CN107210106A - Negative-characteristic thermistor device and its manufacture method - Google Patents
Negative-characteristic thermistor device and its manufacture method Download PDFInfo
- Publication number
- CN107210106A CN107210106A CN201680008674.3A CN201680008674A CN107210106A CN 107210106 A CN107210106 A CN 107210106A CN 201680008674 A CN201680008674 A CN 201680008674A CN 107210106 A CN107210106 A CN 107210106A
- Authority
- CN
- China
- Prior art keywords
- electrode
- outer electrode
- internal electrode
- ceramic body
- internal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C1/00—Details
- H01C1/14—Terminals or tapping points or electrodes specially adapted for resistors; Arrangements of terminals or tapping points or electrodes on resistors
- H01C1/142—Terminals or tapping points or electrodes specially adapted for resistors; Arrangements of terminals or tapping points or electrodes on resistors the terminals or tapping points being coated on the resistive element
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
- H01C17/28—Apparatus or processes specially adapted for manufacturing resistors adapted for applying terminals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
- H01C7/04—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having negative temperature coefficient
Landscapes
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Thermistors And Varistors (AREA)
- Details Of Resistors (AREA)
Abstract
The present invention provides one kind and is difficult to occur solder explosion, and the dhering strength at the interface of outer electrode and ceramic body is high, the small NTC themistor of the rate of change of resistance value during exposed to temperature change and its manufacture method.Negative-characteristic thermistor device of the present invention is comprising ceramic body, the first internal electrode of the inside for being arranged at ceramic body and the second internal electrode, the first outer electrode for being arranged at the end face of ceramic body and being electrically connected with the first internal electrode and is arranged at the other end of ceramic body and the second outer electrode electrically connected with the second internal electrode；Ceramic body contains Mn3O4, first and second internal electrode contains precious metal element, and first and second outer electrode contains Cu, and the diffusion length into first and second internal electrode of the Cu contained by first and second outer electrode is 2~20 μm.
Description
Technical field
The present invention relates to a kind of negative characteristic (or negative temperature coefficient, NTC) thermal resistor and its manufacture method.
Background technology
NTC themistor is widely used in electronic equipment to carry out temperature-compensating or temperature detection.For example, in patent text
Offer and following cascade type resistive element is recorded in 1：The cascade type resistive element, which has, is laminated with multiple ceramic electrical resistance layers and many
The stacking sintered body of individual internal electrode and the first outer electrode and the second external electrical for being formed at the outer surface for being laminated sintered body
Pole；Multiple internal electrodes have first group of multiple internal electrodes and second group of multiple internal electrodes.In patent document 1
In described cascade type resistive element, by will constitute second group internal electrode multipair internal electrode respective one end
In being separated on the same plane in stacking sintered body, gap is relative each other, carries out the micro-adjustment of resistance value.
Following thermal resistor is recorded in patent document 2：Possess the thermal resistor base substrate with internal electrode,
And formation, in the outer electrode of the outer surface of the thermal resistor base substrate, thermal resistor base substrate is the heat using manganese as principal component
Sensitive resistor material, outer electrode is the composition containing copper and lithium borosilicate glass, and heat is diffused to lithium borosilicate glass is made
Diffusion layer in sensitive resistor base substrate.Thermal resistor described in patent document 2 makes lithium borosilicate glass due to being formed with
Glass diffuses to the diffusion layer on the surface of thermal resistor base substrate, thus with higher mechanical strength.
[prior art literature]
[patent document]
No. 4419960 publications of [patent document 1] Japanese Patent No.
No. 3414147 publications of [patent document 2] Japanese Patent No.
The content of the invention
Invent problem to be solved
The outer electrode of NTC themistor usually contains the metal ingredients such as Ag as conductive component.If containing
Voltage is applied to NTC themistor under the atmosphere of moisture, then have in outer electrode contained metal ingredient and a reaction of moisture and
The situation of ionization.The metal ingredient ionized in an outer electrode is moved to another outer electrode, is reduced and with Cu
Form separate out.The phenomenon is referred to as Ion transfer (also referred to as " migrating ").If producing Ion transfer, it may cause outside one
Portion's electrode and the short circuit of another outer electrode.
In order to suppress in outer electrode the migration of contained conductive component, develop with containing being difficult to what is migrated compared with Ag
Cu as the outer electrode of conductive component NTC themistor.Outer electrode containing Cu can be by that will contain Cu particles
Conducting paste (outer electrode thickener) be coated on the both ends of the surface of ceramic body, and implement calcination processing and formed.Contain Cu's
The calcining of outer electrode is carried out at the higher temperature of the calcining compared with the outer electrode containing Ag.The present inventors are conceived to：In
When carrying out calcination processing under high temperature, contained Cu is diffused in internal electrode in outer electrode, and its result is in outer electrode and pottery
The interface of porcelain base substrate forms Ke Kendaer hole (Japaneses：カーケンダルボイド).It there are and diffuse in internal electrode
Cu amount it is more, form the tendency of bigger Ke Kendaer holes.Present inventors found that：If Cu diffuses to internal electrode
Middle formation Ke Kendaer holes, then exist and solder explosion easily occur when installing NTC themistor, and outer electrode and ceramics
The problem of dhering strength at the interface of base substrate is reduced.Furthermore, so-called " solder explosion " refers to be installed on by NTC themistor
During substrate, blown out as water vapor by the moisture being present in outer electrode and solder is blown to winged phenomenon.The opposing party
Face, it is desirable to which NTC themistor shows stable characteristic within the scope of wider temperature.Therefore, more satisfactory is exposed to temperature
The rate of change of the resistance value of NTC themistor during degree change is smaller.
Be difficult to occur solder explosion it is an object of the invention to provide one kind, the interface of outer electrode and ceramic body it is close
Conjunction intensity is higher, and the less NTC themistor of rate of change and its manufacture method of resistance value during exposed to temperature change.
The technological means solved the problems, such as
The present inventors, which are repeated, conscientiously to be studied, and is as a result found：By controlling to carry out during the calcination processing of outer electrode
Temperature conditionss, the generation of Ke Kendaer holes can be suppressed.And then, present inventors found that：By selecting appropriate temperature point
Cloth, can suppress the generation of solder explosion, improve the dhering strength at the interface of outer electrode and ceramic body, and reduce the exposure to temperature
The rate of change of resistance value during degree change, so as to complete the present invention.
The first technical scheme of the present invention provides a kind of negative-characteristic thermistor device, and it includes：
Ceramic body；
First internal electrode：The inside of ceramic body is arranged at, is exposed in the end face of ceramic body；
Second internal electrode：The inside of ceramic body is arranged at, is exposed in the other end of ceramic body；
First outer electrode：The end face of ceramic body is arranged at, is electrically connected with the first internal electrode；
Second outer electrode：The other end of ceramic body is arranged at, is electrically connected with the second internal electrode；
Ceramic body contains Mn3O4；
First internal electrode and the second internal electrode contain precious metal element；
First outer electrode and the second outer electrode contain Cu；
Cu contained by first outer electrode and the second outer electrode into the first internal electrode and the second internal electrode
Diffusion length is more than 2 μm and less than 20 μm.
