JP2020019700A - Organic-inorganic hybrid film, surface stress sensor, and method for producing organic-inorganic hybrid film - Google Patents

Abstract

To provide a film that can be used as a sensitive film of a surface stress (MSS) sensor, has excellent productivity and reproducibility, and does not deteriorate in its shape even when exposed to steam of high-concentration volatile organic compounds (VOCs), and has excellent structural stability.SOLUTION: An organic-inorganic hybrid film has an SiOskeleton modified with an organic functional group containing at least one selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a boron atom, and a phosphorus atom, the organic-inorganic hybrid film having a shape like a coffee ring.SELECTED DRAWING: Figure 2

Description

  The present invention relates to an organic-inorganic hybrid film, a surface stress sensor, and a method for manufacturing an organic-inorganic hybrid film.

Generally, an olfactory sensor has a detection unit (sensitive film) that enables highly sensitive and highly selective detection of an analyte gas or odor as a target. The mechanism by which the sensitive film detects alanite gas and odor is as follows. First, a surface stress is generated when a functional group contained in the sensitive film interacts with gas molecules. Gas molecules can be detected by converting the surface stress into an electric signal by deformation of the piezoresistance fixed at four points.
For example, Patent Document 1 discloses that a film containing metal oxide nanoparticles can be used as a sensitive film of a surface stress (MSS) sensor. In Patent Document 1, specifically, a porous material or a granular material is coated on a sensor main body of a type for detecting a physical parameter, and the physical property is obtained by adsorbing analyte molecules by the porous material or the granular material. A sensor for detecting the analyte molecule by a change in parameters is described, and it is disclosed that an aminopropyl group- and octadecyl group-modified silica titania hybrid granular material and metal organic structure (MOF) nanoparticles are used as the granular material. ing.

On the other hand, silica has various forms of its existence, and there is a suitable form depending on the use.
For example, Patent Document 2 discloses that a spherical colloidal silica particle having an average particle diameter of 10 to 80 nm and a metal oxide-containing silica that joins the spherical colloidal silica particle have a particle diameter (D1 nm) measured by a dynamic light scattering method and a spherical shape. The ratio D1 / D2 of the average particle diameter (measured particle diameter by nitrogen adsorption method / D2 nm) of the colloidal silica particles is 3 or more, and D1 is 50 to 500 nm, and the spherical colloidal silica particles are connected only in one plane. A stable silica sol having an SiO ₂ concentration of 1 to 50% by weight in which beaded colloidal silica particles are dispersed in a liquid medium is disclosed.
Patent Document 3 discloses a method for producing associated silica fine particles in which two or more primary particles having an average particle diameter in a range of 5 to 500 nm are associated with each other,
(A) General formula (1): Si (OR ¹ ) ₄ (1)
(Wherein, R ¹ is the same or different and is a monovalent hydrocarbon group having 1 to 6 carbon atoms)
In a mixed medium of a hydrophilic organic solvent and water in the presence of a basic substance, at least one compound of the tetrafunctional silane compound represented by and a partial hydrolysis condensation product of the tetrafunctional silane compound Hydrolysis, condensation reaction, a step of generating core particles of hydrophilic silica fine particles,
(B) adding the association-promoting additive into the system to associate the core particles to form a core-particle aggregate;
(C) At least one compound of the tetrafunctional silane compound represented by the general formula (1) and a partial hydrolysis condensation product of the tetrafunctional silane compound is further added to the system, and hydrolysis and condensation are performed. There is disclosed a method for producing associated silica fine particles, which comprises a step of causing the core particle aggregates to react and grow and associate to generate associated silica fine particles.

  In Patent Document 4, a step of covalently bonding an alkyl group having at least one amino group to a surface of a silica particle having a positive surface potential while maintaining the positive surface potential to modify the surface of the silica particle. A method for producing silica particles having an amino group on the particle surface is disclosed.

International Publication No. WO 2016/121155 International Publication No. 2000/015552 JP 2012-25596A JP 2009-274923 A

  The metal oxide sensitive film in Patent Document 1 is said to be able to realize high sensitivity, selectivity, and stability, but metal oxide is not excellent in solvent dispersibility. Therefore, they are suspended in a solvent and applied on the MSS sensor surface using spray coating. At this time, it is difficult to control the amount of coating, and the productivity is low due to the backing of the membrane, and the reproducibility of the sensor is reduced.

Patent Documents 2 and 3 disclose rosary, associative, and chain silicas, but do not disclose silica particles modified with an organic functional group. Utilization is not disclosed.
Patent Document 4 discloses silica particles surface-modified with an amino group, but does not disclose that silica has a chain continuous structure.

  INDUSTRIAL APPLICABILITY The present invention can be used as a receptor for detecting a gas or an odor component, in particular, an organic-inorganic hybrid which can be used as a sensitive film of a surface stress (MSS) sensor, has high sensitivity as a receptor, and is excellent in productivity and reproducibility. It is an object to provide a membrane. Further, the organic-inorganic hybrid film of the present invention can be used as a sensitive film of an MSS sensor. For example, even if it is exposed to a high-concentration volatile organic compound (VOC) vapor or the like, there is no shape deterioration. It is an object to provide a film, that is, a film having excellent structural stability.

The present inventors have conducted intensive studies in order to solve the above problems, and as a result, a predetermined organic-inorganic hybrid film can be used as a receptor for detecting gas and odor components, with good productivity and good reproducibility, The film can be formed on the membrane of the MSS sensor, and the film has been found to be excellent in structural stability and sensitivity, and the present invention has been completed.
That is, the present invention is as follows.

[1]
A carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a boron atom, and a SiO _3/2 skeleton modified with an organic functional group containing at least one selected from the group consisting of phosphorus atoms,
Having a coffee ring shape,
Organic-inorganic hybrid membrane.
[2]
The organic-inorganic hybrid film is a silica particle film,
The organic-inorganic hybrid film according to [1].
[3]
The organic-inorganic hybrid film includes a continuous chain structure formed by bonding silica particles to each other,
The organic-inorganic hybrid film according to [1] or [2].
[4]
Including chain-like silica particles modified with an organic functional group,
The organic-inorganic hybrid film according to any one of [1] to [3].
[5]
The organic functional group includes at least one selected from the group consisting of a carbon unsaturated bond, an aromatic atom, a nitrogen atom, an oxygen atom, a sulfur atom, and a fluorine atom.
The organic-inorganic hybrid film according to any one of [1] to [4].
[6]
Having a BET specific surface area of 0 m ² / g or more and 1000 m ² / g or less,
The organic-inorganic hybrid film according to any one of [1] to [5].
[7]
Having a BET total pore volume of 0 cm ³ / g or more and 1.5 cm ³ / g or less,
The organic-inorganic hybrid film according to any one of [1] to [6].
[8]
The thermal weight loss rate of organic components in TGA is 3% or more and 70% or less;
The organic-inorganic hybrid film according to any one of [1] to [7].
[9]
Made from N, N-dimethylformamide and / or propylene glycol monomethyl ether dispersion of linear silica particles modified with organic functional groups,
The organic-inorganic hybrid film according to any one of [1] to [8].
[10]
A surface stress sensor having the organic-inorganic hybrid film according to any one of [1] to [9].
[11]
A step of obtaining a coating liquid in which chain silica particles modified with an organic functional group are dispersed in an organic solvent,
A step of applying the coating liquid on the surface stress sensor surface using an inkjet device,
A method for producing an organic-inorganic hybrid film, comprising:

  An organic-inorganic hybrid film of the present invention can be obtained with good reproducibility by preparing a highly dispersible coating solution for producing an organic-inorganic hybrid film and applying the coating solution using, for example, an inkjet method. . Further, the organic-inorganic hybrid film of the present invention is excellent in productivity. Furthermore, the organic-inorganic hybrid film of the present invention is excellent in sensitivity, and has excellent structural stability without shape deterioration even when exposed to a high concentration of VOC vapor or the like.

