JP5126816B2 - Method for producing organic vehicle and paste containing the organic vehicle - Google Patents

Description

  The present invention relates to a method for producing an organic vehicle used when producing multilayer ceramic electronic components such as multilayer ceramic capacitors and multilayer ceramic substrates, and plasma displays, and a paste containing the organic vehicle.

  Multi-layer ceramic electronic components are usually obtained by screen-printing a conductive paste for internal electrodes on a ceramic green sheet serving as a dielectric layer, and alternately stacking several tens of layers and firing them together to obtain a ceramic laminate. It is obtained by applying and baking a conductive paste for external electrodes on a ceramic laminate.

  As the ceramic green sheet, a ceramic slurry in which an organic binder such as polyvinyl butyral resin and an organic solvent such as ethanol are mixed with ceramic dielectric powder and formed into a sheet shape by a doctor blade method is used. As the conductive paste, a paste obtained by dispersing a conductive material such as a metal powder such as nickel, copper, silver, or palladium in an organic vehicle is used.

  The organic vehicle is usually obtained by dissolving a resin component used as a binder in an organic solvent. Cellulose resins such as ethyl cellulose and nitrocellulose have been used as the organic binder used in the conductive paste, and terpineol, butyl carbitol acetate and the like have been used as the organic solvent as shown in Patent Document 1. .

  By the way, as the multilayer ceramic electronic components become thinner, when the conductive paste is printed on the ceramic green sheet, a so-called sheet attack phenomenon occurs in which the solvent contained in the organic vehicle erodes the green sheet layer. There was a problem. This leads to the occurrence of delamination after firing. Therefore, as a solvent with less erosion to the green sheet layer, Patent Document 2 discloses hydrogenated terpineol, Patent Document 3 includes isobornyl acetate and nopyrulacetate, and Patent Document 4 includes a paste solvent using hydrogenated terpineol acetate. Proposed.

  However, since these solvents have a lower dissolving power in cellulosic resins than terpineol, if they are stored in the state of an organic vehicle, the physical characteristics of the organic vehicle change over time. This causes a decrease in the dispersibility of conductive materials such as metal powders such as nickel, copper, silver, and palladium, and further leads to deterioration of the electrical characteristics of the multilayer ceramic capacitor.

  In addition, the conductive paste produced using an organic binder mainly composed of a cellulose-based resin and a base metal powder such as nickel or copper has poor thermal decomposability, and in firing in a reducing atmosphere with a low firing temperature, There is a problem that carbon remains after firing. This causes a decrease in conductivity.

Therefore, as shown in Patent Document 5, the use of an acrylic resin excellent in thermal decomposability has been proposed.
However, when a conductive paste is produced using an organic binder mainly composed of this acrylic resin, the thermal decomposability is improved, but the viscosity is reduced. As a result, when the conductive paste was applied, there was a problem that the desired thickness could not be obtained due to sagging after application or reduction in thickness. If the addition amount of the organic binder is increased in order to increase the viscosity, the solid content concentration of the resin component contained in the conductive paste increases, so that the conductive paste becomes difficult to sinter. Further, when the molecular weight of the organic binder resin is increased in order to increase the viscosity, a stringing phenomenon occurs in the conductive paste.

  Therefore, in Patent Document 6, as an external electrode application, an organic binder mainly composed of an acrylic resin that can exhibit a high viscosity at a low solid content concentration and does not cause a stringing phenomenon even when an acrylic resin is used by solution polymerization. Has been proposed, but it has not been applied as an internal electrode. When used as an internal electrode application, it is necessary to use a polymerization solvent that does not cause sheet attack.

Furthermore, in recent years, a plasma display panel (PDP) has attracted attention as a lightweight and thin large-sized display, and an organic vehicle is used in a process of applying an electrode layer, for example, in the manufacturing process of the PDP.
JP-A-2-5591 JP-A-7-21833 JP 2002-270456 A Japanese Patent No. 2976268 JP 59-199778 A JP 2004-79480 A

  The present invention relates to an organic vehicle having a high viscosity, excellent stability, and not eroding a green sheet when the paste is printed on a green sheet layer when producing a multilayer ceramic electronic component or a plasma display. It is an object of the present invention to provide a paste containing the organic vehicle produced by the production method by solution polymerization of a resin serving as an organic binder in an organic solvent.

