JPH04246594A - Water-repellent and oil-repellent intaglio plate and its manufacture - Google Patents

Abstract

PURPOSE:To obtain a water repellent and oil repellent intaglio plate in which precision and yield of intaglio offset printing are improved by decreasing residue of ink on a surface of the intaglio plate after squeegeeing by a method wherein a chemically adsorbed monomolecular film containing fluorine is formed on the surface. CONSTITUTION:After washing an intaglio plate 1 with organic solvent, solution in which non-aqueous solvent mixed with material containing a carbon fluoride group and a chlorosilane group is dissolved is prepared, and the intaglio plate 1 is dipped therein. Then, since a naturally oxidized film has been formed on a film of the intaglio plate 1, many hydroxide groups are contained in the surface of the oxidized film, and a SiCl group of the material containing the carbon fluoride group and the chorosilane group is reacted with the hydroxide group to generate reaction of dechlorination. Therefore, a chemically adsorbed monomolecular film 6 containing fluorine is formed in a state of chemical combination with a surface of the intaglio plate 1 over the whole surface of the intaglio plate 1. Since this carbon fluoride monomolecular film 6 is excellent in water repellence and oil repellence, residue of ink on the surface of the intaglio plate after squeegeeing can be decreased.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention is applicable to electronic components such as circuit boards, liquid crystal display devices, and thermal heads that require fine patterns, such as dielectric materials (insulators, magnetic materials) and conductors (
The present invention relates to a water- and oil-repellent intaglio plate used when forming wiring (wires, resistors), color filters, and resist patterns by intaglio printing, and a method for manufacturing the same.

0002

[Prior Art] Conventionally, technology for forming fine conductive patterns has been used in the manufacture of electronic components such as circuit boards, liquid crystal display devices, and thermal heads.In recent years, manufacturing methods using conventional photoresists have been used. In comparison, methods for manufacturing fine patterns using various printing methods have been proposed from the viewpoints of productivity, cost, large area, etc. Among these, intaglio offset printing technology is particularly attracting attention as an alternative to conventional screen printing technology [Nikkei Electronics special edition "Flat Panel Display '90" (1988).
9) Posted].

A typical conventional example of the above-mentioned intaglio offset printing will be explained below with reference to FIGS. 4(A) and 4(B). FIG. 4(A) is a perspective view showing an intaglio plate, and FIG. 4(B) is a sectional view showing the operation of filling the intaglio plate with ink. In FIG. 4, 1 is an intaglio plate, 2 is a concave pattern, 3 is ink, 4 is a squeegee, and 5 is an ink residue. Further, the arrow indicates the direction in which the squeegee 4 moves, and the movement of the squeegee 4 fills the concave pattern 2 with the ink 3.

0004

[Problems to be Solved by the Invention] However, when printing is actually performed using the intaglio offset printing method with the above conventional configuration, the pitch of the printing pattern (total of line width and interline width) is several tens of μm or less. However, the finer the pattern, the higher the incidence of defects such as open and short circuits, and the lower the yield of printed circuit boards. To deal with such problems, it is possible to perform overprinting for open defects, or to transfer ink received at different positions to the same place, as proposed in Japanese Patent Application Laid-Open No. 57-169357. Therefore, methods have been devised to reduce the occurrence of open defects such as those caused by defects in intaglio plates and blanket rubber for transfer, but there is a problem in that they are not suitable for mass production.

On the other hand, very few methods have been proposed to reduce the occurrence of short-circuit defects, and in fact, when a thermal head is made using an intaglio offset printing method,
An analysis of the cause of short-circuit defects reveals that over 90% of the causes are ink residue on the surface of the intaglio plate.

In the future, as the pitch of the printed pattern becomes finer, the width between the lines will become shorter, and even a small amount of ink remaining 5 between the concave patterns 2 will cause a short circuit, which was not a problem in the case of a conventional wide pitch. The probability of it becoming defective increases. In addition, the narrower pitch leads to an increase in the number of grooves per unit length of the groove pattern 2, and as a result, the squeegee 4 vibrates finely (the unevenness caused by the groove pattern 2 of the intaglio plate 1 causes the squeegee to vibrate). This means that the ink 3 inside the concave pattern 2 may be physically blown away), even if the squeegee could be squeegeeed without any problem under the conventional squeegee conditions. There was also a new problem: simply by narrowing the pattern pitch, ink residue was more likely to occur.

[0007] As a countermeasure for this new problem of ink residue on the intaglio surface, research has been conducted to smooth the intaglio surface and find optimal conditions for the squeegee (material, hardness, polishing, etc.). The reality is that results that satisfy these requirements have not yet been obtained.

The present invention solves the above-mentioned problems of the conventional example, and by providing an intaglio plate with excellent water and oil repellency, the amount of ink remaining on the surface of the intaglio plate after squeegeeing is reduced, and intaglio offset printing is greatly improved in terms of accuracy and yield. The object of the present invention is to provide an improved water- and oil-repellent intaglio plate and a method for producing the same.

[0009]

[Means for Solving the Problems] In order to solve the above-mentioned problems, a water- and oil-repellent intaglio plate and a method for producing the same according to the present invention are those in which a chemically adsorbed monomolecular film containing fluorine is formed on the surface of the intaglio plate. Intaglio plates are generally made of glass, ceramic, or metal, and contain hydroxyl groups on the surface, and have a chlorosilane group (SiClnX3-n group, n=1,2,3
, X is a functional group), for example, a fluorine carbon group and a chlorosilane group containing a chlorosilane group. A monomolecular film made of the substance is deposited on the surface of the intaglio plate by reacting the chlorosilyl groups of a substance containing a plurality of chlorosilyl groups, or by contacting with a non-aqueous solvent containing a substance containing a plurality of chlorosilyl groups, the hydroxyl groups of the intaglio plate and the above A step of reacting the chlorosilyl groups of a substance containing a plurality of chlorosilyl groups to precipitate the substance on the surface of the intaglio plate, and using a non-aqueous organic solvent to produce siloxane made of a substance containing a plurality of excess chlorosilyl groups remaining on the surface of the intaglio plate. Fluoride is applied to the surface of the intaglio by forming a monomolecular film, and chemically adsorbing a silane surfactant containing a linear carbon chain with a chlorosilane group at one end onto the intaglio to accumulate a monomolecular adsorption film. A carbon-based chemically adsorbed monomolecular cumulative film is formed.

0010

[Operation] Since the water- and oil-repellent intaglio plate constructed in this way has an extremely thin fluorocarbon monomolecular film with a thickness on the nanometer level formed on the surface of the intaglio plate, the accuracy of the intaglio plate is not impaired. In addition, this fluorocarbon-based monomolecular film has excellent water and oil repellency, so even when intaglio printing is performed using extremely sticky ink, it reduces the amount of ink remaining on the intaglio surface after squeegeeing. becomes possible. Furthermore, the friction between the squeegee and the intaglio can be reduced, and the life of the squeegee and the intaglio can be extended. Therefore, it is possible to provide an intaglio plate with a high printing yield.

[0011]

EXAMPLES (Example 1) A water- and oil-repellent intaglio plate according to an example of the present invention and a method for manufacturing the same will be described below with reference to the drawings. FIG. 1 is a perspective view showing an intaglio plate 1 according to the present invention. The intaglio plate 1 is a glass intaglio plate 1 in which a glass chrome mask used for exposing semiconductors is immersed in a hydrofluoric acid-based etchant to partially etch the intaglio plate 1. An intaglio pattern 2 is provided on the surface, and a chemically adsorbed monomolecular film 6 is further formed on the surface to make it water and oil repellent.

