JP2022028305A - Composition and method for producing the same - Google Patents

Abstract

To provide a novel composition which is obtained by blending a water-soluble compound having a plurality of hydroxyl groups in one molecule and a polyfunctional compound having two or more groups reactive with a hydroxyl group in one molecule and is suppressed in gelatinization in a short time and to provide a method for producing the same.SOLUTION: There is provided a method for producing a composition obtained by blending a polyvinyl alcohol, a polyfunctional compound having two or more groups reactive with a hydroxyl group in one molecule and water, wherein in the composition, the ratio of the blending amount of a solvent other than water to the blending amount of water is 0.2 mass% or less. There is provided a method for producing a composition which comprises: a step of preparing an aqueous solution of the polyfunctional compound by heating an aqueous solution of the polyfunctional compound; and a step of mixing an aqueous solution of the polyvinyl alcohol and an aqueous solution of the polyfunctional compound.SELECTED DRAWING: None

Description

The present invention relates to a composition and a method for producing the same.

A compound having a plurality of hydroxyl groups in one molecule usually has a higher water solubility as the number of hydroxyl groups increases. For example, polyvinyl alcohol has water solubility because it has a large number of hydroxyl groups even though it is a resin component.
If a water-insoluble compound can be obtained by a simple process using such a water-soluble compound, it is useful as a functional material.

For example, a water-soluble polymer substance having a plurality of hydroxyl groups in one molecule such as polyvinyl alcohol, a boron-containing compound having a plurality of boronic acid groups in one molecule, and capture of heavy metal ions in one molecule. By reacting with a site and a heavy metal ion trapping compound having one boronic acid group, the water-soluble polymer substance is cross-linked by the boron-containing compound, and the heavy metal ion trapping is carried out on a hydroxyl group in the polymer substance. It is disclosed that a water-insoluble polymer gel to which a compound is bound has been prepared (see Patent Document 1).

The boronic acid group is a group capable of reacting with a hydroxyl group, and the boron-containing compound crosslinks the water-soluble polymer substance. That is, the polymer gel becomes water-insoluble by cross-linking the water-soluble polymer substance at the hydroxyl group site with the boron-containing compound, and further, the heavy metal ion trapping compound is bonded to another hydroxyl group. It can be easily prepared by blending these raw materials. The polymer gel can easily capture heavy metal ions in water and is useful as a water purification agent.

Japanese Patent No. 5489921

On the other hand, since the reaction in which the water-soluble polymer substance is crosslinked by the boron-containing compound proceeds rapidly, the water-insoluble polymer substance is water-insoluble from the water-soluble polymer substance in a short time of, for example, several tens of seconds. A polymer gel is produced. As described above, it is desirable that the gelation proceeds rapidly from the viewpoint that the target product can be obtained in a short time, but for example, in the case of forming a film, the composition obtained by blending the raw materials is used. If any operation is desired, it is necessary to perform this operation in a short time until the gelation is completed, and there is room for improvement in terms of handleability of the composition.

The present invention comprises a water-soluble compound having a plurality of hydroxyl groups in one molecule and a polyfunctional compound having two or more groups capable of reacting with the hydroxyl groups in one molecule, and gel in a short time. It is an object of the present invention to provide a novel composition in which the conversion is suppressed, and a method for producing the same.

The present invention adopts the following configuration.
[1]. The composition is composed of a mixture of polyvinyl alcohol, a polyfunctional compound having two or more groups capable of reacting with a hydroxyl group in one molecule, and water. A composition in which the ratio of the blending amount of a solvent other than water to the blending amount of water is 0.2% by mass or less.
[2]. The composition according to [1], wherein the polyfunctional compound is an aromatic compound having two or more groups represented by the formula "-B (OH) ₂ " in one molecule.
[3]. The polyfunctional compound is selected from the group consisting of 1,4-phenylenediboronic acid, 1,3-phenylenediboronic acid, 1,3,5-benzenetrisboronic acid and 2,5-thiophenediboronic acid. The composition according to [1], which is one kind or two or more kinds.

[4]. The composition according to any one of [1] to [3], wherein the composition further contains a dye, a dye, a pigment, an enzyme or a catalyst.
[5]. In the composition, the blending amount of PVA per 1 L of the composition is 0.03 to 1 unit mol, and the blending amount of the polyfunctional compound per 1 L of the composition is 1 to 16 mmol. 1] The composition according to any one of [4].
[6]. A method for producing a composition, wherein the composition comprises polyvinyl alcohol, a polyfunctional compound having two or more groups capable of reacting with a hydroxyl group in one molecule, and water. The ratio of the blending amount of the solvent other than water to the blending amount of the water is 0.2% by mass or less, and the production method is carried out by heating the aqueous dispersion of the polyfunctional compound. A step of preparing an aqueous solution of the functional compound, a step of mixing the aqueous solution of the polyvinyl alcohol and the aqueous solution of the polyfunctional compound, and a step of obtaining a reaction product of the polyvinyl alcohol and the polyfunctional compound. A method for producing a composition.

According to the present invention, a water-soluble compound having a plurality of hydroxyl groups in one molecule and a polyfunctional compound having two or more groups capable of reacting with hydroxyl groups in one molecule are blended in a short time. A novel composition in which gelation is suppressed, and a method for producing the same are provided.

It is the image pickup data of the film containing the PVA-DBA reaction product as a main component acquired in Example 1. FIG. 6 is imaging data of a film containing a PVA-DBA reactant as a main component, which was acquired by using FE-SEM in Example 1. It is the data of the infrared absorption spectrum by FT-IR of the film containing the PVA-DBA reaction product as a main component and the powder of DBA acquired in Example 1. It is a graph which shows the evaluation result of the water resistance of the film obtained in Example 1. FIG. It is a graph which shows the evaluation result of the stability of the film obtained in Example 1 with respect to the aqueous solution which has different pH. It is a graph which shows the measurement result of the absorption spectrum of the membrane obtained in Example 4. It is a graph which shows the measurement result of the absorption spectrum of the membrane obtained in Example 5. It is a graph which shows the evaluation result of the long-term stability of the composition obtained in Example 6. It is a graph which shows the evaluation result of the long-term stability of the composition obtained in Example 7. It is a graph which shows the evaluation result of the long-term stability of the composition obtained in Example 8. It is a graph which shows the evaluation result of the long-term stability of the composition obtained in Example 9. It is a graph which shows the evaluation result of the manufacturing suitability of a film of the composition obtained in Example 10. It is a graph which shows the evaluation result of the manufacturing suitability of a film of the composition obtained in Example 11. It is a graph which shows the evaluation result of the manufacturing suitability of a film of the composition obtained in Example 12. It is a graph which shows the evaluation result of the manufacturing suitability of a film of the composition obtained in Example 13.

<< Composition >>
The composition according to one embodiment of the present invention is a polyfunctional compound having polyvinyl alcohol (sometimes referred to as “PVA” in the present specification) and two or more groups capable of reacting with a hydroxyl group in one molecule. (In the present specification, it may be simply referred to as a "polyfunctional compound") and water are blended, and in the composition, the blending amount of a solvent other than water with respect to the blending amount of the water is The ratio is 0.2% by mass or less.
In the composition of the present embodiment having such a composition, gelation is suppressed in a short time after the compounding of the polyvinyl alcohol, the polyfunctional compound and water, and gelation can be suppressed for a long period of time. The composition is excellent in handleability.

The composition of the present embodiment contains, as a main component, a reactant produced by the reaction of the hydroxyl group in the PVA and the group capable of reacting with the hydroxyl group in the polyfunctional compound.
That is, the reactant has a cross-linking site formed by the reaction of the hydroxyl group in the PVA with the group in the polyfunctional compound.
More specifically, as the reactant, for example, an intramolecular cross-linking compound in which one or more of the cross-linking sites (that is, intramolecular cross-linking sites) are formed in one molecule of PVA; two molecules or three. Intermolecular cross-linking compound in which one or more of the above-mentioned cross-linking sites (that is, inter-molecular cross-linking sites) are formed between PVAs of molecules or more; / Examples include intermolecular cross-linking compounds.

In the present specification, the "main component" is the total of the materials in the material when focusing on a specific component other than the solvent in the target material (for example, the reaction product, the solid substance described later, etc.). It means a component in which the ratio of the content (mass) of the component to the mass is more than 50% by mass, and the ratio is, for example, 70% by mass or more, 80% by mass or more, or 90% by mass or more. There may be.

The number of hydroxyl groups in PVA that reacts with one group capable of reacting with a hydroxyl group at the time of producing the reactant (during the production of the composition) is appropriately determined according to the type of the group capable of reacting with the hydroxyl group. It is determined. For example, when the group capable of reacting with a hydroxyl group is a group represented by the formula “−B (OH) ₂ ”, the number of hydroxyl groups in PVA that reacts with one said group is 2.

Regardless of whether the reaction product is an intramolecular cross-linking compound, an intermolecular cross-linking compound, or an intramolecular / intermolecular cross-linking compound, the reaction product includes, for example, two hydroxyl groups existing in the vicinity of each other in PVA. Reacts with one of the above groups (groups capable of reacting with hydroxyl groups) in one molecule of the polyfunctional compound, and further, two hydroxyl groups present in the vicinity of each other, which are different from the above in PVA. However, those having one or more cross-linking sites formed by reacting with another one of the above groups (groups capable of reacting with a hydroxyl group) in the polyfunctional compound can be mentioned. Here, as "two hydroxyl groups existing in the vicinity of each other in PVA", for example, in PVA, they are bonded to two carbon atoms adjacent to each other with a methylene group ( _-CH2- ) in between. Two hydroxyl groups can be mentioned.

A solid substance can be produced by drying the composition of the present embodiment. The solid substance is obtained by removing a solvent such as water in the composition, and contains the reaction product as a main component.
The solid matter is water-insoluble because its dissolution is suppressed even when it is immersed in water.

<PVA (polyvinyl alcohol)>
In the present embodiment, PVA (polyvinyl alcohol, polyvinyl acetate saken product) is not particularly limited.

The saponification degree of PVA is preferably 50 to 99%, more preferably 60 to 99%, still more preferably 70 to 99%, in terms of availability and usability of PVA. It is particularly preferably 75 to 90%.

