TWI282331B - Coating material for thick green sheet, method of manufacturing thereof, method of manufacturing thick green sheet, thick green sheet, and method of manufacturing electronic components - Google Patents

Abstract

The present invention provides a coating material for thick green sheet that can realize relatively thick coating and that, with respect to a sheet resulted from the coating, excels in cutting property (strength to be cut), air permeability and handling easiness, wherein the disclosed coating material enables formation of a sheet of high bonding strength; a process for producing the coating material for thick green sheet; a process for producing a thick green sheet; a thick green sheet; and a process for producing an electronic component. There is provided a coating material for thick green sheet comprising a ceramic powder, a binder resin composed mainly of a butyral resin, and a solvent, wherein the solvent contains a good solvent capable of dissolving the binder resin to a high degree and a poor solvent whose capability of dissolving the binder resin is lower than that of the good solvent. The poor solvent is contained in a ratio ranging from 30 to 60 mass% based on the whole solvent. The good solvent is an alcohol, while the poor solvent is toluene, xylene, mineral spirit, benzyl acetate, solvent naphtha, etc.

Description

1282331 IX. Description of the Invention: [Technical Field] The present invention relates to a film which can be coated with a relatively thick film, and which is excellent in the cutting property (strength which can be cut) of a thin plate which is formed after coating, and a thin plate A coating material for a thick film green sheet, a method for producing a thick film green sheet, a method for producing a thick film green sheet, a thick film green sheet, and a method for producing a thick film green sheet for a sheet having a high adhesion property, and a method for producing a thick film green sheet A method of manufacturing an electronic component. [Prior Art] In the manufacture of ceramics, such as CR built-in substrates and ceramic capacitors, it is usually first prepared from ceramic powder, binder (acryl (acry), shrinkage). A ceramic coating composed of an aldehyde (butyra 1) resin, a plasticizer, and an organic solvent (toluene, MEK). Next, the ceramic coating material is coated on a PET film by a doctor blade (d〇ct〇r method or the like), and then dried and peeled to obtain a ceramic green enamel plate. Secondly, the ceramic green sheet is printed. After the internal electrodes are dried, 'the layers are stacked into a slice to form a green chip, spleen; after the ancient embryos of ～2 and σ2 are sintered, terminal electrodes are formed to produce a laminate. For electronic components such as ceramic capacitors, in the case of manufacturing a layered capacitor, the thickness of the thin plate formed by the inner Qiu Xue and the tantalum electrode is about 1 to m from 100 to 100, depending on the electrostatic capacitance required for the capacitor. In addition, in the laminated ceramic capacitor, the side portion of the electric > slice is out of the direction >, the internal electrode is not formed. 2030-6478-PF1 1282331 corresponds to the The dielectric layer of the portion where the internal electrode is not formed has a thickness coefficient of about 10 to several hundreds//m, and this portion is formed by using a relatively thick ceramic sheet which is not printed with an internal electrode. Extremely printed embryonic thin Since the thickness is relatively thin, the raw sheet of the film is used, and when the outer portion is formed, the number of layers is increased, the number of manufacturing is increased, and the manufacturing cost is increased by the combination. The larger the number of dielectric layers in the capacitor, the higher the capacitance, and (4) the slice size is limited, so it is necessary to thinen: the electric layer. The dielectric layer is made of submicron ^, (submicr〇n order) The dielectric particles are wrapped in a resin (adhesive) to form a thin plate, and the laminate is sintered to obtain a thin green sheet which is related to the thin layer of the dielectric layer. Further, because of the thin sheet It is easy to be brittle, so as a resin for molding a thin plate and as a high-strength binder resin, the inventors of the present invention proposed to use a polyvinyl condensate (PGlyviny®) (10) resin. Thereby, a dielectric green sheet having a thickness of 2 or less can be produced and can be processed without damage. The ceramic portion used for the laminated chip capacitor has a dielectric layer (inner layer) which is sandwiched between the internal electrode layers in order to obtain a capacitance, and a cover portion (outer layer) which forms the outer side of the slice. The outer layer is required to have a certain thickness in order to protect the internal structure with respect to the inner layer as required. In addition, the physical properties of the sheet required for the inner layer are compactness, smoothness, and strength. In the outer layer, it is adhesive, air permeability, and cuttability, and the physical properties are required to be more important. In this way, the outer layer is opposite to the required physical properties of the inner layer and can be said to be quite different from 2030-6478-ρρι 6 1282331. Therefore, in the case of a coating for a raw sheet which has been specialized for the inner layer, a sheet which satisfies the physical properties required for the outer layer is generally not formed by coating. Here, it is known that k has a resin composition, or a method of adding an additive which compensates for the property which the resin does not have. For example, in the following patent document i, the physical properties of the sheet are controlled by a blend of resins. Further, in Patent Document 2 below, the adhesion-imparting agent is added to improve the adhesion of the sheet. <Don't be, patent literature! In the method, the raw embryonic sheet and the outer layer are respectively formed of a raw material sheet in the inner layer to form a composition of a different binder resin. In this method, in the de-bonding agent engineering using the heated raw slice, there is a possibility that the inner f and the outer layer are debonded by different materials B, the slice strength is damaged, and the crack is broken. Further, in the method of Patent Document 2, it is considered that the adhesion-imparting agent is placed, and the adhesion of the sheet is improved. However, since the adhesion-imparting agent is also a kind of the resin component, the same problem as in Patent Document i is obtained. [Patent Document 1] Japanese Patent Laid-Open Publication No. Hei 2 No. Hei. No. Hei. In view of the circumstances, it is an object of the present invention to provide a film which can be coated with a relatively thick film, and which is excellent in cuttability (strength: strength) of a thin plate which is formed after coating, and which has good air permeability and excellent workability, and can be formed. Next, the coating for thick film green sheet of thin sheet and the thick film green sheet 2030-6478-PF1 7 1282331 The manufacturing method of the soil material, the manufacturing method of the thick film raw sheet, the thick film raw sheet and the electronic component Production method. Means for Solving the Problem ^ In order to achieve the above object, the coating for thick film green sheet according to the present invention is a binder resin having a ceramic powder and a butyra 1 resin as a main component. And a coating for a thick film green sheet with a solvent, wherein: the solvent contains a good solvent for dissolving the binder resin well, and the binder resin is compared with the good solvent. The poor solvent having a low solubility; the poor solvent is contained in an amount of from 3 〇 to 6 〇 by mass based on the total amount of the solvent. In the present invention, the poor solvent system is defined as a solvent which does not completely dissolve the binder resin, or a solvent which is partially dissolved but which is largely insoluble, or a solvent which does not swell but swells. On the other hand, a good solvent is a solvent which dissolves the binder resin well in a solvent other than a poor solvent. It is preferred that the poor solvent contains a solvent having a boiling point higher than the high boiling point of the above good solvent. The good solvent is an alcohol, and the poor solvent contains: toluene, xyiene, mineral spirit, benzylacetate, solvent naphtha (s〇lvent naphtha) At least one of industrial gasoline (kerosene), kerosene, cyclohexane, heptanone, and ethylbenzene (ethyl 2030-6478-PF1 8 1282331 benzene) is preferred. Examples of the alcohol which is a good solvent include, for example, methanol (methan), ethanol, propan〇i, and butanol. Further, in the case where mineral oil concentrate (MSP) is contained as a poor solvent, the mineral spirits are preferably contained in an amount of more than 7% and less than 15%, based on the entire solvent. When the amount of addition of Msp is too small, the air permeability tends to be deteriorated. When the amount of addition is too large, the surface smoothness of the thin plate is lowered, and thick film formation tends to be difficult. In the present invention, a thin layered green sheet which is capable of thinning the dielectric layer is used, and the same is used as the binder resin of the material of the material, and the other solid organic components are further used. 'It is possible to use a micropowder pigment (ceramic research) to form a thick film of raw embryonic sheet. Further, the green sheet formed by the coating for a thick film green sheet of the present invention is improved in air permeability, cuttability, and adhesion, and the handleability of the thick film green sheet is improved. Therefore, the manufacture of the thick film green sheet becomes the county, and it is easy to manufacture the electric φ sub element in which the thick film green sheet is manufactured. Eight, a capital ..., ~ π, Ai also hindered the growth of the smashed slabs of the slabs of the moon containing the binder resin, 1π one of his solid organic components, the manufacture of thick Hong Kong embryo sheet, so the use of raw embryo cut Wang Sheng slice ( The green chip) is used to control the heating of the cement. Yi Yi, that is, a thin sheet of a coating for forming a thin layer of a raw sheet for forming an inner layer, and a thin plate for forming a thick film of a raw film for forming an outer layer, causing a debonding reaction under the same external vehicle J 4 4 . Because j does not damage the strength of the slice, and there is no damage such as cracks. In the present invention, the poor solvent is contained in the amount of 3 2030-6478-PF1 9 1282331 with respect to the entire solvent. The inside / ° is preferably in the range of 30 to 50% by mass. The poor solvent of Berry. If the effect is too low, the effect of the present invention is lowered. When the temperature is too high, the filter characteristics are deteriorated, and the thick film tends to be difficult. The butyral resin is preferably polyvinyl butyral (p〇lyvinyl butyralHu), and the degree of polymerization of the polyethylene or enol shrinkable disk resin is from 1,000 to 1,700, and the degree of butyralization of the resin is More than 64% and less than 78%, the amount of residual acetohydrazide (acetyl) is less than 6%. * The polyvinyl alcohol shrinking plate is intended to be a thin layered green embryo capable of thinning the dielectric layer. The resin with the same binder resin contained in the coating for thin plates has a tendency to obtain sufficient mechanical strength in the field of thinning. In addition, when the degree of polymerization is too large, there is surface roughness in the case of thinning. In addition, when the degree of butyric acidification of the polyvinyl chloroprene resin is too low, the solubility in the coating tends to be deteriorated, and when it is too high, the surface roughness of the sheet tends to be deteriorated. When the amount of the base material is too large, the surface roughness of the sheet tends to be deteriorated. Originally, it is difficult to form a thick film green sheet by using a polyvinyl butyral resin suitable for thinning. However, in the present invention, By adjusting the composition of the agent in the coating In this method, a resin similar to the polyvinyl butyral resin suitable for thinning is used as a binder resin to form a thick film green sheet. The binder resin is in comparison with the ceramic powder. It is preferable that the amount of the binder resin is too small. When the amount of the binder resin added is too small, sufficient bonding strength tends to be insufficient in the sheet forming process, and when the amount is too large, the sheet strength tends to be too high. 2030-6478-PF1 10 1282331, a method for producing a coating for a thick film green sheet according to any one of the above aspects of the present invention, which is characterized in that: The average particle diameter of the ceramic powder (the base material) dispersed in the coating material for the thick-film green sheet is not the average particle diameter of the ceramic powder dispersed in the coating for the thick-film green sheet. In the method of particle size of less than 8〇%, the powder of the above-mentioned ceramics is pulverized. In the thin layer of the coating for the raw sheet, in order to make the sheet thin, the average particle size relative to the base material is used to make the thin raw embryo thin. (4) After the coating The average particle diameter of the powder body is pulverized by the fine particle diameter of 4 or less. In contrast, the coating for the thick film green sheet of the present invention is relative to the powder of the base material. When the average particle diameter becomes too small, the sheet is too low, and the adhesion becomes poor, and the workability is deteriorated, and the workability is lowered, which makes it difficult to thicken the film. Thus, in the past, the ceramic powder was fine and must be pulverized. The pottery body is dispersed in the paint. For example, strict management of the crushing level of the coffee to the coffee must disperse the Tao Jing powder in the paint, but the control is difficult in the present invention by using the solvent as a solvent. However, it is easy to disperse the ceramic (four) body in (10) and (4). Moreover, the present invention can shorten the time for the production of the paint (pigment dispersion, resin kneading). The method for producing a raw sheet is characterized in that: a process for preparing a thick film green sheet for a member of the above-mentioned member, and a coating process; and a coating for forming a thick film green sheet using the coating for the thick film green sheet; 6478-PF1 11 1282331 system . The thick film green sheet according to the present invention is characterized in that the thick film green sheet according to any one of the above is used for the manufacture of a thick film green sheet which is suitable for use in, for example, ceramics. The outer layer portion of the electric valley (the portion which is not entangled in the internal electrode layer and does not contribute to the characteristics). The method for manufacturing the ceramic electronic component of the present invention, comprising: preparing a thick film according to any one of the above a process for coating a raw sheet; a method for forming an outer raw sheet by using a coating for a thick film green sheet; t preparing a binder tree containing the coating for the thick film green sheet

