CN110737172B - UV curing powder photoresist composition, manufacturing method thereof and manufacturing method of color film substrate - Google Patents
UV curing powder photoresist composition, manufacturing method thereof and manufacturing method of color film substrate Download PDFInfo
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133509—Filters, e.g. light shielding masks
- G02F1/133514—Colour filters
- G02F1/133516—Methods for their manufacture, e.g. printing, electro-deposition or photolithography
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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Abstract
The invention provides a UV curing powder photoresist composition, a manufacturing method thereof and a manufacturing method of a color film substrate. The UV-curable powder photoresist composition of the invention is in powder form and does not contain solvent. In the manufacturing method of the color film substrate, the UV curing powder photoresist composition is adopted to manufacture the color photoresist, so that a vacuum drying process, a pre-baking/natural cooling process and a developing process in the manufacturing process of the traditional color filter layer can be omitted, the energy consumption cost is reduced, the method is green and environment-friendly, in addition, the UV curing powder photoresist composition has no active diluent, the curing shrinkage rate of a coating film is low, the problem of the height difference between the color photoresist formed by the traditional spraying and the rib wall can be solved, the risks of film surface wrinkles and the like caused by uneven shrinkage of a surface layer film and a bottom layer film are reduced, and the preparation method takes a black matrix as a retaining wall, so that the preparation process of the rib wall is omitted.
Description
Technical Field
The invention relates to the technical field of display, in particular to a UV curing powder photoresist composition and a manufacturing method thereof, and a manufacturing method of a color film substrate.
Background
A Thin Film Transistor Liquid Crystal Display (TFT-LCD) has many advantages such as a Thin body, power saving, and no radiation, and is widely used. Most of the existing liquid crystal display devices in the market are backlight liquid crystal display devices, which include a liquid crystal display panel and a backlight module (backlight module). Generally, a Liquid Crystal display panel is composed of a Color Filter (CF) substrate, a TFT array substrate, a Liquid Crystal (LC) and a Sealant (Sealant) sandwiched between the Color Filter substrate and the TFT array substrate; the molding process generally comprises: front Array (Array) process, CF process (film, yellow light, etching and stripping), middle Cell (TFT Array substrate and CF substrate bonding), and back Module assembly (Module) process (driving IC and printed circuit board bonding); wherein, the front-stage Array process mainly forms a TFT substrate to control the movement of liquid crystal molecules; the front CF process mainly forms a CF substrate; the middle Cell process is mainly to add liquid crystal between the TFT substrate and the CF substrate; the back module assembly process mainly drives the integration of IC pressing and printed circuit board, and further drives the liquid crystal molecules to rotate and display images.
The CF substrate is a main device used by the LCD to realize color display, and its basic constitution generally includes: a glass substrate, a Black Matrix (BM), a color filter layer, etc. The color filter layer achieves a color display effect mainly through the color photoresist, light emitted by the backlight source is modulated by liquid crystal molecules and enters the CF substrate, red (R) photoresist, green (G) photoresist and blue (B) photoresist of the color filter layer on the CF substrate are used for filtering, red, green and blue light rays are respectively displayed, and the photoresists of different colors respectively transmit light of corresponding color wave bands, so that the color display of the display is realized.
At present, the manufacturing method of the color filter layer in the TFT-LCD technology is mainly a pigment dispersion method, but the utilization rate of the light resistance is very low by the pigment dispersion method, so that the cost is greatly wasted. Under the circumstances, a method for manufacturing a color filter layer with high precision and high photoresist utilization rate comes into the sight of researchers, namely an Ink Jet Printing (IJP) method, namely a method for manufacturing an existing color film substrate, and adopts an Ink jet printing technology to manufacture the color filter layer thereon, and specifically comprises the following steps:
step S10, as shown in fig. 1, providing a substrate 100, forming a black matrix 200 on the substrate 100, and forming a rib wall (rib wall)300 on the black matrix 200, wherein the rib wall 300 encloses a plurality of pixel grooves on the substrate 100;
step S20, as shown in fig. 2, spraying a certain amount of photoresist material in the pixel groove to form a wet photoresist film 400;
in step S30, as shown in fig. 3, the wet photoresist film 400 formed in step S20 is subjected to an Ultraviolet (UV) curing process, a vacuum drying process (VCD) and a pre-baking/natural cooling process (HP/CP) to form a dry color photoresist 450.
