TW593582B - Photo-curable pigment-type ink-jet ink composition and applications thereof - Google Patents

Abstract

A photo-curable pigment-type ink-jet ink composition includes: 5 to 95 wt% of water; 0.01 to 40 wt% of a pigment with an average particle size of 10 nm to 85 nm; and 3 to 75 wt% of a photo-curable component. A photo-curable pigment-type ink-jet ink composition according to the present invention has good transparency and is applicable in the production of a color filter having a wide color range.

Description

593582 Case No. 91138095 _η Revision V. Description of the Invention (1) The technical field to which the invention belongs The present invention relates to a light-curable pigment-type inkjet ink composition U, and particularly to a light-curable pigment-type including a small particle size pigment Inkjet ink composition. Prior technology in recent years: With the growth of the market for notebook computers, color TVs, automotive TVs and video monitors, the demand for color LCD screens has rapidly increased. Color filters are an important part of color LCD screens. Increase. The color filter is a RGB (Red, Gree η, B 1 ue) three primary colors, arranged on the glass substrate into a micro-dot matrix pattern (Micro-dot Matrix Pattern), and then BM (Black Matrix; black matrix) Separated products. At present, each color filter factory widely uses a pigment dispersion method (Pigment dispersion met hod) to make a color filter, and a color photoresist (c ο 1 〇rresist) is coated on the substrate by spin coating. A lithographic color area is made by exposure and development. Color photoresist is a photoresist that evenly disperses color pigments in it. It has the characteristics of light reaction and thermal hardening. The R, G, and B three-color color photoresists must be made into color filters through three coating exposure, development processes. It needs to go through the same manufacturing process three times. In a continuous production line, three sets of the same equipment must be prepared in series to increase the equipment investment cost. In addition, increasing the number of operating steps will also reduce production yield. The current emerging method for making color filters is the inkjet method. Compared with the traditional pigment dispersion method of spin coating / exposure development, the inkjet method has a process

593582 Tiger 91138095 January 5. Description of invention (2) Simplification (> 2/3), environmental protection, material reduction (> 90%), many advantages. When manufactured by the inkjet method, the RGB crosslinkable ink can be sprayed into the fine color block area of the color filter with an inkjet head. This method can not only reduce the spin coating of three color photoresists in the traditional process. The exposure and development process reduces the investment cost of three sets of coating and exposure development manufacturing equipment on each production line. It is also because the color material is injected into the color block area through the inkjet method, unlike the traditional spin coating on the glass substrate after rotation. Only a small amount of color photoresist is left, which solves the problem of low material usage. The production of color filters by inkjet is a revolutionary technological evolution. In today's patent literature, the typical inkjet production process methods can be summarized into two categories: withinkreceive 1 ayer and without Ink absorbing layer process method (without ink receive layer). Patents using ink absorbing layer processes such as U · S · Patent No. 6, 177, 214, JP2000275421, JP2000187111, JP2000162425, JP2000155208, JP2000121827, etc., most of which are Canon's patents, such processes are usually used without UV curing Functional ink, because the color block area between BM is coated with an ink absorbing layer, the ink is sprayed into the color block area and absorbed by the ink absorbing layer to be fixed on the glass substrate. The other process is an ink-free process. Because the color cross light sheet is made of glass, unlike the traditional inkjet printing paper, glass does not absorb ink. Therefore, the color filter produced by the inkjet method must use a crosslinkable ink and then be cured by ultraviolet light. , So that the ink can be fixed on the glass substrate. For example, JP11184093, JP11124528, JP10268126, US6162510, J P 0 9 2 9 2 5 1 6 use a crosslinkable ink to make a color filter by an inkjet method. Among them, JP1118_9 3 mentioned the use of pigments with an average particle size of 0.3 # m (300 nanometers), which is a relatively large particle size. The large particle size of pigments will cause serious scattering and penetration.

Page 6 593582 _Case No. 91138095_Year Month Date_Charm_ 5. Description of the invention (3) The small degree will not be conducive to the transmittance requirements of the color filter. The other patents do not mention related descriptions of pigment particle size. _ Summary of the invention The purpose of the present invention is to solve the above-mentioned problems, and to provide a light-hardenable pigment-type inkjet ink composition, which includes a pigment having a small particle diameter, and has a better penetration? In addition, the ink composition including a small particle diameter of the present invention is suitable for making a color filter by an inkjet method, has a wide color gamut, bright colors, and is full, which is beneficial to improving the image quality of the color filter. In order to achieve the purpose of the present invention, the photo-curable pigment inkjet ink of the present invention ¥ The water composition includes: 5 to 95 wt% water; 0.01 to 40 wt% average particle diameter of 10 nm to 85 nm pigments; and 3 to 75 wt% of light-curable ingredients ^ The light-curable pigment-type inkjet ink composition of the present invention can be used to make color filters by inkjet, and therefore, the present invention also provides a color filter The manufacturing method of the light sheet includes the following steps. First, a transparent substrate is provided, which has a light shielding portion thereon, and an opening is formed between the light shielding portions. Next, a photocurable pigment-type inkjet ink composition was printed on the openings between the light-shielding portions by an inkjet printing method. The present invention also provides a color light-transmitting sheet, which includes: a light-shielding portion located on a transparent substrate with an opening formed between the light-shielding portions; and a light-transmitting color block located between the light-shielding portion and the opening Above, the light-transmitting color patch includes 0.1 to 40 wt% of an average particle diameter of 10 nm to 85 nm.

Page 7 593582 Case No. 9113, such as the month of 1995 Amendment V. Description of the invention (4) Pigment. The present invention also provides a liquid crystal display panel, which includes the above-mentioned color light-transmitting sheet. Appreciation method for color filter neck. The light transmittance of color materials is dye and pigment, so the inkjet water is a dispersion of the particle size and purity of dye-type crosslinked materials, and the product is made of transparent filters, which can maintain the accuracy of dispersion. Variation, so that it can be matched to match the system, the establishment of the ink method technology bottle is a requirement, the liquid-phase ink, and the development of the color because of the color, the high-color printing method of color granulation, ink preservation in the ink cartridge process The smallest traveler is designed with circuit control to spray, which is one quality and two uniform. Difficulty in color If the desire is smaller, the smaller the inkjet material, the more the ink can be used in the spray to maintain the overall structure of the ink droplets. The intersection of color and color requires the process and structure of the light film. The dispersion of the color material in the inkjet ink is stably divided into dyes and pigments. The color filter is high, and the light resistance (backlight resistance) is strong. Each has its advantages and disadvantages. Dye-type inks have better light transmission properties, but light resistance is inferior to liquid two-phase solutions. The dispersion stability control is low, but pigments have better light resistance. In the development of micronized pigments, it is necessary to reduce the size of pigments, and the color refraction, scattering, and brightness and vividness of the color will greatly improve the luminosity, and the color gamut can be widened. The core technology of the work includes qualitatively the RGB triplet containing photopolymerizable monomers and thermosetting monomers. Because color filter inkjet inks are extremely south, the long-term inkjet inks have the smallest droplet size and inkjet speed in the long-term use state and viscosity, surface tension, pH and other basic objects. Ink cartridge runner, nozzle, cartridge, precision inkjet hardware and ink preparation technology

593582

In order to achieve the birth of a color filter, the present invention provides a small particle size and better penetration. The present invention relates to an ink composition, which includes pigmented components having an average particle diameter of 5 to 9 5 in a range of 10 π in to 8 5 n in. Production demand. Pigmented ink composition with a view to providing a photo-curable pigment-type inkjet wt% water; 0.01 to 40 wt% flat 'and 3 to 75 wt% photo-hardenable The present invention provides for the first time The pigments with a sieve diameter of 10 nm to 8 5 nm and a photo-hardenable and ink-receptive ink composition of Xie and Teng g. ^ # The average particle size of pigments with good soil quality and ugliness is 10 to 50 nm, and more preferably 10 to 30 nm. The photohardenable component suitable for use in the present invention may be a monomer, an oligomer, or a resin, for example, may contain a c = c double bond. The photo-curable pigment-type inkjet ink composition of the present invention may have a surface tension of 20 to 65 mN / in and a viscosity of 1 to 70 cps. The ink composition of the present invention may further include a photoinitiator of 0.05 to 15 wt%, and a preferred amount is 0.1 to 10 wt%. The photocurable pigment-based spray of the present invention The ink composition can be used to make a color dope by an inkjet method. Figures 1a to 1c show schematic cross-sectional views of the manufacturing process of the method of making a color phosphor film for an ink-absorbing layer according to the present invention. Referring to FIG. 1a, first, a transparent substrate 1 is provided, which has a light-shielding portion 2 on it, such as a black matrix (BM), and an opening 3 is formed between the light-shielding portions 2. Next, referring to Fig. 1b, the photocurable pigment-type inkjet ink composition 4 of the present invention is printed on the openings 3 between the light shielding portions 2 by an inkjet printing method. The inkjet ink composition 4 may include three colors of R (red), g (green), and B (blue). & Next, referring to FIG. 1c, the inkjet ink composition 4 is hardened and shaped.

593582 Case No. 91138095 JF -___ η a Amend ‘V. Description of the invention (6) The light-transmitting color block 9 is formed. The hardening method can be heat treatment or ultraviolet irradiation. Figs. 2a to 2d show schematic cross-sectional views of a manufacturing process of a method for manufacturing a color filter with an ink absorbing layer according to the present invention. Referring to FIG. 2a, first, a transparent substrate 1 is provided, which has a light-shielding portion 2 on it, such as a black matrix (BM), and an opening 3 is formed between the light-shielding portions 2. Next, referring to FIG. 2b, an ink absorbing layer 21 is formed on the transparent substrate 1. Next, referring to Fig. 2c, the photocurable pigment-type inkjet ink composition 4 of the present invention is printed on the ink-absorbing layer 21 by an inkjet printing method. Next, referring to Fig. 2d, the inkjet ink composition 4 is hardened to form a light-transmitting color patch 9. The hardening method may be heat treatment or ultraviolet light irradiation. (Preliminary Example) The red pigment Pigment Red 254 (Ciba) was ground to obtain self-made pigment concentrates LIR1 and NDR004. LIR1 has a pigment solid content of 15.62%, a viscosity of 14 cps, a surface tension of 54 mN / ffl, and an average particle size of 13.8 nm. Pigment concentrate NDR 0 0 4 has a pigment solids content of 11.1%, a viscosity of 2.9 lcps, a surface tension of 4 2 · 5 m N / m, and an average particle size of 6 5 · 4 nm. The green pigment P i g «1 e n t G r e e η 3 6 (C i b a) was ground to obtain the self-made pigment concentrates NDG001 and NDG003. NDG001 has a pigment solids content of 11.87%, a viscosity of 3.54 cps, a surface tension of 31.9 mN / m, and an average particle size of 81.2 nm. Pigment concentrate NDG00 3 had a pigment solid content of 8.38%, a viscosity of 2.4 cps, a surface tension of 37.9 mN / in, and an average particle size of 145.1 nm. The blue pigment Pigment Blue 15: 6 (Cib a company) was ground to obtain homemade pigment concentrates LIB2 and NDB02. LIB2 pigment solids content

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— Case No. 91138095 V. Description of the invention (7) 13.73%, viscosity 7.35cps, surface tension 5l 5mN / m, average particle size 1 4 · 3nm. Pigment Concentration Solution of Pigment Concentrate NDB0 0 2 〖n 81% in dibutyl u 3, viscosity 1.98 cps, surface tension 33.4 inN / m, average particle size 58 meters The above six pigment concentrates were diluted with water Measure the UV-V isib 丨 e spectrum to 〇65% / Τ ', observe the relationship between particle size and transmittance, ϋν — V isib 1 e spectrum as shown in Figures 3 to 5' Each pigment The relationship between the particle size of the concentrated solution and the penetration is shown in Table 1. From Figures 3 to 5 and Table f, it can be seen that 'the smaller the particle size of the pigment, the more the color is affected by the refraction and scattering of light', the penetration of the solution will be increased, and the light transmission of the printed product will be improved. TABLE 1 · Relationship between the particle size of each pigment concentrate and the transmittance The color of the pigment concentrate sample is almost the average particle size (nanometer) Penetration 00 LiRl Red 13.8 94.17 NDR004 Red 65.4 88 · 72 NDC001 Green 81.2 95.2 NDC003 Color Record 145.1 90.7 L1B2 blue 14.3 83 · 4 NDB002 blue 58.1 78.6 (Example 1) The red light-hardening inkjet ink uses a light initiator 2-hydroxy-2 methyl-1-phenyl-propan-1 -one (7 parts by weight ), Photo-hardenable compound SR 268 (Sartomer, 21 parts by weight), and vinyl-pyrrolidone (12 parts by weight) are mixed and stirred for 10 minutes, and then a surfactant BYK3 33 (BYK, 0.6 parts by weight) is added with Co-solvent 2 _ pyrr ο 1 id ο ne (2 0 parts by weight)

Page 11 593582 _Case No. 9138095 Rev. ___ V. Description of the invention (8) Bell, then add 80 parts by weight of water, stir with a high-speed homogenizer with 50000 rpm for 5 minutes, stand still After the foam disappeared, the red pigment concentrate LIR 1 (20 parts by weight) was added and stirred for 5 minutes to prepare a light-hardening inkjet ink. Inkjet ink pH 7.38, viscosity 7.7 cps, surface tension 3 7. 5 m N / m ° (Example 2) Green and color light hardening type inkjet ink uses a light initiator 2-hydroxy-2 methyl-1 -phenyl-propan-1-one (7 parts by weight), light-curable compound SR 2 68 (2 1 parts by weight, main ingredients: Tetraethylene glycol Diacrylate), vinyl- · pyrrol i done (20 parts by weight) mixed and stirred l 〇minutes, and then add the surfactant β YK 3 3 3 (0. 6 parts by weight, the main component is: polyether modified polydioxanyl oxalate copolymer) and co-solvent 2-pyrrolidone (20 parts by weight) mixed Stir for 10 minutes, and then add 80 parts by weight of water. Stir for 5 minutes with a 50000 r pm rotary mallet on a high-speed homogenizer. Allow the foam to disappear and add the green pigment concentrate MDG 0 0 1 (2 0 parts by weight), and stirred for 5 minutes to prepare a light-hardening inkjet ink. Inkjet ink ρ Η 7 · 6 2. Viscosity 16 · 9 cps, surface tension 3 5 · 5 m N / m ○ (Example 3) Blue light-hardening inkjet ink summer photoinitiator 2-hydroxy- 2 methyl-1-phenyl-propan-1-one (7 parts by weight), photo-hardenable compound SR 268 (18 parts by weight), vinyl-pyrrol i done (14 parts by weight), mix and stir for 10 minutes, and then add the interface / Tongue agent Β YK 3 3 3 (0. 6 parts by weight) and co-solvent 2-pyrrolidone (20 parts by weight a: parts) are mixed and taxed for 10 minutes'. Then β q parts by weight of water is added to

Page 12 593582 __ Case No. 91138095_ year month day ___ V. Description of the invention (9) The high-speed stirring homogenizer is stirred with a 500 Orpm rotary hammer for 5 minutes, and left to stand until the foam disappears, and then the blue pigment concentrate LI B2 (20 parts by weight), and stirred for 5 minutes to prepare a photo-curable inkjet ink. Inkjet ink pH 7.66, viscosity 12.9 cps, and surface tension 38.5 mN / m. (Example 4) Making a color filter The three-color ink obtained in Example 1-3 was put into an HP5 1 62 6 ink cartridge, and printed on a glass substrate by an inkjet printer, and a black array ( BM) is 20 microns wide and the color patch area is 90 microns wide. First print the red patch area, bake at 120 ° C for 3 minutes after printing, then print the green patch area, bake at 120 ° C for 3 minutes after printing, and finally print the blue patch area. After printing, bake at 120 ° C for 3 minutes, and irradiate with UV light for 10 minutes to fix the color block on the glass substrate. The partial image of the color filter product in the microscopic observation system is shown in Figure 6. (Comparative Example 1) The procedure of the red light-hardening inkjet ink is the same as in Example 1, but the pigment concentrate used is a red pigment concentrate with an average particle size of 105 · 4 nm. The viscosity of the inkjet ink obtained is 4.59cps 3. The surface tension is 30.5mN / m. (Comparative Example 2) The steps of green light-hardening inkjet ink are the same as those in Example 2, but the pigment concentrate used is a green pigment concentrate with an average particle diameter of 1 8 · 5 nm, and the viscosity of the inkjet ink obtained is 5.11 cps. The surface tension is 30,5mN / m. (Comparative Example 3) Blue light-hardening inkjet ink

P.13 593582 _Case No. 9113 & 095_ Years and Months Amendment _ V. Description of the invention (10) The procedure is the same as in Example 3, but the pigment concentrate used is a pigment concentrate with an average particle size of 11.5 nm. The viscosity of the resulting inkjet ink was 4 · 21 cps: the surface tension was 30.0 mN / m. (Comparative Example 4) The procedure for making a color filter is the same as that of Example 4, but the three-color ink used is the ink of Comparative Examples 1 to 3. (Example 5) Comparison between the present invention and the comparative example The color filter of the present invention obtained in Example 4 and the color filter of 4 obtained in Comparative Example 4 were used. The color filter was Photal LCF-6 0 0 0 The sheet spectrum measurement system measures the chromaticity coordinates and draws a color gamut diagram as shown in FIG. 7. It can be seen from FIG. 7 that the color filter products using the pigment with a smaller particle diameter in the embodiment are compared with the products using the pigment with a larger particle diameter, which has a wider color gamut, which is beneficial to improving the quality of the color filter. Although the present invention has been disclosed as above with preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make changes and retouching without departing from the spirit and scope of the present invention. The scope of protection shall be as defined by the scope of the patent application attached hereafter. ®

Page 14 593582 _Case No. 91138095_ Year Month Day_ Correction_ Round type brief description Figures 1a to 1c show schematic cross-sectional views of the manufacturing process of the method for making a color filter without an ink absorbing layer according to the present invention. -Figures 2a to 2d show schematic cross-sectional views of the manufacturing process of the method for making a color filter with an ink absorbing layer according to the present invention. Figure 3 shows the UV-Visible spectra of red pigment concentrates with different particle sizes ^. Figure 4 shows the UV-Visible spectra of green pigment concentrates with different particle sizes. Figure 5 shows the UV-Visible spectra of blue pigment concentrates with different particle sizes. FIG. 6 shows a partial microscopic image of the color filter of the present invention. Fig. 7 shows a comparison of the color gamut of the color filter of the present invention and the color filter of the comparative example. Explanation of reference numerals 1 to transparent substrate, 2 to light-shielding portion, 2 1 to ink-absorbing layer, 3 to opening, 4 to ink composition, and 9 to light-transmitting color patch.

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Claims (1)

593582 _ Case No. 91138095_2 February 23 amending the trip, VI. Patent application scope 1. A photocurable pigment inkjet ink composition, which includes: 5 to 95% by weight of water; < 0. 0 1 to 4 0 wt% pigments with an average particle size of 10 nm to 8 5 nm; and 3 to 75 wt (% i) a photohardenable component that contains a C = C double bond. 2. If the scope of patent application is the first The photocurable pigment-type inkjet ink composition according to item 1, wherein the photocurable component is a monomer, an oligomer, or a resin. 3. The photocurable pigment-type inkjet device according to item 1 of the scope of patent application Ink composition, wherein the average particle diameter of the pigment is 10 to 50 nm. 4. The photocurable pigment type inkjet ink composition according to item 3 of the patent application scope, wherein the average particle diameter of the pigment It is 10 to 30 nm. 5. The photocurable pigment inkjet ink composition according to item 1 of the patent application range, wherein the surface tension of the ink composition is between 20 and 65 m N / m. 6. The photocurable pigment inkjet ink composition according to item 1 of the scope of patent application, wherein The viscosity of the ink composition is between 1 and 70 cps. 7. The photocurable pigment inkjet ink composition according to item 1 of the scope of patent application, which further comprises 0.05 to 15 wt% 8. A method for manufacturing a color filter, comprising: providing a transparent substrate having a light-shielding portion thereon, an opening formed between the light-shielding portions; and a photo-hardenable pigment Type inkjet ink composition prints by inkjet printing Page 16 593582 _ Case No. 91138095 _ month a_ί ± ^ ._ VI. The scope of the patent application is on the opening between the light-shielding parts, where the photocurable pigment inkjet ink composition is the first in the scope of patent application The photocurable pigment-based inkjet ink composition described in the item. 9. The method for manufacturing a color filter according to item 8 of the scope of patent application, which further comprises hardening the inkjet ink composition after inkjet printing. 10. The method for manufacturing a color filter according to item 8 of the scope of patent application, further comprising the step of forming an ink absorbing layer on the transparent substrate before inkjet printing. 1 1. The method for manufacturing a color filter as described in item 8 of the scope of patent application, wherein the light shielding portion is a black matrix. 1 2. The method for manufacturing a color filter as described in item 8 of the scope of patent application, wherein the photohardenable component is a monomer, a polymer, or a resin. 1 3. The method for manufacturing a color filter as described in item 8 of the scope of patent application, wherein the average particle diameter of the pigment is 10 to 50 nm. 14. The method for manufacturing a color filter as described in item 13 of the scope of patent application, wherein the average particle diameter of the pigment is 10 to 30 nm. 15. The method for manufacturing a color filter according to item 8 of the scope of the patent application, wherein the surface tension of the ink composition is between 20 and 65 mN / m. 16. The method for manufacturing a color filter as described in item 8 of the scope of patent application, wherein the viscosity of the ink composition is between 1 and 70 cps. 17. The method for manufacturing a color filter as described in item 8 of the scope of the patent application, further comprising a photoinitiator of 0.05 to 15 wt%. 1 8.—A color filter comprising: Page 17 593582 _ Case No. 91138095 _ year month day_ί ± ^ _ VI. Patent application scope-a light-shielding part, located on a transparent substrate, an opening is formed between the light-shielding parts; and Located on the opening between the light-shielding portions, the light-transmitting color patch includes pigments having an average particle diameter of 0.1 to 40 wt% from 10 nm to 85 nm. 19. The color filter according to item 18 of the scope of the patent application, wherein the light shielding portion is a black matrix. 20. The color filter according to item 18 of the scope of patent application, wherein the average particle diameter of the pigment is 10 to 50 nm. 2 1. The color filter according to item 20 of the scope of patent application, wherein the average particle diameter of the pigment is 10 to 30 n m. 2 2. The color filter according to item 18 of the scope of patent application, which can be used in a liquid crystal display panel. Page 18