JPS5943342A - Humidity sensor material - Google Patents

Abstract

PURPOSE:To obtain an excellent humidity sensor material with a high sensitivity even in the low humidity area free from hysteresis in which electric resistance varies linearly according to the humidity by employing a polymer of a specified synthetic phospholipid monomer or a cross-linked body thereof. CONSTITUTION:A solution of a synthetic phospholipid monomer represented by the formula I (X is CH3 or H, R polymerizable group containing a vinyl group or the like as represented by the formulaII-IV and the like and (n) integer) and N.N'=methylene bisacrylamide or the like or that of a compound polymerized with the synthetic phospholipid monomer and a polymer such as polyvinyl alchol is applied on a ceramic substrate 1 such as Al2O3 having comb- shaped metal electrodes 2 and 3 and leads 4 and 5 formed thereon or therwise of make a humidity sensor. Thus, a applicable in a wide humidity range is obtained with a quick absorption or desorption of H2O molecule, an excellent response speed a better linearity with respect to humidity variation.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a humidity sensor material used for humidity measurement, 151 control, adjustment, etc. (7).

In recent years, humidity has been measured, controlled, and adjusted in various fields, and there is a high demand for high-performance, compact, lightweight, and easy-to-handle electrical humidity sensor materials, and the development of these materials has been actively carried out. In general, using metal oxides such as silver, selenium, and metal oxides for silicon semiconductors.
ζ and oxidation workers:・Many wet sensorial phases 11I are known, such as those using n-isomers, but rrumaniuno・, selenium, silicon 1′; j+
Those using f+ require a long time to stabilize the material.
Reproducibility and stability of characteristics tf
There is also a problem with the toxicity of lζ-selenium.Also, those using gold, '%ti', and compounds generally have a resistance of 176<176% and have a high resistance to oxidation. hand 2
．． For example, when using S11\, it is similar to magnetite! The surface of the Red Recycle (Fe3O4) gradually oxidizes due to the heat treatment in the process of 71. Since it is easy to change to 4p″ezOq, 'fb' is stable in raw 1st life.
Those using tOs + Li, , U-Fe2(,), and oxide semiconductors for threads have low IO to 11 of -S, and the manufacturing method is complicated and requires a large number of steps. Second IIj
The stability of the current 1st year is really low/J,,:]
I can't see it.

In this way, the second generally known groove!, +
Q: 1, there are various unresolved issues in B < 4 Hinza interest rate, '! '! +' low H, H1 once (from area to high) Umo resistance is steep and linear over a wide range of stardom, even if hypsis is force, <, and co... in low humidity area. Practical measurement <jf It has a low resistance value and can be manufactured inexpensively by a single industry, etc. 412 + 2, 1
[blasphemy] Ha ('t, J" 1) The one who likes the mountain, her.
! In the mix, everyone is jJt'j and 2ru and itsu-C is also M'
l U is good.

Here, ni wood base l'i bright convex j, (F is between as in !
In order to solve this problem, various studies were conducted and the result was a synthetic phospholipid expressed by the general formula C?f.

(I made these soups) ζ・I'ri1', I just added these to the old days. As the humidity increases, the resistance of 'C increases in the uI line, and even in the low humidity region it has a practically constant 'J fig 717: resistance value, and the hysteresis of almost line tk with respect to humidity λ. 1.i “i%” such as no rinse etc.
We have discovered that a moisture-supporting material that exhibits excellent properties, is inexpensive, and can be used for a long time.This invention has been achieved. ,
General formula, - (wherein,
) Synthetic phospholipid monomers represented by these 1. −
j! (combined nj? rimmer or these'ff: Qi 44
At least one of the given polymers was used as a moisture sensitive material.

In the present invention, moisture sensitivity +4 (r;
] (and the monocyclic chain (+1'L ; 1jlj 'f ij to which vinyl monomers with moderate substituents are bonded. These moisture-sensitive I) It is thought that the phospholipid having the present invention plays a role similar to Tt, and the reason why the present invention exhibits the above-mentioned excellent /l+2 moisture properties is the (1f)
It depends on the phospholipid having a pair of ions in the molecule as shown in the structural formula as a lotus element, and the pair of ions in the phospholipid/E)i is 1 fF, lI, 0 Regarding the adsorption and desorption of molecules i'A, -Ij is 8'H, and the adsorption and desorption point of 20 molecules is 1! l″i:J: -Fi+, (and is considered to be constant-electrically positive. Also, in the present invention, the moisture sensitivity 'r# tffk &u' is expressed by the above general formula.

) It can be considered that t- does not depend on the type according to . There are many types of polymerizable groups including vinyl groups in 1"4, and there is little need to limit them to all specific groups. However, I to R are the following groups, that is, C) b = CX ■ CJ, 'b "" CX C0Nl-IC) b--2nd ('j bifurcated i, j -1f cit mooriyo, 'jA stage 1'l
'5 (,?1 et 7)''j<:I4r'sK;IFf
J brother's story sheet'(・(upper)
117j %: 3 possible/, -C ino-± new 1, Megu, Mizumotori ``1 by Ihi', l real hint ν-t 1 material C soil ti self X, lj: 4tthi other than menu n tl
: Basic phosphorus'J stone: l'j 'a: 几-tr
10) iyrrinzukiji'Jto1yuntsuma niriranoL i
j situation 7) match) Cu11! Sea (-Nori 6th year old/[Toshide soil? ib 'c (already; l) times 4M O, -) I
Yg+ Humidity '17 Saty:i: JiJI it'p
a tt h.

This incident occurred in January when the IS started...
, transparent Joc's stomach/i-nii 1 ゛J-heart material is ', J'L 'I"j", 11 (1112" n at? 112 C1 (3 polymethacrylic acid methi 7L -CH,s L C C-0-Cf-IS.

1 t,)-C-C4b 1 CH1 NN'-population/bisacrylamide cH2-2CHell-2at.

1 CONI-1-(゛月, 心, 1i(-C('), etc. are most preferably used 1, or the above A1:ζjil!j
It is also preferable to use a porous yr body Q'< - iris r, ! - with oak composition made of glass, ceramic, etc. Externally 1. A, 14 A) 5. Example 1 Moisture sensitive and beneficial 2-O11□...Formula, Cll.

薯CH2=C − i.e. 2-(methacryloyloxy)-ethyl-2--(
Phospholipid monomer 11 of trimebul ammonium)-etherphosphonate and 0.05 F of NN'-mebucin bisacrylamide were dissolved in 3.5 m of distilled water with stirring to form an aqueous solution. j! 'I made it. Pass this through a glass filter (
After drying the substrate in 7 days, it was degassed under reduced pressure and then spin-coated onto an At203 ceramic substrate on which a rectangular gold electrode was formed as shown in FIG. 1 to form a thin n.

After that, 311-! 250W crystal pressure mercury lamp! J pre-irradiation 7
] l (combined to give a humidity sensitivity of 111:\).

- A pair of combs! −1 Rikin'Tt 4(q i, i:
It was formed by screen printing gold/black smear on an A4 os ceramic board and firing it at sieve temperature. The measured lead wire 47'j and the sensing groove IJLj of the lead attachment part -4- were peeled off and the lead pA was joined at 1 (7) to form a humidity sensor cell.

In Figure 1, 1 is A403, (A;...
, 2゜3 tJ, 1 □ () is laid out in a comb shape on the same surface, 7'iT Taku, (C5.1゜5 i,, L Kono 11J
y+? , 213 K-t 71(':/l[)'g
; 'Song (city between 1 ki 2 and 3', r, L: llV anti and ton ke valley)-i was measured by changing the measurement frequency to 1.2011 otsu, 11G z and 10 bar r-IZ 9th. 2 Figure 1, 9 in this humid 1 sho Senri cell, Zhou? 7.
Measured at 14 I KHz 2 to 1 to the relative cavity of the lifting platform 9'J 7fz) Resistance A;: IP expressed as a logarithm of 1!
In the 1′ gender diagram, ′ et 9, rotation i゛ + (+ to this pure tl, Q
-The sensor material has a wide fiiij IJ)-→jiL surrounding 1) left, which means 4-1(wai, the logarithm of fii'+ is i
n, a sharp change on the line surface -, Jru (-Togane Z?
・Ru. Moreover, the low humidity of 20 inches (〈-mo・even!j resists A 11', 1, can be measured as l?i''107Ω)
i'i: ; Surrounded by Q, 1, I' (-I 7-2, change the measurement frequency to 18 + 11, and ri ζ So) Negative is also relative i'; f, C to the resistance value for I'ji ” Most of the changes were in the quality agency.

Next, in Figure 3, the frequency is set as 1 (↑III) and 17-
A picture of a relative humidity boat and an electric kimmer at 1゛-s match (
In Figure 7, FL il, 1.20KL-1z,,b←E
ll to H-7, -c 6'', 1 (l JG17. to j
, -Rir1iiCi (+ru. Same figure \ra medium temperature JP"r-
4jjj area 7jz et al+1i1i'M j,! ＞('p
10 with j (J, r79 fi-i, > pI Z). Ki W M &: I, V for increasing and changing in a sudden way
You can see that low frequencies are very sensitive.

Similarly, we conducted a humidity cycle test and found that there was almost no hysteresis and the response speed was extremely fast.
Rt, fr knee.

The illustrated example is a typical example, but if the humidity sensor material gold of the present invention is used, the tendency will be the same even though there will be slight differences in slope due to differences in composition.
.

Furthermore, this ability tti f! '11), synthetic phospholipid t'
1 Mono-r-'s Shiyu ■P Masa ← Trade name (-DI''
W, but by combining IiN with other trace polymerization methods such as combining solution j■, bulk Φ combination, etc.
(J, needless to say, 3, lHl of this example)
, Akane molecule thin +1-1='! (C- used in N formation can be produced, so it shows an extremely fast response hole 1^fI, and it is easy to form a j-box.
I [have the advantage of being able to do things].

Example 2 ``5\Formation +- (shown as a material for libinyl anosycol: added Δ;
2-(methacrylic[+yloxy): J-7'-ru2
-(Trimethylanjin!-Uno) Ethylposbonate phospholipid IT knob 12, polyvinyl alcohol: J-ru 0
52, and N, N'-Methi t/Nbis J' Kurilua ζl・゛(1,05 t f U:, f
it flM j'll! I, i, - water f:':'
IP
, NideAt, 0. A moisture-sensitive film was formed on a ten-dimensional substrate-J2.

Figure 4 shows this humidity 1. (1 centimeter 14 to 1-1 Hz & 1
．． ",・Relative humidity-P,,,; air resistance bamboo 1 (1 is 1°, same [n1 (・(-yo) 1+4 compared to Example 1-
The resistance value is a little off, but -1, 1, l; J-r: White 11
1's externality (haya t; 1: υ is directly converted to y (-togawa kai,), circumference i7!J, number 1- on the contrary 1
lllll f t, p c +4 sweat mo -d 1
1self 1iJ J,'+i, Ibi1 ni'/+i
/r5 Li1i, Mirail, Naka-) fC.

Next, in Fig.
'Row j,, II1, Ih: Show (-, but from the same figure'
,tx]tQH(XIJ], iηHowever7'L: About the song -
Z”・(・)su, the rise is l: f) Sieve? W I
=W, f, :1,EVCE',-'? C “
-9 can be seen. This is Boribigo 4, Rua sword Kotoru is force II; ;F
+tf1<na-)teZ) especially 12. ) thing and I')
51. j) 3, However, the characteristics such as sensitivity and response speed are ',)()application βt++ i and times, etc., and the table B7.
It is observed that a stronger good Ijj4 thin film can be obtained by using the 4-forming interest.

In addition, in the relative humidity-'Il and air resistance characteristics of this Example 2, 0
Accordingly, 7;1. Can lower air resistance. Also, in this case - inside the wet IW + I material expressed by the general formula described above, X is -CH5, R is C112=CC200 (CH,2)n-, and -(methacryloyl mexi) edge 2ray 2
-()! 7 methyl ammonium), ethyl phosphonate to the synthetic phospholipid h monomer (-).Although we have shown an example using polyvinyl alcohol as a phospholipid-forming material and 1-, other highly water-soluble materials such as polyethyleneimine, poly-L-alanine, etc. Even when a molecular polymer is used, the same tendency as that of moisture sensitivity t;L is exhibited.

Furthermore, if all other synthetic phospholipid monomers are used, each synthetic phospholipid monomer or polymer obtained by polymerizing these may be added to the solvent used as a solvent, and a pure high molecular weight polymer as the synthetic forming material. For example, in the above general formula,
X is -CIJ,, 1(is CH,, 2-(:C= 0 ()-(CH,).-5 11) Synthesis of nibur phosponate Phospholipid monomers or polymers prepared by combining them with dimethylformamide, solubilized in dimethylformamide, polymethacrylate [
Polymer 7 (i) polymers such as methyl and poly(vinyl A) can be used as thin film forming materials, and exhibit the moisture-sensitive properties of the same materials.

In addition, in this example, synthetic phospholipid 1'c'c i (<
The moisture content of the molded polymer and the moisture produced by forming it on the base B (we have shown an example using the cent material, but the above 1 to 4)
In f;, a wet I-jiao tenza material consisting of a zero-forming phospholipid monomer and a thin film-forming material was used in the same manner, and the result was approximately the same as 1. Example 3 2-(methacryloyl A, , containing the aqueous solution in a porous glass plate with corners and poles on both sides 77-3,
The relative humidity-frost and air resistance characteristics of the obtained Senza cell measured at I KHz are shown in Figure 6.2 From the same figure,
A damp room sensor material in which a porous material is impregnated with a synthetic phospholipid monomer is shown in Example 1. It is clear that the resistance value U shows a measurable value even in the low humidity region (-).

Group IJ1. in which the porous 4ij material is impregnated with such synthetic phospholipid hair tufts or a polymer obtained by polymerizing them. It has the advantage that it is extremely easy to manufacture.

As is clear from the explanation below, the humidity sensitive material according to the present invention, that is, the resistance to relative humidity [1'' over a wide humidity range, the logarithm of which is directly PJ1
Since the temperature and slope are steep, it is possible to achieve a high humidity level (-1).In addition, there is almost no hysteresis due to the 7-sole cycle, making it practical even in low humidity areas. The above measurable resistance value is lowered by lowering the measurable resistance value, and the response speed is lower and faster.
3. The relationship between relative humidity and capacitance is like a switch! 1"!
￥ Can be used as a highly sensitive N/λ point sensor using t't', etc. Industrial equipment, home? jf, chemical products, ni・(
扛(U suffix m) Requires humidity control in a wide area lIl
] You can expect excellent effects by using 1.

[Brief explanation of drawings]

