CN115144439A - Vulcanization detection sensor and method for manufacturing vulcanization detection sensor - Google Patents
Vulcanization detection sensor and method for manufacturing vulcanization detection sensor Download PDFInfo
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- 238000004073 vulcanization Methods 0.000 title claims abstract description 269
- 238000001514 detection method Methods 0.000 title claims abstract description 203
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 238000000034 method Methods 0.000 title description 6
- 239000004020 conductor Substances 0.000 claims abstract description 129
- 239000000758 substrate Substances 0.000 claims abstract description 70
- 230000001681 protective effect Effects 0.000 claims abstract description 42
- 229920005989 resin Polymers 0.000 claims description 22
- 239000011347 resin Substances 0.000 claims description 22
- 230000000873 masking effect Effects 0.000 claims description 20
- 238000007747 plating Methods 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 238000005987 sulfurization reaction Methods 0.000 claims description 7
- 238000009966 trimming Methods 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 230000008878 coupling Effects 0.000 claims description 2
- 238000010168 coupling process Methods 0.000 claims description 2
- 238000005859 coupling reaction Methods 0.000 claims description 2
- 239000011810 insulating material Substances 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 60
- 238000010586 diagram Methods 0.000 description 9
- 239000010949 copper Substances 0.000 description 8
- 229910052946 acanthite Inorganic materials 0.000 description 7
- 238000007650 screen-printing Methods 0.000 description 7
- 229910052709 silver Inorganic materials 0.000 description 7
- XUARKZBEFFVFRG-UHFFFAOYSA-N silver sulfide Chemical compound [S-2].[Ag+].[Ag+] XUARKZBEFFVFRG-UHFFFAOYSA-N 0.000 description 7
- 229940056910 silver sulfide Drugs 0.000 description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000010304 firing Methods 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 239000004332 silver Substances 0.000 description 6
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 238000005486 sulfidation Methods 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N17/00—Investigating resistance of materials to the weather, to corrosion, or to light
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Abstract
The invention provides a vulcanization detection sensor capable of accurately detecting the vulcanization degree. The vulcanization detection sensor includes: a rectangular parallelepiped insulating substrate (2); a pair of surface electrodes (3) formed on both longitudinal ends of the surface of the insulating substrate (2); a vulcanization detection conductor (4) formed at the middle position of the pair of surface electrodes (3); a pair of resistors (5) connected in series between the two surface electrodes (3) through a vulcanization detection conductor (4); and an insulating protective film (6) covering a part of the vulcanization detection conductor (4) and the entire two resistors (5), wherein the vulcanization detection conductor (4) has an exposed portion (4 a) protruding from the insulating protective film (6) to the outside.
Description
Technical Field
The present invention relates to a vulcanization detection sensor for detecting an accumulated vulcanization amount in a corrosive environment and a method of manufacturing such a vulcanization detection sensor.
Background
Generally, as internal electrodes of electronic components such as chip resistors, ag (silver) -based electrode materials having a low specific resistance are used, but silver becomes silver sulfide when exposed to a sulfide gas, and the electronic components are broken due to low conductivity of silver sulfide (increase in specific resistance). In recent years, therefore, sulfidation measures have been taken, such as adding Pd (palladium) or Au (gold) to Ag to form an electrode that is difficult to sulfidize, or making the electrode a structure that is difficult to reach with sulfidation gas.
However, even when these measures for vulcanization are applied to electronic components, it is difficult to completely prevent disconnection when the electronic components are exposed to a vulcanization gas for a long period of time or when the electronic components are exposed to a vulcanization gas at a high concentration. Therefore, as described in patent document 1 (publication No. JP 202112068), a vulcanization detection sensor has been proposed so far, which can detect the degree of accumulated vulcanization of an electronic component and detect a risk before the electronic component fails due to a vulcanization disconnection or the like.
When the thus configured vulcanization detection sensor is mounted on a circuit board together with other electronic components and the circuit board is used in an ambient atmosphere containing a vulcanization gas, ag constituting the vulcanization detection conductor changes to silver sulfide depending on the concentration of the vulcanization gas and the elapsed time, and the conductivity decreases, and the resistance value between the pair of electrodes gradually increases, resulting in disconnection of the electronic component (vulcanization detection sensor). Therefore, the degree of vulcanization can be detected by detecting the resistance value change and the conduction state of the vulcanization detection conductor.
Disclosure of Invention
In such a sulfide detection sensor, metals such as Ag (silver) and Cu (copper) are used as materials of the sulfide detection conductor, and metals such as Ag and Cu are also used as electrode materials, and when the TCR (temperature coefficient of resistance) of the metal is very high and the ratio of the resistance value of the sulfide detection conductor to the resistance value of the entire product becomes large to some extent, the resistance value at the time of sulfide detection fluctuates depending on the ambient temperature, and accurate detection is difficult.
