JP6975246B2 - Lead-free thick film low antibody and electronic components containing it - Google Patents

Description

The present invention relates to lead-free thick film low antibodies and electronic components containing them. More specifically, the first network and the second network intersect each other to form a dual network structure, so that even if the lead component is removed, the temperature characteristics, current noise, overload characteristics and over a wide resistance range can be obtained. The present invention relates to a lead-free thick film low antibody having improved antistatic properties and electronic components containing the same.

Thick film resistance compositions for the production of thick film low antibodies generally consist of an organic vehicle consisting of a glass component, a conductor material and a binder and a solvent for adjusting the resistance value and imparting binding property. ) And the like, and by printing such a composition on a substrate and then firing it, a thick film low antibody is formed.

The conventional thick film resistance composition uses a glass component such as lead oxide-based glass and a conductive material such as ruthenium oxide or a compound of ruthenium oxide and lead, and contains lead. Of these, ruthenium oxide (RuO ₂ ) -based thick film resistor (Thick Film Resistor) can realize a wide range of resistance values by adjusting the ratio of _{RuO 2 and the glass component, and has excellent temperature resistance.} Since it has a coefficient, it has been widely applied to chip resistors and hybrid microcircuits.

However, lead-containing glass has recently tended to be banned from use due to environmental regulations, and is known to be inferior in interbondability with aluminum nitride substrates due to its low adhesive strength and blister generation. ing. When glass containing a lead component is used, oxides, especially lead oxide (PbO), can react with aluminum nitride, which is a substrate, to cause blistering. Further, when lead oxide in glass is sintered, it reacts with aluminum nitride and generates nitrogen gas in the process of being reduced to lead (Pb), which may cause low adhesive strength. Therefore, it is important to select a lead-free glass composition that does not contain lead and has good interbondability with aluminum nitride. Further, in general, _{the temperature coefficient of RuO 2} has a high positive temperature coefficient of 5,670 ppm / ° C. Therefore, the composition of the glass component should be adjusted or a component having a low temperature coefficient of resistance should be added. Therefore, it is necessary to make efforts to lower the temperature coefficient of final thick film resistance.

Korean Publication No. 10-2006-0056330 (Patent Document 1) has a high resistance value and a short temperature characteristic and a short resistance value by using a glass component containing NiO, which is substantially free of lead. A low-antibody paste capable of providing a low-antibody with a small time overload is disclosed, and in Korean Publication No. 10-2014-0025338 (Patent Document 2), oxidation having a rutile-type (rutile) crystal structure is disclosed. A composition for a thick film resistor and a thick film low antibody having sufficient performance even if the content of rutile is low using rutile (RuO _{2) powder are disclosed.}

However, as described above, when the glass component is changed or rutileium oxide having a rutile-type crystal structure is used, the growth of particles is suppressed during firing of the resistance composition, the specific resistance is lowered, and the thick film is low. Electrical properties such as resistivity stability, temperature characteristics (TCR) and current noise (C-noise) of the antibody were significantly reduced. _{Further, since the RuO 2} powder and the glass component are generally simply mixed during the production of the resistance composition, it is difficult to obtain a uniform mixed state between the components. Therefore, it is difficult to obtain a uniform fine composition after firing with the thick-film low antibody, and as a result, the change in the electrical characteristics of the thick-film low antibody increases, and the stability of the thick-film low antibody decreases. The problem still remained.

Korean Published Patent No. 10-2006-0056330 Korean Published Patent No. 10-2014-0025338

In order to solve the above problems, the present invention is derived from a first glass precursor mixture containing a silicon oxide, a barium oxide, a boron oxide and an aluminum oxide, and a ruthenium-based composite oxide. A first network and a second network derived from a second glass precursor mixture containing a silicon oxide, a boron oxide, and an aluminum oxide, the first network and the second network. The network aims to provide lead-free thick film low antibodies formed crossover with each other.

Further, the first network and the second network form a crosslinked structure to form a double network structure, so that a fine conductive path is uniformly formed and the temperature characteristics are wide in a wide resistance range even without a lead component. , It is an object of the present invention to provide a lead-free thick film low antibody having improved resistance spraying, current noise, overload characteristics and antistatic characteristics.

Another object of the present invention is to provide an electronic component containing the above-mentioned lead-free thick film low antibody.

The lead-free thick film low antibody of the present invention for achieving the above-mentioned object is a first glass precursor mixture containing a silicon oxide, a barium oxide, a boron oxide, and an aluminum oxide. It comprises a first network derived from a ruthenium-based composite oxide and a second network derived from a second glass precursor mixture containing a silicon oxide, a boron oxide and an aluminum oxide. The first network and the second network may be formed so as to intersect each other.

The second network may form a continuous phase, the first network may form a dispersed phase within the continuous phase, and the dispersed phase may form a crosslinked structure.

The first glass precursor mixture and the second glass precursor mixture are further mixed with any one or more selected from transition metal oxides, alkali metal oxides and alkaline earth metal oxides. It may be included.

The transition metal oxide is one or a mixture of two or more selected from _{Nb 2} O ₅ , Ta ₂ O ₅ , TiO ₂ , MnO ₂ , CuO, ZrO ₂ , WO _{3 and ZnO.} The alkali metal oxide is _{a mixture of any one or more selected from Na 2} O, K ₂ O and Li ₂ O, and the alkaline earth metal oxide is selected from SrO, CaO and MgO. It may be any one or a mixture of two or more.

_{The softening point (T 1} ) of the first glass precursor mixture may be 600 to 800 ° C., and the softening point (T ₂ ) of the second glass precursor mixture may be 500 to 700 ° C. ..

The softening point (T ₁ ) of the first glass precursor mixture and the softening point (T ₂ ) of _{the second glass precursor mixture may be T 1 −} T ₂ at 50 to 150 ° C.

The lead-free thick film low antibody has an X-ray diffraction pattern using CuKα rays, and diffraction peaks in the regions of 2θ = 27 to 29 ° and 2θ = 30 to 32 ° can be located.

前記式１中、
前記Ａ_２θ０は、２θ＝２０〜３６゜領域の全ての回折ピーク面積強度の和であり、
前記Ａ_２θ１は、２θ＝２７〜２９゜領域の回折ピーク面積強度であり、
前記Ａ_２θ２は、２θ＝３０〜３２゜領域の回折ピーク面積強度である。 The lead-free thick film low antibody may have a peak area intensity satisfying the following formula 1 in an X-ray diffraction pattern using CuKα rays.

In the above formula 1,
A _2θ0 is the sum of the intensity of all diffraction peak areas in the region of 2θ = 20 to 36 °.
A _2θ1 is the diffraction peak area intensity in the region of 2θ = 27 to 29 °.
The A _2θ2 is the diffraction peak area intensity in the region of 2θ = 30 to 32 °.

The lead-free thick film low antibody can have a peak area intensity ratio satisfying the following formula 2 in an X-ray diffraction pattern using CuKα rays.

前記式２中、
前記Ａ_２θ１は、２θ＝２７〜２９゜領域の回折ピーク面積強度であり、
前記Ａ_２θ２は、２θ＝３０〜３２゜領域の回折ピーク面積強度である。

In the above formula 2,
A _2θ1 is the diffraction peak area intensity in the region of 2θ = 27 to 29 °.
The A _2θ2 is the diffraction peak area intensity in the region of 2θ = 30 to 32 °.

The lead-free thick film low antibody may have a resistance (Rs) value of 10Ω / □ to 10MΩ / □ and a resistance value spraying (CV) of 5% or less.

The lead-free thick film low antibody may have 20 or less bubbles having a particle size of 80 μm or more in an area of 1 mm × 1 mm.

The present invention may be an electronic component containing the lead-free thick film low antibody described above.

The electronic component may be a circuit board, a chip resistor, an isolator element, a CR composite element, a module element, a capacitor or an inductor.

The lead-free thick film low antibody according to the present invention is said to be remarkably excellent in temperature characteristics, current noise, overload characteristics and antistatic properties in a range of resistance values wider than those of conventional lead-free thick film low antibodies containing lead. There are advantages.

The lead-free thick film low antibody according to the present invention has excellent surface uniformity and resistance value spraying (CV) by forming a crosslinked structure between the first network and the second network to form a double network structure. It has the advantage of being able to provide a low antibody that is low and has excellent stability.

It is a photograph which observed the surface uniformity of the lead-free thick film low antibody by one Example and one comparative example of this invention with an optical microscope. It is an XRD measurement graph of the lead-free thick film low antibody by one Example of this invention. It is an XRD measurement graph of the lead-free thick film low antibody by one Example and one comparative example of this invention. It is a comparative XRD measurement graph after drying and firing of the lead-free thick film low antibody by one Example and one comparative example of this invention. It is a figure which showed the SEM photograph of the surface and the cross section of the lead-free thick film low antibody by one Example of this invention. FIG. 5 (a) is the surface of the low antibody, and FIG. 5 (b) is the cross section of the low antibody.

Hereinafter, the lead-free thick film low antibody according to the present invention and the electronic component containing the lead-free thick film low antibody according to the present invention will be described in more detail by way of examples. However, the following examples are merely references for explaining the present invention in detail, and the present invention is not limited thereto and can be realized in various forms.

Also, unless otherwise defined, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention belongs. The terminology used herein is merely to effectively describe a particular embodiment and is not intended to limit the invention.

The present invention comprises a first network derived from a first glass precursor mixture containing a silicon oxide, a barium oxide, a boron oxide, an aluminum oxide and a ruthenium-based composite oxide, and silicon oxidation. A second network derived from a second glass precursor mixture containing a substance, a boron oxide, and an aluminum oxide is included, and the first network and the second network are formed so as to intersect each other. We have found that it is possible to form a lead-free thick film low antibody, and have completed the present invention.

As used herein, the term "double network" refers to firing a conductive composite powder and a second glass precursor mixture in which a first network is formed by heat-treating a ruthenium-based composite oxide and a first glass precursor mixture. By doing so, a second network is formed, and it means that the first network and the second network intersect each other to form a denser conductive path.

As used herein, "lead-free" means that the lead component in the thick film low antibody is 1000 ppm or less, preferably 500 ppm or less.

Hereinafter, an embodiment of the present invention will be described in more detail.

The lead-free thick film low antibody of the present invention is derived from a first glass precursor mixture containing a silicon oxide, a barium oxide, a boron oxide, and an aluminum oxide, and a ruthenium-based composite oxide. The first network and the second network include a network of 1 and a second network derived from a second glass precursor mixture containing a silicon oxide, a boron oxide and an aluminum oxide. May be formed at crossing each other. As described above, when the first network and the second network intersect each other to form a double network, fine conductive paths are uniformly formed, the surface uniformity is excellent, and the resistance value is wide in a wide resistance range. It can improve spraying, temperature characteristics, current noise, overload characteristics and antistatic characteristics.

According to the uniformity of the present invention, the second network may form a continuous phase, the first network may form a dispersed phase within the continuous phase, and the dispersed phase may form a crosslinked structure. The crosslinked structure may mean that the entire dispersed phase is linked to each other and that some of the dispersed phases are linked to each other to form a crosslinked structure. Specifically, for example, the dispersed phase, which is the first network, is formed in the continuous phase formed in the second network, and all or part of the dispersed phase of the first network is formed with each other with the second network. They can be linked to form a crosslinked structure. The crosslinked structure is preferable because it can secure a fine and uniform conductive path and improve better resistance value dispersion, temperature characteristics, current noise, overload characteristics and antistatic characteristics.

