JP2003012938A - Composition for forming oxygen-sensitive film and oxygen-sensitive film - Google Patents

Abstract

(57) Abstract: An oxygen-sensitive film having excellent emission intensity and / or pressure sensitivity is provided. The composition for forming an oxygen-sensitive film comprises an oxygen-quenching molecule, a polymer compound having a metalloxane bond and having a hydrophobic functional group, and a particulate material. The presence of particulate matter in the matrix of the polymer compound, in other words, the formation of a matrix that had been conventionally a single and uniform matrix was combined to positively impart a non-uniform field to the matrix. Thereby, as a result, the emission intensity and the pressure sensitivity change depending on the degree of the non-uniformity, and the emission intensity and the pressure sensitivity are improved.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an oxygen-sensitive composition having sensitivity to oxygen, and more specifically, to a film formation containing a molecule having oxygen quenching property and capable of visualizing pressure information of oxygen-containing gas. For compositions.

[0002]

2. Description of the Related Art Conventionally, a film forming composition comprising a molecule such as Pt porphyrin having oxygen quenching property and a binder has been known as an oxygen sensitive composition. Molecules such as porphyrin, utilizing the luminescence emitted when returning to the ground state from the energy level excited by ultraviolet rays, the oxygen-quenching molecule, when the molecule in the excited state returns to the ground state, It utilizes the oxygen quenching effect of quenching by the action of oxygen. That is, by utilizing the transition from the excited state to the ground state of a molecule having an oxygen quenching action, it becomes possible to relate the quenching action to the oxygen concentration, and the quenching action is caused in an atmosphere in which the oxygen concentration is proportional to the partial pressure. It becomes possible to correlate with pressure. Such an oxygen-sensitive composition has a film-forming ability and is made into a coating (pressure-sensitive luminescent coating material) to be applied in a film form on the surface of an object, and is used for wind tunnel experiments of objects.

Visualization information Vol.18 No.69 (April 1998) is used as the oxygen quenching molecule and the binder in the pressure-sensitive paint.
"Technology for measuring pressure distribution using pressure-sensitive paint" (Keisuke Asai),
Visualization Information vol.17 Suppl. No.1 (July 1997) "Various pressure-sensitive paint sample characteristics test" (Keisuke Asai et al.), JP-A-7-12661, JP-A-11-344388 Are disclosed.

As the oxygen quenching molecule, high quantum efficiency and excellent oxygen sensitivity are required, and porphyrin-based compounds, ruthenium complexes, aromatic compounds and the like are used. On the other hand, a binder for imparting a film of oxygen-sensitive molecules to the surface of an object satisfies oxygen permeability, adhesion to solids, surface smoothness, etc. in order to exhibit the oxygen quenching action of the molecule. It is described that a thermoplastic silicone copolymer (such as GP197) such as a dimethylpolysiloxane polymer solution, a silicone-polyurethane copolymer, a silicone-polyester copolymer, and a silicone rubber (RTV) can be used. . Further, JP-A-11-344388 discloses that when a silica gel plate for thin layer chromatography (TLC plate) is used as a binder, a porphyrin compound is dissolved in tetrahydrofuran and adsorbed.

[0005]

The above-mentioned various binders are all binders having high oxygen permeability, but in that case, the pressure sensitivity and responsiveness of the oxygen-sensitive film-like material obtained are mainly those of the binder itself. It is governed by oxygen permeability. Therefore, the pressure sensitivity and responsiveness are limited by the type of polymer, and as a result, it is difficult to improve the pressure sensitivity and responsiveness. Also, T
The LC plate has a relatively high pressure sensitivity, but since it has a plate shape, it has a problem of poor adhesiveness when a film-like body is formed to measure the pressure of the target object surface.

[0006]

In order to solve the above-mentioned conventional problems, the present inventors have paid attention to a binder in an oxygen-sensitive composition as a matrix in which oxygen quenching molecules are dispersed and studied. Then, the above-mentioned problems are solved and the photoreactivity of the oxygen-quenching molecule is improved by the complexation of the matrix or the non-uniformity of the matrix, and the pressure sensitivity and the emission intensity of the oxygen-sensitive film are improved. The inventors have found that they can be achieved and completed the present invention.

That is, the inventors of the present invention have made the particulate matter present in a matrix of a polymer compound capable of forming a film having oxygen permeability, in other words, it is conventionally single and uniform. The matrix was composited so that a non-uniform field was positively applied to the matrix. As a result, it was confirmed that the emission intensity and the pressure sensitivity were changed depending on the degree of the nonuniformity, and the emission intensity and the pressure sensitivity were improved.

Furthermore, the present inventors used a polymer compound having a metalloxane bond and a hydrophobic functional group as a matrix, and by allowing particles to be present in this matrix, the matrix was complexed. Alternatively, it has been found that by providing a non-uniform field in the matrix, the emission intensity and pressure sensitivity are improved.

Therefore, according to the present invention, the following means are provided. (1) A composition for forming an oxygen-sensitive film, comprising an oxygen-quenching molecule, a polymer compound capable of forming a film having oxygen permeability, and a particulate matter. (2) A composition for forming an oxygen-sensitive film, comprising an oxygen-quenching molecule, a polymer compound having a metalloxane bond and having a hydrophobic functional group, and a particulate material. (3) The polymer compound has a siloxane bond,
(2) The composition for forming an oxygen-sensitive film described in (2). (4) The composition for forming an oxygen-sensitive film according to any of (1) to (3), wherein the particulate matter is a particle having an affinity for oxygen. (5) The oxygen-sensitive film forming composition as described in any of (1) to (4), wherein the oxygen quenching molecule is a porphyrin compound. (6) A method for producing a composition for forming an oxygen-sensitive film, comprising:
By hydrolyzing and polycondensing a raw material containing a hydrolyzable metal compound having a hydrophobic functional group, having a metalloxane bond,
And a step of synthesizing a polymer compound having a hydrophobic functional group, and a step of separating a sol containing the polymer compound and then drying to obtain a gelled product. (7) The method according to (6), comprising a step of dissolving the gelled product and the oxygen quenching molecule in a solvent that dissolves the gelled product and the oxygen quenching molecule. (8) The method according to (6) or (7), wherein in the polymer compound synthesizing step, the hydrolyzable metal compound is trialkoxysilane having one hydrophobic functional group. (9) Metal oxide particles are further added to the solvent,
The method according to any one of (6) to (8). (10) The metal oxide particles are silica particles,
(9) The method as described. (11) The method according to any of (6) to (10), wherein the oxygen quenching molecule is a porphyrin compound. (12) The solvent is dichloromethane, (6) to
The method according to any one of (11). (13) An oxygen-sensitive film, comprising an oxygen-permeable matrix, oxygen-quenching molecules retained by the matrix, and particulate matter retained by the matrix. (14) The oxygen-sensitive membrane according to (13), wherein the oxygen-permeable matrix contains a polymer compound having a metalloxane bond and a hydrophobic functional group. (15) The particulate matter is an oxygen-affinity particle, (1
3) or the oxygen-sensitive film as described in (14). (16) The oxygen-sensitive film according to any of (13) to (15), wherein the oxygen-quenching molecule is a porphyrin compound. (17) The oxygen-sensitive film according to (15), wherein the oxygen-affinity particles are metal oxide particles having a particle size of 1 μm to 50 μm. (18) The metal oxide particles have a thickness of 10 nm to 500 nm.
The oxygen-sensitive film according to (15), which is a metal oxide particle having a particle size of. (19) An oxygen-sensitive film, wherein a product obtained by hydrolyzing and polycondensing a raw material containing a hydrolyzable metal compound having a hydrophobic functional group is separated, and the product and the oxygen-quenching molecule are separated. A film obtained by preparing a composition containing, and applying the composition to the surface of an object and drying the composition. (20) The film as described in (19), wherein a composition is prepared by further adding metal oxide particles to the separated product. (21) A product obtained by in-situ generation of a metal oxide by the hydrolysis / polycondensation is separated, and a composition containing this product and an oxygen quenching molecule is prepared. ) The oxygen-sensitive film described above. (22) A method of forming the oxygen-sensitive film according to (13) to (21) on the surface of an object and measuring the pressure distribution on the surface. (23) An apparatus for forming the oxygen-sensitive film according to (13) to (21) on the surface of an object and measuring the pressure distribution on the surface.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The oxygen-sensitive film-forming composition of the present invention comprises an oxygen-quenching molecule, a polymer compound capable of forming a film having oxygen permeability, and a particulate matter, preferably oxygen. And particles having an affinity with each other (hereinafter referred to as oxygen affinity particles). When the composition is applied to a solid surface, the polymer compound forms an oxygen-permeable film into a matrix, and the oxygen-quenching molecule retained in the matrix and the particulate matter retained in the matrix (preferably, An oxygen-sensitive film) is formed.

The oxygen-sensitive film of the present invention scatters the light emitted by the oxygen-quenching molecule dispersed in the matrix by containing the particulate matter in the matrix. This light scattering effect increases the emission intensity of the oxygen-sensitive film. Further, by dispersing and holding the oxygen-affinity particles such as metal oxide particles, the extinction degree of the emission intensity with respect to the oxygen concentration, that is, the pressure sensitivity is increased. It is considered that the increase in pressure sensitivity is due to the following action of the oxygen affinity particles. That is, it is considered that the oxygen-affinity particles in the matrix exert an adsorbing action on oxygen diffusing through the matrix. For this reason, the oxygen concentration becomes high in the vicinity of the oxygen affinity particles, and the oxygen concentration becomes non-uniform. However, it is presumed that the probability of contact between oxygen-quenching molecules and oxygen increases near the oxygen-affinity particles, and as a result, the quenching degree increases and the pressure sensitivity increases even with the same oxygen concentration.

At the same time, the oxygen-affinity particles have a shielding effect of inhibiting diffusion of oxygen in the oxygen-permeable matrix, so that oxygen tends to stay near the oxygen-affinity particles and the oxygen concentration may increase. It is possible. This may increase pressure sensitivity.

The oxygen affinity particles preferably have an oxygen affinity higher than the affinity of oxygen contained in the matrix. It is considered that the presence of such a difference in affinity between the matrix and the particles facilitates the accumulation of oxygen concentration in the vicinity of the particles having oxygen affinity, and that the above-described pressure sensitivity increasing effect is effectively exhibited. Become. To this end, for example, it is effective to lower the oxygen affinity of the matrix and / or increase the oxygen affinity of the oxygen-affinity particles.

In particular, it is a preferable mode to use a polymer compound having a hydrophobic functional group in the matrix. When the hydrophobic functional group is introduced into the matrix, the compatibility with the hydrophobic oxygen-quenching molecule is increased, and the oxygen-quenching molecule is favorably dispersed and retained. As a result, the concentration of oxygen-quenching molecules that can be dispersed and held in the matrix can be increased, and the emission intensity can be increased. At the same time, the introduction of hydrophobic groups also improves the oxygen permeability of the matrix. Further, it becomes easier to obtain a difference in oxygen affinity between the particles having oxygen affinity and the pressure sensitivity is also improved.

The oxygen-affinity particles may be particles having an affinity for oxygen, but preferably include a molecule having an oxygen atom, and more preferably an oxide particle.
It is typically a metal oxide particle. The particle morphology and the dispersion morphology in the matrix are not limited. The metal oxide particles have good oxygen affinity and can easily control desorption of oxygen. It should be noted that the improvement of pressure sensitivity is to detect a minute pressure difference on the object surface,
Contributes to the measurement of minute pressure distributions. Further, the improvement of the emission intensity contributes to the improvement of the measurement accuracy during pressure measurement.

The oxygen-permeable film forming composition of the present invention, the oxygen-permeable film, and the method for producing them will be described in detail below. (Oxygen-permeable film forming composition) The oxygen-permeable film forming composition of the present invention comprises an oxygen quenching molecule, a polymer compound capable of forming a film having oxygen permeability, and particulate matter. Contains. As the oxygen-quenching molecule, a light-emitting photoexciting substance that causes a quenching phenomenon by oxygen can be used. When an oxygen-quenching molecule is irradiated with excitation light having a wavelength corresponding to its absorption spectrum, the molecule in the excited state emits luminescence having a longer wavelength than the excitation light when returning to the ground state. But,
When oxygen molecules are present around molecules in the excited state, oxygen loses energy and falls to the ground state without emitting luminescence. That is, the luminescence intensity (lifetime) of the oxygen-quenching molecule changes depending on the oxygen concentration around the photoexcitation substance. Therefore, the oxygen concentration can be measured by measuring the intensity, and when the ratio of the oxygen component in the surrounding gas is kept constant, the measured value of the oxygen concentration is associated with the pressure to determine the pressure. It becomes possible to measure.

The quenching process is diffusion-controlled, and the emission intensity (I) is Stan-Volme (Stern-Volme).
According to the equation (1) of r). I ₀ / I = 1 + k _Q τ ₀ [O ₂ ] = 1 + k (T) P (1) I ₀ : Emission intensity when oxygen concentration is zero k _Q : O ₂ quenching rate constant τ ₀ : Lifetime of excited molecule in the absence of oxygen [O ₂ ]: oxygen concentration P: pressure K (T): proportional constant (temperature) In general, it is difficult to accurately estimate I ₀ .
The equation (1) is normalized based on the value (I _ref ) at the atmospheric pressure (P _ref ) which is usually a known pressure. I _ref / I = A + B (P / P _ref ) ... (2) A (T) = 1 / [1 + K (T) P _ref ], B = K (T) P _ref / [1 + K (T) P _ref ] (3) That is, the reciprocal of the emission intensity ratio is a linear function of the pressure ratio. A typical oxygen-quenching molecule or an oxygen-sensitive film containing it follows the formula (2). B is a coefficient called pressure sensitivity and serves as an index for evaluation of the oxygen quenching molecule or the oxygen sensitive film containing it.

Examples of such oxygen quenching molecules include:
Conventionally known are porphyrin compounds, metal complex compounds, polycyclic aromatic hydrocarbon compounds, fullerene compounds and the like. Examples of the porphyrin-based compound include those having octaethylporphyrin (OEP) or tetraphenylporphyrin (TFPP) as a skeleton and platinum, palladium, or zinc as a coordination metal. Typically, platinum octaethylporphyrin (PtOE
P), palladium octaethylporphyrin (PdOE
P), zinc tetraphenylporphyrin (ZnTFP
P) etc. can be mentioned. These may be used alone or in combination of two or more, but octaethylporphyrin type is preferable, and platinum octaethylporphyrin is most preferable.

Examples of the metal complex compounds include ruthenium (RuII) complex, osmium (OsII) complex and iridium (IrII) complex. The ruthenium complex is [Ru
(II) (L) ₃ ²⁺ ] (L is a ligand), and as the ligand, 2,2-bipyridine (bpy, R
u (bpy), 1,10-phenanthroline (phe)
n, Ru (phen)), 4,7-diphenyl-4,7
-Phenanthroline (Ph ₂ phen, Ru (Ph ₂ ph
en)) can be exemplified. Furthermore, these ligands can be used for osmium (OSII) or iridium (Ir).
The complex provided for (III)) can also be illustrated. These can be used alone or in combination of two or more.

The polycyclic aromatic hydrocarbon compounds include pyrene and perylene.
Etc. Furthermore, as fullerene compounds,
There are C ₆₀ and C ₇₀ .

Of these, oxygen quenching molecules include
A porphyrin compound is preferred, octaethylporphyrin is more preferred, and platinum octaethylporphyrin is still more preferred.

The content of the oxygen quenching molecule can be set as necessary, but is preferably about 0.0001 wt% to 0.1 wt% with respect to the polymer compound, and more preferably about 0. 0.0001 wt% to 0.005 wt%
Is. Particularly, in the case of octaethylporphyrin (preferably platinum octaethylporphyrin), about 0.0
001 wt% to 0.01 wt% is preferable,
More preferably, about 0.0001 wt% to 0.001 w
t%, and most preferably about 0.001 wt%.

The composition has a polymer compound capable of forming a film having oxygen permeability. Various polymers can be used in addition to the polymer compounds used in conventionally known oxygen-sensitive membranes. For example, silicone polymer type, silicone rubber type, polystyrene type, silica gel, silica type by sol-gel method and the like can be mentioned. GP, which is a polydimethylsiloxane polymer, as a silicone polymer
197 (Genesee Polymer Cor)
p.), a silicone rubber type, a room temperature curable silicone rubber such as vinyl silicone rubber GE RTV-118, a polystyrene type polystyrene, a silica gel type silica gel plate for thin layer chromatography, a sol-gel type silica. Examples thereof include a polymer compound having a siloxane skeleton obtained by hydrolysis / polycondensation of alkoxysilane.

In the present composition, it is preferable to use a polymer compound having a low oxygen affinity in relation to the oxygen affinity particles described later. It is more preferable to use a polymer compound having a hydrophobic functional group and a metalloxane skeleton. Examples of such a polymer compound include a product obtained by hydrolyzing and then self-condensing an organometallic compound having a hydrophobic functional group, typically a product obtained by a sol-gel method, and having a metalloxane skeleton. And a polymer compound having a hydrophobic functional group is preferred. Such a compound is obtained by hydrolysis / polycondensation using an organometallic compound having a hydrophobic functional group and two or more hydrolyzable groups as a starting material. The hydrophobic functional group may form a part of the main chain of the polymer skeleton, or may be provided by being bonded to a constituent atom of the main chain.

Such a hydrolyzable organometallic compound can be represented by, for example, the following formula. _{^{R 1 m -M- (OR 2)}} n (1) (wherein, M is a metal atom, R ¹ is each independently a hydrocarbon group having at least one carbon atom, R ² is Each independently represents a hydrogen atom or a hydrocarbon group having at least one carbon atom, and m is 1
The above is an integer, and n is an integer of 2 or more and is an integer obtained by subtracting m from the valence of the metal atom M. ) Further, an organometallic compound represented by the following formula (2) can also be used. R ¹ _m —M—X _n Formula (2) (wherein M is a metal atom, R ¹ is independently a hydrocarbon group having at least one carbon atom, and X is independently, It is a halogen atom, m is an integer of 1 or more, and n is an integer of 2 or more and is an integer obtained by subtracting m from the valence of a metal atom.)

In these formulas (1) and (2), M is preferably silicon (Si), aluminum (Al), titanium (Ti), niobium (Nb), zirconium (Zr) or the like. When M is silicon, the resulting compound has a siloxane skeleton having a Si-O bond, in the case of aluminum, an alloxane skeleton having an Al-O bond, and in the case of titanium,
Those having a corresponding metalloxane bond, such as those having a titanooxane skeleton having a Ti—O bond, are provided. Aluminum, titanium, and silicon are preferable, and at least silicon is more preferable. Preferably, only silicon is used. Note that M is 1
It is possible to obtain a cocondensate by using one kind or two or more kinds of organic metal compounds as raw materials in combination of two or more kinds.

In these equations (1) and (2), R
¹ corresponds to the hydrophobic functional group in the hydrolyzable organometallic compound. R ¹ is preferably a hydrocarbon group having 1 to 10 carbon atoms, more preferably a linear or branched alkyl group having 1 to 6 carbon atoms, or an alicyclic carbon group having 4 to 8 carbon atoms. It is a hydrogen group. R ¹ can be an aromatic cyclic hydrocarbon group having 6 to 18 carbon atoms. More preferably, it is a linear or branched alkyl group having 1 to 6 carbon atoms, and an aromatic cyclic hydrocarbon group having 6 to 14 carbon atoms. As the linear alkyl group, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group,
An n-butyl group, an iso-butyl group, a tert-butyl group and the like can be preferably used. More preferably, a methyl group,
An ethyl group and the like. Further, as the aromatic cyclic hydrocarbon group, a phenyl group, a benzyl group, a diphenyl group, a triphenyl group and the like can be preferably used. More preferably, it is a phenyl group or a diphenyl group. More preferably, it is a phenyl group only. One kind or two as R ¹
It is possible to combine more than one kind and use one or more kinds of organometallic compounds as raw materials,
It is also possible to obtain a cocondensate.

The number (m) of R ¹ groups is an integer of 1 or more, preferably 2 or less, more preferably 1. This is because if the number of R ¹ is large, as a result, it becomes difficult to obtain a three-dimensional metalloxane skeleton by hydrolysis and polycondensation.

The organometallic compound represented by the formula (1) is O
It has an R ² group. The OR ² group corresponds to the hydrolyzable group. The OR ² group is a hydroxyl group and / or an alkoxyl group. In the case of an alkoxyl group, R ² is preferably an alkyl group, more preferably a chain alkyl group having 1 to 5 carbon atoms. Most preferably, it is a methyl group or an ethyl group. The number (n) of hydroxyl groups and / or alkoxyl groups is 2 or more, more preferably 3 or more. When the metal atom is silicon, it preferably has three alkoxyl groups and / or hydroxyl groups.
Preferred organometallic compounds include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, diphenyltrimethoxysilane, diphenyltriethoxysilane and the like. You can More preferred are phenyltrimethoxysilane, phenyltriethoxysilane, diphenyltrimethoxysilane and diphenyltriethoxysilane, and even more preferred are phenyltrimethoxysilane and phenyltriethoxysilane.

The organometallic compound represented by the formula (2) has a halogen group. The halogen group corresponds to the hydrolyzable group. As the halogen atom, chlorine, bromine, fluorine, iodine and the like can be used. Chlorine and bromine are preferable. The number of halogen groups is 2 or more, and more preferably 3 or more. When the metal atom is silicon,
It is preferable to have three halogen groups.

As mentioned above, the formulas (1) and (2) are exemplified as typical compounds as starting materials for obtaining the preferable polymer compound. However, at least one hydrophobic functional group is provided, and the compounds after hydrolysis are heavy. Any condensable organometallic compound may be used. The hydrolyzable group may have any of an alkoxyl group, a hydroxyl group, a halogen group, and a hydrocarbon group. The hydrophobic functional group can be selected in relation to the structure of the oxygen quenching molecule used. From this viewpoint, as the hydrophobic functional group, a phenyl group, a diphenyl group,
An aromatic cyclic hydrocarbon group such as a triphenyl group can be selected.

By hydrolyzing such a starting material in an acid or an alkali and conducting a polycondensation reaction, a polymer compound preferable in the present invention can be obtained. The hydrolysis / polycondensation reaction can be carried out by employing the conditions generally used as the sol-gel method.

As a result of the polycondensation reaction, hydrolysis / polycondensation products are produced in the reaction solution. In the reaction solution, a polymer compound having a hydrophobic functional group and having a metalloxane skeleton is produced. On the other hand, depending on the conditions and the like, a compound having a metalloxane bond but having a relatively small content of hydrophobic functional groups may be produced. That is, there may be a case where particles or the like mainly composed of the metal oxide or substantially composed of the metal oxide are produced. In such a case, only the polymer compound having a hydrophobic functional group and a metalloxane skeleton may be separated from the reaction system and used as the polymer compound of the present invention, or if the content of the hydrophobic functional group is A relatively small amount of the product fraction can be simultaneously separated from the reaction system and used in combination with the polymer compound. At the same time, this fraction has a relatively small content of hydrophobic functional groups with respect to the matrix, and thus can function as oxygen affinity particles.

The particulate matter contained in the present composition is contained. The presence of the particulate matter not only increases the emission intensity due to light scattering, but also improves the dispersed state of the oxygen quenching molecule contained in the present composition, and has the effect of improving the emission intensity or pressure sensitivity. The particulate matter preferably has an oxygen affinity. The affinity for oxygen is also the adsorption action of oxygen. The oxygen affinity particles are preferably particles containing an oxide. The oxygen-affinity particles are preferably particles containing a metal oxide, and more preferably particles substantially consisting of a metal oxide. The metal oxide is
Silicon dioxide (silica, SiO ₂ ), alumina (Al ₂ O
₃ ), titania (TiO ₂ ), magnesia (MgO), MnO ₂ , CaO, ZnO, NiO, ZrO ₂ , Pb
O ₂ , AgO, etc. can also be used. Preferred are silica, alumina, titania, etc., and more preferred is silica.
These metal oxides can be used alone or in combination of two or more.

The oxygen affinity particles preferably have a higher oxygen affinity than the polymer compound capable of forming the oxygen permeable matrix. Metal oxides can usually meet this requirement. When the polymer compound has a hydrophobic functional group such as a hydrocarbon group such as an alkyl group, the oxide-containing particles can easily meet this requirement.

The form and size of the oxygen-affinity particles are not particularly limited. The morphology varies depending on the material of the oxygen-affinity particles, but for example, in the case of so-called ceramic particles made of metal oxide, it can be in the shape of irregular chips, spheres, flakes, needles, or the like. The size (particle size) of the oxygen-affinity particles such as the metal oxide particles can be set to the μm size level. That is, about 1 μm to 50
The particle size may be μm, but more preferably about 1
μm to 20 μm. On the other hand, the oxygen affinity particles have nm
It can also be a size level size. That is,
About 2 nm to 500 nm, more preferably 10 n
m-500 nm, more preferably 10 nm-
It is 50 nm. Further, it is 2 nm to 20 nm. The composition may include only μm level particles or only nm level particles, but may also include particles of both sizes. When using the μm level particles, it is easy to prepare the composition by adding such particles to the composition, but when using the nm level particles, it is necessary to obtain a dispersion state of such particles. May be added to the composition, but preferably, it is contained in the composition by being generated in situ during the hydrolysis / polycondensation reaction of the polymer compound having a siloxane skeleton. Is preferred.

In the present composition, the particulate matter is preferably contained in the polymer compound in an amount of about 1 wt% to 50 wt%, more preferably about 1 wt% to 20 wt%.
Is. Especially when using metal oxide particles, about 1 w
t% to 20 wt% is preferable, and more preferably about 5 wt% to 15 wt%. In the case of silica particles, it is preferably about 5 wt% to 15 wt%,
Most preferably, it is about 10 wt%.

The composition may contain other components, if desired. Additives, sensitizers, etc. that improve the film forming property can be included.

The present composition described above can also be produced by mixing in advance particulate materials such as polymer compounds, oxygen quenching molecules and metal oxide particles. Further, in the presence of a polymer compound having a metalloxane skeleton such as a silicone resin or a siloxane skeleton prepared in advance, a hydrolyzable metal compound such as a metal alkoxide is caused to undergo hydrolysis / polycondensation (sol-gel reaction). The metal oxide particles may be compounded in the polymer compound. In this case, it is preferable to introduce a hydrophobic hydrocarbon group into the polymer compound prepared in advance. Furthermore, even when a hydrolyzable metal compound is hydrolyzed and polycondensed (sol-gel reaction) to generate a polymer compound having a metalloxane skeleton, at the same time a particulate metal oxide is generated in situ. Good. In order to obtain such a composite system, a hydrolyzable metal compound that easily forms a polymer compound as a matrix and a hydrolyzable metal compound that easily forms metal oxide particles dispersed in the matrix are included in advance. Alternatively, it can be achieved by controlling the reaction system. For example, in the former case, when a hydrolyzable organometallic compound having a hydrophobic hydrocarbon group and a hydrolyzable metal compound not having a hydrophobic hydrocarbon group are used as reaction materials, a metalloxane having a hydrophobic hydrocarbon group is obtained. A polymer compound having a skeleton,
A product containing metal oxide particles is easily obtained. Also,
In a system for producing a polymer compound having a hydrophobic hydrocarbon group using a hydrolyzable organometallic compound having a hydrophobic hydrocarbon group, oxide particles of the same metal having no such hydrophobic hydrocarbon group However, it tends to be easily produced as a by-product.

The metal oxide particles include silicon dioxide (silica, SiO ₂ ), alumina (Al ₂ O ₃ ), titania (TiO ₂ ), magnesia (MgO), MnO ₂ and C.
To form aO, ZnO, NiO, ZrO ₂ , PbO ₂ , AgO, etc., hydrolyzable compounds of these metals are used. Preferably, hydrolyzable compounds of these metals which produce silica, alumina, titania and the like are used. Most preferably, it is a hydrolyzable silicon compound. The size of the metal oxide particles to be generated in-situ, the individual form thereof, and the dispersion form depend on the molecular weight of the metal oxide to be formed, and the dispersion form in the finally obtained film is the film formation. It depends on the method and conditions.

As the raw materials used in the production of the present composition, the components preferable as the above-mentioned constituents of the present composition can be similarly used in the present production method.

As an example of the present composition and manufacturing method, a polymer having a siloxane skeleton having a phenyl group is produced by using phenyltriethoxysilane as a starting material to cause hydrolysis / polycondensation (sol-gel method). The compound was obtained, and platinum octaethylporphyrin (Pt as an oxygen quenching molecule was obtained.
Preparation of a composition containing OEP) and silica particles will be described.

First, when a mixed solution of phenyltriethoxysilane and ethanol is refluxed at about 60 ° C. and diluted hydrochloric acid (for example, 0.15N) is added dropwise, hydrolysis / polycondensation proceeds, resulting in phenylsilicon polymer. And a colorless and transparent ethanol solution of the polymer is obtained. When the oxygen-quenching molecule is dissolved in this solution, it may be used as it is, but since PtOEP is not dissolved in ethanol of this example, the product is separated from the reaction system and then mixed with PtOEP which is the oxygen-quenching molecule. To do. The separation is performed, for example, by dropping the polymer solution into excess water. In this case, the oily product (sol) is separated.
When the metal oxide particles are produced at the same time or when the metal oxide particles are contained as a by-product, the metal oxide particles are also separated at the same time as the polymer.

An oily substance (sol) is separated from water and dried by vacuum drying or the like to prepare a hydrolysis / polycondensation product (which may include metal oxide particles in addition to a polymer compound). it can. The hydrolysis / polycondensation product and the oxygen quenching molecule are dissolved in a solvent in which both are dissolved.
When metal oxide particles are contained in the separated product, it is not necessary to add the metal oxide separately, but from the viewpoint of quantity or particle size, the metal oxide particles are separately added. It can also be added. It is particularly effective in the case of adding metal oxide particles of the μm level to increase the light scattering effect. Oily substance (sol) separated from water
In the case of the above, when it becomes a gel by drying, the solvent of the composition easily penetrates, and thereby the dispersed state of the oxygen quenching molecule becomes good. Further, when the metal oxide particles generated in-situ are contained in the gel, the dispersed state of the metal oxide particles is maintained well even if the solvent is added. In this step, dichloromethane can be used as a solvent capable of dissolving the gel and platinum octaethylporphyrin. Other,
A halogenated hydrocarbon solvent such as 1,2-dichloroethane or chloroform can also be used.

In such a step, a composition containing phenyl silicone polymer (polyphenyl siloxane) as a polymer compound, PtOEP as an oxygen quenching molecule, and silica particles as a particulate material can be obtained. As the solvent constituting the composition, an appropriate solvent can be selected depending on the combination of the polymer compound and the oxygen quenching molecule. When metal oxide particles are separately added, various metal oxide particles such as titania and alumina can be used as well as silica particles. In addition, since the application method (application method) differs depending on the shape of the solid on which the oxygen-sensitive film is to be formed by applying this composition, it is possible to obtain work physical properties according to the application method. The composition and additives are selected.

Next, the step of forming an oxygen-sensitive film with the composition and the resulting oxygen-sensitive film will be described. The composition for forming an oxygen-sensitive film obtained as described above is applied to a solid surface (including the inner surface) to form an oxygen-sensitive film. The film forming method is not particularly limited, but a spin coating method, an air brush method, a dipping method, a spray method, or the like can be used. In the case of a flat plate, the spin coating method can be preferably used, and in the case of a curved surface, the air brush method, the dipping method and the like can be preferably used.

By forming a film of the present composition, an oxygen permeable film is used as a matrix, and oxygen quenching molecules dispersed in this matrix and particles (oxygen affinity particles) dispersed in this matrix are provided. An oxygen sensitive film (pressure sensitive coating) is formed. The matrix varies depending on the type of polymer compound used in the composition, but is a polymer compound having a metalloxane skeleton having a hydrophobic functional group,
It is preferable from the viewpoint of affinity and oxygen permeability for highly hydrophobic oxygen-quenching molecules such as porphyrins. Furthermore, when the polymer compound has a metalloxane skeleton having a hydrophobic functional group, when it contains oxygen affinity particles or metal oxide particles as particles, it has an affinity for oxygen between the oxide particles and the matrix. Since the difference in properties becomes large, the oxygen adsorption action by the oxygen affinity particles or the metal oxide particles, the contact probability between the oxygen quenching molecule and oxygen,
It is advantageous for increasing pressure sensitivity. In particular, when an alkyl group having 1 to 5 carbon atoms or an aromatic cyclic hydrocarbon group such as a phenyl group, a diphenyl group and a triphenyl group is provided as the hydrophobic functional group, these effects are effectively enhanced. To be done.

Due to the non-uniformity due to the inclusion of particulate matter in the oxygen permeable matrix, the contact between oxygen and oxygen quenching molecules is not only dependent on the diffusion of oxygen, but the pressure sensitivity is enhanced by some other action. Also, the light scattering effect increases the emission intensity. Furthermore, when the particulate matter is an oxygen affinity particle or an oxide particle such as a metal oxide,
Due to the adsorption action of these particles and oxygen, non-uniformity of oxygen permeation or existing state in the oxygen permeable matrix is increased, and pressure sensitivity is greatly enhanced. This is because when the particulate matter, especially the oxygen-affinity particle or the metal oxide particle is held in the matrix, the matrix environment around the oxygen-quenching molecule is changed to an environment preferable for improving the pressure sensitivity and the emission intensity. Conceivable. Such a particulate matter may have a size of μm or a size of nm, but if the particulate matter is a finer particle, such an environmental change can be caused in a wider range as compared with the amount of particles added.

The membrane may retain particulates of the above-mentioned μm size level and / or particulates of the above-mentioned nm size level, but preferably includes both sizes of particulates. In particular, it is preferable that the metal oxide particles have a size of nm (about 2 nm to 20 nm) and are dispersed in the matrix because the pressure sensitivity is uniformly enhanced in the film. In addition, it is preferable that a network-shaped or secondary agglomerated particle-shaped agglomerated region formed by fine particles of nm size is formed uniformly or dispersed in the entire film. In particular, it is more preferable that the structure has an interpenetrating structure with the polymer forming the matrix.

In order to disperse and maintain the nm level oxide particles in a preferable state in the matrix, the metal oxide particles are generated in situ at the same time as the hydrolysis polycondensation reaction of the polymer compound having a metalloxane skeleton. Or let
Alternatively, an oxygen-sensitive film obtained by forming a film containing a composition containing a product obtained by causing a hydrolysis polycondensation reaction of a metal oxide in the presence of a polymer compound prepared in advance It is preferable. In particular, an oxygen-quenching molecule is mixed with a hydrolysis polycondensation reaction product of a hydrolyzable metal compound, the hydrolysis polycondensation product containing oxide particles of the metal produced in situ at the same time as the polymer compound. An oxygen-functional film obtained by forming a film of the above composition is a preferred form. Most preferably, it contains a polymer compound having a hydrophobic functional group and a siloxane skeleton, which is obtained by hydrolysis polycondensation, and at the same time contains a hydrolysis polycondensation reaction product containing silica particles produced in situ. It is a film obtained by forming a film of the composition. This film preferably contains a porphyrin type, more preferably platinum octaethylporphyrin as an oxygen quenching molecule. Further, the hydrophobic functional group is preferably an alkyl group having 1 to 5 carbon atoms, or an aromatic cyclic hydrocarbon group such as a phenyl group and a diphenyl group. Incidentally, as the hydrolyzable metal compound in this case,
A trialkoxysilane having one of these hydrophobic functional groups is preferable, and trimethoxysilane or ethoxysilane is more preferable. The hydrophobic functional group is preferably a phenyl group.

In particular, a polymer compound having a hydrophobic functional group and having a siloxane skeleton, which is generated by hydrolysis polycondensation, silica particles generated in situ, and a particle size of about 2 μm to 2 μm
Oxygen sensitive membranes with 0 μm added silica particles are preferred. This film preferably contains a porphyrin type, more preferably platinum octaethylporphyrin as an oxygen quenching molecule. Further, the hydrophobic functional group is preferably an alkyl group having 1 to 5 carbon atoms, or an aromatic cyclic hydrocarbon group such as a phenyl group and a diphenyl group.

The oxygen-sensitive film can also be obtained by a method other than the method of forming a film by applying a composition containing a polymer compound, an oxygen quenching molecule, and particulate matter to a solid surface. Further, the nm-sized particulate matter or the μm-sized particulate matter is typically oxide particles such as metal oxides, but it contains a polymer compound and an oxygen quenching molecule, and is a particulate matter. It may be applied to the film by applying a partial composition that lacks to the solid surface after it is not completely solidified, or the particulate matter may be adhered or generated on the solid surface in advance, and this adhesion Alternatively, it can be formed by applying the partial composition to the production region.

Further, the high molecular compound or the high molecular compound and the particulate matter may be applied to the solid surface in advance, and then the composition containing the oxygen quenching molecule may be applied to obtain the oxygen-sensitive film. it can. In this case, the polymer compound is
In addition to a film-like body having a surface irregular shape and a porous body, a form having tubular pores may be formed. The film (matrix) previously formed on the solid surface may be a film of a polycondensation product having a metalloxane skeleton obtained by the sol-gel method as described above, or may be formed by oxidative firing, anodic oxidation or the like. The particulate matter may be contained in the composition, or may be provided on the film side in advance.

The oxygen-sensitive film can be used not only for measuring the oxygen concentration but also for measuring the pressure in an atmosphere in which the proportion of oxygen components is kept constant. The oxygen-sensitive film has a pressure distribution, an oxygen concentration distribution, and
In particular, the fluctuation can be easily measured. Further, it is useful for various pressure distribution measurement and diagnostic techniques in that it is possible to visualize the variation of oxygen concentration and / or pressure in a plane. In particular, it is useful for wind tunnel experiments in aerospace, measurement of pressure surface distribution in high-speed fluid equipment such as turbochargers, and the like. Luminescence intensity (image)
Can be converted into oxygen concentration or pressure by image processing or the like.

The oxygen-sensitive film of the present invention can be applied to the measurement of pressure distribution by having the following constitution.
The measurement system (apparatus) includes an object to be measured provided with the oxygen-sensitive film, an excitation light source that illuminates the measurement surface of the object, a photodetector that detects luminescence, and a computer that executes image acquisition and processing. And have.
Laser, discharge lamp (xenon,
Mercury, etc.), halogen lamps, LEDs, etc. can be used. Since the xenon lamp has a flat spectrum from the ultraviolet region to the visible region, a necessary excitation wavelength can be extracted by using an interference filter or the like.

For detecting luminescence, a photomultiplier tube,
Besides a point sensor such as a silicon diode, a CCD camera can be used. At the time of detection, a bandpass filter corresponding to the emission wavelength is provided according to the type of luminescence to be detected. The object to be measured may be placed in a chamber whose atmosphere and temperature can be adjusted as needed.

When a pressure load such as fluid pressure is applied to the measurement surface of the excited object to be measured, the luminescence image thereof is taken in by a detection device such as a CCD camera.
It is recorded on a video recorder, etc., and input to a computer for image processing. The image processing can adopt a procedure usually performed in this field,
For example, a pre-processing step such as dark subtraction / averaging of the image, a step of calculating the ratio of the luminescence image between no load and a pressure load for each pixel, and a pressure conversion step using a calibration formula can be adopted. Since it is necessary to measure the temperature distribution for pressure measurement, a temperature measuring means for the measurement surface is provided. A thermocouple, an infrared camera, a temperature sensitive paint, or the like can be used as the temperature measuring means.

[0058]

The present invention will be described below with reference to specific examples.
The present invention is not limited to the following specific examples. (Example 1) Preparation of composition for forming oxygen-sensitive film In the composition of Example 1, a polymer compound having a phenyl group-introduced siloxane skeleton was used as the polymer compound forming the oxygen-permeable matrix. Then, using platinum octaethylporphyrin as an oxygen quenching molecule,
As the particles, crushed silica particles having a particle size of about 2 to 5 μm were used.

First, phenyltriethoxysilane (50.9 ml, 0.21 mol), which is a starting material for a polymer compound, was mixed with ethanol (49 ml), and the mixture was refluxed at 60 ° C. to dilute hydrochloric acid (0.15 N, 10.8 ml). ) Was dripped.
This solution was stirred for 3 hours, left overnight, and further stirred for 3 hours. During this period, the hydrolysis / polycondensation reaction of phenyltriethoxysilane proceeded, and an ethanol solution containing a colorless transparent liquid phenylsilicon polymer was obtained. Next, this solution was added dropwise to excess water to separate a hydrolysis / polycondensation product as an oily substance (sol). The separated product was transparent. Add about 2 more of this isolate.
It was vacuum dried for 0 hour to obtain a white gel.

Dichloromethane capable of dissolving platinum octaethylporphyrin and phenylsilicon polymer was added to and dissolved in the obtained gel body. Furthermore, a predetermined amount of platinum octaethylporphyrin and silica particles were added to obtain a composition for forming an oxygen-sensitive film as a transparent orange solution. The composition of each component is dichloromethane 10m.
1 g of phenyl silicone polymer gel body and 1 mg of platinum octaethylporphyrin, and 1 g of gel body
On the other hand, by adding silica particles in the range of 0 to 20 wt%, compositions 1 to 5 having different contents of five kinds of silica particles
Got

Example 2 Measurement of Pressure Sensitivity and Luminous Intensity in Compositions 1 to 5 With respect to the compositions 1 to 5 obtained in Example 1, pressure sensitivity and luminescent intensity were measured using a measuring device shown in FIG. Was measured.

Compositions 1 to 5 were coated on a glass substrate (Corning # 7059, 20 mm square) by spin coating (spin coating condition 2000 rpm, 10 sec), and N ₂
The film was dried for 3 hours in a flow dryer (60 ° C.) to give a film for evaluation.

The pressure sensitivity was measured by using a xenon lamp as an excitation light source, passing through an ultraviolet ray transmitting visible light absorbing filter, and applying ultraviolet light (383) to the sample placed in the vacuum chamber.
nm) or visible light (537 nm), and the emission pattern of the sample was observed by a CCD camera through a bandpass filter (wavelength 645 nm) and recorded by a video recorder. The sample was set to be inclined by 45 degrees from the light irradiation direction. The pressure inside the chamber was measured with a semiconductor pressure sensor, and the vacuum degree was adjusted with a manual pump and a valve. The sample temperature at each pressure was measured with a thermocouple. The obtained emission pattern is used as a reference pressure (P
_ref) (normalized by the emission pattern at atmospheric pressure), with obtaining the emission intensity (I) at each pressure P, the emission intensity ratio (I _{re f} / I) was calculated, Stan - performs approximation by-Volmer plot, The pressure sensitivity was calculated. FIG. 1 shows the amount of silica particles added and the pressure sensitivity (excitation wavelength 383n
m), FIG. 2 shows the relationship between the amount of silica particles added and the emission intensity (excitation wavelength 383 nm and 537 nm), and FIG. 3 shows the emission intensity (excitation wavelength 383 nm) in the sample containing 10 wt% silica. ) And pressure.

As shown in FIG. 1, the maximum pressure sensitivity was exhibited when the amount of silica added in the composition was 10 wt%. Further, when the amount of silica added was in the range of 5 to 15 wt%, the pressure sensitivity was approximately stable and exhibited a certain level or more. Further, in order to stabilize the pressure sensitivity, the amount of silica added is more preferably 5 to 10 wt%. As shown in FIG. 2, the emission intensity is maximum when the amount of silica added is approximately 10 wt%, and a certain amount or more of emission intensity is obtained in the range of 5 to 20 wt%, preferably in the range of 10 to 15 wt%. Met.

In FIG. 3, P _ref represents atmospheric pressure,
P indicates the measured pressure, I _ref is the emission intensity under atmospheric pressure, and I is the emission intensity at a predetermined pressure. As shown in FIG. 3, it can be seen that the emission intensity (I) is higher as the pressure is lower, and the pressure and the emission intensity have a linear relationship. Both of them followed the Stern-Volmer relational expression. The slope of this straight line corresponds to the pressure sensitivity, indicating that the pressure sensitivity was high in the sample containing 10 wt% silica. In addition, in the samples using the compositions 1 to 5, it was confirmed that the emission intensity increased as the pressure decreased below the atmospheric pressure in any of the compositions, and it was confirmed that the two have a linear relationship. .

