JP7145490B2 - laminate - Google Patents

Description

The present invention relates to laminates .

As a simple pressure sensing element, a polymer material that emits fluorescence or changes the fluorescence wavelength in response to a change in pressure is known. In Patent Document 1, "a layered compound consisting of a layer of fine particles of a compound derived from a clay mineral, one or more fluorescent compounds sandwiched between a plurality of layers, and a compound filled between the layers, which contains more than the fine particles. and a binder having a large molecular size, wherein the fluorescent compound fluoresces when the layer is deformed by an externally applied mechanical force." It is

WO2015/034070

Although the pressure-sensitive material described in Document 1 can detect the pressure applied to the structure by the change in fluorescence wavelength or the like, it is possible to detect smaller changes in pressure, such as changes in air pressure in the space where the material is placed. However, it was not possible to detect the decompression state.
The present invention has been made in view of the above, and provides a laminate containing a composite whose optical properties change when placed under reduced pressure, in other words, a composite whose reduced pressure state can be detected by changes in optical properties. The task is to provide

As a result of intensive studies aimed at achieving the above object, the inventors of the present invention have found that the above object can be achieved with the following configuration.

[1] A support and a detection layer containing a composite formed on the support, wherein the composite comprises a layered clay mineral and a formula 1 below held by the layered clay mineral. and at least one specific organic compound selected from the group consisting of organic compounds represented by formula 2 described later, wherein the specific organic compound is a positive of the layered clay mineral A laminate that retains more than 70% equivalent of ion exchange capacity.
[2] The laminate according to [1], wherein the layered clay mineral has an iron atom content of 8000 mass ppm or less based on the total mass of the layered clay mineral as determined by inductively coupled plasma mass spectrometry.
[3] The laminate according to [1] or [2], wherein the layered clay mineral is a smectite clay mineral.
[4] The laminate according to [3], wherein the smectite clay mineral does not contain montmorillonite.
[5] The laminate according to [3] or [4], wherein the smectite clay mineral is trioctahedral.

ADVANTAGE OF THE INVENTION According to this invention, the composite_body|complex which can detect a pressure reduction state by the change of an optical physical property can be provided. Moreover, according to this invention, a laminated body can also be provided.

It is a perspective view of a layered product concerning an embodiment of the present invention. FIG. 2 is a diagram showing absorbance (transmittance) of visible light immediately after preparation of composite 1, after standing under reduced pressure, and in the atmosphere. 1 is an ESR (Electron Spin Resonance) spectrum of Complex 2; 3 is the ESR spectrum of complex 3; ESR spectrum of Complex C.

The present invention will be described in detail below.
Although the description of the constituent elements described below may be made based on representative embodiments of the present invention, the present invention is not limited to such embodiments.
In this specification, a numerical range represented by "-" means a range including the numerical values before and after "-" as lower and upper limits.

In the notation of a group (atom group) in the present specification, the notation that does not indicate substitution or unsubstituted includes not having a substituent as well as one having a substituent, as long as the effect of the present invention is not impaired. It is something to do. For example, an "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). This is also the same for each compound.

[Complex]
A composite according to an embodiment of the present invention is selected from the group consisting of a layered clay mineral, an organic compound represented by Formula 1 and an organic compound represented by Formula 2, which are retained in the layered clay mineral, and which will be described later. and at least one selected specific organic compound, wherein the specific organic compound is retained in an equivalent amount exceeding 70% of the cation exchange capacity of the layered clay mineral. Although the mechanism by which the effects of the present invention are obtained by the complex is not necessarily clear, the present inventors presume as follows.
In addition, the following mechanism is an assumption, and even if the subject of the present invention is solved by a mechanism other than the following mechanism, it shall be included in the scope of the present invention.

The composite has a predetermined amount of a specific organic compound held in a layered clay mineral (typically between layers). All of the specific organic compounds have at least one cationic group (=N ⁺ (R)-) in the molecule, and transfer of electrons within or between molecules, specifically, radicals (or , radical cations), and the optical properties change. In the composite according to the embodiment of the present invention, since the specific organic compound is retained in an amount exceeding 70% equivalent of the cation exchange capacity of the layered clay mineral, the distance between the specific organic compounds is short, and the specific organic compound One of the characteristics is that electron transfer easily occurs between molecules.