According to the uniformity of the present invention, the first network can be derived from the first glass precursor mixture and the ruthenium-based composite oxide. The first glass precursor mixture and the ruthenium-based composite oxide can be produced into a conductive composite powder having a first network formed by heat treatment. The ruthenium-based composite oxide is heat-treated with the first glass precursor mixture in one step to form a first network, and then mixed with the second glass precursor mixture and fired in two steps without firing. When the composite oxide is simply mixed with the first glass precursor mixture and the second glass precursor mixture and fired at one time, the ruthenium-based composite oxide having the shape of _{XRuO 3} is decomposed into _{XO and RuO 2.} The specific resistance is lowered, and the resistance value stability of the produced thick-film low antibody is significantly lowered. Not only that, it can be difficult to maintain electrical properties such as temperature and current noise properties. In the XRuO ₃ and XO, X is selected from Ca, Sr, Ba and the like.

In order to solve the above-mentioned problems, a conductive composite powder in which a ruthenium-based composite oxide having a perovskite structure and a first glass precursor mixture are heat-treated to form a first network is used. It forms a stable network structure.

The conductive composite powder according to the uniformity of the present invention is obtained by heat-treating a mixture of the ruthenium-based composite oxide and the first glass precursor mixture at a heat treatment temperature in a specific range, pulverizing the mixture, and then refining the second glass. It can be mixed with a precursor mixture. The average particle size of the conductive composite powder is not limited, but for example, when the particle size of each conductive composite powder is measured and the volume is accumulated from small particles, the total volume corresponds to 50%. D ₅₀ can be 2.0 μm or less. It may be preferably 1.0 to 2.0 μm. By being pulverized to the above range, the miscibility with the second glass precursor mixture is excellent, and the first network intersecting with the second network can be uniformly formed, which is preferable.

According to the uniformity of the present invention, the heat treatment temperature can be heat-treated at 700 to 900 ° C. for 10 to 60 minutes in order to form a dense and uniform first network. Preferably, the heat treatment can be performed at 700 to 850 ° C. for 10 to 40 minutes, but is not limited thereto.

The conductive composite powder formed as described above can form a uniform primary network structure, and the ruthenium-based composite oxide is combined with the first glass precursor mixture by heat treatment during the production of the lead-free thick film low antibody. By forming the first network, the reactivity between the ruthenium-based composite oxide and the second glass precursor mixture is suppressed, the ruthenium-based composite oxide does not decompose, and a stable and uniform double network is formed. The structure can be formed.

When the thick film low antibody is produced by the conductive composite powder alone, there are problems that the electrical properties are insufficient, the fluidity is insufficient, and the smoothness of the thick film low antibody and the adhesive force with the substrate are significantly lowered. Since it can occur, it is preferable to mix it with the second glass precursor mixture and then calcin it to form a dense dual network structure.

According to the uniformity of the present invention, the first glass precursor mixture can contain silicon oxide, barium oxide, boron oxide and aluminum oxide. The silicon oxide may be silicon dioxide (SiO ₂ ), the barium oxide may be barium oxide (BaO), and the boron oxide may be boron trioxide (B ₂ O ₃ ). The aluminum oxide may be aluminum oxide (Al ₂ O ₃ ). By including the silicon oxide, barium oxide, boron oxide and aluminum oxide, the reactivity with the ruthenium-based composite oxide can be further improved, and the first network structure can be formed more densely. preferable. Further, it is possible to improve the compatibility between the first network and the second network induced by the ruthenium-based composite oxide and the first glass precursor mixture, which is preferable.

In particular, by including barium oxide in the first glass precursor mixture, it is possible to form a crystal structure in which a more stable first network is formed by a reaction with a ruthenium-based composite oxide. The crystal structure may be a B-Ba-Si-Al-based partial crystal structure. By forming the partial crystal structure, mutual fusion with the second glass precursor mixture does not occur, the division between the first network structure and the second network becomes clear, and a double network can be formed. In addition, the formation of ruthenium oxide due to the reaction between the ruthenium-based composite oxide and the second glass precursor mixture in the firing process of the lead-free thick film low antibody can be suppressed, and a more stable lead-free thick film low antibody can be suppressed. Can be obtained, which is preferable.

According to the uniformity of the present invention, the ruthenium-based composite oxide is not limited as long as it is a ruthenium-based composite oxide having a perovskite-type crystal structure that is self-evidently known in the art. For example, it may be a mixture of any one or more selected from calcium lutenate (CaRuO ₃ ), strontium _{lutenate (SrRuO 3} ) and barium lutenate (BaRuO _3). The ruthenium-based composite oxide according to an embodiment of the present invention is used mix the _{(Ca 1-x-y Sr} x Ba y) or using RuO ₃ alone, other ruthenium composite oxide be able to. As an example of the above, (Ca _1-x-y Sr _x Bay) RuO _{3 satisfies} 0 <x <0.8, 0 ≦ y <0.8, 0 <x + y <0.9.

The ruthenium-based composite oxide having a perovskite-type crystal structure is particularly preferable because it can play a role of maintaining temperature characteristics (TCR) and overload characteristics (STORL) at 1 KΩ or more.

According to the uniformity of the present invention, the ruthenium-based composite oxide is not limited, but the ruthenium-based composite oxide produced by the production method of Korean Registered Patent No. 10-0840893 may be used.

For example, 1) a step of dissolving a ruthenium metal powder in a strong acid or a strong base or alkaline melting to produce a ruthenium salt aqueous solution, and 2) a strontium compound containing a dispersant in the ruthenium salt aqueous solution produced in the above step. A step of mixing an aqueous solution to obtain a hydrated strontium lutenate, and 3) a step of heat-treating the hydrated strontium lutenate obtained in the above step at 320 to 1,000 ° C. to obtain a strontium lutenate powder. 4) The strontium lutenate powder obtained in the above step may be used by removing impurities by using an inorganic acid, but the present invention is not limited thereto.

Due to the uniformity of the present invention, the ruthenium-based composite oxide has a high specific resistance, no structural change occurs in the heat treatment and firing processes, and the resistance value is sprayed at a resistance value of 5% or less, which is a lead-free thickness having excellent electrical characteristics. It is preferable because it can form a membrane low antibody.

According to the uniformity of the present invention, the conductive composite powder in which the first network is formed can contain 20 to 80% by weight of the ruthenium-based composite oxide and 80 to 20% by weight of the first glass precursor mixture. More preferably, it can contain 30 to 70% by weight of the ruthenium-based composite oxide and 70 to 30% by weight of the first glass precursor mixture. More preferably, the first network can be formed by containing 40 to 60% by weight of the ruthenium-based composite oxide and 60 to 40% by weight of the first glass precursor mixture.

According to the uniformity of the present invention, when the ruthenium-based composite oxide and the first glass precursor mixture are contained in the above range, the first network structure is uniformly formed, and the temperature characteristics (TCR) and overload are increased. The characteristics (STORL) and antistatic characteristics (ESD) are significantly improved, which is preferable. Further, as a conductive material, it is possible to prevent the temperature characteristics from moving in the (−) direction, which is preferable for maintaining the stability of the crystal structure.

According to the uniformity of the present invention, the second network can be derived and formed from the second glass precursor mixture. The second glass precursor mixture is mixed with the conductive composite powder in which the first network is formed and fired, so that the first network and the second network intersect each other to form a double network. Can be done. As described above, the first network and the second network intersect each other to form a dual network, which is excellent in resistance value dispersion (CV) and resistance value reproducibility, temperature characteristics (TCR), and overload characteristics. It is possible to obtain a lead-free thick film low antibody having excellent (STOR) and antistatic properties (ESD).

According to the uniformity of the present invention, the conductive composite powder and the second glass precursor mixture can be contained in a 10:90 to 90:10 weight ratio, more preferably 20:80 to 80:20 weight ratio. A second network can be formed to form a dual network.

Further, when it is contained in the above range, the electrical characteristics of the lead-free thick film low antibody are improved, and a lead-free thick film low antibody having a uniform surface can be formed, which is preferable.

According to the uniformity of the present invention, the lead-free thick film low antibody is doubled by mixing the conductive composite powder in which the first network is formed and the mixture of the second glass precursor to form the second network. It can have a network structure. Even if a double network structure is formed by screen-printing a mixture of the conductive composite powder on which the first network is formed and the mixture of the second glass precursor on the substrate at the time of manufacturing the substrate and then firing the mixture. good. The substrate may be an alumina substrate, but is not limited thereto.

According to the uniformity of the present invention, the firing temperature can be heat-treated at 700 to 900 ° C. for 10 to 60 minutes. Preferably, the heat treatment can be performed at 800 to 900 ° C. for 10 to 40 minutes, but is not limited thereto.

According to the uniformity of the present invention, the first glass precursor mixture and the second glass precursor mixture are made of transition metal oxides, alkali metal oxides and the like in order to improve the reactivity with the ruthenium-based composite oxide. It may further comprise any one or more mixtures selected from alkaline earth metal oxides.

According to the uniformity of the present invention, the transition metal oxide is selected from Nb ₂ O ₅ , Ta ₂ O ₅ , TiO ₂ , MnO ₂ , CuO, ZrO ₂ , WO ₃ and ZnO. The above mixture may be used. The transition metal oxide is contained in the first glass precursor mixture and the second glass precursor mixture to be produced as a lead-free thick film low antibody, thereby improving the temperature characteristics of the lead-free thick film low antibody. It can be made to be preferable.

The alkali metal oxide may be any one or a mixture of two or more selected from _{Na 2} O, K ₂ O and Li _{2 O.} The alkali metal oxide is preferable because it is contained in the first glass precursor mixture and the second glass precursor mixture and the softening point can be adjusted.

The alkaline earth metal oxide may be any one or a mixture of two or more selected from SrO, CaO and MgO. The alkali earth metal oxide can regulate the reactivity with the ruthenium-based composite oxide.

According to the uniformity of the present invention, the specific composition of the first glass precursor mixture is, for example, SiO ₂ 10 to 40% by weight, B ₂ O ₃ 10 to 30% by weight, BaO 5 to 40% by weight, Al _2. It can be contained in a content of O ₃ 2 to 15% by weight, a transition metal oxide of 0.1 to 20% by weight, and an alkali metal oxide and an alkaline earth metal oxide of 15 to 40% by weight. Preferably, SiO ₂ 15 to 35% by weight, B ₂ O ₃ 15 to 30% by weight, BaO 10 to 30% by weight, Al ₂ O ₃ 4 to 15% by weight, transition metal oxide 5 to 20% by weight, and alkali metal. Oxides and alkaline earth metal oxides can be contained in a content of 15-35% by weight. It is preferable that the composition is composed as described above because it has excellent reactivity with the ruthenium-based composite oxide and can improve the electrical characteristics and durability.

According to one aspect of the present invention, the specific composition of the second glass precursor mixture, for _example, SiO 2 5 to 30 _{wt%, B} 2 O 3 10 to 40 _{wt%, Al} 2 O 3 2 to 15 wt% , Transition metal oxides can be contained in a content of 0.1 to 35% by weight and alkali metal oxides and alkaline earth metal oxides in an amount of 20 to 60% by weight. _Preferably, SiO 2 5 to 20 _{wt%, B} 2 O 3 20 to 40 _{wt%, Al} 2 O 3 2 to 10% by weight, a transition metal oxide 2-30 wt% and alkali metal oxides and alkaline earth metal It can be contained in an oxide content of 25-60% by weight. By being composed as described above, it has excellent compatibility and compounding with the conductive composite powder, maintains the density of lead-free thick film low antibody and a smooth calcined surface, and is uniform with the conductive composite powder. It is effective because it can form a dense dual network structure.

Further, when it is contained in the composition of the second glass precursor mixture, the stability of the second glass precursor mixture is excellent, the coating film strength of the lead-free thick film low antibody of the coating film is improved, and the softening point is increased. It is possible to prevent the above, and the electrical properties of the lead-free thick film low antibody are improved, which is preferable.

Due to the uniformity of the present invention, the second network further adds inorganic particles and conductive powder to the second glass precursor mixture in order to maintain the density and smooth and uniform surface of the lead-free thick film low antibody. It can be included to form a second network.

According to the uniformity of the present invention, the inorganic particles are one or a mixture of two or more selected from _{Nb 2} O ₅ , Ta ₂ O ₅ , TiO ₂ , MnO ₂ , CuO, ZrO _{2 and ZnO.} May be. The inorganic particles are preferably produced as a lead-free thick film low antibody of the first glass precursor mixture and the second glass precursor mixture because the electrical properties and fluidity can be improved.

The conductive powder is one or more selected from Ag, Au, Pd, Pt, Cu, Ni, W, Mo, Zn, Al, RuO ₂ , IrO ₂ , Rh ₂ O _{3 and AgPd.} May be a mixture of. The conductive powder is contained in the first glass precursor mixture and the second glass precursor mixture to be produced as a lead-free thick film low antibody, thereby improving the electrical properties of the lead-free thick film low antibody. It can be made to be preferable.

More specifically, by uniformity, the second network comprises 10-65% by weight of the conductive composite powder, 10-60% by weight of the second glass precursor mixture, 0.01-40% by weight of the conductive powder and It can be derived containing 0.1 to 10% by weight of inorganic particles. Preferably, it may be derived containing 15-60% by weight of the conductive composite powder, 15-60% by weight of the second glass precursor mixture, 1-20% by weight of the conductive powder and 0.1 to 6% by weight of the inorganic particles. However, it is not limited to this. When the conductive composite powder, the second glass precursor mixture, the conductive powder and the inorganic particles are included in the above range, a uniform and dense double network structure is formed, and the temperature characteristic (TCR) and the overload characteristic ( It is preferable because a lead-free thick film low antibody having improved STOL) and antistatic properties (ESD) and excellent smoothness and adhesion to a substrate can be produced.

The uniformity of the present invention allows the second glass precursor mixture to further include a vehicle consisting of an organic solvent and a binder to form a second network. The vehicle should meet suitable rheological properties in order to mix the conductive composite powder with the second glass precursor mixture and apply it to screen printing and the like. Thus, the second glass precursor mixture can be mixed with conventional vehicles and applied to the formation of pastes, paints, or inks. The vehicle is not limited as long as it is obvious in the art, and is selected from, for example, terpineol, carbitol, butyl carbitol, cellosolve, butyl cellosolve and esters thereof; toluene, xylene and the like. A solution in which one or more organic solvents; a binder resin which is a mixture of any one or more selected from ethyl cellulose, nitrocellrose, acrylic acid ester, methacrylic acid ester, rosin and the like; and the like are mixed. Can be used. If necessary, it may further contain one or more mixtures selected from plasticizers, viscosity modifiers, surfactants, antioxidants, metal organic compounds and the like.

The compounding ratio of the vehicle is not limited as long as it is applicable to a normal lead-free thick film low antibody, and can be adjusted according to an application method such as printing.

The vehicle can preferably be further contained in an amount of 0.01 to 100 parts by weight with respect to 100 parts by weight of the conductive composite powder, the second glass precursor mixture, the conductive powder and the inorganic particles. More preferably, it can further contain from 0.1 to 50 parts by weight, but is not limited thereto.

Further, the viscosity can be adjusted by further containing an organic solvent which is the same as or different from the organic solvent used in the vehicle, and the miscibility between the second glass precursor mixture and the conductive composite powder can be improved. It is not limited to. The organic solvent is preferably further contained in an amount of 10 to 200 parts by weight with respect to 100 parts by weight of the conductive composite powder, the second glass precursor mixture, the conductive powder and the inorganic particles. More preferably, it can further contain 20 to 100 parts by weight, but is not limited thereto.

According to the aspect of the present invention, the softening point (T ₁ ) of the first glass precursor mixture may be 600 to 800 ° C., and the softening point (T ₂ ) of the second glass precursor mixture may be set. It may be 500 to 700 ° C. In the case of the softening point of the first glass precursor mixture in the above range, the reactivity with the ruthenium-based composite oxide is improved, the first network can be formed more uniformly, and the partial crystal structure is formed during the heat treatment. Can have and is preferred. Further, in the case of the softening point of the second glass precursor mixture in the above range, the firing temperature is 800 to 900 ° C., and the formation of the second network intersecting with the first network is easy, and the lead-free thick film is formed. It is preferable that the surface uniformity of the low antibody is improved and the resistance value spraying is reduced, so that excellent electrical properties can be exhibited. The fact that the first glass precursor mixture and the second glass precursor mixture have different softening points as described above can be adjusted depending on whether or not they have barium oxide, and the barium oxide can be adjusted. By not including the above in the second glass precursor mixture, it is possible to prevent the phenomenon that the resistance value spraying (CV) becomes high due to the high reactivity with the substrate during the formation of the second network.

According to one aspect of the present invention, the first softening point of the glass precursor mixtures _{(T 1)} and the softening point of the second glass precursor mixture _{(T 2) is,} T 1 -T ₂ at the 50 to 150 ° C. There may be. _Preferably, T 1 -T ₂ it may be 80 to 110 ° C.. When the difference in softening points as described above is shown, the mutual fusion of the first network and the second network does not occur at the time of firing, and the first network and the second network form a double network in which they intersect with each other. Can be preferred.

In the present specification, the X-ray diffraction pattern obtained by using CuKα rays includes the X-ray diffraction results measured by the θ-2θ method at normal temperature and pressure, and is measured at a speed (scan rate) of 2 ° / min. Includes the X-ray diffraction results obtained.

According to the uniformity of the present invention, the lead-free thick film low antibody has diffraction peaks in the regions of 2θ = 27 to 29 ° and 2θ = 30 to 32 ° in an X-ray diffraction pattern using CuKα rays. The diffraction peak in the region is a diffraction peak indicated by the formation of a double network of lead-free thick film low antibody, and the lead-free thick film low antibody having the diffraction peak has surface uniformity and electrical. It can be shown that the characteristics are excellent.

As shown in FIG. 2, the lead-free thick film low antibody of one embodiment of the present invention was formed on a substrate, dried at 150 ° C. for 10 minutes, and then calcined at 850 ° C. for 10 minutes. Formed a heavy network. When observing the X-ray diffraction pattern, it can be confirmed that the diffraction peak is located in the regions of 2θ = 28 ° and 2θ = 30 °.

Further, as shown in FIG. 3, after forming the lead-free thick film low antibody of one embodiment of the present invention on a substrate for comparison with the lead-free thick film low antibody of one comparative example, 150 After drying at ℃ for 10 minutes, it was calcined at 850 ° C. for 10 minutes, and the X-ray diffraction pattern was observed. Unlike one embodiment of the present invention, in one comparative embodiment, the diffraction peaks are not located in the regions of 2θ = 28 ° and 2θ = 30 °, as in the configuration of the lead-free thick film low antibody of the present invention. , It can be confirmed that the dual network in which the first network and the second network are crossed and connected to each other is not formed.

According to the uniformity of the present invention, the lead-free thick film low antibody can have a peak area intensity satisfying the following formula 1 in an X-ray diffraction pattern using CuKα rays.

In the above formula 1,
A _2θ0 is the sum of the intensity of all diffraction peak areas in the region of 2θ = 20 to 36 °.
A _2θ1 is the diffraction peak area intensity in the region of 2θ = 27 to 29 °.
The A _2θ2 is the diffraction peak area intensity in the region of 2θ = 30 to 32 °.

を満たすことができる。 Preferably, the peak area intensity is

Can be met.

When the lead-free thick film low antibody of the present invention has a peak area intensity satisfying the above formula 1, it can be shown that the first network and the second network intersect each other to form a double network. can. By forming the double network structure, the resistance value spraying, temperature characteristics, current noise, overload characteristics and antistatic characteristics of the lead-free thick film low antibody can be further improved, and a uniform surface can be formed. ,preferable.

According to the uniformity of the present invention, the lead-free thick film low antibody can have a peak area intensity ratio satisfying the following formula 2 in an X-ray diffraction pattern using CuKα rays.

In the above formula 2,
A _2θ1 is the diffraction peak area intensity in the region of 2θ = 27 to 29 °.
The A _2θ2 is the diffraction peak area intensity in the region of 2θ = 30 to 32 °.

を満たすことができる。 Preferably, the peak area intensity ratio is

Can be met.

When the lead-free thick film low antibody of the present invention has a peak area intensity ratio satisfying the above formula 2, it indicates that a denser and more uniform dual network with the first network and the second network was formed. be able to. By forming the structure of the dense and uniform dual network, the resistance value spraying, temperature characteristics, current noise, overload characteristics and antistatic characteristics of the lead-free thick film low antibody are further improved, and a uniform surface is obtained. It can be formed and is preferable.

As shown in FIG. 4, the lead-free thick film low antibody of one embodiment of the present invention has a crystal structure in the drying process and crystals after firing in the process before forming a second network after firing. When comparing the structures, it should be confirmed that the second network is formed more densely and uniformly by showing the area intensity of the diffraction peak more strongly in the region of 2θ = 30 to 32 ° as the firing is performed. Can be done. On the other hand, in the case of the lead-free thick film low antibody produced in one comparative example, the first network and the second network as in the configuration of the lead-free thick film low antibody of the present invention even after the double network is fired. It can be confirmed that a dual network in which the networks are crossed and connected to each other is not formed.

The lead-free thick film low antibody of the present invention may have 20 or less bubbles having a particle size of 80 μm or more, preferably 70 μm or more, in an area of 1 mm × 1 mm, as observed with an optical microscope. Preferably, the number of bubbles may be 5 or less in the 1 mm × 1 mm area. More preferably, the number of bubbles may be 0 or less in the 1 mm × 1 mm area, that is, no bubbles may exist. The smaller the number of bubbles as described above, the more lead-free thick film low antibody having excellent surface uniformity is produced, and the more excellent the surface uniformity, the smaller the resistance value spraying (CV), and the more stable electrical characteristics are exhibited. Is possible and preferable. As the lead-free thick film low antibody of the present invention, as shown in FIG. 1, a lead-free thick film low antibody having excellent surface uniformity in which no bubbles are substantially generated is produced, and resistance value spraying (CV) is produced. ) Is low, and it is a lead-free thick film low antibody having stable electrical properties.

According to the uniformity of the present invention, the lead-free thick film low antibody may have a resistance (Rs) value of 10Ω / □ to 10MΩ / □ and a resistance value spraying (CV) of 5% or less.

More specifically, the lead-free thick film low antibody has a resistance (Rs) value of 10Ω / □ to 10MΩ / □, a resistance value spraying (CV) of 5% or less, and a temperature characteristic (TCR). , -100 to 100 ppm / ° C., and the overload characteristic (STORL) measured at 1/8 W rated power may be 0.15% or less.

More preferably, the lead-free thick film low antibody has a resistance (Rs) value of 10Ω / □ to 10MΩ / □, a resistance value spraying (CV) of 5% or less, and a temperature characteristic (TCR) of −. The overload characteristic (STORL) measured at 70 to 70 ppm / ° C. and 1/8 W rated power may be 0.1% or less. A lead-free thick film low antibody satisfying the above physical characteristics has advantages of excellent resistance value stability, smoothness, and excellent adhesion to a substrate.

According to the present invention, the electronic component can include the above-mentioned lead-free thick film low antibody.

According to the uniformity of the present invention, the lead-free thick film low antibody is applied as an electronic component to a single-layer or multi-layer circuit board, a chip resistor, an isolator element, a CR composite element, a module element, a capacitor, an inductor, or the like. obtain.

Hereinafter, the lead-free thick film low antibody according to the present invention and the electronic component containing the lead-free thick film low antibody according to the present invention will be described in more detail by way of examples. However, the following examples are only one reference for explaining the present invention in detail, and the present invention is not limited to this, and can be realized in various forms.

Also, unless otherwise defined, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention belongs. The terms used in the description herein are solely for the purpose of effectively describing a particular embodiment and are not intended to limit the invention.

Further, the unit of the additive not specifically described in the specification may be% by weight.

[Physical characteristic measurement method]
1. 1. Evaluation of Coefficient of Variation (CV) Twenty lead-free thick-film low antibodies of the present invention are prepared, and their respective resistance values are measured using a multimeter. The mean and standard deviation values for these values are calculated, the standard deviation of the resistance values is divided by the mean value to derive the resistance value dispersion (CV), and the unit is expressed as a percentage.

2. 2. Evaluation of temperature coefficient of resistance (TCR) The evaluation was made by confirming the rate of change of the resistance value when the temperature was changed to 125 ° C. based on the room temperature of 25 ° C. Specifically, the resistance values at 25 ° C and 125 ° C are expressed by R ₂₅ and R ₁₂₅ (Ω / □), and the TCR is derived by the following mathematical formula, and the unit is ppm / ° C. ..

[Formula]

とした。ここで、Ｒは、抵抗値（Ω／□）である。また、計算した試験電圧が２００Ｖを超える抵抗値を有する低抗体に対しては、試験電圧を２００Ｖで行った。 3. 3. Evaluation of short-time overload characteristics After applying a test voltage to a lead-free thick-film low antibody for 5 seconds, leave it for 30 minutes and check the rate of change in resistance before and after that. evaluated. The test voltage was 2.5 times the rated voltage. The rated voltage is

And said. Here, R is a resistance value (Ω / □). Further, for a low antibody having a resistance value in which the calculated test voltage exceeds 200 V, the test voltage was 200 V.

4. Evaluation of antistatic property (ESD) Using the ESD test equipment (ELECTRO STATIC DISCHARGE SIMULATOR ESS-066) on the fired lead-free thick film low antibody, a voltage of 1 kV was turned on at a speed of several nanos for 1 second (on), 1 Turn off for seconds and apply 5 times. The changes in the resistance value before applying the voltage of 1 kV and the resistance value after applying the voltage were calculated.

5. Crystal structure confirmed by XRD After placing the lead-free thick film low antibody horizontally on the sample plate using "X-ray diffraction Ultratima IV" manufactured by Rigaku equipped with XRD measurement equipment, 2θ under the following conditions. Values were measured from 10 ° to 80 °. The measurement conditions were tube voltage: 40 kV, tube current: 40 mA, and X-ray: CuKα (wavelength λ = 1.541 Å). A diffraction peak was confirmed by X-ray diffraction measurement.

6. Confirm the surface uniformity of lead-free thick-film low antibody with an optical microscope Use an optical microscope to determine the number of low-antibody bubbles formed on the surface at magnifications of x50, x100, and x500. It was evaluated quantitatively.

[Examples 1-24 and Comparative Examples 1-9]
1) Production of Conductive Composite Powder with First Network Formed The composition of the first glass precursor mixture or the second glass precursor mixture shown in Table 1 below is shown in Table 2 below. The ruthenium-based composite oxide and the first glass precursor mixture or the second glass precursor mixture were weighed so as to have a composition having such a content (g), and mixed in a ball mill for 2 hours. Further, the sintered body obtained after heat treatment at 800 ° C. for 30 minutes was pulverized for 12 hours using a pulverizer, and a conductive composite having a first network having an average particle size of 1.5 μm of the final powder was formed. The powder was produced.

2) Production of lead-free thick film resistance composition 12% by weight of ethyl cellulose resin as an organic binder and BCA (BCA) are mixed according to the composition and content (g) as shown in Examples and Comparative Examples in Table 3 below. Butyl Carbitol Acetate) 3: An organic vehicle composed of 88% by weight of an organic solvent having a TPNL (Terpineol) 16 weight ratio was used, and a dispersant (BYK-111) was used as an additive. The above composition was stirred with a P / L mixer for 2 hours and then dispersed 5 times with a 3-roll mill and 5 times with compression. The obtained paste-like lead-free thick film resistance composition was aged at 65 ° C. for 24 hours, the viscosity was adjusted with an additional organic solvent TPNL (terpineol), and then the mixture was prepared by a filtration step.

3) Production of lead-free thick film low antibody Ag-Pd conductor paste was screen-printed on a 96% pure alumina substrate with U-pattern and dried at 150 ° C. for 10 minutes. Ag was 95% by weight and Pd was 5% by weight. The dried test piece was calcined at 850 ° C. for 10 minutes. The lead-free thick film resistance composition according to the embodiment was screen-printed on an alumina substrate on which a conductor was formed into a predetermined shape of 1 mm × 1 mm, dried at 150 ° C. for 10 minutes, and then fired at 850 ° C. for 10 minutes. A lead-free thick film low antibody having a thickness of 8.5 μm was produced.

As shown in Table 4, it was confirmed that the lead-free thick film low antibody of the present invention is remarkably excellent in temperature characteristics, overload characteristics and antistatic characteristics in a wide range of resistance values. It was also confirmed that a uniform and dense low antibody with excellent surface uniformity and low resistance spraying (CV) was produced.

Furthermore, it was confirmed that the lead-free thick film low antibody produced according to the examples of the present invention had a lower current noise than the lead-free thick film low antibody produced according to the comparative example.

As illustrated in FIG. 5, the second network is shown in the continuous phase in a darker shape, and the first network is shown in the continuous phase in a brighter shape than the dispersed phase. It was confirmed that the dispersed phase formed a network structure in which a double network structure was formed. It was confirmed that the lead-free thick film low antibody of the present invention having the dual network as described above further improved the surface uniformity, and improved the resistance value spraying (CV) and the electrical characteristics.

In the case of Comparative Examples 1 to 8, the conductive composite powder in which the first network was formed was not contained, and the ruthenium-based composite oxide could not be formed by containing the ruthenium-based composite oxide, so that the ruthenium-based composite oxidation could not be formed. As shown in FIG. 1, when the substance is decomposed and has an uneven surface of the lead-free thick film low antibody, the resistance value stability is remarkably reduced and the physical properties of the temperature characteristics are lowered. confirmed. Further, in the case of Comparative Example 9, by producing a lead-free thick film low antibody by applying only the conductive composite powder in which the first network was formed, the fluidity is lowered when the lead-free thick film low antibody is formed, and the low antibody is formed. It was confirmed that the uniformity of the surface of the surface was significantly reduced, the adhesive force with the substrate was significantly reduced, and the manufacturing stability was lowered.

As described above, the lead-free thick film low antibody and the electronic component containing the lead-free thick film low antibody have been described by the matters specified in the present invention and limited examples, which facilitates a more general understanding of the present invention. The present invention is not limited to the above-described embodiment, and any person who has ordinary knowledge in the field to which the present invention belongs can make various modifications and modifications from the above description. It can be transformed.

Therefore, the idea of the present invention should not be limited to the above-described embodiment, and not only the scope of claims described later, but also anything having a modification equal to or equivalent to the scope of claims, etc. Can be said to belong to the category of the idea of the present invention.

Claims (13)

A first network derived from a first glass precursor mixture containing a silicon oxide, a barium oxide, a boron oxide, and an aluminum oxide and a ruthenium-based composite oxide.
It comprises a second network derived from a second glass precursor mixture containing silicon oxide, boron oxide and aluminum oxide.
A lead-free thick film low antibody, wherein the first network and the second network are formed so as to intersect each other. The lead-free thick film according to claim 1, wherein the second network forms a continuous phase, the first network forms a dispersed phase in the continuous phase, and the dispersed phase forms a crosslinked structure. Low antibody. The first glass precursor mixture and the second glass precursor mixture are further mixed with any one or more selected from transition metal oxides, alkali metal oxides and alkaline earth metal oxides. The lead-free thick film low antibody according to claim 1. The transition metal oxide is one or a mixture of two or more selected from _{Nb 2} O ₅ , Ta ₂ O ₅ , TiO ₂ , MnO ₂ , CuO, ZrO ₂ , WO _{3 and ZnO.}
The alkali metal oxide is any one or a mixture of two or more selected from _{Na 2} O, K ₂ O and Li _{2 O.}
The lead-free thick film low antibody according to claim 3, wherein the alkaline earth metal oxide is a mixture of any one or more selected from SrO, CaO and MgO. The softening point (T ₁ ) of the first glass precursor mixture is 600 to 800 ° C., and the softening point (T ₂ ) of the second glass precursor mixture is 500 to 700 ° C. The lead-free thick film low antibody according to claim 1. Softening point of the first glass precursor mixture _{(T 1)} and the softening point of the second glass precursor mixture _{(T 2) is} characterized by T 1 -T ₂ is 50 to 150 ° C., The lead-free thick film low antibody according to claim 5. The lead-free thick film low antibody according to claim 1, wherein the diffraction peaks in the regions of 2θ = 27 to 29 ° and 2θ = 30 to 32 ° are located in an X-ray diffraction pattern using CuKα rays. The lead-free thick film low antibody according to claim 7, which has a peak area intensity satisfying the following formula 1 in an X-ray diffraction pattern using CuKα rays.

In the above formula 1,
A _2θ0 is the sum of the intensity of all diffraction peak areas in the region of 2θ = 20 to 36 °.
A _2θ1 is the diffraction peak area intensity in the region of 2θ = 27 to 29 °.
The A _2θ2 is the diffraction peak area intensity in the region of 2θ = 30 to 32 °. The lead-free thick film low antibody according to claim 8, which has a peak area intensity ratio satisfying the following formula 2 in an X-ray diffraction pattern using CuKα rays.

In the above formula 2,
A _2θ1 is the diffraction peak area intensity in the region of 2θ = 27 to 29 °.
The A _2θ2 is the diffraction peak area intensity in the region of 2θ = 30 to 32 °. The lead-free thick film low antibody according to claim 1, wherein the resistance (Rs) value is 10Ω / □ to 10MΩ / □, and the resistance value spraying (CV) is 5% or less. The lead-free thick film low antibody according to claim 1, wherein the number of bubbles having a particle size of 80 μm or more is 20 or less in an area of 1 mm × 1 mm. An electronic component comprising the lead-free thick film low antibody according to any one of claims 1 to 11. The electronic component according to claim 12, which is a circuit board, a chip resistor, an isolator element, a CR composite element, a module element, a capacitor or an inductor.

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