In described negative-characteristic thermistor device, Cu contained by the first outer electrode and the second outer electrode to first
Preferably more than 10 μm and less than 20 μm of diffusion length in internal electrode and the second internal electrode.
In described negative-characteristic thermistor device, by the first outer electrode and the second outer electrode in ceramic body
The thickness of end be set as X, by the Cu contained by the first outer electrode and the second outer electrode to the first internal electrode and
When diffusion length in second internal electrode is set as Y, X/Y value preferably more than 2.0, X/Y value more preferably more than 2.0 and
4.0 it is following.
In described negative-characteristic thermistor device, the first internal electrode and the second internal electrode preferably contain Ag and Pd.
The second technical scheme of the present invention provides a kind of manufacture method of negative-characteristic thermistor device, including following process：
Prepare the process for being internally provided with the ceramic body of the first internal electrode and the second internal electrode：Ceramic body contains
Mn3O4, the first internal electrode and the second internal electrode contain precious metal element, and the first internal electrode is in the end face of ceramic body
Expose, the second internal electrode exposes in the other end of ceramic body；
The process for modulating the outer electrode thickener containing Cu particles；
The process for being coated with outer electrode thickener respectively at the end face of ceramic body and other end；
The outer electrode thickener calcination processing of end face and other end will be coated on, formation is arranged at the first of end face
Outer electrode and be arranged at other end the second outer electrode process；
When determining the temperature of calcination processing every 1 second, the value of the summation S of more than 750 DEG C of temperature in temperature is determined
For more than 50000 and less than 250000.In the process, S value preferably more than 200000 and less than 250000.
In the process, the first internal electrode and the second internal electrode preferably contain Ag and Pd.
The effect of invention
The negative-characteristic thermistor device of the present invention can suppress the generation of solder explosion, can improve by being constituted with described
The dhering strength at the interface of outer electrode and ceramic body.Think that its reason is：By suppressing Cu contained in outer electrode
Internally electrode in diffusion, the generation of the Ke Kendaer holes at the interface of outer electrode and ceramic body can be suppressed.In addition,
The negative-characteristic thermistor device of the present invention by being constituted with described, the rate of change of resistance value during exposed to temperature change compared with
It is small.Think that its reason is：The diffusion in internally electrode by moderately producing Cu contained in outer electrode, external electrical
The engagement of pole and internal electrode becomes firm.In addition, the present invention negative-characteristic thermistor device manufacture method can by with
The composition and one kind is provided and is difficult to occur solder explosion, the dhering strength at the interface of outer electrode and ceramic body is higher, and
The less negative-characteristic thermistor device of rate of change of resistance value during exposed to temperature change.Think that its reason is：Pass through control
Temperature Distribution during calcination processing processed, can control the diffusion length in Cu contained in outer electrode internally electrode.
Brief description of the drawings
Fig. 1 is the diagrammatic cross-sectional view of the NTC themistor of an embodiment of the present invention.
Fig. 2 briefly represents the connection disc electrode (Japanese on the surface of the substrate used in embodiment：ラ Application ド Electricity Very)
Configuration.
The configuration of NTC themistor 1 when Fig. 3 briefly represents to determine terminal strength characteristics.
Embodiment
Hereinafter, embodiments of the present invention are illustrated referring to the drawings.But, embodiment as shown below is to illustrate
For the purpose of, the present invention is not limited to implementation below.It is the size of inscape described below, material, shape, relative
As long as configuration etc. is then not meant to that the scope of the present invention is only defined in this without special record, and is only to illustrate example.In addition, depositing
In order to clearly illustrate and exaggerate the feelings of the size, shape, the position relationship that represent each diagrammatically shown inscape etc.
Shape.
[NTC themistor]
The diagrammatic cross-sectional view of the composition for the NTC themistor 1 for representing an embodiment of the present invention is shown in Fig. 1.Fig. 1
Shown NTC themistor 1 is included：Ceramic body 2；It is arranged at the inside of ceramic body 2 and in one end of ceramic body 2
The first internal electrode 31 that face 21 is exposed；It is arranged at the inside of ceramic body 2 and exposes in the other end 22 of ceramic body 2
The second internal electrode 32；Outside first for being arranged at the end face 21 of ceramic body 2 and being electrically connected with the first internal electrode 31
Electrode 41；And it is arranged at the other end 22 of ceramic body 2 and the second outer electrode electrically connected with the second internal electrode 32
42.Furthermore, as shown in figure 1, in NTC themistor described in this manual, by parallel to from the one of ceramic body 2
End face 21 is referred to as " length direction " or " L directions " towards the direction in the direction of other end 22, will in horizontal plane perpendicular to length
The direction in degree direction is referred to as " width " or " W directions ", and the direction that will be perpendicular to length direction and width is referred to as " thickness
Direction " or " T directions ".In addition, the face that will be perpendicular to L directions is referred to as WT faces, the face that will be perpendicular to W directions is referred to as LT faces, will hang down
Directly it is referred to as LW faces in the face in T directions.
(ceramic body)
In the present embodiment, ceramic body 2 contains Mn3O4.Ceramic body 2 is except Mn3O4, can also contain NiO, Co3O4、
Fe2O3、Al2O3、ZrO2、TiO2, CuO, ZnO etc..The composition of ceramic body 2 can include such as Mn-Ni-Fe classes ceramics, Mn-Ni-
Al-Zr classes ceramics, Mn-Ni-Fe-Ti classes ceramics, Mn-Ni-Co- (Al, Cu) class ceramics, Mn-Co-Fe class ceramics etc..
(internal electrode)
In the NTC themistor 1 of present embodiment, internal electrode is by the first internal electrode 31 and the second internal electrode
32 are constituted.First internal electrode 31 and the second internal electrode 32 in the inside of ceramic body 2 mutually relative mode to configure.The
The one end of one internal electrode 31 exposes in the end face 21 of ceramic body 2.The one end of second internal electrode 32 is in ceramic blank
Expose the other end 22 of body 2.The NTC themistor 1 of present embodiment can include multiple first internal electrodes 31 and multiple
Second internal electrode 32.First internal electrode 31 and the second internal electrode 32 contain precious metal element as conductive component.It is interior
Contained precious metal element is not particularly limited in portion's electrode, can contain the element of more than 1 selected from Pd, Ag and Pt.Internal electricity
Pole can contain the base metal elements such as Ni, Cu as conductive component in addition to the precious metal element, also.Institute in internal electrode
The precious metal element contained for example can be Pd.Internal electrode (the first internal electrode and the second internal electrode) preferably contains Ag and Pd
It is used as precious metal element.Ag is also contained in addition to Pd by internal electrode, contained Cu can be suppressed in outer electrode internally
Diffusion in electrode, its result can suppress the generation of the Ke Kendaer holes at the interface of outer electrode and internal electrode.In addition,
Internal electrode during situation also containing Ag, can reduce material cost in addition to Pd.If suppressing the generation of Ke Kendaer holes,
Then suppress that solder explosion occurs when installing NTC themistor.In addition, if suppressing the generation of Ke Kendaer holes, then can
Suppress the reduction of the dhering strength at the interface of outer electrode and ceramic body.When internally electrode contains Ag and Pd situation, Ag
And Pd can exist with the state of alloy (AgPd alloys).Containing ratio for Ag and Pd is not particularly limited, and can suitably be selected
Arbitrary containing ratio.When internally electrode contains Ag and Pd situation, preferably contain 10 on the basis of Ag and Pd total amount
More than weight % Pd.
(outer electrode)
In the NTC themistor 1 of present embodiment, outer electrode is by the first outer electrode 41 and the second outer electrode
42 are constituted.First outer electrode 41 is arranged at the end face 21 of ceramic body 2, is electrically connected with the first internal electrode 31.Outside second
Portion's electrode 42 is arranged at the other end 22 of ceramic body 2, is electrically connected with the second internal electrode 32.First outer electrode 41 can be with
As shown in Figure 1, configured in the way of the part extension in the end face 21 of ceramic body 2 and side.Furthermore, ceramic blank
" side " of body 2 refers to all faces beyond end face (21 and 22).Similarly, the second outer electrode 42 can be in ceramic body 2
Other end 22 and side a part extension mode configure.First outer electrode 41 and the second outer electrode 42 contain Cu
It is used as conductive component.Outer electrode can also contain glass ingredient except Cu.Glass ingredient is to promote the burning of outer electrode
Knot, and assign mechanical strength to outer electrode and add.The composition of outer electrode is not particularly limited, but can for example contain 60 bodies
Product more than % and below 95 volume % metal ingredient, more than 5 volume % and below 40 volume % glass ingredient.For outside
The composition of contained glass ingredient is not particularly limited in electrode, can suitably be set according to intended applications.Outer electrode
In contained glass ingredient can for example contain and be selected from alkaline-earth metal, Cu, Si, Ti, Zn, alkali metal, Sr, Al and Bi at least one.
The NTC themistor of present embodiment can be by as described as follows, by the conductive paste containing Cu particles
(outer electrode thickener) is coated on the both ends of the surface of ceramic body, implements calcination processing and is formed.By being applied in the calcination processing
A part for contained precious metal element spreads into outer electrode in heating, internal electrode, on the contrary, contained in outer electrode
A Cu part internally spread in electrode.Now, due to the diffusion in Cu contained in outer electrode internally electrode
The difference of speed and the diffusion velocity into outer electrode of precious metal element contained in internal electrode, and in outer electrode and pottery
Ke Kendaer holes are formed in the interface of porcelain base substrate.If forming such a Ke Kendaer holes, outer electrode and ceramic body
Interface dhering strength reduction.And then, there is following situation：The Cu spread in oriented internal electrode amount is more, and formation is got over
The tendency of big Ke Kendaer holes, so that Ke Kendaer holes expose in external electrode surface.There is water in surrounding environment
During the situation divided, the Ke Kendaer holes that moisture can expose certainly are penetrated into outer electrode.In this kind of situation, installed by reflow
During Deng NTC themistor being installed on into substrate, have the moisture vaporization being present in outer electrode and blow out the feelings of vapor
Shape.If the moisture such as vapor self-electrode is blown out, solder, which is blown, to fly and becomes scattered about on substrate.The phenomenon is commonly known as " weldering
Material explosion ".If Ke Kendaer holes expose in external electrode surface, easily occurs solder explosion.It is as described above that
Sample, internal electrode is diffused to by Cu contained in outer electrode, can reduce outer electrode and ceramic body interface it is closely sealed
Intensity, can occur solder explosion in the installation of NTC themistor.
On the other hand, it is believed that pass through metal ingredient contained in outer electrode and metal ingredient phase contained in internal electrode
Mutually mobile, the engagement of outer electrode and internal electrode becomes firm.It is therefore contemplated that Cu contained preferably in outer electrode to
Diffusion in internal electrode produces the degree fully engaged to outer electrode and internal electrode.
Diffusing capacity in outer electrode in contained Cu internally electrode can by the diffusion in Cu internally electrode away from
From estimation.Diffusion length in outer electrode in contained Cu internally electrode is obtained by operating as follows：To NTC heat
The section of sensitive resistor carries out Wavelength dispersion type x ray spectrum analysis (WDX), and the intensity of the Cu-K α to being obtained carries out ASCII
Conversion, binarization is carried out using image processing software, thereby makes the distribution map of Cu compositions, determines Cu's in the distribution map
Diffusion length.
In the NTC themistor of present embodiment, in outer electrode (the first outer electrode and the second outer electrode)
Diffusion length in contained Cu internally electrode (the first internal electrode and the second internal electrode) for more than 2 μm and 20 μm with
Under.If diffusion length is more than 2 μm, the engagement of outer electrode and internal electrode can be made firm.If outer electrode with it is interior
The engagement of portion's electrode firmly, then can be throughout the stable characteristic of wider temperature range display.The internal electrode of NTC themistor
And outer electrode is varied with temperature and expansion or shrinkage.Now, because of the difference of thermal coefficient of expansion, and to outer electrode and internal electrode
Junction surface apply load.If the engagement of outer electrode and internal electrode is insufficient, have because destroying external electrical the load
The anxiety of the engagement of pole and internal electrode.Its result：The resistance value of NTC themistor is caused to increase, the rate of change of resistance value becomes
Greatly.In contrast, in the NTC themistor of present embodiment, because outer electrode is securely engaged with internal electrode, therefore
And when being easy to the situation by being applied with load exposed to the temperature change throughout wider temperature range, it is also difficult to destroy
The engagement of outer electrode and internal electrode.Therefore, the NTC themistor of present embodiment can reduce the electricity after thermal cycling test
The rate of change of resistance.Thermal cycling test can be for example, by the repeatedly heating of specific times within the temperature range of -55 DEG C~150 DEG C
Carried out with cooling.If diffusion length is below 20 μm, the Ke Kenda at the interface of outer electrode and ceramic body can be suppressed
The generation of your hole.The result is that the reduction of the dhering strength at the interface of outer electrode and ceramic body can be suppressed.And then, due to
It can prevent Ke Kendaer holes from exposing in external electrode surface, be penetrated into so moisture can be suppressed in outer electrode, presence can be reduced
The amount of moisture in outer electrode.The result is that the generation of solder explosion when can suppress to install NTC themistor.
