JP2009110946A - Ink composition for printing, and forming method of black matrix and bus electrode of front plate for plasma display panel using above composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ink composition for printing capable of achieving both conductivity and black chromaticity, and further, capable of forming a black matrix and a bus electrode on a substrate with one kind of an ink composition for printing. <P>SOLUTION: The ink composition for printing is for forming a film of a desired printing pattern by printing on a transparent electrode provided on the surface of a transparent substrate, drying and burning the formed film of the printing pattern, and forming the black matrix and the bus electrode of a front plate for a plasma display panel. The composition includes conductive metal powder, black pigment powder, glass frit, resin components, solvent constituents and a dispersant, the glass frit colored in black by color pigment. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a printing ink composition that can be used for forming a black matrix of a front plate for a plasma display panel (hereinafter referred to as PDP) or a bus electrode, and a PDP using the composition. The present invention relates to a method of forming a black matrix and a bus electrode on a front plate, and a fired body formed by this method.

  In recent years, a PDP attracting attention as a large color display is composed of a front plate and a back plate used as a display unit. In the front plate, a black matrix is formed on the transparent electrode of the front plate in order to increase display contrast.

  Also, the pattern of the bus electrode is prepared by applying a black photosensitive paste to the entire surface of the front plate, further adjusting the photosensitive silver paste to a predetermined thickness, drying it, It is formed by photolithography that exposes and develops according to the shape of the pattern (see, for example, Patent Document 1).

Further, when forming the front plate electrode for PDP by the intaglio offset printing method, using a transfer body in which the surface rubber layer is made of silicone rubber, (1) with black ink containing black metals on a transparent substrate A step of pattern printing, and (2) a step of laminating and printing a conductive metal ink on the black ink pattern, and (3) a step of firing the layered and printed ink pattern at 500 ° C. or higher, Before the PDP, wherein the black ink contains the resin (A) and the silicone oil (B) in a ratio of 3 to 50 parts by weight of (B) with respect to 100 parts by weight of (A). A method for manufacturing a face plate has been proposed (see, for example, Patent Document 2).
JP 2003-151450 A ([0040] to [0047]) JP 2004-362830 A (Claim 1)

  The reason why the two types of pastes are required to be applied to the bus electrode is that the black photosensitive paste can make the bus electrode black enough, but the conductivity is insufficient, whereas the photosensitive silver paste This is because although it is possible to make the conductivity good, it is difficult to achieve both good conductivity and sufficient blackness, such as insufficient blackness.

  In the photolithography method as described in Patent Document 1, most of the black paste and silver paste applied to the entire surface of the front plate are washed and removed after the exposure / development process, which is problematic in terms of material utilization efficiency. There is. In addition, since it is necessary to repeat the processes such as coating, exposure, and development in each of the black photosensitive paste and the photosensitive silver paste, a large cost is required for manufacturing the bus electrode.

  Moreover, regarding the electrode forming method by the intaglio offset printing method as in Patent Document 2, the problem of material utilization efficiency can be cleared, but black ink and conductive metal ink need to be printed twice at a time. There is still a problem in terms of production efficiency.

  The objective of this invention is providing the ink composition for printing which can improve blackness, without impairing electroconductivity.

  Another object of the present invention is to provide a printing ink composition that can be commonly used for forming a black matrix and a bus electrode.

  Still another object of the present invention is to provide a method for forming a black matrix and a bus electrode of a PDP front plate using the above printing ink composition, and a fired body formed by this method.

  According to the first aspect of the present invention, a plasma display is formed by printing on a transparent electrode provided on the surface of a transparent substrate to form a coating film having a desired printing pattern, and drying and baking the coating film having the formed printing pattern. A printing ink composition for forming a black matrix and a bus electrode of a front plate for a panel, the composition comprising a conductive metal powder, a black pigment powder, a glass frit, a resin component, a solvent component, and a dispersant, A printing ink composition characterized in that the glass frit is colored black with a coloring pigment.

  The invention according to claim 2 is the invention according to claim 1, wherein the element contained in the color pigment is one or more elements selected from the group consisting of Cr, Fe, Co, Mn and Cu. Is a printing ink composition.

  The invention according to claim 3 is the invention according to claim 1 or 2, and is an ink composition for offset printing having a viscosity of 1 to 10 Pa · s.

  The invention according to claim 4 is the invention according to claim 1 or 2, and is an ink composition for screen printing having a viscosity of 10 to 1000 Pa · s.

  The invention according to claim 5 forms the coating film of the printing pattern by printing the printing ink composition according to any one of claims 1 to 4 on the transparent electrode provided on the surface of the transparent substrate, A method for forming a black matrix and a bus electrode of a front plate for a plasma display panel, wherein the formed coating film of the printed pattern is dried and baked.