The production suitability for producing the solid substance using the composition of the present embodiment may change depending on the degree of saponification of PVA. For example, when the degree of saponification of PVA is preferably 70 to 90%, more preferably 70 to 86%, still more preferably 70 to 82%, a solid substance may be produced more easily.

The weight average molecular weight of PVA is preferably 6000 to 190000 in terms of availability and suitability for use of PVA.
Further, the weight average molecular weight of PVA may be, for example, any of 8000 to 11000, 12000 to 24000, 30000 to 51000, and 145000 to 187000.

As used herein, the term "weight average molecular weight" means a polystyrene-equivalent value measured by a gel permeation chromatography (GPC) method, unless otherwise specified.

The characteristics of the composition of the present embodiment and the production suitability for producing the solid product using the composition may change depending on the weight average molecular weight of PVA. For example, when the weight average molecular weight of PVA is small, a wider range can be selected as the blending amount of PVA and the polyfunctional compound than when the weight average molecular weight is large, and a more uniform composition can be obtained. The solid may be more easily produced from the composition. From this point of view, the weight average molecular weight of PVA is preferably 8000 to 51000, more preferably 8000 to 24000, and even more preferably 8000 to 11000.

In the composition, for example, only one kind of PVA having the same degree of saponification may be blended, or two or more kinds of PVA having different saponification degrees may be blended.
In the composition, for example, only one kind of PVA having the same weight average molecular weight may be blended, or two or more kinds of PVA having different weight average molecular weights may be blended.
When two or more types of PVA having different saponification degrees or weight average molecular weights are blended, the combination and ratio of these two or more types of PVA can be arbitrarily selected according to the purpose.

The blending amount of PVA in the composition is preferably adjusted according to the number of hydroxyl groups in PVA. Here, "the number of hydroxyl groups in PVA" means "the number of structural units having one hydroxyl group in PVA" and "the number of structural units in PVA that can be considered to be derived from vinyl alcohol". , Is synonymous with.
In the present specification, the unreacted hydroxyl group derived from PVA, the reacted hydroxyl group derived from PVA, and the acetyloxy group in the structural unit derived from PVA and derived from vinyl acetate in the composition. When the total amount of PVA is 1 mol, the blending amount of PVA is referred to as "1 unit mol".

In the above composition, the blending amount of PVA per 1 L of the composition is preferably 0.03 to 1 unit mol, more preferably 0.03 to 0.75 unit mol, and 0.03 to 0.5 unit. It is more preferably mol.

<Polyfunctional compound>
In the present embodiment, the polyfunctional compound is not particularly limited as long as it has two or more groups capable of reacting with a hydroxyl group in one molecule.

The polyfunctional compound is preferably an organic compound.
The polyfunctional compound, which is an organic compound, may be either an aliphatic compound or an aromatic compound.

The polyfunctional compound, which is an aliphatic compound, may be either a saturated aliphatic compound or an unsaturated aliphatic compound.
The polyfunctional compound which is an aliphatic compound may be either a chain aliphatic compound or a cyclic aliphatic compound, and in the case of a cyclic aliphatic compound, a monocyclic aliphatic compound and a polycyclic aliphatic compound. It may be any of.
In the present specification, the aliphatic compound having only a chain structure and not having a cyclic structure is a chain aliphatic compound, and the aliphatic compound having a cyclic structure regardless of the presence or absence of the chain structure is defined as an aliphatic compound. It is a cyclic aliphatic compound.

The polyfunctional compound which is an aromatic compound may be either a monocyclic aromatic compound or a polycyclic aromatic compound, or may be any of an aromatic hydrocarbon and an aromatic heterocyclic compound.

The aromatic heterocyclic compound has one or two or more atoms other than carbon atoms (that is, heteroatoms) as atoms constituting the ring skeleton of the aromatic ring (in other words, it has an aromatic heterocycle). If it is a thing, it is not particularly limited.
Examples of the aromatic heterocyclic compound include a sulfur-containing aromatic heterocyclic compound having a sulfur atom as the heteroatom, an oxygen-containing aromatic heterocyclic compound having an oxygen atom as the heteroatom, and the heteroatom. Examples thereof include a nitrogen-containing aromatic heterocyclic compound having a nitrogen atom.

Examples of the aromatic compound include benzene derivatives, naphthalene derivatives, thiophene derivatives and the like.
In the present specification, when a structure in which one or more hydrogen atoms are substituted with a group other than a hydrogen atom is assumed in a specific compound, the compound having such a substituted structure is referred to as the above-mentioned specific compound. It is referred to as a "derivative" of the compound of. For example, 1,4-phenylenediboronic acid, which will be described later, is a benzene derivative.
As used herein, the term "group" includes not only an atomic group formed by bonding a plurality of atoms but also a single atom, unless otherwise specified.

The polyfunctional compound is preferably an aromatic compound in that the solid substance having a higher effect of suppressing gelation of the composition and having better properties can be obtained.

The group of the polyfunctional compound capable of reacting with the hydroxyl group is not particularly limited, but is preferably a group represented by the formula “−B (OH) ₂ ”.

The polyfunctional compound has one molecule of a group represented by the formula "-B (OH) ₂ " in that the solid substance having a higher effect of suppressing gelation of the composition and having further good properties can be obtained. It is more preferable that the aromatic compound has two or more of them.

The upper limit of the number of groups capable of reacting with the hydroxyl group of one molecule of the polyfunctional compound is not particularly limited.
From the viewpoint of availability of the polyfunctional compound, ease of production, and the like, the number of the polyfunctional compounds is preferably 2 to 4, preferably 2 or 3.

The two or more groups of the polyfunctional compound capable of reacting with the hydroxyl group may be all the same, all may be different, or only a part thereof may be the same. However, in that the composition in which gelation is suppressed in a short time can be more easily obtained, it is preferable that at least a part of two or more groups capable of reacting with a hydroxyl group are the same, and all of them are the same. Is more preferable.

In the polyfunctional compound, the bond positions of at least two groups capable of reacting with the hydroxyl group are preferably different from each other, and the bond positions of all the groups capable of reacting with the hydroxyl group may be different from each other. By using such a polyfunctional compound, the composition in which gelation is suppressed in a short time can be more easily obtained.

The polyfunctional compound may have, for example, a group that imparts a new function to the reactant (in the present specification, it may be referred to as a "functional imparting group"). As the polyfunctional compound having such a group (functionality-imparting group), for example, a structure in which two or more hydrogen atoms in the functional compound described later are replaced with a group having a group capable of reacting with a hydroxyl group is used. What you have is mentioned. The group having a group capable of reacting with the hydroxyl group may be composed of only a group capable of reacting with the hydroxyl group, or may be a group having a structure in which a group capable of reacting with the hydroxyl group is bonded to another group. good. That is, as an example of the polyfunctional compound having the functional imparting group, one having a structure in which a group capable of reacting with the hydroxyl group is directly bonded to the functional compound and a group capable of reacting with the hydroxyl group are included in the functional compound. Examples thereof include those having a structure bonded via a linking group.

The polyfunctional compound blended in the composition may be only one kind, may be two or more kinds, and when there are two or more kinds, the combination and ratio thereof depend on the purpose. Can be selected arbitrarily.
It is preferable that only one kind of the polyfunctional compound is blended in the composition in terms of improving the stability of the reaction product and facilitating the production of the composition.

The polyfunctional compound is selected from the group consisting of 1,4-phenylenediboronic acid, 1,3-phenylenediboronic acid, 1,3,5-benzenetrisboronic acid and 2,5-thiophenediboronic acid. It is more preferable that the number is one or more.

The polyfunctional compound exemplified here may have a substituent.
When the polyfunctional compound has a substituent, it means that one or more hydrogen atoms not constituting a hydroxyl group in the polyfunctional compound are substituted with a group other than the hydrogen atom.

In the polyfunctional compound, when the number of substituted hydrogen atoms is two or more, the substituents may be all the same, all may be different, or only a part thereof may be the same. good.
In the polyfunctional compound, the substitution position of the hydrogen atom is not particularly limited.

The substituent has, for example, an alkyl group, an alkoxy group, and a structure in which two or more methylene groups ( _-CH2- ) that are not adjacent to each other in the alkyl group are substituted with an oxygen atom (-O-). Examples thereof include substituted alkyl groups, amino groups, cyano groups, halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.).

The alkyl group in the substituent may be linear, branched or cyclic.

The number of carbon atoms of the linear or branched alkyl group is not particularly limited, but is preferably 1 to 12.
Examples of such linear or branched alkyl groups include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. n-Pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 1-methylbutyl group, n-hexyl group, 2-methylpentyl group, 3-methylpentyl group, 2,2-dimethylbutyl group, 2,3- Dimethylbutyl group, n-heptyl group, 2-methylhexyl group, 3-methylhexyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3,3-dimethyl Examples thereof include a pentyl group, a 3-ethylpentyl group, a 2,2,3-trimethylbutyl group, an n-octyl group, an isooctyl group, a nonyl group, a decyl group, an undecyl group and a dodecyl group.
The number of carbon atoms of the linear or branched alkyl group may be, for example, any one of 1 to 10, 1 to 8, 1 to 6 and 1 to 4.

The cyclic alkyl group may be either monocyclic or polycyclic.
The number of carbon atoms of the cyclic alkyl group is not particularly limited as long as it is 3 or more, but it is preferably 3 to 12.
Examples of the cyclic alkyl group include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, norbornyl group, isobornyl group, 1-adamantyl group and 2-. Examples thereof include an adamantyl group and a tricyclodecyl group.
The cyclic alkyl group may have, for example, any of 3 to 10, 3 to 8, and 3 to 6 carbon atoms.

The alkyl group may be a mixture of a linear or branched chain structure and a cyclic structure.
Examples of the alkyl group in which such a chain structure and a cyclic structure are mixed include the above-mentioned linear or branched chain such as a cyclopentylmethyl group, a 1-cyclopentylethyl group, a cyclohexylmethyl group, and a 1-cyclohexylethyl group. A group having a structure in which one or more hydrogen atoms in the alkyl group in the form are substituted with the above-mentioned cyclic alkyl group; methylcyclopentyl group, ethylcyclopentyl group, methylcyclohexyl group, ethylcyclohexyl group, dimethylcyclohexyl group. Examples thereof include a group having a structure in which one or more hydrogen atoms in the above-mentioned cyclic alkyl group are substituted with the above-mentioned linear or branched alkyl group.
The number of carbon atoms of the alkyl group in which the chain structure and the cyclic structure are mixed is not particularly limited as long as it is 4 or more, but it is preferably 4 to 24.