4 is a film shape image of the surface of the MSS sensor in Example 1 with a laser microscope. 5 is an SEM image of an organic-inorganic hybrid film manufactured in Example 2. 9 is an SEM image of an organic-inorganic hybrid film manufactured in Example 3. 16 is a microscope image of an MSS sensor chip obtained by applying the same coating liquid prepared in Example 16 to all four channels of one MSS sensor chip. It is a figure which shows the 3rd electric signal obtained by measurement of ethanol 100 ppm and 25 degreeC. 9 is a laser microscope image of the organic-inorganic hybrid film manufactured in Comparative Example 4. FIG. 13 is a box plot of the response intensity of the sensors manufactured in Example 16 and Comparative Example 4 under the same conditions for five or more samples.

  Hereinafter, a mode for carrying out the present invention (hereinafter, referred to as “the present embodiment”) will be described in detail, but the present invention is not limited thereto. Various modifications are possible without departing from the gist of the invention.

[Organic-inorganic hybrid membrane]
The organic-inorganic hybrid film of the present embodiment is modified with an organic functional group including at least one selected from the group consisting of carbon atoms, nitrogen atoms, oxygen atoms, sulfur atoms, halogen atoms, boron atoms, and phosphorus atoms. It has a SiO _3/2 skeleton and has a coffee ring shape.

The SiO _3/2 skeleton modified with the organic functional group contained in the organic-inorganic hybrid film can be represented by RSiO _3/2 . Here, R represents an organic functional group.
The raw material of the organic-inorganic hybrid film can be a coating liquid having high dispersibility. For example, by applying the coating liquid by an ink jet method, an organic-inorganic hybrid film can be obtained with good reproducibility. Further, the organic-inorganic hybrid film of the present embodiment is also excellent in productivity. Furthermore, the organic-inorganic hybrid film of the present embodiment is excellent in sensitivity, and has excellent structural stability without shape deterioration even when exposed to high-concentration VOC vapor.

  The organic functional group in the present embodiment preferably contains at least one aromatic ring. When the organic functional group contains an aromatic ring, humidity resistance and sensitivity tend to be further improved. The aromatic ring may be appropriately selected in consideration of the use of the sensor and the like, and is not particularly limited. Examples thereof include an aromatic hydrocarbon group such as a phenyl group, a naphthyl group, a p-tolyl group, and a biphenyl group; Substituted aromatic hydrocarbon groups such as a group, 4-methoxyphenyl group, 4-aminophenyl group and pentafluorophenyl group; 3-furyl group, 3-thienyl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl A heterocyclic hydrocarbon group such as a group; a metallocene such as a ferrocenyl group; and the like. The organic functional group in the present embodiment may include one kind of the above-described aromatic ring alone, or may include two or more kinds thereof in combination.

When the SiO _3/2 skeleton of this embodiment contains at least one aromatic ring, an alkyl group (preferably having 1 to 18 carbon atoms) and an ether group are provided between the aromatic ring and the silicon atom. , A carbonyl group, a carboxyl group, an amide group, a urethane bond, a urea bond, an imide group, an imine group and the like. From the viewpoint of increasing the response sensitivity, it is preferable that the aromatic ring be directly bonded to the Si atom in the SiO _3/2 skeleton without using a spacer.

From the viewpoint of achieving both structural stability and selectivity to various gas molecules, the SiO _3/2 skeleton in the present embodiment preferably includes a copolymerized structure of an aromatic ring structure and a non-aromatic ring structure.

  The organic functional group in the present embodiment includes a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom such as fluorine, chlorine, bromine, and iodine atom, a boron atom, and a phosphorus atom. These atoms may be used alone or in combination of two or more. By including these atoms, the responsiveness to highly polar gas and / or odor molecules can be increased. From the viewpoint of enhancing structural stability, the organic functional group preferably contains one or more atoms selected from the group consisting of a nitrogen atom, an oxygen atom, a sulfur atom, and a fluorine atom. The organic functional group in the present embodiment is more preferably a saturated carbon bond, a carbon unsaturated bond, an aromatic atom, a nitrogen atom, an oxygen atom, a sulfur atom, a fluorine atom, a chlorine atom, a bromine atom, a halogen atom such as an iodine atom, a boron atom, It contains a phosphorus atom, and more preferably contains a carbon unsaturated bond, an aromatic, a nitrogen atom, an oxygen atom, a sulfur atom, and a fluorine atom.

The organic functional group in the present embodiment is not limited to the following. For example, a linear or branched hydrocarbon group which may have a substituent such as a halogen atom (for example, a 3-chloropropyl group, a methyl group An alicyclic hydrocarbon group which may have a substituent such as a linear or branched C _1-8 alkyl group such as ethyl group, propyl group, isopropyl group and octyl group; Group, cyclobutyl group, cyclopentyl group, _C5-6 cycloalkyl group such as cyclohexyl group), aromatic hydrocarbon group which may have a substituent such as halogen atom (for example, phenyl group, naphthyl group, pentafluorophenyl) Group), vinyl group, allyl group, acrylic group, (meth) acrylic group, (meth) acryloyloxyalkyl group (for example, (meth) acryloyloxypropyl Groups such as (meth) acryloyloxy C _1-3 alkyl group), an epoxy group, glycidyl oxy group (e.g., 3-glycidyloxy propyl glycidyl oxy C _1-3 alkyl group such group), (epoxy cycloalkyl) alkyl Groups (eg, 2- (3,4-epoxycyclohexyl) ethyl group), hydroxy group, ether group, carbonyl group, carboxyl group, ester group, urethane group, urea group, mercapto group, mercaptoalkyl group (eg, mercaptoalkyl group) Propyl group or other mercapto C _1-3 alkyl group), sulfide group, amino group (for example, primary amino group, secondary amino group, tertiary amino group), aminoalkyl group (for example, amino C _1-3 alkyl group), (aminoalkyl amino) alkyl group (e.g., 3- (2-aminoethyl A (amino) propyl group), an imidazolyl group, an imidazolylalkyl group (for example, a 3- (2-imidazolin-1-yl) propyl group), an alkylaminoalkyl group (for example, a 3- (dimethylamino) propyl group), an amide group, Examples include a heterocyclic aromatic group, an oxime group, an imide group, an imine group, a halogen group, a nitrile group, a phosphone group, and a phosphate group.
Among these, the organic functional group is preferably a linear or branched hydrocarbon group which may have a substituent, an alicyclic hydrocarbon group which may have a substituent, or a substituent, from the viewpoint of availability. Aromatic hydrocarbon group, vinyl group, allyl group, (meth) acryloyloxyalkyl group, glycidyloxyalkyl group, (epoxycycloalkyl) alkyl group, mercaptoalkyl group, aminoalkyl group, (aminoalkyl It is preferably at least one selected from the group consisting of an amino) alkyl group, an imidazolylalkyl group, an alkylaminoalkyl group, and a hydroxy group.
These functional groups may be used alone or in combination of two or more.

