CN102650827A - Photosensitive resin composition and liquid crystal display applying same - Google Patents
Photosensitive resin composition and liquid crystal display applying same Download PDFInfo
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Abstract
The invention discloses a photosensitive resin composition and a liquid crystal display applying the same, relating to the field of manufacturing of the liquid crystal display and solving the problem that the display performance of the liquid crystal display is affected due to the poor surface smoothness and adhesion force of an existing photosensitive resin composition. According to the photosensitive resin composition provided by the embodiment of the invention, the adhesion property of the composition is promoted because 0.005%-10% of adhesion promoter is adopted and is the combination of a silane coupling agent and an acid ester adhesion promoter, and the surface smoothness of the composition is improved because 0.01%-2.5% of wetting and leveling agent is adopted. Meanwhile, the photosensitive resin composition provided by the embodiment of the invention has the advantages of high photosensitiveness, good film uniformity and excellent mechanical properties and the like, and is mainly used for manufacturing liquid crystal display.
Description
Technical field
The present invention relates to the manufacturing field of LCD, relate in particular to the photosensitive resin composition and use its LCD.
Background technology
The structure of LCD is at colored filter substrate and thin film transistor (TFT) (Thin Film Transistor; TFT) filling liquid crystal material in the gap of the 1-10 μ m of the opposed formation of substrate; With encapsulants such as epoxy resin its periphery is sealed to form then, so the homogeneity of cel-gap also is one of important performance that influences by LCD.For guaranteeing the homogeneity of cel-gap, normally in cel-gap, lay chock insulator matter (Spacer).The material for preparing chock insulator matter is in recent years developed to the photosensitive resin composition by glass, plastics gradually.
In addition, along with popularizing rapidly of colour liquid crystal display device, people also improve constantly the requirement that the LCD color shows.When people pursued high color reprodubility and contrast, the visible angle of liquid crystal display also became the Key Performance Indicator that people select LCD.For improving the visible angle of LCD; Main at present IPS (the In-Plane Switching that adopts; Plane conversion), FFS (Fringe Field Switching, fringe field switching technology) and MVA (Multi-Domain Vertical Alignment, pixel segmentation vertical orientation) technology; Wherein, In the MVA technology, need on panel, form protrusion, it makes the liquid crystal molecule at same pixel region obtain a plurality of directions of orientation as the region limits device, thereby improves the visible angle of LCD.At present, the material of preparation protrusion adopts the photosensitive resin composition more.
In the process of above-mentioned chock insulator matter of usability photopolymer resin preparation of compositions and protrusion, the inventor finds that the surface smoothness and the adhesion of existing photosensitive resin composition is relatively poor, thereby has influenced the display performance of LCD.
Summary of the invention
Embodiments of the invention provide a kind of photosensitive resin composition and use its LCD, and this photosensitive resin composition has surface smoothness and adhesion preferably.
For achieving the above object, embodiments of the invention adopt following technical scheme:
A kind of photosensitive resin composition comprises: alkali soluble resin, percentage by weight are 8%～45%; Ethylene unsaturated monomer, percentage by weight are 5%～30%; Light trigger, percentage by weight are 0.05%～3.5%; Adhesion promoter is the combination of silane coupling agent and acid ester class adhesion promoter, and the percentage by weight of said adhesion promoter is 0.005%～10%; Solvent, percentage by weight are 15%～75%; Moistening flatting agent, percentage by weight are 0.01%～2.5%; Adjuvant, percentage by weight are 0%～10%.
A kind of LCD comprises the assembly of being processed by above-mentioned photosensitive resin composition.
The photosensitive resin composition that the embodiment of the invention provides and using in its LCD; Because having adopted percentage by weight is 0.005%～10% adhesion promoter; And this adhesion promoter is the combination of silane coupling agent and acid ester class adhesion promoter, makes the adhesion performance of said composition obtain to promote; Because having adopted percentage by weight is 0.01%～2.5% moistening flatting agent, make the surface smoothness performance of said composition obtain to promote.
Description of drawings
In order to be illustrated more clearly in the embodiment of the invention or technical scheme of the prior art; To do to introduce simply to the accompanying drawing of required use in embodiment or the description of the Prior Art below; Obviously, the accompanying drawing in describing below only is some embodiments of the present invention, for those of ordinary skills; Under the prerequisite of not paying creative work property, can also obtain other accompanying drawing according to these accompanying drawings.
Fig. 1 is each composition and percentage by weight tabulation in the photosensitive resin composition of the embodiment of the invention.
Embodiment
Embodiments of the invention provide a kind of photosensitive resin composition, comprising: alkali soluble resin, percentage by weight are 8%～45%; Ethylene unsaturated monomer, percentage by weight are 5%～30%; Light trigger, percentage by weight are 0.05%～3.5%; Adhesion promoter is the combination of silane coupling agent and acid ester class adhesion promoter, and the percentage by weight of said adhesion promoter is 0.005%～10%; Solvent, percentage by weight are 15%～75%; Moistening flatting agent, percentage by weight are 0.01%～2.5%; Adjuvant, percentage by weight are 0%～10%.
Embodiments of the invention provide a kind of LCD again, comprise the assembly of being processed by above-mentioned photosensitive resin composition.
The photosensitive resin composition that the embodiment of the invention provides and using in its LCD; Because having adopted percentage by weight is 0.005%～10% adhesion promoter; And this adhesion promoter is the combination of silane coupling agent and acid ester class adhesion promoter, makes the adhesion performance of said composition obtain to promote; Because having adopted percentage by weight is 0.01%～2.5% moistening flatting agent, make the surface smoothness performance of said composition obtain to promote.
To combine the accompanying drawing in the embodiment of the invention below, the technical scheme in the embodiment of the invention is carried out clear, intactly description, obviously, described embodiment only is the present invention's part embodiment, rather than whole embodiment.Based on the embodiment among the present invention, those of ordinary skills are not making the every other embodiment that is obtained under the creative work prerequisite, all belong to the scope of the present invention's protection.
The composition and the percentage by weight of the photosensitive resin composition of the embodiment of the invention are as shown in Figure 1, comprising: alkali soluble resin A, percentage by weight are 8%～45%; Ethylene unsaturated monomer, percentage by weight are 5%～30%; Light trigger, percentage by weight are 0.05%～3.5%; Adhesion promoter is the combination of silane coupling agent and acid ester class adhesion promoter, and the percentage by weight of said adhesion promoter is 0.005～10%; Solvent, percentage by weight are 15%～75%; Moistening flatting agent, percentage by weight are 0.01%～2.5%; Adjuvant, percentage by weight are 0～10%, and this photosensitive resin composition has characteristics such as light sensitivity height, filming performance be good.
Wherein, the percentage by weight of alkali soluble resin is preferably 8%～40%; The percentage by weight of ethylene unsaturated monomer is preferably 5%～28%; The percentage by weight of light trigger is preferably 0.05%～3.0%; The percentage by weight of adhesion promoter is preferably 3%～7%; The percentage by weight of solvent is preferably 15%～70%; The percentage by weight of adjuvant is preferably 0.01%～10%.
Above-mentioned photosensitive resin composition can be acid number at 100mg KOH/g～350mg KOH/g aromatic acid (methyl) acrylic acid half ester, also can be acid number at 20mg KOH/g～350mg KOH/g and have the resin of following general formula or have the composition of the resin of following general formula:
Wherein, X is methyl or hydrogen atom; R
2Be alkyl or alkoxy.
Above-mentioned ethylene unsaturated monomer is to contain in the epoxy resin of a plurality of methylbenzene epoxide groups any one on acid anhydrides and the main chain of acid, hydroxyl of polyester acrylate, maleimide, phthalimide, 2-hydroxyl-4-phthalimide, the hydroxyl of aliphatic urethane acrylate, polyether acrylate, acrylic ester, hydroxyl, or is two or more combinations.
Above-mentioned light trigger can be selected radical photoinitiator or cationic photoinitiator for use; The perhaps combination of radical photoinitiator and cationic photoinitiator is used to make respective components under the irradiation of ultraviolet light, Raolical polymerizable and/or cationic polymerization can take place.Light trigger can be oxime ester lightlike initiating agent, like Ciba OXE 01, CGI 242, Ciba OXE 02 etc.; Also can be α-amido ketone light trigger, as 369,379,907 etc.; Can also be acylphosphine oxide, acetophenone system is to contain morpholine tertiary amine base and thioether group in the photoinitiator molecules like the sulfur-bearing acetophenone, has the collaborative effect that causes with the compound use of thioxanthone; Light trigger can also be for carrying the Hydrogen initiating agent, as: fragrant ketone, for example: 2-phenyl benzyl-2-dimethyl amine-1-(4-morpholine benzyl phenyl) butanone, benzophenone and derivant thereof, methyl o-benzoylbenzoate, thioxanthone etc.; Light trigger also can be selected small molecule salt photoinitiator or luxuriant molysite photoinitiator for use.Above-mentioned available light trigger can use separately, also can mix the back use by different types of light trigger.
Above-mentioned adhesion promoter is the combination of silane coupling agent and acid ester class adhesion promoter.Wherein, but acid ester class adhesion promoter can be selected acid esters such as acid single functionality acrylic ester, acid polyfunctional acrylic ester, acid polyester acrylate, acid acrylate, acidic methylene acrylic ester copolymerization phosphate, epoxy phosphate ester, acrylic acid-hydroxy methacrylate for use.
Above-mentioned solvent can be acid flux material, basic solvent or neutral flux.Wherein, acid flux material can be selected for use: formic acid, acetate, chloroform etc.; Basic solvent can be selected for use: ketone, ester, ether, aromatic hydrocarbon etc.; Neutral flux can be selected for use: aliphatic hydrocarbon, cycloalkane compound, aromatic hydrocarbon etc.Solvent 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, BC, BC acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, xylene, isopropyl alcohol or normal butyl alcohol.Solvent one of is preferably in propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexane, BC, propionic acid-3-ether ethyl ester, BC acetate and the gamma-butyrolacton or two or more combinations.Solvent can be alkane, alkene, alkynes, aldehyde, ketone, ether, ester etc., also can be aromatics, like benzene,toluene,xylene etc., can also be epoxy compound, aromatic hydrocarbons, halogenated hydrocarbons, aliphatic hydrocarbon, silane, siloxane etc.
Above-mentioned moistening flatting agent is the conventional type surfactant, perhaps is response type surfactant active, perhaps is the combination of conventional type surfactant and response type surfactant active.Wherein, the conventional type surfactant comprises conventional type silicone based surperficial auxiliary agent and fluorine class surface auxiliary agent, and silicone based surperficial auxiliary agent comprises diphenyl polysiloxane, methyl phenyl silicone, organically-modified siloxane, fluorinated siloxane etc.The conventional type surfactant specifically can be the fluorine carbon moistening flatting agent of fluorine silicon anionic.Fluorine class surface auxiliary agent comprises: fluorine carbon moistening flatting agent FSWET-1010; The nonionic fluorinated surfactant is like: Megaface470,475,477,550,554 etc.Being defined as of response type surfactant active: add this activating agent and coating surface material generation chemical reaction behind such surfactant, thereby play the effect of levelling.
Above-mentioned adjuvant is foam-breaking agent, light stabilizer, antioxidant etc., can add wherein one or more.
Below through the composition of specific embodiment explanation photosensitive resin composition and the evaluation of result of adhesion and surface smoothness thereof.
Embodiment 1
The percentage by weight of each component of photosensitive resin composition of present embodiment is seen the row of embodiment one correspondence in the table 1, is specially: alkali soluble resin, 17%; Ethylene unsaturated monomer, 8%; Light trigger, 0.3%; Adhesion promoter, 0.08%; Solvent, 74.59%; Moistening flatting agent, 0.01%; Adjuvant, 0.02%.
Embodiment 2
The percentage by weight of each component of photosensitive resin composition of present embodiment is seen the row of embodiment two correspondences in the table 1, is specially: alkali soluble resin, 14%; Ethylene unsaturated monomer, 8%; Light trigger, 0.8%; Adhesion promoter, 3.07%; Solvent, 73.98%; Moistening flatting agent, 0.13%; Adjuvant, 0.02%.
Embodiment 3
The percentage by weight of each component of photosensitive resin composition of present embodiment is seen the row of embodiment three correspondences in the table 1, is specially: alkali soluble resin, 20%; Ethylene unsaturated monomer, 12%; Light trigger, 1.2%; Adhesion promoter, 3%; Solvent, 63.42%; Moistening flatting agent, 0.3%; Adjuvant, 0.08%.
Embodiment 4
The percentage by weight of each component of photosensitive resin composition of present embodiment is seen the row of embodiment four correspondences in the table 1, is specially: alkali soluble resin, 20%; Ethylene unsaturated monomer, 15%; Light trigger, 1.5%; Adhesion promoter, 5.1%; Solvent, 55.45%; Moistening flatting agent, 2.8%; Adjuvant, 0.15%.
The percentage by weight of each component of photosensitive resin composition of present embodiment is seen the row of embodiment five correspondences in the table 1, is specially: alkali soluble resin, 35%; Ethylene unsaturated monomer, 22%; Light trigger, 2%; Adhesion promoter, 6.05%; Solvent, 31.75%; Moistening flatting agent, 2.2%; Adjuvant, 1%.
Embodiment 6
The percentage by weight of each component of photosensitive resin composition of present embodiment is seen the row of embodiment six correspondences in the table 1, is specially: alkali soluble resin, 40%; Ethylene unsaturated monomer, 25%; Light trigger, 2.2%; Adhesion promoter, 8.08%; Solvent, 20.32%; Moistening flatting agent, 2.2%; Adjuvant, 2.2%.
Embodiment 7
The percentage by weight of each component of photosensitive resin composition of present embodiment is seen the row of embodiment seven correspondences in the table 1, is specially: alkali soluble resin, 40%; Ethylene unsaturated monomer, 24%; Light trigger, 2.5%; Adhesion promoter, 8.08%; Solvent, 18.72%; Moistening flatting agent, 2.4%; Adjuvant, 4.3%.
The percentage by weight of each component of photosensitive resin composition of present embodiment is seen the row of embodiment eight correspondences in the table 1, is specially: alkali soluble resin, 45%; Ethylene unsaturated monomer, 30%; Light trigger, 3%; Adhesion promoter, 10%; Solvent, 4.5%; Moistening flatting agent, 2.5%; Adjuvant, 5%.
Embodiment 9
The percentage by weight of each component of photosensitive resin composition of present embodiment is seen the row of embodiment nine correspondences in the table 1, is specially: alkali soluble resin, 35%; Ethylene unsaturated monomer, 22%; Light trigger, 2%; Adhesion promoter, 13%; Solvent, 18%; Moistening flatting agent, 3.2%; Adjuvant, 6.8%.
The percentage by weight of each component of photosensitive resin composition of present embodiment is seen the row of embodiment ten correspondences in the table 1, is specially: alkali soluble resin, 7.5%; Ethylene unsaturated monomer, 4.5%; Light trigger, 0.054%; Adhesion promoter, 1.6%; Solvent, 78.14%; Moistening flatting agent, 0.006%; Adjuvant, 8.2%.
Table 1
Wherein, ACAZ200 in the table 1 and SB 401 are alkali soluble resin, and EBE 1290N is an ethylene unsaturated monomer; Irgacure 379 is a light trigger; A-186 is the silane coupling agent, and CD9051 is acid lipid adhesion promoter, and PMA is a solvent; Tego Glide 432 is the conventional type surfactant, and MegafaceRS-75 is a response type surfactant active.
Last two row of table 1 are to the surface smoothness of each embodiment of photosensitive resin composition and the evaluation of result of adhesion, and wherein, " △ " ecbatic is identical with prior art, and " zero " ecbatic is superior to prior art, and " * " ecbatic is than prior art difference.
From table 1, can know: among the embodiment 9, because the percentage by weight of adhesion promoter is 13%, the percentage by weight of moistening flatting agent is 3.2%, has all surpassed specified scope, makes surface smoothness and adhesion performance variation; Among the embodiment 10,, be lower than specified scope, and the percentage by weight of adhesion promoter is 1.6%, belongs in the specified scope, make the surface smoothness degradation, and adhesion performance is excellent because the percentage by weight of moistening flatting agent is 0.006%; Among the embodiment 4,, surpassed specified scope, so the surface smoothness performance is identical with prior art, does not obtain to promote because the percentage by weight of moistening flatting agent is 2.8%.
Among the embodiment 1,3,8; Though the percentage by weight of adhesion promoter all belongs in the specified scope; But owing to only adopted a kind of adhesion promoter (silane coupling A-186 or acid ester class adhesion promoter CD9051); Make adhesion performance identical, do not obtain to promote with prior art.
Other embodiment is because adopted the moistening flatting agent in the specified weight percentage ranges; Adopted simultaneously in the specified weight percentage ranges, by the adhesion promoter that combines of silane coupling agent and acid ester class adhesion promoter, and make surface smoothness and adhesion performance acquisition lifting.
The embodiment of the invention is added in the photosensitive resin composition through the composition with silane coupling agent (A-186 in the table 1) and acid ester class adhesion promoter (CD9051 in the table 1), has significantly improved the adhesion (seeing embodiment 2,4,5,6,7,10) between photosensitive resin composition and other interlayers and substrate.
In addition; The embodiment of the invention preferably adopts the moistening flatting agent that comprises conventional type surfactant (the Tego Glide432 in the table 1) and response type surfactant active (the Megaface RS-75 in the table 1); Thus; Significantly improve the wetting flow leveling of coating surface, thereby made the coating surface flatness obtain remarkable improvement the (seeing embodiment 3,5,6,7,8).
The embodiment of the invention also provides a kind of LCD, comprises the assembly of being processed by above-mentioned photosensitive resin composition.This assembly can be the chock insulator matter of laying in the cel-gap, perhaps for the panel raising thing of the visible angle that is used to improve LCD, also can be optical filter, and this assembly has the surface smoothness and the adhesion of improvement.
Advantages such as the photosensitive resin composition that the embodiment of the invention provides has also that light sensitivity height, film uniformity are good, mechanical property and good mechanical performance.
The embodiment of the invention is mainly used in the manufacturing LCD.
The above; Be merely embodiment of the present invention, but protection scope of the present invention is not limited thereto, any technician who is familiar with the present technique field is in the technical scope that the present invention discloses; The variation that can expect easily or replacement all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of said claim.
Claims (15)
1. a photosensitive resin composition is characterized in that, comprising:
Alkali soluble resin, percentage by weight are 8%～45%;
Ethylene unsaturated monomer, percentage by weight are 5%～30%;
Light trigger, percentage by weight are 0.05%～3.5%;
Adhesion promoter is the combination of silane coupling agent and acid ester class adhesion promoter, and the percentage by weight of said adhesion promoter is 0.005%～10%;
Solvent, percentage by weight are 15%～75%;
Moistening flatting agent, percentage by weight are 0.01%～2.5%;
Adjuvant, percentage by weight are 0%～10%.
2. photosensitive resin composition according to claim 1 is characterized in that, the percentage by weight of said alkali soluble resin is 8%～40%.
3. photosensitive resin composition according to claim 1 and 2; It is characterized in that; Said alkali soluble resin is aromatic acid (methyl) the acrylic acid half ester of acid number at 100mg KOH/g～350mg KOH/g, perhaps for acid number at 20mg KOH/g～350mg KOH/g, have the resin of following general formula or have the composition of the resin of following general formula:
Wherein, X is methyl or hydrogen atom; R
2Be alkyl or alkoxy.
4. photosensitive resin composition according to claim 1 is characterized in that, the percentage by weight of said ethylene unsaturated monomer is 5%～28%.
5. according to claim 1 or 4 described photosensitive resin compositions; It is characterized in that; Said ethylene unsaturated monomer is to contain in the epoxy resin of a plurality of methylbenzene epoxide groups any one on acid anhydrides and the main chain of acid, hydroxyl of polyester acrylate, maleimide, phthalimide, 2-hydroxyl-4-phthalimide, the hydroxyl of aliphatic urethane acrylate, polyether acrylate, acrylic ester, hydroxyl, perhaps is two or more combinations.
6. photosensitive resin composition according to claim 1 is characterized in that, the percentage by weight of said light trigger is 0.05%～3.0%.
7. according to claim 1 or 6 described photosensitive resin compositions, it is characterized in that said light trigger is radical photoinitiator, cationic photoinitiator, or the combination of radical photoinitiator and cationic photoinitiator.
8. photosensitive resin composition according to claim 1 is characterized in that, the percentage by weight of said adhesion promoter is 3%～7%.
9. according to claim 1 or 8 described photosensitive resin compositions; It is characterized in that, but said acid ester class adhesion promoter is in acid single functionality acrylic ester, acid polyfunctional acrylic ester, acid polyester acrylate, acid acrylate, acidic methylene acrylic ester copolymerization phosphate, epoxy phosphate ester, the acrylic acid-hydroxy methacrylate any one.
10. photosensitive resin composition according to claim 1 is characterized in that, said moistening flatting agent is the conventional type surfactant, perhaps is response type surfactant active, perhaps is the combination of conventional type surfactant and response type surfactant active.
11. photosensitive resin composition according to claim 1 is characterized in that, the percentage by weight of said solvent is 15%～70%.
12., it is characterized in that said solvent is ketone compounds, ester type compound, ether compound, aliphatic compound, cycloalkane compound or aromatic hydrocarbon according to claim 1 or 11 described photosensitive resin compositions.
13. photosensitive resin composition according to claim 1 is characterized in that, the percentage by weight of said adjuvant is 0.01%～10%.
14., it is characterized in that said adjuvant is one or more in foam-breaking agent, light stabilizer or the anti-oxidant according to claim 1 or 13 described photosensitive resin compositions.
15. a LCD is characterized in that, comprises the assembly of being processed by each described photosensitive resin composition of claim 1～14.
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| CN108517155A (en) * | 2018-04-27 | 2018-09-11 | 天津梓明涂料制造有限公司 | A kind of aqueous crackle coating applied to plastic products |
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| CN110941140B (en) * | 2018-09-21 | 2023-09-15 | 旭化成株式会社 | Photosensitive resin composition |
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