The present invention relates to a method for producing an organic vehicle for a paste used in producing a multilayer ceramic electronic component or a plasma display, wherein an alkyl (meth) acrylate is added in an organic solvent used in the paste. The present invention relates to a method for producing an organic vehicle characterized by subjecting a monomer as a main component to solution polymerization.
The organic solvent preferably has an ester compound or an ether compound having a boiling point of 150 to 300 ° C. and a butyral resin dissolution amount of 70 mg or less with respect to 25 g of the organic solvent.
The organic solvent is preferably at least one selected from the group of compounds represented by the following formulas (I) to (XXI).

Of the above organic solvents, isobornyl propionate, isobornyl n-butyrate, isobornyl isobutyrate, hydrogenated terpinyl acetate, and hydrogenated terpinyl propionate are preferable.
Moreover, it is preferable that the organic vehicle solution-polymerized using the said organic solvent is 0.1-500 Pa.s of the viscosity of 10% of solid content, and TI value is 1.0-1.5.
Next, this invention relates to the paste containing the organic vehicle manufactured with the said manufacturing method.

According to the present invention, an organic vehicle excellent in paste stability without eroding a green sheet and used in manufacturing multilayer ceramic electronic components and plasma displays and a paste containing the organic vehicle are provided at a lower cost. I can do it.
For example, when used as a conductive paste for internal electrodes of multilayer ceramic capacitors, when manufacturing multilayer ceramic capacitors, the sheet attack phenomenon is achieved by using a solvent that is less erosive to the ceramic green sheet layer as the solvent for solution polymerization. It is possible to produce an organic vehicle which does not generate
In addition, since the organic vehicle of the present invention has good compatibility between the (co) polymer contained in the organic vehicle and the organic solvent, the vehicle does not change with time. For this reason, excellent paste stability can be maintained without gelling or showing a high TI value while having a low solid content and a high viscosity.
Furthermore, if the organic vehicle of the present invention is used, it is not necessary to dissolve the resin in the solvent again after the solution polymerization and during paste preparation, and the solvent used in the solution polymerization can be used as it is, thereby simplifying the manufacturing process. It becomes possible.

The present invention is described in detail below.
The organic vehicle of the present invention is a mixture of a (co) polymer synthesized with an organic solvent used in solution polymerization.
First, the manufacturing method of the organic vehicle of this invention is demonstrated.
The organic vehicle for paste of the present invention is obtained by solution polymerization of a monomer mainly composed of an alkyl (meth) acrylate ester in an organic solvent used for the paste with a polymerization initiator, and then mesh filtration. be able to.

Here, although it does not specifically limit as alkyl (meth) acrylic acid ester, The C1-C10 alkyl (meth) acrylate excellent in thermal decomposability is preferable. More preferably, it is a methacrylate excellent in thermal decomposability.
Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, ter-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2 -Hydroxy (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, 1, Examples include 6-hexanediol (meth) acrylate, isobornyl (meth) acrylate, terpinyl (meth) acrylate, hydrogenated terpinyl (meth) acrylate, and allyl (meth) acrylate. That.
However, the present invention is not limited to these. These monomers can be used alone or in combination of two or more.

  These alkyl (meth) acrylic acid esters are preferably contained in an amount of 60 to 100% by weight in the (co) polymer contained in the organic vehicle. More preferably, it is 90 to 100% by weight. If it is less than 60% by weight, the polymerization does not proceed easily, and a viscosity suitable for the purpose cannot be obtained.

Other copolymerizable monomers contained in the organic vehicle include carboxylic acids such as (meth) acrylic acid, maleic acid, itaconic acid, vinylphthalic acid, carboxylic acid anhydrides, vinyl acetate, chloride Examples include monomers other than alkyl (meth) acrylates such as vinyl, N-vinylpyrrolidone, styrene, α-methylstyrene, ethylene, acrylonitrile, acrylamide, and N-methylacrylamide.
However, the present invention is not limited to these. These monomers can be used alone or in combination of two or more.

