JPH10236009A - Intaglio for printing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To keep the release property of ink high, and prevent the release property from decreasing due to the repetition of printings by treating the surface of glass with a silylation agent. SOLUTION: The surface of a substrate made of glass in treated with a silylation agent before usage, and preferably, the silylation agent is applied on the surface of the glass substrate on the surface of which recessed parts are formed, and heated to obtain this intaglio. At this time, as the silylation agent, the application of organohalosilane is preferable, and as the one which is most suitably applied, dichlorodimethylsilane and trichloromethylsilane can be counted. When such a silylation agent is applied on the surface of the glass substrate, the silylation agent and the glass quickly react at a normal temperature, and a strong bond between the atoms is formed. The surface of the substrate treated in such a manner has a high water repellence, and is excellent in the release property of ink, and at the same time, even after the repetition of printings, an excellent transfer property of ink can be maintained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an intaglio printing plate, and more particularly, to an intaglio printing plate suitable for manufacturing color filters for liquid crystal displays, high-density electronic circuit boards, and the like.

[0002]

2. Description of the Related Art In the above-mentioned color filters, electronic circuit boards and the like, it is necessary to form a fine pattern having a line width of about 10 to 150 μm with extremely high precision. Therefore, the photolithography method has been conventionally used for the production, but there is a problem that the production cost is high.
Attempts have been made to reduce costs by using a printing method that has a simple process and mass productivity.

In order to form a fine pattern with high precision by a printing method, the printed shape must be excellent, that is, faithfully reproducing the line width and thickness of the pattern, and the shape of the pattern edge must be sharp. Something is required. Intaglio offset printing is the most suitable printing method for forming fine patterns with high precision among various printing methods, especially when using a blanket whose surface rubber layer is made of silicone rubber. It is known that the transfer of the ink from the blanket to the printing substrate is extremely excellent, and that the printed shape becomes good.

However, since the intaglio used in the intaglio offset printing method is usually made of glass or metal and has low ink releasability, the ink in the intaglio recess is not completely transferred to the blanket. A phenomenon (piling) in which a part thereof remains inside the concave portion occurs.
As a result, for example, in the case of forming a color filter layer composed of red (R), green (G), and blue (B) in the production of a color filter, there is no significant effect, but the line of the pattern is larger than the color filter layer. Narrow width,
When forming a black matrix layer that requires higher precision, the line width and thickness are uneven due to the occurrence of piling, the pattern edge is rounded, and the printed shape is degraded. There is a problem that the image quality of the liquid crystal display is adversely affected, such as a decrease in contrast and color unevenness.

[0005]

The problem to be solved by the present invention is disclosed in
JP-A-39065 discloses a printing intaglio in which the surface of an intaglio recess is coated with silicone rubber to improve ink releasability for the purpose of suppressing piling. However, since the silicone rubber has a problem of swelling with the solvent of the ink, the adhesiveness to the intaglio and the mechanical strength of the silicone rubber itself decrease, and it is not possible to suppress the piling for a long time.

Further, the above publication discloses a method of printing after forming a layer of a hot-melt adhesive in an intaglio recess, and according to this method, ink is easily transferred from the intaglio to the blanket. However, it is not practical because the printing process becomes extremely complicated. JP-A-2-13534
In JP-A-8, in order to enhance the ink releasability, a polytetrafluoroethylene resin (tetrafluoroethylene resin) is provided on the surface.
An intaglio printing plate having a coating film formed thereon is disclosed. However, the coating film is formed by the plasma CVD method, and has a problem of high cost. In addition, the thickness of the formed coating film is extremely thin, usually about 0.05 μm. Since the film strength is low, there is also a problem that the ink releasability does not last for a long time and the ink releasability decreases when printing is repeated.

On the other hand, the present inventors preferably apply a water-repellent treatment to the intaglio surface in order to improve the ink releasability of the intaglio, and it is most effective to use a silicone-based material for the water-repellent treatment. Was found. However, even if a silicone rubber, which is particularly excellent in ink releasability among the silicone-based materials, is used, there is a problem that the adhesion to the intaglio and the mechanical strength are reduced with time, as described above. When dimethyl silicone oil is applied to the surface of the intaglio plate and heated, a highly water-repellent coating film is formed on the intaglio surface, but the durability of the coating film is low. The problem of lowering occurs.

