JP2001124720A - Manufacturing method of chip-shaped moisture-sensing element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the manufacturing method of a chip-shaped moisture- sensing element that can be mounted onto the surface of an electronic circuit board without changing the characteristics of a macromolecular moisture-sensing film. SOLUTION: In the manufacturing method of a chip-shaped moisture-sensing element that has a macromolecular moisture-sensing film between a pair of electrodes, and an end part electrode for soldering for mounting onto the surface of an electronic circuit board, when metal or alloy plating for improving a soldering property is made to the end electrode, the plating is carried out while a conductor part where the pair of electrodes is included, and a part other than the end part electrode is exposed is being protected by resist.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a moisture-sensitive element in the form of a chip-shaped electronic component which can be surface-mounted on an electronic circuit board.

[0002]

2. Description of the Related Art As a humidity sensing element for sensing humidity and dew condensation,
There is a moisture-sensitive element using a polymer-based moisture-sensitive film, and specific examples of the mode of the moisture-sensitive film include the following. The first uses a change in electrical resistance in which conductive particles are dispersed in a hygroscopic polymer, the second uses a change in ionic conductivity due to dissociation of an ionic substance by water adsorption, and the third uses It utilizes the change in the dielectric constant due to the adsorption of moisture.

Conventionally, a moisture-sensitive element using a polymer-based moisture-sensitive film has been inserted and mounted in an electronic circuit via a lead wire as disclosed in Japanese Patent Application Laid-Open No. 9-5274.

[0004] More specifically, these moisture-sensitive elements are made of a conductive oxide such as ruthenium oxide on an alumina substrate.
It has a structure in which a polymer moisture-sensitive film is formed on a comb-shaped electrode pattern made of a metal such as gold or carbonaceous particles such as carbon black, and a lead wire is usually taken out from the end of the alumina substrate. ing. When mounting on an electronic circuit board, the lead wire is inserted into the electronic circuit board and mounted.

As described above, a conventional moisture-sensitive element using a polymer-based moisture-sensitive film requires a lead wire to be mounted on an electronic circuit board, thus increasing the cost. Also, with the miniaturization of electronic devices, the space allowed for moisture-sensitive elements is also limited. Therefore, a moisture-sensitive element in the form of a chip-shaped electronic component that can be surface-mounted on an electronic circuit board is desired.

In the manufacturing process of the chip-shaped electronic component, there is a silver electrode baking process for forming an end electrode. However, since the baking is performed at about 800 ° C., an organic polymer material is decomposed. For this reason, it is not possible to bake the silver electrode after forming the polymer-based moisture-sensitive film in advance. In addition, an end electrode for soldering to the electronic circuit board is plated with solder, tin, gold, or the like to avoid poor soldering.
Plating is performed by a method such as barrel plating. However, if the moisture-sensitive film is formed first, there is a high risk that the moisture-sensitive film contacts the electrolytic solution for plating to change the characteristics. Also,
If barrel plating is performed on an electrode substrate on which a moisture-sensitive film is not formed, solder, tin, etc. will precipitate on the comb electrode, or if a conductive oxide such as ruthenium oxide is used for the comb electrode, reduction will occur. As a result, the electrode pattern is damaged. Also, if the end electrodes are solder-plated or tin-plated before forming the comb-shaped electrodes, the solder or tin will melt when the comb-shaped electrodes are baked.

[0007] As described above, it is difficult to form a chip-shaped electronic component from a moisture-sensitive element, which must form a moisture-sensitive film on the element surface which is susceptible to heat and contamination, due to various restrictions in manufacturing.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide a chip-shaped moisture-sensitive element in the form of a chip-shaped electronic component that can be surface-mounted on an electronic circuit board without changing the characteristics of a polymer-based moisture-sensitive film. It is to provide a manufacturing method.

[0009]

The above object is achieved by the present invention described below. (1) A method for manufacturing a chip-shaped moisture-sensitive element having a polymer-based moisture-sensitive film between a pair of electrodes and having an end electrode for soldering for surface mounting on an electronic circuit board, When plating a metal or alloy to improve solderability on the end electrodes, the plating is performed in a state that includes the pair of electrodes and protects exposed conductors other than the end electrodes with resist. A method for producing a chip-shaped moisture-sensitive element. (2) The method for manufacturing a chip-shaped moisture-sensitive element according to the above (1), wherein the plating of metal or alloy for improving the solderability is plating of solder, tin or gold. (3) After forming the pair of electrodes, the end electrode is subjected to the plating to remove the resist, and thereafter, the polymer-based moisture-sensitive film is provided with the chip-shaped moisture-sensitive element according to the above (1) or (2). Manufacturing method. (4) The polymer-based moisture-sensitive film is obtained by dispersing conductive particles in a hygroscopic polymer, and the hygroscopic polymer is selected from the following i) to vi): The method for producing a chip-shaped moisture-sensitive element according to any one of (1) to (3). i) A polymer of a polyetheramine having two or more amino groups and an epoxy compound having two or more epoxy groups and further having an ether bond. ii) A polymer of a polyetheramine having two or more amino groups, an epoxy compound having two or more epoxy groups, and further having an ether bond, and a water-soluble nylon. iii) A mixture of a polymer of a polyetheramine having two or more amino groups, a polymer of an epoxy compound having two or more epoxy groups, and further having an ether bond, and water-soluble nylon. iv) Polyetheresteramide. v) A polymer of polyetheresteramide, water-soluble nylon, and an epoxy compound having two or more epoxy groups. vi) Mixture of polyetheresteramide and water-soluble nylon. (5) The method for producing a chip-shaped moisture-sensitive element according to the above (4), wherein the polyether skeleton of the polyetheramine is propylene oxide and / or ethylene oxide. (6) The method for producing a chip-shaped moisture-sensitive element according to the above (4) or (5), wherein the polyetheramine has two or three primary amino groups at a terminal. (7) The polyetheramine has a molecular weight of 100 to 5
(4) The method for producing a chip-shaped moisture-sensitive element according to any one of the above (4) to (6). (8) The method for producing a chip-shaped moisture-sensitive element according to any one of the above (4) to (7), wherein the epoxy compound is represented by the following formula (1).