  These copolymerizable monomers are contained in an amount of 0 to 40% by weight, preferably 0 to 10% by weight, in the (co) polymer contained in the organic vehicle. Although these copolymerizable monomers may not be added, for example, by adding acrylic acid, it is possible to increase the adsorption power of the organic vehicle to the base metal powder and improve the dispersibility of the base metal powder. . When the addition amount exceeds 40% by weight, the thermal decomposability of the organic vehicle is decreased, and the polarity of the (co) polymer is increased, and it is particularly difficult to be compatible with an ester solvent or an ether solvent. Absent.

  Furthermore, as polymerization initiators, various peroxides such as BPO (benzoyl peroxide), lauryl peroxide, hydrogen peroxide, etc., which decompose by heat to release radicals, and azobis, which is a solvent-soluble azo initiator, are used. Examples include isobutyronitrile, azobisisovaleronitrile, azobiscyanopentane, and the like. BPO (benzoyl peroxide) and azobisisobutyronitrile are preferable. However, the present invention is not limited to these.

  The usage-amount of the said polymerization initiator is 0.01-20 weight% normally with respect to a monomer, Preferably it is 0.1-3.0 weight%. If the amount of the polymerization initiator is less than 0.01% by weight, the reaction is difficult to proceed, which is not preferred.

As the organic solvent for solution polymerization, it is preferable to use an organic solvent having a low sheet attack property, a low viscosity and a high viscosity, and possessing physical properties as an organic vehicle excellent in stability when made into a paste. Considering the drying property and paste stability of the organic solvent when printed as a paste, and the erodibility to the green sheet when used for multilayer ceramic electronic components, the boiling point of the organic solvent is 150 to 300 ° C. Is preferred. If the boiling point is less than 150 ° C., the organic solvent volatilizes during printing and the solid content of the paste increases, and on the other hand, if it exceeds 300 ° C., the solvent removal takes a long time.
Further, as one of the indicators of sheet attack property, it is preferable to use an organic solvent having a butyral resin dissolution amount of 70 mg or less, more preferably 50 mg or less as a main component with respect to 25 g of the organic solvent.
Furthermore, when used for an electrode paste, an ester compound or an ether compound having a lower polarity than the alcohol compound is preferable because it does not erode the green sheet.
The use of a solvent represented by the above formulas (I) to (XXI) with less erosion to the ceramic green sheet layer is more preferable because an organic vehicle that does not cause a sheet attack phenomenon can be produced. Among them, if at least one selected from the group consisting of isobornyl propionate, isobornyl n-butyrate, isobornyl isobutyrate, hydrogenated terpinyl acetate, hydrogenated terpinyl propionate is used, low It is more preferable because an organic vehicle that does not cause a sheet attack phenomenon while maintaining a high viscosity at a solid content and excellent paste stability can be produced.

However, the present invention is not limited to these. These organic solvents can be used alone or in combination of two or more. Moreover, when mixing 2 or more types of organic solvents, the organic solvent whose boiling point is less than 150 degreeC can also be used.
For example, terpineol, hydrogenated terpineol, borneol, benzyl alcohol, 2-ethyl-1-hexanol, 1-decanol, 1-undecanol, 1,2-ethanediol, 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, diethylene glycol, butyl carbitol acetate, ethylene glycol diacetate, propylene glycol diacetate, butylene glycol diacetate, Ethylene glycol dipropionate, propylene glycol dipropionate, butylene glycol dipropionate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether Tate, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, kerosene, isophorone, tetrahydrofuran, dioxane, diethyl ether, dibutyl ether, n-hexane, cyclohexane, methylcyclohexane, n-heptane, cycloheptane, n- Octane, isooctane, n-nonane, cyclononane, 1-methyl-4-isopropylcyclohexane, n-decane, hexadecane, dodecane, undecane, tridecane, paramentane, mineral spirit, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, hexane There are ethyl acid, 2-ethylhexyl acetate, acetone, methylene chloride, ethylene chloride, carbon tetrachloride, etc. , But it is not limited thereto. Among them, 1-methyl-4-isopropylcyclohexane, n-hexane, cyclohexane, methylcyclohexane, n-heptane, cycloheptane, n-octane, isooctane, n-nonane, cyclononane, 1-methyl-4-isopropylcyclohexane, n- When mixed with low-polarity hydrocarbon compounds such as decane, hexadecane, dodecane, undecane, tridecane, paramentane, and mineral spirit, the erosion to the green sheet can be further suppressed.

  In the solution polymerization reaction, the monomer ratio at the start of the reaction is preferably 5 to 150% by weight with respect to the organic solvent. More preferably, it is 60 to 100% by weight. When the monomer ratio is less than 5% by weight, polymerization is difficult to proceed, which is not preferable. When it exceeds 150% by weight, the amount of the organic solvent is too small and the organic vehicle is solidified. However, if the monomer ratio is 100% by weight or more based on the organic solvent, the viscosity of the produced organic vehicle may be too high, or the solid content concentration of the resin component contained in the organic vehicle may be too high. It is preferred to dilute to an appropriate viscosity after the polymer is made.

Although the said solution polymerization reaction system is not specifically limited, It can react also by a batch reaction or a continuous reaction.
Although the said reaction temperature changes also with the polymerization initiator to be used, reaction is normally performed by heating to 0-200 degreeC, Preferably it is 30-150 degreeC, More preferably, it is 50-120 degreeC. When the reaction temperature is less than 0 ° C., the reaction rate is extremely slow. On the other hand, when the reaction temperature exceeds 200 ° C., it is not preferable because a high molecular weight copolymer is hardly formed.

  Moreover, although the said reaction time changes also with the organic solvent to be used, it is 0.1 to 50 hours normally, Preferably it is 0.3 to 20 hours. If it exceeds 50 hours, the molecular weight of the copolymer becomes too large, which is not preferable, and if it is less than 0.1 hour, the molecular weight of the (co) polymer is too low and the viscosity of the conductive paste does not increase. .

The number average molecular weight of the (co) polymer contained in the organic vehicle is preferably 10,000 to 900,000. More preferably, it is 100,000 to 800,000.
When the number average molecular weight of the (co) polymer is less than 10,000, the molecular weight is too small and the viscosity of the conductive paste does not increase. This is not preferable because a pulling phenomenon occurs.

In addition, as mentioned above, the organic vehicle is synthesized by solution polymerization of an alkyl (meth) acrylic acid ester as a main component in an organic solvent with a polymerization initiator without deactivating the catalyst. It can be obtained by mesh filtration as it is.
Here, the mesh at the time of mesh filtration is not particularly limited, but is generally made of polyethylene or stainless steel having a pore diameter of 0.5 to 10 μm.

  The pyrolysis temperature of the organic vehicle of the present invention is preferably 300 ° C. or lower. More preferably, it is 250-300 degreeC. When the thermal decomposition temperature exceeds 300 ° C., carbon remains after the paste is fired, and the conductivity may be lowered. The thermal decomposition temperature of the organic vehicle of the present invention is such that the organic vehicle is dried at 80 ° C. for 24 hours, the organic solvent is removed, and then heated at 10 ° C./min using TGA, and the weight loss rate becomes 50% by weight. The temperature is measured as the pyrolysis temperature.

  The organic vehicle of the present invention may contain various additives such as thickeners and diluents and dispersants as necessary.

Next, the conductive paste containing the organic vehicle manufactured by the manufacturing method of the present invention will be described.
The conductive paste corresponds to a noble metal electrode layer. In the organic vehicle of the present invention obtained by solution polymerization of a resin serving as an organic binder in an organic solvent, a metal powder such as nickel, copper, silver or palladium is added. It is dispersed.
The (co) polymer mainly composed of alkyl (meth) acrylic acid ester contained in the organic vehicle is preferably 1 to 50% by weight. More preferably, it is 5 to 30% by weight. If it is less than 1% by weight, the viscosity of the paste is too low, and it is not preferable because it sags after application or the thickness becomes thin. On the other hand, if it exceeds 50% by weight, the solid content concentration of the copolymer as the resin component is high. This is not preferable because the conductive paste is difficult to sinter.

A paste is obtained by blending the metal powder with the organic vehicle of the present invention.
The density | concentration of the metal powder in a paste is 30 to 90 weight% normally, Preferably it is about 40 to 80 weight%. If the concentration of the metal powder is less than 30% by weight, the electrode thickness after firing becomes too thin, which is not preferable. On the other hand, if the concentration exceeds 90% by weight, the strength of the dried film becomes too weak.

  In addition, a dispersant may be added to the conductive paste containing the organic vehicle of the present invention in order to improve the dispersibility of the metal powder, or a glass frit may be added to increase the adhesive strength after firing. . Furthermore, it is possible to contain a thickener and a thixotropic agent.

Here, the TI value will be described. The TI value is a value representing the thixotropic property of the organic vehicle and indicates the degree of viscosity change with respect to shear rate change. In the conductive paste of the present invention, it is preferably 1.0 to 1.5, more preferably Is 1.0 to 1.2. If it is less than 1.0, sagging occurs when printing the conductive paste on the ceramic green sheet, and an appropriate thickness cannot be maintained. On the other hand, if it exceeds 1.5, blurring occurs during printing. It is not preferable because printing cannot be performed with a uniform thickness.
The TI value can be calculated by measuring at 0.5 rpm and 5.0 rpm at 25 ° C. with a digital viscometer HBDV-1 manufactured by Brookfield, and obtaining each measured value at 0.5 rpm / 5.0 rpm.
TI value (measured value) of the present invention = viscosity at 0.5 rpm / viscosity at 5.0 rpm

  Moreover, as a viscosity of the organic vehicle of this invention, 0.1-500 Pa.s (25 degreeC) is preferable when solid content concentration is 10 weight%. More preferably, it is 0.3 to 350 Pa · s. If it is less than 0.1 Pa · s, the metal powder cannot be maintained in a dispersed state and a uniform paste cannot be produced. On the other hand, if it exceeds 500 Pa · s, the metal powder is difficult to knead.

Hereinafter, the present invention will be described more specifically with reference to examples.
Example 1 (Synthesis of organic vehicle (I))
In a 300 ml glass separable flask equipped with a stirrer, a cooling tube, a thermometer, and a nitrogen gas introduction tube, 23.5 g of methyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd., purity 99%), isobornyl methacrylate 23. 5 g (manufactured by Wako Pure Chemical Industries, Ltd., purity 98%), methacrylic acid 3.0 g (manufactured by Wako Pure Chemical Industries, Ltd., purity 98%), Nyper BMT K40 0.08 g (manufactured by Nippon Oil & Fats Co., Ltd.) , And isobornyl isobutyrate (formula I; R = 3) 50.0 g (manufactured by Yashara Chemical Co., Ltd., purity 99%) were added, stirred and heated to 80 ° C. while continuously bubbling nitrogen gas. Warmed up. After heating, the mixture was stirred at 80 ° C. for 2 hours for copolymerization. Two hours later, 66.7 g of isobornyl isobutyrate was added, and the solid content concentration of the copolymer contained in the organic vehicle was adjusted to 30%. The prepared organic vehicle was removed by filtration through a 200 μm mesh to obtain 150.0 g (yield 90.0%) of the organic vehicle (I).

Examples 2 to 21 (Synthesis of Organic Vehicle Examples (II) to (XXI))
In Examples 2 to 21, as shown in Table 1 below, the synthesis was performed in the same manner as in Example 1 except that the monomer, the weight ratio of the monomer, and the solvent were changed, and the organic vehicle (II ) To (XXI) were obtained.

Comparative Example 1 (Synthesis of Organic Vehicle Example (XXII))
A 300 ml glass separable flask equipped with a stirring bar and a thermometer was charged with 70.0 g of terpineol (manufactured by Yasuhara Chemical Co., Ltd., purity 95%), and the temperature was raised to 70 ° C. while stirring. After the temperature increase, 30.0 g of acrylic resin (Oricox manufactured by Kyoeisha Chemical Co., Ltd.) was added and stirred at 65 to 70 ° C. for 3 hours to dissolve ethyl cellulose. After dissolution, the prepared organic vehicle was filtered through a 200 μm mesh and filtered to obtain 90.0 g of organic vehicle (XXII) (yield 90.0%).

Comparative Example 2 (Synthesis of Organic Vehicle Example (XXIII))
A 300 ml glass separable flask equipped with a stir bar and a thermometer was charged with 70.0 g of hydrogenated terpinyl acetate (manufactured by Yasuhara Chemical Co., Ltd., purity 98%) and heated to 70 ° C. with stirring. After the temperature increase, 30.0 g of acrylic resin (Oricox manufactured by Kyoeisha Chemical Co., Ltd.) was added and stirred at 65 to 70 ° C. for 3 hours to dissolve ethyl cellulose. After dissolution, the prepared organic vehicle was filtered through a 200 μm mesh and filtered to obtain 90.0 g (yield 90.0%) of the organic vehicle (XXIII).

Comparative Example 3 (Synthesis of Organic Vehicle Example (XXIV))
A 300 ml glass separable flask equipped with a stir bar and a thermometer was charged with 92.0 g of terpineol (manufactured by Yasuhara Chemical Co., Ltd., purity 95%) and heated to 70 ° C. while stirring. After the temperature increase, 8.0 g of ethyl cellulose (std-45 manufactured by DOW CHEMICAL) was added and stirred at 65 to 70 ° C. for 3 hours to dissolve the ethyl cellulose. After dissolution, the prepared organic vehicle was filtered through a 200 μm mesh and filtered to obtain 90.0 g of organic vehicle (XXIV) (yield 90.0%).

Comparative Example 4 (Synthesis of Organic Vehicle Example (XXV))
A hydrogenated terpinyl acetate 92.0 g (manufactured by Yasuhara Chemical Co., Ltd., purity 98%) was charged into a 300 ml glass separable flask equipped with a stirring bar and a thermometer, and the temperature was raised to 70 ° C. while stirring. After the temperature increase, 8.0 g of ethyl cellulose (std-45 manufactured by DOW CHEMICAL) was added and stirred at 65 to 70 ° C. for 3 hours to dissolve the ethyl cellulose. After dissolution, the prepared organic vehicle was removed by filtration through a 200 μm mesh to obtain 90.0 g (yield 90.0%) of the organic vehicle (XXV).

  The following physical properties were evaluated for 25 organic vehicles (Examples (I) to (XXV)) synthesized by the above methods (Examples 1 to 21 and Comparative Examples 1 to 4). The results are shown in Table 2.

(Molecular weight distribution measurement)
0.05 g each of 21 kinds of the organic vehicles (I) to (XXI) (the organic vehicles obtained in Examples 1 to 21) of the present invention and the organic vehicles (XXII) to (XXV) of Comparative Examples 1 to 4 were weighed. The sample was diluted with 10 mL of THF, and the number average molecular weight of the copolymer contained in the organic vehicle was measured using GPC (Waters 510, manufactured by Waters Corporation).

(Viscosity and TI value measurement)
21 types of organic vehicles (I) to (XXI) of the present invention at 25 ° C. and 0.5 rpm using a digital viscometer HBDV-1 manufactured by Brookfield (organic vehicles obtained in Examples 1 to 21) The viscosities of the organic vehicles (XXII) to (XXV) of Comparative Examples 1 to 4 were measured.
The 25 types of vehicles (I) to (XXV) were diluted with an organic solvent similar to the organic solvent used at the time of preparation so that the solid content was 30 wt% and 10 wt%.
Moreover, TI value was computed like the following formula from the viscosity measured at 0.5 rpm and 5.0 rpm in 25 degreeC using the same apparatus.
TI value (measured value) of the present invention = viscosity at 0.5 rpm / viscosity at 5.0 rpm

(Pyrolytic)
Twenty-one organic vehicles (I) to (XXI) (organic vehicles obtained in Examples 1 to 21) of the present invention and organic vehicles (XXII) to (XXV) of Comparative Examples 1 to 4 at 80 ° C. and 3 mmHg. The organic solvent was removed by drying for 24 hours. Then, it heated at 10 degree-C / min using TGA, the temperature at which the weight loss rate became 50 weight% was measured, and it was set as the thermal decomposition temperature.

(Paste stability)
21 types of the organic vehicles (I) to (XXI) (organic vehicles obtained in Examples 1 to 21) of the present invention and the organic vehicles (XXII) to (XXV) of Comparative Examples 1 to 4 were added to 25 g of Pd ( A conductive paste was prepared by kneading 25 g of palladium) powder. This paste was stored at 25 ° C. for 30 days, and the presence or absence of gelation after 30 days of preparation was observed. When gelation occurs, the quality of the paste is reduced, which increases the possibility of causing a complaint. Moreover, the produced paste was screen-printed on a green sheet, and the thickness after printing was measured. When gelation was confirmed by visual inspection and the thickness after printing was uneven at the edge, the paste stability ×, viscosity change was observed, but when printed with a uniform film thickness, Paste stability (triangle | delta), When gelatinization was not confirmed visually and the film thickness after printing was uniform, it evaluated as paste stability (circle).

(Sheet attack)
Put 50 mg of butyral resin (S-LEC BH-3 manufactured by Sekisui Chemical Co., Ltd.) and 25 g of each organic solvent of Examples and Comparative Examples into a 50 mL stoppered test tube, and stir with a stirrer at 60 ° C. for 2 hours. Warm up. After completion of heating, the supernatant was collected and further subjected to centrifugation at 2000 rpm for 5 minutes. 1 g of the supernatant was taken, 50 mg of a standard (Adeka Stub AO-20 manufactured by Asahi Denka Kogyo Co., Ltd.) was added, and GPC was measured. After the measurement, the amount (mg) of butyral resin dissolved in 25 g of each organic solvent was calculated from the peak area ratio corresponding to the molecular weight of the butyral resin and the peak area of the sample.
As a result, when the amount of butyral resin exceeds 70 mg, a sheet attack phenomenon occurs when a conductive paste containing the organic vehicle is printed on a green sheet, leading to the occurrence of delamination. On the other hand, it was shown that the smaller the amount of butyral resin dissolved, the less likely the erosion to the green sheet occurred and the lower the sheet attack.

(Comprehensive evaluation)
The physical properties of the organic vehicle, which did not erode the green sheet, had a low solid content and a high viscosity, and had excellent stability when made into a paste, were comprehensively evaluated.
Regarding the five items shown below, an organic vehicle satisfying all the judgment items was regarded as a comprehensive evaluation ◯, and an organic vehicle having a judgment item not satisfying at least one was regarded as a comprehensive evaluation ×.
Viscosity: Viscosity at 10% solid content is 0.1 to 500 Pa · s
TI value: TI value is 1.0 to 1.5
Thermal decomposability: Thermal decomposition temperature is 300 ° C or less Paste stability: Conductive paste has no change over time and can be printed uniformly Sheet attack property: Butyral resin dissolution amount is 70 mg or less

As shown in Table 2, the organic solvent of the ester and ether compounds used in the organic vehicle of the present invention [organic vehicles of Examples (I) to (XXI)] was dissolved in butyral resin with respect to 25 g of the organic solvent. Therefore, when the vehicle is used as the internal electrode conductive paste, the erosion to the green sheet and the accompanying delamination can be suppressed.
In addition, the organic vehicle of the present invention uses a comparative example (XXII) and (XX) in spite of using a (co) polymer mainly composed of alkyl (meth) acrylate as a resin component of the organic binder. XXV) It has a lower viscosity than an organic vehicle but has a high viscosity and an appropriate TI value.
Moreover, since it is excellent in thermal decomposability, the carbon content hardly remains at the time of firing, and it is suitable for low temperature firing in a reducing atmosphere.
Furthermore, as in the organic vehicle of Comparative Example (XXV), ester compounds and ether compounds that are less polar than alcohol compounds are gelled or show high TI values when the cellulose resin is dissolved, resulting in poor printability. It becomes. However, since the organic vehicle of the present invention has good compatibility between the copolymer contained in the organic vehicle and the organic solvent, the vehicle does not change with time. For this reason, the sheet attack phenomenon and the accompanying degeneration are maintained while gelling as in the case of dissolving a cellulose resin such as ethyl cellulose, and maintaining high stability even when made into a paste without showing a high TI value. Lamination phenomenon can be suppressed.
In addition, it is not necessary to re-dissolve the resin in the organic solvent when preparing the paste after solution polymerization by solution polymerization of the resin that becomes the organic binder in the organic solvent used for the paste. Since the organic solvent can be used as it is, the manufacturing process can be simplified.
Therefore, by using the organic vehicle of the present invention, it becomes possible to produce a multilayer ceramic electronic component at a low cost corresponding to the reduction in thickness, the increase in density, and the reduction in shortage.

  The organic vehicle obtained by the present invention can be used for multilayer ceramic electronic components such as ceramic capacitors, inductors, varistors and thermistors. The external electrode and internal electrode of the capacitor are preferable, and an organic vehicle for paste used when manufacturing the internal electrode is more preferable. The present invention can also be used for pastes obtained by mixing various metal powders or glass with the organic vehicle of the present invention. Examples of the paste include electrode pastes and glass pastes. Electrode paste and glass paste including internal electrodes can also be used for the barrier ribs of the plasma display.

Claims (4)

A group consisting of the following formulas (I) to (XXI), which is an organic solvent used for manufacturing an organic vehicle for a paste used in manufacturing a multilayer ceramic electronic component or a plasma display A method for producing an organic vehicle, comprising subjecting a monomer mainly composed of an alkyl (meth) acrylate ester to solution polymerization in at least one selected organic solvent .
[However, in Formula (I), R < ₁ > is a C2-C4 hydrocarbon. ]
[In the formula (II), R ₂ is H or CH ₃ , and R ₃ is a hydrocarbon having 1 to 2 carbon atoms. ]
[In the formula (III), R ₄ is H or CH ₃ , and R ₅ is a hydrocarbon having 1 to 2 carbon atoms. ]
[In the formula (IV), R ₆ is H or CH ₃ , and R ₇ is a hydrocarbon having 1 to 2 carbon atoms. ]
[In the formula (V), R ₈ is H or CH ₃ , and R ₉ is a hydrocarbon having 1 to 2 carbon atoms. ]

[In Expression _{(VI), R 10} is H or _{CH 3, R 11} is a hydrocarbon having 1 to 2 carbon atoms. ]
[However, in the formula _{(VII), R 12} is H or _{CH 3, R 13} is a hydrocarbon having 1 to 2 carbon atoms. ]
[However, in Formula (VIII), l is an integer of 1-4. ]
[However, in Formula (IX), m is an integer of 1-4. ]
[However, in Formula (X), n is an integer of 1-4. ]
[In the formula (XI), R ₁₄ is H or CH ₃ , and R ₁₅ is a hydrocarbon having 1 to 4 carbon atoms. ]
[In the formula (XII), R ₁₆ is H or CH ₃ , and R ₁₇ is a hydrocarbon having 1 to 4 carbon atoms. ]
[In the formula (XIII), a is an integer of 0 to 3. When a = 0, o = 2 or 3, and when a = 1-3, o = 1 or 2. ]


[However, in Formula (XIV), b is an integer of 0-4, p is an integer of 1-3. ]
[However, in Formula (XV), c is an integer of 0-4, q is an integer of 1-3. ]
[However, in Formula (XVI), d is an integer of 0-4, r is an integer of 1-3. ]
[However, in Formula (XVII), R ₁₈ is a hydrocarbon having 1 to 3 carbon atoms. ]
[However, in the formula _{(XVIII), R 19} is a hydrocarbon of 1 to 3 carbon atoms. ]
[In the formula (XIX), R ₂₀ is a hydrocarbon having 1 to 3 carbon atoms. ]
[However, in Formula (XX), R ₂₁ is a hydrocarbon having 1 or 2 carbon atoms. ]







[In the formula (XXI), R ₂₂ is a hydrocarbon having 1 or 2 carbon atoms. ]
The organic solvent is at least one selected from the group consisting of isobornyl propionate, isobornyl n-butyrate, isobornyl isobutyrate, hydrogenated terpinyl acetate, and hydrogenated terpinyl propionate. The method for producing an organic vehicle according to claim 1 . Organic vehicle is a solution polymerization using an organic solvent, the viscosity of the solid content of 10% are 0.1~500Pa · s, and TI value of 1.0 to 1.5, to claim 1 or 2 The manufacturing method of the organic vehicle as described. The paste containing the organic vehicle manufactured with the manufacturing method of any one of Claims 1-3 .