Accordingly, an object of the present invention is to provide an intaglio printing plate having high ink releasability and which does not decrease in ink repetition even when printing is repeated.

[0009]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have conducted various studies on various silicone-based materials. As a result, when the surface of a glass substrate was treated with a silylating agent, an ink was obtained. The present inventors have found a new fact that an intaglio printing plate having high releasability and having high ink releasability even when printing is repeated can be obtained, and the present invention has been completed.

That is, the intaglio printing for printing of the present invention is characterized by being made of glass and having its surface treated with a silylating agent. In the intaglio printing plate of the present invention, the surface of the glass substrate is treated by applying a silylating agent or by applying a silylating agent and heating.
When the silylating agent is applied to the surface of the glass substrate, the silylating agent and the glass quickly react at room temperature, and the formula: -S
It is considered that a strong bond represented by i-O-Si- is formed. The surface of the substrate treated in this way has high water repellency, excellent ink releasability, and excellent durability. As a result, excellent ink transferability can be maintained for a long period of time.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the intaglio printing plate of the present invention will be described in detail. As described above, the intaglio printing plate of the present invention is obtained by treating the surface of a glass substrate with a silylating agent, and more specifically, the surface inside the recess (inner surface).
The entire surface of the glass substrate containing is treated with a silylating agent.

Examples of the silylating agent include organohalosilanes, silazanes such as hexamethyldisilazane, N, O-bis (trimethylsilyl) acetamide (BSA), and N-trimethylsilylacetamide (MS).
A), N, N'-bis (trimethylsilyl) urea (B
TSU), N-trimethylsilyldiethylamine (TD
EA), N-trimethylsilylimidazole (TSI)
M) and the like, and among them, organohalosilane is preferably used.

The organohalosilanes are further divided into the following six general formulas (1) to (6). RSiH ₂ X (1) RSiHX ₂ (2) RSix ₃ (3) R ₂ SiHX (4) R ₂ SiX ₂ (5) R ₃ SiX (6) (wherein X represents a halogen atom and R represents an alkyl group , An aryl group or an aralkyl group.) Examples of the halogen atom corresponding to X in the above general formulas (1) to (6) include fluorine, chlorine, bromine and iodine.

Examples of the alkyl group corresponding to R include groups having 1 to 6 carbon atoms such as methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, n-pentyl and n-hexyl. can give. Examples of the aryl group include groups such as phenyl and naphthyl. Examples of the aralkyl group include groups such as benzyl and phenethyl.

In the present invention, the boiling point is normal temperature (20 ° C.)
If it is above, any of the silylating agents exemplified above can be used.However, from the viewpoints of adhesion to a glass surface, water repellency, and availability, the above general formulas (1) to (6) Among the organohalosilanes to which it belongs, it is preferred to use an organochlorosilane in which the group X is a chlorine atom. In addition, the above general formula
Among (1) to (6), general formulas (3),
It is preferable to use the organohalosilane of (5) or (6).

Among the organohalosilanes exemplified above, dichlorodimethylsilane and trichloromethylsilane are most preferably used. Especially,
When dichlorodimethylsilane is used, two methyl groups are arranged on the surface of the intaglio plate, so that more excellent water repellency is exhibited. As the glass substrate in the present invention, for example, soda lime glass, non-alkali glass, quartz glass, low alkali glass, low expansion glass and the like can be used. Above all, soft glass such as soda lime glass is preferably used because a fine pattern can be reproduced with high accuracy.

The depth of the concave portion formed on the surface of the glass substrate is not particularly limited, but is usually 2 to 10 μm, preferably 3 to 10 μm, depending on the thickness of the ink layer formed on the substrate.
It is set in the range of 6 μm. The pattern of the concave portion may be appropriately set according to a desired print image, and examples thereof include a stripe pattern and a dot pattern. The line width of the pattern may be set as appropriate according to the desired print image, but is usually set in the range of 10 to 100 μm.