In the vulcanization detection sensor described in patent document 1, since the vulcanization detection conductor and the resistor are connected in series between the pair of electrodes, when the resistance value of the resistor is set to, for example, 1K Ω, the ratio of the resistance value of the resistor to the resistance value of the entire product becomes large, whereas the ratio of the resistance value of the vulcanization detection conductor to the resistance value of the entire product becomes small, and the TCR can be improved. However, in the case where the ratio of the resistance value of the vulcanization detection conductor to the resistance value of the entire product is decreased, even if the vulcanization of the vulcanization detection conductor is increased, the resistance value of the entire product is not substantially changed, and since the vulcanization is determined at the point when the vulcanization detection conductor is hardly in conduction (hereinafter, in the present application, the decrease in the conductivity of the vulcanization detection conductor due to vulcanization and the disconnection of the electronic component due to vulcanization are also collectively referred to as disconnection), it is impossible to detect the sign of disconnection of the electronic component.
The present invention has been made in view of the above-described circumstances of the prior art, and a first object thereof is to provide a vulcanization detection sensor capable of accurately detecting the degree of vulcanization, and a second object thereof is to provide a method for manufacturing such a vulcanization detection sensor.
To achieve the first object, a vulcanization detection sensor according to the present invention includes: a rectangular parallelepiped insulating substrate; a pair of surface electrodes formed on both longitudinal ends of the main surface of the insulating substrate; a vulcanization detection conductor formed between the pair of surface electrodes and made of a material containing a metal vulcanized by a vulcanization gas; a resistor formed so as to be connected to the pair of surface electrodes through the vulcanization detection conductor; a sulfuration gas impermeable insulating protective film formed to cover a part of the sulfuration detection conductor and the whole resistor; the resistor and the vulcanization detection conductor are connected so that a current passing through the vulcanization detection conductor is the shortest path, and the vulcanization detection conductor has an exposed portion exposed to the outside from the insulating protective film.
In the vulcanization detection sensor configured as described above, since the vulcanization detection conductor has an exposed portion exposed to the outside from the vulcanization gas-impermeable insulating protective film in the resistor and the vulcanization detection conductor connected in series between the pair of surface electrodes, when the vulcanization detection conductor is placed in an ambient atmosphere containing a vulcanization gas, vulcanization starts from the exposed portion of the vulcanization detection conductor and proceeds to vulcanization of the vulcanization detection conductor at the portion covered with the insulating protective film. Metals such as silver and copper constituting the vulcanization detection conductor change to silver sulfide and copper sulfide due to vulcanization, and the resistance value of these sulfides rises to several M Ω or more, so that the current path flowing between a pair of electrodes changes as vulcanization progresses, and the resistance value of the entire product gradually increases. Thus, even if the ratio of the resistance value of the vulcanization detection conductor to the resistance value of the entire product is reduced, the sign of the disconnection can be accurately detected based on the continuous change of the resistance value with the progress of vulcanization.
In the vulcanization detection sensor having the above configuration, when the resistor is formed in a belt-like pattern having a meandering portion in a channel shape (a shape like a letter "124676767and the vulcanization detection conductor is formed in a region surrounded by the meandering portion and connected to the resistor, a current path greatly changes as vulcanization proceeds, and the degree of vulcanization can be accurately and easily detected.
In this case, the vulcanization detection conductor has a linking conductor portion extending in the transverse direction of the insulating substrate; and a plurality of connecting conductor portions extending in the longitudinal direction of the insulating substrate, crossing the connecting conductor portions, and having both end portions connected to meandering portions of the resistors; in the case of a configuration in which one end side of the connection conductor portion is an exposed portion, the degree of vulcanization can be detected gradually by breaking a line from the connection conductor portion on the side close to the exposed portion as vulcanization proceeds (the line becomes difficult to flow).
In the vulcanization detection sensor having the above-described configuration, if the resistor has an adjusting portion at a position away from the meandering portion, and a trimming groove for adjusting the resistance value is formed in the adjusting portion, the initial resistance value of the entire product can be set with high accuracy.
In the vulcanization detection sensor having the above configuration, the resistor is formed of the first resistor connected to any one of the surface electrodes and the second resistor connected to any other one of the surface electrodes, and when the vulcanization detection conductor is formed between the first resistor and the second resistor, the current path existing between the first resistor and the second resistor is gradually narrowed as vulcanization progresses, whereby the progress of vulcanization can be detected, and the sign of a broken wire of the electronic component can be accurately detected.
In this case, when the first resistor and the second resistor are formed in an L-shaped pattern that is line-symmetric with respect to a straight line passing through the center portion of the vulcanization detection conductor in the lateral direction of the insulating substrate, the current path greatly changes as vulcanization progresses, and the degree of vulcanization can be accurately and easily detected.
