JP2020134200A - Fine particle detection material and fine particle detection method using the same - Google Patents

Abstract

To provide a fine particle detection material capable of acquiring the information of the particle diameter and amount of a fine particle and the information of particle component and particle surface characteristic, and provide a detection method using the material.SOLUTION: The fine particle detection material includes a POSS network polymer containing a basket-type silsesquioxane (POSS) as a component, the POSS network polymer includes a chromic molecule showing the solvatochromism, and POSSes are cross-linked to each other via a methylene chain and are used for detecting a hydrophobic fine particle. The method of detecting a hydrophobic fine particle uses the detection material.SELECTED DRAWING: Figure 1

Description

The present invention relates to a fine particle detection material suitable for detecting fine particles, particularly hydrophobic fine particles such as micro and nanoplastics, and a fine particle detection method using the material.

In recent years, the problem of fine particles existing in the environment has surfaced. In the atmosphere, particulate matter typified by PM2.5 easily penetrates deep into the respiratory tract, and there is concern about health effects on humans, and environmental standards have been established. In water bodies, the existence of microscopic pieces of plastic, microplastics of μm size, and nanoplastics of nm size has been clarified, and there is concern about the impact on the ecosystem. However, there are few examples of scientifically evaluating the extent of micro / nanoplastics present in actual water bodies and their impact on ecosystems, and it is essential to accumulate data.

Under such circumstances, regarding the technology for detecting micro / nanoplastics in the environment, for microplastics with a relatively large size of submicron or larger, measurement with a microscope after recovery by a net, or Fourier transform infrared spectroscopy (FT) as necessary. The detection method is being established, such as composition analysis by −IR) (for example, Non-Patent Document 1). On the other hand, no detection method has been established for smaller fine particles, especially nano-sized fine particles.

The general methods for detecting nanoparticles are as follows. As a method for measuring the particle size and particle size distribution, a microscope method that directly measures using an optical microscope or an electron microscope, or dynamic light scattering that irradiates laser light, calculates the diffusion rate from the fluctuation of scattered light, and converts it into particle size. There are methods, a laser diffraction scattering method that analyzes the angle-dependent scattering / diffraction profile after laser light irradiation, and a centrifugal sedimentation method that calculates from the difference in sedimentation rate due to centrifugation (for example, Patent Document 1 and Non-Patent Document 2). .. Regarding the number of particles, in addition to the above-mentioned microscopy method and centrifugal sedimentation method, a light scattering method (for example, Patent Document 2 and Non-Patent Document 3) in which a flow cell is irradiated with laser light to measure the number of scattered light pulses is opposed. A light shielding method that detects light shielding by particles as a signal drop has been reported. In addition to the above physical methods, detection by photochemical methods has also been attempted, and the applicant has also reported a compound that adsorbs to particles and changes the emission spectrum according to the size of the particles (the applicant). Non-Patent Document 4).

However, none of these methods provided information on the particle components, only some information such as the number and size of particles, and did not determine the amount of plastic fine particles present in the environmental sample. ..

To solve this problem, a method combining atomic force microscopy (AFM) and infrared spectroscopy (IR) or Raman spectroscopy has been proposed in recent years (for example, Non-Patent Document 5). However, this method requires a very expensive device, and the amount of samples that can be processed at one time is small, resulting in an increase in the number of measurements, resulting in a very complicated measurement.

Japanese Unexamined Patent Publication No. 2008-39539 Japanese Unexamined Patent Publication No. 62-255850

Environmental Science & Technology (2012), Vol.46, 3060-3075 AIST Measurement Standard Report (2007), Vol.6, No.4, p.185-200 AIST Metrology Standard Report (2011), Vol.8, No.2, p.213-243 journal of material chemistry c (2015), vol.3,12539-12545 Analytical Methods (2017), Vol.9, 1384-1391

The present invention solves the above-mentioned problems, and obtains information on particle components and particle surface characteristics in addition to information on the particle size and amount of fine particles by a novel and simple method different from the conventional ones. The present invention provides a fine particle detection material capable of producing particles and a detection method using the material, and provides a detection material for detecting hydrophobic fine particles in an environmental sample and a detection method using the material.

As a result of intensive research, the present inventors include a POSS network polymer containing cage-type silsesquioxane (POSS) as a constituent component, and the POSS network polymer has a chromic molecule exhibiting solvatochromism. Moreover, it has been found that a fine particle detection material in which POSS are crosslinked with each other via a methylene chain solves the above-mentioned problems, and has led to the present invention.

That is, the first aspect of the present invention contains a POSS network polymer containing cage-type silsesquioxane (POSS) as a constituent component, and the POSS network polymer has a chromic molecule exhibiting solvatochromism, and It is an object of the present invention to provide a fine particle detection material, which comprises cross-linking POSSs with each other via a methylene chain and is used for detecting hydrophobic fine particles.

The second aspect of the present invention is a method for detecting hydrophobic fine particles, which comprises a POSS network polymer containing a cage-type silsesquioxane (POSS) as a constituent component, and the POSS network polymer is solvatochromism. It is an object of the present invention to provide a method for detecting hydrophobic fine particles, which comprises using a fine particle detection material having a chromic molecule showing the above and having POSS crosslinked with each other via a methylene chain.

By using the fine particle detection material of the present invention, whether or not there are hydrophobic fine particles, particularly nano-sized plastic fine particles having a particle size of less than 1 μm, in the environmental solution, and the content thereof can be determined only by irradiating light. Is possible. This change in emission color is large, and it is possible to perform visual discrimination as well as measurement by a spectrophotometer or the like, and an extremely simple detection method is provided.

It is a graph which shows the change of the emission spectrum when the POSS network polymer of this invention obtained in Example 1 was mixed with various fine particles having different particle diameters.

It is a graph which shows the change of the emission spectrum when the coumarin POSS obtained in Comparative Example 1 is mixed with various fine particles having different particle diameters.

Hereinafter, the present invention will be described in detail.
The fine particle detection material of the present invention contains cage-type silsesquioxane (POSS) as a constituent component. POSS is a siloxane-based compound whose main clavicle is composed of a SiO bond, and is a kind of silsesquioxane represented by the composition formula of (RSiO _1.5 ) _n , and has n = 8, 10 or 12 POSS. It has been reported. In the present invention, any POSS can be used. From the viewpoint of relatively easy synthesis, the following description will be made on behalf of n = 8.

式中、ＲはＨ（水素原子）または有機官能基（Ｒ’）を有するリンカーであり、それぞれ同一であっても異なっていてもよい。なお、有機官能基（Ｒ’）を有するリンカーは１つ以上、好ましくは２つ以上、より好ましくは３つ以上、最も好ましくは８である。 The cage-type silsesquioxane (POSS) has a composition of (RSiO _1.5 ) ₈ and has a three-dimensional structure as shown in the following formula [I], mainly having a cubic structure of silica. In addition, it is a general term for substances having an organic functional group at the apex.

In the formula, R is a linker having H (hydrogen atom) or an organic functional group (R'), which may be the same or different. The number of linkers having an organic functional group (R') is one or more, preferably two or more, more preferably three or more, and most preferably eight.

In the present invention, a compound in which a cage-type silsesquioxane (POSS) molecule is not bound to another POSS molecule via an organic functional group (R') is referred to as "POSS", and POSS is an organic functional group (POSS). A compound (polymer) in the form of being three-dimensionally chemically bonded to another POSS molecule via R') is referred to as "network POSS polymer" or "POSS network polymer". The network POSS polymer is not limited to a compound in which one type of POSS molecules having the same R are bound to each other via an organic functional group (R'), and two or more types of POSS molecules having different Rs are organic functional groups. It may be a compound bound via (R').

The POSS network polymer of the present invention has a chromic molecule exhibiting solvatochromism (hereinafter, may be simply referred to as “chromic molecule”), and the chromic molecule exhibiting the solvatochromism is via a linker (L). It is bound to POSS.

A chromic molecule is a molecule that has the property of chromism, which is a phenomenon in which the color changes due to an external stimulus. "Solvatochromism" means a property showing a phenomenon that the color changes according to the polarity of a solvent in addition to the phenomenon of chromism.

The linker (L) is represented in place of the linker (R) having an organic functional group (R') in the formula [I]. Examples of the linker include various organic functional groups, preferably groups having an organic functional group at the terminal, for example, an amino group, a vinyl group, a glycidyl group and the like, and these linkers are introduced into the eight vertices of POSS. Among them, in order to maintain water solubility, it is preferable to have a polar group and a terminal functional group for binding to the following cross-linking agent, and amino acids are relatively easy to synthesize. Alkyl groups are most preferably exemplified. The alkyl group of the aminoalkyl group has 1 to 5 carbon atoms, preferably 2 to 4 carbon atoms, and most preferably 3 carbon atoms. Further, the terminal amino group may be in the form of ammonium ion, and in that case, the pair of anions is not particularly limited, and examples thereof include hydrochloride, nitrate, acetate, and sulfate. The introduction of those linkers is carried out by a method already known. For example, the introduction of 3-aminopropyl as a linker can be carried out by dissolving 3-aminopropyltriethoxysilane in methanol and condensing it with hydrochloric acid.

In the present invention, a solvertochromic molecule that recognizes the polarity of the surface of fine particles, particularly hydrophobicity, and changes depending on the polarity of the solvent is used.

As the solvertochromic molecule, an intramolecular charge transfer transition (ICT) -type molecule is preferably exemplified. ICT is a phenomenon found in conjugated compounds having an electron donating group and an electron attracting group, and the energy level of the ground state or excited state changes depending on the polarity of the solvent molecule because the charge is biased in the molecule. As a result, the color development and the fluorescent color also change. In the present invention, a luminescent solver chromic molecule is preferable because of its high detection sensitivity. Strictly speaking, the concept of chromism is a phenomenon in which a change in the environment is accompanied by a change in color, but in the case of a luminescent solvertochromic molecule, it is generally known that the emission intensity changes as the emission color changes. Therefore, in the present invention, the color change includes the change from colorless to color development and vice versa.

It is desirable that the ICT molecule has a staggered intramolecular charge transfer (TICT) property from the viewpoint of increasing the color change. TICT exhibits a larger emission wavelength change because after electron transfer from the electron donating group occurs, the electron donating group is twisted to be out of conjugation. The structure of the TICT-based molecule in the present invention is not particularly limited, but the electron donating group includes a (di) alkylamino group (representing both a monoalkylamino group and a dialkylamino group), a phenyl group and the like, as well as an alkyl group. , A functional group in which a bulky substituent is introduced into an alkoxy group is exemplified. Examples of the electron attracting group include a carboxyl group, a cyano group, a cyanato group, a thiocyanato group, an aldehyde group, a nitro group, a nitroso group, an aminocarbonyl group, a thiocarboxyl group and a salt thereof, a dithiocarboxyl group, a thiocarbonyl group, and an acyl group. Examples thereof include a thioacyl group, a sulfinic acid group, a sulfonic acid group, a sulfinyl group, a sulfonyl group, an oxysulfonyl group, a thiosulfonyl group and an aminosulfonyl group. If the electron donating group or the electron attracting group itself is a conjugated system, both may be directly bonded, but if it is not a conjugated system, it must be bonded via a conjugated compound such as an aromatic compound. There is.

Of these, the electron donating group is preferably a dialkylamino group from the viewpoint of the strength of its donating property, and the electron attracting group is preferably a carboxyl group from the viewpoint of binding to the POSS having the above-mentioned alkylamino group at the apex. As the aromatic compound to which the electron donating group and the electron attracting group are bonded, it is preferable that the absorption, emission wavelength, and emission brightness can be adjusted by the substitution position and the substituent, and the benzene ring and the xanthene are preferable. Examples of compounds (derivatives) having a skeleton, a pyrromethene skeleton, a xanthene skeleton, and the like. Of these, a coumarin skeleton compound (coumarin derivative) is preferable from the viewpoints of being able to be adjusted in a wide range of wavelengths in the visible light region, having moderate hydrophobicity, and being relatively inexpensive. Among the coumarin derivatives, a coumarin derivative having a dialkylamino group and a carboxyl group, for example, a coumarin compound having a diethylamino group and a carboxyl group, particularly a 7-diethylaminocoumarin-3-carboxylic acid is most preferably exemplified.

The method for introducing the chromic molecule into the POSS may be carried out according to a known method depending on the terminal group (linker) at the apex of the POSS. For example, a known method for forming an amide bond by condensing an amino group at the linker terminal with a carboxyl group in a chromic molecule can be mentioned. In this method, condensation is carried out using a carbodiimide-based, imidazole-based condensing agent, triazine-based condensing agent, uronium-based condensing agent, halouronium-based condensing agent, or the like. Among these condensing agents, triazine-based condensing agents are most preferable because they can be used in highly polar solvents and can be reacted under mild conditions, and 4- (4,6-dimethoxy) on the market is the most preferable. -1,3,5-triazine-2-yl) -4-methylmorpholinium chloride n hydrate (DMT-MM) is preferred.

The POSS network polymer of the present invention has chromic molecules, and the content thereof is indicated by the rate of introduction of chromic molecules into POSS (introduction rate). The introduction rate is not particularly limited, but is preferably 5% to 50%, and most preferably 10% to 30% of the POSS vertices (8 vertices) on average. If the introduction rate is lower than this range, the effect as a fluorescent dye cannot be expected, and if it exceeds this range, the following POSS cross-linking becomes difficult. The introduction rate in the present invention is the ratio (average) of the chromic molecules actually introduced to the total functional groups into which the chromic molecules present in all POSS molecules can be introduced, and is not necessarily the ratio (average) of the chromic molecules to one POSS molecule. It is not necessary that the chromic molecule is introduced at the above introduction rate.

The introduction rate of chromic molecules can be calculated using a nuclear magnetic resonance apparatus (NMR). Specifically, ¹ H-NMR spectrum is measured, and among the peaks derived from the organic functional groups of POSS, the peak area on the highest magnetic field side (A _H ) and the peak area on the lowest magnetic field side ( _AL ) are determined. Just compare. This is because the peak on the highest magnetic field side hardly causes a peak shift due to the introduction of chromic molecules, whereas the peak on the lowest magnetic field side causes a peak shift and the area decreases. For example, aminopropyl group (linkers) introducing a chromic molecule into POSS to the functional group, the use of DMSO-d6 as a deuterated solvent, the peak around 2.8ppm peak area in the vicinity of 0.7 ppm _{(A H)} It can be calculated from the area ( _AL ).
Specifically, it is calculated from the following formula. However, this formula is the formula in POSS before making it a POSS network polymer.
[Introduction ratio _{(%)] = [A H} -A L] × 100 / A H

The POSS network polymer of the present invention is formed by bonding and cross-linking POSS to each other via a methylene chain, and more specifically, POSS to each other via a linker (L) by a cross-linking agent having a methylene chain.・ It is a bridge. The methylene chain may be linear or may have a branched chain. The length of the methylene chain is not particularly specified, but is preferably 1 to 18, more preferably 2 to 12, and most preferably 2 to 8. If the number of carbon atoms is longer than this, the water solubility of the POSS network polymer is lowered, which is not preferable.

The methylene chain terminal functional group of the cross-linking agent having a methylene chain is not particularly limited, but may be appropriately selected depending on the functional group of the linker at the apex of POSS, preferably the terminal functional group.

Specific cross-linking agents applicable to the present invention include dicarboxylic acids having 2 to 10 carbon atoms, preferably 3 to 10 carbon atoms, more preferably 4 to 10 carbon atoms, particularly suberic acid, maronic acid, suberic acid, glutaric acid. Adiponic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 3-ethyl-3-methylglutaric acid, etc., preferably succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 3 -Ethyl-3-methylglutaric acid and the like, more preferably succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and the like are exemplified.

In order to crosslink POSS with each other by a methylene chain, the functional group of the linker and the functional group of the crosslinking agent may be reacted and bonded. For example, when POSS having an aminoalkyl group at the apex is bonded and crosslinked as a linker, the methylene chain terminal group of the crosslinking agent is preferably a carboxyl group. In this case, in order to bond and crosslink the POSS with a cross-linking agent, the above-mentioned method for forming an amide bond may be followed.

The degree of cross-linking of POSS is about 10 to 80%, preferably about 20 to 70%. If the degree of cross-linking is too large, it is difficult to obtain water solubility, and if it is too small, the effect of suppressing aggregation of the chromic molecule-introduced POSS by the network cannot be expected. The degree of cross-linking can be adjusted by adjusting the amount of the cross-linking agent acting on one POSS molecule. Further, the degree of cross-linking can be calculated from the ¹ H-NMR spectrum as well as the introduction rate of the chromic molecule described above. Specifically, ¹ H NMR spectrum is measured, and among the peaks derived from the organic functional groups of POSS, the peak area (A _H ) on the highest magnetic field side and the peak area ( _AL ) on the lowest magnetic field side are compared. Then, the introduction rate of chromic molecules should be subtracted. Specifically, it is calculated from the following formula.
Crosslinking degree _{(%)] = [A H} -A L] × 100 / A H - chromic molecule introduction rate should be noted that the degree of crosslinking in the present invention, with respect crosslinkable total functional groups present in the POSS whole molecule , It is the average ratio actually crosslinked by the methylene chain, and it is not always necessary that the POSS1 molecule is crosslinked with the degree of crosslink.

The order of introduction of the chromic molecule and cross-linking is not particularly limited, but it is preferable to introduce the chromic molecule first. This is because if cross-linking is performed first, the contact probability between the organic functional group and the chromic molecule decreases, and it becomes difficult to introduce the chromic molecule.

The POSS network polymer of the present invention is water soluble. Here, "water-soluble" means that the POSS network polymer is at least 0.1 g or more, preferably 0.5 g or more, more preferably 0.8 g or more, still more preferably 0.8 g or more in dry weight with respect to 1 liter of water. It refers to the case where 1.0 g or more is dissolved.

To obtain a water-soluble POSS network polymer, water is added to the solid network polymer synthesized according to the above method, the water-soluble component is dissolved in water by stirring, standing, sonication, etc., and then filtration or centrifugation is performed. Only the water-soluble fraction needs to be separated by a separation operation such as separation. The water-soluble fraction thus obtained may be used as it is for detecting fine particles, or may be appropriately concentrated, diluted, and dried by a known method for storage to obtain an aqueous solution having a desired concentration or a solid state. You may.

The POSS network polymer of the present invention can detect hydrophobic fine particles, and the fine particle detection material containing the POSS network polymer can be used to detect hydrophobic fine particles.
Thus, a POSS network polymer containing cage-type silsesquioxane (POSS) as a constituent component is contained, the POSS network polymer has a chromic molecule exhibiting solvatochromism, and POSS are crosslinked with each other by a methylene chain. Provided is a microparticle detection material, characterized in that it is used for detecting hydrophobic microparticles.
Since the POSS network polymer of the present invention is water-soluble, the fine particle detection material can measure an environmental sample in a water area.

The fine particles to which the fine particle detection material of the present invention is particularly suitable as a detection target are fine particles having a certain hydrophobic surface. Specifically, it is a fine particle composed of a component showing a water contact angle of 60 ° or more at the time of bulk. Such fine particles may be organic or inorganic, and particles whose surface is processed and coated with a hydrophobic component are also detection target particles.
The contact angle is an index showing the ease of wetting and spreading on the surface of a liquid solid. When the liquid is water, it is called the water contact angle, and the smaller the value, the more hydrophilic it is, and the larger the value, the more hydrophobic it is. The water contact angle in the present invention means a "static contact angle" which is a contact angle on a stationary solid surface. The method of determining the water contact angle (θ) is to drop a small amount of water on the solid surface of the target substance so that the influence of gravity can be ignored, and the contact radius (r) and height (h) of the formed water droplets. ) Is calculated by the following formula.
θ = 2 arctan (h / r)
Since it is difficult to determine the contact angle on the surface of fine particles by a simple method, the water contact angle in the bulk (solid size of a general size) state of the substance forming the fine particles is applied. The water contact angle in the bulk state including the polymer has been reported in various documents, and the polymer exemplified in the present invention is based on them. In the polymer exemplified in the present invention, when the water contact angle is unknown, a test piece may be prepared and measured by the above method. Further, in the present invention, the characteristic showing a water contact angle of 60 ° or more at the time of bulk is referred to as "hydrophobicity".

As a component having a water contact angle at the time of bulk (hereinafter, simply referred to as "water contact angle" (also referred to as "bulk contact angle") of 60 ° or more, more specifically, various organic polymers. For example, polymethyl methacrylate (PMMA) (water contact angle: 66 to 67 °), polylactic acid (PLA) (water contact angle: 76 to 88 °), polystyrene (PS) (water contact angle: 81 to 91 °). , Polypropylene (PP) (water contact angle: 104 °), polyethylene (PE) (water contact angle: 94 °), polyamide (PA) (water contact angle: 70 °), fluororesin (water contact angle: 82 to 108 °) °), Polyethylene terephthalate (PET) (water contact angle: 81 °), polyvinyl chloride (PVC) (water contact angle: 87 °), polyimide (PI) (water contact angle: 68-76 °), polycarbonate (water) Contact angle: 80 °) (see Non-Patent Documents 6 to 13) and the like. When the water contact angle has a value in a certain range, for example, polymethyl methacrylate (PMMA) (water contact angle (bulk contact)). Angle): In the case of 66 to 67 °), in the present invention, the case where the lower limit value of the water contact angle is 60 ° or more is referred to as “hydrophobicity”.
Non-Patent Document 6: Journal of Japanese Rheology Society (2012), Vol.40, No.3, 143-149
Non-Patent Document 7: Polymer Papers (2014), Vol.71, No.8, 343-351
Non-Patent Document 8: Progress in Polymer Science (2010), Vol.35, 338-356
Non-Patent Document 9: Journal of Japan Rubber Association (1987), Vol.60, No.5, 246-255
Non-Patent Document 10: Langmuir (2007), vol.23, 9785-9793
Non-Patent Document 11: Surface Technology (1995), Vol.46, No.11, 1050-1053
Non-Patent Document 12: Recent Advances in Polyimide (1995), 70-73
Non-Patent Document 13: Bulletin of Akita National College of Technology (2000), Vol.35, 42-46

The second aspect of the present invention is a method for detecting hydrophobic fine particles, which comprises a POSS network polymer containing a cage-type silsesquioxane (POSS) as a constituent component, and the POSS network polymer is solvatochromism. The present invention relates to a method for detecting hydrophobic fine particles, which comprises using a fine particle detection material having a chromic molecule showing the above and characterized in that POSS are crosslinked with each other by a methylene chain.

As the fine particle detection material used in this method, the above-mentioned material is used. The fine particle detection material has a POSS network polymer structure in which a POSS compound is crosslinked with a methylene chain, and has an ability to adsorb to fine particles. Further, the POSS network polymer has a specific chromic molecule introduced therein, and the emission color can be changed depending on whether it is adsorbed on fine particles or not. In particular, when a solvertochromic molecule showing staggered intramolecular charge transfer is introduced, it has a bimodal emission spectrum because it exhibits different emission colors at the aggregation site and the other portion in the network. Further, the ratio of the two can be changed depending on whether the particles are adsorbed on the fine particles or not. The change is due to the hydrophobicity of the surface of the fine particles, and responds only to hydrophobic fine particles having a small particle size and exhibiting a water contact angle of a certain level or more. The hydrophobic fine particles that can be detected with a certain degree of accuracy are hydrophobic fine particles having a particle size of less than 1 μm, particularly, a particle size of less than 1 μm to about 20 nm, and particularly about 600 nm to about 20 nm. The mechanism for detecting these particles is not clear, but it is thought that the apparent contact angle changes depending on the particle size, and the smaller particles become more hydrophobic. In the present invention, the "particle size" means the average particle size based on the light scattering intensity.

The method for detecting the hydrophobic fine particles is described in more detail.
It contains a POSS network polymer containing a cage-type silsesquioxane (POSS) as a constituent component, the POSS network polymer has a chromic molecule exhibiting solvatochromism, and POSS are crosslinked with each other via a methylene chain. Detection liquid preparation step of preparing a detection liquid containing a fine particle detection material and water, which is characterized by the above:
A sample solution preparation step in which a detection solution prepared in the detection solution preparation step and an environmental sample solution containing fine particles are mixed to prepare a sample solution;
An irradiation step of irradiating the sample solution obtained in the sample solution preparation step with excitation light, and a luminescence analysis step of analyzing the luminescence emitted from the sample solution by the irradiation step;
including.

Detection liquid preparation step The POSS network polymer containing "cage-type silsesquioxane (POSS) as a constituent component" used in the detection liquid preparation step is contained, and the POSS network polymer has a chromic molecule exhibiting solvatochromism. Further, as the "fine particle detection material" characterized in that the POSS are crosslinked with each other by a methylene chain, the above-mentioned material is used.

The fine particle detection material is mixed with water and mixed so as to have a chromic molecule equivalent of 0.1 mM to 10 mM, more preferably 0.5 mM to 5 mM in the POSS network polymer. Even if the concentration exceeds or falls below this concentration, aggregation accompanied by a change in emission color does not occur, or the aggregation is too strong, so that it becomes difficult for the surface of plastic fine particles or the like to interact with hydrophobic fine particles.

The detection solution is preferably stored at the above aqueous solution concentration for a certain period of time before being subjected to the following sample solution preparation step. By performing this operation, the network polymer forms aggregates and exhibits a different emission color than in the presence of hydrophobic fine particles. The storage time is preferably 3 hours or more, more preferably 12 hours or more. If it is shorter than this time, aggregation may be insufficient.

The detection solution having the above concentration is diluted when it is used for use in the following sample solution preparation step, but it may be diluted and adjusted to the concentration after the following dilution in the detection solution preparation step and stored.

Sample solution preparation step Next, the detection solution obtained above is mixed with an environmental sample solution (aqueous solution).
It is preferable to dilute the detection liquid obtained in the detection liquid preparation step prior to the mixing.
The dilution is 0.1 μM to 100 μM, more preferably 0.5 μM to 50 μM, and most preferably 1.0 μM to 20 μM in terms of chromic molecules in the POSS network polymer. .. Below this range, the color change is below the detection limit, and above this range, the ratio of hydrophobic fine particles to uncontacted network polymer increases, and as a result, the emission intensity of the changed emission color is the emission of the original emission color. It becomes weaker than the strength, making it difficult to identify the change.

The detection solution and the environmental sample solution (aqueous solution) are mixed at a ratio of 1: 1 (detection solution: environmental sample solution) (volume ratio).

Irradiation step The sample solution obtained in the sample solution preparation step is irradiated with excitation light.
The light to irradiate may include light capable of exciting chromic molecules in the POSS network polymer. For example, when 7-diethylaminocoumarin-3-carboxylic acid is used as the chromic molecule, it may be irradiated with excitation light having a wavelength of 330 to 480 nm. For convenience, it may be irradiated with a commercially available black light or the like.

Emission analysis step The light emitted from the sample solution by the irradiation step, that is, the luminescence (hereinafter referred to as "sample solution luminescence") is analyzed.

For qualitative measurement and analysis, after irradiating the sample solution with light, visually observe the light emitted from the sample solution and the light emitted by irradiating the detection solution in the same manner (hereinafter referred to as "detection solution emission"). It is possible to compare with.

If the emission of the sample solution is visually observed to emit a color different from that of the detection solution, the particle size of the sample solution is less than 1 μm, remarkably less than 1 μm to about 20 nm, more remarkably about 600 nm to about 20 nm, and more. Remarkably, it is shown that hydrophobic fine particles of about 500 nm to about 20 nm are contained. The larger the change in the emission color, the more hydrophobic fine particles or or smaller nanoparticles are contained. In the present invention, the "emission color change" corresponds to the difference in wavelength on the spectrum of visible light. For example, when 7-diethylaminocoumarin-3-carboxylic acid is used as the chromic molecule, the sample solution becomes smaller as the particle size of the contained hydrophobic fine particles becomes smaller, or as the hydrophobicity of the surface of the fine particles becomes higher. The luminescence is observed as yellow → yellow-green → blue-green → blue. By this visual observation, the presence of hydrophobic fine particles having a particle size of less than 1 μm can be confirmed. Further, when visually observed, it is shown that the larger the emission color change is, the more hydrophobic fine particles having a particle size of less than 1 μm are present, or the more hydrophobic the surface of the fine particles is.

For quantitative measurement and analysis, a spectrophotometer is used to measure and compare the emission intensity and spectral distribution of the detection liquid emission and the sample solution emission. When a TICT-type chromic molecule is used, two peaks, a long wavelength side peak and a short wavelength side peak, are usually observed in the spectral distribution of the detection liquid emission. Comparing the spectral distributions of the detection liquid emission and the sample solution emission, if the spectral distribution of the sample solution emission shows an increase in the intensity of the peak on the short wavelength side, it means that hydrophobic particles having a particle size of less than 1 μm are contained. It is shown that the larger the change in strength, the more fine particles having a smaller particle size are present, or the more hydrophobic the surface of the fine particles is. For example, when 7-diethylaminocoumarin-3-carboxylic acid is used as the chromic molecule, two peaks are observed at about 470 nm and about 560 nm in the case of the detection solution containing no fine particles, and the peak at about 560 nm is large. Occupy a part. In comparison, in the case of a sample solution containing fine particles, the peak intensity at about 470 nm increases. The more particles with a smaller particle size, or the higher the hydrophobicity of the surface of the fine particles, the greater the change in the strength.

It is possible to adjust the range of detectable particle sizes by varying the length of the crosslinked methylene chains that form the POSS network polymer. Specifically, the longer the length of the methylene chain, the more sensitively it is possible to detect nanoplastics having a larger particle size.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

[Raw materials and their adjustment]
(1) POSS compound:
-Octammonium POSS was synthesized by the following procedure.
50 g of 3-aminopropyltriethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to 400 mL of methanol (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.), and 65 mL of concentrated hydrochloric acid was gradually added with stirring.
After reacting at room temperature for 5 days, the precipitated white precipitate was filtered through filter paper (Kiriyama Glass Co., Ltd., No. 5A), the filtrate was washed with cold methanol, vacuum dried, and aminoPOSS (octaammonium POSS) 10. 3 g was obtained.
Confirmation of amino POSS was performed by confirming an NMR spectrum and a high-resolution MS spectrum.
(2) Chromic molecule 7-diethylaminocoumarin-3-carboxylic acid (coumarin D1421) (manufactured by Tokyo Chemical Industry Co., Ltd.)
(3) Dicarboxylic acid (methylene chain unit)
・ A. Succinic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)
・ B. Adipic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)
・ C. Sebacic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)

[Comparative Example 1]
500 mg of coumarin D1421 was dissolved in 25 mL of DMSO (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.), 1.1 g of DMT-MM (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was added, and the reaction was carried out at room temperature for 1 hour with stirring. Then, 1.2 g of octaammonium POSS and 0.43 mL of triethylamine (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) were added, and the reaction was carried out at room temperature for 24 hours. The reaction solution was slowly added dropwise to 250 mL of acetonitrile (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) containing 0.1 v / v% concentrated hydrochloric acid, and the mixture was stirred at room temperature for 1 hour. The precipitated precipitate is filtered through a hydrophobic PVDF filter (manufactured by Millipore) having a pore size of 0.45 μm, washed with acetonitrile, vacuum dried, and 1.2 g of yellow powder (hereinafter referred to as “coumarin POSS”). Got From ¹ H-NMR spectrum analysis of coumarin POSS, the introduction rate of coumarin D1421 into amino POSS was 26%. 16 mg of the obtained coumarin POSS was dissolved in 10 mL of water to obtain an aqueous coumarin POSS solution having a concentration of 1 mM. That is, the obtained coumarin POSS has a water solubility of at least 1.6 g / L.

[Example 1]
22 mg of succinic acid was dissolved in 5 mL of DMSO, 120 mg of DMT-MM was added, and the reaction was carried out at room temperature for 1 hour with stirring. Then, 100 mg of coumarin POSS obtained in Comparative Example 1 and 62 μL of triethylamine were added, and the reaction was carried out at room temperature for 48 hours. The reaction solution was slowly added dropwise to 50 mL of acetonitrile containing 0.1 v / v% concentrated hydrochloric acid, and the mixture was stirred at room temperature for 1 hour. The suspension containing the precipitate was centrifuged at 2,000 × g for 30 minutes, the supernatant was discarded, acetonitrile was added to the obtained precipitate, suspended, and the precipitate was centrifuged again to wash the precipitate. This operation was repeated again, and the obtained precipitate was vacuum dried. The precipitate obtained here is a POSS network polymer, and includes water-soluble ones and non-water-soluble ones. Next, the obtained precipitate was suspended in water and extracted by ultrasonic waves, and then filtered through a hydrophilic PVDF filter (manufactured by Millipore) having a pore size of 0.45 μm. The resulting filtrate contains a water-soluble POSS network polymer. When the obtained filtrate was freeze-dried and the dry weight was measured, it was found that this water-soluble POSS network polymer had a water solubility of at least 1.5 g / L. Moreover, when the ¹ H-NMR spectrum of the freeze-dried solid was measured, the degree of cross-linking was 55%. Based on this result, the filtrate was diluted to 1 mM in terms of coumarin D1421 to obtain 22 mL of a yellow liquid.

[Example 2]
28 mg of adipic acid was dissolved in 5 mL of DMSO, 120 mg of DMT-MM was added, and the reaction was carried out at room temperature for 1 hour with stirring. Then, 100 mg of coumarin POSS obtained in Comparative Example 1 and 62 μL of triethylamine were added, and the reaction was carried out at room temperature for 48 hours. The reaction solution was slowly added dropwise to 50 mL of acetonitrile containing 0.1 v / v% concentrated hydrochloric acid, and the mixture was stirred at room temperature for 1 hour. The suspension containing the precipitate was centrifuged at 2,000 × g for 30 minutes, the supernatant was discarded, acetonitrile was added to the obtained precipitate, suspended, and the precipitate was centrifuged again to wash the precipitate. This operation was repeated again, and the obtained precipitate was vacuum dried. The precipitate obtained here is a POSS network polymer, and includes water-soluble ones and non-water-soluble ones. Next, the obtained precipitate was suspended in water and extracted by ultrasonic waves, and then filtered through a hydrophilic PVDF filter (manufactured by Millipore) having a pore size of 0.45 μm. The resulting filtrate contains a water-soluble POSS network polymer. When the obtained filtrate was freeze-dried and the dry weight was measured, it was found that this water-soluble POSS network polymer had a water solubility of at least 2.3 g / L. Moreover, when the ¹ H-NMR spectrum of the freeze-dried solid was measured, the degree of cross-linking was 45%. Based on this result, the filtrate was diluted to 1 mM in terms of coumarin D1421 to obtain 34 mL of a yellow liquid.

[Example 3]
38 m of sebacic acid was dissolved in 5 mL of DMSO, 120 mg of DMT-MM was added, and the reaction was carried out at room temperature for 1 hour with stirring. Then, 100 mg of coumarin POSS obtained in Comparative Example 1 and 62 μL of triethylamine were added, and the reaction was carried out at room temperature for 48 hours. The reaction solution was slowly added dropwise to 50 mL of acetonitrile containing 0.1 v / v% concentrated hydrochloric acid, and the mixture was stirred at room temperature for 1 hour. The suspension containing the precipitate was centrifuged at 2,000 × g for 30 minutes, the supernatant was discarded, acetonitrile was added to the obtained precipitate, suspended, and the precipitate was centrifuged again to wash the precipitate. This operation was repeated again, and the obtained precipitate was vacuum dried. The precipitate obtained here is a POSS network polymer, and includes water-soluble ones and non-water-soluble ones. Next, the obtained precipitate was suspended in water and extracted by ultrasonic waves, and then filtered through a hydrophilic PVDF filter (manufactured by Millipore) having a pore size of 0.45 μm. The resulting filtrate contains a water-soluble POSS network polymer. When the obtained filtrate was freeze-dried and the dry weight was measured, it was found that this water-soluble POSS network polymer had a water solubility of at least 1.1 g / L. Moreover, when the ¹ H-NMR spectrum of the freeze-dried solid was measured, the degree of cross-linking was 34%. Based on this result, the filtrate was diluted to 1 mM in terms of coumarin D1421 to obtain 15 mL of a yellow liquid.

The results of evaluation of the polymer fine particle detection ability of Examples and Comparative Examples are shown below. The materials, equipment, and measurement conditions used for the evaluation are as follows.
(1) Fine particles A: PS fine particles (particle size: 50 nm, 100 nm, 200 nm, 500 nm, 1 μm) (manufactured by micromod)
B: PMMA fine particles (particle size: 25 nm) (manufactured by micromod)
C: PLA fine particles (particle size: 250 nm, 2 μm) (manufactured by micromod)
D: Silica fine particles (particle size: 40 nm, 460 nm, 950 nm (prepared according to Non-Patent Documents 14 and 15))
Non-Patent Document 14: JOURNAL OF COLLOID AND INTERFACE SCIENCE (1968), vol.26, 62-69
Non-Patent Document 15: Journal of Material Research (2002), vol.18, No.3, 649-653

The bulk contact angle of the fine particles is as follows.
A: PS fine particles (particle size: 50 nm): bulk contact angle (81 to 90 degrees)
PS fine particles (particle size: 100 nm: bulk contact angle (81 to 90 degrees)
PS fine particles (particle size: 200 nm: bulk contact angle (81-90 degrees)
PS fine particles (particle size: 500 nm: bulk contact angle (81 to 90 degrees)
PS fine particles (particle size: 1 μm): Bulk contact angle (81-90 degrees)
B: PMMA fine particles (particle size: 25 nm): bulk contact angle (66 to 67 degrees)
C: PLA fine particles (particle size: 250 nm): bulk contact angle (76-80 degrees)
PLA fine particles (particle size: 2 μm): bulk contact angle (76-80 degrees)
D: Silica fine particles (particle size: 40 nm): bulk contact angle (0 to 42 degrees)
Silica fine particles (particle size: 460 nm): bulk contact angle (0 to 42 degrees)
Silica fine particles (particle size: 950 nm): bulk contact angle (0 to 42 degrees)
The bulk contact angle of the silica fine particles is based on Non-Patent Documents 16 to 17.
Non-Patent Document 16: UNITED STATES DEPARTMENT OF THE INTERIOR GEOLOGICAL SURVEY (1990)
Non-Patent Document 17: Proceedings of the Society of Instrument and Control Engineers (1996), Vol.32, No.5, 617-645

(2) Emission spectrum measurement Fluorometer: FluoroMax-4 (manufactured by HORIBA, Ltd.)
Excitation wavelength: 427 nm
(3) Visual observation UV lamp: Compact UV Lamp UVGL-25 (manufactured by UVP)
Excitation wavelength: 365 nm

[Test example]
The liquids obtained in Examples 1 to 3 and Comparative Example 1 were allowed to stand at room temperature for 2 days to allow aggregation to proceed. Each of these detection solutions was diluted 100-fold with pure water to a concentration of 10 μM in terms of coumarin D1421, and the fine particles were adjusted to 58 cm ² / mL in terms of surface area with a pure water suspension and 1 in volume ratio. It was mixed so as to be 1: 1.
The obtained mixed solution was irradiated with a UV lamp, and the color change was visually observed and the emission spectrum was measured. Table 1 shows the evaluation results of visual observation of the emission color, and FIGS. 1 and 2 show typical changes in the emission spectrum.

As shown in Table 1, in Coumarin D1421 and Comparative Example 1, no visual change in emission color was observed between the presence and absence of fine particles, whereas in Examples 1 to 3, a specific type and specific were observed. It can be seen that the emission color changes in the presence of fine particles of the size of.
Specifically, the emission color changes in the presence of PS fine particles of 500 nm or less, PMMA fine particles of 25 nm, and PLA fine particles of 250 nm, and large size PS fine particles (1000 nm), PLA fine particles (2000 nm), and silica fine particles of all sizes. No change in emission color is seen.
It is considered that the change in the emission color is due to the network POSS of the present invention adsorbing on the fine particles and changing the emission intensity according to the affinity hydrophobicity on the surface of the fine particles. When the bulk contact angle is 60 ° or more as defined in the present invention, such a change in emission color is observed, but when the bulk contact angle is less than 60 °, such a change in emission color is not observed.

More detailed analysis is possible by measuring the emission spectrum.
As shown in FIG. 2, when the coumarin POSS of Comparative Example 1 was used, no change in the emission spectrum was observed when any of the fine particles was added, whereas it was obtained in Example 1 shown in FIG. It was found that when PS fine particles, PLA fine particles, and PMMA fine particles were added, the emission peak showing blue color around 470 nm increased when the network POSS was used, and these changes led to the results in Table 1. There is.
It can be seen that in the PS fine particles and the PLA fine particles, the increase in the blue emission peak decreases as the particle size increases, and the particle size can be determined by spectral analysis.
Further, it can be seen that even if the fine particles are small, the increase in blue light emission is small in the PMMA fine particles, no change is observed in the silica fine particles, and the degree of increase in blue light emission is changed according to the surface hydrophobicity.
These characteristics are not only useful as a material for determining whether or not plastic fine particles are present in water, but also the type (surface characteristics) of the plastic constituting the fine particles, the particle size of the particles, and the particles. It is also shown to be useful for determining the amount of.

From the above disclosure items, for example, the following is provided as a more specific aspect of the invention according to the first aspect of the present invention.
(1) A POSS network polymer containing cage-type silsesquioxane (POSS) as a constituent component is contained, the POSS network polymer has a chromic molecule exhibiting solvatochromism, and POSS are connected to each other via a methylene chain. A fine particle detection material, which is obtained by cross-linking and is used for detecting hydrophobic fine particles.
(2) The fine particle detection material according to (1) above, wherein the solvertochromic molecule is a molecule showing staggered intramolecular charge transfer.
(3) The fine particle detection material according to (1) or (2) above, wherein the solvertochromic molecule is a coumarin derivative having a dialkylamino group.
(4) The fine particle detection material according to any one of (1) to (3) above, wherein the solvertochromic molecule is a coumarin derivative having a carboxyl group.
(5) The fine particle detection material according to any one of (1) to (4) above, wherein the chiren chain has 2 to 8 carbon atoms.
(6) The fine particle detection material according to any one of (1) to (5) above, wherein the cross-linking between POSS and the methylene chain is via an amide bond.
(7) The fine particle detection material according to any one of (1) to (6) above, wherein POSS has an aminopropyl group at the apex.
(8) The fine particle detection material according to any one of (1) to (7) above, wherein the introduction rate of the solvertochromic molecule into POSS is 10% to 30%.
(9) The fine particle detection material according to any one of (1) to (8) above, wherein the cross-linking between POSS by methylene chains is 10% to 80%.
(10) The fine particle detection material according to any one of (1) to (9) above, wherein the POSS network polymer is water-soluble.
(11) The fine particle detection material according to any one of (1) to (10) above, wherein the hydrophobic fine particles have a water contact angle of 60 ° or more.
(12) The fine particle detection material according to any one of (1) to (11) above, wherein the hydrophobic fine particles are polymer fine particles.
(13) The fine particle detection material according to any one of (1) to (12) above, wherein the hydrophobic fine particles are selected from the group consisting of polymethyl methacrylate, polylactic acid, polystyrene, derivatives thereof and mixtures thereof.
(14) The fine particle detection material according to any one of (1) to (13) above, wherein the size of the hydrophobic fine particles is less than 1 μm.

Further, as a more specific aspect of the invention according to the second aspect of the present invention, for example, the following is provided.
(1) A method for detecting hydrophobic fine particles, which comprises a POSS network polymer containing cage-type silsesquioxane (POSS) as a constituent component, and the POSS network polymer has a chromic molecule exhibiting solvatochromism. The method for detecting hydrophobic fine particles, which comprises using a fine particle detection material in which POSS are crosslinked with each other via a methylene chain.
(2) A POSS network polymer containing cage-type silsesquioxane (POSS) as a constituent component is contained, the POSS network polymer has a chromic molecule exhibiting solvatochromism, and POSS are connected to each other via a methylene chain. Detection liquid preparation step of preparing a detection liquid containing a fine particle detection material and water, which is characterized by being crosslinked;
A sample solution preparation step of preparing a sample solution by mixing the detection solution prepared in the detection solution preparation step with an environmental sample solution containing fine particles or determining whether or not the fine particles are contained;
An irradiation step of irradiating the sample solution obtained in the sample solution preparation step with light; and a luminescence analysis step of analyzing the luminescence emitted from the sample solution by the irradiation step.
A method for detecting hydrophobic fine particles, including.
(3) The method for detecting hydrophobic fine particles according to (1) or (2) above, wherein the solvertochromic molecule is a molecule exhibiting staggered intramolecular charge transfer.
(4) The method for detecting hydrophobic fine particles according to any one of claims to 3, wherein the solvertochromic molecule is a coumarin derivative having a dialkylamino group.
(5) The method for detecting hydrophobic fine particles according to any one of (1) to (4) above, wherein the solvertochromic molecule is a coumarin derivative having a carboxyl group.
(6) The method for detecting hydrophobic fine particles according to any one of (1) to (5) above, wherein the methylene chain has 2 to 8 carbon atoms.
(7) The method for detecting hydrophobic fine particles according to any one of (1) to (6) above, wherein the cross-linking between POSS and the methylene chain is via an amide bond.
(8) The method for detecting hydrophobic fine particles according to any one of (1) to (7) above, wherein the POSS has an aminopropyl group at the apex.
(9) The method for detecting hydrophobic fine particles according to any one of (1) to (8) above, wherein the number of solved chromic molecules introduced into POSS is 10% to 30%.
(10) The method for detecting hydrophobic fine particles according to any one of (1) to (9) above, wherein the cross-linking between POSS by methylene chains is 10% to 80%.
(11) The method for detecting hydrophobic fine particles according to any one of (1) to (10) above, wherein the POSS network polymer is water-soluble.
(12) The method for detecting hydrophobic fine particles according to any one of (1) to (11) above, wherein the hydrophobic fine particles have a water contact angle of 60 ° or more.
(13) The method for detecting hydrophobic fine particles according to any one of (1) to (12) above, wherein the hydrophobic fine particles are polymer fine particles.
(14) The hydrophobic fine particles according to any one of (1) to (13) above, wherein the hydrophobic fine particles are selected from the group consisting of polymethyl methacrylate, polylactic acid, polystyrene, derivatives thereof and mixtures thereof. How to detect.
(15) The method for detecting hydrophobic fine particles according to any one of (1) to (14) above, wherein the size of the hydrophobic fine particles is less than 1 μm.
(16) The method for detecting hydrophobic fine particles according to any one of (2) to (15) above, wherein the light emission analysis is performed by comparing the light emitted from the detection liquid and the light emitted from the sample solution.
(17) The method for detecting hydrophobic fine particles according to any one of (2) to (16) above, which comprises visually performing luminescence analysis.
(18) The method for detecting hydrophobic fine particles according to any one of (2) to (16) above, wherein the emission analysis is performed with a spectrophotometer.

Claims (16)

It contains a POSS network polymer containing cage-type silsesquioxane (POSS) as a constituent component, the POSS network polymer has a chromic molecule exhibiting solvatochromism, and POSS are crosslinked with each other via a methylene chain. A fine particle detection material, characterized in that it is used for detecting hydrophobic fine particles. The fine particle detection material according to claim 1, wherein the solvertochromic molecule is a molecule that exhibits staggered intramolecular charge transfer. The fine particle detection material according to claim 1 or 2, wherein the solvertochromic molecule is a coumarin derivative having a dialkylamino group. The fine particle detection material according to any one of claims 1 to 3, wherein the solvertochromic molecule is a coumarin derivative having a carboxyl group. The fine particle detection material according to any one of claims 1 to 4, wherein the methylene chain has 2 to 8 carbon atoms. The fine particle detection material according to any one of claims 1 to 5, wherein the cross-linking between the POSS and the methylene chain is via an amide bond. The fine particle detection material according to any one of claims 1 to 6, wherein the POSS has an aminopropyl group at the apex. The fine particle detection material according to any one of claims 1 to 7, wherein the introduction rate of the solvertochromic molecule into POSS is 10% to 30%. The fine particle detection material according to any one of claims 1 to 8, wherein the cross-linking between POSS by a methylene chain is 10% to 80%. The fine particle detection material according to any one of claims 1 to 9, wherein the POSS network polymer is water-soluble. The fine particle detection material according to any one of claims 1 to 10, wherein the hydrophobic fine particles have a water contact angle of 60 ° or more. The fine particle detection material according to any one of claims 1 to 11, wherein the hydrophobic fine particles are polymer fine particles. The fine particle detection material according to any one of claims 1 to 12, wherein the hydrophobic fine particles are selected from the group consisting of polymethyl methacrylate, polylactic acid, polystyrene, derivatives thereof, and mixtures thereof. The fine particle detection material according to any one of claims 1 to 13, wherein the size of the hydrophobic fine particles is less than 1 μm. A method for detecting hydrophobic fine particles, which comprises a POSS network polymer containing cage-type silsesquioxane (POSS) as a constituent component, and the POSS network polymer has a chromic molecule exhibiting solvatochromism. , A method for detecting hydrophobic fine particles, which comprises using a fine particle detection material in which POSS are crosslinked with each other via a methylene chain. It contains a POSS network polymer containing a cage-type silsesquioxane (POSS) as a constituent component, the POSS network polymer has a chromic molecule exhibiting solvatochromism, and POSS are crosslinked with each other via a methylene chain. Detection liquid preparation step of preparing a detection liquid containing a fine particle detection material and water, which is characterized by the above:
A sample solution preparation step of preparing a sample solution by mixing the detection solution prepared in the detection solution preparation step with an environmental sample solution containing fine particles or determining whether or not the fine particles are contained;
An irradiation step of irradiating the sample solution obtained in the sample solution preparation step with light; and a luminescence analysis step of analyzing the luminescence emitted from the sample solution by irradiation.
A method for detecting hydrophobic fine particles, including.

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