The alkoxy group in the substituent has a monovalent structure in which the above-mentioned alkyl group is bonded to an oxygen atom, for example, a methoxy group, an ethoxy group, a cyclopropyloxy group, a cyclopentylmethyloxy group, a methylcyclopentyloxy group and the like. The basis of is mentioned.
The alkoxy group preferably has 1 to 24 carbon atoms.

Examples of the substituted alkyl group in the substituent include a group having a structure in which two or more methylene groups that are not adjacent to each other in the above-mentioned alkyl group are substituted with an oxygen atom.
The number of methylene groups substituted with oxygen atoms is not particularly limited and is determined according to the number of carbon atoms of the alkyl group before substitution with oxygen atoms, but is preferably 2 to 6, for example, 2. It may be any of 4 and 2 to 3.

In the composition, the blending amount of the polyfunctional compound per 1 L of the composition is preferably 1 to 16 mmol, more preferably 1 to 14.5 mmol, still more preferably 1 to 13 mmol.

In the composition, it is preferable that the blending amount of PVA per 1 L of the composition and the blending amount of the polyfunctional compound per 1 L of the composition are both in the above-mentioned numerical range.
For example, in the composition, the blending amount of PVA per 1 L of the composition is 0.03 to 1 unit mol, and the blending amount of the polyfunctional compound per 1 L of the composition is 1 to 16 mmol. The compounding amount of PVA per 1 L of the composition is 0.03 to 0.75 unit mol, and the compounding amount of the polyfunctional compound per 1 L of the composition is 1 to 14.5 mmol. More preferably, the blending amount of PVA per 1 L of the composition is 0.03 to 0.5 unit mol, and the blending amount of the polyfunctional compound per 1 L of the composition is further preferably 1 to 13 mmol. ..

<Water>
In the above composition, the blending amount of water is not particularly limited, but the ratio of the blending amount of water to the total blending component may be, for example, 95 to 99.9% by mass.

<Other ingredients>
The composition may further contain other components that do not fall under any of PVA, the polyfunctional compound, and water, as long as the effects of the present invention are not impaired.
The other components blended in the composition may be only one kind, two or more kinds, and when two or more kinds, the combination and the ratio thereof depend on the purpose. Can be selected arbitrarily.

The other component may be, for example, any of an organic compound, an inorganic compound, and a complex of an organic compound and an inorganic compound.
The organic compound may be, for example, a polyamide, a protein, or the like, or may be a compound other than these. Further, the organic compound may be, for example, an organometallic compound having a metal atom or an organic compound having no metal atom.
The inorganic compound may be, for example, a metal compound having a metal atom or a non-metal compound having no metal atom.
The complex may be, for example, a complex.

More specifically, as the other component, for example, a solvent other than water, a functional compound, and a monofunctional compound having a functional group (in the present specification, it is simply referred to as "functional monofunctional compound". There is) etc.
As used herein, the term "solvent" means a component that is liquid at room temperature and pressure and is used to dissolve or disperse a compounding component other than the solvent.
As used herein, the term "normal temperature" means a temperature that is not particularly cooled or heated, that is, a normal temperature, and examples thereof include a temperature of 15 to 25 ° C.

[Solvents other than water]
The solvent other than water is preferably one that is uniformly miscible with water at room temperature (water-soluble). By using such a water-soluble solvent, it is easy to obtain the composition having higher uniformity (less precipitate).

Examples of the water-soluble solvent include alcohols such as methanol, ethanol and 2-propanol; ethers such as diethyl ether, tetrahydrofuran (THF) and 1,2-dimethoxyethane (dimethylserosolve); acetone, methyl ethyl ketone (MEK) and cyclohexanone. Ketones such as; nitriles such as acetonitrile; amides such as N, N-dimethylformamide (DMF), N, N-dimethylacetamide; sulfoxides such as dimethyl sulfoxide and the like.
Among these, the solvent other than water is preferably one that can be removed by drying under normal pressure, for example, one having a boiling point of 100 ° C. or lower.

However, in the above composition, the ratio of the blending amount of the solvent other than water to the blending amount of water is 0.2% by mass or less. By producing the composition by the method described later, the uniformity is higher (less precipitates) and the composition is more uniform even if a solvent other than water is not used or the amount used is very small. The composition is obtained in which gelation is suppressed in a short time immediately after production. Further, the composition has a low risk by not using a flammable solvent as the solvent or by using a small amount of the flammable solvent. In addition, the composition may contain a component that is unstable with respect to a solvent other than water because a solvent other than water is not used or the amount used is very small. Here, the "component that is unstable with respect to a solvent other than water" originally has a component that decomposes in the coexistence of a solvent other than water, or that the structure changes significantly even if it is not decomposed. It means an ingredient that cannot exert its function.

In the above composition, the ratio of the blending amount of the solvent other than water to the blending amount of water is more preferably 0.1% by mass or less, further preferably 0.05% by mass or less, and 0% by mass. %, That is, it is particularly preferable that a solvent other than water is not blended (does not contain a solvent other than water).

[Functional compound]
The functional compound is a compound that imparts a new function to the composition or a solid substance (the reaction product) obtained by using the composition, and does not correspond to the polyfunctional compound.
The functional compound is preferably a compound that does not react with either PVA or the polyfunctional compound.

Preferred functional compounds include, for example, dyes, dyes, pigments, enzymes, catalysts, proteins and the like.
That is, the preferred composition further includes a dye, a dye, a pigment, an enzyme, or a catalyst.
The dyes, dyes, pigments and the like color the composition or solid matter. Some dyes and pigments correspond to dyes and some do not.
The enzyme, catalyst, or the like imparts an enzyme function, a catalytic function, or the like to the composition or solid substance. Some catalysts correspond to enzymes and some do not.
Some of the proteins correspond to enzymes and some do not.

The dyes, dyes and pigments may be known.
Examples of the dye include gold nanoparticles (also known as AuNPs), Prussian blue (also known as PB), tris (2,2'-bipyridyl) ruthenium (II) chloride hexahydrate (also known as Rubpy), and N. -Ethyl or N-methyl quaternized 4-[(4-aminophenyl) (4-imino-2,5-cyclohexadiene-1-iriden) methyl] -2,7-naphthalenedisulfonate hydroxide Intramolecular salt sodium Examples thereof include salt (also known as EG, Eriogreen B) and myoglobin.
The structural formulas of Rubpy and EG are shown below.

The enzyme, catalyst and protein may be known.
Examples of the enzyme include glucose oxidase, horseradish peroxidase and the like.
Examples of the protein include albumin and the like.
Some of the enzymes, catalysts and proteins are unstable to solvents other than water (eg, alcohols, ethers, etc.), but the composition does not use or uses solvents other than water. Since the amount is very small, such unstable substances are also stably present in the composition.

The reaction product in the composition can have a network structure by adjusting the reaction conditions between PVA and the polyfunctional compound, for example, by increasing the number of cross-linking sites. .. Then, at the time of producing the composition (at the time of producing the reaction product), by blending the functional compound, the reaction product having a network structure and containing the functional compound inside the network structure can be obtained. Can be manufactured.
In the reaction product containing such a functional compound, if the size of the functional compound is smaller than the size of the mesh, the reaction product is in a liquid containing the reaction product (for example, in the composition). The functional compound contained in the reaction product can be moved to the outside of the reaction product via a mesh, and the functional compound existing outside the reaction product can be moved to the inside of the reaction product through the mesh. It is possible to move to. That is, in this case, the functional compound can move inside and outside the reaction product, and the reaction product can be encapsulated and released from the functional compound through a mesh after its formation. On the other hand, if the size of the functional compound is larger than the size of the mesh, in the liquid containing the reactant (for example, in the composition), the functional compound contained in the reactant passes through the mesh. Therefore, the functional compound existing outside the reaction product is immovable to the outside of the reaction product, and the functional compound existing outside the reaction product is immovable inside the reaction product via the mesh. That is, in this case, the functional compound is immovable inside and outside the reactant, and the reactant is unable to release the functional compound through the mesh after its formation, and the functional compound is contained. Is maintained.

As described above, by drying the composition containing the reaction product, the water-insoluble solid substance containing the reaction product as a main component can be obtained. When the solid substance containing the functional compound that can be moved inside and outside the reaction product is immersed in water or an aqueous mixed solvent containing water as a main component, the functional compound is released from the reaction product. May elute in water or in the aqueous mixed solvent. Then, when it elutes, the characteristics of the solid substance (reactant) change. For example, when the functional compound is a water-soluble dye, the solid substance before being immersed in water or the aqueous mixed solvent is colored according to the dye contained, but is colored in water or the aqueous mixed solvent. After being immersed in the solid substance, the degree of coloring depending on the dye is reduced or the coloring is lost. On the other hand, when the functional compound is a water-soluble dye that cannot be moved inside and outside the reaction product, the solid substance depends on the dye contained in the water or before and after immersion in the aqueous mixed solvent. Is colored.

When the functional compound is, for example, an enzyme or catalyst that cannot move inside or outside the reaction product, the solid substance can be used as the enzyme or catalyst supported on the carrier. In this case, the solid has the same excellent effect as a conventional enzyme or catalyst supported on a carrier.

In the composition, the blending amount of the functional compound per 1 L of the composition is preferably, for example, 0.05 to 5 mmol. When the blending amount is at least the lower limit value, the effect of using the functional compound in the composition and the solid matter can be obtained more remarkably. When the blending amount is not more than the upper limit value, excessive use of the functional compound is suppressed.

In the composition, the blending amount of the functional compound per 1 L of the composition may be in a further limited range depending on the type of the functional compound.
For example, when the functional compound is the dye, the blending amount of the functional compound (dye) per 1 L of the composition is preferably 0.1 to 1 mmol, preferably 0.1. It is more preferably ~ 0.7 mmol, and even more preferably 0.1 to 0.4 mmol.

[Functional monofunctional compound]
The functional monofunctional compound has only one group capable of reacting with a hydroxyl group in one molecule, and has one or two or more functional-imparting groups in one molecule, and has the above-mentioned function. It is a compound that does not correspond to a sex compound.
The group capable of reacting with the hydroxyl group of the functional monofunctional compound is the same as the group capable of reacting with the hydroxyl group of the polyfunctional compound.
The functional-imparting group of the functional monofunctional compound is the same as the functional-imparting group that the polyfunctional compound may have.

Unlike the polyfunctional compound, the functional monofunctional compound does not form the cross-linking site, but imparts a new function to the reactant.

Examples of the functional monofunctional compound include those having a structure in which one hydrogen atom in the functional compound is substituted with a group having a group capable of reacting with a hydroxyl group. The group having a group capable of reacting with the hydroxyl group is the same as in the case of the polyfunctional compound having the above-mentioned functional imparting group. That is, as an example of a functional monofunctional compound, one having a structure in which a group capable of reacting with the hydroxyl group is directly bonded to the functional compound, and a group having a group capable of reacting with the hydroxyl group attached to the functional compound via a linking group. Those having a combined structure are mentioned.
As a functional monofunctional compound, more specifically, for example, in a polyfunctional compound having a functional group, one or two or more hydroxyl groups are used so that only one group can react with the hydroxyl group. Examples thereof include compounds having a structure in which a reactive group is substituted with a hydrogen atom.

The blending amount of the functional monofunctional compound per 1 L of the composition in the composition can be appropriately adjusted depending on the type of the functional monofunctional compound, and for example, the said in the composition, per 1 L of the composition. It may be the same as the blending amount of the functional compound.

When the other component does not correspond to any of the solvent other than water, the functional compound, and the functional monofunctional compound, in the composition, the other component with respect to the total amount of the compounded components. The proportion of the compounding amount of the above is preferably 10% by mass or less, more preferably 5% by mass or less, further preferably 3% by mass or less, and particularly preferably 1% by mass or less.

In the composition, the ratio of the total blending amount of PVA, the polyfunctional compound, and water to the total blending component is preferably 90% by mass or more, more preferably 95% by mass or more. It is more preferably 97% by mass or more, and particularly preferably 99% by mass or more.
The composition satisfying the conditions of such a blending amount is more effective in suppressing gelation in a short time immediately after production.

At the time of producing the composition, the reaction produced by the reaction product is, for example, as shown below, PVA and a compound represented by the following general formula (11) (in the present specification, "Compound (11)". ) ”) And react to produce a compound represented by the following general formula (1) (in this specification, it may be referred to as“ compound (1) ”). Can be mentioned. However, this is an example of a reaction produced by the reactant.

（式中、Ｇは有機基であり；Ｚ^１、Ｚ^２及びＺ^３は、それぞれ独立に水酸基と反応可能な基であり；ｎは０以上の整数であり；Ｚ^１０は、前記Ｚ^１と、ＰＶＡ中の水酸基と、の反応によって、前記Ｚ^１から誘導された基であり；Ｚ^２０は、前記Ｚ^２と、ＰＶＡ中の水酸基と、の反応によって、前記Ｚ^２から誘導された基であり、前記Ｚ^１０及びＺ^２０は、互いに同一であっても異なっていてもよい。）

(In the formula, G is an organic group; Z ¹ , Z ² and Z ³ are groups capable of independently reacting with a hydroxyl group; n is an integer of 0 or more; Z ¹⁰ is the above Z ¹ and , Is a group derived from Z ¹ by reaction with a hydroxyl group in PVA; Z ²⁰ is a group derived from Z ² by reaction with Z ² and a hydroxyl group in PVA. Yes, the Z ¹⁰ and Z ²⁰ may be the same or different from each other.)

The compound (11) is the polyfunctional compound.
The compound (1) is a reaction product formed by reacting a hydroxyl group in the PVA with a group capable of reacting with the hydroxyl group in the polyfunctional compound (compound (11)).

In the formula, G is an organic group, and is a group consisting of compound (11) excluding Z ¹ , Z ² and Z ³ .
G may be either an aliphatic group or an aromatic group.

The aliphatic group in G may be either a saturated aliphatic group or an unsaturated aliphatic group.
The aliphatic group in G may be linear, branched chain (that is, chain aliphatic group) or cyclic (aliphatic cyclic group), and when it is cyclic, monocyclic and cyclic and It may be any of polycyclic.

The aromatic group in G may be either monocyclic or polycyclic, and may be either an aromatic hydrocarbon group or an aromatic heterocyclic group.
Examples of the aromatic group include a group obtained by removing n + 2 hydrogen atoms from an aromatic compound.
Examples of the aromatic compound include benzene, naphthalene, thiophene and the like.

The aliphatic group and aromatic group in G may have a substituent.
The fact that the aliphatic group or aromatic group in G has a substituent means that one or more hydrogen atoms in the aliphatic group or aromatic group are substituted with a group other than the hydrogen atom. Means.

In G, when the number of hydrogen atoms substituted is two or more, the substituents may be all the same, all may be different, or only a part may be the same.
In G, the substitution position of the hydrogen atom is not particularly limited.

Examples of the substituent include an amino group, a cyano group, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.) and the like.

In terms of obtaining the solid substance having a higher effect of suppressing gelation of the composition and better properties, G is preferably an aromatic group which may have a substituent, and is preferably a substituent. Any of the aromatic hydrocarbon group and the aromatic heterocyclic group which may have the above is preferable.

In the formula, Z ¹ , Z ² and Z ³ are groups capable of independently reacting with a hydroxyl group. That is, Z ¹ , Z ² and Z ³ may all be the same, all may be different, or only a part may be the same.
Examples of the group capable of reacting with the hydroxyl group include a group represented by the formula “−B (OH) ₂ ”.

^In the formula, n defines the number of Z3 bound to G in compound (11) and compound (1), and is an integer of 0 or more.
The upper limit of n is determined according to the type of G and is not particularly limited.
Usually, n is preferably 0 to 2, more preferably 0 or 1.

The binding positions of Z ¹ , Z ² and Z ³ in compound (11) are not particularly limited.
The binding positions of Z ¹ and Z ² in compound (11) are preferably different from each other, and the binding positions of Z ¹ , Z ² and Z ³ in compound (11) may all be different from each other. ..

In the formula, Z ¹⁰ is a group derived from Z ¹ by the reaction of Z ¹ with the hydroxyl group in PVA. Z ¹⁰ is determined by the type of Z ¹ .
Similarly, Z ²⁰ is a group derived from Z ² by the reaction of Z ² with a hydroxyl group in PVA. Z ²⁰ is determined by the type of Z ² .
Z ¹⁰ and Z ²⁰ may be the same as or different from each other.

Among the compounds (11), the compound (11) in the case where the group containing a phenylene group having a substituent and capable of reacting with the hydroxyl group is a group represented by the formula “−B (OH) ₂ ” is selected as the compound (11). For example, a compound represented by the following formula can be mentioned.

These compounds can be produced, for example, by introducing various functional groups into various known boronic acids by a known substitution reaction or the like. Further, as these compounds, commercially available products can also be used.

Among the functional monofunctional compounds, the functional-imparting group imparts the characteristics as a dye, and the group capable of reacting with the hydroxyl group is a group represented by the formula "-B (OH) ₂ ". Examples of the compound in the above case include a compound represented by the following formula.

Among these compounds, the compound having an amide bond (-NH-C (= O)-) in the molecule is, for example, a raw material compound having an amino group for forming the amide bond according to a known method. , A raw material compound having a carboxy group or a chlorocarbonyl group, can be produced by reacting the amino group with the carboxy group or the chlorocarbonyl group to form an amide bond.
On the other hand, among these compounds, the compound having an ether bond (-O-) in the molecule is, for example, a raw material compound having a hydroxyl group (-OH) for forming the ether bond according to a known method. Using a raw material compound having a group having a structure in which one hydrogen atom in the hydrocarbon skeleton is substituted with a halogen atom (in this specification, it may be referred to as a “halogen atom-containing group”), It can be produced by reacting the hydroxyl group with the halogen atom-containing group to form an ether bond.

The composition is, for example, a coating agent for preventing the adhesion of proteins or cells to biochemical instruments or medical instruments, a coating agent for paper microanalytical chips, a ship bottom antifouling paint, and an antifogging coating agent. , Antistatic coating agent, organic solvent resistant coating agent, coating material for forming an interface layer for chemically modifying a solid surface with functional molecules (for example, for detecting non-uniform catalyst carrier, separating material carrier, heavy metal ion, etc.) Can be used in applications such as solid-state chemical sensor carriers, water pollutant adsorbents, adsorbent carriers for resource recovery, etc.).

<< Method of manufacturing composition >>
The method for producing a composition according to an embodiment of the present invention comprises a mixture of polyvinyl alcohol (PVA), a polyfunctional compound having two or more groups capable of reacting with a hydroxyl group in one molecule, and water. A method for producing a composition, wherein the ratio of the blending amount of a solvent other than water to the blending amount of water in the composition is 0.2% by mass or less, and the manufacturing method is the polyfunctionality. A step of preparing an aqueous solution of the polyfunctional compound by heating an aqueous dispersion of the compound (sometimes referred to as “step (A)” in the present specification), the aqueous solution of polyvinyl alcohol, and the above. A step of obtaining a reaction product of the polyvinyl alcohol and the polyfunctional compound by mixing an aqueous solution of the polyfunctional compound (in this specification, it may be referred to as "step (B)"). , Have.
By the above-mentioned production method, the composition according to the above-mentioned embodiment of the present invention can be produced.

<Process (A)>
In the step (A), an aqueous solution of the polyfunctional compound is prepared by heating the aqueous dispersion of the polyfunctional compound.
Since the polyfunctional compound has low water solubility or does not have water solubility, it is usually not easy to prepare an aqueous solution thereof, but the temperature of the aqueous dispersion of the polyfunctional compound is above a certain value. By raising the temperature to the above, an aqueous solution of the polyfunctional compound can be obtained.

The aqueous dispersion of the polyfunctional compound is obtained by mixing the polyfunctional compound and water and sufficiently stirring the obtained mixed solution.

The concentration of the polyfunctional compound in the aqueous dispersion of the polyfunctional compound is not particularly limited, and is a concentration that can appropriately realize the blending amount of the polyfunctional compound per 1 L of the composition in the composition described above. Is preferable.
Generally, the concentration is preferably 1 to 30 mM, more preferably 2 to 25 mM. When the concentration is at least the lower limit value, the composition can be produced more efficiently. When the concentration is not more than the upper limit value, an aqueous solution of the polyfunctional compound can be more easily prepared.
In the present specification, the concentration unit "M" represents "mol / L", and the concentration unit "mM" represents "mmol / L".