In order to achieve the second object, a method for manufacturing a vulcanization detection sensor according to the present invention includes: a step of forming a pair of surface electrodes having a predetermined interval on a main surface of a large-sized substrate made of an insulating material; a step of forming a pair of back electrodes having a predetermined interval on a face opposite to a main face of the large-sized substrate; forming a vulcanization detection conductor made of a material containing a metal vulcanized by a vulcanization gas and a resistor connected to the pair of surface electrodes through the vulcanization detection conductor between the pair of surface electrodes; forming a sulfuration gas impermeable insulating protective film so as to cover a part of the sulfuration detection conductor and the entire resistor; forming a masking resin layer covering an exposed portion of the vulcanization detection conductor exposed from the insulating protective film; a step of dividing the large-sized substrate into strip-shaped substrates by a first division after the formation of the masking resin layer; forming a pair of end face electrodes on two dividing faces of the strip-shaped substrate to conduct between the front electrode and the back electrode; a step of dividing the strip-shaped substrate into a plurality of chip substrates for the second time after the end-face electrodes are formed; forming a pair of external electrodes covering the end surface electrodes by applying plating to the chip substrate; removing the masking resin layer after the external electrode is formed to expose the exposed portion to the outside; wherein a notch portion having a concave shape in plan view is formed in an outer edge portion of the insulating protective film, and the exposed portion of the vulcanization detection conductor is disposed inside the notch portion.
In this way, when the exposed portion of the vulcanization detection conductor is disposed inside the cut-out portion formed in the insulating protective film and the plating process is performed in a state where the exposed portion is covered with the masking resin layer, peeling of the masking resin layer due to contact between products during the plating process is reduced, and the masking resin layer is removed after the formation of the external electrode, whereby a vulcanization detection sensor capable of accurately detecting a sign of a wire break can be manufactured.
According to the present invention, a vulcanization detection sensor capable of accurately detecting the vulcanization degree can be provided.
Drawings
Fig. 1 is a plan view of a vulcanization detection sensor relating to a first embodiment of the present invention;
FIG. 2 is a cross-sectional view taken along line II-II of FIG. 1;
FIG. 3 is a cross-sectional view taken along line III-III of FIG. 1;
fig. 4 is an explanatory diagram showing a current path accompanying vulcanization of the vulcanization detection sensor;
fig. 5 is an explanatory diagram showing a relationship between elapsed time and a resistance value of the vulcanization detection sensor;
fig. 6 is a plan view of a vulcanization detection sensor relating to a second embodiment of the present invention;
fig. 7 is an explanatory diagram showing a current path accompanying vulcanization of the vulcanization detection sensor;
fig. 8 is an explanatory diagram showing a relationship between elapsed time and a resistance value of the vulcanization detection sensor;
fig. 9 is a plan view of a vulcanization detection sensor relating to a third embodiment of the present invention;
fig. 10 is an explanatory diagram showing a relationship between an elapsed time and a resistance value of the vulcanization detection sensor;
fig. 11 is a plan view of a vulcanization detection sensor relating to a fourth embodiment of the present invention;
fig. 12 is a plan view of a vulcanization detection sensor relating to a fifth embodiment of the present invention;
fig. 13 is a plan view of a vulcanization detection sensor relating to a sixth embodiment of the present invention;
fig. 14 is a plan view showing a manufacturing step of the vulcanization detection sensor;
fig. 15 is a sectional view showing a manufacturing process of the vulcanization detection sensor.
Description of the reference numerals
1, 20, 30, 40, 50, 60 vulcanization detection sensor
2. Insulating substrate
2A large-sized substrate
2B strip-shaped substrate
2C chip-shaped substrate
3. Meter electrode
4. Vulcanization detection conductor
4a exposed part
4b connecting conductor part
4c connecting conductor part
5. Electric resistor
5a meandering section
5b adjustment part
5A first resistor
5B second resistor
6. Insulating protective film
7. Back electrode
8. End face electrode
9. External electrode
10. Base coat
11. Outer coating
11a notch part
41. Trimming trenches
61. Masking resin layer
II-II line
III-III line
Line P
Detailed Description
Hereinafter, embodiments of the present invention will be described with reference to the drawings.
Fig. 1 is a plan view of a vulcanization detection sensor relating to a first embodiment of the present invention, fig. 2 is a sectional view taken along line II-II of fig. 1, and fig. 3 is a sectional view taken along line III-III of fig. 1.