FIG. 2 is a conceptual cross-sectional diagram showing the water- and oil-repellent treatment, in which the intaglio plate 1 is washed with an organic solvent and then treated with a non-aqueous solution containing a substance containing fluorocarbon groups and chlorosilane groups. Using a solvent, e.g. CF3(CF2)7(CH2)2SiCl3, 1
% solution [80% n-hexadecane (toluene, xylene, dicyclohexyl may also be used),
10% carbon tetrachloride, 8% chloroform] and immersed the intaglio plate 1 for about 2 hours. Since a natural oxide film is formed on the film of the intaglio plate 1, the surface of this oxide film contains many hydroxyl groups. The SiCl group of the substance containing a fluorocarbon group and a chlorosilane group reacts with the hydroxyl group, and a dechlorination reaction occurs over the entire surface of the intaglio 1.

[0013]

[Chemical formula 1]

The following bonds were formed, and a chemically adsorbed monomolecular film 6 containing fluorine could be formed with a film thickness of about 15 angstroms in a state of chemical bonding with the surface of the intaglio plate 1. Note that the chemically adsorbed monomolecular film 6 was not peeled off at all because it had extremely strong chemical bonds. Also, intaglio 1
Even if the material is a metal such as copper, nickel, or zinc other than glass or ceramic, the surface is covered with a natural oxide film, so naturally it contains hydroxyl groups, and the same chemical adsorption monomolecular film 6 as mentioned above is adsorbed. It could be formed using the same method by simply adjusting the time.

Next, intaglio offset printing was attempted using this intaglio plate 1. First, an intaglio plate (hereinafter referred to as an untreated intaglio plate) that is simply a glass chrome mask used for exposure of semiconductors as an intaglio plate without any surface treatment is used as a conventional intaglio plate, and an untreated intaglio plate is coated with fluorine according to the present invention. A water- and oil-repellent intaglio plate 1 (hereinafter referred to as a treated intaglio plate) was prepared by forming a chemically adsorbed monomolecular film 6 containing the following on its surface.

[0016] The printing machine used was one in which the stage on which the intaglio plate and the printing material were placed was moved with high precision by a computer-controlled servo motor. The printing material was a glazed alumina substrate (60 x 230 mm, thickness 0.8 mm) used as a facsimile thermal head.
), and etching resist ink and gold resinate ink were used as printing inks. As a printing method,
First, a solid pattern of gold resinate was printed on a glazed alumina substrate using a screen printing method, and this was fired to create a glazed alumina substrate on which a thin film of gold was formed. Next, an etching resist was printed on the glazed alumina substrate on which the gold thin film was formed using an intaglio offset printing machine, and then the gold on the surface of the glazed alumina substrate was etched using a gold etchant. A comparison was made using an untreated intaglio and a treated intaglio. Finally, the etching resist was removed, and a gold electrode pattern for an A4 size thermal head with a pitch of 50 microns was formed (hereinafter referred to as an etching substrate).

[0017] Also, using gold resist ink instead of etching resist ink, a gold electrode pattern of an A4 size thermal head with a pitch of 50 microns was directly printed on the alumina glaze substrate by an intaglio offset printing method. Incidentally, in the same manner as described above, a comparison was made using an untreated intaglio plate and a treated intaglio plate as the metal intaglio plate 7. The glazed alumina substrate on which this gold electrode pattern was printed was fired to obtain a substrate similar to the etched substrate (hereinafter referred to as a directly printed substrate).

The printing yields of etched substrates and directly printed substrates were investigated below. Printing yield is evaluated by the number of shorts and open defects in the 50 micron pitch wiring parts, which are approximately 20,000 locations in each sample out of 10 samples for thermal heads, and the evaluation results are shown below. show.

[0019] In etched substrate, untreated intaglio short
85 locations Open 25 locations Processed intaglio Short 8 locations
Open 4 places Direct printing board, untreated intaglio short 13
3 locations open 38 locations processed intaglio short 5 locations
Opens From the results of four or more locations, it can be seen that the occurrence of shorts and opens is lower in the treated intaglio than in the untreated intaglio in both etched substrates and direct printed substrates. When we observed the short-circuited areas of a sample made using an untreated intaglio plate under a microscope, we found that about 90% of the short-circuited areas were caused by ink remaining between the lines of the fine pattern. Furthermore, when we investigated the causes of open circuits in each sample, we found that most of them were caused by foreign objects (dust). Furthermore, the number of dust was lower in the treated intaglio than in the untreated intaglio. This was because less foreign matter adhered to the treated intaglio than to the untreated intaglio. Furthermore, compared to untreated intaglio, treated intaglio allows the squeegee to slide better against the intaglio (less friction), and the problem of ink splashing caused by the squeegee when the pattern pitch becomes small, which was a problem in the past, was reduced. . From these results,
Furthermore, the pattern of the intaglio 1 can be made into a fine pattern.

[0020] Furthermore, by installing an intaglio offset printing machine in a screen room in the future, the yield can be further increased.

Of the chemisorption monomolecular film 6 formed on the entire surface of the intaglio plate 1, the chemisorption monomolecular film 6 inside the intaglio pattern 2 (groove) may be removed. In this case, even if water-based ink or the like is used, the ink 3 will not be repelled (become water- and oil-repellent) within the intaglio pattern 2, and stable printing can be performed. In addition, the chemically adsorbed monomolecular film 6 of the desired portion
To remove it, attach a sticky substance (resin such as polyisobutylene) to the surface of the chemically adsorbed monomolecular film 6 in the area you want to leave, and then use oxygen plasma (oxygen asher used to remove photoresist, etc.). This allows you to remove unnecessary parts.

(Embodiment 2) A second embodiment of the present invention will be described below with reference to FIG. A metal intaglio plate 7 that is hydrophilic as a material for the intaglio plate 1 but contains a small proportion of hydroxyl groups
(metals such as aluminum, stainless steel, silver, etc.), substances containing multiple trichlorosilyl groups [e.g., SiCl
4, or SiHCl3, SiH2Cl2, Cl-(S
iCl2O)n-SiCl3 (n is an integer). In particular, Si
If Cl4 is used, it has a small molecule and high activity towards hydroxyl groups, so it has a great effect of uniformly making the intaglio surface hydrophilic.] When immersed for about 30 minutes in a solution of 1% by weight dissolved in a non-aqueous solvent such as chloroform solvent, , Figure 3(A)
As shown in the figure, there are hydrophilic OH groups 8 on the surface of the metal intaglio plate 7.
is present to some extent, a dehydrochlorination reaction occurs on the surface and a chlorosilane monomolecular film of a substance containing a plurality of trichlorosilyl groups is formed.

For example, if SiCl4 is used as a substance containing a plurality of trichlorosilyl groups, a small amount of hydrophilic OH groups 8 are exposed on the surface of the metal intaglio plate 7, so a dehydrochlorination reaction occurs on the surface.

[0024]

[Case 2]

Molecules are formed on the surface via -SiO- bonds. After that, by washing with a non-aqueous solvent such as chloroform and further washing with water, the SiCl4 molecules that have not reacted with the metal intaglio plate 7 are removed, and the surface is

[
0026

[Chemical formula 3]

A siloxane monomolecular film 9 such as the following is obtained. Incidentally, the siloxane monomolecular film 9 formed at this time is completely bonded to the metal intaglio plate 7 through the chemical bond of -SiO-, so that it will not peel off at all. Moreover, the obtained siloxane monomolecular film 9 has many SiOH bonds on the surface,
As shown in FIG. 3(B), approximately three times as many OH groups 8 as the original OH groups are generated.

Therefore, a non-aqueous solvent containing a substance containing a fluorocarbon group and a chlorosilane group, such as C
Using F3(CF2)7(CH2)2SiCl3, 1%
A solution [80% n-hexadecane (
toluene, xylene, dicyclohexyl), 1
0% carbon tetrachloride, 8% chloroform], and immersed the metal squeegee 7 on which the siloxane monomolecular film 9 having a large number of SiOH bonds was formed on the metal intaglio plate 7 for about an hour.

[0029]

[C4]

As shown in FIG. 3(C), a chemically adsorbed monomolecular film 6 containing fluorine is chemically bonded to the surface of the metal intaglio plate 7 to form a film thickness of approximately 15 angstroms. was completed. Note that the chemically adsorbed monomolecular film 6 containing fluorine had extremely strong chemical bonds, so it did not peel off at all.

Furthermore, in the above examples, CF3(CF2)7(CH2)2SiCl3 was used as the fluorocarbon surfactant, but C═C or C≡C groups may be added or incorporated into the alkyl chain portion. If this is done, the hardness of the chemisorbed monomolecular film 6 containing fluorine can be further improved since it can be crosslinked by electron beam radiation of about 5 megarads after the chemisorption monomolecular film 6 containing fluorine is formed.

In addition to the above-mentioned fluorocarbon surfactants, CF3CH2O(CH2)15SiCl3CF3(CH
2) 2Si(CH3)2(CH2)15SiCl3F(
CF2)8(CH2)2Si(CH3)2(H2)9S
iCl3 CF3COO(CH2)15SiCl3CF3(CF2
)5(CH2)2SiCl3 etc. was confirmed to be usable.

Next, intaglio offset printing was attempted using this metal intaglio plate 7. First, a metal intaglio plate that has not been subjected to any surface treatment as a conventional intaglio plate (hereinafter referred to as an untreated metal intaglio plate) and a chemically adsorbed monomolecular film 6 containing fluorine according to the present invention are applied to the untreated metal intaglio plate. A water- and oil-repellent metal intaglio plate 7 (hereinafter referred to as treated metal intaglio plate) was prepared by forming on the surface.

[0034] The same intaglio offset printing machine, ink, and printing material as in Example 1 were used, and similar printing experiments were conducted using etching resist ink and gold resinate ink as in Example 1. . Here, a comparison was made using an untreated metal intaglio and a treated metal intaglio as the metal intaglio (hereinafter referred to as metal intaglio etching substrate).

[0035] Also, using gold resist ink instead of etching resist ink, a gold electrode pattern of an A4 size thermal head with a pitch of 50 microns was directly printed on the alumina glaze substrate by an intaglio offset printing method. In the same manner as described above, a comparison was made using an untreated metal intaglio plate and a treated metal intaglio plate as the metal intaglio plate 7. The glazed alumina substrate on which this gold electrode pattern was printed was fired to obtain a substrate similar to the etched wiring substrate (hereinafter referred to as a metal intaglio directly printed substrate).

The printing yields of the metal intaglio etched substrate and the metal intaglio directly printed substrate were investigated below. Printing yield is evaluated by the number of shorts and open defects in the 50 micron pitch wiring parts, which are approximately 20,000 locations in each sample out of 10 samples for thermal heads, and the evaluation results are shown below. show.

In metal intaglio etching substrate, untreated metal intaglio short
85 locations Open 25 locations
Treated metal intaglio short 8 places Open 4 places In metal intaglio direct printing board, untreated metal intaglio short 1
33 places open 38 places Treated metal intaglio Short 5 places Open From the results of 4 or more places, shorts and opens occur more often with treated metal intaglio than with untreated metal intaglio on etched substrates and direct printing substrates. It can be seen that there are few

When the short-circuited area of the sample made using an untreated metal intaglio was observed under a microscope, it was found that approximately 9.
It was found that 0% was caused by ink remaining between the lines of the fine pattern portion. Furthermore, when we investigated the causes of open circuits in each sample, we found that most of them were caused by foreign objects (dust). Furthermore, the number of dust was lower in the treated metal intaglio than in the untreated metal intaglio. This is because, as in the first example, less foreign matter adhered to the treated metal intaglio than to the untreated metal intaglio.

Furthermore, of the chemisorption monomolecular film 6 formed on the entire surface of the intaglio plate 1, the chemisorption monomolecular film 6 inside the intaglio pattern 2 (groove) may be removed. In this case, even if water-based ink or the like is used, the ink 3 will not be repelled (become water- and oil-repellent) within the intaglio pattern 2, and stable printing can be performed. In addition, in order to remove the chemisorption monomolecular film 6 of the desired portion, it is necessary to remove the chemisorption monomolecular film 6 of the desired portion.
After attaching a sticky substance (resin such as polyisobutylene) to the surface, unnecessary portions can be removed by using oxygen plasma (oxygen asher used for removing photoresist, etc.).

[0040]

[Effects of the Invention] As described above, the water- and oil-repellent intaglio plate according to the present invention is constructed, and an extremely thin fluorocarbon monomolecular film with a film thickness on the nanometer level is formed on the surface of the intaglio plate, which impairs the accuracy of the intaglio plate. Never. Additionally, this fluorocarbon-based monomolecular film has excellent water and oil repellency, making it difficult for ink stains to occur on the surface of the intaglio plate, thus greatly increasing printing yields and having great industrial value. .

[Brief explanation of the drawing]

FIG. 1 is a perspective view showing the structure of an intaglio plate according to an embodiment of the present invention.

[Figure 2] Conceptual cross-sectional diagram of the surface of the intaglio plate of the present invention enlarged to the molecular level

[Fig. 3] (A) to (C) A cross-sectional process conceptual diagram showing the second embodiment of the present invention, with the surface of an intaglio plate enlarged to the molecular level.

[Fig. 4] (A) A perspective view showing a conventional intaglio plate. (B) A sectional view showing the work of filling ink into a conventional intaglio plate.

[Explanation of symbols]

1 Intaglio 2 Intaglio pattern 3 Ink 4 Squeegee 5 Ink remaining 6　Chemisorption monolayer 7 Metal intaglio 8 OH group 9 Siloxane monolayer

Claims (7)

[Claims] 1. A water- and oil-repellent intaglio plate, characterized in that a chemically adsorbed monomolecular film containing fluorine is formed on the surface. 2. A water- and oil-repellent intaglio plate, characterized in that a chemically adsorbed monomolecular film containing fluorine is partially formed. 3. A water- and oil-repellent intaglio plate, characterized in that a chemically adsorbed monomolecular film containing fluorine is formed on the surface via at least a siloxane monomolecular film. 4. After thoroughly cleaning the processed intaglio plate, one end has a chlorosilane group (SiClnX3-n group, n=1,
2, 3, X is a functional group) and a fluorocarbon group at one end is immersed in an organic solvent in which a chlorosilane surfactant is dissolved, and a chemically adsorbed monomolecular film made of the chlorosilane surfactant is prepared. A method for producing a water- and oil-repellent intaglio plate, comprising the step of forming a water- and oil-repellent intaglio plate over the surface of the intaglio plate. 5. After thoroughly washing the processed intaglio plate, it is brought into contact with a non-aqueous solvent containing a substance containing a plurality of chlorosilyl groups to separate the hydroxyl groups of the intaglio plate and the chlorosilyl groups of the substance containing a plurality of chlorosilyl groups. a step of precipitating a substance containing a plurality of chlorosilyl groups on the surface of the intaglio plate, and washing and removing the excess substance containing a plurality of chlorosilyl groups remaining on the intaglio plate using a non-aqueous organic solvent,
A step of forming a monomolecular film made of a substance containing a plurality of silole groups on the intaglio plate by reacting with water, and a chlorosilane group (SiClnX3-n group, n=1,2,3, X is a functional group) at one end. and a step of chemically adsorbing a chlorosilane surfactant containing a linear fluorocarbon group at one end onto the intaglio to form a monomolecularly adsorbed film. Production method. Claim 6: S as a substance containing a plurality of chlorosilyl groups
iCl4, or SiHCl3, SiH2Cl2, Cl
The method for producing a water- and oil-repellent intaglio plate according to claim 5, characterized in that -(SiCl2O)n-SiCl3 (n is an integer) is used. 7. CF3-(CF2)n-R-SiXpCl3-p(n
is 0 or an integer, R represents an alkyl group, C═C, C≡C, or a functional group containing a silicon or oxygen atom, but may be omitted; X is H or a substituent such as an alkyl group; p is 0 or 1 or 6. The method for producing a water- and oil-repellent intaglio plate according to claim 5, characterized in that 2) is used.