The concentration of the polyfunctional compound in the aqueous solution of the polyfunctional compound is the same as the concentration of the polyfunctional compound in the aqueous dispersion of the polyfunctional compound.

The heating temperature of the aqueous dispersion (the temperature of the aqueous dispersion during heating) is preferably 55 ° C. or higher, more preferably 60 ° C. or higher, and even more preferably 65 ° C. or higher. When the heating temperature of the aqueous dispersion is at least the lower limit, an aqueous solution of the polyfunctional compound can be more easily prepared.

The upper limit of the heating temperature of the aqueous dispersion is not particularly limited as long as the effect of the present invention is not impaired.
For example, the heating temperature of the aqueous dispersion is preferably 80 ° C. or lower in terms of suppressing deterioration of the polyfunctional compound.

The heating time of the aqueous dispersion is not particularly limited as long as the aqueous solution of the polyfunctional compound can be satisfactorily prepared, and can be appropriately adjusted according to the heating temperature of the aqueous dispersion.
For example, the heating time of the aqueous dispersion may be 5 to 60 minutes.

In the step (A), an aqueous solution of the polyfunctional compound may be prepared in which a component other than the polyfunctional compound is dissolved or dispersed (in other words, a component other than the polyfunctional compound is further contained). ..
As the component other than the polyfunctional compound, for example, the other component (a component that does not correspond to any of PVA, the polyfunctional compound, and water) which is a compounding component of the composition described above may be used. Can be mentioned.

The aqueous solution of the polyfunctional compound containing a component other than the polyfunctional compound may be prepared, for example, by heating an aqueous dispersion containing the polyfunctional compound and other components, or the polyfunctional compound. An aqueous solution of the polyfunctional compound may be prepared by heating the aqueous dispersion of the above, and the aqueous solution may be prepared by mixing the aqueous solution with components other than the polyfunctional compound. Further, the aqueous solution of the polyfunctional compound containing a component other than the polyfunctional compound is polyfunctional by performing both of these, that is, by heating an aqueous dispersion containing the polyfunctional compound and other components. An aqueous solution containing the compound and other components (hereinafter referred to as "first aqueous solution") is prepared, and then this aqueous solution (first aqueous solution) is mixed with a component other than the polyfunctional compound. A target aqueous solution (hereinafter referred to as "second aqueous solution") may be prepared. In this case, the components other than the polyfunctional compound used in the preparation of the first aqueous solution and the components other than the polyfunctional compound used in the preparation of the second aqueous solution may be the same or different from each other.

When preparing an aqueous solution of the polyfunctional compound containing a component other than the polyfunctional compound, the component other than the polyfunctional compound may be mixed alone with the object, or may be used as an aqueous solution or an aqueous dispersion. It may be mixed with the object.

<Process (B)>
In the step (B), an aqueous solution of PVA and an aqueous solution of the polyfunctional compound are mixed to obtain a reaction product of the PVA and the polyfunctional compound. The reaction at this time is carried out between the hydroxyl group in PVA and the group capable of reacting with the hydroxyl group in the polyfunctional compound. This produces the reactants described above.

The step (B) is preferably performed in an aqueous solution of the polyfunctional compound in a state where precipitation of the polyfunctional compound is not observed.
For that purpose, the temperature of the aqueous solution of the polyfunctional compound when mixed with the aqueous solution of PVA is preferably the same as the heating temperature of the aqueous dispersion described above.

The concentration of PVA in the aqueous solution of PVA is not particularly limited, and is preferably a concentration that can appropriately realize the blending amount of PVA per 1 L of the composition in the composition described above.
Usually, the concentration is preferably 0.05 to 0.6 unit M, more preferably 0.08 to 0.5 unit M. When the concentration is at least the lower limit value, the composition can be produced more efficiently. When the concentration is not more than the upper limit value, the handleability of the aqueous solution of PVA becomes better.
In the present specification, "1 unit M", which is an amount related to the concentration of PVA, means that the total amount of the amount of hydroxyl groups and the amount of acetyloxy groups in a liquid material such as a solution or a dispersion is 1 mol. Represents the concentration of PVA.

The amount of the aqueous solution of PVA used in the step (B) is preferably an amount that can appropriately realize the blending amount of PVA per 1 L of the composition in the composition described above.
Similarly, the amount of the aqueous solution of the polyfunctional compound to be used is preferably an amount that can appropriately realize the blending amount of the polyfunctional compound per 1 L of the composition in the composition described above.
In the step (B), the blending amount of PVA is preferably 1 to 250 times by mass, more preferably 2 to 200 times by mass, based on the blending amount of the polyfunctional compound. When the blending amount of PVA is in such a range, the effect of suppressing gelation in a short time immediately after the production of the composition becomes higher.

The temperature of the aqueous solution of PVA when mixed with the aqueous solution of the polyfunctional compound is not particularly limited, but is preferably 15 to 40 ° C, more preferably 18 to 30 ° C.

When mixing the aqueous solution of PVA and the aqueous solution of the polyfunctional compound, the aqueous solution of PVA may be added to the aqueous solution of the polyfunctional compound, or the aqueous solution of the polyfunctional compound may be added to the aqueous solution of PVA.

When mixing the aqueous solution of PVA and the aqueous solution of the polyfunctional compound, all of these aqueous solutions may be added all at once or dropped.

In the step (B), it is preferable to mix the aqueous solution of PVA and the aqueous solution of the polyfunctional compound, and then stir the obtained mixed solution for a certain period of time or longer.
The temperature of the mixed solution at the time of stirring is preferably 15 to 80 ° C, and may be, for example, any of 15 to 60 ° C, 15 to 50 ° C, and 15 to 30 ° C.
The stirring time of the mixed solution can be appropriately adjusted depending on the temperature at the time of stirring, but is preferably 10 to 60 seconds, more preferably 15 to 30 seconds.

In the step (B), an aqueous solution of PVA may be prepared in which a component other than PVA is dissolved or dispersed (in other words, a component other than PVA is further contained).
Examples of the components other than PVA include other components (components that do not correspond to PVA, the polyfunctional compound, and water) that are the compounding components of the composition described above.

An aqueous solution of PVA containing a component other than PVA can be prepared by mixing PVA, a component other than PVA, and water.

When preparing an aqueous solution of PVA containing a component other than PVA, the component other than PVA may be mixed alone with the object, or may be mixed with the object as an aqueous solution or an aqueous dispersion. ..

In the production method of the present embodiment, by adjusting the conditions of the step (B), the desired final product composition can be obtained immediately after the completion of the step (B). Further, after the completion of the step (B), if necessary, another step described later may be carried out to obtain a composition as a target final product.

<Other processes>
The production method of the present embodiment may have other steps that do not correspond to any of the step (A) and the step (B) as long as the effects of the present invention are not impaired.

The other steps can be arbitrarily selected depending on the intended purpose, and are not particularly limited.
The other steps may be performed before the step (A), between the steps (A) and the step (B), or after the step (B).
The other steps may be of only one type, may be of two or more types, and when there are two or more types, the combination thereof can be arbitrarily selected according to the purpose.
The number of the other steps may be only 1 or 2 or more for one kind of step.

As the other step, more specifically, for example, the other component (a component that does not correspond to any of PVA, the polyfunctional compound, and water) and the first composition for producing the composition. 1 A step of preparing the composition or a second intermediate composition for producing the composition by mixing the intermediate composition (in the present specification, it may be referred to as "step (C)"). There is).

Both the first intermediate composition and the second intermediate composition are intermediate-stage compositions in the process of producing the target composition, which are used for producing the composition which is the target final product. , The second intermediate composition is obtained by using the first intermediate composition.
Examples of the first intermediate composition include, but are not limited to, a composition in which PVA, the polyfunctional compound, and water are blended.

As used herein, the term "composition" simply means "a composition that is a target end product" unless otherwise specified.

In the step (C), when the other component and the first intermediate composition are mixed, the other component may be added to the first intermediate composition, or the first intermediate composition may be added to the first intermediate composition. It may be added to other components.

When the other components and the first intermediate composition are mixed, all of them may be added all at once or added dropwise.
The other components may be mixed alone with the first intermediate composition, or may be mixed with the first intermediate composition as an aqueous solution or an aqueous dispersion.

In the production method of the present embodiment, when the other components are blended, the blending amount of the other components is 1 to 250 mass by mass with respect to the blending amount of the polyfunctional compound, regardless of the timing of blending. It is preferably double, and more preferably 2 to 200 mass times. When the blending amount of the other component is in such a range, the effect of suppressing gelation in a short time immediately after the production of the composition becomes higher, and the other component is used. The effect will be higher.

In the production method of the present embodiment, in the composition which is the target final product obtained in the final step (that is, the step (B) or the other step), a solvent other than water is used with respect to the blending amount of water. The ratio of the blending amount of is 0.2% by mass or less.
In the above-mentioned production method, even if a solvent other than water is not used or the amount used is very small, the uniformity is higher (less precipitates) and the gel is gelled in a short time immediately after production. The composition in which the formation is suppressed is obtained. Further, in the above-mentioned production method, the risk is low by not using a flammable solvent as the solvent or by using a small amount. Further, in the above-mentioned production method, the composition containing a component unstable with respect to a solvent other than water can also be produced because a solvent other than water is not used or the amount used is very small.

In the production method, the composition containing the reaction product as a main component is finally obtained by performing the step (B) using the aqueous solution of the polyfunctional compound prepared in the step (A). In addition to suppressing gelation in a short period of time, this composition enables the production of the water-insoluble solid matter by its drying. The solid matter can be used for various purposes.

<< How to use the composition (manufacturing method of solid material) >>
As described above, the composition of the present embodiment is mixed with water (containing water) and dried to form the solid substance. The solid substance contains the reaction product as a main component and is water-insoluble. That is, the composition of the present embodiment can be used as a raw material for producing a water-insoluble solid substance.

The solid material forms a composition layer by placing the composition on the surface of the object to be manufactured by, for example, a spray method, a casting method, a dip method, a stamp method, an inkjet method, or the like. Then, it can be produced by drying the composition layer.
By adjusting the shape of the composition layer, the shape of the solid matter can be adjusted. For example, by making the composition layer a thin layer, the solid substance in the form of a film can be produced.
By such a method, the solid matter having a large area can be easily produced.