[0010]

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[In the formula (1), A represents a divalent to tetravalent aliphatic saturated hydrocarbon group, an aliphatic ether group or a heterocyclic group, and k is an integer of 2 to 4. (9) The method according to any one of the above (4) to (8), wherein the amine value and the epoxy value of the hygroscopic polymer are 1: 1 to 1: 4. (10) The polyetheresteramide has the following formula (2)
(4) The method for producing a chip-shaped moisture-sensitive element according to the above (4).

[0012]

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[In the formula (2), R represents 2 to 12 carbon atoms.
Represents an alkylene group, m is an integer of 6 to 12, and n
Is an integer of 1 to 4, p is an integer of 1 to 70, q
Is an integer of 5 to 200, and r is an integer of 3 or more. (11) In the above formula (2), m is 11 and n
The method for producing a chip-shaped moisture-sensitive element according to the above (10), wherein is 2. (12) The method for producing a chip-shaped moisture-sensitive element according to any one of the above (4) to (11), wherein the water-soluble nylon has an ether structure. (13) The method for producing a chip-shaped moisture-sensitive element according to the above (12), wherein the water-soluble nylon comprises a structural unit represented by the following formula (3) and / or a structural unit represented by the following formula (4).

[0014]

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[0015]

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[In the formula (3), R ₁ has 2 to 4 carbon atoms.
Represents an alkylene group. (14) The water-soluble nylon is used in an amount of 0.1 to 0.1% based on the total weight of the polyetheramine and the epoxy compound or the weight of the polyetheresteramide.
The method for producing a chip-shaped moisture-sensitive element according to any one of the above (4) to (13), which is 50 wt%. (15) The conductive particles have a specific surface area of 30 to 300 m ² / g.
The method for producing a chip-shaped moisture-sensitive element according to any one of the above (4) to (14), which is carbon black.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The chip-shaped moisture-sensitive element obtained by the present invention has a polymer-based moisture-sensitive film between a pair of electrodes and is used by being surface-mounted on an electronic circuit board. It has an end electrode for attaching.

At the time of the above-mentioned soldering, in order to improve the solderability and avoid poor soldering, the above-mentioned end electrodes are plated with a metal or alloy such as solder plating, tin plating or gold plating. Such plating is performed by barrel plating or the like.At this time, since the exposed conductors other than the end electrodes to be plated are protected by resist, plating is applied to the conductors other than the end electrodes to be plated. Can be prevented. The conductors other than the end electrodes are mainly the pair of electrodes, and the polymer-based moisture-sensitive film is usually provided so as to cover, for example, a pair of comb-shaped electrodes that are a pair of electrodes. Due to the presence of the resist, a metal or alloy is deposited on the comb-shaped electrode portion where the polymer-based moisture-sensitive film is formed, or is contaminated by the electrolytic solution in the plating bath. When the conductive oxide is used, the conductive oxide is reduced and the electrode pattern can be prevented from being damaged. Then, after plating, the resist is removed, and thereafter, formation of the polymer-based moisture-sensitive film can be performed without any trouble. Further, since the polymer-based moisture-sensitive film is formed after the plating, it is possible to prevent the polymer moisture-sensitive film from being contaminated by the electrolytic solution in the plating bath and changing the characteristics of the moisture-sensitive film.

The moisture-sensitive element according to the manufacturing method of the present invention is not limited as long as it has a moisture-sensitive film between a pair of electrodes and is in the form of a chip-shaped electronic component. Good.

As shown in FIG. 1, the chip-shaped moisture-sensitive element 1 has a pair of comb-shaped electrodes 4 on an insulating substrate 2, and the pair of comb-shaped electrodes 4 are engaged with each other via a gap 5 at a fixed distance. It is arranged on the insulating substrate 2. And the insulating substrate 2
The moisture-sensitive film 3 is provided on the comb-shaped electrode 4 as shown in the figure. The comb-shaped electrode 4 is connected to the electrode 8 in the form of teeth of a comb.

On the lower surface of the insulating substrate 2, there are provided a pair of electrodes 6 for making an electrical connection with the electronic circuit substrate. Further, an end face electrode 7 for establishing electrical conduction between the electrode 6 and the electrode 8 is formed on the end face. That is, the electrodes 6, 8
And the end face electrode 7 constitute an end electrode, and the end electrode is
An electrical connection is made between the sensor portion including the moisture sensitive film 3 of the moisture sensitive element 1 and the electronic circuit board. An electrode 6 constituting an end electrode,
The outermost surface portions of the electrode 8 and the end electrode 7 are plated with a metal or an alloy for improving solderability so as to be surely surface-mounted on the electronic circuit board.

The shape of the chip-shaped moisture-sensitive element 1 is a rectangular parallelepiped or a cube, and the size is 5 mm square or less (usually 0.3 mm or less).
(mm square or more), and the height is preferably 1 mm or less (usually 0.3 mm or more).

Referring to FIG. 1, as the insulating substrate 2 used in the present invention, any material can be used as long as it has good adhesion to the moisture sensitive film 3 and has electrical insulation. Well, for example, glass or epoxy resin,
A heat-resistant plastic such as polyimide or BT resin, a ceramic such as alumina, or a metal coated with insulation is used.

The comb-shaped electrode 4 is not particularly limited as long as it is commonly used, and contains carbon particles such as Au, RuO ₂ , carbon black and graphite, and further contains glass frit as required. High-temperature sintering of a low-resistance paste or the like can be used. Also, A
If it is a metal such as u, the electrode pattern can be formed by vapor deposition. In this case, the gap between the electrodes can be reduced, and the resistance value of the moisture-sensitive element can be reduced. The gap between the electrodes is usually 0.05
About 1 mm.

The electrodes 6, 7, 8 may be formed by screen printing using, for example, a silver-palladium alloy or the like.

The following method is used as an example of the method for manufacturing the chip-shaped moisture-sensitive element of the present invention.

Taking the case where an alumina substrate is used as an insulating substrate as an example, as shown in FIG. 2, a division groove 10 is formed in an alumina substrate 9. In order to finally have the form of FIG.
For example, the electrodes 6 and 8 are screen-printed and baked with an Ag-Pd alloy. The comb-shaped electrode 4 is screen-printed with a conductive paste such as ruthenium oxide and baked. The primary division of the alumina electrode substrate on which the electrodes are formed is performed to obtain the strip 11 (FIG. 2). A conductor 12 is formed on the side surface in the same manner as the electrodes 6 and 8 using, for example, a silver-palladium alloy, and the electrodes 6 and 8 are electrically connected. Next, secondary division is performed to obtain individual products 13 (FIG. 2). In FIG. 2, the electrodes are not shown.

The individual electrode substrates are arranged on a pallet. It is also possible to put a mark on one side of the electrode substrate so that the electrode substrates made individually on the pallet can be automatically arranged with their front and back aligned.

In order to prevent the metal or alloy from depositing on the three portions of the comb-shaped electrode and depositing the metal or alloy only on the electrodes 6, 7, and 8, the three-part comb-shaped electrode is covered with a resist. After plating of metal or alloy by a method such as barrel plating, the resist is removed.

Arrange them on a pallet and screen-print the moisture-sensitive paste. By curing, the moisture-sensitive film 3 is formed.
In this manner, a chip-shaped moisture-sensitive element in which the comb-shaped electrode 3 is not plated with a metal or an alloy, is not contaminated with a plating solution (electrolyte), or the pattern of the comb-shaped electrode 3 is not damaged. can get.

In the present invention, the metal or alloy plating for improving the solderability is solder plating, tin plating, gold plating, or the like. These platings are preferably performed by barrel plating as described above. Any method may be used. Generally, electroplating is preferred. Electroplating may be performed according to a usual method, and a pretreatment (polishing,
Cleaning by acid immersion or degreasing), plating bath composition, electrolysis conditions, and the like also follow known methods.

As the resist, any known resist may be used, and some resists are cured by heat and others are dried by heat. For example, epoxy resin, acrylic resin, cinnamic acid resist, rubber resist, o-
It is preferable to use a mixed system of a naphthoquinonediazide compound and a cresol novolak resin, and a commercially available product (for example, MA-830 manufactured by Taiyo Ink Mfg. Co., Ltd.) can be used. A coating film (preferably a printing film) of such a resin is formed, cured or dried at a temperature of about 80 to 200 ° C. for a time of about 10 to 180 minutes, and used as a resist. In order to obtain the effect as a resist, the film thickness after curing or drying is preferably 1 to 50 μm.

The resist can be removed by chemical etching, and an acid or alkali solution is used. Specifically, a normal method is used.

The moisture-sensitive film used in the present invention may be of any type as long as its physical quantity such as electric resistance and dielectric constant changes with changes in humidity. One that uses the change in electric resistance value by dispersing conductive particles such as black, one that uses the change in ionic conductivity of a porous ceramic or a polymer electrolyte containing a quaternary ammonium salt, Those utilizing changes in the dielectric constant such as molecules are used.

In particular, in the present invention, it is preferable to use a moisture-sensitive film in which conductive particles are dispersed in a hygroscopic polymer, and any of the following i) to iv) is preferably used as the hygroscopic polymer. preferable.

I) a polyetheramine having two or more amino groups, and a polyetheramine having two or more epoxy groups,
A polymer with an epoxy compound having an ether bond. ii) A polymer of a polyetheramine having two or more amino groups, an epoxy compound having two or more epoxy groups, and further having an ether bond, and a water-soluble nylon. iii) A mixture of a polymer of a polyetheramine having two or more amino groups, a polymer of an epoxy compound having two or more epoxy groups, and further having an ether bond, and water-soluble nylon. iv) Polyetheresteramide. v) A polymer of polyetheresteramide, water-soluble nylon, and an epoxy compound having two or more epoxy groups. vi) Mixture of polyetheresteramide and water-soluble nylon.

These are excellent in heat resistance and are unlikely to be denatured by heat (temperature of about 150 to 300 ° C.) during soldering.

First, the above hygroscopic polymers i) to iii) will be described. The hygroscopic polymer is a polymer of a polyetheramine having two or more amino groups and an epoxy compound having two or more epoxy groups and further having an ether bond. Or a polyetheramine having two or more amino groups, an epoxy compound having two or more epoxy groups, and further having an ether bond,
It is a polymer with water-soluble nylon. Alternatively, the hygroscopic polymer has a polyetheramine having two or more amino groups, a polymer having two or more epoxy groups, and an epoxy compound having an ether bond, and a water-soluble nylon. It may be a mixture. Further, both may be mixed. It is preferable that the water-soluble nylon also has an ether bond and has enhanced hydrophilicity. Usually, it is considered that polyetheramine, epoxy compound and water-soluble nylon are copolymerized.

The above-mentioned hygroscopic polymer used in the present invention begins to absorb moisture in a humidity region of less than 90% RH, particularly 60% RH or more and less than 90% RH. Instead, humidity in a low humidity region of less than 90% RH can be detected. In particular, the humidity-sensitive element of the present invention has a
Humidity in an area of 100% RH can be detected.

Further, since the amount of moisture absorption is as large as 10 to 20 wt%, the filling amount of the conductive particles can be large, and stable resistance / humidity characteristics can be obtained. It is considered that the hygroscopicity of the hygroscopic polymer used in the present invention is mainly expressed by an ether bond (-O-), and an amino group and a hydroxyl group also contribute. If the water-soluble nylon also has an ether bond, the moisture absorption increases accordingly. The resistance value of the moisture sensitive element of the present invention when dried is 400Ω.
Sufficient characteristics can be stably obtained with a resistance value change of about 4 to 6 digits.

In addition, the humidity sensitive element of the present invention has extremely stable resistance humidity characteristics even when repeatedly exposed to a dry atmosphere and a high humidity atmosphere, and its change is extremely small.

Further, even when exposed to a high-temperature and high-humidity atmosphere for a long time, the change in resistance-humidity characteristics is extremely small. In particular, from such a viewpoint, it is preferable to use a polymer of a polyetheramine and an epoxy compound and a water-soluble nylon, or a mixture of a polymer of a polyetheramine and an epoxy compound and a water-soluble nylon as the hygroscopic polymer. .

In addition, since a moisture-sensitive film in which conductive particles are dispersed in a hygroscopic polymer is used, direct current measurement is possible.
The measurement circuit can be simplified and the cost is low.

First, the polyetheramine used for the hygroscopic polymer will be described. The polyetheramine refers to a polyoxyalkyleneamine and is a compound containing a primary amino group at a terminal of a polyether skeleton.

The polyether skeleton may be any of alkylene oxides, but is preferably propylene oxide (PO), ethylene oxide (EO) or mixed EO / PO. In the case of mixed EO / PO, EO / PO is arbitrary, but the larger the EO / PO, the lower the humidity can be detected. E
If it has an O skeleton, it is completely dissolved in water, and if it has only an EO skeleton, it is much more reactive than the others. When the EO skeleton is used, the resistance value increases due to low humidity.
Stability against repeated operations tends to decrease.