The thin layer of the raw material sheet of the lunar phase R type of the binder resin; I - the monthly coating of the thin layer of the raw sheet, so that the inner raw sheet is thinner than the outer raw sheet a process for forming; a process of laminating the inner electrode layer by interposing the inner electrode layer to obtain a laminate; + laminating the outer raw sheet at both end faces of the laminated body of the other layer to obtain The process of raw embryo sectioning; and the process of sintering the aforementioned raw embryo section. ^ The coating for the thin layered green sheet is preferably the same type of ceramic powder as the above-mentioned thick film green: the ceramic powder used for the special material: the material used for the k material. By using the same type of ceramic powder, it is easy to manufacture the ceramic components of 2030-6478-PF1 12 1282331. The average particle size of the ceramic powder contained in the coating for a V thin layered green sheet is 'h', ten, and one. The average particle diameter of the ceramic powder contained in the coating for the embryonic sheet is smaller and lighter. By forming this relationship, hunting can simultaneously satisfy the thinning of the inner raw sheet and the thick film of the outer raw sheet. , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , The average particle diameter of the powder does not become a method of granulating the granules, and the process of pulverizing the ceramic powder; and the octagonal to the terracotta prior to dispersing the coating for the thin layered green sheet The average particle size of the body is obtained by dispersing the coating material for the thin layered green sheet, and the average particle diameter of the ceramic powder is 8% by volume or less to pulverize the ceramic powder. By this method, it is possible to simultaneously satisfy the thinning of the inner raw sheet and the thick gland of the outer raw sheet. ^, Bu, can ease the strict management of the ceramic powder in the thick film raw sheet metal coatings. [Embodiment] Hereinafter, the present invention will be described based on the embodiment shown in the drawings. First, as one embodiment of the present invention, a coating for a raw enamel plate (dielectric paste) and an electronic component manufactured using a raw metal sheet, the overall configuration of the laminated ceramic capacitor is explained. As shown in Fig. 1, the capacitors and the hook-free capacitors 1 have a capacitor body part 2030-6478-PF1 1282331 having a structure in which the inner dielectric layer 2 and the inner electrode layer 3 are formed. The both end portions of the body 10 are formed on the internal electrode layer 3 in which the component body π is disposed, and the pair of terminal electrodes 4 are electrically connected to each other. The shape of the capacitor component body 1G is not particularly limited, but is usually formed into a rectangular parallelepiped shape. In addition, there is no particular limitation on the size thereof, and it may be appropriately sized according to the application, but it is usually about long (G 6 to 5 6 _, 杈 good) x high (0·1 to 1·9 mm, and 〇·3 ~h 6_ is better).

The internal electrode layer 3 is laminated such that the respective end faces are alternately exposed on the surfaces of the opposite ends of the capacitor body 1b. The pair of terminal electrodes 4 are opened at both end portions of the capacitor component body 1 and are connected to the exposed end faces of the internal electrode layers 3 which are alternately arranged to constitute a capacitor circuit. In the electric valley component main body 10, the outer dielectric layer 2 () is disposed at both outer end portions of the inner electrode layer and the inner dielectric layer 2 in the stacking direction to protect the inside of the component body 10. The composition of the φ dielectric layers 2 and 20 and the inner dielectric layer 2 and the outer dielectric layer 20 are not particularly limited, and are, for example, composed of the following dielectric ceramic compositions. The dielectric ceramic composition of the present embodiment is made of a dielectric material such as titanic acid calcium, titanic acid strontium, and/or titanic acid barium. Composition. Further, the conditions such as the number of layers or the thickness of the inner dielectric layer 2 shown in Fig. 1 may be appropriately determined depending on the purpose or use, but in the present embodiment 2030-6478-PF1 14 1282331 type, the inner layer The thickness of Lei-曰2 is about 5/5 m, and the thinner η is reduced to 3 // m. In addition, the thickness of the outer dielectric layer 2 is, for example, about 100 Å to hundreds of Å. The internal electrode layer 3 is not particularly limited by the conductive material contained in the internal electrode layer 3, but the constituent material of the inner dielectric layer 2 is resistant. Reducing metal. As a conductive material, it is used as a φ 金属 人才 talent, wood, Ni, Cu, Ni alloy or Cu. In the case where Nl is used as the internal electrode layer: the main component of 3 The dielectric body is not returned; ^ _ , _ depending on the original method, the so-called low-oxygen partial pressure (reduction environment) into the 4 butyl sintering method D Jg _ 士 » ^ On the other hand, the electricity system does not The method of reducing the composition is determined by a chemical composition, etc. The thickness of the internal electrode layer 3 may be appropriately determined depending on the application, etc., but is usually about 0.5 to 5/m. The conductive material contained in the electrode 4 is not particularly limited, but usually Cu or a Cu alloy or Ni "Ni alloy or the like is used. Of course, g or an Ag Pd alloy or the like can also be used. Further, in this embodiment, the price can be used. Lower Ni, Cu, or alloys of these. The thickness of the sub-electrode may be appropriately determined depending on the application, etc., but is usually preferably about 10 to 50/zm. The manufacturing method of the laminated ceramic capacitor is followed by the laminated ceramic capacitor according to one embodiment of the present invention. The manufacturing method will be described. (1) First, in order to manufacture a ceramic green sheet of the electric layer 2 of the inner layer 2030-6478-PF1 15 1282331 shown in the second figure after sintering, a thin layer dielectric coating (thin film) is prepared. A thin layered dielectric coating is composed of an organic solvent-based coating obtained by kneading a dielectric material (ceramic powder) and an organic vehicle (vchi c 1 e). The electric material is suitably selected from a composite oxide or various compounds which become oxides, such as carbonates, nitrates, hydroxides, organometallic compounds, etc., and can be used in combination. Dielectric materials, usually, The average particle diameter is 〇·1 to 3 #m or less, and it is preferable to use a powder of about 〇·^ or less. Also, in order to form a thin green sheet as much as possible, it is preferable to use a thinner thickness than the raw sheet. It An organic vehicle is a material in which a binder resin is dissolved in an organic solvent. As a binder resin used in an organic vehicle, this embodiment uses polyvinyl butyral (polyvinyl butyral). Resin. The degree of polymerization of the polyvinyl butyral resin is preferably 1 Å or more and 17 Å or less, and preferably 1400 to 1 700. Further, the degree of butyralization of the resin is more than 64% and less than 78. %' is more than 64% and preferably 70% or less, and the residual vinegar base amount is preferably less than 6%' and 3% or less. The degree of polymerization of the polyvinyl butyral resin can be, for example, polyvinyl alcohol of a raw material. The degree of polymerization of a polyvinyl acetal resin was measured. Further, the degree of butyric acidification can be measured according to, for example, JISK6728. Further, the residual acetohydrazide amount can be measured in accordance with JIS K6728. When the degree of polymerization of the polyvinyl butyric acid resin is too small, in the case of a thin layer formation of, for example, 5/zni or less, preferably about 3 #m or less, it is difficult to obtain sufficient mechanical strength. Further, when the degree of polymerization is too large, there is a tendency that the surface roughness of the thin 2030-6478-PF1 16 1282331 is deteriorated. Further, when the degree of butyralization of the polyvinyl butyral resin is too low, the solubility in the coating tends to be deteriorated, and when it is too late, the surface roughness of the sheet tends to deteriorate. Further, when the amount of the vinegar mash is too large, the surface roughness of the sheet tends to deteriorate.

The organic solvent to be used in the organic vehicle is not particularly limited, and for example, terpineol, alcohol (alc〇h〇1), butyl carbol〇1, acetone (for example) can be used. 〇 〇 ) ) 、 甲苯 甲苯 甲苯 甲苯 甲苯 甲苯 甲苯 甲苯 甲苯 甲苯 甲苯 甲苯 甲苯 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 The content of the aromatic solvent is not more than 2 parts by mass in the inner part of the enamel. The content of the aromatic solvent is too small, and the surface roughness of the thin plate is increased. If there is too much, the coating will pass through the characteristics of the core sheet, and the surface sugar content will increase and deteriorate. • As an alcohol solvent, methanol, ethanol, and propanol (pr〇pan〇1) are exemplified. Butanol (butan〇〇, etc.. as - Xiangzhi Department of cold-bin 'J', there are no toluene (t〇luene), xylene (state acetacetate benzylacetate), etc. Pre-setting at least one type of alcohol solvent in the dielectric powder and other formations It is preferred that it is not easily dissolved in the solvent, and the usual method tends to. In the method of the present embodiment, the fat is dissolved in the above-mentioned good solvent, and the component is added, so that the dispersibility of the coating, methanol, ethanol, propanol, butanol can be improved. When the solution is added, the binder resin of the south polymerization degree is deteriorated because the dispersibility of the coating is deteriorated because the ceramic powder and the like are added to the solution of the high polymerization degree binder, and the undissolved resin is suppressed 2030. -6478-PF1 1282331

^lL. Further, the solvent other than the above solvent does not increase the solid content concentration, and the lacquer adhesion tends to change with time. In the present embodiment, in the dielectric coating, the binder resin is used. In addition, a xylene resin may be added as an adhesion-imparting agent. The xylene-based resin may be added in a range of 1 〇 里 以下 % or less, and 0.1 or more 相对 相对 mass to the mass portion of the ceramic powder. % or less is more preferable, and it is more preferably in a range of more than 1.0% by mass or less. The amount of the xylene-based resin added is too small, and the adhesion tends to decrease. Further, when the amount is too large, the adhesion is increased. The surface roughness of the thin plate is increased, and the lamination of many sheets becomes difficult, and the tensile strength of the thin plate is lowered, and the workability of the thin plate is lowered. In the dielectric coating, it may be contained as needed. Various dispersants, plasticizers, additives other than charged agents, dielectrics, glass glazes, insulators, and the like.

In the five embodiments, the dispersant is not particularly limited, but a non-ionic (face _i〇n) knife of the polyethylene glycol (_yethylene glyeQl) system is used: U Gui's hydrophilicity The oleophilic balance (HL(1) value A 5 to 6. Dispersant, the amount of the dispersant is preferably 〇·5 mass parts or more and 1.5 mass parts or less, more than 5 mass parts or more. The quality is less than the above. When the above range is exceeded, the viscosity of the coating increases and the surface roughness of the sheet increases. Further, in addition to the dispersant of the polyethylene glycol-based nonionic dispersant, the viscosity of the coating increases. And the surface roughness of the sheet is increased, and the sheet stretchability is lowered, so it is not good. 2030-6478-PFi 18 1282331 The amount of the dispersant added is too small, the ancient plant & * t ^, V, there is a seesaw surface When the roughness is increased, the tensile strength and the stacking property of the sheet tend to decrease. In the present embodiment, 'as a plasticizer, Ui〇Ctyl phthalate is used. Preferably, it is contained in 40 parts of the mass of the binder resin. 7〇 mass unit less than the preferred amount of the unit, while the portion 4〇~6〇 better quality. Compared with other plasticizers, dioctyl phthalate is preferred in terms of both sheet strength and sheet stretching, and in particular, is superior to peeling strength from the support body and is easily peeled off. Further, when the content of the plasticizer is too small, the sheet stretchability is small and the flexibility tends to be small. Further, when the content is too large, the plasticizer bleeds out from the sheet, and segregation of the plasticizer to the sheet tends to occur, and the dispersibility of the sheet tends to decrease. Further, in the present embodiment, the dielectric coating material contains water at a mass portion of not less than 6 parts by mass based on the mass portion of the dielectric powder, and is preferably 1 to 3 parts by mass. When the water content is too small, the change in the characteristics of the coating material according to the moisture absorption becomes large, and the viscosity of the coating material tends to increase, and the filtration characteristics of the coating tend to deteriorate. Further, when the water content is too large, separation or sedimentation of the coating material occurs, the dispersibility is deteriorated, and the surface roughness of the sheet tends to be deteriorated. In the present embodiment, at least one of a hydrocarbon-based solvent, an industrial gasoline, a kerosene, and a solvent naphtha is added to the mass portion of the dielectric body powder at a mass of 3 or more. 15 mass parts or less, preferably 5 to 10 mass parts. By adding these additives, the sheet strength can be improved and the surface roughness of the thin electrode can be improved. When the amount of addition of these additives is too small, 2030-6478-PF1 19 1282331 has little effect of addition, and when the amount of addition is too large, there is a tendency that the strength of the sheet and the surface roughness of the sheet are deteriorated. The binder resin is preferably contained in an amount of 5% by mass based on the mass portion of the dielectric powder. When the content of the binder resin 1 is too small, the strength of the sheet is lowered and the stackability (adhesiveness at the time of lamination) tends to deteriorate. Further, when the content of the binder resin is too large, segregation of the binder resin occurs and the dispersibility tends to be deteriorated, and the thickness of the surface of the thin plate tends to deteriorate. Further, in the case where the total volume of the ceramic powder and the binder resin and the plasticizer is 100% by volume, the volume fraction of the dielectric powder is 62.42 ° /. It is preferably 72.69% or less, preferably 63 93% or more and 72 69% or less. When the volume specific gravity is too small, the segregation of the binder tends to cause the knife-like property to deteriorate, and the surface roughness tends to deteriorate. In addition, if the volume is too large, the thickness of the sheet is reduced, and the stacking property is deteriorated. Further, in the present embodiment, it is preferable that the dielectric coating contains a charge-removing agent, and the charge-removing agent is an imidazoline-based charge-removing agent. In the case where the charging agent is not a ruthenium (iv), the charging effect J is removed, and there is a tendency that the sheet strength, the sheet stretching degree, or the adhesion property are deteriorated. In addition to the charged agent, it is contained in the mass part of the ceramic powder, and is contained in the oi bei σ 卩 or more. 75 mass parts or less, preferably in the 0 · 25~ 〇 · 5 mass: the addition amount of the charged agent is too When the amount is small, the effect of removing the charging is small, and when it is too large, the surface roughness/roughness of the sheet is deteriorated, and the strength of the sheet tends to deteriorate. When the effect of charging is removed, when it is peeled off from the ceramic sheet, it is easy to generate static electricity when it is used as a supporting sheet of 2030-6478-PF1 20!282331, and wrinkles are likely to occur in the raw sheet. situation. In the case of a dielectric coating, first, a pottery body is dispersed in a slurry by a ball mill or the like (pigment dispersion engineering). This = material dispersion engineering, at the same time in the ceramic powder (pigment) crushing project also, the binary penetration, even if the average particle size of the ceramic powder can be known. In the present embodiment, in the pigment dispersion process, the average particle diameter of the ceramic powder dispersed after the slurry is made with respect to the average particle diameter of the ceramic powder (base metal) dispersed in the mud before the mud is loaded. It is preferable that the pigment is crushed and dispersed in such a manner that it is preferably 8% or less and less than 8% by weight. Next, a dispersant and other additives are added to the slurry containing the ceramic powder and dispersed to obtain a dispersion coating (dispersant addition and dispersion). Finally, in the dispersion coating, a binder resin is added and kneaded (a resin mixing process). a dielectric coating (a thin-layered raw sheet for strips) obtained by a ruthenium method, and a load sheet 3 as a support in the manner shown in FIG. 2 by a doctor blade method or the like ( On the upper side, the inner raw sheet 2a is formed with a thickness of preferably 〇·5 2 1〇"m. The inner sheet 2a is dried after the load sheet 3 is formed. The inner raw sheet is dried at a temperature of 50 to 1 Torr. (: Preferably, the drying time is preferably from 1 to 20 minutes. The thickness of the inner raw sheet after drying is reduced to a thickness of 5 to 25% compared with that before drying. The inner raw sheet 2a after drying It is preferable that the thickness is 3 #m or less. (2) Next, after sintering, in order to manufacture a ceramic green sheet of the electric layer 20 of the outer layer 2030-6478-PF1 21 1282331 shown in the figure, a thick film dielectric is prepared. Coating (coating for thick film green sheet) This thick film dielectric coating is subjected to the following adjustments in the same manner as the above thin layer dielectric coating. Thick film dielectric coating, thin layering The dielectric coating is composed of an organic solvent-based coating obtained by kneading a dielectric material (ceramic powder) and an organic vehicle, and is used as a binder resin for a thick film dielectric coating. The same resin used for thin-layer dielectric coatings. The organic solvent used as an organic vehicle for thick-film dielectric coatings is a good solvent for the good dissolution of the binder resin. a poor solvent with a solvent and a low solubility to a binder resin, a poor solvent The content of the solvent is in the range of 30 to 6 % by mass based on the entire solvent, and the solvent is a solvent having a higher boiling point than the good solvent. The good solvent is, for example, an alcohol or a poor solvent, and contains: benzene (ΐ) 〇丨uene ), xylene, minerai spirit, benzylacetate, solvent naphtha, gasoline (gasoline), kerosene, gh At least one of heptanone and ethyl benzene. Examples of alcohols as good solvents include methanol, ethanol, propanol, butanol. Further, in the case where mineral oil concentrate (MSP) is contained as a poor solvent, the mineral oil concentrate alone is preferably in a range of more than 7% and less than 1% with respect to the entire solvent. MSP When the amount of addition is too small, the air permeability tends to be deteriorated. When the amount of addition is too large, the surface smoothness of the thin plate is lowered, and the thick film 2030-6478-PF1 22 1282331 tends to be difficult. The poor solvent 'is relative to the solvent. , the content is 30~60% by mass Preferably, it is in the range of 30 to 50% by mass. The mass % of the poor solvent is too low, and the effect of the present invention is lowered. When the temperature is too high, the filtration characteristics are deteriorated. The tendency to get a suitable coating.

The binder resin is preferably in a mass ratio of 4 to 6.5, with respect to the mass portion of the ceramic powder. When the amount of the binder resin added is too small, sufficient strength or adhesion tends to be insufficient in the molding and processing of the sheet. When the amount is too large, the sheet strength tends to be too high. In the adjustment of the thick film dielectric coating, firstly, the ball powder is dispersed in the slurry by a ball mill (bau xian), etc. (pigment dispersion work) 4 pigment dispersion spear is 'at the same time in Tao Xianfen The crushing process of the body (pigment) also has a degree of progress, and even if the (four) powder has a change in the average particle size, it can be known. In the present embodiment, in the pigment dispersion process, the average particle diameter of the ceramic powder dispersed in the body (the base material) before being dispersed in the mud is not made. 8 broken and dispersed.仃顋枓 碍 碍 碍 碍 碍 碍 碍 碍 碍 碍 碍 碍 碍 碍 碍 碍 碍 碍 碍 碍 碍 碍 碍 碍 碍 碍 碍 碍 碍 碍 碍 碍 碍 碍 碍 碍 碍 碍 碍 碍 碍 碍 碍 碍 碍 碍 碍In the film dielectric coating, the average particle size of the ceramic powder is too small, and the density of the thin plate becomes high = the body property is lowered, and the thick film becomes difficult. Because of the & intersection, the body is not shredded by the way, there must be ceramic: Baiyi wants to make the pottery powder in the mud 2030~6478-PFl 1282331 scattered. For example, it is strictly controlled at a crushing level of 100% to 90%, and it is necessary to disperse the ceramic powder in the mud, but the control is difficult. In the present embodiment, the solvent is allowed to be pulverized to 80% by the use of a poor solvent, and the process of dispersing the ceramic powder in the slurry is facilitated. Next, a dispersant and other additives are added to the slurry containing the ceramic powder and dispersed to obtain a dispersion coating (dispersant addition and dispersion). Finally, in the dispersion coating, a binder resin is added and kneaded (a resin mixing process). The thick film dielectric coating (coating for thick film green sheet) obtained by this method is used as a support sheet by a doctor blade (d〇ct〇rblade) method or the like as shown in Fig. 2 Preferably, the outer raw sheet is formed by a thickness of 10 to 100/zm, and a thickness of about 30,000# m. The outer side is formed, and the thin plate 2Ga' is dried after the load sheet 3{) is formed. The load sheet 30 is made of, for example, a PET film or the like. The drying temperature of the outer raw sheet is preferably 50 to 100 ° C, and the drying is preferably 1 to 20 minutes. The thickness of the outer side raw sheet after drying is reduced to a thickness of 5 to 25% compared to that before drying. After drying, the outer side of the green sheet 2〇a has a thickness of 1 〇" The outer raw sheet 2Qa obtained by peeling off the load thin plate 3 is a part of the outer dielectric shown in Fig. 1. - (3) ... person's on the surface of the green sheet 2a, the internal electrode layer 3 as shown in Fig. 1 is formed. The method of forming the internal electrode 353 is not particularly limited, but examples thereof include a crucible, a thin material, a transfer method, and the like. 2030-6478 - Pp]_ 1282331 Thereafter, as shown in Fig. a, the inner peak of the interactive formation m compensates for the inner raw sheet 2a formed by the electrode layer, and in the layering direction thereof or The outer layer of the raw embryo sheet 20a is laminated. 'Collective body: Γ: The layered body obtained by the Γ method, cut into the specified layer = size, after the maturation of the embryo slice m, the detachment is performed, in order to make the dielectric layer 2 and reoxidize,孰 Treatment. The debonding agent treatment can be carried out under normal conditions, but in the case where the internal conductor material of the internal lightning layer is Ni or Ni T*, f > i 荨 金属 金属 metal, under the following conditions It is better to carry out the heating rate: 5~300 °c / hour, especially Β 1 Λ will be 疋, 10~5 (TC / hour, keep the temperature: 200~40 (TC, special 3 nr 疋, 250~350 °C, Hold time: 〇. 5~2 0 hours, μ 曰, four T w 疋 1~10 hours, Environment: The mixed gas of N2 and Η2 has been humidified. The sintering conditions are preferably as follows.幵 Temperature speed: 5 0~5 0 0 ° C / hour, Du σ t β, especially, 200~300 ° C / hour, 保持 Keep the temperature · · 1100~1 300 ° C, turn brother, 丨η, The sign is 1,150~1 250 °C, hold time: 〇·5~8 hours, special, 丨η 0 pay 疋, 1~3 hours, cooling rate: 50~50 0°C/hour, ϊσϊ θ τ 'Specially, 200 to 300 ° C / hour, ambient gas: N has been humidified, mixed with I, etc.. Among them, 'the air in the sintering environment 惫 # 2 τ < 虱虱 partial pressure system in 1 0 2 Pa or less, especially in the range of 10-2 to 10-8 Pa, and the τ season is preferable. When the above range is exceeded, there is a tendency for the internal electrode layer to oxidize, and when the partial pressure of the helium gas is too low, Have

2030-6478-PF1 2S 1282331 The electrode material of the internal electrode layer causes abnormal sintering, which causes a tendency to break. After the heat treatment such as sintering, the holding temperature or the maximum temperature is preferably 1 000 ° C or more, preferably 1 000 to 110 (rc is better. When heat treatment = temperature or maximum temperature, below the aforementioned range τ because of dielectric When the oxidation of the bulk material is not sufficient, the life of the insulation resistance tends to be short. When the temperature exceeds the above (5), the Ni of the internal electrode is oxidized, and not only the capacitance is lowered, but also the life of the material material is delayed. The oxygen eight pressure is better than the oxygen partial pressure of the reducing environment during sintering, preferably Η, ~1Pa. Below the above range, the re-oxidation of the dielectric a layer 2 is more than the above In the range, there is a tendency for the internal electrode layer 3 to oxidize. Next, other heat treatment conditions are as follows. Holding time: 0 to 6 hours, in particular, 2 to 5 hours, small Japanese cooling rate: 50~ 50 〇 小 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , 。 。 。 。 。 。 。 In this case, the water temperature is 〇 〇 饥 饥 较佳 较佳 ^ 外 外 ’ ’ 脱 脱 脱 脱 脱 脱 脱 脱 脱 脱 脱 脱 脱 脱 脱 脱 脱 脱 脱 脱 脱 脱 脱These treatments are carried out continuously. έ & amp ^ ^ ^ ^ ^ ^ ^ ^ ^ 结 结 结 结 结 结 结 结 结 结 结 结 结 结 结 结 结 结 结 结 结 结 结 结 结 结 结 结 结 结 结 结 结 结 结 结On the other hand, the independent management of the people ^· Ding does not have some sputum, mouth, in the knot, in the I gas or the humidified I gas 俨 幵 / dish until the temperature of the (four) agent treatment to maintain the temperature Brother and then come to my brother and then continue 2030-6478-PFi 26 1282331 Continue to warm up better, cool until the heat λτ ^ < Guarantee, after the degree, once again into a Ν 2 gas or has been humidified ν It is better to continue cooling. In the case of this,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, In this way, the sintered body (the part body (8), the grinding and sanding device (sand blast, the 工#工山展 coating forms the terminal electrodes 6, 8 and the sub-electrode is, for example, the sintering condition of the Λ coating) Μ minutes to about i hours is better. Then, because _Required = on the 6th and 8th, by forming the sound of the electric ore, etc., it is necessary to "form the sub-electrode to form a cushion. Further, the terminal electrode is selected by the coating material, and the above-mentioned electrode coating is prepared in the same manner." The laminated ceramic capacitor of the present invention manufactured by the present invention is used on a printed circuit board by a soldering iron, etc., and is used in various electronic devices. In the present embodiment, the dielectric coating (thin layering) For the production method of the raw material sheet and the laminated ceramic capacitor using the raw sheet, it is possible to manufacture even a very thin raw sheet by using a binder resin containing a resin as a main component. A thin layered green sheet having a strength capable of withstanding peeling from the support and having good adhesion and workability. For example, the thickness of the sintered dielectric layer (sintered raw sheet) can be thinned into a thin layer. , m is lower than '3...lower, and 2"m or less is better: this thin layered green sheet in the present embodiment can also increase the number of layers because the surface has a small coarse sugar content. 2030-647 8-PF1 27 1282331 In addition, in this embodiment, The thin layered dielectric coating (thin layer: coating for thin sheets) and the dispersing agent for the manufacture of special types of laminated ceramics using a layer of raw materials, HLB uses a specific range of dispersion ^ so 'even For example, the following thin and thin raw green sheets can be extracted from the strength of the loaded sheet, and have good f and operability. In addition, the surface roughness of the sheet is also small, and the stack (four) plate is interposed with the electrode layer. Carrying out most of the lamination. Further, the thick film dielectric coating (thick film greening 'plate coating) and the manufacturing method of the laminated ceramic capacitor using the coating are adopted in this embodiment. The thin layered dielectric coating of the dielectric layer contains the same: but the same butadiene-based resin, which does not change the other solid shape of the resin, and the use of the fine powder pigment (ceramic powder) to form a thick film The embryonic board is two and one, and the thick film dielectric coating of the present embodiment is formed, the emulsion property, the cutting property and the adhesion property of the #plate are improved, and the operation of the thick film green sheet is prepared. Ancient ma S &quot;. Therefore, the manufacture of a thick film green sheet becomes easy and it is easy to manufacture an electronic component manufactured by using a thick film green sheet. In addition, in the present application type, At τ material π # ^ ^ ^ does not change the binder resin and other mouth-shaped rich components contained in the thin-layer dielectric coating, and produces a thick film of raw slabs, so The control of the debonding agent engineering using the raw heat is "easy. That is, the thin plate of the thin layer dielectric coating which forms the inner layer, and the thick film dielectric cold material which forms the outer layer" The plate is subjected to the reaction of the twisting agent at the same timing. Therefore, it does not cause damage such as damage. L makes the slice strength impaired and there is no crack 2030-6478-PF1 28 1282331 - Again, the invention is not limited In the above-described embodiments, various changes can be made within the scope of the present invention. For example, the method of the present invention is not limited to the method of manufacturing a laminated ceramic capacitor, and is also applicable to a method of manufacturing other laminated electronic components. EXAMPLES Hereinafter, the present invention will be described based on the more detailed examples, but the present invention is not limited to these examples. Example 1 a Preparation of a coating for a thick film green sheet using BaTi〇3 powder (BT-〇2/ 1t Xue Industrial Co., Ltd. as a pottery The raw material of the rice knives is made of (Ba〇.6Ca〇.4)Si〇3: 1.48 mass parts, γ2〇3: ι_ 〇1 mass parts, with respect to 100 parts of the BaTi〇3 powder. MgC〇3: 0·72% by mass, Cr2〇3: 〇·13% by mass, and V2〇5: 〇45% by mass of 'Preparation of ceramic powder by-component additives. Only the sub-components were added to the ball mill at the beginning. The mixture is mixed and sublimed, that is, 'subcomponent additive (total amount 8.8 g), ethanol: 6 g, η propanol · 6 g, xylene: 2 g, and dispersant (〇· lg), using a ball mill, The pulverization was carried out for 20 hours. As a binder, 15% lacquer (BH6, manufactured by Sekisui Chemical Co., Ltd.) was dissolved in ethanol/η-propanol di p 1 using BH6 (polyvinyl butyral resin/pvB). In addition, as a dispersing agent, a polyethylene glycol-based nonionic dispersing agent (HLB=5 to 6) is used. The preparation of the subcomponent additive is added to i 〇3 : 1 91 · 2g. Crushing mud, ethanol · · 37g, η - propanol · · 37g, diterpene benzene · · 50g, 2030-6478-PFl 29 1282331 mineral spirits (MSP): 15g, as a plasticizer Component D〇p (dioctyl Phthalate): 6g, a polyethylene glycol-based nonionic dispersant (HLB = 5~6) as a dispersing agent: 14g, BH6 (poly Vinyl butyral resin/PVB)! 5% lacquer (丨acquer) (BH6 manufactured by Sekisui Chemical Co., Ltd. is dissolved in ethanol/n-propanol = 1: )) as a solid component of 6 mass% (8Og in paint addition) . Thereafter, the dispersion coating was mixed in a ball mill to prepare a ceramic coating (coating for thick film green sheet) by mixing 2%. In the production of the ceramic coating, the average particle size of the ceramic powder dispersed in the coating is set to be equal to the average particle diameter of the ceramic powder (base metal) dispersed before the coating, as shown in the following table! As shown, it is 8% or more of a: the formula "breaking and dispersing of the pigment. That is, the average particle diameter dBa of BaTi〇3 as a base material before being dispersed in the coating material is 〇.623, and the average particle diameter of BaTi〇3 is equal to &amp; 〇5... m, a breaking condition of 82.2%. Further, the average health value means the average particle diameter of 50% of the full volume of the ceramic powder, and is defined by, for example, ISRi629 and the like. The particle size is measured by the micro-track HRA manufactured by Nikkiso Co., Ltd., and the degree of polymerization of the polyglycolic acid as a binder resin contained in the ceramic coating is determined. %, the residual gambling base amount is 3 ± 2%. The binder resin is contained in a ceramic coating material in an amount of 6 parts by mass based on 1 part by mass of the pottery powder (including the pottery powder side component additive). As the plasticizer, the DOP is contained in the ceramic coating with respect to P 3 in the binder resin i 〇 50. The fraction 2030-6478-PF1 30 !282331 mass ::: the nonionic dispersant ' is relative to the ceramic powder 10. Berry mouth, the amount is in the mass of 〇·7. In addition, as shown in Table 1, in the paint, the good solvent and the solvent, the content of 'p-propanol was 68.2% by mass, and the poor solvent: one contained was mass%, lean. Part of the solvent

Msp, ^...Yes! It is 22.7 mass%. That is, the poor solvent composed of ρ xylene contained d 1 · 8 mass% with respect to the entire solvent. Regarding the ceramic paint, the results of the investigation according to the characteristics are shown in the evaluation of the characteristics of the data. (4) Kiriyama's product number 〇.5C, retaining particle size 4/zm filter paper, at the pressure of 〇1 liver 3 Next, the coating of 1 5 〇g was evaluated by the time of the filter paper area of 28.26 cm 2 . The shorter the pass time, the better the filter characteristics. The good filtration characteristics mean that there is less debris in the coating and the binder resin dissolves well. The filter time is 5 minutes or less. It is judged to be good under the total judgment (〇). Further, in the case where the filtration time is longer than 5 minutes, it is judged as χ in Table 1. 1 | Solvent data Pigment property Μ Μ ι ι ι 贫 贫 贫 贫 贫 贫 贫 贫 贫 贫 贫 贫 贫 贫 贫 贫 贫 贫 贫 贫 贫 贫 贫 贫 贫 贫 贫 贫 贫 贫 贫 贫 贫 贫 贫 贫 贫 贫 贫 贫 贫 贫 贫 贫 贫 贫[wt%] [wt%] [wt%] [^m] [//m] [%] [〇 or 乂] f // m] ΓΟ or χ] Comparative Example la 20.3 6.3 Diphenylbenzene 14.1 0.608 0.486 79.9 〇8 χ Comparative Example lb 27.3 9.1 Diphenylbenzene 18.2 0. 623 0.51 81.9 〇13 13 〇〇Example la 31.8 9.1 Diphenylbenzene 22.7 0.623 0.512 82.2 〇~~ Example lb 40.9 9.1 Dimethyl stupid + toluene 31.8 0 623 0.506 81.2 〇13 V—f 〇Example lc 54.5 9.1 Dimethyl benzene + toluene 45.5 ^ 0. 623 0. 524 84.1 〇17 〇Comparative example lc 63.6 9.1 Diphenylbenzene 1 54.5, 0.623 - X Cannot be coated 31 2030-6478-PF1 1282331

The production of the raw sheet is obtained by coating the coating obtained by the above-mentioned method with a wire bar coater ((10) (4) on a m帛 film (loading sheet) as a supporting film, and drying it to determine the thickness of the coatable sheet. As shown in the table, under the thickness of the dried, it can be made into a 13" raw embryo sheet. ', the evaluation of the raw sheet

七浐先 .r ^ ,, judge iU/z HU

Bay, 'j疋 ventilation. In addition, the tensile strength of the sheet was measured. Furthermore, based on these results, the total determination is made. 10 (4) The evaluation of pressure loss is carried out by applying 426 厚度 to the thickness of 5/^ and 2 pieces of weight 9 ς S + Gonggong to become the thin plate of i ln square, the way of measuring the heart (4) The pressure of the thin plate: Part. In the air permeability determination, #29嶋 is judged (Ο), otherwise it is judged as bad (χ). 2030*-^478~PFl Thin plate tensile strength is determined by instr〇 N5543 «'The thin plate that will be pierced into the shape of the reading is used as the sample: or the sample is stretched at the speed of the stretching speed wmin, and the strength is 32 1282331 degrees (MPa), and the average value is calculated. Because of the thick film, the private ,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, The second degree (g/Cffi3) is from the end of the measured value of the amount and volume of the thin plate. When the density of the thin plate is more than 3.3g/cm3, the thinness of the thin plate is reduced, as shown in Fig. 3 It is difficult, so in the case of Milu (:) on 3., it is judged to be good (9), otherwise the heart is judged.