Next, a method for manufacturing an intaglio printing plate according to the present invention will be described. The intaglio printing plate of the present invention can be obtained by applying a silylating agent to the surface of a glass substrate having a concave portion formed on the surface, and drying or heating at room temperature. Examples of a method for applying the silylating agent include application using a dipping method, a spin coater, a bar coater, or the like. However, since the silylating agent (particularly, the organohalosilane exemplified above) also reacts with moisture in the air, it is applied in a short time. It is preferable to use a coating method using a bar coater (bar coating method).

The silylating agent exemplified above reacts promptly with the glass surface at room temperature, so that it is not necessary to perform heat treatment after coating. However, when heat treatment is performed, the effect of the surface treatment is reduced even if printing is repeated. This is preferable because it is difficult to perform the process. This heat treatment is suitably performed in a temperature range of 150 to 350 ° C., preferably 200 to 300 ° C., for 0.1 to 2 hours, preferably 0.5 to 1 hour. If the temperature of the heat treatment exceeds the above range, there is a possibility that adverse effects such as cracking and distortion of the intaglio plate itself may occur.

In the intaglio printing for printing according to the present invention, the amount of the silylating agent to be applied is 0.1 to 100 cm ² per surface of the glass substrate.
Suitably 5 to 2 ml. Since the silylating agent (particularly, organohalosilane) has high reactivity, when the coating amount exceeds the above range, there is a possibility that a problem that it becomes difficult to remove an excess silylating agent may occur. On the other hand, when the coating amount is less than the above range, the effect of the present invention of enhancing the ink releasability may not be obtained.

Next, the method of using the intaglio printing plate of the present invention will be described. The intaglio printing for printing of the present invention, as described above,
The purpose is to enhance the ink releasability to facilitate the transfer of the ink from the intaglio to the blanket, that is, to improve the transferability of the ink from the intaglio to the blanket. The object of the present invention is to reproduce the printed image of the printing medium with high precision on the surface of the printing medium.

Therefore, when performing intaglio offset printing using the intaglio printing for printing of the present invention, the blanket is excellent in the ink receptivity from the intaglio and the transferability of the ink from the blanket to the printing material is excellent. It is preferable to use a fine pattern from the viewpoint of reproducing a fine pattern with high accuracy. As the blanket, for example, a blanket whose surface rubber layer is made of silicone rubber is suitably used. Various silicone rubbers such as a millable type, a room temperature curing (RTV) type, and an electron beam curing type can be used as the silicone rubber.

The surface rubber layer made of the silicone rubber preferably has a smooth surface, and more specifically, the surface roughness is preferably 0.5 μm or less, more preferably 10-point average roughness, more preferably. 0.3 μm or less. The hardness (JISA) of the silicone rubber is preferably from 20 to 80 degrees, and more preferably from 40 to 60 degrees. In order to adjust the hardness of the silicone rubber, silicone oil, silicone gel, or the like may be appropriately blended.

As a support for the blanket, if the surface is flat, a plastic such as polyethylene terephthalate (PET), polyether sulfone (PES), polyester, polycarbonate (PC) or a metal plate such as aluminum or stainless steel is used. Etc. can be used. The blanket may be provided with a porous foam layer between the surface rubber layer and the support or on the back surface of the support. The thickness of the foam layer, the expansion ratio, and the like may be appropriately set in consideration of the printability of the blanket.

[0025]

The present invention will be described below with reference to examples and comparative examples. (Manufacture of Intaglio for Printing) Example 1 As a glass substrate, a soda-lime glass substrate having a concave portion formed of a stripe pattern having a depth of 4 μm and a line width of 50 μm was formed on the surface.

Dichlorodimethylsilane (KA-22 manufactured by Shin-Etsu Chemical Co., Ltd.) was applied to the surface of the glass substrate by a bar coating method. In this application, 300 m
About 1 ml of dichloromethylsilane was used for the pattern in the area of mx370 mm, and excess dichlorodimethylsilane was removed. After the application, the glass substrate was left at room temperature to react dichlorodimethylsilane with the substrate surface to obtain an intaglio printing plate. The intaglio printing plate was uniformly treated on both the surface of the substrate and the inner surface of the recess.

Example 2 In the same manner as in Example 1, dichlorodimethylsilane (described above) was applied to the surface of a glass substrate by dip coating, and then the glass substrate was heated at 290 ° C. for 0.5 hour for printing. An intaglio for printing was obtained. Example 3 An intaglio printing plate was obtained in the same manner as in Example 1 except that trichloromethylsilane (KA-13 manufactured by the company) was used instead of dichlorodimethylsilane.