  The invention according to claim 6 is the invention according to claim 5, wherein printing when forming the coating film is performed by an offset printing method using a printing ink composition having a viscosity of 1 to 10 Pa · s. This is a method of forming a black matrix and a bus electrode of a front panel for a plasma display panel.

  The invention according to claim 7 is the invention according to claim 5, wherein printing when forming the coating film is performed by a screen printing method using a printing ink composition having a viscosity of 10 to 1000 Pa · s. This is a method of forming a black matrix and a bus electrode of a front panel for a plasma display panel.

  The invention according to claim 8 is a fired body formed by the method according to any one of claims 5 to 7.

  According to the present invention, a printing ink composition containing a conductive metal powder, a black pigment powder, a glass frit, a resin component, a solvent component, and a dispersant, and the glass frit is colored black with a color pigment on a substrate. By performing pattern printing, drying, and baking, it is possible to collectively form a black matrix and bus electrodes that achieve both good conductivity and sufficient blackness. Furthermore, this invention can provide the method of forming the black matrix and bus electrode of the front plate for PDP using this printing ink composition, and the fired body formed by this method.

  Next, the best mode for carrying out the present invention will be described with reference to the drawings.

  The printing ink composition of the present invention is printed on a transparent electrode provided on the surface of a transparent substrate to form a coating film having a desired printing pattern, and after the coating film having the formed printing pattern is dried, printing is performed. It is a composition for firing a coating film of a pattern to form a black matrix and a bus electrode of a front panel for a plasma display panel.

  The printing ink composition includes a powder component composed of pigment powder and glass frit, a resin component, a solvent component, and a dispersant. The pigment powder is composed of a conductive metal powder and a black pigment powder. When the conductive metal powder is 100 parts by mass, the pigment powder is preferably blended so that the black pigment powder has a ratio of 2 to 50 parts by mass. -20 mass parts is more preferable. It is preferable to mix so that the glass frit is 5 to 30 parts by mass with respect to 100 parts by mass of the conductive metal powder, and more preferably 10 to 20 parts by mass. About the ratio of a resin component and a solvent component, when making a resin component into 100 mass parts, it is preferable to mix | blend so that a solvent component may be a ratio of 30-200 mass parts, and also 40-100 mass parts is more preferable. When the total amount of the pigment powder is 100 parts by mass, it is preferably blended so that the total of the resin component and the solvent component is 20 to 200 parts by mass, and more preferably 30 to 100 parts by mass. Moreover, 2-30 mass parts is preferable and, as for the compounding quantity of a dispersing agent, when the sum total of a pigment powder is 100 mass parts, 3-20 mass parts is more preferable.

  The printing ink composition of the present invention is characterized in that the glass frit constituting the printing ink composition is colored black with a coloring pigment. Since the glass frit constituting the printing ink composition is colored black by the color pigment, the blackness is lowered even if the content of the black pigment powder is reduced and the content of the conductive metal powder is increased. And good conductivity can be obtained. Alternatively, by replacing the conventional glass frit contained in the printing ink composition with colored glass as it is at the same ratio, higher blackness can be obtained while maintaining the conductivity of the prior art. As a result, the bus electrode and the black matrix formed by the printing ink composition of the present invention are higher in blackness and good conductivity than the black matrix and the bus electrode formed by the conventional printing ink composition. Is obtained.

  The element contained in the coloring pigment for coloring the glass frit is preferably one or more elements selected from the group consisting of Cr, Fe, Co, Mn and Cu. This colored pigment is called an inorganic heat-resistant pigment, and is a metal oxide or composite oxide of the above elements. Among these, composite oxides of Cr and Fe, Mn and Co, and Mn and Cu are particularly preferable.

  The glass frit is composed of one or more oxides selected from the group consisting of lead oxide, bismuth oxide, zinc oxide, boron oxide, silicon oxide, aluminum oxide, phosphorus oxide, calcium oxide and titanium oxide, An oxide having a softening point of ˜500 ° C. is preferred. The glass frit used in the present invention is colored black by the color pigment, and can be obtained, for example, by the following method. First, the color pigment is added and mixed with the oxide, which is a glass raw material, so that the content is preferably 5 to 20% by mass, and the mixture is put into a platinum crucible and melted at a temperature of 1200 to 1500 ° C. Next, the obtained glass is granulated or poured into a stainless steel roller to form flakes. Further, the glass frit colored in black is obtained by adjusting the flaked glass with a pulverizer such as a ball mill using an alumina ball mill, preferably with an average particle diameter of 0.1 to 1.0 μm. Obtainable.

  As the conductive metal powder, it is preferable to use a powder having an average particle diameter in the range of 0.1 to 1.0 μm. Examples of the conductive metal powder include silver powder, copper powder, aluminum powder, gold powder, and nickel powder.