In the total of the filter characteristics, the coating thickness determination, the air permeability determination, the strength determination, and the density determination result, it is judged that all are good (〇): good, and one of them is judged to be defective (χ) , judged as bad: These results are shown in Table 2. Example 1 b ^ except that two parts of a poor solvent are replaced by two benzene and toluene, and xylene is a solvent of the same boiling point, and the amount added is Μ 8 % by mass based on the entire solvent, from MSP + work toluene + toluene In the same manner as in Example la, a ceramic coating material and a green sheet were produced in the same manner as in Example la, except that the amount of the solvent was 40.9% by mass. The results are shown in Tables 1 and 2. Example 1 c In addition to the substitution of diphenylbenzene and anthracene in a portion of the poor solvent, and the amount of diphenylbenzene as a solvent, the amount of addition is 45.5% by mass of the solvent, from MSP + diphenylbenzene. The poor solvent composed of benzene and benzene was used in the same manner as in Example la, except that the total amount of the solvent was 54.5 mass%, 2030~6478-PFl 33 1282331, and the ceramic enamel coating and the raw sheet were produced. The same decision. The results are shown in Tables 1 and 2. Comparative Example 1 a In addition to BaTi (h) having a mean particle diameter d50 of 〇.608 /zm dispersed in the base material before the coating, the result of mixing by a ball mill was used to make 0.486 by the average particle diameter d50 of 〇3. m, the ratio of the ratio of d5 前 before mixing to 79.9% is formed, and the content of MSP and xylene is 6.3 mass% and 14.1 mass%, respectively, based on the solvent. In the same manner as in Example la, a pottery paint and a green sheet were produced in the same manner as in Example la, and the same judgment was made in the same manner as in Example la, except that the poor solvent composed of the xylene was formed in an amount of 2% by mass. The results are shown in Table 2 and Table 2. Comparative Example 1 b The content of the total amount of the solvent was 18 2% by mass, and the poor solvent composed of MSP + benzene was formed in an amount of 20.3% by mass based on the entire solvent. In the same manner as in Example la, a ceramic coating and a green sheet were produced, and the same judgment was made. The results are shown in Tables i and 2. Comparative Example 1 c Xylene, the content of the solvent was formed with respect to the entire solvent. 5 quality of poor solvent composed of MSP + xylene, In the same manner as in Example la, a ceramic coating and a green sheet were prepared in the same manner as in Example la, and the same determination was carried out. The results are shown in Tables 1 and 2, as shown in Table 1 and Table. As shown in Fig. 2, the MSp+ high boiling point and the solvent of the poor solvent are in the range of 30 to 60% by mass based on the total amount of the solvent: 2030-6478-PF1 !28233l, and it is confirmed that it can be formed. The thickness of the raw film of the thick film is reversed. In addition, the air permeability, the cutting property and the adhesion of the green sheet formed by the coating for the thick film green sheet of the present embodiment are improved, and the thick film is thick. The raw embryo is thin, and it is confirmed that the manufacture of the thick film green sheet is made easy, and the manufacture of electronic components manufactured by the thick film (four) board becomes easy. In addition, as shown in Table 1 and Table As shown in Fig. 2, the mineral phase oil (mineral immortal (1) alone is relatively good in the range of more than 7% and less than the total amount of the solvent. It is also confirmed that the amount of Msp added is too small, and there is ventilation. The tendency of sexual deterioration. Furthermore, as shown in Tables 1 and 2, it can be confirmed by making the solvent There is a poor solvent, and it is possible to make the pulverization of the base material (in our coating base material) I easy to disperse the ceramic powder in the coating. As explained above, according to the present invention, it is possible to provide a The film which can be =, the cutting property of the thin plate which is formed after coating (the strength which can be cut), the more the inflammation and the good ventilation of the binding plate, the thicker the film, the thicker the membrane, the green soil The manufacturing method of the small splicer, the thick film raw slab = the manufacturing method of the coating electronic component for the thick film raw sheet, the manufacturing method of the board, the thick film raw sheet and the simple diagram of the figure are related to The invention•, Α...< 灵 型 悲 之 之 层 谓 谓 ) ) ) ) ) ) ) ) ) ). A schematic cross-sectional view of the ndenser). The second picture is the first picture of the first eve + ', the electricity used in the manufacturing process of the 2030-6478-PF1 1282331 thin section of the important part of the profile. Fig. 3 is a cross-sectional view showing an important part of a green chip used in the manufacturing process of the capacitor shown in Fig. 1. [Main component symbol description] 1~Laminated ceramic capacitor; 2a~ inside raw metal sheet; 4~terminal electrode; 2 0~outer dielectric layer; 30~loaded thin plate; 2~inside dielectric layer; 3~internal electrode layer 10 ~ Capacitor part body; 20a ~ lateral raw embryo sheet; 100 ~ raw embryo section. 2030-6478-PF1 36

Claims (1)

i:~ w- Ten, the scope of application for patents··11~1~ Coating for thick film green sheet, ceramic powder, binder with tyral: :tyral resin as the main component (―solvent, / It is characterized in that: "There is a poor solvent which makes the binder resin well dissolved" and a poor solvent which is less soluble in the above-mentioned binder resin than the above-mentioned good solvent; The solvent is contained in an amount of 30 to 60% by mass based on the total amount of the solvent; the medium is contained in the shell/yarn medium, and the solvent is higher than the solvent of the above-mentioned good solvent; the butanalaldehyde resin is polyethylene. The degree of polymerization of the polyvinyl butyral resin (p〇lyvinyl butyral resin) is from 1 〇〇〇 to 1 700, and the degree of butyralization of the resin is more than 64% and less than 78%. The amount of residual acetohydrazide (acetyl) is less than 6%. 2. The coating for thick film green sheet of the invention according to the scope of the invention, wherein the good solvent is an alcohol, and the poor solvent comprises: toluene , xylene, mineral spirit, phenyl acetate Benzylacetate, at least one of solvent naphtha, gasoline, kerosene, heptanone, and ethyl benzene. The coating for thick film green sheet of the first aspect of the invention, wherein the binder resin is contained in a mass portion of 4 to 6.5 with respect to the mass portion of the ceramic powder. 2030-6478-PF1 37 1282331 The invention relates to a method for producing a coating for a film raw sheet, which is a coating for thickening of a raw sheet of a raw material according to the scope of the patent application, characterized in that it is dispersed in front of the coating for the thick film green sheet The average particle size of the ceramic powder, so that the average particle size of the porcelain private body dispersed in the ceramic m _ τ recognition and M raw embryonic enamel coating, not the edge of the present, +, coffee &amp; In the way of particle size under /gU, Yang shredded ceramic powder. 5. A thick film raw embryo sheet into the itn + method, which is characterized by: preparation as in the scope of patent application, and Knowing that the coating for m raw embryo sheet is thicker as described above Thin process of raw embryos. 6-layer thick film raw embryo sheet formed by plate coating. M: Livestock household identification. Ming Wei flute 1ε *攸8 special test. Use as patent application The thick film green sheet is made of paint. 7. The method of the pottery and electronic components of the pottery and electronic components, and the method of the soil dry d垅, including: the standard injury is as claimed in the patent scope 1 • ^ &lt; Process for producing raw sheet metal; process; forming the outer raw sheet by using the thick film (4) coating of the above-mentioned thick film; using the thin layered raw sheet for the wood to make the outer embryo The process of forming the inner raw sheet of the enamel is carried out; 2030-6478-PF1 38 !282331 The inner raw sheet is laminated by the internal electrode layer to obtain a layered body process; The process of obtaining the green chip by laminating the outer raw sheet to the both ends of the laminate in the direction of the stacking; and the process of sintering the green slice. 8. The manufacturer of the ceramic electronic component according to item 7 of the patent application, wherein the coating for the thin layered green sheet is the same as the ceramic powder contained in the coating for the raw sheet of the film. The ceramic powder of the kind, 9. The method for preparing the electronic component of the invention of the patent item f7, wherein the average particle diameter of the coating for the thin layered green sheet is smaller than the thick film of the raw sheet The average particle size of the 2-body ceramic powder is used. 7 a. 10. The pottery method of claim 9 of the patent scope includes: 〒 1 1 造 , , , , 相对 相对 相对 相对 相对 相对 相对 相对 相对 相对 相对 相对 相对 相对 相对 相对 相对 相对 相对 相对 相对 相对 相对 相对 相对 相对 相对 相对 相对 相对 相对 相对 相对&; 呦 呦 呦 呦 丨 使 使 使 使 使 使 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 厚 厚 厚 厚 厚 厚 厚 厚 厚 厚 厚 厚 厚 厚 厚 厚 厚 厚And the average particle diameter of the carcass after dispersing in the thin layered green sheet: the ceramic is dispersed relative to the average particle which is dispersed in the thin layered green sheet The process of pulverizing the ceramic powder by using a coating of m or less. Method, 2030-6478-pp^ 1282331 VII. Designated representative map: (1) The representative representative of the case is: (1). (2) A brief description of the symbol of the representative figure: a laminated ceramic capacitor; 2~ inner dielectric layer; 3~ internal electrode layer; 4~ terminal electrode; 10~capacitor part body; 20~ outer dielectric layer. 8. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: No 0 2030-6478-PF1 4