(Example 3) GP197 (Genesee polymer Corp) which is a commercially available dimethylsiloxane
1% of platinum octaethylporphyrin, and 10 wt% (as amount relative to dimethylsiloxane) of crushed silica particles having a particle size of about 2 to 5 μm, and mixed to prepare a composition. A sample was prepared in the same manner as in Example 2 and pressure sensitivity was determined. The result was 0.75. This is the pressure sensitivity (reference value) of 0.6 obtained with the composition of GP197 and platinum octaethylporphyrin.
It was a value superior to 3 to 0.67. From this, the effectiveness of adding silica particles was clear.

Example 4 Two kinds of compositions obtained by applying the composition 1 containing 0 wt% of silica and the composition 4 containing 10 wt% of silica to the glass substrate by the method described in Example 2 were used. As a result of observation with an electron image), in the film obtained from the composition 4, silica particles of about 2 to 20 μm were dispersed. On the other hand, in the film obtained from the composition 1, a uniform film formation state was observed. Furthermore, when a transmission electron image was observed by TEM, the amounts of hydrocarbon compounds considered to be derived from phenyl groups in both the films obtained from composition 1 and composition 4 were higher in Si and O content than in the surroundings. It was found that there is a region where there is relatively little. In this region, compound particles mainly containing SiO ₂ were present. It was presumed that such particles were SiO ₂ particles that were formed in-situ when the phenyl group-containing polysiloxane was formed during the hydrolysis polycondensation reaction of phenyltriethoxysilane.

[0068]

According to the composition and film of the present invention, it is possible to provide an oxygen-sensitive film having excellent emission intensity and / or pressure sensitivity.

[Brief description of drawings]

FIG. 1 is a diagram showing the relationship between the amount of silica added and pressure sensitivity.

FIG. 2 is a diagram showing the relationship between the amount of silica added and the emission intensity.

FIG. 3 is a diagram showing a relationship between a light emission intensity ratio and pressure in a silica-added system and a silica-free system.

FIG. 4 is a diagram showing an apparatus for evaluating an oxygen-sensitive film.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08L 85/00 C08L 85/00 G01L 5/00 101 G01L 5/00 101Z (72) Inventor Motohiro Tomomi Aichi 1 Nagatoge, Nagakute-cho, Aichi-gun, Nagatoji 1 Yokomichi F-term (reference) 2F051 AB03 BA01 4F071 AA67 AA69 AB18 AB26 AC02 AC18 BB02 BC01 4J002 CP031 CQ001 DE077 DE087 DE097 DE107 DE137 DE147006 GR00 EA066 E017006

Claims (23)

[Claims] 1. A composition for forming an oxygen-sensitive film, comprising: An oxygen-quenching molecule, A polymer compound capable of forming a film having oxygen permeability, A particulate matter, and a composition containing. 2. A composition for forming an oxygen-sensitive film, comprising an oxygen-quenching molecule, a polymer compound having a metalloxane bond and having a hydrophobic functional group, and a particulate matter. object. 3. The oxygen-sensitive film-forming composition according to claim 2, wherein the polymer compound has a siloxane bond. 4. The oxygen-sensitive film forming composition according to claim 1, wherein the particulate matter is a particle having an affinity for oxygen. 5. The oxygen-sensitive film-forming composition according to claim 1, wherein the oxygen-quenching molecule is a porphyrin-based compound. 6. A method for producing a composition for forming an oxygen-sensitive film, which comprises hydrolyzing and polycondensing a raw material containing a hydrolyzable metal compound having a hydrophobic functional group, and having a metalloxane bond, A method comprising a step of synthesizing a polymer compound having a hydrophobic functional group, and a step of separating a sol containing the polymer compound and then drying to obtain a gelled product. 7. The method according to claim 6, comprising the step of dissolving the gelled product and the oxygen quenching molecule in a solvent that dissolves the gelled product and the oxygen quenching molecule. 8. The method according to claim 6 or 7, wherein in the step of synthesizing the polymer compound, the hydrolyzable metal compound is trialkoxysilane having one hydrophobic functional group. 9. The method according to claim 6, further comprising adding metal oxide particles to the solvent. 10. The method of claim 9, wherein the metal oxide particles are silica particles. 11. The method according to claim 6, wherein the oxygen-quenching molecule is a porphyrin compound. 12. The method according to claim 6, wherein the solvent is dichloromethane. 13. An oxygen-sensitive film, comprising an oxygen-permeable matrix, oxygen-quenching molecules retained by the matrix, and particulate matter retained by the matrix.
film. 14. The oxygen-sensitive membrane according to claim 13, wherein the oxygen-permeable matrix contains a polymer compound having a metalloxane bond and having a hydrophobic functional group. 15. The oxygen-sensitive film according to claim 13, wherein the particulate matter is an oxygen-affinity particle. 16. The oxygen-sensitive film according to claim 13, wherein the oxygen-quenching molecule is a porphyrin-based compound. 17. The oxygen-affinity particles are 1 μm to 50 μm.
The oxygen-sensitive film according to claim 15, which is a metal oxide particle having a particle diameter of m. 18. The metal oxide particles are 10 nm to 50 nm.
The oxygen-sensitive film according to claim 15, which is a metal oxide particle having a particle diameter of 0 nm. 19. An oxygen-sensitive membrane, wherein a product obtained by hydrolyzing and polycondensing a raw material containing a hydrolyzable metal compound having a hydrophobic functional group is separated, and this product and oxygen quenching property are separated. A film obtained by preparing a composition containing molecules and applying the composition to the surface of an object and drying the composition. 20. The coating film according to claim 19, wherein metal oxide particles are further added to the separated product to prepare a composition. 21. A product obtained by in-situ generation of a metal oxide during the hydrolysis / polycondensation is separated, and a composition containing this product and an oxygen quenching molecule is prepared. The oxygen-sensitive film according to claim 19. 22. A method of forming an oxygen-sensitive film according to claim 13 on the surface of an object and measuring the pressure distribution on the surface. 23. An apparatus for forming the oxygen-sensitive film according to claim 13 on the surface of an object and measuring the pressure distribution on the surface.