Contained Cu internally electrode (the first inside electricity in outer electrode (the first outer electrode and the second outer electrode)
Pole and the second internal electrode) in diffusion length be preferably more than 10 μm and less than 20 μm.If diffusion length is more than 10 μm,
Then the engagement of outer electrode and internal electrode can be made more firm.Its result can be by the NTC themistor after thermal cycling test
The rate of change of resistance value becomes smaller.
Occurring for solder explosion when installing NTC themistor can be by the outer electrode of the end face for controlling ceramic body
Thickness further suppress.Think the height phase of the thickness and Ke Kendaer holes in the outer electrode of the end face of ceramic body
During than sufficiently large situation, Ke Kendaer holes are difficult to expose in the surface of outer electrode, and its result can suppress solder explosion
Occur.The height of Ke Kendaer holes can be approximate with the diffusion length in Cu contained in outer electrode internally electrode.
In the NTC themistor of present embodiment, by outer electrode (the first outer electrode and the second outer electrode) in ceramics
The thickness of the end of base substrate is set as X, by Cu's contained in outer electrode (the first outer electrode and the second outer electrode)
When internally the diffusion length in electrode (the first internal electrode and the second internal electrode) is set as Y, X/Y value is preferably 2.0
More than.If X/Y value is more than 2.0, Ke Kendaer holes are difficult to the surface for being exposed to outer electrode, and its result can enter one
Step suppresses the generation of solder explosion.X/Y value is more preferably more than 2.0 and less than 4.0.If X/Y value, can below 4.0
Suppress the generation of solder explosion, while further reducing the rate of change of the resistance value of the NTC themistor after thermal cycling test.
[manufacture method of NTC themistor]
Hereinafter, one of the manufacture method of the NTC themistor of an embodiment of the present invention is illustrated, but this hair
The manufacture method of bright NTC themistor is not limited to method as shown below.The method of present embodiment includes as follows
Process：Prepare the process for being internally provided with the ceramic body of the first internal electrode and the second internal electrode；Modulation contains Cu particles
Outer electrode thickener process；The process that outer electrode thickener is coated with other end respectively at the end face of ceramic body；
The outer electrode thickener for being coated on end face and the other end is subjected to calcination processing, formation is arranged at the first of end face
The process of second outer electrode of the outer electrode with being arranged at other end.
First, preparation is internally provided with the ceramic body of the first internal electrode and the second internal electrode.Ceramic body contains
Mn3O4.First internal electrode and the second internal electrode contain precious metal element.First internal electrode is in the end face of ceramic body
Expose, the second internal electrode exposes in the other end of ceramic body.Ceramic body is using such as steps described below system
Make.
(making of raw cook)
First, raw cook is made according to following steps.As the raw material of ceramic body, Mn can be used3O4、NiO、Co3O4、Fe2O3、
Al2O3、ZrO2、TiO2, the metal oxide such as CuO, ZnO.Each raw material is weighed according to the composition of target ceramic body.Jiang Shui and point
Powder is added in weighed each raw material and mixed using ball mill, is added adhesive resin and is obtained ceramic slurry.It is logical
Cross doctor blade method to shape the ceramic slurry, so as to obtain the raw cook that thickness is 10~60 μm or so.
(modulation of internal electrode thickener)
By by noble metal powder and organic vehicle hybrid modulation internal electrode thickener.As noble metal powder, it can be used
The AgPd alloy powders such as Pd powder, Ag70Pd30 alloys, Pt powder etc..Noble metal powder is preferably AgPd alloy powders.Pass through
Using AgPd alloy powders, the internal electrode containing Ag and Pd can be formed.Internally electrode also feelings containing Ag in addition to Pd
During shape, it can further suppress the diffusion in Cu contained in outer electrode internally electrode, and material cost can be reduced.Your gold
The average grain diameter of category powder is preferably more than 0.1 μm and less than 5.0 μm.Internal electrode thickener preferably contains more than 60 weight %
And the organic vehicle of 90 noble metal powder and more than 10 weight % and below 40 weight % below weight %.Organic vehicle is for example
It can be prepared by the way that ethyl cellulose is dissolved in into terpinol.The content of ethyl cellulose in organic vehicle is preferably 5 weights
Measure more than % and below 20 weight %.
(making of layered product)
Internal electrode thickener is printed as defined shape on raw cook, so as to form electrode pattern.Electrode will be formed with
The raw cook of pattern pressurizes with not forming the raw cook of electrode pattern with defined order stacking regulation piece number and obtains mother layer stack.
The mother layer stack is cut into defined size and strip (Japanese is obtained：チ ッ プ shapes) layered product.
(burning till)
The layered product of strip is burnt till with specific Temperature Distribution, and obtains ceramic body.It is configured at obtained ceramics
The first internal electrode and the second internal electrode of the inside of base substrate preferably contain Ag and Pd.Also contain in addition to Pd in internal electrode
When having Ag situation, in following calcination processings, it can further suppress the expansion in the internally electrode of the Cu contained by outer electrode
Dissipate.
(modulation of outer electrode thickener)
By the way that Cu powder, frit, organic vehicle are kneaded with modulated external electrode paste.The average grain diameter of Cu powder compared with
Good is more than 0.1 μm and less than 5 μm.As Cu powder, preferably using spherical Cu powder and flat Cu powder mixing
Thing.By in spherical Cu powder add flat Cu powder, can suppress in following calcination processings outer electrode to
The sintering shrinkage in face direction.Its result can obtain thickening, the of excellent in reliability outside of thickness in the corner of obtained outer electrode
Electrode.As frit, B can be used2O3-SiO2Class frit, B2O3-SiO2- ZnO classes frit, B2O3-SiO2- alkali earths glass
Glass material etc..The transition point of frit is preferably more than 400 DEG C and less than 650 DEG C, and softening point is preferably more than 500 DEG C and 750 DEG C
Below.The average grain diameter of frit is preferably more than 0.1 μm and less than 5 μm.Organic vehicle for example can be by by acrylic resin
It is dissolved in terpinol and prepares.The content of acrylic resin in organic vehicle be preferably more than 5 weight % and 40 weight % with
Under.
(coating of outer electrode thickener)
In the end face of ceramic body and other end respectively by outer electrode paste into defined shape.Painting can be made
Outer electrode after cloth is dried.The coating thickness of outer electrode thickener can suitably be set according to the thickness of target external electrode
It is fixed.
(calcination processing)
By the end face and the outer electrode thickener calcination processing of other end that are coated on ceramic body, formation is arranged at one
First outer electrode of end face and the second outer electrode for being arranged at other end.It is internal by applying heat in calcination processing
A part for precious metal element contained by electrode spreads into outer electrode, on the contrary, a part of the Cu contained by outer electrode
Internally spread in electrode.Now, because of the diffusion velocity in the internally electrode of the Cu contained by outer electrode and internal electrode institute
The difference of the diffusion velocity into outer electrode of the precious metal element contained, and formed in the interface of outer electrode and ceramic body
Ke Kendaer holes.Present inventors found that can be by controlling Temperature Distribution when carrying out calcination processing, and suppress Ke Kendaer
The generation of hole.In the method for present embodiment, the Temperature Distribution in calcination processing is to set as follows：Every 1
Second determine calcination processing temperature when, determine temperature in more than 750 DEG C temperature summation S value be more than 50000 and
Less than 250000.S values are bigger, and the heat that outer electrode and internal electrode are put in calcination processing is bigger.By controlling S
Value, can control the diffusion of the internally electrode of the Cu compositions of Cu outer electrodes in calcination processing.If S values are more than 50000,
Then the engagement of outer electrode and internal electrode can be made firm.Think that its reason is：It is enough to make outer electrode and internal electrode
The Cu firmly measured is engaged to diffuse in internal electrode from outer electrode.Pass through the NTC heat manufactured by the method for present embodiment
In sensitive resistor, because the engagement of outer electrode and internal electrode is firm, thus the resistance value after thermal cycling test can be reduced
Rate of change.If S values are less than 250000, the Cu contained by outer electrode can be suppressed and diffused in internal electrode, its result can
Suppress to produce Ke Kendaer holes in the interface of outer electrode and ceramic body.By manufactured by the method for present embodiment
In NTC themistor, the generation of Yin Kekendaer holes is suppressed, thus can improve the boundary of outer electrode and ceramic body
The dhering strength in face.In addition, can prevent Ke Kendaer holes from exposing in external electrode surface, thus moisture can be suppressed penetrate into outer
In portion's electrode, the generation that solder when its result can suppress to install NTC themistor bursts.S values are preferably more than 200000
And less than 250000.If S values are more than 200000, the engagement of outer electrode and internal electrode can be made further firm, its
As a result the rate of change of the resistance value after thermal cycling test can further be reduced.Manufactured NTC thermistor utensil in this way
Have the following advantages：It is difficult to occur solder explosion, the dhering strength at the interface of outer electrode and ceramic body is high, and exposed to temperature
The rate of change of resistance value during change is smaller.
(formation of plating layer)
According to circumstances, by being electrolysed plating plating layer can be formed in external electrode surface.Plating layer, which has to improve, to be installed
When solder wettability or heat resistance function.The composition of plating layer can suitably be selected according to composition of outer electrode etc.
Select.For example, Ni layers of plating can be formed in the surface of outer electrode, Sn layers of plating is formed on plating Ni layers.
Embodiment
[making of NTC themistor]
According to step as shown below, the NTC themistor of embodiment 1~8 and comparative example 1~3 is made.
(making of raw cook)
Prepare Mn3O4、Fe2O3And NiO is used as the raw material of ceramic body.Each original is weighed according to the composition of target ceramic body
Material.Water and dispersant are added in weighed each raw material and mixed using ball mill, and then adds adhesive resin
To obtain ceramic slurry.The ceramic slurry is shaped by doctor blade method, the raw cook of 50 μm of thickness is obtained.
(modulation of internal electrode thickener)
Prepare two kinds of internal electrode thickeners of Pd class internal electrode thickeners and Ag30Pd70 class internal electrode thickeners.In Pd classes
Portion's electrode paste is made by the way that the weight % of Pd powder 80 and the weight % of organic vehicle 20 of 1 μm of average grain diameter are mixed.
Ag70Pd30 class internal electrode thickeners are by by the weight % of Ag70Pd30 alloy powders 80 of 1 μm of average grain diameter and organic
The weight % of supporting agent 20 is mixed and is made.Furthermore, organic vehicle is made by the way that ethyl cellulose is dissolved in into terpinol.It is organic
The content of ethyl cellulose in supporting agent is 20 weight %.
(making of layered product)
Internal electrode thickener is printed for defined shape, formation electrode pattern on raw cook.Electrode pattern will be formed with
Raw cook and do not form the raw cook of electrode pattern and be laminated regulation piece number according to regulation order, pressurize and obtain mother layer stack.Will
The mother layer stack be cut to as defined in size and obtain the layered product of strip.
(burning till)
The layered product of strip is burnt till with defined Temperature Distribution, to obtain ceramic body.In the present embodiment, table is made
4 kinds of ceramic body C-1~C-4 shown in 1.
[table 1]
(modulation of outer electrode thickener)
By 3 μm of the weight % of flat Cu powder 64 of average grain diameter, the spherical weight of shape Cu powder 16 of 1 μm of average grain diameter
Measure %, the BaO-ZnO-B for 1 μm of the average grain diameter that transition point is 620 DEG C, softening point is 720 DEG C2O3-SiO2The weight of class frit 5
% is measured, and the weight % of organic vehicle 15 that acrylic resin is dissolved in into terpinol and obtained is concocted, and is kneaded and is obtained
Outer electrode thickener.Furthermore, the content of the acrylic resin in organic vehicle is 20 weight %.
(calcination processing)
Using the ceramic body and outer electrode thickener of the C-1~C-4, embodiment 1~8 and comparative example 1~3 are made
NTC themistor.The species of ceramic body used in each embodiment and comparative example is represented in table 5 below.In ceramics
The two ends face (WT faces) of base substrate is respectively coated outer electrode thickener, dries it.The coating thickness root of outer electrode thickener
Suitably set according to the thickness of target external electrode.To be coated with the ceramic body of the outer electrode thickener in control be N2/H2O/
H2Apply calcination processing in the tunnel cave of atmosphere, thereby obtain the NTC themistor that two ends face is configured with outer electrode.In
During calcination processing, passed through by the sheath for making to be configured with thermocouple in tunnel cave, the temperature in 1 second measure tunnel cave
Degree.Calculate the summation S values of more than 750 DEG C of temperature in the temperature determined using thermocouple.By each embodiment and the S of comparative example
Value is shown in table 5.
(formation of plating layer)
By be electrolysed plating the both ends of the surface for the ceramic body for being configured at NTC themistor 2 outer electrodes it is each
Individual surface forms Ni layer of plating, is formed in Ni layer of the plating by being electrolysed plating and plates Sn layers.By such a mode, embodiment 1 is obtained
~8 and the NTC themistor of comparative example 1~3.
[evaluating characteristics of NTC themistor]
For each embodiment and the NTC themistor of comparative example obtained, outer electrode is evaluated with following step
The thickness X of ceramic body end, the diffusion length Y in the internally electrode of the Cu compositions in outer electrode, solder explosion are special
Property, thermal cycle characteristic, terminal strength characteristics.
(thickness X of the end of outer electrode)
NTC themistor is carried out after hardening of resin, the LT faces of NTC themistor are ground, make external electrical
Expose in the section of pole.It is ground until about 1/2 position (1/2W positions) of the W sizes of NTC themistor.It is outer for 2
The each of portion's electrode, the section of the outer electrode exposed with metallurgical microscopes (BX-60 of Olympus companies manufacture) observation, makes
The most thick part of outer electrode is measured with image processing software (Stream that Olympus companies manufacture).For each
The NTC themistors of n=10 (i.e. the outer electrodes of n=20) are carried out the operation, calculated outer by embodiment and comparative example
The average value of the measured value of portion's thickness of electrode.The average value is set as to the thickness X of the end of outer electrode.As a result it is shown in
In table 5.
(the diffusion length Y of Cu compositions in outer electrode internally in electrode)
Using with method identical method illustrated in the assay method of the thickness X of the end of outer electrode, make
Expose in the section of the 1/2W positions of NTC themistor.Ion milled processed is carried out to the section, then carried out at carbon coating
Reason.Wavelength dispersion is carried out to the section after ion milled processed and carbon coating processing using JEOL companies manufacture/JXA-8100
Type X-ray spectral analysis (WDX).WDX condition determination is shown in table 2.
[table 2]
The intensity of Cu-K α to being obtained carries out ASCII conversions, and the distribution map of Cu compositions is made using image processing software
(binarization figure).Furthermore, 20 are set the threshold in binarization.According to the distribution map of gained, to 2 outer electrodes
Each, determines the diffusion length in the internally electrode of Cu compositions.To n=5 NTC themistors (i.e. n=10 outside
Portion's electrode) operation is carried out, calculate the average value of diffusion length.The Cu compositions average value being set as in outer electrode to
Diffusion length Y in internal electrode.As a result it is shown in table 5.
(solder burst characteristics)
The NTC themistor of each embodiment and comparative example respectively prepares 1000, is burst with following step measurements solders special
Property.First, the substrate to install each NTC themistor is prepared.Disc electrode is connected in the surface configuration of substrate.Fig. 2 tables
Show the configuration of the connection disc electrode 5 of substrate surface.The welding paste material (solder thickener) for Sn-3Ag-0.5Cu will be constituted on substrate
Connection disc electrode 5 on 200 μm of thickness of coating.Connect the interelectrode distance 51 of disc electrode 5, the size (L cuns) 52 in L directions and
The size (W cuns) 53 in W directions is to be set as the size shown in Table 3 below according to the species of ceramic body.Furthermore, Fig. 2 L side
The L directions, W directions and T directions of ceramic body are corresponded respectively to, W directions and T directions.
[table 3]
Configure NTC themistor on the connection disc electrode for being coated with welding paste material, under nitrogen atmosphere with peak temperature
280 DEG C of progress reflows of degree.Using each terminal pad electrode portion of the NTC themistor amplified after sem observation reflow, observation has
Solder explosion without spray form.On each embodiment and comparative example, in the NTC themistor for the solder explosion for occurring spray form
During for the situation of less than 5, it is judged to, with especially excellent solder burst characteristics, representing with " ◎ " in table 5 below.In hair
When the NTC themistor of the solder explosion of raw spray form is more than 6 and the situation of less than 100, it is determined as having well
Solder burst characteristics, represented in table 5 with " 〇 ".It it is 101 in the NTC themistor for the solder explosion for occurring spray form
During the situation of the above, it is determined as that solder burst characteristics are poorer, is represented in table 5 with "×".
(thermal cycle characteristic)
The NTC themistor of each embodiment and comparative example respectively prepares 10, with following step measurements thermal cycle characteristics.It is first
First, the substrate to install each NTC themistor is prepared.The welding paste material (solder thickener) for Sn-3Ag-0.5Cu will be constituted
In the thickness of 200 μm of coating on the connection disc electrode on substrate.Connect the chi being dimensioned so as to shown in the table 3 of disc electrode
It is very little.Configure NTC themistor on the connection disc electrode for being coated with welding paste material, under nitrogen atmosphere with peak temperature 260
DEG C carry out reflow.The initial resistance of each NTC themistor after reflow is determined by using the two-terminal method of digital multimeter
T0.Then, thermal cycling test is carried out within the temperature range of -55 DEG C~150 DEG C.Thermal cycling test is in 2 DEG C/minute of programming rate
Clock, 5 DEG C/min of cooling rate, 2000 circulations of progress under conditions of 1 minute retention time when -55 DEG C and 150 DEG C.Survey
The resistance T of each NTC themistor after the completion of fixed 2000 circulations.Use the T measured0And T value, according to following formula meter
Calculate resistance change rate.
[number 1]
For each embodiment and comparative example, when resistance change rate is not up to 1% situation, it is determined as with especially excellent
Thermal cycle characteristic, is represented in table 5 below with " ◎ ".It is more than 1% and during not up to 3% situation in resistance change rate, judges
With good thermal cycle characteristic, to be represented in table 5 with " 〇 ".When resistance change rate is more than 3% situation, it is determined as
Thermal cycle characteristic is poorer, is represented in table 5 with "×".
(terminal strength characteristics)
Prepare the NTC themistor of each embodiment and comparative example, with following step measurements terminal strength characteristicies.Terminal is strong
Degree characteristic is the strong and weak index of the dhering strength at the interface for representing outer electrode and ceramic body.Fig. 3 represents that measure terminal is strong
The configuration of NTC themistor 1 during degree characteristic.First, prepare to the substrate 6 for the NTC themistor 1 for installing each.
The welding paste material (solder thickener) 7 for Sn-3Ag-0.5Cu will be constituted in the thickness of 200 μm of coating on the connection disc electrode 5 on substrate 6
Degree.Under the size (W cuns) in the W directions of connection disc electrode 5 and the size (T cuns) in T directions are set as according to the species of ceramic body 2
State the size shown in table 4.Furthermore, L directions, W directions and T directions in Fig. 3 correspond respectively to the L directions of ceramic body, W directions
And T directions.
[table 4]
An outer electrode in 2 outer electrodes (being represented in Fig. 3 with symbol 4) of NTC themistor is as shown in Figure 3
Like that, be fitted vertically with substrate 6, under nitrogen atmosphere with the progress reflows of 260 DEG C of peak temperature.By pressure meter, (village field makes
Intra-company of institute manufacture mechanical strength measuring machine) terminal be close to the outer electrode 4 for being not secured to substrate 6, in the horizontal with
The speed of 0.5mm/ seconds applies load until NTC themistor 1 comes off from substrate 6.To amplify the NTC heat that sem observation comes off
The WT faces of sensitive resistor 1 and the surface of substrate 6.Observed in both of the WT faces in NTC themistor 1 and the surface of substrate 6
During the situation of ceramic body 2 or solder, it can be considered that ceramic body 2 or solder are destroyed.In the situation, it is determined as NTC temperature-sensitives
Resistor 1 has excellent terminal strength characteristics, is represented in table 5 with " 〇 ".In in the non-residual ceramic base substrate in the surface of substrate 6
During 2 situation, it can be considered and produce destruction with the interface of ceramic body 2 in the outer electrode 4 of NTC themistor 1.In the situation
When, it is determined as that the terminal strength characteristics of NTC themistor 1 is bad, is represented in table 5 with "×".
(overall merit)
As overall merit, as long as thering is 1 to be judged as in solder burst characteristics, thermal cycle characteristic and terminal strength characteristics
The NTC themistor of "×" is to be judged as not representing with "×" in table 5 for practical application.It is used as overall merit, weldering
Material burst characteristics, thermal cycle characteristic and terminal strength characteristics are not judged as "×", and solder burst characteristics and thermal cycle are special
Property both be judged as the NTC themistor of " ◎ " and be judged as with especially excellent characteristic, with " ◎ " table in table 5
Show.As overall merit, solder burst characteristics, thermal cycle characteristic and terminal strength characteristics are not judged as "×", and solder
Burst characteristics and only any one NTC themistor for being judged as " ◎ " of thermal cycle characteristic are judged as with excellent spy
Property, represented in table 5 with " 〇 ".
[table 5]
As known from Table 5：Confirm solder burst characteristics, thermal cycle characteristic and the end of the NTC themistor of embodiment 1~8
Sub- strength characteristics is excellent.Particularly diffusion length Y has for the NTC themistor of more than 10 μm of embodiment 2~4 and 6~8
Especially excellent thermal cycle characteristic.In addition, the thickness X of the end of outer electrode is sufficiently large compared with diffusion length Y, and X/Y is 2.0
The NTC themistor of embodiment 1~3 and 5~8 above has especially excellent solder burst characteristics.
On the other hand, in the NTC themistor of comparative example 1, diffusion length Y is not to 2 μm.This is considered as because S values
Not to 50000.The thermal cycle bad characteristic of the NTC themistor of comparative example 1.This is considered as because diffusion length Y is smaller, outside
The engagement of portion's electrode and internal electrode is inadequate, so making the bond breakage of outer electrode and internal electrode by thermal cycling test.
In addition, in the NTC themistor of comparative example 2 and 3, diffusion length Y has exceeded 20 μm.This be considered as because S values for more than
250000 value.The terminal strength characteristics of the NTC themistor of comparative example 2 and 3 is bad.This is considered as because in outer electrode
Cu diffuse in internal electrode, so in the interface of outer electrode and ceramic body produce Ke Kendaer holes, external electrical
The dhering strength reduction at pole and the interface of ceramic body.X/Y value for more than 2.0 embodiment 1~3 and 5~8 in, occur
Solder explosion NTC themistor be 1000 in have less than 5.On the other hand, X/Y value not to 2.0 comparative example 2
And in 3, occur the NTC themistor of solder explosion to have more than 6 and less than 100 in 1000.This be considered as because
Ke Kendaer holes expose in the surface of outer electrode in comparative example 2 and 3.In addition, passing through embodiment 1 and 3 and embodiment 5
And 6 comparison, it is known that in S value identical situations, use the embodiment 5 and 6 containing Ag and Pd internal electrode NTC heat
The diffusion length Y of Cu in sensitive resistor is shorter than the NTC thermistor using the only embodiment 1 and 3 of the internal electrode containing Pd
The diffusion length Y of Cu in device.It is therefore contemplated that by using the also internal electrode containing Ag in addition to Pd, can suppress outside
Diffusion in the internally electrode of Cu contained by electrode.
Industrial applicability
The negative-characteristic thermistor device of the present invention is due to being difficult to occur solder explosion, outer electrode and ceramic blank when mounted
The dhering strength at the interface of body is higher, and throughout the stable characteristic of wider temperature range display, so can be used for requiring that height can
By property and high performance electronic equipment.
Symbol description
1 negative-characteristic thermistor device (NTC themistor)
2 ceramic bodies
The end face of 21 ceramic bodies
The other end of 22 ceramic bodies
31 first internal electrodes
32 second internal electrodes
4 outer electrodes
41 first outer electrodes
42 second outer electrodes
5 connection disc electrodes
The interelectrode distance of 51 connection disc electrodes
The size (L cuns) in the L directions of 52 connection disc electrodes
The size (W cuns) in the W directions of 53 connection disc electrodes
6 substrates
7 welding paste material
Claims (8)
1. a kind of negative-characteristic thermistor device, it includes：
Ceramic body；
First internal electrode：The inside of the ceramic body is arranged at, is exposed in the end face of the ceramic body；
Second internal electrode：The inside of the ceramic body is arranged at, is exposed in the other end of the ceramic body；
First outer electrode：The end face of the ceramic body is arranged at, is electrically connected with first internal electrode；
Second outer electrode：The other end of the ceramic body is arranged at, is electrically connected with second internal electrode；
The ceramic body contains Mn3O4；
First internal electrode and second internal electrode contain precious metal element；
First outer electrode and second outer electrode contain Cu；
Cu contained by first outer electrode and second outer electrode to first internal electrode and described second
Diffusion length in internal electrode is more than 2 μm and less than 20 μm.
2. negative-characteristic thermistor device as claimed in claim 1, it is characterised in that first outer electrode and described second
The diffusion length into first internal electrode and second internal electrode of Cu contained by outer electrode is more than 10 μm
And less than 20 μm.
3. negative-characteristic thermistor device as claimed in claim 1 or 2, it is characterised in that by first outer electrode and
The thickness of the end in the ceramic body of second outer electrode is set as X, by first outer electrode and institute
State the setting of the diffusion length into first internal electrode and second internal electrode of the Cu contained by the second outer electrode
During for Y, X/Y value is more than 2.0.
4. such as negative-characteristic thermistor device according to any one of claims 1 to 3, it is characterised in that X/Y value be 2.0 with
It is upper and less than 4.0.
5. such as negative-characteristic thermistor device according to any one of claims 1 to 4, it is characterised in that first inside electricity
Pole and second internal electrode contain Ag and Pd.
6. a kind of manufacture method of negative-characteristic thermistor device, including following process：
Prepare the process for being internally provided with the ceramic body of the first internal electrode and the second internal electrode：The ceramic body contains
Mn3O4, first internal electrode and second internal electrode contain precious metal element, and first internal electrode is in described
The end face of ceramic body exposes, and second internal electrode exposes in the other end of the ceramic body；
The process for modulating the outer electrode thickener containing Cu particles；
The process for being coated with the outer electrode thickener respectively at the end face of the ceramic body and the other end；
To be coated on the outer electrode thickener calcination processing of the end face and the other end, formation be arranged at this one
First outer electrode of end face and be arranged at the other end the second outer electrode process；
When determining the temperature of the calcination processing every 1 second, the value of the summation S of more than 750 DEG C of temperature in temperature is determined
For more than 50000 and less than 250000.
7. method as claimed in claim 6, it is characterised in that the value of the S is more than 200000 and less than 250000.
8. method as claimed in claims 6 or 7, it is characterised in that first internal electrode and second internal electrode
Contain Ag and Pd.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015-025774 | 2015-02-12 | ||
| JP2015025774 | 2015-02-12 | ||
| PCT/JP2016/050203 WO2016129300A1 (en) | 2015-02-12 | 2016-01-06 | Negative temperature coefficient thermistor and method for manufacturing same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107210106A true CN107210106A (en) | 2017-09-26 |
| CN107210106B CN107210106B (en) | 2018-12-28 |
Family
ID=56614526
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201680008674.3A Active CN107210106B (en) | 2015-02-12 | 2016-01-06 | Negative-characteristic thermistor device and its manufacturing method |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP6428797B2 (en) |
| CN (1) | CN107210106B (en) |
| TW (1) | TWI584309B (en) |
| WO (1) | WO2016129300A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2021057556A (en) | 2019-10-02 | 2021-04-08 | Tdk株式会社 | NTC thermistor element |
| JP7434863B2 (en) | 2019-12-06 | 2024-02-21 | Tdk株式会社 | NTC thermistor element |
| CN116813325A (en) * | 2023-04-01 | 2023-09-29 | 东莞市科蓬达电子科技有限公司 | Production process of thermosensitive ceramic |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1477653A (en) * | 2002-07-25 | 2004-02-25 | ������������ʽ���� | Negative characteristic thermosensitive resistor and manufacturing method thereof |
| JP2004104093A (en) * | 2002-07-16 | 2004-04-02 | Murata Mfg Co Ltd | Method for manufacturing negative characteristic thermistor |
| CN1723514A (en) * | 2002-12-09 | 2006-01-18 | 松下电器产业株式会社 | Electronic part with external electrode |
| CN1975940A (en) * | 2006-12-22 | 2007-06-06 | 上海维安热电材料股份有限公司 | NTC thermosensitive resistor and producing method thereof |
| US20100328843A1 (en) * | 2009-06-30 | 2010-12-30 | Murata Manufacturing Co., Ltd. | Laminated ceramic electronic component and manufacturing method therefor |
| WO2014175034A1 (en) * | 2013-04-25 | 2014-10-30 | 株式会社村田製作所 | Multi-layer ceramic capacitor and method for manufacturing same |
| JP2014207254A (en) * | 2013-04-10 | 2014-10-30 | 株式会社村田製作所 | Ceramic electronic part |
-
2015
- 2015-11-12 TW TW104137397A patent/TWI584309B/en active
-
2016
- 2016-01-06 WO PCT/JP2016/050203 patent/WO2016129300A1/en active Application Filing
- 2016-01-06 JP JP2016574684A patent/JP6428797B2/en active Active
- 2016-01-06 CN CN201680008674.3A patent/CN107210106B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004104093A (en) * | 2002-07-16 | 2004-04-02 | Murata Mfg Co Ltd | Method for manufacturing negative characteristic thermistor |
| CN1477653A (en) * | 2002-07-25 | 2004-02-25 | ������������ʽ���� | Negative characteristic thermosensitive resistor and manufacturing method thereof |
| CN1723514A (en) * | 2002-12-09 | 2006-01-18 | 松下电器产业株式会社 | Electronic part with external electrode |
| CN1975940A (en) * | 2006-12-22 | 2007-06-06 | 上海维安热电材料股份有限公司 | NTC thermosensitive resistor and producing method thereof |
| US20100328843A1 (en) * | 2009-06-30 | 2010-12-30 | Murata Manufacturing Co., Ltd. | Laminated ceramic electronic component and manufacturing method therefor |
| JP2014207254A (en) * | 2013-04-10 | 2014-10-30 | 株式会社村田製作所 | Ceramic electronic part |
| WO2014175034A1 (en) * | 2013-04-25 | 2014-10-30 | 株式会社村田製作所 | Multi-layer ceramic capacitor and method for manufacturing same |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2016129300A1 (en) | 2016-08-18 |
| TWI584309B (en) | 2017-05-21 |
| JP6428797B2 (en) | 2018-11-28 |
| JPWO2016129300A1 (en) | 2017-09-14 |
| TW201629994A (en) | 2016-08-16 |
| CN107210106B (en) | 2018-12-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103515480B (en) | Method of manufacturing thick-film electrode | |
| CN102576586B (en) | ESD protection device and method for manufacturing same | |
| JP6184731B2 (en) | Silver-bismuth powder, conductive paste and conductive film | |
| US10074466B2 (en) | NTC component and method for the production thereof | |
| JP2013251256A (en) | Low silver content paste composition, and method of making conductive film from said low silver content paste composition | |
| JP5668837B2 (en) | Electronic component mounting structure | |
| CN107210106B (en) | Negative-characteristic thermistor device and its manufacturing method | |
| KR102225427B1 (en) | Substrate for power module, method for manufacturing same, and power module | |
| CN104081468A (en) | Electroconductive paste for bonding metal terminal, electronic component having metal terminal, and method for manufacturing same | |
| CN108473379A (en) | It is combined with the ceramics of the thick film paste of metal or metal hybrid foil between two parties | |
| US9337355B2 (en) | Voltage nonlinear resistor and multilayer varistor using same | |
| JP6727588B2 (en) | Conductive paste | |
| WO2016186185A1 (en) | Cu paste composition for forming thick film conductor, and thick film conductor | |
| CN103797669B (en) | ESD protective device and manufacture method thereof | |
| JP2010108696A (en) | Resistive paste, and resistor | |
| JP2001118424A (en) | Copper alloy powder for conductive paste | |
| JP5265256B2 (en) | Ceramic wiring board | |
| JP5215914B2 (en) | Resistor film manufacturing method, resistor film, and resistor | |
| CN106876067A (en) | The manufacture method of high conductivity thick film aluminium cream | |
| JP2010010405A (en) | Resistor paste, thick film resistor and method of manufacturing thick film substrate | |
| JP6290131B2 (en) | Conductive paste for glass substrate, method for forming conductive film, and silver conductive film | |
| CN204668039U (en) | Electronic devices and components multilayer alloy electrode | |
| JPH09275002A (en) | Thick-film resistor and chip resistor using the resistor and its manufacture | |
| KR800001624B1 (en) | Air firable base metal condoctors | |
| JP2016054239A (en) | Laminated variable varistor and manufacturing method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |