JPH05142152A - Amine sensor - Google Patents

Abstract

PURPOSE:To quickly return an amine sensor to its initial level so as to improve the continuously measuring characteristic of the sensor by removing an amine compound adhering to a sensor film by cleaning the sensor film with blowing air. CONSTITUTION:This amine sensor is provided with a main body which detects and determines a subject, namely, an amine compound from the variation of light reflectivity caused when its sensor film which is provided on a substrate and composed mainly of a conductive polymer comes into contact with the subject and a cleaning means which cleans the sensor film for removing the subject adhering to the sensor film.

Description

Detailed Description of the Invention

[0001]

The present invention relates to the detection of amine compounds,
It relates to an amine sensor for quantification.

[0002]

2. Description of the Related Art Heretofore, as a sensor using a conductive polymer, a gas sensor utilizing a phenomenon that the conductive polymer is colored or becomes highly conductive by contact with ammonia, SO _3, etc. is known.

However, since this is electrically detected and quantitatively determined, it has drawbacks in anti-bacterial and water resistance. Further, manufacturing such as attaching electrodes is complicated.

By the way, the present applicant has proposed various sensors for detecting a change in the physical properties of a sensor film such as a dye film that comes into contact with a test chemical substance such as water as a change in light reflectance. Proposed (Japanese Patent Laid-Open No. 2-16944)
No. 9, JP-A No. 2-193045, Japanese Patent Application No. 2-3201.
08, Japanese Patent Application No. 3-91056, etc.).

Since such a sensor utilizes the change in the light reflectance, it has the advantage that the element structure is simple and the manufacturing is easy as compared with the conventional sensor for electrically detecting and quantifying. Have.

Therefore, it is significant to obtain a sensor for detecting various substances which makes use of such advantages.

[0007] For example, when a fish or the like is stored in a refrigerator, the smell of the fish is transferred to other foods, and the taste of the other foods may be impaired. Therefore, a deodorant or the like is usually placed in the refrigerator. However, it is difficult to judge the effectiveness of the deodorant and the like, and even if the deodorizing effect has disappeared, it is often placed as it is. In such a case, the above-mentioned accident can be avoided by installing a sensor for detecting the smell of fish in the refrigerator and checking whether or not there is a deodorizing effect.

By the way, the substances that cause the smell of fish are
It is a low-ranking aliphatic amine such as methylamine produced by decomposition of fish meat. Further, not limited to such substances, most of amine compounds emit an odor, and development of a sensor for detecting and quantifying amine compounds is desired.

Obtaining a sensor for detecting and quantifying methylamine and the like is expected to be used as a sensor for detecting the freshness of fish.

[0010]

SUMMARY OF THE INVENTION A main object of the present invention is to provide a long-life amine sensor which can detect and quantify an amine compound continuously with high accuracy and has a simple device structure.

[0011]

These objects are achieved by the present invention described in (1) to (15) below.

(1) A substrate and a polymerized film which is a sensor film containing a conductive polymer as a main component and which is provided on the substrate, and the light generated when the polymerized film comes into contact with an amine compound as an analyte. An amine sensor, comprising: a sensor main body for detecting and quantifying the analyte by a change in reflectance; and a cleaning unit for cleaning the analyte adsorbed on the polymerized film.

(2) The amine sensor according to (1) above, wherein the cleaning means is a blowing means for blowing air onto the surface of the polymerized film.

(3) The amine sensor according to (2) above, wherein the blown air is warm air.

(4) The sensor body has a light emitting means and a light receiving means, irradiates the polymer film with light from the light emitting means, and the reflected light is received by the light receiving means. (1) to (3) for detecting and quantifying
The amine sensor according to any one of 1.

(5) The amine sensor according to any one of (1) to (4) above, wherein the polymer film contains a dopant.

(6) The amine sensor according to any one of (1) to (5), wherein the conductive polymer is a polyaniline compound.

(7) The amine sensor according to the above (6), wherein the polymer film is obtained by forming, then washing and acid-treating.

(8) The amine sensor according to the above (7), wherein the film formation is performed by electrolytic polymerization of an aniline compound in an acidic solution, and the acid treatment is performed by immersion in an acid solution.

(9) The amine sensor according to any one of the above (1) to (7), wherein air is blown to the polymerized film every predetermined time.

(10) The amine sensor according to any one of (1) to (9), wherein the polymer film is irradiated with light intermittently.

(11) The amine sensor according to any one of the above (1) to (10), which imparts intensity to the light radiated to the polymer film.

(12) The amine sensor according to any one of the above (1) to (11), wherein the polymer film is irradiated with light for increasing the temperature of the polymer film during the cleaning.

(13) The light intensity is increased by maintaining the irradiation of the polymer film with light for a predetermined time.
Amine sensor.

(14) The amine sensor according to the above (12), wherein the intensity of light to be irradiated is increased to increase the intensity of light.

(15) The amine sensor according to any one of the above (1) to (14), which is adapted to give an alarm when the intensity of the reflected light from the polymerized film becomes smaller than a predetermined value.

[0027]

FUNCTION AND EFFECT The polymer film of the present invention contains a conductive polymer such as polyaniline and has a reflectance of preferably 10% or more with respect to light having a predetermined wavelength.

Moreover, when the conductive polymer comes into contact with the amine compound, the conductive polymer is bonded to the amine compound or electrically interacts with the amine compound to change the physical properties of the film.

This change in the physical properties of the film changes the light reflectance of the polymer film, especially the specular reflectance. At this time, the bond between the conductive polymer and the amine compound is reversibly carried out, which enables the detection and quantification of the amine compound to be detected.

When the conductive polymer is a polyaniline compound such as polyaniline, the polymer film may be formed, washed, and then immersed in an acid solution such as a hydrochloric acid solution having a predetermined concentration for acid treatment. Preferably, this improves the sensitivity in detection and quantification and stabilizes the characteristics.

Further, in the present invention, since the amine compound bound to the polymer film is cleaned by blowing air, the initial level can be quickly restored and the characteristics of continuous measurement can be improved.

[0032]

[Specific Structure] The specific structure of the present invention will be described in detail below.

In the present invention, an amine compound is detected,
A polymer film is used for quantification.

The polymer film of the present invention has a so-called bronze luster having a reflectance, particularly a specular reflectance, of 10% or more, more preferably 20% or more, particularly at a wavelength in any wavelength range from visible to infrared. It is preferable to have

The absorption rate of the polymer film in the present invention is 60% or less, preferably 40% or less,
It is desirable that the maximum wavelength of reflection (λRmax) in the polymer film be different from the maximum wavelength of absorption (λAmax), and it is particularly desirable that λRmax-λAmax ≧ 50 nm.

By using such a polymer film, substantially sufficient sensitivity can be obtained. This is because if the reflectance is less than 10%, it becomes difficult to detect the test chemical substance as a change in reflectance.

As the reflectance measurement or readout wavelength, a wavelength of about 600 to 1200 nm is usually used.

The material forming the polymer film having such a reflectance is preferably a conductive polymer having delocalized electrons or a material obtained by adding a dopant as a carrier to the conductive polymer.

When the polymerized film comes into contact with the test amine compound, the delocalized electrons and carriers are sensitive to the test chemical amine compound.

As such a conductive polymer, a conductive polymer which is a conjugated polymer is preferable.

The conjugated polymer conductive polymer is not particularly limited, but preferably used as the conjugated polymer compound are A) polyacetylene-based polyacetylene, polydiacetylene, and poly-1-alkyne which is a derivative thereof. , Polycyanoacetylene, polyphenylacetylene, polychlorophenylacetylene, polymethylazomethene, poly-1,6-heptadiyne, difluoroacetylene, etc .;

B) Polyphenylene system Polyparaphenylene, polybiphenylene, polymetaphenylene and its derivatives, polyparaphenylene sulfide, polyparaphenylene selenide, polyparaphenylene oxide, polyparaphenylene vinylene, polyparaphenylene azomethine, polyparaphenylene. Azophenylene,
Polyphenylene vinylene, poly-2,5-diethoxyphenylene vinylene, poly-p-dimethylaminostyryl vinyl, polyphenylene vinylene, polydiphenylene vinylene, polyphenylenearylene, polypyrene, polyazulene, polyfluorene, polynaphthalene vinylene, etc .;

C) Heterocyclic polymers Polypyrrole, polybipyrrole and its 3-substituted derivatives, and derivatives such as poly-N-methylpyrrole, polythiophene, polybithiophene, polytertienyl, polythienothiophene, polydithienothiophene and poly-3-
Poly-3-alkylthiophenes such as methylthiophene and 3-substituted derivatives such as poly-3-thiophene-alkene sulfonate, polythiophene vinylene, polyfuran, polyselenophene, polytellurophene, polyisothionaphthene, polyisonaphthothiophene and the like;

D) Ionic Polymer Polyaniline compound, polyaminopyrene, ionic polypyrrole, etc .;

E) Ladder Polymer Polybiphenylene, polyacene, polybenzothiophine, polynaphthyridine (polypyridinopyridine), polycyanodiene (polypyrazinopyrazine), polyarenemethanoid, polyperinaphthalene, polyperianthracene, etc .;

F) Others Polyoxadiazole, poly [Fe phthalocyanine],
Quinoid, polymetacyclophane, etc .; and the like.

Of these, polyaniline compounds are preferable in view of water resistance, sensitivity to amine compounds and the like.

The conductivity thereof is 1.0 × 10 ^-12 ~
About 1.0 × 10 ⁶ S / cm is preferable.

Such a polymer may be obtained by a usual electrolytic polymerization method, gas phase polymerization method, catalyst polymerization method, solid phase polymerization method or the like.

A dopant can be added to such a conductive polymer.

There is no particular limitation on the dopant that may be added to the conductive polymer, but as the dopant that is particularly preferably used, I ₂ , AsF ₅ , H ₂ SO ₄ and FeCl in the case of the polyacetylene-based conductive polymer are used. ₃
Etc; AsF in the case of polyphenylene-based conductive polymer
₅ , AsF ₃ , I ₂ , H ₂ SO ₄ , alkali metal, etc .;
ClO ₄ ⁻ , BF ₄ ⁻ , I in the case of a heterocyclic conductive polymer
₂ , alkali metals and the like; and the like.

These dopants are added to the conductive polymer in an amount of about 6 to 7% or more.

To add the dopant, a conventional method may be used.

By such a doping process, the conductivity of 1.0 × 10 ^{2 to} 1.0 × 10 ⁶ S / cm is exhibited.

The test chemical substance in the present invention is an amine compound. The analyte is usually gaseous, but may be liquid in some cases.

The amine compound may be an aliphatic amine, an aromatic amine or the like, and may be a primary amine, a secondary amine or a tertiary amine.

Among such amine compounds, the amine compounds to which the present invention is preferably applied are exemplified below. In the following, they are classified by odor. (1) An amine having camphor aroma N-dimethylamine bromide N, N-dibromomethylamine Isoamyl chloroamine thionylethylamine N-chlorobutylamine N-chlorodiethylamine N-chlorodimethylamine N-chloroethylamine N-chloropropramine Cyclobutylamine Isobutylchloramine Isobutyldichloroamine

(2) Amine having a scent of flowers Diphenylamine

(3) Amine having a rotten odor Dimethylamine Methylamine α-naphthylamine Trimethylamine Triethylamine Tri (n-butyl) amine

(4) Aromatic amine N-nitrosodiethylamine

(5) Amine having garlic odor Acetylallylamine Camphorylamine

The amine sensor of the present invention can detect and quantify one or more of the above amine compounds, and can also use a mixture of two or more compounds as the test chemical substance.

The amine compound reversibly adsorbs to the conductive polymer and makes an electrical interaction.

As described above, the physical properties of the polymer film change due to the adsorption or electrical interaction between the polymer film and the amine compound to be tested, and the light reflectance thereof changes. Then, this is utilized to detect the amine compound.

It is considered that the change in the light reflectance in this case is caused by the change in the film physical properties such as the film thickness, the film density and the refractive index of the polymer film.

That is, in the present invention, the change in the physical properties of the film due to the adsorption or electrical interaction between the polymer film and the amine compound is detected by the change in the light reflectance of the polymer film to quantify the amine compound. ..

In addition to the change in reflectance with monochromatic light, it is also possible to detect the change in the amount of reflected light or transmitted light by allowing the measurement wavelength to have a width. In this case, an LED can be used as the light source, and the amount of change light is large, which is preferable.

The polymer film in the present invention may contain two or more kinds of the above conductive polymers and dopants, and may have a constitution in which a plurality of polymer films are laminated.

To form the polymer film of the present invention, a monomer may be polymerized on a substrate to form a film, or a separately polymerized polymer may be formed on the substrate.

A binder such as various polymers which does not impair the function of the conductive polymer may be used in combination.

The polymer film has a thickness of 0.01 to 100 μm,
It is preferably 0.05 to 5 μm. With such a thin film, the response as a sensor becomes faster.

The material of the substrate in the present invention is not particularly limited, but it is preferably substantially transparent.

This is because the back side of the base can be detected.

Specifically, glass, hard vinyl chloride,
Various resins such as polyethylene terephthalate (PET), polyolefin, polymethylmethacrylate (PMMA), acrylic resin, epoxy resin, polycarbonate resin, polysulfone resin, polyethersulfone, methylpentene polymer, and bisphenol A-terephthalic acid copolymer are listed. Be done.

The shape of such a substrate is not particularly limited, but is usually a plate or a film.

In the present invention, the membrane surface of the sensor membrane may be air-sandwiched with a water-permeable or air-permeable protective plate, or the protective plate may be provided on the membrane surface.

A filter through which the amine compound can selectively pass may be provided on the membrane surface.

In the present invention, after the polymer film is formed on the substrate, it may be punched or cut into a desired size. When this method is used, mass productivity is improved.

Alternatively, a glass fiber may be used as the substrate and a polymerized film may be formed on the end face thereof. Further, a plurality of these may be bundled and used. Alternatively, the end faces may be ground by bundling and a polymer film may be formed on the end faces.

The conductive polymer forming the polymerized film in the present invention is preferably a polyaniline compound as described above.

This polyaniline-based compound is a conductive polymer in which delocalized electrons are present. In this polymer, in addition to the redox state by the dopant added as a carrier, the ionized state (--NH
₂ ⁺ −) is an ionic polymer in which there is. The dopant in this case is an acid such as hydrochloric acid, which will be described in detail later.

The polyaniline compound is polyaniline or a derivative thereof, and examples of the derivative include poly-N-methylaniline, poly-N-diethylaniline, poly-p-phenylaniline and the like. In some cases, these homopolymers
In addition, it may be a copolymer having different types of aniline or its derivative (monomer) as a constituent unit.

Such a polyaniline compound is obtained by polymerizing aniline which is a monomer or a derivative thereof (collectively referred to as aniline compound), and the polymerization is usually performed.
The electrolytic polymerization method is preferably used. Specifically, a known method of forming a film by electrolytic polymerization in an acidic solution is adopted.

Such a polymerized film is a monomer as described above.
May be polymerized on a substrate to form a film, or a polymer separately polymerized may be formed on the substrate, but a method of polymerizing a monomer on a substrate to form a film is usually preferable. It is used as follows.

First, the monomer is electrolytically polymerized in an acidic solution. Electrolysis at this time is constant current electrolysis or the like, and is performed using a transparent electrode [In ₂ O ₃ (Sn O ₂ ) etc.] as an electrode. In addition, such a transparent electrode may be formed on the substrate on which a film is formed, and the energization amount at this time is 0.1 to 10 mA, preferably 0.5 to 2 mA. You can do this. The electrolysis time may be selected according to the desired film thickness, but is usually 1 to 2 hours. Further, the acidic solution in the above, hydrochloric acid or the like is used as an acid,
The concentration is 0.5 to 2 mol / l, preferably about 1 mol / l. In this way, a polymerized film having a predetermined thickness is formed on the transparent electrode of the base.

In this way, the film is formed and then washed. Such washing may be performed by washing with water or the like, and specifically, by washing the surface of the film with water first and then immersing the entire substrate in water. As a result, mainly unreacted substances such as monomers remaining on the film surface and acids such as hydrochloric acid are removed. Distilled water may be used as the water at this time, and the immersion time is about 10 to 20 minutes.

After washing in this way, this time, acid treatment is carried out using hydrochloric acid. Specifically, a predetermined concentration (0.01
˜3 mol / l, preferably 0.1-1 mol / l) hydrochloric acid solution together with the substrate. The immersion time at this time may be set in consideration of the relationship with the acid concentration so that the sensor characteristics are the best, but from the viewpoint of workability, etc.
It is preferably within 1 hour, and this time is sufficient. In addition to hydrochloric acid, sulfuric acid or the like can be used for the acid treatment.

By carrying out the acid treatment as described above,
It is possible to improve the detection sensitivity and eliminate variations in sensor characteristics among elements. Such an effect is remarkably improved as compared with the case where electrolytic polymerization is performed under constant conditions such as electrolysis conditions and the concentration of an acid solution such as a hydrochloric acid solution.

Even when the method of depositing a separately polymerized polymer on the substrate is employed, a polymer film can be obtained by employing the same method as described above after the deposition.

As described above, the substrate used when the method of forming a film on the substrate is preferably a transparent substrate main body on which a transparent electrode is provided. At this time, the transparent electrode layer may have a resistance value of about 25 Ωcm ^-1 .

Further, as the transparent electrode, SnO ₂ , In
₂ O ₃ , SnO ₂ (Sb ₂ O ₅ ), In ₂ O ₃ (SnO ₂
) And the like. Among them, In ₂ O ₃ (SnO
₂ ) (ITO) is preferably used.

On the other hand, the material of the base body may be the same as the material of the base body. The transparent electrode layer is formed on the substrate body by spraying, CVD, spattering,
Depending on the case, it may be formed by hydrolysis of an organic salt or an inorganic salt, but the substrate having the layer formed thereon is commercially available, and a commercially available product can be used.

An amine sensor according to a preferred embodiment of the present invention is shown in FIG.

In the example shown in FIG. 1, the sensor film 12 which is a polymerized film is formed on the transparent substrate 11, while the light emitting element 21 and the light receiving element 31 are provided on the back surface side of the transparent substrate 11. Are installed, and these are casing 4
It is stored integrally in 0.

The polymer film 12 is in contact with the test atmosphere.

Therefore, the light emitted from the light emitting element 21 enters from the back surface of the base 11, the specular reflectance of the light at this time is detected by the light receiving element 31 also provided on the back surface of the base 11, and the change in the reflectance causes An amine compound, which is a chemical substance, will be detected and quantified.

In this case, it is preferable that the light emitting element 21 and the light receiving element 22 are installed close to each other, and the sensitivity is increased by measuring the reflection due to the specular reflection of 20 ° or less, particularly 5 ° or less. Can be made compact.

The wavelength of the light emitted from the light emitting element 21 in the present invention is any wavelength in the visible to infrared range. The light emitting element 21 is not particularly limited, but is preferably a light emitting diode (LED), a laser diode (LD), or the like.

In the present invention, the irradiation of the light emitted from the light emitting element 21 to the sensor film is preferably intermittent.

By performing the irradiation intermittently, the temperature rise of the sensor film can be suppressed. For this reason, the bond between the amine compound and the sensor film is less likely to be affected by heat, and the measurement accuracy in continuous measurement is remarkably improved.

The irradiation time for intermittent irradiation is not particularly limited, but it is preferable to set the irradiation time as short as possible within the measurable range, for example 0.01 to 100.
It is about msec.

The irradiation interval is not particularly limited, but in order to avoid the temperature rise of the sensor film, it is preferable to set the irradiation interval as long as possible within a range satisfying the required measurement interval. For example, when used as a normal amine sensor, the irradiation interval is about 0.1 to 10 msec.

The intermittent irradiation is performed by the controller 50 composed of a microcomputer or the like.
The intermittent irradiation may directly control the emitted light by intermittently energizing the light emitting element, or may be an indirect method such that continuous emitted light is applied to the sensor film via a chopper plate or the like. You may carry out by physical control.

Further, in any of these methods, control is not limited to a pattern in which irradiation and resting thereof are alternately repeated, and control may be performed to change the irradiation light intensity. The reason why the intermittent irradiation is performed in the present invention is to suppress the temperature rise of the sensor film and make it easier for the analyte to be adsorbed to the polymerized film that is the sensor film.

The light receiving portion 31 is a polymer film, that is, the sensor film 1.
The reflected light from 2 is received, and the electric signal according to the intensity is output. This electric signal is input to the controller 50. The controller 50 compares the electric signal signal with a reference value, and when the electric signal becomes smaller than the reference value, outputs an alarm signal and issues an alarm sound by an alarm 60, for example.

The amine sensor further includes a cleaning mechanism 70.