  The organic functional group is preferably an organic functional group derived from a silane coupling agent. Examples of the silane coupling agent include hydrolyzable metal oxides such as alkoxysilane, acetoxysilane, and chlorosilane. These may be used alone or in combination of two or more. Among these, the hydrolyzable metal oxide is preferably an alkoxysilane from the viewpoint of handleability and versatility of functional groups, and more preferably a trifunctional alkoxysilane from the viewpoint of reactivity.

  The trifunctional alkoxysilane may be copolymerized with a 1,2,4 functional alkoxysilane or the like, and from the viewpoint of increasing the Young's modulus of the organic-inorganic hybrid and increasing the sensitivity, is used together with the tetrafunctional alkoxysilane. Preferably, it is polymerized.

  As the trifunctional alkoxysilane, a silane coupling agent having a methoxy group, an ethoxy group, or an isopropoxy group in the alkoxy group can be used.

  The silane coupling agent can be classified into a silane coupling agent when the organic functional group has an aromatic group and a silane coupling agent when the organic functional group does not have an aromatic group. The ring agent is referred to as an aromatic silane coupling agent and a non-aromatic silane coupling agent.

  As the aromatic silane coupling agent, a commercially available aromatic silane coupling agent can be used and is not particularly limited. For example, phenyl trialkoxy silane, nitrobenzene amide trialkoxy silane, benzyl tri Alkoxysilane, 4-chlorophenyl trialkoxysilane, phenylaminopropyl trialkoxysilane, 4-aminophenyl trialkoxysilane, naphthyl trialkoxysilane, 4-methoxytrialkoxysilane, pentafluorophenyl trialkoxysilane, ferrocenyl trialkoxysilane, Biphenyl trialkoxysilane, 3-furyl trialkoxysilane, 3-thienyl trialkoxysilane, 2-pyridyl trialkoxysilane, 3-pyridyl trialkoxysilane, - pyridyl trialkoxysilane and the like.

  As the non-aromatic silane coupling agent, a commercially available non-aromatic silane coupling agent can be used and is not particularly limited. For example, 3- (2-aminoethylamino) propyl tri- Alkoxysilane, 3-mercaptopropyl trialkoxysilane, vinyl trialkoxysilane, cyclohexyl trialkoxysilane, 3-glycidyloxypropyl trialkoxysilane, 2- (3,4-epoxycyclohexyl) ethyl trialkoxysilane, 3- (dimethylamino ) Propyl trialkoxysilane, 3- (2-imidazolin-1-yl) propyl trialkoxysilane, 3-aminopropyl trialkoxysilane, 3- (methacryloyloxy) propyl trialkoxysilane, 3- (acryloyloxy) propy Trialkoxysilane, allyltrialkoxysilane, methyltrialkoxysilane, ethyltrialkoxysilane, propyltrialkoxysilane, butylalkoxysilane, hexyltrialkoxysilane, octyltrialkoxysilane, decyltrialkoxysilane, dodecyltrialkoxysilane, octadecyltri Alkoxysilane, 3-ureidopropyl trialkoxysilane, cyclohexylaminopropyl trialkoxysilane, hexafluorophenyl trialkoxysilane, 3-chloropropyl trialkoxysilane, 3-bromopropyl trialkoxysilane, 3-piperazinopropyl trialkoxysilane , 3-morpholinopropyl trialkoxysilane, 3-allylaminopropyl trialkoxysilane, Norbornyl trialkoxysilane, piperidinopropyl trialkoxysilane and the like.

  When two or more silane coupling agents are copolymerized, the molar ratio of the aromatic silane coupling agent to the non-aromatic silane coupling agent is preferably from 1:10 to 1: 5. The ratio is preferably from 1: 5 to 1: 1 from the viewpoint of sex, and is preferably from 1: 1 to 10: 1 from the viewpoint of suppressing signal intensity reduction under humidity.

  The organic functional groups in the organic-inorganic hybrid film of the present embodiment can be identified by subjecting the sensitive film on the sensor body to surface element analysis such as SEM-EDX, XPS, and ATR.

It is preferable that the organic-inorganic hybrid film of the present embodiment further contains a filler. By using the filler, the Young's modulus of the organic-inorganic hybrid film can be improved, and the sensitivity can be increased.
The filler in the present embodiment is not particularly limited, and can be selected from various known fillers. Specific examples of the filler include, but are not limited to, polymer beads such as polystyrene, polymethyl methacrylate, and polyphenylene oxide, spherical particles such as acrylic latex, metal nitrides such as silicon nitride, silica, zirconia, titania, and oxides. Metal oxides such as zinc, aluminum oxide, and tin oxide; composite metal compounds such as barium titanate, strontium titanate, and ITO; inorganic metal fillers such as gold, silver, copper, palladium, platinum, iron, and aluminum; carbon nanotubes; At least one selected from carbon materials such as graphene and carbon black can be included.

  The filler in the present embodiment is preferably an inorganic filler from the viewpoint of improving dispersibility and / or coatability. From the same viewpoint as described above, in the present embodiment, a metal compound such as silica, zirconia, titania, and alumina, and an inorganic metal filler such as gold, silver, copper, palladium, platinum, iron, and aluminum are preferable. Metal oxides, such as silica and zirconia, are more preferable in that the influence of signal attenuation due to the above is small, and silica is more preferable in terms of economy.

  The present inventors have found that the decay of the response of common hydrophilic gases such as ethanol and acetaldehyde is more significantly improved even in humid conditions, especially when silica is used. The reason can be considered as follows, but is not limited to the following. That is, the hydroxyl group present in a state bonded to the silica skeleton and the silicon atom is relatively hydrophobic compared to the titania skeleton or the hydroxyl group bonded to the titanium atom in Patent Document 1, and therefore, the water-derived substance is caused by the hydrophobic interaction. It is presumed that the inhibition of adsorption of is suppressed.

  The shape of the filler is not particularly limited, but is preferably spherical, rod-like, plate-like or fibrous, or a shape obtained by combining two or more of these, and more preferably spherical or chain-like. In addition, the spherical shape here means a substantially spherical shape including a spheroid, an oval, and the like in addition to a true spherical shape.

  The size of the spherical filler is not particularly limited, but from the viewpoint of maintaining the dispersibility of the ink, preventing clogging of the nozzle, and improving the applicability in inkjet, the average primary particle diameter is preferably 100 μm or less. Preferably, the thickness is 500 nm or less from the viewpoint of improving the sensitivity, and more preferably 200 nm or less from the viewpoint of further reducing the gap. Here, the average primary particle diameter means a number average value. The average primary particle diameter is measured by a method using a scanning electron microscope described in the Examples section of the present specification, or 50 particles measured by a method understood by those skilled in the art to be equivalent thereto. It is a number average value.

