JP2015060652A - Conductive paste and ceramic electronic component - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a conductive paste and a ceramic electronic component low in sheet attack property, hardly reducing flowability of paste and capable of providing excellent printability.SOLUTION: There is provided a conductive paste containing Ni powder, a binder resin component and an organic solvent. The binder resin component contains cellulose acetate butyrate and synthetic high polymer having the hydroxyl group content of 0.05 to 10.00 wt.%. The butyryl group content of cellulose acetate butyrate of the binder resin component is 32 wt.% or more. An average primary particle diameter of the Ni powder is 10 to 5000 nm. The synthetic high polymer of the binder resin component has a weight average molecular weight of 10000 to 1500000. The synthetic high polymer of the binder resin component is selected from at least one of acryl, methacryl, butyral and urethane. A hydroxyl group substitution ratio of the butyral is 1.5 to 7.0 wt.%.

Description

  The present invention relates to a conductive paste and a ceramic electronic component.

  Patent Document 1 describes a conductive paste composed of conductive powder, an organic vehicle, and an anionic surfactant. The anionic surfactant consists of a sulfosuccinate containing an alkyl group. The conductive powder is made of Ni, Fe, Ag, Pd, Cu or the like. The organic vehicle is made of ethyl cellulose resin, alkyd resin, acrylic resin, or the like.

  And the electrically conductive paste described in patent document 1 has the effect that sufficient viscosity stability can be acquired.

  Patent Document 2 describes a semiconductor electrode that contains at least Ag powder, In powder, and cellulose acetate butyrate resin (binder resin), and preferably Ag powder / In powder is 1 to 4 in weight ratio. ing.

  Further, Patent Document 2 describes a method for manufacturing a semiconductor electrode, which includes a step of applying a conductive paste containing each of the above components on a semiconductor, heating the paste at a temperature higher than the melting point of In, and drying.

  The semiconductor electrode described in Patent Document 2 is excellent in electrical conductivity with a semiconductor, rich in flexibility, and has a long life and high reliability.

JP 2000-231828 A JP 2002-25942 A

  However, when the conductive paste of Patent Document 1 is used for an internal electrode of a multilayer ceramic capacitor, it is widely known that an ethyl cellulose resin or the like is used for an organic vehicle. When this conductive paste is applied to the surface of the dielectric ceramic sheet, there is a problem that the solvent erosion property (hereinafter referred to as sheet attack property) to the dielectric ceramic sheet is high. This is because the ethyl cellulose resin of the conductive paste does not dissolve in the low sheet attack organic solvent of the conductive paste.

  Also, when a conductive paste containing at least cellulose acetate butyrate resin and Ni powder is used to form the semiconductor electrode of Patent Document 2, a printing defect occurs when the conductive paste is printed. Sometimes. This printing defect is a defect in which a portion where a printed coating film is not formed is caused by rubbing (fogging) or the like.

  That is, as in Patent Document 2, the conductive paste containing cellulose acetate butyrate resin as the main component of the binder may not be transferred to the semiconductor sheet to be transferred, resulting in a printing defect. The printing defect is caused by a decrease in fluidity (weak fluidity) of the conductive paste. This decrease in fluidity of the conductive paste is presumed to be due to the small amount of cellulose acetate butyrate resin adsorbed on the Ni powder surface.

  SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a conductive paste and a ceramic electronic component that have a low sheet attack property, a low paste fluidity, and an excellent printability.

  The present invention is a conductive paste containing Ni powder, a binder resin component, and an organic solvent, wherein the binder resin component has cellulose acetate butyrate and a hydroxyl group content of 0.05 to 10.00% by weight. It is a conductive paste characterized by containing a certain synthetic polymer.

  In the present invention, since cellulose acetate butyrate contained in the binder resin component is dissolved in the low sheet attack organic solvent of the conductive paste, when the conductive paste is applied to the surface of the ceramic sheet, The sheet attack property to the ceramic sheet surface by the conductive paste is lowered.

  Furthermore, since the hydroxyl group content of the synthetic polymer contained in the binder resin component is 0.05 to 10.00% by weight, the fluidity of the conductive paste is improved and good printability is obtained.

  Moreover, this invention is a conductive paste characterized by the butyryl group content rate of the cellulose acetate butyrate of a binder resin component being 32 weight% or more.

  In the present invention, when the butyryl group content is 32% by weight or more, the thixotropy of the conductive paste is increased and the printability is further improved.

  Moreover, this invention is an electrically conductive paste characterized by the average primary particle diameter of Ni powder being 10-5000 nm. Here, the average primary particle refers to a particle having the smallest average particle diameter constituting the metal powder.

  In the present invention, the structural viscosity formed by the binder resin component and the Ni powder is strongly expressed. That is, the polymer entanglement of the binder resin component and the structure of the interaction between the Ni metal particles are broken, and the viscosity is greatly reduced.

  The present invention is the conductive paste, wherein the organic solvent is an organic solvent selected from at least one of ethers, esters, ketones, and hydrocarbons.

  More specifically, the organic solvent is D-limonene, P-cymene, α-pinene, acetonyl acetone, acetophenone, anisole, octyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, 2-hexyl acetate, n-acetate. Hexyl, diisobutyl ketone, cyclohexane, cyclohexyl acetate, dihydroterpineol acetate, terpineol acetate, dodecane, dodecyl acetate, triacetin, toluene, phenetol, butyl acetate, butyl butyrate, isoventyl propionate, hexyl acetate, heptyl acetate, benzyl acetate, methyl n -Selected from at least one of amyl ketone and methyl isobutyl ketone.

  In the present invention, compared with the case where an alcohol-based organic solvent is used, the sheet attack property is low, and the fluidity of the paste is further prevented from being lowered, and excellent printability is obtained.

  Moreover, the present invention is a conductive paste characterized in that the synthetic polymer of the binder resin component has a weight average molecular weight of 10,000 to 1500,000.

  When the weight average molecular weight of the synthetic polymer is less than 10,000, the effect of imparting fluidity is weakened. On the other hand, when it exceeds 1500,000, it does not dissolve in the organic solvent.

  The present invention is also the conductive paste, wherein the synthetic polymer of the binder resin component is selected from at least one of acrylic, methacrylic, butyral, and urethane.

  In the case of butyral, the hydroxyl group substitution ratio is 1.5 to 7.0% by weight. When the hydroxyl substitution ratio of the butyral resin is less than 1.5% by weight, the effect is weakened. On the other hand, when it exceeds 7.0% by weight, the compatibility of the synthetic polymer is deteriorated.

  Moreover, this invention is an electroconductive paste characterized by being any one of the paste for screen printing, the paste for gravure printing, and the paste for inkjet printing, for example.

  According to another aspect of the present invention, there is provided a ceramic electronic component characterized in that a conductor pattern is formed using the above-described conductive paste.

  In the present invention, the conductive pattern is formed on the ceramic with the conductive paste that has a low sheet attack property, the flowability of the paste is hardly lowered, and an excellent printability is obtained, so that a print defect is hardly generated. Ceramic electronic components can be provided.

  According to the present invention, it is possible to obtain a conductive paste that has a low sheet attack property, is difficult to reduce the fluidity of the paste, and has excellent printability.

  The above-described object, other objects, features, and advantages of the present invention will become more apparent from the following description of embodiments for carrying out the invention with reference to the drawings.

It is a flowchart for demonstrating the electrically conductive paste which concerns on this invention. It is sectional drawing which shows one Embodiment of the ceramic electronic component which concerns on this invention.

  One embodiment of a conductive paste according to the present invention and a ceramic electronic component in which a conductor pattern is formed using the conductive paste will be described together with a manufacturing method thereof. The ceramic electronic component is, for example, a passive element such as a multilayer ceramic capacitor, a multilayer ceramic inductor, or a multilayer ceramic thermistor, or a multilayer ceramic substrate on which wiring conductors that electrically connect the elements are formed. In the present embodiment, a multilayer ceramic capacitor will be described as an example of a ceramic electronic component.

1. Conductive paste The conductive paste contains Ni powder, a binder resin component, and an organic solvent.

  The binder resin component contains cellulose acetate butyrate and a synthetic polymer having a hydroxyl group content of 0.05 to 10.00% by weight.

  Cellulose acetate butyrate contained in the binder resin component is dissolved in a low sheet attack organic solvent of a conductive paste. Therefore, when the conductive paste is applied to the surface of the ceramic sheet, the sheet attack property to the ceramic sheet surface by the conductive paste is lowered.