In the method, a certain amount of photoresist material is sprayed in the pixel groove surrounded by the rib wall 300, so that the developing process (DEV) is omitted, a large amount of photoresist material is prevented from being wasted in the developing process, and the use amount of raw materials and the material cost are greatly reduced. However, when the IJP technology is used to manufacture the RGB color photoresist 450, the existing photoresist materials used in the industry all belong to mixed liquids, which contain a large amount of solvents, the solid content is mostly about 15-20%, the step difference between the wet photoresist film 400 and the rib wall 300 is smaller after the photoresist material is sprayed, but after UV curing and baking (Oven), the film shrinkage is larger, the step difference between the dry color photoresist 450 and the rib wall 300 is as high as 3 μm or even higher, so that a higher ox horn phenomenon is generated, while the current normal (normal) horn needs to be less than or equal to 1 μm, and the step difference is difficult to be compensated by using other material film layers, and a series of processes such as Cell thickness (gap) will be affected at the later stage.
Disclosure of Invention
The invention aims to provide a UV curing powder photoresist composition which is powdery, does not contain a solvent, is used for manufacturing a color photoresist, can solve the problem of height difference between the traditional color photoresist and a rib wall, reduces risks such as membrane surface wrinkles caused by uneven membrane shrinkage, reduces energy consumption cost and is environment-friendly.
The invention also aims to provide a preparation method of the UV curing powder photoresist composition, and the prepared UV curing powder photoresist composition is used for preparing the color photoresist, can improve the problem of height difference between the traditional color photoresist and the rib wall, reduces the risks of membrane surface wrinkles and the like caused by uneven membrane shrinkage, reduces the energy consumption cost, and is green and environment-friendly.
The invention also aims to provide a manufacturing method of a color film substrate, which is characterized in that the UV curing powder photoresist composition is adopted to manufacture a color photoresist, so that the problem of height difference between the traditional color photoresist and a rib wall can be solved, risks of film surface wrinkles and the like caused by uneven film shrinkage are reduced, the energy consumption cost is reduced, and the method is green and environment-friendly.
In order to achieve the purpose, the invention provides a UV curing powder photoresist composition, which comprises the following raw material components in percentage by mass:
wherein the colorant is a pigment, a dye, or a combination of both;
the UV curable powder photoresist composition is in a powder form.
The resin matrix is selected from one or more of epoxy acrylic resin, polyurethane acrylate, methacrylic acid polyester resin, acrylic acid unsaturated polyester, hyperbranched polyacrylate and polyvinyl ether resin.
The resin matrix has unsaturated bonds, a glass transition temperature of between 44 ℃ and 58 ℃, a viscosity of less than 1000cps at 25 ℃, and shear thinning fluid properties.
The polyurethane acrylate is unsaturated hyperbranched polyurethane acrylate, the whole molecular structure of the polyurethane acrylate is circular, and the polyurethane acrylate is provided with a plurality of unsaturated side branched chains
The polyurethane acrylate is selected from a first high-functionality polyurethane acrylate and a second high-functionality polyurethane acrylate, wherein the structural general formulas of the first high-functionality polyurethane acrylate and the second high-functionality polyurethane acrylate are respectively shown as the following formulas 1 and 2;
wherein 1 is<x<10, M1 is an alkyl group having less than 10 carbon atoms, M3 is an alkyl group having less than 3 carbon atoms, M2 isR is an alkyl group with the number of carbon atoms less than 3.
The epoxy acrylic resin is selected from a first high-functionality epoxy acrylic resin and a second high-functionality epoxy acrylic resin, wherein the structural general formulas of the first high-functionality epoxy acrylic resin and the second high-functionality epoxy acrylic resin are respectively shown as the following formulas 3 and 4;
wherein R1 is an alkyl group having a carbon number of less than 3, and R2 is a cyclohexane group, or an alkyl group having a carbon number of less than 3.
The structural general formula of the polyvinyl ether resin is shown as the following formula 5:
wherein 10< m < 30.
The invention also provides a preparation method of the UV curing powder photoresist composition, which comprises the steps of weighing the resin matrix, the coloring agent, the photoinitiator, the defoaming agent and the flatting agent according to the mass percent of the raw material components in the UV curing powder photoresist composition, and premixing, melting, mixing, extruding, cooling, crushing and granulating the weighed raw material components to prepare powder so as to obtain the UV curing powder photoresist composition.