The number of terminal amino groups is 2 or more, preferably 2
It is preferable to have up to three. That is, diamines and triamines are preferred.

The molecular weight of the polyetheramine is 1
It is preferably from 00 to 5000, particularly preferably from 100 to 2000. If the molecular weight is too large, the resistance value tends to increase from higher humidity. When a mixture is used, the number average molecular weight (Mn) is preferably in the above range.

The diether polyetheramine is synthesized by reacting a dihydric alcohol with an alkylene oxide, preferably propylene oxide and / or ethylene oxide, and then converting the terminal hydroxy group to an amino group. Examples of the diol include ethylene glycol and propylene glycol.

The triamine polyetheramine is synthesized by reacting an initiator triol with an alkylene oxide, preferably propylene oxide, and then converting the terminal hydroxy group to an amino group. Examples of the initiator triol include trimethylolpropane, glycerin and the like.

The total amine value of the polyetheramine used is preferably from 0.3 to 15 meq / g, particularly preferably from 2 to 10 meq / g.
/ G is preferred. It is preferred that 95% or more thereof is a primary amine. If the amine value is larger than this, the crosslink density becomes excessively high, so that the water absorption decreases, and the sensitivity tends to decrease. If it is smaller than this, the degree of crosslinking tends to be low, and the water resistance tends to decrease.

The flash point of the polyetheramine used in the present invention is preferably 100 ° C. or higher, particularly preferably 120 to 300 ° C. If the flash point is lower than this, it becomes difficult to obtain sufficient safety.

Polyetheramine has a water content of 0.5% by weight.
Or less, preferably 0.25 wt% or less.

Examples of such polyetheramines include polyoxymethyleneamine, polyoxyethyleneamine represented by the following formula (5), and polyoxypropyleneamine represented by the following formulas (6) and (7). And polyoxyethylene propylene amine represented by the following formula (8). Further, these derivatives may be used. One kind of polyetheramine may be used alone, or two or more kinds may be used in combination. When two or more kinds are used in combination, the quantitative ratio is arbitrary.

[0054]

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[0055]

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[0056]

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[0057]

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X in the expressions (5) to (7) and a, b and c in the expression (8) are arbitrary integers. A in the formula (7) represents a trivalent aliphatic saturated hydrocarbon group, an aliphatic ether group or a heterocyclic group, and specific examples thereof include the same as the trivalent ones in the formula (1). Can be.

The polyetheramine used in the present invention is commercially available. Examples of polyoxypropylenediamine include Jeffamine D-230, 40 manufactured by Texaco Chemical Co., Ltd.
0, 2000, 4000 etc., as polyoxyethylene diamine, Texaco Chemical Jeffamine EDR-148 etc., and as polyoxyethylene propylene diamine Texaco Chemical Jeffamine ED-600, 900, 2003
Examples of polyoxypropylene triamines include Jeffamine T-403, 3000, and 5000 manufactured by Texaco Chemical Company.

Next, the epoxy compound used for the hygroscopic polymer will be described. The epoxy compound used in the present invention has two or more, preferably two to four epoxy groups, and further has an ether bond. By having an ether group, hydrophilicity is enhanced.

The epoxy group is preferably 1,2-epoxide, but may be 1,3-epoxide, 1,4-epoxide, 1,5-epoxide, or the like.

Among them, those having 2 to 4 glycidyl groups are preferable, and epoxy compounds represented by the following formula (1) are particularly preferable.

[0063]

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In the formula (1), A represents a divalent to tetravalent saturated aliphatic hydrocarbon group, an aliphatic ether group or a heterocyclic group. The carbon chain may have a branch, and may be substituted with a hydroxyl group or the like. k is an integer of 2 to 4. Specifically, the following are mentioned.

[0065]

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Here, n is an integer of 1 to 4.

Examples of such an epoxy compound having an ether structure include sorbitol polyglycidyl ether, sorbitan polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, triglycidyl tris (2 -Hydroxyethyl) isocyanurate, glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, neopentyl glycol diglycidyl ether,
Examples thereof include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether. Further, these derivatives may be used. One epoxy compound may be used alone, or two or more epoxy compounds may be used in combination. When two or more kinds are used in combination, the quantitative ratio is arbitrary.

The epoxy compound used in the present invention is commercially available. Examples of the sorbitol polyglycidyl ether include Denacol EX-611, 612, 614, 61 manufactured by Nagase Kasei.
4B etc., as sorbitan polyglycidyl ether, Nagase Kasei Denacol EX-651, 651A etc., as polyglycerol polyglycidyl ether, Nagase Kasei Denacol EX-512, 521 etc., and as pentaerythritol polyglycidyl ether, Nagase Kasei. Denacol EX-4
11 etc., as the diglycerol polyglycidyl ether, Nagase Kasei Denacol EX-421 etc., as the triglycidyl tris (2-hydroxyethyl) isocyanurate, Nagase Kasei Denacol EX-301 etc., as the glycerol polyglycidyl ether, Nagase Kasei Denacol EX-313, 314, etc., as a trimethylolpropane polyglycidyl ether, Nagase Kasei Denacol EX-321
As for neopentyl glycol diglycidyl ether, Nagase Kasei Denacol EX-211 etc., as ethylene glycol diglycidyl ether, Nagase Kasei Denacol EX-810, 811 etc., and as polyethylene glycol diglycidyl ether, Nagase Kasei Denacol EX
-850, 851, 821, 830, 832, 841, 861 etc., as propylene glycol diglycidyl ether, Nagase Kasei Denacol EX-911 etc., as polypropylene glycol diglycidyl ether, Nagase Kasei Denacol EX-9.
There are 41, 920, 921, 931 and so on.

The epoxy equivalent of the epoxy compound used in the present invention is preferably 50 to 700 WPE, particularly preferably 100 to 250 WPE. If the epoxy equivalent is larger than this, the crosslink density becomes excessively high, so that the water absorption decreases, and the sensitivity tends to decrease. If it is smaller than this, the degree of crosslinking tends to decrease, and the water resistance tends to decrease.

The water solubility of the epoxy compound used in the present invention is preferably 15 to 100%, particularly preferably 20 to 100%. If the water solubility is lower than this, the detectable humidity becomes high and may become 90% RH or more. Here, the water solubility refers to 90 parts by weight of water at 25 ° C.
It refers to the dissolution rate when parts by weight are dissolved.

The flash point of the epoxy compound used in the present invention is preferably 90 ° C. or more, particularly preferably 120 to 300 ° C. If the flash point is lower than this, it becomes difficult to obtain sufficient safety.

The epoxy compound is preferably chlorine or the like.
It may contain 5 wt% or less, more preferably 15 wt% or less.

Next, the water-soluble nylon used for the hygroscopic polymer will be described. The water-soluble nylon used in the present invention preferably has an ether bond, and in particular, the structural unit represented by the following formula (3) and / or the following formula (4)
What consists of a structural unit represented by these is preferable.

[0074]

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[0075]

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In the formula (3), R ₁ represents an alkylene group having 2 to 4 carbon atoms, particularly preferably an ethylene group having 2 carbon atoms.

The degree of polymerization of the water-soluble nylon is preferably from 5 to 100, particularly preferably from 10 to 50.

The ratio of the structural unit represented by the formula (3) to the structural unit represented by the following formula (4) is calculated based on 100 parts by weight of the structural unit represented by the formula (3). The structural unit represented by the formula (4) is preferably 50 parts by weight or less, particularly preferably 10 parts by weight or less. In the present invention, a homopolymer having only the structural unit represented by the formula (3) may be used.

The water solubility of the water-soluble nylon used is water 10
It is preferable to dissolve 1 part or more, especially 10 parts or more based on 0 parts by weight. If the water solubility is lower than this, the moisture absorption of the moisture-sensitive film tends to decrease, and the sensitivity tends to decrease.

Such a water-soluble nylon is obtained by subjecting a polyalkylene glycol to cyanoethylation and hydrogenation to form a diamine, and reacting 1 mol of the diamine with adipic acid, that is, a so-called nylon salt, with caprolactam. Can be Specifically, Japanese Patent Application Laid-Open No. Sho 60-2
What is necessary is just to synthesize | combine according to 47440 gazettes.

The structural unit represented by the above formula (3) and / or
Alternatively, a water-soluble nylon comprising the structural unit represented by the above formula (4) is commercially available as Toray P-70, Toray A-90, or the like.

The polymerization of the polyetheramine, the epoxy compound and the water-soluble nylon is carried out by adding the water-soluble nylon to alcohol or water in an amount of 0.1 to 60% by weight, preferably 0.5 to 3% by weight.
0% by weight, and a polyetheramine and an epoxy compound are added in a total amount of 10 to 80% by weight, preferably 30 to 80% by weight.
60% by weight and dispersed, 80-180 ° C,
Heating may be performed preferably at 120 to 160 ° C. for 30 minutes to 3 hours, preferably 60 minutes to 2 hours. As a dispersion medium,
Ethyl cellosolve, ethylene glycol and the like are preferred.
The polymerization conditions are appropriately selected depending on the water-soluble nylon, polyetheramine and epoxy compound used, and are not limited to the above conditions. In addition, as will be described later, usually, conductive particles are also added to the dispersion medium, coated, and then heated to polymerize.

The polymer produced is generally considered to be a polymer obtained by graft-polymerizing a polyetheramine and an epoxy compound on water-soluble nylon. At this time, nylon is not polymerized, and may be a mixture of a polymer of polyetheramine and an epoxy compound.

The polymerization for obtaining a polymer of a polyetheramine and an epoxy compound may be carried out in the same manner as described above except that no water-soluble nylon is added.

The composition of the polyetheramine and the epoxy compound having an ether structure preferably has an amine value and an epoxy value of 1: 1 to 1: 4, particularly equal amounts, from the viewpoint of characteristic stability. It is also possible to control the resistance / humidity characteristic by shifting the composition from the equivalent amount. In a composition in which the amount of the amine is excessive, the resistance value increases at lower humidity, but the characteristic stability tends to decrease.

The water-soluble nylon is used in an amount of 0.1 to 50 wt% based on the total weight of the polyetheramine and the epoxy compound.
%, Particularly preferably 1 to 10% by weight. If the amount of the water-soluble nylon is more than this, the resistance value tends to gradually decrease when exposed to a high-temperature and high-humidity atmosphere for a long time. If the amount of water-soluble nylon is less than this, the resistance value tends to gradually increase when exposed to a high-temperature and high-humidity atmosphere for a long time.

Polymer 2 of polyetheramine and epoxy compound, polymer of polyetheramine and epoxy compound and water-soluble nylon, or mixture of polymer of polyetheramine and epoxy compound and water-soluble nylon
The water absorption at 5 ° C. and 80% RH is preferably 4 to 20%, particularly preferably 6 to 15%. If the water absorption is higher than this, the change in resistance increases, but when exposed to a high-humidity region, the resistance may not return to the original value while increasing. If the water absorption is lower than this, the polymer will not swell sufficiently at the time of moisture absorption, and the sensitivity will decrease.

Further, in order to enhance the effects of the present invention, a hydrophobic or water-repellent substance may be added. For example,
A silicone oil, particularly a silicone oil modified with a functional group such as an amine or an epoxy group, or a long-chain alkyl having a functional group may be added. When exposed to a high-humidity region when the water absorption of a polymer of a polyetheramine and an epoxy compound and a water-soluble nylon, or a mixture of a polymer of a polyetheramine and an epoxy compound and a water-soluble nylon is high, as described above. In some cases, the resistance value does not return to the original state while increasing, but the addition of these suppresses it. The amount of the hydrophobic or water-repellent substance added is
30% by weight or less, especially 3 to 20% by weight, based on the total weight of polyetheramine, epoxy compound and water-soluble nylon
Is preferred. If the addition amount is more than this, the water absorption of the moisture-sensitive film decreases, and the sensitivity decreases. The functional equivalent of the silicone oil is 100 to 2000 g / mol, especially 2 g.
It is preferably from 00 to 1000 g / mol.

Further, another form of the present invention includes the above iv), v) and vi).
Instead of a polymer of a polyetheramine having two or more amino groups and an epoxy compound having two or more epoxy groups and further having an ether bond, a polyetheresteramide, preferably a compound represented by the following formula (2) May be used (the above v
i)). In this case, it is usually a mixture of polyetheresteramide and water-soluble nylon. Further, those obtained by polymerizing polyetheresteramide and water-soluble nylon by adding an epoxy compound having two or more epoxy groups,
That is, a polymer of polyetheresteramide, water-soluble nylon, and an epoxy compound having two or more epoxy groups may be used as the hygroscopic polymer (v). Further, polyetheresteramide may be used as the hygroscopic polymer (the above iv)). In any case, the same effect as in the case of using a polymer of a polyetheramine having two or more amino groups and an epoxy compound having two or more epoxy groups and further having an ether bond is obtained. Not only in the high humidity region of 90% RH or more, but also in the 90% RH
Humidity in a low humidity region less than H can be detected. This humidity-sensitive element can also detect the humidity particularly in the region of 60 to 100% RH. Further, since the moisture absorption is as large as 10 to 20% by weight, the filling amount of the conductive particles can be increased, and stable resistance / humidity characteristics can be obtained. Moreover, the resistance / humidity characteristics are extremely stable even when repeatedly exposed to a dry atmosphere and a high-humidity atmosphere, or to a high-temperature and high-humidity atmosphere for a long time.

[0090]

Embedded image

Such polyetheresteramides have a linear, regular chain structure of hard polyamide segments and flexible polyether segments. This material has excellent properties such as mechanical properties due to its dual properties. Polyetheresteramide is obtained by reacting a polyamide diacid oligomer with a polyetherdiol oligomer.

The polyetheresteramide used in the present invention is disclosed in French Patent Nos. 2,273,021, 2,401,947 and 2,384,810.
No. 7,007,559, U.S. Pat. Nos. 4,345,064, 4,349,661, 4,345,052, and French Patent Application 910.
No. 3,175, JP-A-7-102062 and the like are preferable. Also, European Patent 0,378,
No. 015, No. 0,476,963, JP-A-10-1
No. 58509.

The polyetheresteramide used in the present invention is preferably represented by the above formula (2).
In the formula (2), R has 2 to 12 carbon atoms, preferably 6 carbon atoms.
-12 represents an alkylene group. The alkylene group represented by R may be linear or branched. The alkylene group may further have a substituent, but is preferably an unsubstituted one. Specifically, a methylene group, an ethylene group, a (n-, i-) propylene group, (n
-, I-, s-, t-) butylene group and the like.

In the formula (2), m is an integer of 6 to 12, preferably 6 to 11. n is 1 to 4, preferably 2
-3. p is 1 to 70, preferably 5 to 30
Is an integer. q is 5 to 200, preferably 10 to 10
It is an integer of 0. r is 3 or more, preferably 3 to 1000
Is an integer.

In particular, in the above formula (2), it is preferable that m is 11 and n is 2.

The degree of polymerization of the polyamide segment p
It is preferable that q and the degree of polymerization q of the polyether segment are larger or equivalent. If the polyamide segment is longer, the water absorption tends to decrease and the sensitivity tends to decrease.

The water absorption at 20 ° C. and 65% RH is preferably 0.3 to 10%, particularly preferably 3 to 8%. If the water absorption is higher than this, the resistance change will increase,
When exposed to a high humidity area, the resistance value may not return to its original state while increasing. If the water absorption is lower than this, the polymer will not swell sufficiently at the time of moisture absorption, and the sensitivity will decrease.

The melting point of the polyetheresteramide represented by the formula (2) is about 120 to 210 ° C., preferably 1 to 210 ° C.
60-210 ° C. The glass transition temperatures are all about -60 ° C. The melting point depends on the polyamide phase.
The glass transition temperature is due to the polyether phase.

Such polyetheresteramides are commercially available as PEBAX33 series, 12 series, 62 series, 11 series, etc., manufactured by Atochem.

The water-soluble nylon is used in an amount of 0.1 to 50% by weight, especially 1 to 2% by weight, based on the weight of the polyetheresteramide.
It is preferable to use 0 wt%. If the amount of the water-soluble nylon is more than this, the resistance value tends to gradually decrease when exposed to a high-temperature and high-humidity atmosphere for a long time. If the amount of water-soluble nylon is less than this, when exposed to a high temperature and high humidity atmosphere for a long time,
The resistance tends to gradually increase.

In order to polymerize the polyetheresteramide and the water-soluble nylon, an epoxy compound having two or more epoxy groups may be added. In this case,
A polymer of polyetheresteramide, water-soluble nylon, and epoxy compound is obtained, but may be a mixture without partially polymerizing.

The epoxy compound having two or more epoxy groups is not particularly limited as long as the polymerization reaction proceeds. However, the epoxy compound having two or more epoxy groups used in the above-mentioned hygroscopic polymer, It is preferable to use an epoxy compound having an ether bond.

The epoxy compound having two or more epoxy groups is not particularly limited, but is preferably used in an amount of 1 to 20% by weight based on the total weight of water-soluble nylon and polyetheresteramide. .

Water absorption at 25 ° C. and 80% RH of a mixture of polyetheresteramide and water-soluble nylon, or a polymer of polyetheresteramide and water-soluble nylon and an epoxy compound having two or more epoxy groups Is preferably 4 to 20%, particularly preferably 6 to 15%. If the water absorption is higher than this, the change in resistance increases, but when exposed to a high-humidity region, the resistance may not return to the original value while increasing. If the water absorption is lower than this, the polymer will not swell sufficiently at the time of moisture absorption, and the sensitivity will decrease.

In the polymerization of polyetheresteramide, water-soluble nylon and an epoxy compound having two or more epoxy groups, 0.1 to 60% by weight, preferably 0.5 to 30% by weight of water-soluble nylon is added to alcohol or water. %, Dispersed by adding a polyetheresteramide and an epoxy compound, and heated at 80 to 180 ° C, preferably 120 to 160 ° C, for 30 minutes to 3 hours, preferably 60 minutes to 2 hours. Good. As the dispersion medium, ethyl cellosolve, ethylene glycol and the like are preferable. The polymerization conditions are appropriately selected depending on the water-soluble nylon, polyetheresteramide, and epoxy compound used, and are not limited to the above conditions. In addition, as will be described later, usually, conductive particles are also added to the dispersion medium, coated, and then heated to polymerize.