  Furthermore, the hydroxyl group content of the synthetic polymer contained in the binder resin component is 0.05 to 10.00% by weight. Therefore, the fluidity of the conductive paste is improved, and good printability is obtained. On the other hand, when the hydroxyl group content is less than 0.05% by weight, the sheet attack property is high and the fluidity of the paste is likely to be lowered, and it is difficult to obtain excellent printability. On the other hand, if it exceeds 10.00% by weight, printing defects due to rubbing occur due to the increase in viscosity.

  The butyryl group content of the cellulose acetate butyrate of the binder resin component is 32% by weight or more.

  When the butyryl group content is 32% by weight or more, the thixotropy of the conductive paste is increased and the printability is further improved.

  Moreover, the average primary particle diameter of Ni powder is 10-5000 nm. Therefore, the structural viscosity formed by the binder resin component and the Ni powder is strongly expressed. That is, the polymer entanglement of the binder resin component and the structure of the interaction between the Ni metal particles are broken, and the viscosity is greatly reduced. When the average primary particle size of the Ni powder is 10 nm or less, white defects due to printing rubbing occur due to the increase in paste viscosity. In addition, when the average primary particle size exceeds 5000 nm, printing bleeding occurs.

  The organic solvent is an organic solvent selected from at least one of ethers, esters, ketones, and hydrocarbons. In this case, compared with the case where an alcoholic organic solvent is used, the sheet attack property is low, and the fluidity of the paste is further prevented from being lowered, and excellent printability is obtained.

  More specifically, the organic solvent is D-limonene, P-cymene, α-pinene, acetonyl acetone, acetophenone, anisole, octyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, 2-hexyl acetate, n-acetate. Hexyl, diisobutyl ketone, cyclohexane, cyclohexyl acetate, dihydroterpineol acetate, terpineol acetate, dodecane, dodecyl acetate, triacetin, toluene, phenetol, butyl acetate, butyl butyrate, isoventyl propionate, hexyl acetate, heptyl acetate, benzyl acetate, methyl n -Selected from at least one of amyl ketone and methyl isobutyl ketone.

  The synthetic polymer of the binder resin component has a weight average molecular weight of 10,000 to 1500,000. When the weight average molecular weight of the synthetic polymer is less than 10,000, the effect is weakened. That is, the fluidity of the paste is easily lowered, and it becomes difficult to obtain excellent printability. When the weight average molecular weight of the synthetic polymer exceeds 1500,000, the synthetic polymer becomes difficult to dissolve in the organic solvent.

  The synthetic polymer of the binder resin component is selected from at least one of acrylic, methacrylic, butyral, and urethane. In the case of butyral, the hydroxyl group substitution ratio is 1.5 to 7.0% by weight. When the hydroxyl substitution ratio of butyral is less than 1.5% by weight, the fluidity of the paste tends to be lowered, and it becomes difficult to obtain excellent printability. When the hydroxyl substitution ratio of butyral exceeds 7.0% by weight, the compatibility deteriorates.

  This conductive paste is used, for example, for screen printing paste, gravure printing paste, inkjet printing paste, and the like.

2. Method for Producing Conductive Paste Next, a method for producing a conductive paste will be described with reference to the flowchart shown in FIG.

In step S1 in FIG. 1, a predetermined amount of Ni powder, cellulose acetate butyrate as a binder resin component, and an organic solvent are weighed.
Next, in step S2, the respective materials are agitated to produce a first mill base.

  Next, in step S3, a predetermined amount of a synthetic polymer having a hydroxyl group content of 0.05 to 10.00% by weight is weighed, put into the first mill base, and stirred. Here, ceramic powder may be kneaded as a sintering inhibiting component. Furthermore, an arbitrary amount of a dispersant may be kneaded as necessary.

  Next, in step S4, the first mill base is kneaded by a dispersion method such as a three-roll mill to uniformly disperse the Ni powder, thereby producing a second mill base.

  Thereafter, in step S5, a varnish in which a predetermined amount of cellulose acetate butyrate and an organic solvent are mixed with the second mill base is produced.

  Next, in step S6, a conductive paste is produced while the varnish is kneaded in the second mill base and the viscosity is adjusted.

  The synthetic polymer having a hydroxyl group content of 0.05 to 10.00 parts by weight may be kneaded at the stage of the second mill base. Moreover, methods other than a three-roll mill may be used for the dispersion method.

3. Ceramic Electronic Component FIG. 2 is a vertical cross-sectional view in the length direction showing a multilayer ceramic capacitor 1 in which internal electrodes are formed using the conductive paste described above. The present invention can also be applied to LC filters, LC modules, and the like.

  The multilayer ceramic capacitor 1 includes a ceramic body 10 and external electrodes 20 and 22 formed on left and right ends of the ceramic body 10.

  The ceramic body 10 is vertically moved so as to sandwich the plurality of inner layer ceramic layers 11, the plurality of inner electrodes 12 and 13 disposed at the interfaces between the plurality of inner layer ceramic layers 11, and the plurality of inner layer ceramic layers 11. The outer layer ceramic layers 15a and 15b are arranged in a rectangular parallelepiped structure.

  The internal electrode 12 and the internal electrode 13 are opposed to each other via the inner ceramic layer 11 made of a dielectric material in the thickness direction. Capacitance is formed in a portion where the internal electrode 12 and the internal electrode 13 are opposed to each other with the inner ceramic layer 11 interposed therebetween. The internal electrodes 12 and 13 are produced using the conductive paste described above.

  The left end portion of the internal electrode 12 is drawn out to the left end surface of the ceramic body 10 and is electrically connected to the external electrode 20. The right end of the internal electrode 13 is drawn out to the right end surface of the ceramic body 10 and is electrically connected to the external electrode 22.

  The multilayer ceramic capacitor 1 having the above-described configuration uses a conductive paste in which the internal electrodes 12 and 13 have a low sheet attack property as described above, and the fluidity of the paste is hardly lowered, and an excellent printability is obtained. Since it is manufactured, it is possible to obtain the multilayer ceramic capacitor 1 in which printing defects are unlikely to occur.

3. Next, a method for manufacturing the above-described multilayer ceramic capacitor 1 will be described.

  An organic solvent such as toluene or echinene is added to the dielectric powder and mixed. Thereafter, a binder and a plasticizer are further added and mixed to prepare a slurry. This slurry is formed into a ceramic green sheet for an inner layer or an outer layer by a doctor blade method.

  Next, the conductive paste film (raw conductor pattern) that becomes the internal electrodes 12 and 13 is printed on the ceramic green sheet for the inner layer by a method such as screen printing, ink jet printing, or gravure printing. It is formed.

  Next, a plurality of ceramic green sheets for the inner layer on which the conductive paste film is formed are laminated so that the drawing directions of the ends of the conductive paste film are alternate. Further, a plurality of ceramic green sheets for outer layers are stacked one above the other so as to sandwich the stacked ceramic green sheets for inner layers, and are pressed. In this way, the ceramic body 10 which is an unfired laminated body to be the body of the multilayer ceramic capacitor 1 is formed.

  Next, the green ceramic body 10 is cut into a predetermined product size. The cut unfired ceramic body 10 is fired to obtain a sintered ceramic body 10.

  The inner layer and outer layer ceramic green sheets and the conductive paste film are fired simultaneously, the inner layer ceramic green sheet becomes the inner layer ceramic layer 11, and the outer layer ceramic green sheet becomes the outer layer ceramic layers 15a and 15b. The film becomes the internal electrodes 12 and 13.

  Next, Cu paste is applied and baked on both ends of the sintered ceramic body 10 to form external electrodes 20 and 22 electrically connected to the internal electrodes 12 and 13, respectively. Further, Ni—Sn plating is formed on the surface layers of the external electrodes 20 and 22 by wet plating. In this way, the multilayer ceramic capacitor 1 is obtained.

  Samples of Examples and Comparative Examples were prepared, and the characteristics of the conductive paste (sheet attack characteristics, printing characteristics, dissolution characteristics) were evaluated.

  1. Example and Comparative Example Characteristic Evaluation Method

(Seat attack characteristics)
The conductive paste produced by the production method shown in FIG. 1 was printed on the ceramic green sheet for inner layer having a thickness of 10 μm of the multilayer ceramic capacitor 1 by screen printing. Then, the ceramic green sheet for inner layers in which the conductive paste film | membrane (raw conductor pattern) used as the internal electrodes 12 and 13 was formed on the surface was dried by predetermined temperature and time in the drying furnace.

  Next, the printed coating film surface (sheet surface on the side where the conductive paste film was formed) of the ceramic green sheet for the inner layer was observed with an optical microscope, and the presence or absence of defects due to sheet attack was evaluated. When there was no defect due to the sheet attack, it was determined as “◯”, and when there was a defect due to the sheet attack, it was determined as “x”.

(Print characteristics)
The conductive paste produced by the production method shown in FIG. 1 was printed on the ceramic green sheet for inner layer having a thickness of 10 μm of the multilayer ceramic capacitor 1 by screen printing. Then, the ceramic green sheet for inner layers in which the conductive paste film | membrane (raw conductor pattern) used as the internal electrodes 12 and 13 was formed on the surface was dried by predetermined temperature and time in the drying furnace.

  Next, the printed coating film surface (sheet surface on the side where the conductive paste film is formed) of the ceramic green sheet for the inner layer was observed with an optical microscope, and the presence or absence of a printing defect (rubbing failure or bleeding failure) was evaluated. . When there was no printing defect, it was determined as “◯”, and when there was a printing defect, it was determined as “x”.

(Dissolution characteristics)
Arbitrary amounts of cellulose acetate butyrate and synthetic polymer were weighed so that the binder resin component would be 10% by weight, and then charged into an organic solvent and stirred for 2 hours. Thereafter, the organic solvent was allowed to stand at room temperature for 1 day, and then it was visually observed whether or not the binder resin component was dissolved in the organic solvent. When the binder resin component was dissolved in an organic solvent and was transparent, it was determined as “◯”. When the binder resin component was not dissolved in the organic solvent and turbidity was observed, it was determined as “x”.

(Comprehensive judgment)
Of the determinations of the evaluation items (sheet attack characteristics, printing characteristics, and dissolution characteristics), if at least one evaluation item has “x”, the overall determination is “x”.

2. First Example and First Comparative Example (Production of Samples of First Example and First Comparative Example)
The conductive pastes of Samples 1 to 5 of the first example were manufactured using the materials shown in Table 1 by the manufacturing method shown in FIG. Using the same manufacturing method, conductive pastes of Samples 6 to 8 of the first comparative example that are outside the scope of the present invention were produced using the materials shown in Table 2.

  In Samples 1 to 5 of the first example, conditions were set so that the hydroxyl group content of the synthetic polymer was 0.05 to 10.00% by weight. On the other hand, the samples 6 to 8 of the first comparative example were set so that the hydroxyl content of the synthetic polymer was three types of 0.01, 15.00, and 0 (not including the synthetic polymer). .

(Characteristic evaluation results of the first example and the first comparative example)
As is clear from Table 1, in the case of Samples 1 to 5 of the first example (that is, in the case of a conductive paste having a hydroxyl content of 0.05 to 10.00% by weight of the synthetic polymer), it is good A printed coating was obtained.

  On the other hand, as is clear from Table 2, in the case of Sample 6 of the first comparative example (that is, in the case of a conductive paste having a hydroxyl group content of 0.01% by weight of the synthetic polymer), the flow of the paste Rubbing due to deterioration in the properties was observed.

  Further, in the case of sample 7 of the first comparative example (that is, in the case of a conductive paste having a hydroxyl group content of 15.00% by weight of the synthetic polymer), rubbing due to an increase in the viscosity of the paste was observed. On the other hand, in the case of Sample 8 of the first comparative example (that is, in the case of a conductive paste not containing a synthetic polymer), rubbing due to a decrease in paste fluidity was observed.

3. Second Example and Second Comparative Example (Production of Samples of Second Example and Second Comparative Example)
The conductive pastes of Samples 9 to 12 of the second example were manufactured using the materials shown in Table 3 by the manufacturing method shown in FIG. With the same manufacturing method, conductive pastes of Samples 13 and 14 of the second comparative example were produced using the materials shown in Table 4.

  In Samples 9 to 12 of the second example, conditions were set so that the butyryl group content of cellulose acetate butyrate, which is a binder resin, was 4 types, 32, 46, 53, and 65% by weight. On the other hand, the samples 13 and 14 of the second comparative example were set so that the butyryl group content of the cellulose acetate butyrate was 20 or 29% by weight.

(Characteristic evaluation results of the second example and the second comparative example)
As is apparent from Table 3, in the case of Samples 9 to 12 of the second example (that is, in the case of a conductive paste having a butyryl group content of cellulose acetate butyrate of 32% by weight or more), a good print coating A membrane was obtained.

  On the other hand, as is apparent from Table 4, in the case of Samples 13 and 14 of the second comparative example (that is, in the case of a conductive paste having a low butyryl group content of cellulose acetate butyrate of less than 32% by weight). The structural viscosity of the paste was lowered, and printing bleeding occurred.

4). Third Example and Third Comparative Example (Production of Samples of Third Example and Third Comparative Example)
The conductive pastes of Samples 15 to 18 of the third example were manufactured using the materials shown in Table 5 by the manufacturing method shown in FIG. With the same manufacturing method, conductive pastes of Samples 19 and 20 of the third comparative example were produced using the materials shown in Table 6.

  Samples 15 to 18 of the third example were set so that the average primary particle size of the Ni powder was four types of 10, 200, 600, and 5000 nm. On the other hand, the samples 19 and 20 of the third comparative example were set so that the average primary particle size of the Ni powder was two types of 5,8000 nm.

(Result of characteristic evaluation of third embodiment)
As is clear from Table 5, in the case of samples 15 to 18 of the third example (that is, in the case of a conductive paste having an average primary particle size of Ni powder of 10 to 5000 nm), a good printed coating film is obtained. It was.

  On the other hand, as is clear from Table 6, in the case of the sample 19 of the third comparative example (that is, in the case of a conductive paste having a low average primary particle size of Ni powder of less than 5 nm), the viscosity of the paste is increased. Caused printing rubbing. On the other hand, in the case of the sample 20 of the third comparative example (that is, in the case of a conductive paste having an Ni powder having an average primary particle size as high as 8000 nm), the structural viscosity decreased and printing bleeding occurred.

5. Fourth Example and Fourth Comparative Example (Preparation of Samples of Fourth Example and Fourth Comparative Example)
The conductive pastes of Samples 21 to 32 of the fourth example were manufactured using the materials shown in Table 7 by the manufacturing method shown in FIG. With the same manufacturing method, conductive pastes of Samples 33 and 34 of the fourth comparative example were produced using the materials shown in Table 8.

  Samples 21 to 32 of the fourth example were set with multiple types of organic solvents. However, with respect to organic solvents that have been found to give good printed coatings in the examples of Table 1, Table 3, Table 5, Table 9 (see below), and Table 11 (see below), Excluded from 4 examples. On the other hand, in the samples 33 and 34 of the fourth comparative example, two kinds of conditions, terpineol and dihydroterpineol, were set as organic solvents.

(Characteristic evaluation results of the fourth example and the fourth comparative example)
As is apparent from Table 7, in the case of Samples 21 to 32 of the fourth example (that is, in the case of a conductive paste in which the organic solvent is ethers, esters, ketones and hydrocarbons), good printing A coating film was obtained.

  On the other hand, as is clear from Table 8, in the case of the samples 33 and 34 of the fourth comparative example (that is, in the case of the conductive paste in which the organic solvent is terpineol or dihydroterpineol), the fluidity of the paste is reduced. Rubbing was observed and defects due to sheet attack were observed.

6). Fifth Example and Fifth Comparative Example (Production of Samples of Fifth Example and Fifth Comparative Example)
Samples 35 to 38 of the fifth example were produced by the manufacturing method shown in FIG. 1 using the materials shown in Table 9. With the same manufacturing method, conductive pastes of Samples 39 and 40 of the fifth comparative example were produced using the materials shown in Table 10.

  In Samples 35 to 38 of the fifth example, four types of weight average molecular weights of 10,000, 70000, 250,000, and 1500000 were set for the synthetic polymer of the binder resin component. On the other hand, in the samples 39 and 40 of the fifth comparative example, two types of weight average molecular weight of the synthetic polymer were set to 7000 and 1800000.

(Characteristic evaluation results of the fifth example and the fifth comparative example)
As is apparent from Table 9, in the case of Samples 35 to 38 of the fifth example (that is, in the case of a conductive paste having a weight average molecular weight of the synthetic polymer of 10,000 to 1500,000), a good printed coating film is obtained. It was.

  On the other hand, as is clear from Table 10, in the case of the sample 39 of the fifth comparative example (that is, in the case of a conductive paste having a low weight average molecular weight of the synthetic polymer of 7000), the fluidity of the paste is reduced. It was found that the prevention was weak. On the other hand, in the case of the sample 40 of the fifth comparative example (that is, in the case of a conductive paste having a high weight average molecular weight of 1800000), the synthetic polymer was insoluble in the organic solvent.

7). Sixth Example and Sixth Comparative Example (Production of Samples of Sixth Example and Sixth Comparative Example)
The conductive pastes of Samples 41 to 43 of the sixth example were manufactured using the materials shown in Table 11 and the manufacturing method shown in FIG. With the same manufacturing method, conductive pastes of Samples 44 and 45 of the fifth comparative example were produced using the materials shown in Table 12.

  In Samples 41 to 43 of the sixth example, three kinds of conditions were set, in which the hydroxyl substitution ratio of butyral of the synthetic polymer was 1.5, 3.1, and 7.0% by weight. On the other hand, in the samples 44 and 45 of the sixth comparative example, two types of butyral hydroxyl substitution ratios of 0.8 and 9.0% by weight were set.

(Characteristic evaluation results of sixth example and sixth comparative example)
As is clear from Table 11, in the case of Samples 41 to 43 of the sixth example (that is, in the case of a conductive paste in which the hydroxyl substitution ratio of butyral is 1.5 to 7.0% by weight), good printing is achieved. A coating film was obtained.

  On the other hand, as is clear from Table 12, in the case of the sample 44 of the sixth comparative example (that is, in the case of a conductive paste having a low hydroxyl substitution ratio of butyral of 0.8% by weight), the fluidity of the paste It was observed that the prevention of decline was weak. On the other hand, in the case of the sample 45 of the sixth comparative example (that is, in the case of a conductive paste having a hydroxyl substitution ratio of butyral as high as 9.0% by weight), the synthetic polymer butyral is compatible with cellulose acetate butyrate. It deteriorated and was insoluble in cellulose acetate butyrate.

  In addition, this invention is not limited to the said embodiment, A various deformation | transformation is carried out within the range of the summary.

1 Ceramic electronic components (multilayer ceramic capacitors)
DESCRIPTION OF SYMBOLS 10 Ceramic main body 11 Ceramic layer for inner layers 12, 13 Internal electrode 15a, 15b Ceramic layer for outer layers 20, 22 External electrode

Claims (10)

A conductive paste containing Ni powder, a binder resin component and an organic solvent,
The conductive resin paste, wherein the binder resin component includes cellulose acetate butyrate and a synthetic polymer having a hydroxyl group content of 0.05 to 10.00% by weight.   2. The conductive paste according to claim 1, wherein a content of butyryl group in the cellulose acetate butyrate of the binder resin component is 32% by weight or more.   The conductive paste according to claim 1 or 2, wherein an average primary particle size of the Ni powder is 10 to 5000 nm.   4. The organic solvent according to claim 1, wherein the organic solvent is an organic solvent selected from at least one of ethers, esters, ketones, and hydrocarbons. 5. Conductive paste.   The organic solvent is D-limonene, P-cymene, α-pinene, acetonylacetone, acetophenone, anisole, octyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, 2-hexyl acetate, n-hexyl acetate, diisobutyl ketone, Cyclohexane, cyclohexyl acetate, dihydroterpineol acetate, terpineol acetate, dodecane, dodecyl acetate, triacetin, toluene, phenetol, butyl acetate, butyl butyrate, isoventyl propionate, hexyl acetate, heptyl acetate, benzyl acetate, methyl n-amyl ketone, methyl isobutyl The conductive paste according to any one of claims 1 to 3, wherein the conductive paste is selected from at least one of ketones.   The conductive paste according to any one of claims 1 to 5, wherein the synthetic polymer of the binder resin component has a weight average molecular weight of 10,000 to 1,000,000.   The conductive paste according to any one of claims 1 to 6, wherein the synthetic polymer of the binder resin component is selected from at least one of acrylic, methacrylic, butyral, and urethane.   The conductive paste according to claim 7, wherein a hydroxyl substitution ratio of the butyral is 1.5 to 7.0 wt%.   The conductive paste according to any one of claims 1 to 8, wherein the conductive paste is any one of a paste for screen printing, a paste for gravure printing, and a paste for inkjet printing. .   A ceramic electronic component, wherein a conductive pattern is formed using the conductive paste according to claim 1.

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