The cleaning mechanism 70 includes the sensor film 1
The sensor film 12 is provided to prevent an object from being deposited on the detection surface of No. 2 and preventing accurate sensing.
The air blower 71 is provided for blowing air to the detection surface and separating the subject bonded to the detection surface. The subject is the sensor film 1
Since it is loosely coupled to the second detection surface, it can be easily separated from the detection surface by blowing air. The blower 71 is preferably provided with a heater 72 on its front surface so that the blown air is warm air. The reason why the air is blown is that the object adsorbed on the sensor film 12 can be easily desorbed. At this time, the irradiation amount of light with which the polymerized film, that is, the sensor film 12 is irradiated may be increased to raise the temperature of the sensor film 12 to enhance the cleaning effect. The irradiation amount may be increased by maintaining the irradiation of light on the sensor film 12 for a predetermined time or by increasing the intensity. As shown in FIG. 1, the temperature sensor 73 for detecting the heating state of the sensor film 12 is provided to make the sensor film 1
Feedback control of the temperature of 2 may be performed.

Experimental Example In order to confirm the cleaning effect of air blowing and warm air blowing, trimethylamine 2000 pp was used as the above amine sensor.
When the blower was placed in an atmosphere of m 3 and the blower was operated at regular intervals, the recovery to the initial level was accelerated as shown in FIG. 2 (Example-1). In addition, when air was blown as warm air in Example-2, the return to the initial level was further accelerated. In the case of the comparative example in which no air was blown, the return to the initial level was slower than that in the example.

When the cleaning mechanism 70 continuously performs the sensing while cleaning, the detection accuracy was maintained even after 10 hours.

The cleaning mechanism 70 may be of a type in which the cleaning is performed by increasing the intensity of light applied to the polymer film and raising the temperature of the polymer film. It can also be used in combination with the above-mentioned blowing. The light intensity may be increased by continuously irradiating the sensor film 12 with light, or may be increased by increasing the intensity of light to be irradiated.

When the place where the amine sensor is installed is, for example, a refrigerator, the controller 50 may use a microcomputer incorporated therein.

In the above embodiment, the detection light is
Although the type of irradiating the surface opposite to the detection surface of the sensor film has been described, the detection surface itself may be irradiated.

With the above structure, the amine sensor of the present invention can detect an amine compound with high accuracy for a long time.

[0113]

[Brief description of drawings]

FIG. 1 is a schematic configuration diagram of an amine sensor according to an embodiment of the present invention.

FIG. 2 is a graph showing the effect of the amine sensor of the present invention.

[Explanation of symbols]

 11 substrate 12 sensor film 21 light emitting part 31 light receiving part 50 controller 70 cleaning mechanism

Claims (15)

[Claims] 1. A light-reflecting film when a substrate and a polymerized film which is a sensor film containing a conductive polymer as a main component are provided on the substrate, and the polymerized film comes into contact with an amine compound as an analyte. An amine sensor, comprising: a sensor main body for detecting and quantifying the analyte according to a change in the rate; and a cleaning unit for cleaning the analyte adsorbed on the polymerized film. 2. The amine sensor according to claim 1, wherein the cleaning unit is a blowing unit that blows air onto the surface of the polymerized film. 3. The amine sensor according to claim 2, wherein the blown air is warm air. 4. The sensor body has a light-emitting means and a light-receiving means, irradiates the polymer film with light from the light-emitting means, and receives the reflected light by the light-receiving means. The amine sensor according to any one of claims 1 to 3, which detects and quantifies. 5. The amine sensor according to claim 1, wherein the polymerized film contains a dopant. 6. The amine sensor according to claim 1, wherein the conductive polymer is a polyaniline-based compound. 7. The polymer film is formed and then washed,
The amine sensor according to claim 6, which is obtained by acid treatment. 8. The amine sensor according to claim 7, wherein the film formation is performed by electrolytic polymerization of an aniline compound in an acidic solution, and the acid treatment is performed by immersion in an acid solution. 9. The amine sensor according to claim 1, wherein air is blown to the polymerized film every predetermined time. 10. The amine sensor according to claim 1, wherein the polymer film is irradiated with light intermittently. 11. The amine sensor according to claim 1, wherein the intensity of the light with which the polymer film is irradiated is varied. 12. The amine sensor according to claim 1, wherein the temperature of the polymer film is raised by increasing the irradiation of light for irradiating the polymer film during the cleaning. 13. The amine sensor according to claim 12, wherein the intensity of light is increased by maintaining the irradiation of the polymer film with light for a predetermined time. 14. The amine sensor according to claim 12, wherein the intensity of light is increased by increasing the intensity of the irradiation light itself. 15. The amine sensor according to claim 1, wherein an alarm is emitted when the intensity of the reflected light from the polymerized film becomes smaller than a predetermined value.