface smoothness A, B and C level.
Be the A level from the neat degree in photosensitive resin rete edge of the present invention shown in the table 2 first and third and four embodiment, show that surface smoothness is better in the embodiment of the invention film forming characteristics.
The film build method of photosensitive resin composition provided by the invention, help improving the quality of forming film of photosensitive resin composition, photosensitive resin rete by the preparation of this film build method has that thermotolerance is strong, alkali resistance is strong, flatness is good, the light transmission rate advantages of higher simultaneously, by this film build method, this photosensitive resin composition can directly apply to the preparation of LCD, organic light emitting display field colored filters such as (OLED).
It should be noted that at last: above embodiment only in order to technical scheme of the present invention to be described, is not intended to limit; Although with reference to previous embodiment the present invention is had been described in detail, those of ordinary skill in the art is to be understood that: it still can be made amendment to the technical scheme that previous embodiment is put down in writing, and perhaps part technical characterictic wherein is equal to replacement; And these modifications or replacement do not make the essence of appropriate technical solution break away from the spirit and scope of embodiment of the invention technical scheme.
Claims (11)
1. a photosensitive resin composition is characterized in that, is formed by pigment, light-cured resin, organic solvent, light trigger and dispersant at least, and wherein, the percentage by weight of described pigment is 4%-15%; The percentage by weight of described light-cured resin is 8%-40%; The percentage by weight of described organic solvent is 40%-80%; The percentage by weight of described light trigger is 0.02-2.5%; The percentage by weight of described spreading agent is 0.5%-15%;
Described light-cured resin is formed by oligomer, monomer, initiator and solvent, and wherein, the percentage by weight of described oligomer is 30%-90%; The percentage by weight of described monomer is 4%-65%; The percentage by weight of described initiator is 0.1%-6.5%; The percentage by weight of described solvent is 2%-45%;
Described oligomer is styrene and the copolymer-maleic anhydride with following general formula:
Wherein: R is alkyl aromatic ether, acrylate, methacrylate, allyl or hydroxyl; R1 is an aromatic radical, and the value of nl is 1-5; The value of n2 is 1-20.
2. photosensitive resin composition according to claim 1 is characterized in that, described monomer is maleimide, phthalimide or 2-hydroxyl-4-phthalimide, or the combination of above-mentioned monomer.
3. photosensitive resin composition according to claim 1 is characterized in that, described pigment is red pigment, yellow uitramarine or orange pigment, or the combination of above-mentioned pigment.
4. photosensitive resin composition according to claim 1 is characterized in that, described light trigger is acetophenone system, acylphosphine oxide, fragrant ketone, aromatic sulfonium salts, salt compounded of iodine or luxuriant molysite, or the combination of above-mentioned light trigger.
5. according to the described arbitrary photosensitive resin composition of claim 1-4, it is characterized in that, comprise that also percentage by weight is the adjuvant of 0.01%-3%.
6. according to the described arbitrary photosensitive resin composition of claim 1-4, it is characterized in that described pigment is weight percentage and is the red pigment of 5%-15%; The percentage by weight of described light-cured resin is 10%-35%; The percentage by weight of described organic solvent is 55%-80%; The percentage by weight of described light trigger is 0.05-2.0%; The percentage by weight of described spreading agent is 1%-10%.
7. photosensitive resin composition according to claim 6 is characterized in that, comprises that also percentage by weight is the adjuvant of 0.02%-2%.
8. the described photosensitive resin preparation of compositions of claim 1 method is characterized in that, comprising:
With percentage by weight is that the light-cured resin of 8%-40% and light trigger that percentage by weight is 0.02-2.5% mix the back to add 2/7ths percentage by weight be that the organic solvent of 40%-80% evenly mixes, and forms Photocurable composition;
With percentage by weight is after the spreading agent of 0.5%-15% and organic solvent that 5/7ths percentage by weight is 40%-80% mix, the adding percentage by weight is that the pigment of 4%-15% carries out dispersion treatment, forms the pigment dispersion of granularity less than 100nm;
Described pigment dispersion and Photocurable composition through stirring or shaking even mixing, are made described photosensitive resin composition.