Figure 1 shows the humidity sensor according to the present invention,
↑1011f Kozu plane 12 of the humidity sensor cell made by 1y
−1, (゛(Figure 92 shows the relative iJ1 in the first embodiment.
Characteristic diagram showing the relationship between 19- and resistance, Figure 3. Characteristic diagram showing the relationship between 1. 5 Figure 11 - 'f: 2r32 in the second example, 1st: eye so (% corresponding to 1, 1 student is l, 帛6 plans, 2I le 3's ability 1) dl-
J = 1, - 4 & 1% figure corresponding to 2 figure which can be 2
). , 1...AL20g ceramic group (anti, 2,3
1 comb blade) 1 comb blade, 4, 5 ・
・Lead wire. Figure 1 2 1 0 0 20 4-0 60 80
100 n vs. shikai degree (pu) Figure 3 ne vs. shikai degree (%) 0 20 40 60 8
0 100neH sentence size 2)4ha1 (%) 0 20 40 60 80
to. Wood Grain Bun Hyakusei B [(%) Wood Grain Text) 312 C [(%) Procedural Amendment Document Showa / Year □ Month '1-1 71, Purport:'] Director-General Kazuo Wakasugi, Toshi 1, -1] 1 case Display Humidity Sensor Material 3 Relationship with Supplementary 1= Person', 1lfl Special n't Application No ((029) Oki Electric Industry Co., Ltd. 71st generation 1211 ノ\, ' ?)li ir: Life'7 No1 ．． ”l ('J'
flfl flll year month 11 (spontaneous) (3, Ura 11' λ1 elephant 4>
- Compensation for the contents of 1i1i11/1' (1) The scope of the claims of the present application is attached to the WJl
-tE -Jru. (2) Modify the formula on page 7 of the specification, CH2=CX C0N1: (-CH2-, to the following formula, CH22CX ■C0NH(C)&)n-. (2) The formula of polymethyl methacrylate on page 9 is corrected as follows. 10] (4) IMJ 10 The formula of the true polyethicine derephthalate-1 is revised as follows, Claim (1)--General formula, 1 R-OP O(CH2)2 N+X3□ 〇- (In the formula, The /h characteristic is that at least one type of polymer obtained by polymerizing Jl et al. or a crosslinked polymer thereof is used as a moisture-sensitive phase! ii
"7 degrees Sen'su phase O・I. (2) lI'existencet'1" The feeling groove A in claim (1) is a general formula, 1 R-0-P-0-(CH2), , N degree) Konza F'+' 2-
1' Q (Autopsy Q'# tT"g?4Question(D !i) t
trl The combined DV of the term m+, 'j 7 fat', i'
(Nanatsuma-5 These were polymerized.''? Lee r, - also (
・, 1, ζ, at least 1 f of a crosslinked polymer
The humidity sensor phase material is characterized by the combination of Akane molecules A1 as iris and membrane formation. (4) The thin Δ forming phase family 10, water, alcohol,
City soluble in chloroform + trimethylformamide. min-f polymer, e.g. polyvinyl alcohol, month 1=
IJ ethyreshinmi/, bo17-f, -phyranine, polyvinyl 7-ridone, starch, glycodan, methacrylate, 7-styrene, polyvinyl chloride, polyacid-resistant vinyl, polyethylene prephthalate The humidity sensor material according to claim 2, which uses at least one of epoxy resin and the like. (5) The synthetic phospholipid monomer described in claim 1 is kneaded and rolled into a porous material t1 consisting of glass, ceramic', and 9-. Q! j ri sentence and Lua (IIj If Senri Comparison fee.

Claims (1)

[Claims] (1) General formula, 1 ROP O(CHt) N+Xs 〇- (In the formula, X is =C) is or -H1it represents a polymerizable group including a vinyl group etc., or an integer number 3. A humidity sensor material characterized in that at least one of the following synthetic phospholipid monomers, polymers obtained by polymerizing these monomers, and polymers obtained by crosslinking these are used as a moisture-sensitive material. (2. Claims ()) The humidity sensitivity is expressed by the general formula, 1 R-0-P-0-(C1i))2N Xs-, and R in the formula is CH2=CX CIh=CX C0NII C1I2-1 In addition, t''-n represents an integer. (3) Scope of Claims Paragraph 1 Δ Self-possessed synthetic phosphor 1' At least 1 (・n and 1.I7 +11
'1 formation (polymer as 3 materials, hikigosho and karana a) C
Humidity sensor material with '1' and 'l'. (4) As the thin film forming agent, a polymer soluble in water, alcohol, chloroform, dimethylformamide, such as polyvinyl alcohol, polyethyleneimine,
Claim 2 which uses at least one of poly L-alanine, polypyrrolidone, starch, glycogen, polymethyl methacrylate, polystyrene, polyvinyl chloride, polyvinyl acetate, polyethylene terephthalate, epoxy resin, etc. Humidity sensor material. (5) A humidity sensor material characterized in that a porous material made of glass, ceramic, etc. is impregnated with the synthetic phospholipid monomer according to claim 1 or a polymer obtained by polymerizing these.