The present inventors have found that the complex according to the embodiment of the present invention having the above-described characteristics has a specific At least part of the organic compound is reduced, resulting in radicals (or radical cations), which changes the optical properties (typically, the absorption spectrum of visible light changes. In other words, the color tone changes). I'm guessing. That is, in the composite according to the embodiment of the present invention, since the distance between the molecules of the specific organic compounds is short, electron transfer between the molecules occurs only by reducing the pressure, and light irradiation (for example, ultraviolet rays) that has been conventionally required It is presumed that the optical properties can be changed without irradiation), etc., and it is possible to detect a minute pressure change (depressurized state) in the space.
Below, each component in the composite according to the embodiment of the present invention will be described in detail.

[Layered clay mineral]
A composite according to an embodiment of the present invention comprises a layered clay mineral. As used herein, the term "layered clay mineral" refers to a fine-grained mineral that exhibits viscosity and plasticity when containing an appropriate amount of water, and that has an orderly layered structure. It may be a substance (synthetic substance).
Its chemical components are not particularly limited, but mainly contain silicic acid, alumina, and water, iron (Fe), magnesium (Mg), calcium (Ca), sodium (Na), and potassium (K ), etc.

Among them, the layered clay mineral has a content of iron atoms measured by inductively coupled plasma mass spectrometry, in that a composite having the superior effect of the present invention can be obtained. With respect to the mass, it is preferably 8000 mass ppm or less, more preferably 5000 mass ppm or less, still more preferably 3000 mass ppm or less, particularly preferably 2000 mass ppm, substantially It is preferably not contained.
In the present specification, the fact that the layered clay mineral does not substantially contain iron atoms means that the content of iron atoms measured using inductively coupled plasma mass spectrometry is, with respect to the total mass of the layered clay mineral, It means 1000 mass ppm or less, more preferably 100 mass ppm or less, and even more preferably 50 mass ppm or less.

Layered clay minerals produced from raw ores may contain iron atoms. For example, according to Table 2.8.1 on page 69 of "Clay Handbook (3rd Edition)" (2009) edited by the Clay Society of Japan, various montmorillonites contain a certain amount of iron atoms. there is

According to the studies of the present inventors, when the content of iron atoms in the layered clay mineral is within the above numerical range, the electrons generated from the specific organic compound are converted into iron atoms (typically present as ions ) is less likely to be stolen (more difficult to be consumed). As a result, when the content of iron atoms in the layered clay mineral is within the above numerical range, a composite having superior sensitivity to pressure changes can be obtained.

Layered clay minerals include layered silicate minerals (phyllosilicate minerals) and the like, and in many cases, the thickness is 0, mainly composed of oxygen (O), silicon (Si), and aluminum (Al). .2 to 0.5 nm tetrahedral sheet and / or from a sheet-like inorganic compound with a large aspect ratio having a long axis direction size of about several tens of nm to 5 μm, in which 1 to 3 layers of octahedral sheets are laminated formed.

The tetrahedral sheet is formed by coordinating four Os to Si to form a tetrahedron of SiO ₄ , and the tetrahedrons share the three Os to form a hexagonal network. Si may also replace Al to form AlO ₄ tetrahedrons. In addition, iron (Fe) and the like may also form tetrahedrons.
In contrast, octahedral sheets are formed by coordinating six hydroxyl groups (OH) or O to Al, and may be formed by magnesium (Mg) and/or Fe instead of Al.

Layered clay minerals are formed by such sheets and/or by stacking and bonding these sheets.
Clay crystals formed by laminating tetrahedral sheets and octahedral sheets in a ratio of 1:1 are generally called kaolin minerals, and examples thereof include kaolinite and halloysite.

Clay crystals formed by combining tetrahedral sheets and octahedral sheets at a ratio of 2:1 (that is, tetrahedral sheet - octahedral sheet - tetrahedral sheet) are pyrophyllite, talc, smectite ( smectite clay minerals), vermiculite, and mica.
Among them, a smectite-based clay mineral is preferable as the layered clay mineral in that a laminate having the effect of the present invention can be obtained.

The smectite-based clay mineral is not particularly limited, and may be natural or synthetic, and includes montmorillonite, saponite, hectorite, stevensite, laponite, and the like.
Among smectite clay minerals, clay minerals other than montmorillonite, which are generally considered to contain a certain amount of iron atoms, are preferred as layered clay minerals in that a composite having the more excellent effects of the present invention can be obtained. More preferred, trioctahedral clay minerals are even more preferred.

Smectite-based clay minerals are broadly classified into 2-octahedral type and 3-octahedral type according to their structures. The former often has trivalent iron and/or aluminum as cations entering the octahedral sheet.
The dioctahedral type includes montmorillonite, beidellite, nontronite, and the like.
The trioctahedral type includes saponite, hectorite, sauconite, laponite, and stevensite.

As already explained, in the complex according to the embodiment of the present invention, the distance between the specific organic compound molecules to be described later is short, so it is presumed that electron transfer between the molecules easily occurs due to the reduced pressure.
At this time, when the composite has a trioctahedral layered clay mineral, the electrons moving between the specific organic compound molecules are less likely to be used for the reduction of the cations entering the octahedral sheet, resulting in better response. (Even if the degree of pressure reduction is small, a clearer color can be obtained).

In addition, the composite according to the embodiment of the present invention may contain one type of layered clay mineral alone, or may contain two or more types in combination.
Moreover, the composite according to the embodiment of the present invention may contain clay minerals other than those described above.

[Specific organic compound held in layered clay mineral]
The composite according to the embodiment of the present invention includes at least It has one specific organic compound.
In the present specification, "held in the layered clay mineral" means a state in which cations such as sodium, calcium, magnesium, and potassium arranged between the layers of the layered clay mineral are exchanged and arranged. Alternatively, it may be simply adsorbed on the surface and/or between layers without undergoing ion exchange, or it may be a combination of the above.

Among them, the organic compound represented by the formula 1 is preferable as the specific organic compound in that a composite having superior effects of the present invention can be obtained.

In Formula 1, each R ₁ independently represents a hydrogen atom or a monovalent hydrocarbon group, L ₁ represents a single bond or a divalent group, and X ₁ represents C or N ⁺ , R ₁ may be bonded to each other to form a ring, wherein R ₂ each independently represents a hydrogen atom or a monovalent hydrocarbon group, L ₂ is a single bond or a divalent wherein X ₂ represents C or N ⁺ , R ₂ may combine with each other to form a ring, and in formulas 1 and 2, the hydrogen atoms bonded to the carbon atoms are each independently may be substituted with a monovalent group, and the above monovalent groups may combine with each other to form a ring.

R ₁ in Formula 1 is preferably a monovalent hydrocarbon group, and the monovalent hydrocarbon group is not particularly limited, but is preferably a hydrocarbon group having 1 to 10 carbon atoms, and an alkyl group having 1 to 10 carbon atoms. An alkyl group having 1 to 6 carbon atoms is preferred, and an alkyl group having 1 to 4 carbon atoms is even more preferred.

The divalent group for L ₁ is not particularly limited, but may be -O-, -NR _X - (R _X is a hydrogen atom or a monovalent group), -C(O)O-, -OC(O)-, -S-, saturated or unsaturated hydrocarbon groups optionally containing heteroatoms, combinations thereof, and the like.

The form of the divalent saturated hydrocarbon group for L ₁ is not particularly limited, and examples thereof include linear, branched, and cyclic alkylene groups.
The form of the divalent unsaturated hydrocarbon group of L ₁ is not particularly limited, but is derived from, for example, an alkenylene group, an alkynylene group, an arylene group, a heteroarylene group, and a condensed aromatic heterocyclic ring in which three or more rings are condensed. divalent groups and groups in which these are combined.

The alkenylene group includes, for example, vinylene group, propenylene group, butenylene group, pentenylene group, 1-methylvinylene group, 1-methylpropenylene group, 2-methylpropenylene group, 1-methylpentenylene group, 3-methyl Examples include pentenylene group, 1-ethylvinylene group, 1-ethylpropenylene group, 1-ethylbutenylene group, and 3-ethylbutenylene group, and vinylene group is preferred.

Examples of alkynylene groups include ethynylene, 1-propynylene, 1-butynylene, 1-pentynylene, 1-hexynylene, 2-butynylene, 2-pentynylene, 1-methylethynylene, 3-methyl-1 -propynylene group, 3-methyl-1-butynylene group and the like, and ethynylene group is preferred.

The arylene group includes, for example, o-phenylene group, m-phenylene group, p-phenylene group, naphthalenediyl group, anthracenediyl group, naphthacenediyl group, pyrenediyl group, naphthylnaphthalenediyl group, biphenyldiyl group (e.g., [1, 1'-biphenyl]-4,4'-diyl group, 3,3'-biphenyldiyl group and 3,6-biphenyldiyl group, etc.), terphenyldiyl group, quaterphenyldiyl group, kinkphenyldiyl group , sexiphenyldiyl group, septiphenyldiyl group, octiphenyldiyl group, nobiphenyldiyl group, deciphenyldiyl group, etc., and o-phenylene group or p-phenylene group is preferable.

The heteroarylene group includes, for example, a carbazole ring, a carboline ring, a diazacarbazole ring (also referred to as a monoazacarboline ring, which represents a ring structure in which one of the carbon atoms constituting the carboline ring is replaced with a nitrogen atom), and triazole. divalent groups derived from rings, pyrrole rings, pyridine rings, pyrazine rings, quinoxaline rings, thiophene rings, oxadiazole rings, dibenzofuran rings, dibenzothiophene rings, indole rings, and the like.

As a divalent group derived from a condensed aromatic heterocyclic ring in which three or more rings are condensed, at least one heteroatom selected from the group consisting of N, O, and S constitutes a condensed ring. It is preferably an aromatic heterocondensed ring contained as an element, specifically, an acridine ring, a benzoquinoline ring, a carbazole ring, a phenazine ring, a phenanthridine ring, a phenanthroline ring, a carboline ring, a cyclazine ring, a kindline ring, tepenidine ring, quinindrine ring, tripenodithiazine ring, tripenodioxazine ring, phenanthrazine ring, anthrazine ring, perimidine ring, diazacarbazole ring (any one of the carbon atoms constituting the carboline ring is replaced with a nitrogen atom ), phenanthroline ring, dibenzofuran ring, dibenzothiophene ring, naphthofuran ring, naphthothiophene ring, benzodifuran ring, benzodithiophene ring, naphthodifuran ring, naphthodithiophene ring, anthrafuran ring, anthradifuran ring, anthrathiophene ring , anthradithiophene ring, thianthrene ring, phenoxathiin ring, and thiophanthrene ring (naphthothiophene ring).

Other forms of the divalent group of L ₁ include a chalcogen atom and a heterohydrocarbon group containing a chalcogen atom. Specific examples include O, S, alkyleneoxy groups, alkylenethio groups, and combinations thereof.

Also, the divalent group of L ₁ may be a divalent group represented by the following formula. In the following formulas, "*" represents a binding position. Further, in the divalent groups below, the hydrogen atoms bonded to each carbon atom may be substituted with a monovalent group, and examples of the monovalent group include the substituent W described later.

In Formula 1, X ₁ represents C or N ⁺ , and N ⁺ is preferred in terms of obtaining a composite having superior effects of the present invention.

As the organic compound represented by Formula 1, organic compounds represented by the following formulas (1a) to (1c) are preferable, and organic compounds represented by (1a) are more preferable.

In the above formula, the forms of R ₁ and L ₁ are the same as the symbols in formula 1 already explained. Although R ₃ in Formula 2 is not particularly limited, a group represented by *-C(Ra)-* is preferred, and Ra includes a hydrogen atom or a monovalent hydrocarbon group for R ₁ .

In Formula 2, R ₂ represents a hydrogen atom or a monovalent hydrocarbon group, and the monovalent hydrocarbon group is not particularly limited, but the monovalent hydrocarbon group of R ₁ in Formula 1 has been described. A form similar to is preferred.
In Formula 2, L ₂ represents a single bond or a divalent group, and the divalent group of L ₂ is not particularly limited, but the same form as described for the divalent group of L ₁ in Formula 1 is preferred.
In Formula 2, X ₂ represents C or N ⁺ , preferably N ⁺ .

The compound represented by formula 2 is not particularly limited, but includes compounds represented by the following formulas (2a) to (2c).

In the above formula, R ₃ represents a divalent group, and R ₃ preferably has the same form as R ₃ in formula 1c already explained.

In the composite according to the embodiment of the present invention, at least one of the specific organic compounds is retained in the layered clay mineral (typically between the layers) in excess of 70% equivalent of the cation exchange capacity of the layered clay mineral. It is Hereinafter, in this specification, the amount of the specific organic compound retained in the layered clay mineral is also simply referred to as "retained amount".

That is, in the composite according to the embodiment of the present invention, at least one of the specific organic compounds is retained in the layered clay mineral, and the retention amount exceeds 70% equivalent of the cation exchange capacity of the layered clay mineral. Complex.
When two or more of the specific organic compounds are retained in the layered clay mineral, the total retention amount of the specific organic compounds is preferably within the above numerical range.

As used herein, the term "retained amount" means the following values.
First, the raw material clay (layered clay mineral) is saturated with Ca ions with a calcium chloride solution (1N), an ammonium acetate solution (1N) is added, and the leached Ca ions are analyzed by atomic absorption spectrometry or coupled plasma emission spectrometry (ICP). ) to determine the cation exchange capacity of the layered clay mineral itself.

Next, the "holding amount" is determined by the charged amount of the specific organic compound when combining the layered clay mineral and the specific organic compound. That is, when the specific organic compound is added in an amount that is equivalent to 80% of the cation exchange capacity of the layered clay mineral and is compounded, the amount of the specific organic compound retained in the resulting composite is equal to the cation exchange capacity. is 80 equivalent % of In addition, when the specific organic compound is added in an amount equivalent to 70% of the cation exchange capacity of the layered clay mineral and composited, the amount of the specific organic compound retained in the resulting composite is the cation exchange capacity. is 70 equivalent % of

Therefore, the upper limit of the "holding amount" is not 100 equivalent %, but the specific organic compound held without exchanging with the cation of the layered clay mineral (for example, the form adsorbed on the surface) is also included. determined by

For example, when the specific organic compound is added in an amount that is equivalent to 160% equivalent of the cation exchange capacity of the layered clay mineral itself and is compounded, the "holding amount" in the resulting complex is 160% equivalent. Become.
On the other hand, in the complex that retains more than 100 equivalent % of the specific organic compound, a part of the retained specific organic compound is retained without undergoing ion exchange (typically by being adsorbed on the surface, etc.) It is presumed that The specific organic compound retained in such a form can also be removed by washing or the like as described in the examples below.
That is, in the present specification, the complex obtained by washing the above-mentioned complex having a retention amount of 160 equivalent % until the specific organic compound no longer elutes in the washing solution is defined as a complex having a concentration of 100 equivalent %.

From the viewpoint of obtaining a composite having more excellent effects of the present invention, the amount of the specific organic compound retained in the composite is preferably 75 equivalent % or more, more preferably 80% equivalent or more, of the cation exchange capacity of the layered clay mineral. More preferably, 85% equivalent or more is still more preferable, and 90% equivalent or more is particularly preferable.
On the other hand, the upper limit of the retention amount of the specific organic compound in the complex is not particularly limited, but is generally preferably 800% equivalent or less, more preferably 160% equivalent or less. Equivalent or less is preferred. In particular, when the specific organic compound is toxic, it is preferably not more than the above upper limit.

The complex may contain components other than the above, and examples of the components other than the above include counterions. Counter ions are not particularly limited, but include halide ions and the like.

[Method for producing composite]
The method for producing the composite is not particularly limited, and any known method used for making a layered clay mineral retain a specific organic compound can be applied without particular limitation.
Among others, the method for producing the composite preferably includes the following steps in this order in order to facilitate the production of the composite.

A step of contacting the layered clay mineral with a solvent to disperse the layered clay mineral in the solvent to obtain a dispersion of the layered clay mineral (step A).
• A step of adding a predetermined amount of a specific organic compound to the dispersion, retaining the specific organic compound in the dispersed layered clay mineral, and obtaining a composite (step B).
The above method for producing a complex may further include a complex purification step (step C) after step B.

(Step A)
Step A is a step of contacting a layered clay mineral with a solvent to disperse the layered clay mineral in the solvent to obtain a dispersion of the layered clay mineral.
The solvent is not particularly limited, and water, organic solvents, and mixtures thereof can be used. , water and a mixture of organic solvents are preferred, water being more preferred.

The organic solvent is not particularly limited, and a known organic solvent can be used, but an organic solvent miscible with water (water-soluble organic solvent) is preferable in that the complex can be obtained more easily. Examples of water-soluble organic solvents include sulfoxides such as dimethylsulfoxide; sulfones such as dimethylsulfone, diethylsulfone, bis(2-hydroxyethyl)sulfone and tetramethylenesulfone; N,N-dimethylformamide and N-methylformamide. , N,N-dimethylacetamide, N-methylacetamide, N,N-diethylacetamide and other amides; N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone, N- Lactams such as hydroxymethyl-2-pyrrolidone and N-hydroxyethyl-2-pyrrolidone; 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, 1,3-diisopropyl- 2-imidazolidinones such as imidazolidinone; ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol, diethylene glycol monomethyl ether, Diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, polyethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol ethyl methyl ether, diethylene glycol isopropyl Ethylene glycol alkyl ethers (alkyl is a lower alkyl group having 1 to 6 carbon atoms) such as methyl ether, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether; propylene glycol monomethyl ether, propylene glycol monomethyl ether 2-acetate, di Propylene glycol monomethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, tripropylene glycol dimethyl ether, propylene glycol-n-propyl ether, propylene glycol-n-butyl ether, dipropylene glycol-n-propyl ether, propylene glycol Propylene glycol alkyl ethers (alkyl is a lower alkyl group having 1 to 6 carbon atoms) such as propylene glycol-n-butyl ether, dipropylene glycol methyl ether acetate, tripropylene glycol-n-butyl ether, polyhydric alcohols, and Derivatives thereof may be mentioned.

The method of bringing the layered clay mineral into contact with the solvent and dispersing the layered clay mineral in the solvent is not particularly limited, but examples include a method of adding the layered clay mineral to the solvent and stirring.

(Step B)
Step B is a step of adding a predetermined amount of the specific organic compound to the dispersion, retaining the specific organic compound in the dispersed layered clay mineral, and obtaining a composite.
The method of adding the specific organic compound to the dispersion is not particularly limited, but a method of directly adding the specific organic compound to the dispersion, or a method of dissolving or dispersing the specific organic compound in advance in a solvent to prepare a specific organic compound solution. , a method of adding the above specific organic compound solution to the dispersion, and the like. The solvent used for the specific organic compound solution is not particularly limited, and the solvent described in step A can be used.

In step B, the ratio of the layered clay mineral and the specific organic compound is adjusted such that the specific organic compound is retained in excess of 70% equivalent of the cation exchange capacity of the layered clay mineral. Specific examples of the method for obtaining the composite include a method of adding the specific organic compound to the dispersion and stirring with a known stirring means (magnetic stirrer, ultrasonic waves, etc.).

(Process C)
Step C is a step of purifying the complex obtained in Step B. The method for producing the complex is not particularly limited, but for example, a method of centrifuging or filtering the complex from the solution containing the complex obtained in step B and washing the obtained complex. is mentioned.
Although the washing liquid used for washing is not particularly limited, it is preferable to use the solvent described in step A.
Step C can adjust the retention amount of the specific organic compound in the complex. That is, by measuring the amount of the specific organic compound eluted into the washing liquid during washing, the amount of the specific organic compound remaining and retained in the composite can be calculated.

[Use of composite]
Since the composite according to the embodiment of the present invention changes its optical properties (typically, its color tone changes) in a decompressed state, it is possible to detect the decompressed state of the space in which the composite is placed. As a typical example, a complex using methylviologen as a specific organic compound becomes blue under reduced pressure (presumably due to radical cations generated by one-electron reduction), so the reduced pressure state in the space , can be detected from the color change of the complex.
The composite according to the embodiment of the present invention can be applied to a pressure sensing element or the like because at least part of the specific organic compound is reduced by stimulation of reduced pressure without light irradiation, and the optical properties change.

[Laminate]
A laminate according to an embodiment of the present invention is a laminate having a support and a sensing layer containing the composite formed on the support.
According to the laminate, it is possible to detect with good sensitivity a minute pressure change (specifically, a reduced pressure state) in the space in which the laminate is arranged.

FIG. 1 is a perspective view of a laminate according to an embodiment of the invention. The laminate 100 has a detection layer 101 on one main surface of a support 102 having a flat plate shape.
In the laminate 100, the sensing layer 101 is arranged on one main surface of the support 102, but the laminate according to the embodiment of the present invention is not limited to the above, and both main surfaces of the support are provided. The sensing layer may be disposed on the surface, or the sensing layer may be disposed on the entire surface of the support.
In addition, in the laminate 100, the sensing layer 101 is arranged on the entire one main surface of the support, but the laminate according to the embodiment of the present invention is not limited to the above, and at least It is sufficient if the detection layer is partially arranged.

Moreover, although the laminate 100 is flat, the shape of the laminate is not limited to the above, and may be a three-dimensional shape having a curved surface.

In the laminate 100, the detection layer 101 is arranged on the surface of the support 102, but the laminate according to the embodiment of the present invention is not limited to the above, and the layer between the support and the detection layer may have other layers. Other layers are not particularly limited, and known layers can be used. Other layers include, for example, an antireflection layer, an undercoat layer, an easy-adhesion layer, and the like.

In addition, the laminate 100 has a support 102 and a detection layer 101, but is not particularly limited as a laminate according to the embodiment of the present invention, and further has a protective layer on the detection layer 101. may The protective layer is not particularly limited, and a protective layer formed from a known material can be used. However, since a laminate having a more excellent effect of the present invention can be obtained, the protective layer may be a support and a support described later. A similar form is preferred.
Further, when the laminate has a protective layer, other layers (for example, an antireflection layer, a topcoat layer, an easy-adhesion layer, etc.) may be provided between the detection layer and the protective layer.

(support)
The laminate has a support. The support is not particularly limited, and organic substances, inorganic substances, combinations thereof, and the like can be used.
More specifically, examples of the support include glass supports such as alkali-free glass, borosilicate glass, float glass, and soda-lime glass.
As the support, polycarbonate-based resin, acrylic-based resin, polyethylene-based resin, polyvinyl chloride-based resin, polyester-based resin, epoxy-based resin, melamine-based resin, phenol resin, polyurethane-based resin, polyimide-based resin, etc. and a resin support.
As the support, paper (for example, filter paper, etc.) can also be used in addition to the above.
Further, the support may be a support with a coating layer, in which the surface of the support is coated with an antireflection layer or the like.

The shape of the support is not particularly limited and can be appropriately selected according to the purpose, and may be rectangular, circular, or three-dimensional with a curved surface.
The laminate may further have a support, and may have a form in which a support, a sensing layer, and a support are laminated in this order.
Moreover, the thickness of the support is not particularly limited, and may be appropriately selected according to the application.

(Detection layer)
The detection layer is a layer containing the already-described composite, and is a layer for detecting a minute pressure change (specifically, a decompression state) by a change in color tone of the composite.
Other components of the sensing layer are not particularly limited as long as they contain the above-described complex, but may contain a binder, a solvent, and the like as components other than the complex.
Although the content of the composite in the sensing layer is not particularly limited, it is preferably 0.1 to 100% by weight with respect to the total weight of the composite.
The thickness of the detection layer is not particularly limited, and may be appropriately selected according to the application.

The binder is not particularly limited, and for example, acrylic resins, alkyd resins, isocyanate resins, urethane resins, epoxy resins, phenol resins, and melamine resins can be used.
Among them, a transparent resin is preferable in that the change in color tone of the composite can be more clearly visually recognized. As for the transparent resin, a sheet with a thickness of 3 mm preferably has a total light transmittance of 85% at a wavelength of 400 to 1400 nm, more preferably 90% or more.

Solvents are not particularly limited, and include water, organic solvents, and mixtures thereof. Among them, water or a mixture of water and an organic solvent is preferable as the solvent in that a laminate having the effect of the present invention can be obtained.

The laminate can detect a pressure change, more specifically, a reduced pressure state, in the space in which it is arranged. Although the degree of pressure reduction is not particularly limited, the gauge pressure is preferably −0.001 MPa or less, more preferably −0.01 MPa or less, and even more preferably −0.1 MPa or less.

The present invention will be described in more detail based on examples below. The materials, amounts used, proportions, treatment details, treatment procedures, etc. shown in the following examples can be changed as appropriate without departing from the gist of the present invention. Therefore, the scope of the present invention should not be construed to be limited by the examples shown below.

[Example 1: Preparation of complex 1]
A saponite dispersion with a cation exchange capacity of 100 cmol/kg (Sumecton SA, manufactured by Kunimine Industries Co., Ltd.) was mixed with a 100 mM methyl viologen solution to an equivalent of 160% of the cation exchange capacity, and then washed with water by centrifugation. was repeated to remove excess methylviologen, and a complex was obtained in which 100% equivalent of methylviologen was retained with respect to the cation exchange capacity of saponite.

The 100% equivalent of the complex was obtained by collecting the supernatant after centrifugation and measuring the absorption peak of methylviologen (around 260 nm) by measuring the absorbance. , the excess methylviologen was judged to have been removed. That is, it was determined that 100% equivalent of methylviologen remained and was retained in the saponite.

[Example 2: Preparation of complex 2]
Composite 2 was prepared in the same manner as in Example 1, except that the charged amounts of the saponite dispersion and the methylviologen solution were adjusted so that the amount of methylviologen retained in the composite was 80% equivalent.

[Example 3: Preparation of complex 3]
Composite 3 was prepared in the same manner as in Example 1, except that the charged amounts of the saponite dispersion and the methylviologen solution were adjusted so that the amount of methylviologen retained in the composite was 160% equivalent.

[Example 4: Preparation of complex 4]
Composite 4 was prepared in the same manner as in Example 1, except that the charged amounts of the saponite dispersion and the methylviologen solution were adjusted so that the amount of methylviologen retained in the composite was 800% equivalent.

[Comparative Example 1: Preparation of Complex C]
Composite C was prepared in the same manner as in Example 1, except that the charged amounts of the saponite dispersion and the methylviologen solution were adjusted so that the amount of methylviologen retained in the composite was 70% equivalent.

[evaluation]
The composites 1 to 3 and composite C were allowed to stand under a reduced pressure of -0.1 MPa for 2 hours, and the absorbance (transmittance) of visible light and the pulsed electron spin resonance (ESR) spectrum were measured. did. A series of evaluation tests were conducted in the dark.
FIG. 2 shows the absorbance (transmittance) according to Example 1. As shown in FIG.
3, 4 and 5 show the ESR spectra of the composites of Example 2, Example 3 and Comparative Example.

Composite 1 exhibited a pale red to purple color immediately after preparation and had an absorption peak near 560 nm. The spectrum “immediately after fabrication” in FIG. 2 corresponds to this.
Next, after standing under reduced pressure for 2 hours, Composite 1 turned blue and exhibited absorption peaks near 400, 475, and 600 nm. The spectrum “after standing under reduced pressure” in FIG. 2 corresponds to this.
When the blue complex was then exposed to air, it turned yellow-green. The "under air" spectrum in FIG. 2 corresponds to this.
From the above results, it was clarified that the optical properties (color tone) of the composite changed under reduced pressure, and the reduced pressure state could be detected.
In addition, a similar change in optical properties (color tone) was confirmed for composite 4 as well.

3 to 5, the vertical axis in each figure corresponds to the absorption intensity and the amount of unpaired electrons. The horizontal axis is the magnetic field strength, and the central value of the peak depends on the g-value specific to the chemical species. The peaks at both ends are signals due to the fine structure of Mn ²⁺ contained in MgO, which is the standard sample.
As can be seen from FIGS. 3 and 4, Composite 3 with a retained amount of 160% equivalents has a higher absorption strength, in other words, similar reduced pressure, compared to Composite 2 with a retained amount of 80% equivalents. It was found that the specific organic compound developed a stronger color even in the state.
On the other hand, as can be seen from FIG. 5, complex C with a retention amount of 70% equivalent did not have the desired effect of the present invention.

100 laminate 101 detection layer 102 support

Claims (5)

a support;
a detection layer that contains the complex formed on the support and detects a reduced pressure state ,
The complex comprises a layered clay mineral and at least one specific compound selected from the group consisting of an organic compound represented by Formula 1 and an organic compound represented by Formula 2 retained in the layered clay mineral. containing an organic compound and
A laminate in which the specific organic compound is retained in an amount exceeding 70% equivalent of the cation exchange capacity of the layered clay mineral.

In Formula 1, each R ₁ independently represents a hydrogen atom or a monovalent hydrocarbon group, L ₁ represents a single bond or a divalent group, and X ₁ represents C or N ⁺ , R ₁ may combine with each other to form a ring,
In Formula 2, each R ₂ independently represents a hydrogen atom or a monovalent hydrocarbon group, L ₂ represents a single bond or a divalent group, and X ₂ represents C or N ⁺ , R ₂ may combine with each other to form a ring,
In formulas 1 and 2, hydrogen atoms bonded to carbon atoms may be independently substituted with monovalent groups, and the monovalent groups may be bonded to each other to form a ring. . 2. The laminate according to claim 1, wherein the layered clay mineral has an iron atom content of 8000 ppm by mass or less relative to the total mass of the layered clay mineral as determined by inductively coupled plasma mass spectrometry. 3. The laminate according to claim 1, wherein the layered clay mineral is a smectite clay mineral. 4. The laminate according to claim 3, wherein the smectite clay mineral does not contain montmorillonite. 5. The laminate according to claim 3, wherein the smectite-based clay mineral is trioctahedral.

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