Example 4 An intaglio printing plate was obtained in the same manner as in Example 2 except that trichloromethylsilane (described above) was used instead of dichlorodimethylsilane. Comparative Example 1 Dimethyl silicone oil (KF96-300cs manufactured by the same company) was applied to the same glass substrate as in Example 1 by a dip coating method, and heated at 290 ° C. for 0.5 hour to form a film on the surface of the glass substrate. An intaglio printing plate having a coating film of about 0.5 μm was obtained.

(Printing Test) Using the intaglio printing for printing obtained in the above Examples and Comparative Examples, the transferability of the ink from the intaglio to the blanket was evaluated. In addition, an intaglio made of soda lime glass (depth 5
A printing test was carried out in the same manner as in Examples 1 to 4 and Comparative Example 1 above, using the same having a concave portion formed of a stripe pattern having a line width of 50 μm and a line width of 50 μm.

The method of the printing test is as follows. The intaglio plate for printing the above Examples, Comparative Examples or blanks, and a blanket whose surface rubber layer was made of silicone rubber (hardness: 32 degrees) were arranged on a normal flatbed offset printing press. Next, a black ink (viscosity: 600 poise) made of a polyester resin was filled in the intaglio recess, and the ink was transferred from the intaglio to the blanket. The transfer speed of the ink from the intaglio to the blanket (the relative movement speed between the intaglio and the blanket) is 30.
mm / s.

Further, the black ink transferred to the blanket was transferred to the surface of a soda lime glass plate as a printing material. The transfer speed of the ink from the blanket to the printing material (the relative movement speed between the blanket and the printing material) is 30.
It was 0 mm / s. (Evaluation of transferability of ink) In the above printing test, the ratio (%) of the ink transferred from the intaglio to the blanket twice after printing on the printing material 10 times and after printing 10,000 times. Was measured. The higher the percentage (%) of the transferred ink, the better the transferability of the ink.

(Evaluation of Printing Shape) The shape of the stripe pattern formed on the printing material by the above printing test was observed with an electron microscope, and the quality of the printing shape was evaluated. The evaluation criteria are shown below. 〇: The printed shape was extremely good. Δ: Problems occurred such that the line width and thickness of the pattern were disturbed and the edges were rounded.

×: Since the transferability of the ink was extremely low, there was a problem that the pattern was blurred. (Evaluation of Hydrophobicity of Intaglio Surface) About 5 μl of distilled water was dropped on each surface of the intaglio printing plates of the above Examples, Comparative Examples, or blanks to form water droplets, and then the contact angle between the water droplets and the intaglio surface. (°) was measured.

The larger the contact angle (°), the higher the water repellency of the surface of the printing intaglio. Table 1 shows the above results.

[0035]

[Table 1]

As is clear from Table 1, the intaglio printing plates of Examples 1 to 4 whose surfaces were treated with a silylating agent had high ink transferability and reduced the contact angle even after repeated printing. Less is. Therefore, complete transfer of the ink was realized over a long period of time, and a pattern having a very excellent printed shape was obtained. On the other hand, in Comparative Example 1, although the water repellency of the surface was high in the early stage of printing and the transferability of the ink was excellent, the water repellency was significantly reduced and the transferability of the ink was also significantly reduced by repeating printing.

In the blank, since the intaglio printing plate was not subjected to the water-repellent treatment, the transferability of the ink was low even at the beginning of printing.

[0038]

As described above in detail, according to the intaglio printing for printing of the present invention, excellent ink transferability can be maintained even when printing is repeated. Accordingly, the intaglio printing plate of the present invention is suitably used, for example, for producing a color filter.

Claims (4)

[Claims] An intaglio printing plate for printing, comprising glass, the surface of which is treated with a silylating agent. 2. The intaglio printing for printing according to claim 1, wherein the treatment comprises applying a silylating agent to the surface of the glass substrate and heating. 3. The intaglio printing plate according to claim 1, wherein the silylating agent is an organohalosilane. 4. The method according to claim 3, wherein said organohalosilane is dichlorodimethylsilane or trichloromethylsilane.
Intaglio printing for printing as described.