  As the black pigment powder, it is preferable to use a powder having an average particle diameter of 0.01 to 0.5 μm. As the black pigment powder, a composition comprising a metal oxide containing one or more metal elements selected from the group consisting of Co, Cr, Cu, Mn, Ru, Fe and Ni, or a composite oxide thereof. Is mentioned.

In addition, the average particle diameter of the glass frit used in the present invention, the conductive metal powder, and the black pigment powder is JIS R 1629 using a laser diffraction / scattering particle size distribution measuring device (LA-910, manufactured by Horiba, Ltd.). The 50% diameter value (D ₅₀ ) in the volume-based integrated fraction when measured according to

  A synthetic resin is mentioned as a resin component. This synthetic resin is not particularly limited as long as it is not carbonized during firing, and specifically, epoxy resin, cellulose resin, urethane resin, butyral resin, acrylic resin, polyester resin, styrene Resins, phenol resins, and the like can be used, and even resins obtained by mixing a plurality of these resins to undergo a crosslinking reaction can be used.

  The solvent component is not particularly limited as long as it is an organic solvent capable of dissolving the resin component. Specifically, alcohol solvents, ketone solvents, ether solvents, carbitol solvents, hydrocarbon solvents. Diol-based solvents, glycol-based solvents, glycol ether-based solvents and the like, and a solvent obtained by mixing a plurality of these solvents can also be used.

  As the dispersant, higher fatty acids are preferred. The length of the fatty chain of the higher fatty acid is not particularly limited, but is preferably C8 or more. Further, dicarboxylic acids in which the terminal functional group of the higher fatty acid has two carbonyl groups are more preferred. This is because the presence of two carbonyl groups improves the dispersibility of the conductive metal powder and the black pigment in the printing ink composition.

  The method for forming the black matrix and the bus electrode of the front plate for PDP of the present invention is to apply the above-mentioned printing ink composition of the present invention on the transparent electrode provided on the surface of the transparent substrate and apply a desired print pattern. A film is formed, and the coating film of the formed printed pattern is dried and baked. Printing is performed by adjusting the viscosity of the printing ink composition according to the printing method. When printing by the offset printing method when forming a coating film, it is preferable to use a printing ink composition prepared so that the viscosity is 1 to 10 Pa · s, preferably 2 to 8 Pa · s. . Also, when printing is performed by screen printing to form a coating film, it is preferable to use a printing ink composition prepared so that the viscosity is 10 to 1000 Pa · s, preferably 100 to 500 Pa · s. It is. Here, in this specification, the viscosity is a value at a rotational speed of 5 rpm measured according to JIS K 5600-2-3 using a rotary cone / plate viscometer (ELD / EMD / EHD manufactured by Tokimec Co., Ltd.). Say.

  A method of forming an electrode for PDP by printing on a glass substrate having a transparent electrode by an intaglio offset printing method using a printing ink composition prepared so that the viscosity is in the range of 1 to 10 Pa · s and baking it. Will be explained.

  First, as shown in FIG. 1A, a flat intaglio 10 having a predetermined concave pattern 10a is prepared as a printing plate, and a predetermined amount of a printing ink composition 11 is supplied to the surface of the flat intaglio 10. The squeegee 12 is applied to the surface of the flat intaglio 10 and is slid to embed the printing ink composition 11 in the intaglio pattern 10a. Next, as shown in FIG. 1B, a blanket roll 13 having a silicone blanket 13a attached to the surface is prepared as a printing blanket, and the printing ink composition 11 is placed on the flat intaglio 10 embedded in the concave pattern 10a. In this state, the blanket roll 13 is pressed, and the blanket roll 13 is rotated to roll on the planographic intaglio 10 so that a portion of the ink 11 embedded in the concave pattern 10 a of the flat intaglio 10 is transferred to the silicone of the blanket roll 13. Transfer to the surface of the rubber sheet 13a. The transfer rate at this time is about 50 to 60%, although it varies depending on the concave pattern of the plane intaglio, the components and ratios contained in the ink composition, or the pressure of the blanket. Next, as shown in FIG.1 (c), the blanket roll 13 which transferred the printing ink composition 11 is press-contacted to the glass substrate 14 (to-be-transferred body) which has a transparent electrode, and the blanket roll 13 is rotated in this state. By rolling on the glass substrate 14 having a transparent electrode, the printing ink composition 11 is transferred in a predetermined pattern onto the surface of the glass substrate 14 having a transparent electrode, thereby forming a coating film having a desired printing pattern. (FIG. 1 (d)). In FIG. 1, the transparent electrode formed on the glass substrate is not shown.

  Furthermore, after drying the glass substrate 14 on which the coating film of this desired printing pattern was formed at 100 to 200 ° C. for 1 to 30 minutes in the air, the heating rate was 6 to 12 ° C./min in the air. Preferably, the firing is performed at a temperature of 8 to 10 ° C./min, 500 to 600 ° C., preferably 540 to 580 ° C. The firing temperature holding time is preferably 5 to 30 minutes, more preferably 10 to 20 minutes.

  As described above, the PDP electrode is formed through the steps of FIGS. 1A to 1D. A black matrix for PDP is formed through the same process.

  The fired body formed in this way has a black matrix and a bus electrode integrated as compared with a fired body formed by a conventional technique, which simplifies the manufacturing process and is excellent in manufacturing cost. .

  Next, using the printing ink composition prepared so that the viscosity is in the range of 10 to 1000 Pa · s, printing is performed on a glass substrate having a transparent electrode by a screen printing method, and baking is performed to form an electrode for PDP. A method will be described.

  First, the screen plate 21 is stretched on the screen frame 22, and the screen plate 21 is fixed in a tensioned state, and a predetermined amount of the ink composition 23 for printing is supplied onto the surface of the screen plate 21 as shown in FIG. . Next, as shown in FIG. 2B, the printing ink composition 23 is embedded in the slit 21a by sliding the scraper 24 in the direction opposite to the printing operation direction shown in FIGS. . Next, as shown in FIG. 2 (c), after the squeegee 25 is placed on the surface of the screen plate 21, as shown in FIGS. 2 (d) and 2 (e), the surface of the screen plate 21 with the squeegee 25 pressurized. The printing ink composition 23 embedded in the slits 21a is slid onto the glass substrate (transfer object) 20 having a transparent electrode. In FIG. 2, the transparent electrode formed on the glass substrate is not shown. The printing ink composition 23 embedded in the slit 21a is ejected when the squeegee 25 passes through the slit 21a of the screen plate 21, as shown in FIG. 2 (e), and transferred to the glass substrate 20 having a transparent electrode. Is done. In this way, the printing ink composition 23 is transferred in a predetermined pattern onto the surface of the glass substrate 20 having the transparent electrode, so that a coating film 26 having a desired printing pattern is obtained (FIG. 2F).

  Furthermore, after drying the glass substrate 20 on which the coating film of this desired printing pattern was formed at 100 to 200 ° C. for 1 to 30 minutes in the air, the heating rate was 6 to 12 ° C./min in the air. Preferably, the firing is performed at a temperature of 8 to 10 ° C./min, 500 to 600 ° C., preferably 540 to 580 ° C. The firing temperature holding time is preferably 5 to 30 minutes, more preferably 10 to 20 minutes.

  As described above, the PDP electrode is formed through the steps of FIGS. 2A to 2F. A black matrix for PDP is formed through the same process.

  The fired body formed in this way has a black matrix and a bus electrode integrated as compared with a fired body formed by a conventional technique, which simplifies the manufacturing process and is excellent in manufacturing cost. .

  Next, examples of the present invention will be described in detail together with comparative examples.

<Example 1>
The conductive metal powder has an average particle diameter of 0.4 μm and a spherical silver powder, and the black pigment powder has an average particle diameter of 0.1 μm and is a composite oxide of spherical Mn, Cu, and Fe. Pigments (composition ratio, Mn: Cu: Fe = 35: 25: 8.3) were prepared. Further, a bismuth oxide-boron oxide glass frit having a softening point of 400 ° C. and containing 10% by mass of a color pigment containing a complex oxide of Cr and Fe was prepared as a glass frit. An acrylic resin was prepared as a resin component, and a glycol ether solvent was prepared as a solvent component. Further, stearic acid, which is a higher fatty acid, was prepared as a dispersant.

  60 parts by mass of the silver powder, 6 parts by mass of the black pigment powder, 12 parts by mass of the glass frit, 18 parts by mass of the acrylic resin, 9 parts by mass of the glycol ether solvent, and 6 parts by mass of the dispersant are mixed, and this mixture is mixed with the planetary mixer. Was then dispersed for 30 minutes, and further dispersed for 3 minutes using a three-roll mill to prepare a paste-like printing ink composition. At this time, the viscosity of the obtained printing ink composition was 6 Pa · s.

  On the other hand, as shown in FIG. 1, a planar intaglio 10 having a plurality of concave patterns having a line width of 150 μm, a depth of 30 μm, and a pitch of 300 μm is prepared as a printing plate used in the intaglio offset printing method, and a thickness of 2. A glass substrate 14 (front electrode substrate: PD200 manufactured by Asahi Glass Co., Ltd.) of 8 mm and diagonal 50 inches was prepared. Further, a blanket roll 13 having a thickness of 700 μm on the surface as a printing blanket and attached with a silicone rubber sheet (room temperature curing type silicone rubber (additional type)) having a hardness of 40 (JIS K 6253 type A) is attached. Using.

  First, a predetermined amount of the above-mentioned printing ink composition 11 was supplied to the surface of the planar intaglio 10, and the printing ink composition 11 was embedded in the concave pattern 10 a of the planar intaglio 10 using a SUS squeegee 12. Next, the blanket roll 13 is rotated in a state of being pressed onto the flat intaglio 10 and is rolled on the flat intaglio 10 so that a part of the printing ink composition 11 embedded in the concave pattern 10 a is transferred to the blanket roll 13. Transferred to the surface of the silicone rubber sheet 13a. Next, the blanket roll 13 is rotated in a state of being pressed against the glass substrate 14 having a transparent electrode, and is rolled on the glass substrate 14 having the transparent electrode, whereby a predetermined pattern is formed on the surface of the glass substrate 14 having the transparent electrode. The printing ink composition 11 was transferred to form a coating film of the printing ink composition having a desired pattern.

  Next, the glass substrate 14 after printing was dried at 150 ° C. for 5 minutes in the air. After this drying, the temperature was raised to 560 ° C. in air at a temperature rising rate of 10 ° C./min, and then held at 560 ° C. for 10 minutes. By passing through the above process, the glass substrate in which the electrode was formed on the surface was produced.

<Example 2>
The conductive metal powder has an average particle diameter of 0.1 μm and a spherical silver powder, the black pigment powder has an average particle diameter of 0.05 μm and a spherical black pigment powder, and the glass frit has a softening point of 400. The same as in Example 1 except that the printing ink composition was prepared using a glass frit colored in black by containing 20% by mass of a coloring pigment containing a complex oxide of Mn and Co. A glass substrate having an electrode formed on the surface was produced.

<Example 3>
The conductive metal powder has an average particle size of 1.0 μm and a spherical silver powder, the black pigment powder has an average particle size of 0.5 μm and a spherical black pigment powder, and the glass frit has a softening point of 400. The same as in Example 1 except that the printing ink composition was prepared using a glass frit colored in black by containing 15% by mass of a color pigment containing a complex oxide of Mn and Cu. A glass substrate having an electrode formed on the surface was produced.

<Example 4>
A glass substrate having an electrode formed on the surface was prepared in the same manner as in Example 1 except that the printing ink composition was prepared with 3 parts by mass of the black pigment powder.

<Example 5>
Other than having prepared a printing ink composition using a glass frit which is colored black by containing 5% by mass of a color pigment containing a composite oxide of Mn and Cu as a glass frit having a softening point of 400 ° C. Produced a glass substrate having electrodes formed on the surface in the same manner as in Example 4.

<Comparative Example 1>
An electrode was formed on the surface in the same manner as in Example 1 except that the glass frit had a softening point of 400 ° C. and a printing ink composition was prepared using a glass frit that was not colored black with a color pigment. A glass substrate was produced.

<Evaluation 1>
About the electrode on the glass substrate obtained in Examples 1-5 and Comparative Example 1, resistance was measured by Lorester (made by Mitsubishi Chemical Corporation). The blackness of the electrode was evaluated by measuring the L value (lightness) with a color computer (manufactured by Suga Test Instruments Co., Ltd.). In addition, the measured value of L value shows that the lightness is so low that a numerical value is small, ie, it is closer to black. The results are shown in Table 1 below.

表１から明らかなように、着色顔料により黒色に着色されているガラスフリットを使用した実施例１〜３と、着色顔料により黒色に着色されていないガラスフリットを使用した比較例１を比較すると、実施例１〜３と比較例１では、黒色顔料粉末を同じ割合で含むにもかかわらず、実施例１〜３では比較例１と同程度の導電性を維持したまま、比較例１よりもＬ値が小さく、すなわち高い黒色度を示した。一方、比較例１よりも黒色顔料粉末の含有割合が低く、導電性粉末の含有割合が高い実施例４，５では、比較例１と同程度のＬ値、すなわち黒色度を示すとともに、導電性においては比較例１よりも良好な結果を示した。このことから、着色顔料により黒色に着色されているガラスフリットを使用した本発明の印刷用インキ組成物が効果的であることが確認された。

As is clear from Table 1, when Examples 1 to 3 using a glass frit colored black with a coloring pigment were compared with Comparative Example 1 using a glass frit not colored black with a coloring pigment, In Examples 1 to 3 and Comparative Example 1, although the black pigment powder was included in the same ratio, Examples 1 to 3 maintained the same level of conductivity as Comparative Example 1 while maintaining the same level of L as Comparative Example 1. The value was small, that is, high blackness was shown. On the other hand, in Examples 4 and 5, in which the content ratio of the black pigment powder is lower than that of Comparative Example 1 and the content ratio of the conductive powder is high, the L value is comparable to that of Comparative Example 1, that is, the blackness is exhibited. The result was better than that of Comparative Example 1. From this, it was confirmed that the printing ink composition of the present invention using a glass frit colored black with a coloring pigment is effective.

<Example 6>
An electrode was formed on the surface in the same manner as in Example 1 except that 10 parts by mass of the acrylic resin and 10 parts by mass of the glycol ether solvent were used to prepare the printing ink composition so that the viscosity was 2 Pa · s. A glass substrate was produced.

<Example 7>
An electrode was formed on the surface in the same manner as in Example 1 except that 15 parts by mass of the acrylic resin and 6 parts by mass of the glycol ether solvent were used to prepare the printing ink composition so that the viscosity was 8 Pa · s. A glass substrate was produced.

<Example 8>
An electrode was formed on the surface in the same manner as in Example 1 except that 5 parts by mass of the acrylic resin and 10 parts by mass of the glycol ether solvent were used to prepare the printing ink composition so that the viscosity was 1 Pa · s. A glass substrate was produced.

<Example 9>
An electrode was formed on the surface in the same manner as in Example 1 except that 15 parts by mass of the acrylic resin and 5 parts by mass of the glycol ether solvent were used to prepare the printing ink composition so that the viscosity was 10 Pa · s. A glass substrate was produced.

<Comparative example 2>
An electrode is formed on the surface in the same manner as in Example 1 except that the ink composition for printing is prepared so that the viscosity is 0.8 Pa · s with 8 parts by mass of the acrylic resin and 16 parts by mass of the glycol ether solvent. A glass substrate was prepared.

<Comparative Example 3>
An electrode was formed on the surface in the same manner as in Example 1 except that 12 parts by mass of the acrylic resin and 4 parts by mass of the glycol ether solvent were used to prepare the printing ink composition so that the viscosity was 15 Pa · s. A glass substrate was produced.

<Evaluation 2>
About the electrode on the glass substrate obtained in Example 1, Examples 6-9 and Comparative Examples 2 and 3, the printability by the intaglio offset printing method was evaluated.

  The specific evaluation method of printability measured the line width of nine places in the predetermined position of each board | substrate about the printing line formed in the surface of the glass substrate after baking, respectively. Among the measured values of the line widths at these nine locations, when the maximum value and the minimum value are both within the range of ± 2 μm with respect to the line width of 150 μm of the concave pattern of the planar intaglio, When one or both of the minimum values exceed the range of ± 2 μm and both the maximum value and the minimum value are within the range of ± 5 μm, it is defined as “good”, and one or both of the maximum or minimum values are ± 5 μm When the range was exceeded, it was determined as “bad”. The maximum value and the minimum value in printability in Table 2 are shown by the difference with respect to the line width of 150 μm of the plane intaglio printing pattern. For example, the measurement data of “+1.2” is 151.2 μm, and “−0.6” is 149.4 μm.

表２から明らかなように、印刷用インキ組成物の粘度が１〜１０Ｐａ・ｓの範囲である実施例１及び実施例６，７では、上記最大値及び最小値の双方が平面凹版の凹状パターンのライン幅１５０μｍに対して±２μｍの範囲内となり、また実施例８，９では、上記最大値又は最小値の一方或いは双方が平面凹版の凹状パターンのライン幅１５０μｍに対して±２μｍ範囲を越え、かつ上記最大値及び最小値の双方が±５μｍの範囲内となり、凹版オフセット印刷法による印刷性において優れた結果が得られた。一方、印刷用インキ組成物の粘度が１Ｐａ・ｓ未満である比較例２、及び印刷用インキ組成物の粘度が１０Ｐａ・ｓを越える比較例３では、上記最大値又は最小値の一方或いは双方が平面凹版の凹状パターンのライン幅１５０μｍに対して±５μｍの範囲を越え、凹版オフセット印刷法による印刷性が不良となった。このことから、塗膜を形成する際の印刷をオフセット印刷法により行う場合には、粘度が１〜１０Ｐａ・ｓになるように調製した印刷用インキ組成物を使用することが好適であることが確認された。

As is apparent from Table 2, in Example 1 and Examples 6 and 7 in which the viscosity of the printing ink composition is in the range of 1 to 10 Pa · s, both the maximum value and the minimum value are concave intaglio patterns. Within the range of ± 2 μm with respect to the line width of 150 μm, and in Examples 8 and 9, one or both of the maximum value and the minimum value exceed the range of ± 2 μm with respect to the line width of 150 μm of the concave pattern of the planar intaglio. In addition, both the maximum value and the minimum value were within a range of ± 5 μm, and excellent results were obtained in printability by the intaglio offset printing method. On the other hand, in Comparative Example 2 in which the viscosity of the printing ink composition is less than 1 Pa · s and in Comparative Example 3 in which the viscosity of the printing ink composition exceeds 10 Pa · s, one or both of the maximum value and the minimum value are The range of ± 5 μm was exceeded with respect to the line width of 150 μm of the concave pattern of the planar intaglio, and the printability by the intaglio offset printing method was poor. From this, when printing by the offset printing method is performed when forming the coating film, it is preferable to use a printing ink composition prepared so that the viscosity is 1 to 10 Pa · s. confirmed.

<Example 10>
A black pigment having an average particle diameter of 0.4 μm and a spherical silver powder is used as a black pigment powder (composition ratio, a composite oxide of spherical Mn, Cu and Fe having an average particle diameter of 0.1 μm and spherical). Mn: Cu: Fe = 35: 25: 8.3) were prepared. Further, a bismuth oxide-boron oxide glass frit having a softening point of 400 ° C. and containing 10% by mass of a color pigment containing a complex oxide of Cr and Fe was prepared as a glass frit. Further, ethyl cellulose resin was prepared as a resin component, and α-terpineol was prepared as a solvent. Further, stearic acid, which is a higher fatty acid, was prepared as a dispersant.

  50 parts by mass of the above silver powder, 5 parts by mass of black pigment powder, 10 parts by mass of glass frit, 10 parts by mass of ethyl cellulose resin, 7 parts by mass of α-terpineol, and 5 parts by mass of a dispersant are mixed, and this mixture is mixed with a planetary mixer. After being used and dispersed for 30 minutes, a paste-like printing ink composition was prepared by further dispersing for 3 minutes using a three-roll mill. The viscosity at this time was 310 Pa · s.

  On the other hand, MT-320 manufactured by Microtech Co., Ltd. was prepared as a screen printing machine, and a polyester screen plate having a surface mesh having a plurality of patterns with a line width of 150 μm and a pitch of 300 μm was prepared as a printing plate. Further, a glass substrate having a thickness of 2.8 mm and a diagonal of 50 inches (front side electrode substrate manufactured by Asahi Glass Co., Ltd .: PD200) was prepared as a transfer target.

  First, a predetermined amount of the printing ink composition was supplied onto the screen plate surface, and the scraper was slid on the screen plate surface to embed the printing ink composition in the slit. Next, the squeegee was placed on the surface of the screen plate, and the squeegee was slid on the surface of the screen plate under pressure, whereby the printing ink composition embedded in the slit was transferred to the glass substrate having a transparent electrode. In this manner, the printing ink composition was transferred in a predetermined pattern onto the surface of the glass substrate having the transparent electrode, thereby forming a coating film having a desired printing pattern.

  Next, the glass substrate after printing was dried in air at 150 ° C. for 5 minutes. After this drying, the temperature was raised to 560 ° C. in air at a temperature rising rate of 10 ° C./min, and then held at 560 ° C. for 10 minutes. By passing through the above process, the glass substrate in which the electrode was formed on the surface was produced.

<Example 11>
A glass substrate having an electrode formed on the surface was prepared in the same manner as in Example 10 except that the printing ink composition was prepared so that the viscosity was 110 Pa · s as 10 parts by mass of α-terpineol.

<Example 12>
A glass substrate having an electrode formed on the surface was prepared in the same manner as in Example 10 except that the printing ink composition was prepared so that the viscosity was 480 Pa · s as 6 parts by mass of α-terpineol.

<Example 13>
A glass substrate having an electrode formed on the surface was prepared in the same manner as in Example 10 except that the printing ink composition was prepared so that the viscosity was 20 Pa · s as 15 parts by mass of α-terpineol.

<Example 14>
Glass with electrodes formed on the surface in the same manner as in Example 10 except that the printing ink composition was prepared so that the viscosity was 970 Pa · s as 9 parts by mass of ethyl cellulose resin and 3 parts by mass of α-terpineol. A substrate was produced.

<Comparative example 4>
Glass with electrodes formed on the surface in the same manner as in Example 10 except that the printing ink composition was prepared so that the viscosity was 8 Pa · s as 12 parts by mass of ethyl cellulose resin and 18 parts by mass of α-terpineol. A substrate was produced.

<Comparative Example 5>
A glass substrate having an electrode formed on the surface was prepared in the same manner as in Example 10 except that the printing ink composition was prepared so that the viscosity was 1250 Pa · s as 3 parts by mass of α-terpineol.

<Evaluation 3>
About the electrode on the glass substrate obtained in Examples 10-14 and Comparative Examples 4 and 5, the printability by the screen printing method was evaluated.

  The specific evaluation method of printability measured the line width of nine places in the predetermined position of each board | substrate about the printing line formed in the surface of the glass substrate after baking, respectively. Of these nine measured line widths, when both the maximum and minimum values are within the range of ± 2 μm for the screen plate slit line width of 150 μm, the value is “very good”. When one or both of the values exceed the range of ± 2μm and both the maximum value and the minimum value are within the range of ± 5μm, it is judged as “good”, and either the maximum value or the minimum value is within the range of ± 5μm When it exceeded the limit, it was defined as “bad”. The maximum value and the minimum value in printability in Table 3 are shown by the difference with respect to the line width of 150 μm of the slit of the screen plate. For example, “+1.1” is 151.1 μm of measurement data, and “−0.3” is 149.7 μm of measurement data.

表３から明らかなように、印刷用インキ組成物の粘度が１０〜１０００Ｐａ・ｓの範囲である実施例１０〜１２では、上記最大値及び最小値の双方がスクリーン版のスリットのライン幅１５０μｍに対して±２μｍの範囲内となり、また実施例１３，１４では、上記最大値又は最小値の一方或いは双方がスクリーン版のスリットのライン幅１５０μｍに対して±２μｍの範囲を越え、かつ上記最大値及び最小値の双方が±５μｍの範囲内となり、スクリーン印刷法による印刷性において優れた結果が得られた。一方、印刷用インキ組成物の粘度が１０Ｐａ・ｓ未満である比較例４、及び印刷用インキ組成物の粘度が１０００Ｐａ・ｓを越える比較例５では、上記最大値又は最小値の一方或いは双方がスクリーン版のスリットのライン幅１５０μｍに対して±５μｍを越え、スクリーン印刷法による印刷性が不良となった。このことから、塗膜を形成する際の印刷をスクリーン印刷法により行う場合には、粘度が１０〜１０００Ｐａ・ｓになるように調製した印刷用インキ組成物を使用することが好適であることが確認された。

As is clear from Table 3, in Examples 10 to 12 where the viscosity of the printing ink composition is in the range of 10 to 1000 Pa · s, both the maximum value and the minimum value are set to a line width of 150 μm of the slit of the screen plate. On the other hand, in Examples 13 and 14, one or both of the maximum value and the minimum value exceed the range of ± 2 μm with respect to the line width of 150 μm of the screen plate slit, and the maximum value described above. And the minimum value are both within the range of ± 5 μm, and excellent results were obtained in printability by the screen printing method. On the other hand, in Comparative Example 4 in which the viscosity of the printing ink composition is less than 10 Pa · s and in Comparative Example 5 in which the viscosity of the printing ink composition exceeds 1000 Pa · s, one or both of the maximum value and the minimum value are The screen width exceeded ± 5 μm with respect to the slit line width of 150 μm, and the printability by the screen printing method was poor. From this, when performing printing when forming a coating film by screen printing, it is preferable to use a printing ink composition prepared so that the viscosity is 10 to 1000 Pa · s. confirmed.

It is the schematic of the intaglio offset printing method of embodiment of this invention. It is the schematic of the screen printing method of embodiment of this invention.

Explanation of symbols

10 Plane intaglio (printing plate)
10a Concave pattern 11 Printing ink composition 12 Blanket roll (printing blanket)
13a Silicone rubber sheet (silicone sheet)
14 Glass substrate (transfer object)
20 Glass substrate (transfer object)
21 Screen 21a Slit 22 Screen Frame 23 Ink Composition for Printing 24 Scraper 25 Squeegee 26 Printed Film

Claims (8)

Printing on the transparent electrode provided on the surface of the transparent substrate to form a coating film of a desired printing pattern, drying and baking the coating film of the formed printing pattern, and a black matrix of a front panel for a plasma display panel And a printing ink composition for forming a bus electrode,
The composition contains conductive metal powder, black pigment powder, glass frit, resin component, solvent component and dispersant,
A printing ink composition, wherein the glass frit is colored black with a coloring pigment.   The printing ink composition according to claim 1, wherein the element contained in the color pigment is one or more elements selected from the group consisting of Cr, Fe, Co, Mn, and Cu.   The ink composition for offset printing according to claim 1 or 2, which has a viscosity of 1 to 10 Pa · s.   The ink composition for screen printing according to claim 1 or 2, which has a viscosity of 10 to 1000 Pa · s.   A printing ink composition according to any one of claims 1 to 4 is printed on a transparent electrode provided on a surface of a transparent substrate to form a coating film having a desired printing pattern. A method for forming a black matrix and a bus electrode of a front plate for a plasma display panel, wherein the coating film is dried and fired.   6. The black matrix and the bus electrode of the front plate for a plasma display panel according to claim 5, wherein the printing at the time of forming the coating film is performed by an offset printing method using a printing ink composition having a viscosity of 1 to 10 Pa · s. Forming method.   6. The black matrix and the bus electrode of the front plate for a plasma display panel according to claim 5, wherein the printing at the time of forming the coating film is carried out by a screen printing method using a printing ink composition having a viscosity of 10 to 1000 Pa · s. Forming method.   A fired body formed by the method according to any one of claims 5 to 7.

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