Examples of the material of the solid substance to be manufactured include resins, glasses, ceramics, metals, natural polymers and the like.
More specifically, examples of the solid matter to be produced include plates, paper (for example, filter paper), non-woven fabrics, tubes (for example, inside capillaries), glass filter paper, and porous bodies.

The drying conditions of the composition layer (composition) are not particularly limited.
For example, the drying may be performed under normal pressure, reduced pressure, or blowing conditions, and may be performed under the atmosphere of the atmosphere or the atmosphere of the inert gas.
The drying temperature is not particularly limited, and either normal temperature drying or heat drying may be used. Room temperature drying can be performed, for example, at a drying temperature of 15 to 25 ° C. The heat drying can be performed, for example, at a drying temperature of 50 to 80 ° C.
The drying may be, for example, natural drying performed at room temperature and under normal pressure.

Although the solid matter is water-insoluble, it is hydrophilic because PVA is used as a compounding component. As described above, the hydrophilic solid substance further has antifog property, antifouling property, wettability, biocompatibility and the like. In addition to being water resistant (water insoluble), the solid has high resistance to organic solvents. In addition, the solid substance has an adsorption inhibitory property on proteins and cells.

Hereinafter, the present invention will be described in more detail with reference to specific examples. However, the present invention is not limited to the examples shown below.

[Example 1]
<< Manufacture of composition >>
At room temperature, an aqueous suspension of DBA having a DBA concentration of 20 mM was prepared.
Next, the aqueous suspension is heated in a hot water bath at 70 ° C. to dissolve the insoluble matter in the aqueous suspension, and a DBA aqueous solution having a DBA concentration of 20 mM in a heated state is prepared. (Step (A)).
Separately, an aqueous PVA solution having a PVA concentration of 0.23 unit M was prepared. As the PVA, one having a saponification degree of 80% and a weight average molecular weight of 9000 to 10000 was used.
The DBA aqueous solution obtained above and in a heated state in which the DBA is still dissolved is added to the PVA aqueous solution at room temperature to mix these aqueous solutions and stir at 20 ° C. for 3 seconds. The desired composition was obtained (step (B)). At this time, the blending amount of PVA was 3.6% by mass with respect to the blending amount of DBA.
In the obtained composition, the blending amount of PVA was 0.15 unit mol per 1 L of the composition, and the blending amount of DBA was 6.7 mmol per 1 L of the composition.

Immediately after production, the composition contained a small amount of precipitate and was a suspension, but it was not gelled and was easy to handle.
Immediately after production, the composition was allowed to stand at room temperature for 1 month, but the properties of the composition did not change during this period.

<< Manufacturing of Membrane >>
The composition (3.6 mL) after storage obtained above is poured into a polystyrene petri dish having an inner diameter of 9 cm at room temperature and air-dried overnight to obtain a reaction product of PVA and DBA (a reaction product of PVA and DBA). Hereinafter, a colorless and transparent film containing (sometimes referred to as “PVA-DBA reactant”) as a main component was produced. The imaging data of the obtained film is shown in FIG.

Imaging data of the obtained film was acquired using a field emission scanning electron microscope (FE-SEM) (“JSM-7500F” manufactured by JEOL Ltd.). This imaging data is shown in FIG.
As a result of analyzing the imaging data, the thickness of the obtained film was 3 μm.

The obtained film and the DBA powder used as a raw material were subjected to a total reflection measurement method (Attenutated Total Reflection, ATR) using a Fourier transform infrared spectrophotometer (“FT / IR-4100” manufactured by Nippon Spectroscopy Co., Ltd.). The infrared absorption spectrum was measured by Fourier Transform Infrared Spectroscopy (FT-IR). The obtained spectral data is shown in FIG.

In the spectral data of the obtained film, a peak derived from the BO _two -plane out-of-plane angular oscillation was observed at a wave number of 660 cm ^-1 . Comparing this peak with the peak of the BO _two -plane out-of-plane angular vibration in the spectral data of the DBA powder, it was confirmed that the BO bond angle was fixed because it showed a high wave number shift. Furthermore, in addition to the fact that the peak of B-OH variable angle vibration was not observed in the spectral data of the membrane, these spectral data showed that the formation of the membrane formed a boronic acid ester bond.

<< Evaluation of membrane >>
<Evaluation of water resistance of membrane>
The membrane (29 mg) obtained above was immersed in water (20 mL) at room temperature and allowed to stand, and one day after the start of immersion, the membrane was taken out of the water and adhered to the membrane. Water was sufficiently removed and the mass of the membrane was measured.
Then, again at room temperature, the membrane was immersed in water (20 mL) and allowed to stand, and 6 days after the start of the immersion again (7 days in total after the start of the immersion), the membrane was removed from the water. It was taken out, water adhering to the membrane was sufficiently removed, and the mass of the membrane was measured. The measurement result of the mass of the film at this time is shown in FIG. In FIG. 4, the vertical axis of the graph shows the mass of the membrane, and the horizontal axis of the graph shows the total immersion time of the membrane in water.

As is clear from FIG. 4, almost no change in the mass of the film was observed from the start of immersion (total immersion time 0 hours) to the 7th day of immersion (total immersion time 7 days), and the obtained film was water-insoluble. I was able to confirm that.

<Evaluation of membrane stability for buffer solutions with different pH>
0.01M hydrochloride buffer (pH 2), 0.05M glycine-hydrogen buffer (pH 3), 0.1M acetate-sodium acetate buffer (pH 4, 5), 0.1M phosphate buffer (pH 6, 7, 8) ), And 0.1 M carbonate-bicarbonate buffer (pH 9, 10) were prepared.
The mass _W0 of the membrane obtained above was measured, then the membrane was immersed in each of the above buffers (20 mL) at room temperature and allowed to stand, and 7 days after the start of immersion. The membrane was taken out of the buffer, the buffer adhering to the membrane was sufficiently removed, and the mass _W7 of the membrane was measured. Then, the ratio of the mass W ₇ of the film after immersion to the mass W ₀ of the film before immersion (W ₇ / W ₀ × 100) was calculated. Table 1 shows these values, and FIG. 5 shows the W ₇ / W ₀ values.

As is clear from Table 1 and FIG. 5, when the pH of the buffer solution was 8 or less, W ₇ was equivalent to W ₀ , and the W ₇ / W ₀ value was about 1. That is, it was confirmed that the membrane obtained above was stable because its dissolution was suppressed in a buffer solution having a pH of 8 or less.
In contrast, when the pH of the buffer was 9 and 10, W ₇ was clearly smaller than W ₀ and the W ₇ / W ₀ value was clearly less than 1. That is, the membrane obtained above was clearly dissolved and unstable in the buffer solutions having pHs 9 and 10. This indicated that the boronic acid ester bond in the PVA-DBA reactant formed by the reaction of PVA and DBA was hydrolyzed under basic conditions.

[Example 2]
<< Manufacture of composition and membrane >>
The composition was produced in the same manner as in Example 1, and a membrane (hereinafter, may be referred to as “PVA-DBA reaction product membrane”) was produced on the bottom surface of a polystyrene petri dish.

<< Evaluation of membrane >>
<Evaluation of membrane hydrophilicity>
For the film obtained above, the contact angle of water was measured using a contact angle meter (“Drop Master DM300” manufactured by Kyowa Interface Science Co., Ltd.). The results are shown in Table 2.

A film containing PVA as a main component (hereinafter, "PVA film") is prepared by the same method as above except that an aqueous PVA solution having a concentration of 0.15 unit M is prepared and this aqueous PVA solution is used instead of the composition. (Sometimes referred to as) was manufactured on the bottom surface of a polystyrene petri dish. As PVA, the same one used in Example 1 was used.

The contact angles of water were measured for the PVA membrane obtained above and the bottom surface of the polystyrene petri dish by the same method as for the PVA-DBA reactant membrane, respectively. The results are shown in Table 2.

As is clear from the above results, the PVA-DBA reaction product membrane and the PVA membrane had a smaller water contact angle and were more hydrophilic than the bottom surface of the polystyrene petri dish. It was speculated that this was due to the influence of the hydroxyl groups present in these membranes. Since the hydroxyl group is a hydrophilic group and the hydroxyl group remains unreacted in the PVA membrane, it is considered that the PVA membrane has a small contact angle of water and is highly hydrophilic. On the other hand, considering the blending amount of PVA and DBA at the time of producing the PVA-DBA reaction product film, 22% of the total number of hydroxyl groups in PVA was used for the reaction with DBA, whereas 78% was used. It is presumed that the PVA-DBA reactant remains unreacted in the PVA-DBA reactant membrane, and therefore the PVA-DBA reactant membrane is presumed to be equivalent to the PVA membrane in terms of water contact angle (hydrophilicity). Was done.

[Example 3]
<< Manufacture of composition >>
The composition was produced in the same manner as in Example 1.

<< Manufacturing of Membrane >>
The composition (1 mL) obtained above was coated by dropping it on the bottom surface of a polystyrene petri dish having an inner diameter of 4 cm at room temperature. Then, the composition (that is, the composition layer) after coating is dried at 20 ° C. for 6 hours to obtain a circular colorless transparent film (PVA) having a diameter of 2 cm and containing a PVA-DBA reaction as a main component. -DBA reactant membrane) was produced.

<< Evaluation of membrane >>
<Evaluation of anti-fog property of film>
The above-mentioned polystyrene petri dish provided with a PVA-DBA reaction product membrane on the bottom surface was put on another polystyrene petri dish having an inner diameter smaller than this and containing hot water (warm water) having a temperature of 40 ° C. At this time, the bottom surface of the petri dish in which the PVA-DBA reaction product film is provided (the surface on which the PVA-DBA reaction product film is provided) faces the side of the petri dish in which the hot water is contained, and the opening of the petri dish in which the hot water is contained. The entire portion was covered with the bottom surface.
Next, the petri dish provided with the PVA-DBA reaction product membrane was visually observed from above.

As a result, it was confirmed that water droplets derived from warm water did not adhere to the bottom surface of the petri dish only in the region where the PVA-DBA reaction product membrane was provided, and that the petri dish had anti-fog properties. Of the bottom surface of the petri dish, the region where the PVA-DBA reaction product membrane was not provided was uniformly observed to have water droplets derived from warm water.
Considering the blending amounts of PVA and DBA at the time of producing the PVA-DBA reaction product film, it was presumed that most of the hydroxyl groups in PVA remained unreacted in the PVA-DBA reaction product film. Since the PVA film also has many hydroxyl groups, it has anti-fog properties, and it was presumed that the hydrophilicity of the PVA-DBA reaction product film is equivalent to that of the PVA film.

[Example 4]
<< Manufacture of composition >>
At room temperature, an aqueous suspension of DBA having a DBA concentration of 20 mM was prepared.
Next, the aqueous suspension is heated in a hot water bath at 70 ° C. to dissolve the insoluble matter in the aqueous suspension, and a DBA aqueous solution having a DBA concentration of 20 mM in a heated state is prepared. (Step (A)).
Separately, an aqueous PVA solution having a PVA concentration of 0.23 unit M was prepared. As PVA, the same one used in Example 1 was used.
The DBA aqueous solution obtained above and in a heated state in which the DBA was still dissolved was added to the PVA aqueous solution at room temperature and mixed (step (B)). At this time, the blending amount of PVA was 3.6% by mass with respect to the blending amount of DBA.
Further, tris (2,2'-bipyridyl) ruthenium (II) chloride hexahydrate (Rubpy) was added to the obtained mixture (corresponding to the first intermediate composition) at room temperature at 20 ° C. The desired composition was obtained by stirring with the mixture for 30 seconds (step (C)). At this time, the compounding amount of Rubpy was 0.5% by mass with respect to the compounding amount of DBA. Rubpy is a cationic water-soluble dye.
In the obtained composition, the blending amount of PVA was 0.15 unit mol per 1 L of the composition, the blending amount of DBA was 6.7 mmol per 1 L of the composition, and the blending amount of Ruby was 1 L of the composition. It was 0.27 mmol.

Immediately after production, the composition contained a small amount of precipitate and was a suspension, but it was not gelled and was easy to handle.
Immediately after production, the composition was allowed to stand at room temperature for 1 month, but the properties of the composition did not change during this period.

<< Manufacturing of Membrane >>
The composition (0.38 mL) after storage obtained above is poured on a glass substrate shaped like a silicon frame having a size of 1 cm × 4 cm at room temperature and air-dried overnight. To produce a yellow and transparent film containing a PVA-DBA reactant as a main component and further containing Ruby.

<< Evaluation of membrane >>
<Evaluation of mass transfer inside and outside the membrane>
The absorption spectrum of the film obtained above was measured using a spectrophotometer (“UV-3600” manufactured by Shimadzu Corporation).
The membrane was then immersed in water at room temperature for 3 hours.
The membrane was then removed from the water and the absorption spectrum of the membrane was measured in the same manner as above.
The measurement results of the absorption spectra of these films are shown in FIG. 6 together with the imaging data of these films.

The film before immersion in water was yellow transparent due to the inclusion of Rubpy, but the film after immersion in water was colorless and transparent. This indicated that Rubpy was eluted from the membrane being immersed in water into the water.
As shown in FIG. 6, the membrane before immersion in water showed an absorption peak derived from Rubpy at a wavelength of around 460 nm, but the membrane before immersion in water did not show such an absorption peak, and the above observation was made. It supported the result.
From the above, it was confirmed that the membrane has the property of moving substances inside and outside the membrane.

[Example 5]
<< Manufacture of composition >>
At room temperature, an aqueous suspension of DBA having a DBA concentration of 20 mM was prepared.
Next, the aqueous suspension is heated in a hot water bath at 70 ° C. to dissolve the insoluble matter in the aqueous suspension, and a DBA aqueous solution having a DBA concentration of 20 mM in a heated state is prepared. (Step (A)).
Separately, an aqueous PVA solution having a PVA concentration of 0.23 unit M was prepared. As PVA, the same one used in Example 1 was used.
The DBA aqueous solution obtained above and in a heated state in which the DBA was still dissolved was added to the PVA aqueous solution at room temperature and mixed (step (B)). At this time, the blending amount of PVA was 3.6% by mass with respect to the blending amount of DBA.
Further, Prussian blue (PB) was added to the obtained mixture (corresponding to the first intermediate composition) at room temperature, and the mixture was stirred at 20 ° C. for 30 seconds to obtain the desired composition (corresponding to the first intermediate composition). Step (C). At this time, the blending amount of PB was 0.2% by mass with respect to the blending amount of DBA. PB is a water-soluble inorganic pigment, and here, nanoparticles having an average particle diameter of 85 nm were used.
In the obtained composition, the blending amount of PVA was 0.15 unit mol per 1 L of the composition, the blending amount of DBA was 6.7 mmol per 1 L of the composition, and the blending amount of PB was per 1 L of the composition. It was 0.27 mmol.

Immediately after production, the composition contained a small amount of precipitate and was a suspension, but it was not gelled and was easy to handle.
Immediately after production, the composition was allowed to stand at room temperature for 1 month, but the properties of the composition did not change during this period.

<< Manufacturing of Membrane >>
The composition (0.38 mL) after storage obtained above is poured on a glass substrate shaped like a silicon frame having a size of 1 cm × 4 cm at room temperature and air-dried overnight. To produce a blue and transparent film containing a PVA-DBA reactant as a main component and further containing PB.

<< Evaluation of membrane >>
<Evaluation of mass transfer inside and outside the membrane>
The absorption spectrum of the film obtained above was measured using a spectrophotometer (“UV-3600” manufactured by Shimadzu Corporation).
The membrane was then immersed in water at room temperature for 3 hours.
The membrane was then removed from the water and the absorption spectrum of the membrane was measured in the same manner as above.
The measurement results of the absorption spectra of these films are shown in FIG. 7 together with the imaging data of these films.

The film before immersion in water was blue-transparent because it contained PB, but the film after immersion in water was also blue-transparent. This indicated that PB did not elute from the membrane being immersed in water into the water.
As shown in FIG. 7, the absorption spectrum of the membrane hardly changed before and after immersion in water, supporting the above observation results.
From the above, it was confirmed that the film has the property of not moving substances inside and outside the film.

From the results of Examples 5 to 6, when the obtained film contains other components that do not correspond to any of PVA, DBA, and water, the inside and outside of the film depends on the type of the other components. It was confirmed that the mobility of the other components in the above was different.

[Example 6]
<< Manufacture of composition >>
In the obtained composition, the blending amount of PVA was 0.1 unit mol, 0.2 unit mol, 0.3 unit mol or 0.4 unit mol instead of 0.15 unit mol per 1 L of the composition, and the blending amount of DBA was However, except that 20 combinations were selected so as to be 2.5 mmol, 5 mmol, 7.5 mmol, 10 mmol or 12.5 mmol instead of 6.7 mmol per 1 L of the composition, as in the case of Example 1. The desired composition was produced in the same manner.
All of the compositions immediately after production contained a small amount of precipitates and were suspensions, but they were not gelled and were easy to handle.

<< Evaluation of composition >>
<Evaluation of long-term stability of composition>
Immediately after production, the composition obtained above was stored at room temperature for 30 days.
Then, the composition after storage was visually observed, and the long-term stability of the composition was evaluated according to the following criteria. The results are shown in FIG.
[Evaluation criteria]
A: The composition contained no precipitate or only a small amount of precipitate, and the composition maintained a solution state and had long-term stability.
B: The composition contained a precipitate and was inferior in long-term stability to that of A.
C: The composition was gelled and did not have long-term stability.

As is clear from FIG. 8, [the amount of DBA compounded per 1 L of the composition (mmol), the amount of PVA compounded per 1 L of the composition (unit mol)] = [10, 0.3], [10, 0. 4], [12.5, 0.3], [12.5, 0.4], that is, the amount of DBA blended per 1 L of the composition is 10 mmol or more, and the blended amount of PVA per 1 L of the composition. When the amount was 0.3 unit mol or more, the composition after storage contained a white precipitate. In addition, the particle size of the colloid forming the precipitate was larger in the composition containing a large amount of PVA or DBA. From these findings, it was speculated that the particles consisting of PVA and DBA aggregated to form a precipitate.

When [the amount of DBA compounded per 1 L of the composition (mmol), the amount of PVA compounded per 1 L of the composition (unit mol)] = [12.5, 0.1], the degree of the composition after storage is Although it was low, it was white and gelled. Assuming that the weight average molecular weight of PVA is 9500 and all DBAs have reacted with PVA, the number of hydroxyl groups (crosslinkable sites) per PVA chain (1 molecule of PVA) is 45.3. In the composition, 62.5% of the hydroxyl groups are capable of reacting with DBA. Therefore, since the number of hydroxyl groups that reacted with DBA per PVA chain was larger than that of other compositions, it was presumed that the composition after storage was gelled.

In this example, when the blending amount of DBA per 1 L of the composition is 7.5 mmol or less, the composition does not depend on the blending amount of PVA per 1 L of the composition (in this case, 0.4 unit mol or less). Had long-term stability.

[Example 7]
<< Manufacture of composition >>
As PVA, instead of PVA having a degree of saponification of 80% and a weight average molecular weight of 9000 to 10000, a PVA having a degree of saponification of 88% and a weight average molecular weight of 13000 to 23000 was used. In the obtained composition, the amount of PVA blended was 0.05 unit mol, 0.1 unit mol, 0.15 unit mol, 0.2 unit mol or 0.25 unit mol instead of 0.15 unit mol per 1 L of the composition. Therefore, 40 combinations were selected so that the blending amount of DBA was 2 mmol, 4 mmol, 6 mmol, 8 mmol, 10 mmol, 12 mmol, 14 mmol, 16 mmol, or 18 mmol instead of 6.7 mmol per 1 L of the composition. Except for, the target composition was produced by the same method as in Example 1.
All of the compositions immediately after production contained a small amount of precipitates and were suspensions, but they were not gelled and were easy to handle.

<< Evaluation of composition >>
<Evaluation of long-term stability of composition>
Immediately after production, the composition obtained above was stored at room temperature for 30 days.
Then, the composition after storage was visually observed, and the long-term stability of the composition was evaluated according to the following criteria. The results are shown in FIG.
[Evaluation criteria]
A: The composition contained no precipitate or only a small amount of precipitate, and the composition maintained a solution state and had long-term stability.
B: The composition contained acicular crystals of DBA and was inferior in long-term stability to the case of A.
C: The composition contained a white precipitate and was inferior in long-term stability to that of A.
D: The composition was gelled and did not have long-term stability.

[Example 8]
<< Manufacture of composition >>
Except for the fact that PVA having a saponification degree of 88% and a weight average molecular weight of 31,000 to 50,000 was used instead of a PVA having a saponification degree of 88% and a weight average molecular weight of 13000 to 23000. Produced the composition in the same manner as in Example 7.

<< Evaluation of composition >>
<Evaluation of long-term stability of composition>
Immediately after production, the composition obtained above was stored at room temperature for 30 days.
Then, the composition after storage was visually observed, and the long-term stability of the composition was evaluated according to the following criteria. The results are shown in FIG.
[Evaluation criteria]
A: The composition contained no precipitate or only a small amount of precipitate, and the composition maintained a solution state and had long-term stability.
B: The composition contained acicular crystals of DBA and was inferior in long-term stability to the case of A.
C: The composition contained a white precipitate and was inferior in long-term stability to that of A.
D: The composition contained a white precipitate immediately after production, and long-term stability could not be evaluated.

[Example 9]
<< Manufacture of composition >>
Except for the fact that PVA having a saponification degree of 88% and a weight average molecular weight of 146000 to 186000 was used instead of the one having a saponification degree of 88% and a weight average molecular weight of 13000 to 23000. Produced the composition in the same manner as in Example 7.

<< Evaluation of composition >>
<Evaluation of long-term stability of composition>
Immediately after production, the composition obtained above was stored at room temperature for 30 days.
Then, the composition after storage was visually observed, and the long-term stability of the composition was evaluated according to the following criteria. The results are shown in FIG.
[Evaluation criteria]
A: The composition contained no precipitate or only a small amount of precipitate, and the composition maintained a solution state and had long-term stability.
B: The composition contained acicular crystals of DBA and was inferior in long-term stability to the case of A.
C: The composition contained a white precipitate and was inferior in long-term stability to that of A.
D: The composition was gelled and did not have long-term stability.
E: The composition contained a white precipitate immediately after production, and long-term stability could not be evaluated.

The composition having a rating of D in Example 7 had already gelled one week after the start of storage.
From the results of Examples 7 to 9, it was found that the larger the amount of DBA and PVA blended, the more likely the white precipitate was to occur in the composition.
In addition, the larger the weight average molecular weight of PVA, the more likely it was that white precipitates would occur in the composition over a wide range of the above-mentioned blending amounts of DBA and PVA. According to the Flory-Stockmayer theory, it is known that the larger the molecular weight of a polymer, the smaller the amount of the cross-linking agent causes the polymer to gel, and Examples 7 to 9 show that the polymer gels. The result of was showing the tendency.
Further, the smaller the amount of PVA is, the easier it is for the entire composition to gel. If the composition is changed when the amount of DBA and PVA is large, a part of the composition may be present. There was a phase separation that appeared to be gelled. From this, when the compounding amount of DBA and PVA was large, the ratio of cross-linking occurring inside the colloidal particles was large, whereas when the compounding amount of PVA was small, the colloidal particles were mixed. It was presumed that the ratio of cross-linking between PVA molecules increased because the size was small or colloidal particles were not generated.

In Examples 7 to 9, if the compounding amount of DBA per 1 L of the composition is 2 to 8 mmol and the compounding amount of PVA per 1 L of the composition is 0.1 to 0.25 unit mol, these formulations are used. There was a tendency for the composition to have long-term stability, regardless of the amount and regardless of the weight average molecular weight of PVA.

[Example 10]
<< Manufacture of composition >>
In the obtained composition, the blending amount of PVA was 0.1 unit mol, 0.2 unit mol, 0.3 unit mol or 0.4 unit mol instead of 0.15 unit mol per 1 L of the composition, and the blending amount of DBA was However, the same method as in Example 1 except that 20 combinations were selected so as to be 2.5 mmol, 5 mmol, 7.5 mmol, 10 mmol or 13 mmol instead of 6.7 mmol per 1 L of the composition. The desired composition was produced in the above.

Immediately after production, the composition contained a small amount of precipitate and was a suspension, but it was not gelled and was easy to handle.
Immediately after production, the composition was allowed to stand at room temperature for 1 month, but the properties of the composition did not change during this period.

<< Evaluation of composition >>
<Evaluation of membrane manufacturing suitability>
The composition obtained above was stored in the same manner as in Example 1, and the PVA-DBA reaction product was mainly used in the same manner as in Example 1 except that the composition after storage was used. An attempt was made to manufacture a film as a component.
Then, the film production suitability of the composition was evaluated according to the following criteria. The results are shown in FIG.
[Evaluation criteria]
A: The film could be manufactured.
B: The film could not be manufactured.

From FIG. 12, the value of [the amount of DBA blended per 1 L of the composition (mmol)] / [the amount of PVA blended per 1 L of the composition (unit mol)] is 0.05 mmol / unit mol or more and the composition. When the blending amount of DBA per 1 L of the product was 7.5 mmol or more, the target film could not be produced. It is presumed that this is because the rigidity of the film once formed was too high due to the increase in the number of reaction sites between PVA and DBA, and the film shrank and collapsed during drying.
In other words, in this example, the value of [the amount of DBA compounded per 1 L of the composition (mmol)] / [the amount of PVA compounded per 1 L of the composition (unit mol)] is less than 0.05 mmol / unit mol. The desired membrane could be produced if there was, or if the blending amount of DBA per 1 L of the composition was less than 7.5 mmol.

[Example 11]
<< Manufacture of composition >>
As PVA, instead of PVA having a degree of saponification of 80% and a weight average molecular weight of 9000 to 10000, a PVA having a degree of saponification of 88% and a weight average molecular weight of 13000 to 23000 was used. In the obtained composition, the amount of PVA blended was 0.05 unit mol, 0.1 unit mol, 0.15 unit mol, 0.2 unit mol or 0.25 unit mol instead of 0.15 unit mol per 1 L of the composition. Example 1 except that 30 combinations were selected so that the blending amount of DBA was 2 mmol, 4 mmol, 6 mmol, 8 mmol, 10 mmol or 12 mmol instead of 6.7 mmol per 1 L of the composition. The desired composition was produced in the same manner as in the case of.

Immediately after production, the composition contained a small amount of precipitate and was a suspension, but it was not gelled and was easy to handle.
Immediately after production, the composition was allowed to stand at room temperature for 1 month, but the properties of the composition did not change during this period.

<< Evaluation of composition >>
<Evaluation of membrane manufacturing suitability>
The composition obtained above is stored in the same manner as in Example 1, and the stored composition (480 μL) is dropped into a polystyrene petri dish having an inner diameter of 4 cm at room temperature and naturally overnight. By drying, an attempt was made to produce a membrane containing a PVA-DBA reactant as a main component.
Then, the film production suitability of the composition was evaluated according to the following criteria. The results are shown in FIG.
[Evaluation criteria]
A: The film could be manufactured.
B: The film could not be manufactured.

[Example 12]
<< Production and evaluation of composition >>
Except for the fact that PVA having a saponification degree of 88% and a weight average molecular weight of 31,000 to 50,000 was used instead of a PVA having a saponification degree of 88% and a weight average molecular weight of 13000 to 23000. Produced and evaluated the composition in the same manner as in Example 11. The results are shown in FIG.

[Example 13]
<< Manufacture of composition >>
Except for the fact that PVA having a saponification degree of 88% and a weight average molecular weight of 146000 to 186000 was used instead of a PVA having a saponification degree of 88% and a weight average molecular weight of 13000 to 23000. Produced and evaluated the composition in the same manner as in Example 11. The results are shown in FIG.

From the results of Examples 11 to 13, it was found that the smaller the weight average molecular weight of the compounded PVA, the more the membrane can be produced from the composition by selecting a wide range as the compounding amount of DBA and PVA.
In Examples 11 to 13, if the compounding amount of DBA per 1 L of the composition is 2 to 4 mmol and the compounding amount of PVA per 1 L of the composition is 0.1 to 0.25 unit mol, these formulations are used. Regardless of the amount and regardless of the weight average molecular weight of PVA, the composition tended to have the suitability for producing a film.
Further, in Examples 11 to 13, if the compounding amount of DBA per 1 L of the composition is 2 to 8 mmol and the compounding amount of PVA per 1 L of the composition is 0.15 to 0.25 unit mol, these are used. Regardless of the blending amount of PVA and the weight average molecular weight of PVA, the composition tended to have suitability for producing a film.

The present invention can be used in all fields of water-insoluble materials obtained by using polyvinyl alcohol.

Claims (6)

It ’s a composition,
The composition comprises polyvinyl alcohol, a polyfunctional compound having two or more groups capable of reacting with a hydroxyl group in one molecule, and water.
In the composition, the ratio of the blending amount of the solvent other than water to the blending amount of the water is 0.2% by mass or less. The composition according to claim 1, wherein the polyfunctional compound is an aromatic compound having two or more groups represented by the formula "-B (OH) ₂ " in one molecule. The polyfunctional compound is selected from the group consisting of 1,4-phenylenediboronic acid, 1,3-phenylenediboronic acid, 1,3,5-benzenetrisboronic acid and 2,5-thiophenediboronic acid. The composition according to claim 1, which is one kind or two or more kinds. The composition according to any one of claims 1 to 3, wherein the composition further contains a dye, a dye, a pigment, an enzyme or a catalyst. Claimed that, in the composition, the blending amount of PVA per 1 L of the composition is 0.03 to 1 unit mol, and the blending amount of the polyfunctional compound per 1 L of the composition is 1 to 16 mmol. Item 2. The composition according to any one of Items 1 to 4. It is a method for producing a composition.
The composition comprises polyvinyl alcohol, a polyfunctional compound having two or more groups capable of reacting with a hydroxyl group in one molecule, and water.
In the composition, the ratio of the blending amount of the solvent other than water to the blending amount of the water is 0.2% by mass or less.
The production method includes a step of preparing an aqueous solution of the polyfunctional compound by heating an aqueous dispersion of the polyfunctional compound.
A method for producing a composition, comprising a step of obtaining a reaction product of the polyvinyl alcohol and the polyfunctional compound by mixing the aqueous solution of polyvinyl alcohol and the aqueous solution of the polyfunctional compound.

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