Further, also in this case, a hydrophobic or water-repellent substance may be added. For example, a silicone oil, particularly a silicone oil modified with a functional group such as an amine or an epoxy group, or a long-chain alkyl having a functional group may be added. A mixture or polymer of polyetheresteramide and water-soluble nylon as described above,
Alternatively, when the water absorption of polyetheresteramide is high, exposure to a high-humidity region may cause the resistance value to rise and not return to its original state. The amount of the hydrophobic or water-repellent substance to be added is preferably 30% by weight or less, particularly preferably 3 to 20% by weight, based on the total weight of the polyetheresteramide and the water-soluble nylon. If the addition amount is more than this, the water absorption of the moisture-sensitive film decreases, and the sensitivity decreases. The silicone oil has a functional group equivalent of 100 to 2000 g / mol, particularly 200 to 1 g / mol.
000 g / mol is preferred.

The conductive particles used in the present invention include carbon-based particles such as carbon black and graphite, and metal powders such as nickel, gold, silver and copper. Particularly, carbon black and the like are preferably used. Carbon black has a specific surface area of 30 to 300 m ² / g,
It is preferably from 150 to 150 m ² / g, particularly preferably from 30 to 75 m ² / g. The average particle size of the primary particles of carbon black is preferably 20 to 50 nm, and those having a well-developed structure are preferable, and the DBP oil absorption is 100 ml / 100 g or more (usually 15
0 ml / 100 g or less) is preferable. In general, it is preferable that the average particle size of the conductive particles (when the particles are not spherical particles, the diameter when the projected area is converted into a circle) is about 20 nm to 3 μm.

The amount of conductive particles in the moisture-sensitive film of the present invention is 5 to 40% by weight in the case of carbon black.
And more preferably 10 to 30% by weight. When the filling amount of the conductive particles is small, the resistance value during drying becomes too high, and the resistance value changes when repeatedly exposed to a dry atmosphere and a high humidity atmosphere. If the amount is too large, the change in the resistance value with respect to the change in the humidity becomes small,
The sensitivity as a moisture-sensitive element decreases. The other conductive particles may have a filling amount according to this.

In the present invention, the method for forming the moisture-sensitive film is not limited, but may be formed by coating using a dispersion containing the constituent material of the moisture-sensitive film. As the dispersion medium, water, alcohols, ethers, and ketones are preferable, and a mixed solvent thereof may also be used. As a coating method, a screen printing method is usually used as described above.

After forming the coating film, it is cured at a temperature of about 80 to 180 ° C. for about 30 minutes to 3 hours. The curing conditions are appropriately selected depending on the polyetheramine and the epoxy compound to be used or the polyetheramine and the epoxy compound and the water-soluble nylon, and are not limited to the above conditions. At this time, the polyetheramine and the epoxy compound or the polyetheramine and the epoxy compound and the water-soluble nylon are polymerized.

The dry thickness of the thus obtained moisture sensitive film is preferably 5 μm or less, particularly preferably 1 to 3.5 μm. Thereby, permeation of moisture is sufficiently ensured.

[0112]

EXAMPLES Hereinafter, the present invention will be described in more detail by showing specific examples of the present invention together with comparative examples.

Example 1 The dividing grooves 1 were arranged vertically and horizontally so that the individual product was 3.2 mm × 1.6 mm.
The electrodes 6 and 8 were printed and baked on the alumina substrate 9 containing 0 with a silver-palladium paste. Printing and baking of four patterns of the comb-shaped electrode were performed using a ruthenium oxide paste. A primary division was performed to obtain a strip 11 (see FIGS. 1 and 2). A silver-palladium paste to be the conductor 12 was applied to the surface of the strip-shaped body 11 and baked to complete all electrode baking. The conductor 12 finally forms the end face electrode 7. The secondary division was performed, and the electrode substrate was formed into an individual product 13. The height is 0.5 mm.

The individual products 13 were arranged on a pallet such that the comb electrode pattern was on the upper surface, and an acrylic resin-based resist (MA-830 manufactured by Taiyo Ink Mfg. Co., Ltd.) was printed so as to cover the comb electrode portions. Resist at 100 ° C, 30
Cured in minutes. The film thickness after this curing was 10 μm.

Barrel plating was performed to form a solder layer only on the electrodes 6 and 8 and the end face electrodes 7 (collectively, end electrodes) on which silver-palladium was baked. The plating was electroplating, the plating bath composition was as follows, and the electrolysis conditions were a current density of 2 A / dm ² . The thickness of the solder was 8 μm.

Plating bath composition Stannous alkanolsulfonate 90 g / l Lead alkanolsulfonate 5 g / l formalin 5 g / l

The individual product having the solder layer formed thereon was immersed in a 3 wt% aqueous sodium hydroxide solution for 30 minutes to remove the solder resist. The individual electrodes having the solder layer formed thereon were arranged on a pallet, and a moisture-sensitive paste in which carbon black was dispersed in a water-absorbing polymer was printed and cured at 150 ° C. for an hour to obtain a chip-shaped moisture-sensitive element.

The following composition was used for the moisture-sensitive paste.

To 3 g of ethyl cellosolve, polyoxypropylenediamine Jeffamine D400 (number average molecular weight: 400, amine value: 4.4 meq /
g, viscosity (20 ° C) 29cp) 0.342g, Jeffamine D2000 (number average molecular weight 2000, amine value 1.
0meq / g, viscosity (20 ° C) 342 cp) 0.228 g, carbon black (Tokai Carbon Toka Black # 45)
00F) 0.36 g, silicone oil modified with an amino group (KF393 manufactured by Shin-Etsu Chemical, molecular weight 700-1000)
2 g was added, and this was added to the Kurabo Industries planetary stirrer KK-10.
Dispersed at 0 for 9 minutes. Then, sorbitol polyglycidyl ether EX614B manufactured by Nagase Kasei (epoxy equivalent 180 WPE, water solubility 90%, viscosity (25 ° C.) 4000 c.
1.087 g of ps and specific gravity (25.degree. C.) 1.26 g were added, and the mixture was further dispersed for 1 minute to obtain a moisture-sensitive paste.

The chip-shaped moisture sensitive element was heated at a preheating temperature of 180 °.
C. and soldered to the electronic circuit board through a solder reflow furnace having a peak temperature of 240.degree.

This moisture-sensitive element was found to operate normally without occurrence of soldering failure to the electronic circuit board. It was possible to detect the humidity in the range of 60 to 100% RH.

Comparative Example 1 A chip-shaped moisture-sensitive element was obtained in the same manner as in Example 1 except that no resist was used and no solder plating was performed, and soldering was performed in the same manner. This resulted in component displacement and component drop.

Comparative Example 2 In Example 1, when the solder plating was performed without using a resist, the pattern of the comb-shaped electrode was damaged and became thin.

In the above description, tin plating was applied instead of solder plating, but similar results were obtained depending on the above configuration. However, the following plating bath compositions were used for tin plating, and the electrolysis conditions were 25 ° C. and the current density was 1 A / dm ² .

Plating bath composition Stannous sulfate 40 g / l Sulfuric acid 60 g / l Cresol sulfonic acid 40 g / l Gelatin 2 g / l β-naphthol 1 g / l

In forming the moisture-sensitive film, water-soluble nylon P-70 manufactured by Toray (relative viscosity: 2.83, water solubility: 100 parts by weight with respect to 100 parts by weight of water) was used as a hygroscopic polymer in the above polymer. Or more of the above polymer and a mixture of the above polymer and water-soluble nylon, furthermore, a product using a polyetheresteramide PEBAX4011 manufactured by Atochem, a polyetheresteramide and a water-soluble polymer. Even if a mixture of nylon or a polymer of polyetheresteramide, water-soluble nylon and the above epoxy compound is used,
Similar results were obtained according to the above configuration.

Further, instead of solder plating and tin plating, gold plating was performed, but similar results were obtained according to the above configuration.

[0128]

According to the present invention, it is possible to obtain a chip-shaped moisture-sensitive element that can be surface-mounted on an electronic circuit board without changing the characteristics of the polymer-based moisture-sensitive film.

[Brief description of the drawings]

FIG. 1 is a perspective view showing one configuration example of a chip-shaped moisture-sensitive element of the present invention.

FIG. 2 is a perspective view showing a part of a manufacturing process of the chip-shaped moisture-sensitive element of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Chip-shaped moisture sensitive element 2 Insulating substrate 3 Moisture sensitive film 4 Comb-shaped electrode 5 Gap 6 Electrode 7 End face electrode 8 Electrode 9 Alumina substrate 10 Divided groove 11 Strip 12 Conductor 13 Pieces (electrode substrate)

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Keisuke Kubota 2-28-1, Kitamagome, Ota-ku, Tokyo Tokyo Wells Co., Ltd. F-term (reference) 2G046 AA09 BA01 BA09 BB02 BC05 BC08 EA02 EA04 FA01 2G060 AA01 AB02 AE19 AF07 AF08 AF11 AG11 BB02 BB10 JA02 5E032 AB10 BA06 BB01 BB20 CA02 CC14 5E033 AA13 AA14 AA32 BB02 BC01 BD01 BG03 BH02

Claims (15)

[Claims] 1. A high molecular humidity sensitive film between a pair of electrodes,
What is claimed is: 1. A method for manufacturing a chip-shaped moisture-sensing element having an end electrode for soldering for surface mounting on an electronic circuit board, comprising plating the end electrode with a metal or an alloy to improve solderability. When applying, including the pair of electrodes,
A method for manufacturing a chip-shaped moisture-sensitive element, wherein the plating is performed in a state where exposed conductors other than the end electrodes are protected with a resist. 2. The method according to claim 1, wherein the plating of a metal or an alloy for improving the solderability is a plating of solder, tin or gold. 3. The chip-shaped moisture-sensitive element according to claim 1, wherein after the pair of electrodes are formed, the end electrodes are plated to remove the resist, and then a polymer-based moisture-sensitive film is provided. Production method. 4. The moisture-sensitive polymer film according to claim 1, wherein the moisture-absorbing polymer has conductive particles dispersed therein, and the moisture-absorbing polymer is selected from the following i) to vi). A method for producing a chip-shaped moisture-sensitive element according to any one of 1 to 3. i) A polymer of a polyetheramine having two or more amino groups and an epoxy compound having two or more epoxy groups and further having an ether bond. ii) A polymer of a polyetheramine having two or more amino groups, an epoxy compound having two or more epoxy groups, and further having an ether bond, and a water-soluble nylon. iii) A mixture of a polymer of a polyetheramine having two or more amino groups, a polymer of an epoxy compound having two or more epoxy groups, and further having an ether bond, and water-soluble nylon. iv) Polyetheresteramide. v) A polymer of polyetheresteramide, water-soluble nylon, and an epoxy compound having two or more epoxy groups. vi) Mixture of polyetheresteramide and water-soluble nylon. 5. The method according to claim 4, wherein the polyether skeleton of the polyetheramine is propylene oxide and / or ethylene oxide. 6. The method according to claim 4, wherein the polyetheramine has two or three primary amino groups at the terminal. 7. The polyetheramine having a molecular weight of 10
The method for producing a chip-shaped moisture-sensitive element according to any one of claims 4 to 6, wherein the number is from 0 to 5000. 8. The method according to claim 4, wherein the epoxy compound is represented by the following formula (1). Embedded image [In the formula (1), A represents a divalent to tetravalent saturated aliphatic hydrocarbon group, an aliphatic ether group or a heterocyclic group, and k is an integer of 2 to 4. ] 9. The method according to claim 4, wherein the hygroscopic polymer has an amine value and an epoxy value of 1: 1 to 1: 4. 10. The method according to claim 4, wherein the polyetheresteramide is represented by the following formula (2). Embedded image [In formula (2), R represents an alkylene group having 2 to 12 carbon atoms, m is an integer of 6 to 12, n is an integer of 1 to 4, p is an integer of 1 to 70, q is an integer of 5 to 200, and r is an integer of 3 or more. ] 11. The method according to claim 10, wherein m is 11 and n is 2 in the formula (2). 12. The method according to claim 4, wherein the water-soluble nylon has an ether structure. 13. The method according to claim 12, wherein the water-soluble nylon comprises a structural unit represented by the following formula (3) and / or a structural unit represented by the following formula (4). Embedded image Embedded image [In the formula (3), R ₁ represents an alkylene group having 2 to 4 carbon atoms. ] 14. The water-soluble nylon according to the total weight of the polyetheramine and the epoxy compound, or the weight of the polyetheresteramide.
The method for producing a chip-shaped moisture-sensitive element according to any one of claims 4 to 13, wherein the content is 0.1 to 50 wt%. 15. The conductive particles have a specific surface area of 30 to 30.
Any of the method of manufacturing the chip-like moisture sensitive element according to claim 4 to 14 carbon black of 0 m ² / g.