As shown in fig. 1 to 3, the vulcanization detection sensor 1 according to the first embodiment is mainly composed of a rectangular parallelepiped-shaped insulating substrate 2, a pair of front electrodes 3 formed on both ends in the lateral direction of the surface of the insulating substrate 2, a vulcanization detection conductor 4 formed between the front electrodes 3, a pair of resistors 5 formed between the vulcanization detection conductor 4 and one (left side in the figure) front electrode 3 and the other (right side in the figure) front electrode 3, an insulating protective film 6 covering most of the vulcanization detection conductor 4 except for the exposed portion 4a and the pair of resistors 5, a pair of back electrodes 7 formed on both ends in the longitudinal direction of the back surface of the insulating substrate 2, a pair of end electrodes 8 formed on both ends in the longitudinal direction of the insulating substrate 2, and a pair of external electrodes 9 formed on the surfaces of the end electrodes 8.
The insulating substrate 2 is obtained by dividing a sheet-like large-size substrate into longitudinal and transverse dividing grooves, and the main component of the large-size substrate is a ceramic substrate containing alumina as a main component.
The pair of top electrodes 3 are obtained by screen printing an Ag paste containing palladium (Pd) in silver (Ag), drying, and firing, and the top electrodes 3 are formed on both longitudinal ends of the insulating substrate 2 so as to face each other with a predetermined gap therebetween.
The vulcanization detection conductor 4 is obtained by screen printing, drying, and firing a metal vulcanized by a vulcanization gas, for example, an Ag paste mainly composed of silver or a Cu-based paste mainly composed of copper, which is easily vulcanized, and is formed in a rectangular shape in the center portion of the insulating substrate 2.
The pair of resistors 5 are obtained by screen printing a resistor paste such as ruthenium oxide, drying, and firing. Both ends of one resistor 5 are connected to the meter electrode 3 and the vulcanization detection conductor 4 on the left side in the figure, and both ends of the other resistor 5 are connected to the meter electrode 3 and the vulcanization detection conductor 4 on the right side in the figure. That is, a pair of resistors 5 is connected in series between the two right and left meter electrodes 3 via the vulcanization detection conductor 4.
The insulating protective film 6 is configured by 2 layers of an undercoat layer 10 and an overcoat layer 11. The undercoat layer 10 is formed by screen printing a glass paste, drying, and firing, and is formed in a rectangular shape so as to cover the entire pair of resistors 5 and most of the vulcanization detection conductor 4 except for both longitudinal ends (both upper and lower ends in fig. 1). The overcoat layer 11 is formed by screen printing an epoxy paste and heat curing, and is formed in a rectangular shape so as to cover the entire undercoat layer 10. However, the exposed portion 4a of the vulcanization detection conductor 4 is exposed to the outside without being covered with the overcoat 11.
The pair of back electrodes 7 are formed by screen printing Ag paste, drying, and firing, and these back electrodes 7 are formed at positions corresponding to the front electrodes 3 on the front surface side of the insulating substrate 2.
The pair of end face electrodes 8 are formed by sputtering Ni/Cr on the end faces of the insulating substrate 2, and these end face electrodes 8 are formed so as to electrically connect the corresponding front electrode 3 and the back electrode 7.
The pair of external electrodes 9 is constructed of 2 layers of a barrier layer which is a Ni plating layer formed by electroplating and an external connection layer which is an Sn plating layer formed by electroplating. The external electrodes 9 coat a part of the back electrode 7 and the surface of the end face electrode 8.
Fig. 4 is an explanatory diagram showing a current path following vulcanization of the vulcanization detection sensor 1 according to the first embodiment, and fig. 5 is an explanatory diagram showing a relationship between an elapsed time and a resistance value of the vulcanization detection sensor 1.
When the vulcanization detection sensor 1 according to the first embodiment is disposed in the ambient atmosphere containing a vulcanization gas, vulcanization starts at the exposed portion 4a of the vulcanization detection conductor 4 protruding to the outside from the overcoat layer 11 of the insulating protective film 6, and the vulcanization continues toward the vulcanization detection conductor 4 located below the insulating protective film 6 as shown by the black portion in fig. 4 (b). Here, since the silver sulfide and the copper sulfide of the vulcanization detection conductor 4 that change due to vulcanization are the resistance value increase number M Ω or more, the current path flowing between the pair of surface electrodes 3 is in the state shown in fig. 4 (a) before vulcanization of the vulcanization detection conductor 4, and thus changes to the state shown in fig. 4 (b) as the vulcanization of the vulcanization detection conductor 4 progresses. Since the current path changes as the vulcanization proceeds, the resistance value of the vulcanization detection sensor 1 gradually increases with the passage of time as shown in fig. 5.
As described above, in the vulcanization detection sensor 1 according to the first embodiment, since the pair of resistors 5 are connected in series between the pair of surface electrodes 3 via the vulcanization detection conductor 4, and the vulcanization detection conductor 4 has the exposed portion 4a exposed to the outside from the insulating protective film 6 impermeable to the vulcanization gas, when the sensor is disposed in the ambient atmosphere containing the vulcanization gas, vulcanization proceeds from the exposed portion 4a of the vulcanization detection conductor 4 to the vulcanization detection conductor 4 in the portion covered with the insulating protective film 6. Since the silver sulfide and the copper sulfide of the vulcanization detection conductor 4 that change due to vulcanization have resistance values that increase by a number M Ω or more, the resistance value of the vulcanization detection sensor 1 gradually increases as the current path flowing between the pair of gauge electrodes 3 changes as vulcanization progresses. Thus, even when the ratio of the resistance value of the vulcanization detection conductor 4 to the resistance value of the entire vulcanization detection sensor 1 is small, the sign of the wire breakage can be accurately detected based on the continuous change in the resistance value as vulcanization progresses.
Figure 6 is a plan view of a vulcanization detection sensor 20 relating to a second embodiment of the present invention, portions corresponding to fig. 1 are denoted by the same reference numerals, and the end face electrodes 8 and the external electrodes 9 are omitted in the drawings.
As shown in fig. 6, the vulcanization detection sensor 20 according to the second embodiment is basically the same as the vulcanization detection sensor 1 according to the first embodiment except that the resistor 5 is formed in a single stripe pattern having a meandering portion 5a of a channel shape (a shape of "\\124675".
That is, the vulcanization detection sensor 20 according to the second embodiment is configured such that the entire resistor 5 formed between the pair of surface electrodes 3 and a part of the vulcanization detection conductor 4 formed in the meandering portion 5a of the resistor 5 are covered with the insulating protective film 6 impermeable to a vulcanization gas, and the exposed portion 4a of the vulcanization detection conductor 4 is exposed to the outside from the insulating protective film 6.
Fig. 7 is an explanatory diagram showing a current path along with vulcanization of the vulcanization detection sensor 20 according to the second embodiment, and fig. 8 is an explanatory diagram showing a relationship between an elapsed time and a resistance value in the vulcanization detection sensor 20.
When the vulcanization detection sensor 20 according to the second embodiment is disposed in the ambient atmosphere containing a vulcanization gas, vulcanization starts at the exposed portion 4a of the vulcanization detection conductor 4 protruding to the outside from the insulating protective film 6, and proceeds to vulcanization of the vulcanization detection conductor 4 located below the insulating protective film 6 as shown by the black portion in fig. 7 (b). Since the silver sulfide resistance value of the vulcanization detection conductor 4 that changes due to vulcanization increases to a value equal to or greater than M Ω, the current path that flows between the pair of counter electrodes 3 changes from the state shown in fig. 7 (a) before vulcanization of the vulcanization detection conductor 4 to the state shown in fig. 7 (b) as the vulcanization of the vulcanization detection conductor 4 progresses. Since the current path changes as the vulcanization proceeds in this way, as shown in fig. 8, when the resistance value of the vulcanization detection sensor 1 gradually increases with the passage of time, the resistance value of the resistor 5 becomes constant at the point when all of the vulcanization detection conductor 4 is vulcanized.
As described above, in the vulcanization detection sensor 20 according to the second embodiment, the resistor 5 is formed in a belt-like pattern (meandering pattern) having the meandering portion 5a of the channel shape (the shape of a letter of 12467675), and the vulcanization detection conductor 4 is formed so as to be connected to the resistor 5 in the region surrounded by the meandering portion 5a, and when compared with the vulcanization detection sensor 1 according to the first embodiment, since the current path can be changed greatly as vulcanization proceeds, the amount of change in the resistance value becomes larger as vulcanization of the vulcanization detection conductor 4 proceeds, and the degree of vulcanization can be detected accurately and easily.
Fig. 9 is a plan view of a vulcanization detection sensor 30 according to a third embodiment of the present invention, and parts corresponding to fig. 6 are denoted by the same reference numerals.
As shown in fig. 9, in the vulcanization detection sensor 30 according to the third embodiment, the vulcanization detection conductor 4 formed in the meandering portion 5a of the resistor 5 includes a connection conductor portion 4b extending in the transverse direction (vertical direction in the drawing) of the insulating substrate 2 and a plurality of (2 in the present embodiment) connection conductor portions 4c extending in the longitudinal direction (horizontal direction in the drawing) of the insulating substrate 2 so as to intersect with the connection conductor portion 4b, and both end portions of the connection conductor portions 4c are connected to the meandering portion 5a of the resistor 5, and the other configuration is basically the same as that of the vulcanization detection sensor 20 according to the second embodiment.
When the vulcanization detection sensor 30 according to the third embodiment having the above-described configuration is disposed in the ambient atmosphere containing a vulcanization gas, vulcanization starts from the exposed portion 4a of the vulcanization detection conductor 4 protruding to the outside from the insulating protective film 6, and vulcanization proceeds to the coupling conductor portion 4b covered with the insulating protective film 6. Further, since the first connecting conductor portion 4c close to the exposed portion 4a is first disconnected as vulcanization proceeds, and then the second connecting conductor portion 4c is disconnected due to further vulcanization, the path length of the current flowing through the resistor 5 gradually becomes longer, and therefore, when the resistance value of the vulcanization detection sensor 30 increases stepwise with the passage of time as shown in fig. 10, the sign of disconnection can be accurately detected based on the stepwise change in the resistance value as vulcanization proceeds. The number of the connection conductor portions 4c formed in the vulcanization detection conductor 4 may be three or more, and the number of the disconnection steps increases as the number of the connection conductor portions 4c increases.
Fig. 11 is a plan view of a vulcanization detection sensor 40 according to a fourth embodiment of the present invention, and portions corresponding to fig. 6 are denoted by the same reference numerals.
As shown in fig. 11, the vulcanization detection sensor 40 according to the fourth embodiment is basically the same as the vulcanization detection sensor 20 according to the second embodiment except that the resistor 5 has an adjusting portion 5b at a position distant from the meandering portion 5a, and a trimming groove 41 for adjusting the resistance value is formed in the adjusting portion 5 b. The trimming groove 41 is formed in the adjusting portion 5b by irradiating a laser beam onto the upper side of the undercoat layer 10 made of a glass material, and after the trimming groove 41 is formed, the undercoat layer 10 is covered with the overcoat layer 11 made of a resin material, whereby the insulating protective film 6 having a 2-layer structure including the undercoat layer 10 and the overcoat layer 11 is formed.
In the vulcanization detection sensor 40 of the fourth embodiment having the above-described configuration, similarly to the vulcanization detection sensor 20 of the second embodiment, since the resistor 5 is formed in a belt-like pattern having the meandering portion 5a of the tunnel shape and the vulcanization detection conductor 4 is formed so as to be connected to the resistor 5 in the region surrounded by the meandering portion 5a, the amount of change in the resistance value increases with vulcanization of the vulcanization detection conductor 4, and the degree of vulcanization can be accurately and easily detected. Further, since the resistor 5 has the adjusting portion 5b for fine adjustment separately from the meandering portion 5a, the initial resistance value of the resistor 5 can be set with high accuracy.
Fig. 12 is a plan view of a vulcanization detection sensor 50 according to a fifth embodiment of the present invention, and portions corresponding to fig. 6 are denoted by the same reference numerals.
As shown in fig. 12, the vulcanization detection sensor 50 according to the fifth embodiment is basically the same as the vulcanization detection sensor 20 according to the second embodiment except that the resistor connected to the vulcanization detection conductor 4 is divided into 2, the first resistor 5A connected to the top electrode 3 on the left side in the drawing and the second resistor 5B connected to the top electrode 3 on the right side in the drawing are formed in an L-shaped pattern in which the central portion of the vulcanization detection conductor 4 and the straight line P passing through the insulating substrate 2 in the lateral direction are line-symmetrical.
In the vulcanization detection sensor 50 according to the fifth embodiment having such a configuration, since vulcanization is started from the exposed portion 4a of the vulcanization detection conductor 4 protruding outside from the insulating protective film 6 toward the vulcanization detection conductor 4 located below the insulating protective film 6, the current path can be changed greatly as the vulcanization of the vulcanization detection conductor 4 proceeds, and the degree of vulcanization can be detected accurately and easily, as in the vulcanization detection sensor 20 according to the second embodiment. In the vulcanization detection sensor 20 according to the second embodiment, the conductive state of the resistor 5 is maintained even when the entire vulcanization detection conductor 4 is vulcanized, but in the vulcanization detection sensor 50 according to the fifth embodiment, the conduction between the first resistor 5A and the second resistor 5B is interrupted at the time when the entire vulcanization detection conductor 4 is vulcanized.
Fig. 13 is a plan view of a vulcanization detection sensor 60 according to a sixth embodiment of the present invention, and parts corresponding to fig. 6 are denoted by the same reference numerals.
As shown in fig. 13, a vulcanization detection sensor 60 according to the sixth embodiment is basically the same as the vulcanization detection sensor 20 according to the second embodiment except that a recessed notch 11a is formed in a planar view so as to surround an exposed portion 4a of a vulcanization detection conductor 4 in an outer edge portion of an overcoat layer 11 constituting an insulating protective film 6.
The manufacturing process of the thus configured vulcanization detection sensor 60 will be described with reference to fig. 14 and 15. Fig. 14 is a plan view showing a manufacturing process of the vulcanization detection sensor 60, and fig. 15 is a sectional view showing the manufacturing process of the vulcanization detection sensor 60.
First, a large-sized substrate from which a plurality of insulating substrates 2 are obtained is prepared. Lattice-like first sub-dividing grooves and second sub-dividing grooves are provided in advance on this large-sized substrate, the squares cut apart by the two dividing grooves become one chip region by one. In fig. 14 and 15, a large-size substrate 2A corresponding to one chip region is shown as a representative example, but actually, the steps described below are completed at once for a large-size substrate corresponding to a plurality of chip regions.
That is, after the Ag paste is screen-printed on the back surface of the large-size substrate 2A, by drying and firing the same, a pair of back electrodes 7 facing each other with a predetermined gap therebetween is formed on the back surface of the large-size substrate 2A. Next, at the same time or before and after the screen printing of the Ag paste on the surface of the large-size substrate 2A, the Ag paste is dried and fired, and as shown in fig. 14 (a) and 15 (a), a pair of counter electrodes 3 facing each other with a predetermined gap is formed on the surface of the large-size substrate 2A (electrode forming step).
Next, after an Ag-based paste mainly composed of Ag or a Cu-based paste mainly composed of Cu is screen-printed on the surface of the large-sized substrate 2A, it is dried and fired, and as shown in fig. 14 (b) and 15 (b), a rectangular vulcanization detection conductor 4 is formed at the intermediate position between the pair of front electrodes 3 (vulcanization detection conductor forming step).
Next, a resistor paste such as ruthenium oxide is screen-printed on the surface of the large-size substrate 2A, dried, and fired, thereby forming a resistor 5 having a meandering shape with both end portions connected to the pair of surface electrodes 3 as shown in fig. 14 (c) and 15 (c) (a resistor forming step). At this time, the meandering portion 5a of the resistor is connected to the vulcanization detection conductor 4 by overlapping the meandering portion 5a of the channel shape (character "\12467) formed in the resistor 5 with the peripheral edge portion of the vulcanization detection conductor 4.
Next, a glass paste is screen-printed on the surface side of the large-size substrate 2A, dried, and fired to form an undercoat layer 10 covering the entire resistor 5 and a part of the vulcanization detection conductor 4, as shown in fig. 14 (d) and 15 (d). One end of the vulcanization detection conductor 4 protrudes outward without being covered with the undercoat layer 10, and this protruding portion serves as an exposed portion 4a of the vulcanization detection conductor 4.
Next, an epoxy resin paste is screen-printed from above the undercoat layer 10 and heat-cured, whereby an overcoat layer 11 covering the undercoat layer 10 is formed as shown in fig. 14 (e) and 15 (e), and the insulating protective film 6 having a 2-layer structure is formed by the undercoat layer 10 and the overcoat layer 11 (protective film forming step). The overcoat layer 11 has a recessed cutout portion 11a in plan view surrounding the exposed portion 4a of the vulcanization detection conductor 4, and the exposed portion 4a is exposed to the outside without being covered with the overcoat layer 11.
Next, a soluble mask is screen-printed and dried from above the exposed portion 4a, whereby a mask resin layer 61 covering the exposed portion 4a surrounded by the cut-out portion 11a is formed as shown in fig. 14 (f) (mask forming step). Also, the masking resin layer 61 may be in contact with the overcoat layer 11, but care must be taken that the upper side of the masking resin layer 61 is lower than the upper side of the overcoat layer 11.
Next, after the large-size substrate 2A is first divided into the strip-shaped substrate 2B along the first dividing grooves, the end face electrodes 8 connected between the front electrodes 3 and the back electrodes 7 are formed on both end portions of the strip-shaped substrate 11B by sputtering Ni/Cr on the divided surfaces of the strip-shaped substrate 2B as shown in fig. 14 g and 15 g (end face electrode forming step).
Next, after the strip-shaped substrate 2B is divided into a plurality of chip-shaped substrates 2C along the second dividing grooves for the second time, the chip-shaped substrates 2C are subjected to plating (barrel plating) to form external electrodes 9 having a 2-layer structure (Ni plating layer and Sn plating layer) covering a part of the back electrodes 7 and the surfaces of the end-face electrodes 8 as shown in fig. 14 h and 15 h (external electrode forming step). Since this plating is performed while rotating the barrel in which the plurality of chip-like substrates 2C are set, the chip-like substrates 2C are brought into contact with each other during the plating, the overcoat 11 of the insulating protective film 6 is formed so as to surround the masking resin layer 61, and peeling of the masking resin layer 61 is prevented by the overcoat 11.
After the external electrode 9 is formed by the plating treatment in this manner, the chip-shaped substrate 2C is immersed in a solution that does not dissolve the overcoat layer 11 and dissolves only the masking resin layer 61, and the masking resin layer 61 is peeled (removed) to expose the exposed portion 4a (masking removal step). Accordingly, the vulcanization detection sensor 60 shown in fig. 13 is completed.
As described above, according to the method of manufacturing the vulcanization detection sensor 60 according to the sixth embodiment, since the cut-out portion 11a surrounding the exposed portion 4a of the vulcanization detection conductor 4 is formed on the overcoat layer 11 of the insulating protective film 6 and the external electrode 9 is formed by plating in a state where the exposed portion 4a is covered with the masking resin layer 61, peeling of the masking resin layer 61 due to contact between products during plating is reduced, and the masking resin layer 61 is removed after the formation of the external electrode 9, whereby the vulcanization detection sensor 60 capable of accurately detecting the sign of a wire break can be manufactured.
In the vulcanization detection sensor according to each of the above embodiments, the end portion of the vulcanization detection conductor 4 protruding outward from the outer edge portion of the insulating protective film 6 is defined as the exposed portion 4a, but the vulcanization detection conductor 4 having an opening formed in a part of the insulating protective film 6 and exposed in the opening may be defined as the exposed portion 4a.
In the vulcanization detection sensor according to each of the above embodiments, since the insulating protective film 6 has a two-layer structure of the undercoat layer 10 and the overcoat layer 11, the insulating protective film 6 having a vulcanization gas impermeability that is less likely to break can be realized by utilizing the high gas barrier property of glass that is a material of the undercoat layer and the flexibility of resin that is a material of the overcoat layer 11. However, since both the undercoat layer 10 and the overcoat layer 11 have impermeability to a sulfuration gas, the insulating protective film 6 having a single-layer structure can be formed without using any of them.
Claims (7)
1. A vulcanization detection sensor characterized by comprising:
a rectangular parallelepiped insulating substrate; a pair of surface electrodes formed on both longitudinal ends of the main surface of the insulating substrate; a vulcanization detection conductor formed between the pair of surface electrodes and made of a material containing a metal vulcanized by a vulcanization gas; a resistor formed so as to be connected to the pair of surface electrodes through the vulcanization detection conductor; a vulcanization-gas impermeable insulating protective film formed so as to cover a part of the vulcanization detection conductor and the entire resistor; the resistor and the vulcanization detection conductor are connected so that a current passing through the vulcanization detection conductor is the shortest path, and the vulcanization detection conductor has an exposed portion exposed to the outside from the insulating protective film.
2. The vulcanization detection sensor of claim 1, wherein said resistor is formed in a belt-like pattern having a meandering portion in a channel shape, and said vulcanization detection conductor is formed in a region surrounded by said meandering portion and connected to said resistor.
3. The cure detection sensor of claim 2, wherein the cure detection conductor comprises: a coupling conductor portion extending in a transverse direction of the insulating substrate; and a plurality of connection conductor portions extending in a longitudinal direction of the insulating substrate so as to intersect the connection conductor portions and having both end portions connected to the meandering portions, wherein one end side of the connection conductor portion is the exposed portion.
4. The vulcanization detection sensor according to claim 2 or 3, wherein the resistor has an adjustment portion at a position away from the meandering portion, and a trimming groove for adjusting the resistance value is formed in the adjustment portion.
5. The vulcanization detection sensor of claim 1, wherein said resistor is formed of a first resistor connected to any one of said meter electrodes and a second resistor connected to any other one of said meter electrodes, and said vulcanization detection conductor is formed between said first resistor and said second resistor.
6. The vulcanization detection sensor according to claim 5, wherein said first resistor and said second resistor are formed in an L-shaped pattern that is line-symmetrical with respect to a straight line that passes through a central portion of said vulcanization detection conductor in a lateral direction of said insulating substrate.
7. A method of manufacturing a vulcanization detection sensor, comprising:
a step of forming a pair of surface electrodes having a predetermined interval on a main surface of a large-sized substrate made of an insulating material;
a step of forming a pair of back electrodes having a predetermined interval on a surface opposite to a main surface of the large-size substrate;
forming a vulcanization detection conductor made of a material containing a metal vulcanized by a vulcanization gas and a resistor connected to the pair of surface electrodes through the vulcanization detection conductor between the pair of surface electrodes;
forming a sulfuration gas impermeable insulating protective film so as to cover a part of the sulfuration detection conductor and the entire resistor;
forming a masking resin layer covering an exposed portion of the vulcanization detection conductor exposed from the insulating protective film;
a step of dividing the large-sized substrate into strip-shaped substrates by a first division after the formation of the masking resin layer;
forming a pair of end face electrodes on two dividing faces of the strip-shaped substrate to conduct between the front electrode and the back electrode;
a step of dividing the strip-shaped substrate into a plurality of chip substrates for the second time after the end-face electrodes are formed;
forming a pair of external electrodes covering the end surface electrodes by applying plating to the chip substrate;
removing the masking resin layer after the external electrode is formed to expose the exposed portion to the outside;
wherein a notch portion having a concave shape in plan view is formed in an outer edge portion of the insulating protective film, and the exposed portion of the vulcanization detection conductor is disposed inside the notch portion.
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| JP2021-057233 | 2021-03-30 | ||
| JP2021057233A JP2022154283A (en) | 2021-03-30 | 2021-03-30 | Sulfuration detection sensor and method for manufacturing the same |
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