The organic-inorganic hybrid film of the present embodiment has a coffee ring type shape.
The coffee ring type is a circular organic-inorganic hybrid film in which the center of the circle is flat and the circumference of the circle is thick. The coffee ring type has, for example, the shape shown in FIG.
In addition, a coffee ring type organic-inorganic hybrid film, for example, as described later, forms a film using a coating liquid in which chain-like silica particles modified with an organic functional group are dispersed in an organic solvent using an inkjet apparatus. Can be obtained by:

  The organic-inorganic hybrid film of the present embodiment can be manufactured without clogging due to ink-jet when manufacturing using an ink-jet apparatus, for example, and is excellent in productivity and excellent in reproducibility of a sensor including the obtained film. In addition, the obtained film does not deteriorate in shape even when exposed to high-concentration VOC vapor, has excellent structural stability, and has higher sensitivity than a film structure having a flat structure. The reason can be considered as follows, but is not limited to the following. If a coffee ring type sensitive film is placed on the surface stress sensor, more film volume will be placed near the piezo, and the stress due to the deformation will be more efficiently propagated to the piezo element, so higher sensitivity can be realized. Can be

  Whether the organic-inorganic hybrid film of this embodiment has a coffee ring shape can be determined from the cross-sectional view of the film. As a coffee ring type, a cross-sectional profile between two points on the diameter of the sensitive film formed in a circular shape is obtained, and from the cross-sectional profile, the film thickness at the center is preferably 80% or less of the film thickness at the maximum. Preferably, there is. When the film thickness at the central portion is 80% or less of the film thickness at the maximum portion, reproducibility of sensitivity tends to increase. Further, it is more preferably 60% or less from the viewpoint of improving the sensitivity, and further preferably 40% or less from the viewpoint of maximizing the response sensitivity.

[Silica particle membrane]
The organic-inorganic hybrid film of the present embodiment is preferably a silica particle film.
The silica particle film of the present embodiment has a spherical shape, a rod shape, a plate shape, a fiber shape, or a shape obtained by combining two or more of these, and preferably has a spherical shape. In addition, the spherical shape here means a substantially spherical shape including a spheroid, an oval, and the like in addition to a true spherical shape. The silica particle film of the present embodiment preferably includes a continuous chain structure formed by bonding silica particles to each other.
One of preferred aspects of the present embodiment is modified with an organic functional group containing at least one selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a boron atom, and a phosphorus atom, It is a silica particle film having a coffee ring shape.

  The silica particle film of the present embodiment is a film containing silica particles. Further, the silica particle film of the present embodiment includes a continuous chain structure formed by bonding silica particles to each other. In the present specification, the silica particles bonded to each other to form a continuous chain structure are also referred to as chain silica particles.

  The continuous chain structure in this embodiment is formed by silica particles being chemically bonded and bonded to each other, and the spherical silica particles are continuously and directly bonded, branched and bonded, and bent. And a ring-shaped structure (these are referred to as pearl necklaces in this specification), and a structure in which a number of thread-like structures are not entangled but are individually observed as continuous spheres ( In this specification, it is expressed as a network). The continuous chain structure is shown, for example, in the SEM images of FIGS. 2 and 3, but is not limited thereto.

  The chemical bond when the silica particles are chemically bonded to each other is not particularly limited as long as the silica particles can be bonded to each other.

The silica particles in the present embodiment are SiO ₃ modified with an organic functional group containing at least one selected from the group consisting of carbon atoms, nitrogen atoms, oxygen atoms, sulfur atoms, halogen atoms, boron atoms, and phosphorus atoms. It is preferable to include a _{/ 2} skeleton and at least SiO ₂ . Preferably, the silica particles further include at least one selected from the group consisting of SiO _3/2 and SiO _1/2 .
The silica particles preferably contain SiO ₂ and at least one selected from the group consisting of SiO _3/2 and SiO _1/2 as main components. Here, “the silica particles are mainly composed of silica” means that the total amount of SiO ₂ , SiO _3/2 and SiO _1/2 is usually more than 50% by mass, preferably 70% by mass, based on the total amount of the silica particles. % By mass, more preferably 80% by mass or more, further preferably 90% by mass or more, still more preferably 95% by mass or more, and still more preferably 98% by mass or more.
Further, the silica particles preferably contain SiO ₂ as a main component.

The chain silica particles can be prepared, for example, by a sol-gel method. Specifically, chain silica particles can be produced by a sol-gel method using an organosilicon compound having three or four functional hydrolyzable groups such as an alkoxy group and a chloro group as a raw material.
The chain silica particles can also be obtained as a commercial product. Commercially available products include, for example, LEVASIL series (manufactured by HC Starck Co., Ltd.), Quartron PL series (manufactured by Fuso Chemical Co., Ltd.), OSCAL series (manufactured by Catalyst Chemical Industry Co., Ltd.); As silica particles, for example, Aerosil 130, 300, 380, TT600, OX50 (all manufactured by Nippon Aerosil Co., Ltd.), Sildex H31, H32, H51, H52, H121, H122 ( Such as Asahi Glass Co., Ltd.), E220A, E220 (Nippon Silica Kogyo Co., Ltd.), SYLYSIA470 (Fuji Silysia Co., Ltd.), SG flake (Nippon Sheet Glass Co., Ltd.), etc., manufactured by Nissan Chemical Co., Ltd. , Snowtex (registered trademark) IPA-ST-UP, MEK-ST-UP, ST-UP, ST-PS-S, ST-PS-M, ST-OUP, ST-PS-SO, ST-PS-MO, ST-AK-PS-S, and the like.

  The silica particle film of the present embodiment is modified with an organic functional group containing at least one selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a boron atom, and a phosphorus atom. The fact that the silica particle film is modified with an organic functional group means that an organic functional group is introduced into the silica particle film.

An organic functional group can be introduced into the silica particle film by modifying the surface of the silica particles constituting the silica particle film with the organic functional group. That is, by modifying the surface of the silica particles constituting the silica particle film with an organic functional group, the surface is selected from the group consisting of carbon atoms, nitrogen atoms, oxygen atoms, sulfur atoms, halogen atoms, boron atoms, and phosphorus atoms. The organic-inorganic hybrid film of the present embodiment containing at least the SiO _3/2 skeleton modified with the organic functional group containing at least one is obtained.

The silica particle film is specifically formed by treating the surface of the commercially available chain silica particles described above with a modifier having an organic functional group and using the chain silica particles modified with an organic functional group. Thereby, a silica particle film modified with an organic functional group can be obtained.
When the chain-like silica particles are prepared by a sol-gel method, for example, an organosilicon compound having an organic functional group separately from a functional hydrolyzable group as an organosilicon compound as a raw material is treated with four functional hydrolyzable groups. By copolymerizing with an organosilicon compound having the following formula, chain silica particles having an organic functional group introduced on the surface and / or inside thereof are obtained. By forming a film using the chain silica particles into which the organic functional group is introduced, a silica particle film modified with the organic functional group can be obtained.
Therefore, the organic-inorganic hybrid film of the present embodiment preferably contains chain silica particles modified with an organic functional group.

In order to introduce an organic functional group, an organosilicon compound having a hydrolyzable group such as alkoxysilane and / or chlorosilane is used as a modifier or a raw material for preparing chain silica particles by a sol-gel method.
The organosilicon compound is preferably an alkoxysilane from the viewpoint of excellent handleability and versatility of functional groups, and more preferably an alkoxysilane having three alkoxy groups from the viewpoint of reactivity.

The size of the chain-like silica particles modified with an organic functional group may be defined by the primary particle diameter, assuming a generally spherical shape, or may be calculated by observing the chain width by electron microscope observation with a TEM / SEM. Good.
The chain width of the chain-like silica particles modified with an organic functional group is generally in the range of 1 nm to 200 nm, and preferably in the range of 1 nm to 100 nm from the viewpoint of increasing the specific surface area. From the viewpoint of improving the density, it is more preferably in the range of 1 nm to 85 nm.

The membrane of the present embodiment includes a continuous chain structure formed by bonding silica particles to each other, so that the rigidity of the chain structure increases the specific surface area and total pores as compared to spherical silica particles. A volume can be formed. The large specific surface area and the total pore volume contribute to an increase in response sensitivity because gas molecules increase the accessibility to the inside of the sensitive membrane on the MSS sensor.
The specific surface area is preferably not more than 0 m ² / g or more 1000 m ² / g, the structure from a more enhanced in view of stability, more preferably not more than 10 m ² / g or more 1000 m ² / g, more preferably 15 m ² / g to 1000 m ² / g, more preferably 15 m ² / g to 800 m ² / g. Here, the specific surface area is a BET specific surface area.
Total pore volume, preferably not more than 0 cm ³ / g or more 1.5 cm ³ / g, from the viewpoint of enhancing the structural stability, and more preferably 0.01 cm ³ / g or more 1.5 cm ³ / g or less There, more preferably 0.02 cm ³ / g or more 1.5 cm ³ / g, even more preferably at most 0.03 cm ³ / g or more 1.0 cm ³ / g. Here, the total pore volume is the BET total pore volume.
The specific surface area and total pore volume of the silica particle membrane can be evaluated by BET measurement of nitrogen adsorption.

[Method for producing chain-like silica particles modified with an organic functional group]
The chain-like silica particles modified with an organic functional group may be obtained by treating a commercially available colloidal silica containing chain-like silica particles with a silane coupling agent. May be obtained by simultaneously performing a condensation reaction with a tetraalkoxysilane. In the present specification, chain silica particles modified with an organic functional group are also referred to as modified chain silica particles.
By using the modified chain silica particles, an organic-inorganic hybrid film having no shape deterioration even when exposed to a high concentration of VOC vapor can be obtained.

When a commercially available colloidal silica containing a chain silica particle is treated with a silane coupling agent to obtain a chain silica particle modified with an organic functional group, as shown in FIG. The structure is such that a condensate of the ring agent is attached. Here, chain silica particles modified with an organic functional group obtained by treating colloidal silica with a silane coupling agent are also referred to as modified chain silica particles A.
The modified chain silica particles A are specifically performed by surface modification in a state where the chain silica particles are dispersed in a dispersion medium, for example, a uniform dispersion of chain silica particles containing alcohol and water. And a step of adding the above-mentioned silane coupling agent in the presence or absence of a catalyst.

  When a chain silica particle modified with an organic functional group is produced by simultaneous condensation of a silane coupling agent and a tetrafunctional alkoxysilane (where the chain silica particle modified with an organic functional group obtained by condensation is , Modified chain silica particles B), for example, in a solvent containing alcohol and water, in the presence or absence of a catalyst, by mixing and reacting a silane coupling agent with a tetrafunctional alkoxysilane. You.

The specific surface area of the modified chain silica particles A becomes smaller than that of the raw material chain silica due to surface modification.
On the other hand, in the modified chain silica particles B, no adhesion is observed on the surface, and the functional groups are non-locally distributed inside and on the surface of the chain structure.

  In order to make it possible to control the reaction rate of the surface modification and the condensation, it is preferable to carry out the surface modification or the condensation of the silane coupling agent with the tetrafunctional alkoxysilane in the presence of a catalyst.

Examples of the type of the catalyst include an acid catalyst and a base catalyst.
Examples of the acid catalyst include an inorganic acid and an organic acid.
Examples of the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, boric acid and the like.
Examples of the organic acid include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, benzoic acid, and p-aminobenzoic acid Acids, p-toluenesulfonic acid, benzenesulfonic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid, citraconic acid, malic acid, glutaric acid and the like.
These acid catalysts can be used alone or in combination of two or more.

Examples of the base catalyst include an inorganic base and an organic base.
Examples of the inorganic base include, for example, alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide; lithium carbonate, potassium carbonate, and carbonic acid. Alkali or alkaline earth metal carbonates such as sodium; metal bicarbonates such as potassium bicarbonate and sodium bicarbonate; ammonia; The ammonia may be aqueous ammonia.
Examples of the organic base include trialkylamines such as triethylamine and ethyldiisopropylamine; N, N-dialkylaniline derivatives having 1 to 4 carbon atoms such as N, N-dimethylaniline and N, N-diethylaniline; pyridine, 2,6 Pyridine derivatives which may have an alkyl substituent having 1 to 4 carbon atoms, such as lutidine;
These base catalysts can be used alone or in combination of two or more.

  It is preferable from the viewpoint of reaction efficiency to add an amount of the catalyst that makes the pH of the reaction system in the range of 0.01 to 6.0 or pH 8 to 14. In order to further increase the efficiency, basic conditions of pH 8 to 14 are added. It is more preferred to carry out the reaction under:

The surface modification and condensation for producing the modified chain silica particles A and the modified chain silica particles B can also be performed in an organic solvent.
Examples of the organic solvent include alcohol solvents, ester solvents, ketone solvents, ether solvents, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, amide solvents, and the like.

  Examples of the alcohol solvent include monohydric alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, and butyl alcohol; polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, glycerin, trimethylolpropane, and hexanetriol; ethylene glycol monomethyl ether , Ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene Glycol monopropyl ether, mono ethers of polyhydric alcohols such as propylene glycol monobutyl ether; and the like.

  Examples of the ester solvent include methyl acetate, ethyl acetate, butyl acetate, γ-butyrolactone, and the like.

  Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl isoamyl ketone, and the like.

  As the ether solvent, in addition to the monohydric alcohols described above, for example, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene Polyhydric alcohol ethers in which all of the hydroxyl groups of polyhydric alcohols such as glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and diethylene glycol diethyl ether are alkyl etherified; tetrahydrofuran; 1,4-dioxane; anisole.

  Examples of the aliphatic hydrocarbon solvent include hexane, heptane, octane, nonane, decane and the like.

  Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene and the like.

  Examples of the amide solvent include dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and the like.

Among the above solvents, alcohol solvents such as methanol, ethanol, isopropanol and butanol; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ether solvents such as ethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether and propylene glycol monoether Ethyl ether and the like; and amide solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like are preferable because they are easily mixed with water.
These solvents may be used alone or a plurality of solvents may be used in combination.

  The denatured linear silica particles are recovered by separating the precipitate and the gel by centrifugation and filtration. Condensates of the silane coupling agent that do not react with the chain structure may be present as residues. The condensate may enter the silica particle membrane. From the viewpoint of the physical durability of the sensitive film, it is preferable that the residue is small.