The invention also provides a manufacturing method of the color film substrate, which comprises the following steps:
step S1, providing a substrate, forming a black matrix on the substrate, wherein the black matrix encloses a plurality of pixel grooves on the substrate;
step S2, spraying the UV curing powder photoresist composition in the pixel groove to obtain a powder photoresist pattern;
and S3, heating the powder photoresist pattern in the pixel groove to level the film surface, and then carrying out UV irradiation on the powder photoresist pattern in the pixel groove to solidify the powder photoresist pattern to obtain the color photoresist.
In the step S3, the powdered photoresist pattern is heated by infrared irradiation.
The invention has the beneficial effects that: the UV curing powder photoresist composition is powdery, does not contain a solvent, is used for manufacturing a color photoresist, can save a vacuum drying process, a pre-baking/natural cooling process and a developing process in the manufacturing process of the traditional color filter layer, reduces energy consumption cost, is green and environment-friendly, has no active diluent, has low curing shrinkage rate of a coating film, can solve the problem of height difference between the traditional color photoresist and a rib wall, and reduces risks such as film surface wrinkles caused by uneven film shrinkage. The manufacturing method of the UV curing powder photoresist composition is simple, and the manufactured UV curing powder photoresist composition is used for manufacturing color photoresist, can improve the problem of height difference between the traditional color photoresist and the rib wall, reduces risks such as membrane surface wrinkles caused by uneven membrane shrinkage, reduces energy consumption cost, and is green and environment-friendly. The manufacturing method of the color film substrate adopts the UV curing powder photoresist composition to manufacture the color photoresist, the UV curing powder photoresist composition does not contain a solvent, a vacuum drying process, a pre-baking/natural cooling process and a developing process in the manufacturing process of the traditional color filter layer can be omitted, the energy consumption cost is reduced, the color film substrate is green and environment-friendly, in addition, the UV curing powder photoresist composition does not contain an active diluent, the curing shrinkage rate of a coating film is low, the problem of high step difference between the color photoresist formed by traditional spraying and a rib wall can be solved, the risks of film surface wrinkles and the like caused by uneven shrinkage of a surface layer film and a bottom layer film are reduced, and the preparation method takes a black matrix as a retaining wall and omits the preparation process of the rib wall.
For a better understanding of the nature and technical aspects of the present invention, reference should be made to the following detailed description of the invention, taken in conjunction with the accompanying drawings, which are provided for purposes of illustration and description and are not intended to limit the invention.
Drawings
The technical solution and other advantages of the present invention will become apparent from the following detailed description of specific embodiments of the present invention, which is to be read in connection with the accompanying drawings.
In the drawings, there is shown in the drawings,
fig. 1 is a schematic diagram of step S10 of a method for manufacturing a color filter substrate in the prior art;
fig. 2 is a schematic view of step S20 of the method for manufacturing a color filter substrate shown in fig. 1;
fig. 3 is a schematic diagram of step S30 of the method for manufacturing a color filter substrate shown in fig. 1;
FIG. 4 is a schematic diagram of a molecular structure of urethane acrylate used in the resin matrix of the UV curable powder photoresist composition of the present invention;
fig. 5 is a schematic flow chart of a manufacturing method of a color film substrate according to the present invention;
fig. 6 is a schematic view of step S1 of the method for manufacturing a color filter substrate according to the present invention;
fig. 7 is a schematic view of step S2 of the method for manufacturing a color filter substrate according to the present invention;
fig. 8 is a schematic diagram of step S3 of the method for manufacturing a color filter substrate according to the present invention.
Detailed Description
To further illustrate the technical means and effects of the present invention, the following detailed description is given with reference to the preferred embodiments of the present invention and the accompanying drawings.
The invention firstly provides a UV curing powder photoresist composition, which comprises the following raw material components in percentage by mass:
wherein the colorant is a pigment, a dye, or a combination of both;
the UV curable powder photoresist composition is in a powder form.
Specifically, the UV curable powder photoresist composition of the present invention may further include other additives, such as a dispersant, etc., in an amount of 0.2 to 1 wt% in addition to the above-mentioned raw material components.
Specifically, the resin matrix is selected from one or more of epoxy acrylic resin, polyurethane acrylate, methacrylic polyester resin, acrylic unsaturated polyester, hyperbranched polyacrylate and polyvinyl ether resin.
Specifically, the resin matrix has a lower glass transition temperature or lower melting point, a viscosity of less than 1000cps at 25 ℃, and shear-thinning fluid properties.
Further, the resin matrix has unsaturated bonds, and the glass transition temperature of the resin matrix is between 44 and 58 ℃.
For example, when the resin matrix comprises urethane acrylate, the urethane acrylate may be unsaturated hyperbranched urethane acrylate, as shown in fig. 4, the molecular structure of which is generally circular, and the circle at the center in fig. 4 represents a polyurethane group to which a plurality of unsaturated side branches are connected, the unsaturated side branches being
For another example, when the resin matrix includes urethane acrylate, the urethane acrylate may also be high-functionality urethane acrylate, and specifically may be selected from a first high-functionality urethane acrylate and a second high-functionality urethane acrylate, which are shown below, wherein the structural general formulas of the first high-functionality urethane acrylate and the second high-functionality urethane acrylate are respectively shown in formula 1 and formula 2 below;
wherein 1 is<x<10, M1 is an alkyl group having less than 10 carbon atoms, M3 is an alkyl group having less than 3 carbon atoms, M2 isR is an alkyl group with the number of carbon atoms less than 3.
For another example, when the resin matrix includes an epoxy acrylate resin, the epoxy acrylate resin may be a high-functionality epoxy acrylate resin, and specifically may be a first high-functionality epoxy acrylate resin and a second high-functionality epoxy acrylate resin as shown below, where the structural general formulas of the first high-functionality epoxy acrylate resin and the second high-functionality epoxy acrylate resin are respectively shown in the following formulas 3 and 4;
wherein R1 is an alkyl group having a carbon number of less than 3, and R2 is a cyclohexane group, or an alkyl group having a carbon number of less than 3.
For another example, when the resin matrix includes a polyvinyl ether resin, the polyvinyl ether resin may be a high-functionality polyvinyl ether resin, and specifically may be a polyvinyl ether resin having a general structural formula shown in formula 5 below:
wherein 10< m < 30.
The UV curing powder photoresist composition is powdery, does not contain a solvent, is used for manufacturing a color photoresist, can save a vacuum drying process, a pre-baking/natural cooling process and a developing process in the manufacturing process of the traditional color filter layer, reduces energy consumption cost, is green and environment-friendly, has no active diluent, has low curing shrinkage rate of a coating film, can solve the problem of height difference between the traditional color photoresist and a rib wall, and reduces risks such as film surface wrinkles caused by uneven film shrinkage.
Based on the UV curing powder photoresist composition, the invention also provides a preparation method of the UV curing powder photoresist composition, which comprises the steps of weighing the resin matrix, the coloring agent, the photoinitiator, the defoaming agent and the leveling agent according to the mass percent of the raw material components in the UV curing powder photoresist composition, and premixing, melting and mixing, extruding, cooling, crushing and granulating the weighed raw material components to prepare powder, thereby obtaining the UV curing powder photoresist composition.
Referring to fig. 5, based on the UV curable powder photoresist composition, the present invention further provides a method for manufacturing a color film substrate, including the following steps:
step S1, as shown in fig. 6, provides a substrate 10, and forms a black matrix 20 on the substrate 10, wherein the black matrix 20 encloses a plurality of pixel grooves 21 on the substrate 10.
Step S2, as shown in fig. 7, the UV curable powder photoresist composition as described above is sprayed into the pixel grooves 21 to obtain the powder photoresist pattern 30.
Step S3, as shown in fig. 8, is to heat the powder resist pattern 30 in the pixel groove 21 to level the film surface, and then to cure the powder resist pattern 30 in the pixel groove 21 by UV irradiation, thereby obtaining the color resist 35.
Specifically, in the step S3, the powdered photoresist pattern 30 may be heated by infrared irradiation or the like.
The manufacturing method of the color film substrate adopts the UV curing powder photoresist composition to manufacture the color photoresist 35, the UV curing powder photoresist composition does not contain a solvent, a vacuum drying process, a pre-baking/natural cooling process and a developing process in the manufacturing process of the traditional color filter layer can be omitted, the energy consumption cost is reduced, the color film substrate is green and environment-friendly, in addition, the UV curing powder photoresist composition does not contain an active diluent, the curing shrinkage rate of a coating film is low, the problem of height difference between the color photoresist formed by traditional spraying and a rib wall can be solved, the risks of film surface wrinkles and the like caused by uneven shrinkage of a surface layer film and a bottom layer film are reduced, and the black matrix 20 is used as a retaining wall in the manufacturing method, and the preparation process of the rib wall is omitted.
In summary, the UV curable powder photoresist composition of the present invention is in a powder form, does not contain a solvent, is used for manufacturing a color photoresist, can omit a vacuum drying process, a pre-baking/natural cooling process, and a developing process in the conventional color filter layer manufacturing process, reduces energy consumption cost, is green and environment-friendly, has no reactive diluent, has a low coating film curing shrinkage rate, can improve the problem of a height difference between the conventional color photoresist and a rib wall, and reduces risks such as film surface wrinkles caused by uneven film shrinkage. The manufacturing method of the UV curing powder photoresist composition is simple, and the manufactured UV curing powder photoresist composition is used for manufacturing color photoresist, can improve the problem of height difference between the traditional color photoresist and the rib wall, reduces risks such as membrane surface wrinkles caused by uneven membrane shrinkage, reduces energy consumption cost, and is green and environment-friendly. The manufacturing method of the color film substrate adopts the UV curing powder photoresist composition to manufacture the color photoresist, the UV curing powder photoresist composition does not contain a solvent, a vacuum drying process, a pre-baking/natural cooling process and a developing process in the manufacturing process of the traditional color filter layer can be omitted, the energy consumption cost is reduced, the color film substrate is green and environment-friendly, in addition, the UV curing powder photoresist composition does not contain an active diluent, the curing shrinkage rate of a coating film is low, the problem of high step difference between the color photoresist formed by traditional spraying and a rib wall can be solved, the risks of film surface wrinkles and the like caused by uneven shrinkage of a surface layer film and a bottom layer film are reduced, and the preparation method takes a black matrix as a retaining wall and omits the preparation process of the rib wall.
As described above, it will be apparent to those skilled in the art that other various changes and modifications may be made based on the technical solution and concept of the present invention, and all such changes and modifications are intended to fall within the scope of the appended claims.
Claims (5)
1. The UV-curable powder photoresist composition is characterized by comprising the following raw material components in percentage by mass:
wherein the colorant is a pigment, a dye, or a combination of both;
the UV-curable powder photoresist composition is in a powder shape;
the resin matrix comprises a polyvinyl ether resin;
the structural general formula of the polyvinyl ether resin is shown as the following formula 5:
wherein 10< m < 30.
2. The UV-curable powder photoresist composition of claim 1, wherein the resin matrix has unsaturated bonds, a glass transition temperature between 44 ℃ and 58 ℃, a viscosity of less than 1000cps at 25 ℃, and shear-thinning fluid properties.
3. The method for preparing the UV-curable powder photoresist composition of claim 1, wherein the UV-curable powder photoresist composition is prepared by weighing a resin matrix, a coloring agent, a photoinitiator, a defoaming agent and a leveling agent according to the mass percent of the raw material components in the UV-curable powder photoresist composition, and premixing, melting and mixing, extruding, cooling, crushing and granulating the weighed raw material components to prepare powder.
4. The manufacturing method of the color film substrate is characterized by comprising the following steps of:
step S1, providing a substrate base plate (10), forming a black matrix (20) on the substrate base plate (10), wherein the black matrix (20) encloses a plurality of pixel grooves (21) on the substrate base plate (10);
step S2 of spraying the UV curable powder resist composition of claim 1 in the pixel grooves (21) to obtain a powder resist pattern (30);
and step S3, heating the powder photoresist pattern (30) in the pixel groove (21) to level the film surface, and then carrying out UV irradiation on the powder photoresist pattern (30) in the pixel groove (21) to solidify the powder photoresist pattern, so as to obtain the color photoresist (35).
5. The method for manufacturing a color filter substrate according to claim 4, wherein in step S3, the powder photoresist pattern (30) is heated by infrared irradiation.
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US20100022676A1 (en) * | 2006-10-03 | 2010-01-28 | Jonathan Rogers | Photocurable compositions comprising a photoinitiator of the phenylglyoxylate type |
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