9. photosensitive resin preparation of compositions method according to claim 8, it is characterized in that, described is that the light-cured resin of 8%-40% and light trigger that percentage by weight is 0.02-2.5% mix the back to add percentage by weight be that the organic solvent of 40%-80% evenly mixes with percentage by weight, also comprise the step for preparing light-cured resin before forming Photocurable composition, be specially:
With percentage by weight be the initiator of 0.1%-6.5% to be dissolved in 1/5th percentage by weight be the solvent of 2%-45%, preparation initiator solution;
With percentage by weight is that 30%-90% oligomer and percentage by weight are that the monomer of 4%-65% evenly mixes, and adding 4/5ths percentage by weight is the solvent of 2%-45%, preparation oligomer monomer mixture solution;
Described initiator solution evenly is added dropwise in the described oligomer monomer mixture solution at interval with Preset Time, 20 ℃-120 ℃ temperature and be filled with under the reaction conditions of nitrogen as protection gas, after 1.5h-16h fully reacts, makes described light-cured resin.
10. photosensitive resin preparation of compositions method according to claim 8 is characterized in that, prepares described light-cured resin and is:
With percentage by weight be the initiator of 0.1%-1.5% to be dissolved in 1/5th percentage by weight be the solvent of 2%-45%, preparation initiator solution;
With percentage by weight is that 30%-90% oligomer and percentage by weight are that the monomer of 4%-65% evenly mixes, and adding 1/5th percentage by weight is the solvent of 2%-45%, preparation oligomer monomer mixture solution;
Percentage by weight with remaining 3/5ths be the solvent of 2%-45% be positioned over temperature be under 5 ℃ of-10 ℃ of environment refrigeration;
Described initiator solution evenly is added dropwise in the described oligomer monomer mixture solution at interval with Preset Time; 20 ℃-120 ℃ temperature and be filled with nitrogen as the protection gas reaction conditions under; after 1.5h-16h fully reacts; disposable adding is through 3/5ths described solvent of refrigeration, by mixed the described light-cured resin that stirs.
11. the film build method of the described photosensitive resin composition of claim 1 is characterized in that,
Comprise:
Spin coating photosensitive resin composition on glass substrate forms the photosensitive resin rete;
With described photosensitive resin rete thermal treatment 3-5min under 50-120 ℃ of temperature;
With the photosensitive resin rete illumination after the thermal treatment is that the ultraviolet light of 100-250mJ/cm2 carries out exposure-processed 2-15s;
Adopt alkaline-based developer to carry out development treatment the photosensitive resin rete after the exposure-processed;
Photosensitive resin rete after the development treatment is toasted 30-60min under 200-250 ℃ of temperature, make optical filter photosensitive resin rete.
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| CN101760042B (en) * | 2008-12-24 | 2013-03-27 | 京东方科技集团股份有限公司 | Pigment dispersion method, pigment mixture, light-cured ink and thermo-cured ink |
| CN102653646B (en) | 2011-06-09 | 2014-08-06 | 京东方科技集团股份有限公司 | Ink used for color filter, and preparation methods of ink and color filter |
| CN102675514B (en) | 2011-07-12 | 2014-04-16 | 京东方科技集团股份有限公司 | Preparation method of aqueous nano-pigment dispersion liquid |
| WO2014021264A1 (en) * | 2012-07-30 | 2014-02-06 | 電気化学工業株式会社 | Copolymer for improving methacrylic resin heat resistance |
| CN103616800B (en) * | 2013-10-21 | 2016-08-10 | 溧阳市东大技术转移中心有限公司 | Photo-curing resin combination |
| CN103607837A (en) * | 2013-10-21 | 2014-02-26 | 溧阳市东大技术转移中心有限公司 | Printed circuit board structure |
| CN103631091B (en) * | 2013-10-22 | 2016-08-17 | 溧阳市东大技术转移中心有限公司 | The preparation method of photo-curing resin combination |
| CN103529647B (en) * | 2013-10-24 | 2017-02-08 | 京东方科技集团股份有限公司 | Photoresist composition, colorful film base plate and display device |
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