Whether the organic-inorganic hybrid film of the present embodiment is modified with an organic functional group can be confirmed by FT-IR, elemental analysis, and thermogravimetric reduction measurement.
The thermogravimetric reduction rate from 150 ° C. to 1000 ° C. is usually 3% or more and 70% or less in order to remove the influence of the adsorbed water. Yes, more preferably 5% or more and 65% or less, and further preferably 5% or more and 55% or less from the viewpoint of improving the thermal stability of the silica particle film.

[Method for producing organic-inorganic hybrid membrane]
The organic-inorganic hybrid film of the present embodiment can be manufactured, for example, by dispersing chain-like silica particles modified with an organic functional group in an organic solvent to obtain a coating solution, and coating the coating solution on an MSS sensor. it can. When applying the coating liquid on the chip of the MSS sensor, an ink jet device can be suitably used. The ink jet device ejects droplets of a coating liquid, and the droplets are applied on a chip of the MSS sensor to form a silica particle film.
The concentration of the chain-like silica particles modified with an organic functional group in the coating liquid is preferably from 0.1 g / L to 50 g / L, and more preferably from 0.5 g / L to 50 g from the viewpoint of productivity. / L or less, and more preferably 0.5 g / L or more and 15 g / L or less from the viewpoint of suppressing nozzle clogging in the inkjet apparatus.

The organic solvent for dispersing the chain silica particles is not particularly limited as long as it is a dispersible solvent.
The boiling point of the organic solvent is preferably 80 ° C. or higher and 250 ° C. or lower, and more preferably 100 ° C. or higher and 250 ° C. or lower, from the viewpoint of suppressing a decrease in productivity due to nozzle clogging, shortening the time required for drying. From the viewpoint of increasing the productivity, the temperature is more preferably from 100 ° C to 200 ° C.

  Examples of the organic solvent include alcohol solvents, ester solvents, ketone solvents, ether solvents, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, amide solvents, and the like.

  Examples of the alcohol solvent include monohydric alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, and butyl alcohol; polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, glycerin, trimethylolpropane, and hexanetriol; ethylene glycol monomethyl ether , Ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene Glycol monopropyl ether, mono ethers of polyhydric alcohols such as propylene glycol monobutyl ether; and the like.

  Examples of the ester solvent include methyl acetate, ethyl acetate, butyl acetate, γ-butyrolactone, and the like.

  Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl isoamyl ketone, and the like.

  Examples of the ether solvent include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and diethylene glycol. Polyhydric alcohol ethers in which all of the hydroxyl groups of a polyhydric alcohol such as diethyl ether are alkyl etherified; tetrahydrofuran; 1,4-dioxane; anisole;

  Examples of the aliphatic hydrocarbon solvent include hexane, heptane, octane, nonane, decane and the like.

  Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene and the like.

  Examples of the amide solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, and the like.

These organic solvents may be used alone or in combination of two or more.
Among these organic solvents, N, N-dimethylformamide and propylene glycol monomethyl ether are preferable because of their excellent safety and solubility.

The organic-inorganic hybrid film of the present embodiment may contain additives such as arbitrary particles, an ionic compound, a resin, and a low molecular compound, in addition to the chain silica particles modified with an organic functional group.
By mixing the above additive in a coating solution and applying it to the MSS sensor surface, a silica particle film containing the above additive can be obtained.

  One embodiment of the present invention is an organic-inorganic hybrid membrane made from N, N-dimethylformamide and / or propylene glycol monomethyl ether dispersion of chain-like silica particles modified with an organic functional group.

[Surface stress (MSS) sensor]
The organic-inorganic hybrid film of the present embodiment can be suitably used as a sensitive film of a piezo element type surface stress (MSS) sensor fixed at four points.
As a method for coating the organic-inorganic hybrid particles on the MSS sensor surface, dip coating, spray coating, spin coating, ink jet spotting, casting, doctor blade, or the like can be used.
In order to apply to a membrane of a 300 μmφ MSS sensor, an inkjet or microjet method is preferable, and a microjet method is more preferable from the viewpoint of productivity.
The film thickness of the organic-inorganic hybrid film may not be uniform because the organic-inorganic hybrid film of the present embodiment has a coffee ring shape. In this case, the thickness of the thinnest portion at the center portion of the sensitive film and the thickness of the thickest portion at the end portion are each usually 10 nm or more and 50 μm or less. The film thickness is preferably from 10 nm to 30 μm from the viewpoint of shortening the time required for drying at the time of production and increasing the productivity, and more preferably from 20 nm to 30 μm from the viewpoint of increasing the sensitivity.
One of the present embodiments is a surface stress sensor having the organic-inorganic hybrid film of the present embodiment.

Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples, but the present invention is not limited thereto.
The chain organically modified silica produced in the following examples and the MSS sensor coated with the same were measured for the following physical properties (1) to (8) according to the following procedures.

(1) Observation of film shape By using a confocal laser microscope (VK09700 Violet Laser (manufactured by Keyence)), by observing the uncoated portion of the sensor and the maximum thickness portion of the sensitive film in the sensor under the following observation conditions, The thickness of the sensitive film was measured. That is, a cross-sectional profile between two points on the diameter of the substantially circular sensitive film is obtained, and the thickness of the central portion is 80% or less of the thickness of the maximum portion from the cross-sectional profile. Those were made into coffee rings and those that exceeded 80% were flattened.
(Observation conditions)
Objective lens: Standard lens 20.0x Measurement area: Surface Measurement mode: Surface shape RPD: Highest priority Measurement quality: High definition Measurement pitch: 0.5 μm
Z measurement distance: 37.92 μm
Wide dynamic range: OFF
Brightness 1: 648
Neutral density filter: 100%
Optical zoom: 1x Average count: 1 Filter: OFF
White balance mode: One push White balance R: 131
White balance B: 138
Reception light amount correction mode: γ correction γ correction value: 0.45
γ offset: 0
Black / white inversion: OFF
Head type: VK-9700
Light intensity eccentricity correction: ON
Field curvature correction: ON
XY calibration: 688 nm / pixel
Z calibration: 1 nm / digit
Vividness: 5
Contrast: 5
Brightness: 0

(2) Specific surface area and total pore volume of continuous chain organically modified silica Measured by BET nitrogen adsorption.

(3) Thermogravimetric Loss Rate The temperature was raised to 1000 ° C at 10 ° C / min in an air atmosphere by TGA, and the thermogravimetric loss at 150 ° C and 1000 ° C was defined as the organic content.

(4) Physical and chemical stability Physical and chemical stability was evaluated based on the structural stability after a saturated vapor test with ethanol and toluene. Specifically, at 25 ° C., after measuring ethanol, toluene, and water-saturated steam (flow rate 30 sccm) 10 minutes / purge purge (under dry nitrogen) 10 minutes three times each, the film shape is deformed by observation with an optical microscope. The sample was evaluated as x, and the sample with no deformation was evaluated as Δ.

(5) Dispersibility of coating liquid The coating liquid was measured by DLS. The smaller the particle diameter in Cumant, the better the dispersibility. In Table 1, the case of 300 nm or less is Δ, the case of more than 300 nm and less than 600 nm is Δ, and the case of 600 nm or more is Is indicated by x.

(6) Ink-jet applicability A clogging occurred during application of 300 pL and 300 shots.

