JP5145132B2 - Black matrix surface treatment aqueous solution and black matrix surface treatment method - Google Patents

Description

  The present invention prevents the pigment component derived from the color filter from adhering to the black matrix and improves the yield when patterning the color filter after forming the black matrix containing nickel as a constituent component on the substrate. The present invention relates to a black matrix surface treatment aqueous solution and a black matrix surface treatment method.

  In recent years, a general display method of a flat panel display that has been rapidly spread is that white light called a backlight has three primary colors of light, red (R), green (G), blue ( It passes through a colored resist called a color filter exhibiting B) and is displayed in color. The unit for controlling the light is assembled for each pixel, and the principle and specification differ depending on the display method of the display.

  Normally, these three primary color filters are regularly patterned in a mosaic or striped pattern on a transparent substrate, but the formation is performed sequentially for each color by R, G, B color resists by etching or photolithography. The method of forming is taken. In addition, before this color filter is formed, the black matrix is patterned so as to be formed on the boundary line of the R, G, and B color filters, thereby improving the contrast of the image and preventing the decrease in color purity. Yes.

  The characteristics required for this black matrix include high light-shielding properties and high pattern fineness. In addition, examples of the forming method include a method of vapor-depositing a metal, a printing method using a printing ink containing a carbon black black dye, photolithography using a photosensitive black resin composition, and the forming method according to each characteristic is adopted. ing.

  Among these methods, a method for depositing a metal is formed by pattern etching by photolithography after forming a metal film. This method has been used since the creation of flat panel displays, and the required characteristics are extremely reliable. In particular, it is widely used for applications that require high-definition display.

The metal used for the black matrix can be etched by a wet process, and chromium (Cr) has been used as a film having excellent corrosion resistance. However, environmental problems are closed as represented by the European Union's ELV (Endo-of-Life Vehicle) Directive (Discarded Vehicle Directive) and the RoHS (Restriction of Hazardous Substitutes) Directive (Restriction of Use of Specific Hazardous Substances in Electronic and Electrical Equipment). As it is improved, proposals have been made for metals that replace chromium (see, for example, Patent Document 1).
JP 2004-317849 A

  The black matrix containing nickel, which has been proposed as an alternative to chromium, has the same processability and light-shielding properties as chromium, but the pigment component contained in the color filter is attached when forming the color filter. Therefore, the adhesiveness with the color filter of another color formed in the subsequent process is remarkably impaired, resulting in a decrease in reliability. Further, it is very difficult to remove the pigment-containing component of the color filter attached to the black matrix containing nickel, and the black matrix is corroded conversely even if it is attempted to remove it with a chemical solution. Even if the physical force such as polishing is used for removal, since the wiring rule is small, the parts other than the target part are damaged, which is not preferable.

Therefore, as described above, the black matrix containing nickel satisfies the required characteristics with a single performance, but in the formation of the actual substrate, the pigment component derived from the color filter adheres to it so that reliability and product yield can be achieved. Had fallen.
Accordingly, the present invention provides an aqueous black matrix surface treatment solution that prevents adhesion of a pigment component during formation of a color filter in manufacturing a substrate using a black matrix containing nickel, is excellent in reliability, and can improve yield. And it aims at providing the surface treatment method of a black matrix.

  As a result of intensive studies to solve the above problems, the present inventors have determined that a substrate on which a black matrix containing nickel is patterned before forming a color filter is a surface containing at least one aminophosphonic acid compound. By treating with a treatment aqueous solution, an adhesion preventing layer is formed on the surface of the black matrix, and as a result, it has been found that, when forming a color filter, a decrease in reliability due to adhesion of the contained pigment component is prevented. It came. Further, the adhesion preventing layer on the surface of the black matrix formed according to the present invention does not impair defects in subsequent processes such as adhesion between the color filter and the black matrix, and further, reliability for display. Was also found.

That is, the present invention is as follows.
(1) A black matrix surface treatment aqueous solution containing at least one aminophosphonic acid compound and treating the surface of a black matrix containing nickel.
(2) The black matrix surface treatment aqueous solution according to (1), wherein the total concentration of the aminophosphonic acid compound is 0.005 to 10% by mass.
(3) The group in which the aminophosphonic acid compound is composed of ethylenediaminetetra (methylenephosphonic acid), propylenediaminepenta (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid), ammonium salts thereof, and alkali metal salts thereof. The aqueous solution for black matrix surface treatment according to (1), which is one or more selected from the group consisting of:
(4) After forming a black matrix containing nickel as a constituent component on a substrate and before forming a color filter, the black matrix surface is treated with the black matrix surface treatment aqueous solution described in (1). It is a surface treatment method of a matrix.

  According to the present invention, in the production of a substrate using a black matrix containing nickel, an aqueous solution for black matrix surface treatment that prevents adhesion of a pigment component accompanying formation of a color filter, is excellent in reliability, and can improve yield. And a black matrix surface treatment method.

(Black matrix surface treatment aqueous solution)
The aqueous solution for black matrix surface treatment (hereinafter sometimes referred to as “surface treatment liquid”) of the present invention may contain at least one aminophosphonic acid compound. There is no particular limitation as long as it does not impair the function of protecting the black matrix surface of the compound. Considering the economical aspect, an aqueous solution containing only the aminophosphonic acid compound is preferable.

  The aminophosphonic acid compound contained in the surface treatment solution only needs to be water-soluble and contain an aminophosphonic acid group. Specifically, ethylenediaminetetra (methylenephosphonic acid), propylenediaminepenta (methylenephosphonic acid), Diethylenetriaminepenta (methylenephosphonic acid). As for its form, free acids or their ammonium salts, alkali metal salts, organic amine salts, etc., and further oxidation of these aminophosphonic acid compounds resulting from oxidation of nitrogen atoms in the molecule to form N-oxides. Things. From the viewpoint of availability and economy, preferred aminophosphonic acid compounds include ethylenediaminetetra (methylenephosphonic acid), propylenediaminepenta (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid), and ammonium salts thereof. Examples include alkali metal salts.

  The component composition constituting the surface treatment liquid only needs to contain one or more aminophosphonic acid compounds listed above, and the concentration range is not particularly limited, but is 0.005 mass% to 10 mass%. It is preferably 0.01% by mass to 5% by mass, and more preferably 0.05% by mass to 2% by mass. By being 0.005 mass%-10 mass%, a black matrix surface can be processed effectively and pigment component adhesion at the time of color filter formation can be prevented.

(Black matrix surface treatment method)
In the black matrix surface treatment method of the present invention, after the black matrix containing nickel as a constituent component is formed on the substrate, the surface of the black matrix before the formation of the color filter is treated with the surface treatment liquid of the present invention. To do. By such treatment, it is considered that an aminophosphonic acid compound is adsorbed on the surface of the black matrix by a chelate bond to form an adhesion preventing layer that prevents adhesion of a pigment component. As a result, it is possible to prevent a decrease in reliability due to the adhering pigment when forming the color filter. Further, the adhesion preventing layer does not impair defects in subsequent processes such as adhesion between the color filter and the black matrix, and further, reliability for display. Furthermore, the yield can be improved.

  There is no particular limitation as long as the surface of the black matrix that is the treatment target is in contact with the surface treatment liquid uniformly, and a dip method and a shower method are exemplified. In addition, what is necessary is just to determine suitably the shower pressure and swing method in a shower system in consideration of liquidity.

  The use temperature of the surface treatment liquid may be appropriately determined depending on the performance of the constituent components, and is performed in the range of 0 ° C to 50 ° C. More preferably, -30 ° C.

  The black matrix containing nickel is formed on the substrate by a known method such as vapor deposition, sputtering, or plating. The form of the black matrix to be formed can be the same as a known one (conventional form using chromium).

  The composition of the black matrix containing nickel may include various metal components and other components as long as Ni is contained in an amount of 50% by mass or more. For example, examples of the metal component include morbden, tantalum, iron, aluminum, zirconium, tungsten, and titanium. A part of the black matrix may be oxidized to form an oxide or the like.

  After the surface treatment is performed by the black matrix surface treatment method of the present invention, a known colored resist of red (R), green (G), or blue (B) is provided on the substrate and the black matrix, A color filter is formed.

  Hereinafter, although an Example is given and a further detail is demonstrated, these Examples do not limit this invention.

(Examples 1-9)
A film containing Ni serving as a black matrix is formed by sputtering on a glass substrate having a thickness of 360 mm × 465 mm and a thickness of 0.7 mm. Then, a positive resist is patterned by a photolithography method, and Ni is used as a mask. The containing film was etched with an etching solution to form a grid-like black matrix having a line width of 100 to 500 μm, a line pitch of 200 to 800 μm, and a thickness of 200 nm. Then, after being immersed in the surface treatment liquid under the conditions shown in Table 1 (surface treatment of the black matrix), it was washed with pure water at room temperature and dried by nitrogen blowing.

  Then, in the yellow room, negative color resists of red, green, and blue are applied on a black matrix by a spin coater, pre-baked at 70 ° C. for 90 seconds on a hot plate, and then sodium bicarbonate at room temperature. The film was immersed in a system developer for 180 seconds, washed with pure water, and dried with nitrogen blow to produce each color filter.

  Subsequently, the surface of the black matrix was observed with an SEM (scanning electron microscope 15,000 to 50,000 times). Table 1 shows “◯” when the pigment component derived from the color resist does not remain, “Δ” when the pigment component remains partially, and “x” when the pigment component remains on one side.

  Note that CR2A20R manufactured by JSR Corporation was used as a red color resist, CR8A20B manufactured by JSR Corporation was used as a blue color resist, and CR5A20G manufactured by JSR Corporation was used as a green color resist.

  Further, ethylenediaminetetra (methylenephosphonic acid) was desalted with a cation exchange resin and then neutralized with ammonia water before use.

(Comparative Example 1 and Reference Examples 1-6)
A black matrix was formed on the substrate in the same manner as in the previous example except that it was immersed in the surface treatment solution under the conditions shown in Table 2 (Comparative Example 1 was not immersed in the surface treatment solution). A color filter was prepared. Subsequently, the surface of the black matrix was observed with an SEM (scanning electron microscope) in the same manner as in the example. The results are shown in Table 2 below.

In the comparative example, even when the pigment component derived from the color resist was red, green, or blue, adhesion to the black matrix was observed. On the other hand, in all of the examples, adhesion of the pigment component derived from the color resist to the black matrix was not observed.
Further, in the reference example using a simple chelating agent or other surface treatment liquid considered to be effective, adhesion of the pigment component was observed in any of red, green, and blue.

Claims (4)

  An aqueous solution for black matrix surface treatment containing at least one aminophosphonic acid compound and treating the surface of a black matrix containing nickel.   The black matrix surface treatment aqueous solution according to claim 1, wherein the total concentration of the aminophosphonic acid compound is 0.005 to 10 mass%.   The aminophosphonic acid compound is selected from the group consisting of ethylenediaminetetra (methylenephosphonic acid), propylenediaminepenta (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid), ammonium salts thereof, and alkali metal salts thereof. The aqueous solution for black matrix surface treatment according to claim 1, wherein the aqueous solution is one or more kinds.   The surface of the black matrix treated with the aqueous solution for black matrix surface treatment according to claim 1, after forming a black matrix containing nickel as a constituent component on a substrate and before forming a color filter. Processing method.