(7) Response sensitivity After measuring ethanol (at a flow rate of 30 sccm) for 10 minutes / purge purging (under dry nitrogen) for 10 minutes at 25 ° C. three times, the third peak intensity was 2 mV / bridge voltage per 1 V (Vb = 1 V). Those with Vb or more were evaluated as "〇", those with 1 mV / Vb or more and less than 2 mV / Vb, and those with less than 1 mV / Vb were evaluated as x.

(8) Reproducibility Five or more samples were prepared under the same conditions, and their response intensities were measured. When the ratio between the maximum and the minimum of the response intensity was 1.5 or less, "reproducible"("high" in the table) was used, and when it exceeded 1.5, "no reproducibility"("low" in the table) was used.

<Example 1>
A separable flask was charged with 50 g of IPA-UP (manufactured by Nissan Chemical Industries, Ltd.), which is a dispersion of chain colloidal silica in 2-propanol, 80 g of water, 20 g of 28% aqueous ammonia, and 400 g of 2-propanol. Further, vinyltriethoxysilane 25 was added. Then, the mixture was reacted at 80 ° C. for 6 hours.
After the reaction solution was air-cooled, the precipitate was isolated by centrifugation at 6000 rpm for 10 minutes. The precipitate was sufficiently washed with ethanol, and dissolved with N, N-dimethylformamide to a concentration of 1 g / mL to obtain a coating solution. A part of the precipitate was dried at 80 ° C. under vacuum, and the amount of thermogravimetric loss was measured.
The above coating solution (300 pL) was applied as 300 drops using a micro jet on the surface of an MSS sensor arranged on a hot plate at 80 ° C to obtain a silica particle film.
FIG. 1 shows a laser microscope photograph of the obtained silica particle film. As shown in FIG. 1, the silica particle film had a coffee ring shape. Table 1 shows the measurement results of the physical properties of the above measurements (1) to (7).

<Example 2>
120 g of ethanol, 6.8 g of vinyltriethoxysilane, 9.3 g of tetraethoxysilane, and 3.6 g of 28% aqueous ammonia were mixed and left at room temperature until gelation. The gel was separated from the liquid by filtration, washed sufficiently with ethanol, and dissolved with N, N-dimethylformamide to a concentration of 1 g / ml to obtain a coating solution. A part of the chain-modified silica obtained as a gel was dried under vacuum at 80 ° C., and the thermogravimetric loss was measured.
The above coating solution (300 pL) was applied as 300 drops using a micro jet on the surface of an MSS sensor arranged on a hot plate at 80 ° C to obtain a silica particle film. Table 1 shows the measurement results of the physical properties of the above measurements (1) to (7). FIG. 2 shows an SEM image (image of the chain organically modified silica) of the obtained silica particle film.

<Example 3>
A silica particle film was obtained in the same manner as in Example 1 except that vinyltriethoxysilane was changed to 79.3 g of phenyltrimethoxysilane.
FIG. 3 shows an SEM image (image of the chain organically modified silica) of the obtained silica particle film.

<Example 4>
A silica particle film was obtained in the same manner as in Example 2, except that vinyltriethoxysilane was changed to 8.59 g of phenyltriethoxysilane.

<Example 5>
A silica particle film was obtained in the same manner as in Example 2, except that the amount of ethanol was changed to 180 g.

<Example 6>
Vinyltrimethoxysilane was changed to 29.5 g of 3-aminopropyltriethoxysilane, and the obtained precipitate was dissolved in propylene glycol monomethyl ether instead of N, N-dimethylformamide to obtain a coating solution. Except for this, a silica particle film was obtained in the same manner as in Example 1.

<Example 7>
Vinyltriethoxysilane was changed to 7.91 g of 3-aminopropyltriethoxysilane, and the obtained precipitate was dissolved in propylene glycol monomethyl ether instead of N, N-dimethylformamide to obtain a coating solution. Except for this, a silica particle film was obtained in the same manner as in Example 1.

<Example 8>
A silica particle film was obtained in the same manner as in Example 1, except that vinyltrimethoxysilane was changed to 31.8 g of 3-mercaptopropyltriethoxysilane.

<Example 9>
A silica particle film was obtained in the same manner as in Example 2, except that 8.51 g of 3-mercaptopropyltriethoxysilane was used instead of vinyltriethoxysilane.

<Example 10>
A silica particle film was obtained in the same manner as in Example 1, except that vinyltrimethoxysilane was changed to 36.9 g of octyltriethoxysilane.

<Example 11>
A silica particle film was obtained in the same manner as in Example 1, except that vinyltrimethoxysilane was changed to 27.2 g of cyclohexyltrimethoxysilane.

<Example 12>
A silica particle film was obtained in the same manner as in Example 1, except that vinyltrimethoxysilane was changed to 38.7 g of 3- (methacryloyloxy) propyltriethoxysilane.

<Example 13>
A silica particle film was obtained in the same manner as in Example 1, except that vinyltrimethoxysilane was changed to 98.6 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.

<Example 14>
A silica particle film was obtained in the same manner as in Example 1, except that vinyltrimethoxysilane was changed to 109.8 g of 3- (2-imidazolin-1-yl) propyltriethoxysilane.

<Example 15>
A silica particle film was obtained in the same manner as in Example 1, except that 79.3 g of vinyltrimethoxysilane was changed to a mixture of 14 g of phenyltrimethoxysilane and 20.2 g of pentafluorophenyltrimethoxysilane.

<Example 16>
In a separable flask, 27.1 g of phenyltrimethoxysilane was added to 50 g of a 2-propanol dispersion of chain colloidal silica IPA-ST-UP (Nissan Chemical), 90 g of water, 10 g of 28% aqueous ammonia, and 300 g of 2-propanol. The reaction was performed at 80 ° C. for 4 hours.
After the reaction solution was air-cooled, the precipitate was isolated by centrifugation at 6000 rpm for 10 minutes. After sufficiently washing the sample with ethanol, the sample was dissolved in N, N-dimethylformamide to a concentration of 10 g / mL to obtain a coating solution. A part of the sample was dried under vacuum at 80 ° C., and the thermogravimetric loss was measured.
A surface stress sensor with a sensitive film is obtained by applying 20 drops of the above coating liquid at a rate of 600 pL per drop using an ink jet device on the surface of an MSS sensor arranged on a 50 ° C. hot plate. Was.
FIG. 4 is an image of a microscope in which the same coating liquid is applied to all four channels of one MSS sensor chip.
FIG. 5 is a third electrical signal obtained by measuring ethanol at 100 ppm and 25 ° C. ch1 to ch4 were similarly applied under the conditions of Example 16.

<Example 17>
10 g of phenyltrimethoxysilane, 10 g of water, 30 g of ethanol and 28% aqueous ammonia were mixed and reacted at 80 ° C. for 2 hours. The precipitate was isolated by centrifugation at 6000 rpm for 10 minutes. After sufficiently washing the sample with ethanol, the sample was dissolved in N, N-dimethylformamide to a concentration of 10 g / mL to obtain a coating solution. The coating solution was applied on the surface of an MSS sensor arranged on a hot plate at 80 ° C., using a microjet, in an amount of 600 pL per drop, 20 drops.

<Example 18>
The operation was carried out in the same manner as in Example 16, except that 27.1 g of phenyltrimethoxysilane was changed to 37.6 g of 4-chlorophenyltriethoxysilane.

<Example 19>
The operation was performed according to Example 16, except that 27.1 g of phenyltrimethoxysilane was changed to 30.4 g of 4-methoxyphenyltrimethoxysilane.

<Example 20>
The operation was carried out in the same manner as in Example 16, except that 27.1 g of phenyltrimethoxysilane was changed to 31.5 g of 3-furyltriethoxysilane.

<Example 21>
The operation was carried out in the same manner as in Example 16, except that 27.1 g of phenyltrimethoxysilane was changed to 33.9 g of 3-thienyltriethoxysilane.

<Example 22>
The operation was carried out according to Example 16, except that 27.1 g of phenyltrimethoxysilane was changed to 23.3 g of 4-aminophenyltrimethoxysilane.

<Example 23>
The operation was carried out in the same manner as in Example 16 except that 27.1 g of phenyltrimethoxysilane was changed to 29 g of p-tolyltrimethoxysilane.

<Example 24>
The operation was performed in the same manner as in Example 16 except that 27.1 g of phenyltrimethoxysilane was changed to 27.1 g of phenyltrimethoxysilane and 37.5 g of 3- (2-imidazolinepropyl) triethoxysilane.

<Example 25>
The operation was performed in the same manner as in Example 16 except that 27.1 g of phenyltrimethoxysilane was changed to 27.1 g of phenyltrimethoxysilane and 21.6 g of 3-ureidopropyltriethoxysilane.

<Example 26>
The procedure was as in Example 16, except that 27.1 g of phenyltrimethoxysilane were changed to 27.1 g of phenyltrimethoxysilane and 25.3 g of 3- [bis [(diphenylphosphino) methyl] amino] propyltrimethoxysilane. Was done.

<Example 27>
The operation was performed in the same manner as in Example 16, except that IPA-ST-UP (Nissan Chemical Products) 50 g was changed to IPA-ST-L (45 nm spherical silica) 25 g.

<Comparative Example 1>
Silica titania particles (granular) were synthesized according to WO 2016/121155.
Specifically, co-hydrolysis and condensation polymerization of 3-aminopropyltriethoxysilane and titanium tetraisopropoxide (TTIP) in an aqueous solution of ammonia-based isopropanol (IPA) in which octadecylamine (ODA) is dissolved. Synthesized. The above synthesis reaction was performed using a Teflon (registered trademark) microreactor having a micrometer-sized Y-shaped channel. There were four precursor solutions: solution 1: 3-aminopropyl liethoxysilane / IPA, solution 2: H ₂ O / IPA / ammonia, solution 3: TTIP / IPA, solution 4: H ₂ O / IPA, and solution 1. To solution 4 in the same volume. The precursor solution was simultaneously sent at a constant rate by a syringe pump. The solution 1 and the solution 2 and the solution 3 and the solution 4 were mixed in a parallel microreactor, and the liquid discharged from both reactors was further mixed in another microreactor to form one reaction liquid. The reaction solution was discharged into a separately prepared precursor solution 5: ODA / H ₂ O / IPA, and stirred at a constant speed until the discharge was completed. Thereafter, the mixture was allowed to stand at room temperature to obtain a nanoparticle dispersion. After the reaction solution was air-cooled, the precipitate was isolated by centrifugation at 6000 rpm for 10 minutes. After thoroughly washing the precipitate with ethanol, the precipitate was suspended in water so as to have a concentration of 1 g / ml, and a coating solution was obtained by ultrasonic treatment.
An attempt was made to apply 300 pL of the coating solution as 300 drops using a microjet on the surface of an MSS sensor arranged on a hot plate at 80 ° C. However, clogging of the inkjet dispenser of the coating liquid occurred, and the coating could not be performed.
Physical and chemical stability were evaluated on samples applied by spray coating.

<Comparative Example 2>
The 2-propanol dispersion IPA-UP (Nissan Chemical) was diluted with 2-propanol to 1 g / ml to prepare a coating solution. An attempt was made to apply 300 pL of the coating solution as 300 drops using a microjet on the surface of an MSS sensor arranged on a hot plate at 80 ° C. However, clogging of the inkjet dispenser of the coating liquid occurred, and the coating could not be performed.
Physical and chemical stability were evaluated on samples applied by spray coating.

<Comparative Example 3>
10 g of phenyltrimethoxysilane, 10 g of water, 30 g of ethanol and 28% aqueous ammonia were mixed and reacted at 80 ° C. for 2 hours. The precipitate was isolated by centrifugation at 6000 rpm for 10 minutes. After sufficiently washing the precipitate with ethanol, the precipitate was dissolved in N, N-dimethylformamide to a concentration of 1 g / ml to obtain a coating solution.
The coating solution (300 pL) was applied as 300 drops using a micro jet on the surface of an MSS sensor arranged on a hot plate at 80 ° C to obtain a film. Note that the film did not contain SiO ₂ .
Table 1 shows the measurement results of the physical properties of the above measurements (1) to (7). After measuring the physical properties of (4) three times each under saturated vapors of ethanol and toluene, the film shape was clearly deformed by observation with an optical microscope.

<Comparative Example 4>
The solution of Example 16 was used to apply 60 shots of 200 pL each to flatten the film shape. FIG. 6 shows an image of the laser microscope. Further, sensors of Example 16 and Comparative Example 4 were manufactured under the same conditions for 5 or more samples, and the response intensity was shown in a box plot in FIG. As shown in FIG. 7, the response intensity of Comparative Example 4 varied and the reproducibility was low. That is, the reproducibility was lowered due to the flat film shape.

  The organic-inorganic hybrid of the present invention can be used as a sensitive film of a surface stress (MSS) sensor.

Claims (11)

A carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a boron atom, and a SiO _3/2 skeleton modified with an organic functional group containing at least one selected from the group consisting of phosphorus atoms,
Having a coffee ring shape,
Organic-inorganic hybrid membrane. The organic-inorganic hybrid film is a silica particle film,
The organic-inorganic hybrid film according to claim 1. The organic-inorganic hybrid film includes a continuous chain structure formed by bonding silica particles to each other,
The organic-inorganic hybrid membrane according to claim 1. Including chain-like silica particles modified with an organic functional group,
The organic-inorganic hybrid film according to claim 1. The organic functional group includes at least one selected from the group consisting of a carbon unsaturated bond, an aromatic atom, a nitrogen atom, an oxygen atom, a sulfur atom, and a fluorine atom.
The organic-inorganic hybrid film according to claim 1. Having a BET specific surface area of 0 m ² / g or more and 1000 m ² / g or less,
The organic-inorganic hybrid film according to claim 1. Having a BET total pore volume of 0 cm ³ / g or more and 1.5 cm ³ / g or less,
The organic-inorganic hybrid film according to claim 1. The thermal weight loss rate of organic components in TGA is 3% or more and 70% or less;
The organic-inorganic hybrid film according to claim 1. Made from N, N-dimethylformamide and / or propylene glycol monomethyl ether dispersion of linear silica particles modified with organic functional groups,
The organic-inorganic hybrid film according to claim 1.   A surface stress sensor comprising the organic-inorganic hybrid film according to claim 1. A step of obtaining a coating liquid in which chain silica particles modified with an organic functional group are dispersed in an organic solvent,
A step of applying the coating liquid on the surface stress sensor surface using an inkjet device,
A method for producing an organic-inorganic hybrid film, comprising: