JP7158002B2 - Aqueous solution of colloid, method for producing the same, and method for flame-retardant processing of base material - Google Patents

Description

TECHNICAL FIELD The present invention relates to an aqueous colloidal solution, a method for producing the same, and a method for processing a base material to make it flame-retardant. More specifically, the present invention relates to an aqueous colloidal solution, a method for producing the same, and a flame-retardant processing method for substrates such as leather, fibers, and textiles using such an aqueous colloidal solution.

A substance in which particles having a diameter of 1 nm to 10 μm as a dispersoid are stably dispersed in a solvent as a dispersion medium is called a “colloid” and has been used in various industrial fields for a long time. Its properties have been studied. Colloids in which the dispersion medium is water include molecular colloids, micellar colloids, and dispersed colloids, depending on the structure of the dispersoids, and there are many production methods for these colloids depending on the dispersoids.

For example, a molecular colloid can be produced satisfactorily using a polymer having a hydrophilic structural part in the molecule, such as having a hydrophilic group. Even a compound that does not have a hydrophilic structure such as a hydrophilic group can sometimes form a micellar colloid by using an oil. More specifically, Patent Document 1 discloses a technique for obtaining a hydrophilic colloid composition in which a photographic aid, which is a water-insoluble compound, is dispersed by using a predetermined oil-forming agent. ing. Alternatively, for hydrophobic metal oxides, as described in Patent Document 2, a metal chloride is hydrolyzed in water to obtain a precipitate, and the obtained precipitate is dispersed in an alkaline aqueous solution. In some cases, dispersed colloids can be obtained.

JP-A-58-130337 Japanese Patent Publication No. 35-006616

However, the technique described in Patent Document 1 cannot prevent the components of the oil-forming agent from remaining in the resulting micellar colloid, and such residual components may deteriorate the quality of the aqueous colloid solution. rice field. In addition, the technique described in Patent Document 2 could only be applied to limited compounds.

Accordingly, an object of the present invention, which has been made in view of such circumstances, is to provide a colloidal aqueous solution in which a water-insoluble substance is dispersed and which does not substantially contain an oily component.
A further object of the present invention is to provide a method for producing an aqueous colloidal solution, which can satisfactorily produce an aqueous colloidal solution in which a water-insoluble substance is dispersed and which does not substantially contain an oily component.
A further object of the present invention is to provide a method for imparting flame retardancy to a base material using the aqueous colloidal solution in which a flame retardant as a water-insoluble substance is dispersed.

That is, an object of the present invention is to advantageously solve the above-mentioned problems. colloidal aqueous solution in which colloidal particles comprising (B) are dispersed in an aqueous solvent, wherein the content of the colloidal particles in the colloidal aqueous solution is 0.01% by mass or more and 30% by mass or less; In addition, the content of the oily component in the water solvent of the aqueous colloidal solution is 1% by mass or less when the total mass of the colloidal particles is 100% by mass. The colloidal aqueous solution according to the present invention, which is obtained by dispersing colloidal particles in an aqueous medium, does not substantially contain an oily component, and therefore can be suitably used for various purposes. A "colloidal particle" contains both the substance (A) and the component (B) in one particle.
In addition, the melting point of the substance (A) can be measured by the method described in the Examples according to differential scanning calorimetry (DSC).
Also, that a certain substance or component is "insoluble in water" means that the solubility in water at 1 atm and 20°C is less than 1% by mass.
Further, the water-dispersible component (B) means a component whose water-dispersibility can be confirmed by the test method described in the examples of the specification.
Furthermore, "substantially free of oily components" means that the content of oily components in the water solvent of the aqueous colloidal solution is 1% by mass or less.

Moreover, in the colloidal aqueous solution according to the present invention, it is preferable that the component (B) contains at least one compound containing a hydrophilic portion and a hydrophobic portion. This is because when the component (B) contains at least one compound (b1) containing a hydrophilic portion and a hydrophobic portion, the colloidal particles are highly stable, and the stability of the aqueous colloidal solution can be further enhanced. .

Furthermore, in the colloidal aqueous solution according to the present invention, it is preferable that the colloidal particles have a volume average particle diameter D90 of 10 μm or less. This is because when the volume average particle diameter D90 of the colloidal particles is 10 μm or less, the colloidal particles are less likely to settle in the colloidal aqueous solution, and the dispersion stability of the colloidal aqueous solution can be further enhanced.
In addition, "volume average particle diameter D90" means the particle diameter at which the cumulative volume calculated from the small diameter side becomes 90% when the volume-based particle diameter distribution of the colloidal particles is obtained, and the method described in the examples. can be measured by

In the colloidal aqueous solution according to the present invention, the substance (A) may be a flame retardant. The colloidal aqueous solution of the present invention containing a flame retardant as the substance (A) can be favorably used in flame-retardant processing of substrates such as leather, fibers, and textiles.

An object of the present invention is to advantageously solve the above problems, and a method for producing a colloidal aqueous solution according to the present invention is a method for producing a colloidal aqueous solution for obtaining any of the colloidal aqueous solutions described above. A heating and mixing step of heating and mixing the substance (A) and the component (B) at a heating temperature T ₁ ° C. of 40 ° C. or higher and lower than 280 ° C. to obtain a heated mixture; , a cooling step of obtaining a cooled mixture at a cooling temperature of T ₂ ° C. or lower, which is 90 ° C. or lower and lower than the heating temperature T ₁ ° C., and stirring and mixing the cooled mixture and water to mix the substance (A) and and a hydrating step of forming colloidal particles composed of the component (B) and obtaining a colloidal aqueous solution in which the colloidal particles are dispersed in water. Through the above steps, the colloidal aqueous solution of the present invention can be produced satisfactorily.
All temperatures described in this specification are temperatures at 1 atm unless otherwise specified.

Further, in the method for producing a colloidal aqueous solution according to the present invention, the water addition step includes adding water to the cooling mixture while stirring to create an opaque mixture having a water content of 0.01% by mass or more and 50% by mass or less ( An opaque mixture forming step for obtaining C), and preparing and stirring water in an amount three times or more the amount of the opaque mixture (C), gradually adding the opaque mixture to the water to form a colloid a colloidal particle forming step of obtaining an aqueous solution. Colloidal particles can be formed more satisfactorily by carrying out the above-described two-step hydration operation in the hydration step.

Moreover, in the method for producing a colloidal aqueous solution according to the present invention, it is preferable that the opaque mixture (C) has a viscosity of 1 mPa·s or more and 10 ⁷ Pa·s or less. By setting the viscosity of the opaque mixture (C) within the above range, colloidal particles can be formed more satisfactorily.
The viscosity of the opaque mixture (C) can be measured by the method described in Examples.

Here, the object of the present invention is to advantageously solve the above problems, and the method for flame retarding a base material of the present invention uses the colloidal aqueous solution of the present invention, wherein the substance (A) is a flame retardant. and a step of applying a flame retardant treatment to the base material. Since the colloidal aqueous solution of the present invention does not substantially contain an oily component, it can effectively suppress the occurrence of undesired quality deterioration of the base material to be flame retarded.

According to the present invention, it is possible to provide a colloidal aqueous solution in which a water-insoluble substance is dispersed and which does not substantially contain an oily component.
Furthermore, according to the present invention, it is possible to provide a method for producing an aqueous colloidal solution, which can satisfactorily produce an aqueous colloidal solution in which a water-insoluble substance is dispersed and which does not substantially contain an oily component.
Furthermore, according to the present invention, it is possible to provide a method for imparting flame retardancy to a base material using the colloidal aqueous solution in which a flame retardant as a water-insoluble substance is dispersed.

Hereinafter, embodiments of the present invention will be illustrated in detail. The aqueous colloidal solution of the present invention can be efficiently produced through the method for producing an aqueous colloidal solution of the present invention (hereinafter also simply referred to as "the production method of the present invention").
Here, the colloidal aqueous solution of the present invention is a processing solution for flame-retardant processing and antistatic processing of substrates such as leather, fibers, and textiles; and a material for forming functional thin films such as magnetic thin films.

(colloid aqueous solution)
The colloidal aqueous solution of the present invention is a colloidal aqueous solution in which colloidal particles comprising a water-insoluble substance (A) having a melting point of 250° C. or less and a water-dispersible component (B) are dispersed in an aqueous solvent. The content of the colloidal particles in the colloidal aqueous solution is 0.01% by mass or more and 30% by mass or less, and the content of the oil component in the water solvent of the colloidal aqueous solution is 100% by mass of the total mass of the colloidal particles. %, it is 1% by mass or less. In other words, the colloidal aqueous solution of the present invention contains 1% by mass or less of an oily component, and does not substantially contain an oily component. Therefore, in the colloidal aqueous solution of the present invention, the quality of the colloidal aqueous solution itself deteriorates due to the oily component, the quality of the object to which the colloidal aqueous solution is applied deteriorates, and the process using the colloidal aqueous solution does not deteriorate. contamination, etc., can be effectively suppressed. As described above, the colloidal aqueous solution of the present invention can contain colloidal particles consisting of a substance (A) and a component (B) that satisfy predetermined properties, water, and optional additives that can be added depending on the application. Each component will be described in detail below.

<Colloidal particles>
The colloidal aqueous solution of the present invention contains colloidal particles consisting of substance (A) and component (B). More specifically, the colloidal aqueous solution of the present invention comprises colloidal particles dispersed in water as a solvent. The colloidal particles are not particularly limited, but have a structure in which a core portion made of the substance (A) is enclosed by a shell portion made of the component (B), or a mixture of the substance (A) and the component (B) It can take a micelle structure consisting of The colloidal particles can be stably dispersed in water by the action of component (B).

<<Material (A)>>
The substance (A) that can be contained in the colloidal aqueous solution of the present invention includes water-insoluble substances having a melting point of 250° C. or lower. The melting point of substance (A) must be 250° C. or lower, preferably 200° C. or lower, and more preferably 150° C. or lower. If the melting point of the substance (A) is equal to or lower than the above upper limit, colloidal particles can be formed satisfactorily. Moreover, the melting point of the substance (A) is not particularly limited, and can usually be 0° C. or higher.

Specifically, the substance (A) is a compound that satisfies the superior conditions and can function as a flame retardant, an antistatic agent, a water repellent, a lubricant, or the like. Among them, as flame retardants, phosphazene-based flame retardants such as SPS-100, SPB-100 and SPE-100 manufactured by Otsuka Chemical Co., Ltd., PX-200 and CR-741 manufactured by Daihachi Chemical Co., Ltd., Phosphate flame retardants such as CR-7335 and triphenyl phosphate (TPP), phosphinate metal salt flame retardants such as Exolit manufactured by Qualiant Chemicals Co., Ltd., ammonium polyphosphate flame retardants, and those manufactured by ADEKA Co., Ltd. Examples include intumescent flame retardants such as Adekastab FP-2000 series and halogen flame retardants. Examples of antistatic agents include conductive carbon materials such as carbon powder, and conductive polymers such as polyaniline, polypyrrole, and polythiophene. Commercially available conductive polymer products that can function as antistatic agents include the Belectron series manufactured by Sanyo Chemical Industries, Ltd., and the like.

<<Component (B)>>
Component (B) that can be contained in the colloidal aqueous solution of the present invention includes compositions containing at least one compound or a plurality of compounds that themselves can be dispersed in water to form a colloid. Candidate compounds or compositions are tested according to the determination method described in the section <Water dispersibility of component (B)> in Examples to determine whether they can be blended as component (B) in the present invention. can be determined. The colloidal aqueous solution of the present invention can be obtained by stably forming colloidal particles in which the component (B) includes the above-mentioned substance (A) in the aqueous medium.

Here, the colloidal aqueous solution of the present invention preferably contains compound (b1) having a hydrophilic portion and a hydrophobic portion. In addition, multiple types of compounds may be included as the compound (b1). Moreover, the compound (b1) is preferably liquid under the conditions of 23° C. and 1 atm.
Such compounds include, for example, alkylene oxide adducts of phenolic resins such as bisphenol A ethylene oxide adducts; active agents. These can be prepared by reacting hydrophobic compounds such as phenolic resins and alcohols having the above-mentioned predetermined number of carbon atoms with hydrophilic compounds such as ethylene oxide and propylene oxide. Alternatively, commercially available products such as the "Naroacty (registered trademark)" series manufactured by Sanyo Chemical Industries, Ltd. and the "Shin-Etsu Silicone" series manufactured by Shin-Etsu Chemical Co., Ltd. can be suitably used as the compound (b1).

Here, the compound (b1) preferably has an HLB value of 3 or more. The HLB value of compound (b1) is preferably 6 or more, more preferably 8 or more, and preferably 19 or less. When the HLB value is 3 or more, the stability of the colloidal dispersion can be enhanced. The HLB value can be calculated according to the Griffin method (HLB value=20×sum of formula weights of hydrophilic portions/molecular weight).

The compound (b1) preferably has a weight average molecular weight of 400 or more, preferably less than 1,000,000, more preferably less than 100,000, and less than 10,000. is more preferred, and less than 1,000 is particularly preferred. When the weight-average molecular weight of compound (b1) is within the above range, the productivity of the colloidal aqueous solution is excellent. In particular, in the production method of the present invention, which will be described later, by adopting a compound having a weight average molecular weight of 400 or more as the compound (b1), it is possible to suppress the formation of a precipitate due to crystallization in the cooling step. Colloidal particles can be efficiently formed in the process. Moreover, in the production method of the present invention, which will be described later, by adopting a compound having a weight average molecular weight of less than 1,000,000 as the compound (b1), the viscosity of the mixture obtained in the heating and mixing step is excessively increased. can be suppressed, and the mixture can be prepared with high workability.

Furthermore, compound (b1) is preferably a polydisperse compound having a polydispersity (i.e., molecular weight distribution) of 1 or more, which can be calculated according to the formula: weight average molecular weight/number average molecular weight. The polydispersity of compound (b1) is more preferably 1 or more, even more preferably 1.3 or more.

The component (B) may be a component consisting only of the compound (b1), or may further contain another compound (b2) different from the compound (b1). Such other compounds (b2) include, without particular limitation, acrylic polymers or copolymers, polyethylene terephthalate (PET) polymers or copolymers, phenolic polymers or copolymers, polystyrene polymers or copolymers, and the like. The other compound (b2) may have only the hydrophilic portion or may have only the hydrophobic portion. Also, the preferred molecular weight range of the other compound (b2) may be the same range as that of the compound (b1).

In addition, the component (B) has the absolute value of the difference between the SP (Solubility Parameter) value of the structural unit having the largest mass ratio in the entire component (B) and the SP value of the substance (A) is 2.5 or less. is preferable, and 2.0 or less is more preferable. The SP value can be calculated using J-OCTA, which is commercially available software.

In addition to the absolute value of the SP value difference described above, the criteria for selecting a suitable combination of the substance (A) and the component (B) include transparency or semi-transparency when mixed under predetermined conditions. A clear mixture is obtained. The conditions for such mixing are the same as the heating and mixing step in the production method of the present invention, which will be described later, and are heating and mixing at a heating temperature of 40° C. or more and less than 280° C. When the substance (A) and the component (B) are mixed according to the above conditions at a mass ratio (A):(B) = 1:2, the substance used when a mixture that can be determined to be transparent is obtained. It can be judged that the combination of (A) and component (B) was a suitable combination. Here, in this specification, "transparent or translucent" is measured using a spectrophotometer, and the total light transmittance is 50% or more with respect to deionized water as a reference according to the Beer-Lambert law. means that

<<Volume average particle size distribution of colloidal particles>>
The colloidal particles preferably have a volume average particle diameter D90 of 10 μm or less, more preferably 1 μm or less. When the volume-average particle diameter D90 is equal to or less than the upper limit, sedimentation of the colloidal particles in the colloidal aqueous solution can be suppressed satisfactorily. Incidentally, the volume average particle diameter D90 of the colloidal particles can usually be 0.1 μm or more.

<Content ratio of colloidal particles>
The content of colloidal particles in the colloidal aqueous solution should be 0.01% by mass or more and 30% by mass or less, preferably 0.1% by mass or more and 20% by mass, based on the total mass of the colloidal aqueous solution being 100% by mass. can be: An appropriate amount of the colloidal particles can be determined according to the application. Also, the content of colloidal particles can be adjusted by increasing or decreasing the blending amount of water as a solvent.

<Oil component ratio>
In the colloidal aqueous solution of the present invention, the content of the oil component in the water solvent should be 1% by mass or less, preferably 0.5% by mass or less, or more, based on 100% by mass of the total mass of the colloidal particles. It is preferably 0.1% by mass or less, particularly preferably 0% by mass. By producing the aqueous colloidal solution of the present invention according to the production method of the present invention, which will be described later, it is possible to make it substantially free of oily components. This is because there is no need to use an oily component when preparing colloidal particles. Here, the “oil component” is a component different from the substance (A) and the component (B) at room temperature, and has a boiling point of less than 100° C. at 1 atm and a It means a water-insoluble component that volatilizes under vacuum conditions.Oil components include various hydrocarbon oils and various ester oils that satisfy such conditions.

<Optional additives>
Optional additives that the colloidal aqueous solution of the present invention may contain include, but are not limited to, antioxidants, ultraviolet absorbers, and the like.

(Method for producing colloidal aqueous solution)
The method for producing a colloidal aqueous solution of the present invention includes a heating and mixing step of heating and mixing the substance (A) and the component (B) as described above at a heating temperature T ₁ ° C. of 40 ° C. or more and less than 280 ° C. to obtain a heated mixture. and a cooling step of obtaining a cooled mixture by setting the temperature of the heated mixture to a cooling temperature T ₂ ° C. or lower, which is 90 ° C. or lower and less than the heating temperature T ₁ ° C.; and a water adding step of forming colloidal particles composed of A) and component (B) and obtaining a colloidal aqueous solution in which the colloidal particles are dispersed in water. In the production method of the present invention, the heating and mixing step, the cooling step, and the water adding step are carried out in this order, so that the aqueous colloidal solution of the present invention can be efficiently produced. That is, the substance (A) and the component (B) are heated and mixed in the above heating and mixing step, and the water-insoluble substance (A) and the water-dispersible component (B) are uniformly mixed. mixtures can be prepared. Then, in the cooling step, the heated mixture obtained in the heating and mixing step is cooled to a temperature below a predetermined temperature, and then the water adding step is performed, so that the core portion made of the substance (A) is converted into the component (B) Colloidal particles that are encapsulated by the shell portion can be formed satisfactorily.
Each step will be described in detail below.

<Heating and mixing process>
In the heating and mixing step, the substance (A) and the component (B) are heated and mixed at a heating temperature T ₁ °C of 40°C or more and less than 280°C to obtain a heated mixture. Here, as the substance (A), the same substance as the substance described in the section (colloid aqueous solution) <<substance (A)>> can be used. Further, as the component (B), the same components as those described in the section (colloid aqueous solution) <<component (B)>> can be used. Incidentally, the component (B) may contain water in addition to the various compounds described above. The ratio of water that can be contained in component (B) added in the heating and mixing step is preferably 1% by mass or less, and 0.5% by mass or less, based on the total mass of component (B) as 100% by mass. It is more preferable to have In addition, the component (B) may not contain water. The water content in component (B) can be measured according to the Karl Fischer method as described in Examples.

The heating temperature T ₁ °C in the heating and mixing step must be 40°C or higher and lower than 280°C, preferably 60°C or higher and lower than 200°C, and more preferably 80°C or higher and lower than 150°C. When the heating temperature T ₁ °C is equal to or higher than the above lower limit, the heated mixture can be efficiently prepared. Further, when the heating temperature T ₁ °C is equal to or lower than the above upper limit value, it is possible to effectively suppress deterioration of the substance (A) and the component (B).

More specifically, when the substance (A) is a substance that is solid under conditions of 23° C. and 1 atm, and the component (B) contains a compound (b1) that is liquid under conditions of 23° C. and 1 atm In the heating and mixing step, the mixture of the substance (A) and the component (B) is heated at the heating temperature T ₁ ° C., and the substance (A) is converted into the component (B) (among them, the compound (b1)) is preferably dissolved. The heating temperature T ₁ °C may be the set temperature of a heating mechanism such as a heater used for heating in the heating and mixing step.

Then, at the same time as the heating is started, or after the substance (A) is sufficiently dissolved after heating for several minutes, stirring of the mixture is started to obtain a stirred mixture containing the substance (A) and the component (B). obtain. Such stirring is not particularly limited, and can be performed using a high-speed stirring device such as a lab mixer. Also, the stirring speed is not particularly limited, but may be 300 rpm or higher. In addition, while stirring is performed, heating may be continued, and heating may be temporarily stopped. As for the timing of ending stirring and heating, either one of stirring and heating may be completed first, and then the other may be completed, or both may be completed at the same time. The end timing can be uniquely determined by confirming that the stirred mixture has become transparent or translucent by visual observation or measurement using a spectrophotometer.

Even if the substance (A) is a liquid substance under the conditions of 23° C. and 1 atm, whether the stirred mixture has become transparent or translucent can be measured visually or using a spectrophotometer. By checking, the end timing of stirring and heating can be determined.

<Cooling process>
In the cooling step, the temperature of the heated mixture obtained in the heating and mixing step is cooled to a cooling temperature T2°C or _lower to obtain a cooled mixture. It should be noted that the cooling temperature T2° _C may be the temperature of the cooling mixture itself. The cooling temperature T2° _C must be 90°C or lower and _less than the heating temperature T1°C. The cooling temperature T2° _C is preferably 80°C or lower. If the cooling temperature T2° _C is equal to or lower than the above upper limit, colloidal particles can be efficiently formed in the subsequent water adding step. The cooling in the cooling step is not particularly limited, and can be performed by allowing the heated mixture obtained in the above step to stand at room temperature.

<Hydrating process>
In the hydration step, the cooled mixture and water are stirred and mixed to form colloidal particles composed of the substance (A) and the component (B), and a colloidal aqueous solution is obtained in which the colloidal particles are dispersed in a water solvent. The temperature of the water that can be mixed with the cooling mixture in the adding step is preferably 90°C or lower, more preferably 80°C or lower, and even more preferably lower than 70°C. If the temperature of the water that can be mixed with the cooled mixture in the adding step is equal to or lower than the above upper limit, precipitation of the substance (A) in the aqueous colloidal solution can be suppressed satisfactorily. Furthermore, the temperature of the water that can be mixed with the cooling mixture in the adding step is preferably lower than the temperature of the cooling mixture. Moreover, it is preferable that the absolute value of the difference between the temperature of the water that can be mixed with the cooling mixture in the adding step and the temperature of the cooling mixture is 10° C. or more.

Here, in the hydration step, the operation of mixing the cooled mixture and water may be performed in one step, or may be performed in two steps as described later. Whether the hydration step is performed in one step or in two steps can be appropriately selected based on the content of water in component (B). More specifically, when the content of water in component (B) is 0.01% by mass or more, the adding step may be performed in one step or in two steps. Therefore, from the viewpoint of reducing the number of steps and increasing the production efficiency, the adding step can be performed in one step. Alternatively, when the uniformity of the colloidal particles to be obtained is more important than the reduction in the number of steps, even when the water content in the component (B) is 0.01% by mass or more, the water addition step should be carried out in two stages. can be done. Moreover, when the content of water in the component (B) is less than 0.01% by mass, it is preferable to carry out the hydration step in two stages from the viewpoint of facilitating the formation of colloidal particles.

First, when the hydration step is performed in one step, water of 500% by volume or more is prepared when the total amount of the cooling mixture is 100% by volume, and the cooling mixture is stirred while the water is stirred. is slowly added. The stirring speed is not particularly limited, but may be, for example, 300 rpm or higher. Moreover, the addition time of the cooling mixture is not particularly limited, and may be 1 minute or more and 300 minutes or less.

Moreover, when the hydration step is performed in a two-step operation, an opaque mixture forming step and a colloidal particle forming step can be carried out. First, in the opaque mixture forming step, the cooled mixture is stirred while adding water to obtain an opaque mixture (C). Here, the water content in the opaque mixture (C) should be 0.01% by mass or more and 50% by mass or less. If the water content is 0.01% by mass or more, the colloidal aqueous solution obtained in the subsequent colloidal particle forming step can be homogenized. Moreover, if the water content is 50% by mass or less, it is possible to satisfactorily suppress the precipitation of the substance (A) in the water solvent in the subsequent colloidal particle forming step. The water content is preferably 0.1% by mass or more from the viewpoint of further improving the uniformity of the colloidal aqueous solution, and 5% by mass from the viewpoint of shortening the stirring time in the colloidal particle forming step and improving production efficiency. % or more is more preferable. Further, the water content is more preferably 30% by mass or less from the viewpoint of further improving the stability of the colloidal aqueous solution, and is 20% by mass or less from the viewpoint of easily determining the uniformity of the colloidal aqueous solution. It is even more preferable to have The stirring speed in the opaque mixture forming step is not particularly limited, but may be, for example, 300 rpm or higher. Moreover, the addition time of water is not particularly limited, and may be 30 seconds or more and 60 minutes or less.

Here, the viscosity of the opaque mixture (C) is preferably 1 mPa·s or more, more preferably 10 mPa·s or more, preferably 10 ⁷ Pa·s or less, and more preferably 10 ⁵ Pa·s or less. preferable. When the viscosity of the opaque mixture is 10 ⁴ mPa·s or less, it means the viscosity at a rotation speed of 100 rpm, and when it exceeds 10 ⁴ mPa·s, it means the viscosity at a rotation speed of 1 rpm. This is because colloidal particles can be formed more satisfactorily by setting the viscosity of the opaque mixture (C) within the above range. The viscosity of the opaque mixture can be adjusted within a desired range by increasing or decreasing the amount of water added in the opaque mixture forming step.

Then, in the colloidal particle forming step, water in an amount three times or more the amount (by volume) of the opaque mixture (C) is prepared and stirred, and the opaque mixture (C) is gradually added to the water. A colloidal aqueous solution is obtained in which colloidal particles formed from the opaque mixture (C) are dispersed in a water solvent. The colloidal aqueous solution obtained through such steps is a micellar colloidal aqueous solution.
Here, from the viewpoint of better balancing both the stability of the resulting colloidal aqueous solution and the production efficiency, the amount of water prepared in the colloidal particle formation step should be at least 7 times the amount of the opaque mixture (C). is preferred. The stirring speed in the colloidal particle forming step is not particularly limited, but may be, for example, 300 rpm or higher. Also, the addition time of the opaque mixture is not particularly limited and may be 1 minute or more and 100 minutes or less.

Prior to adding the opaque mixture (C) to water in the colloidal particle forming step, desired additive components may optionally be added to water. That is, in the colloidal particle forming step, water, the additive component added to the water, and the opaque mixture (C) may coexist. As the additive component, for example, an acrylic acid ester monomer unit and/or a methacrylic acid ester monomer unit as a main component (more than 50% by mass with respect to 100% by mass of the total monomer units constituting the polymer) and acrylic polymers and copolymers.

In addition, the method of the present invention may include a step of adding an optional additive after the colloidal particle forming step.

(Method for making substrate flame-retardant)
The method for imparting flame retardancy to a substrate of the present invention is characterized by including the step of subjecting a substrate to a flame retardant treatment using the colloidal aqueous solution of the present invention (containing a flame retardant as the substance (A)). . Since the aqueous colloidal solution of the present invention is used in the method for imparting flame retardancy to a base material of the present invention, the base material to be subjected to flame retardant processing is less likely to suffer from undesired quality deterioration attributable to oily components. More specifically, for example, when leather is used as the base material, the presence of oily components may cause uneven dyeing. It may be possible to suppress uneven dyeing.

<Flame retardant treatment process>
The flame retardant treatment step for flame retarding substrates such as leather, fibers, and textiles is not particularly limited as long as the colloidal aqueous solution of the present invention containing a flame retardant is used as the substance (A). It can be implemented by any known method. For example, when the substrate is leather or fabric, the leather can be flame retarded by adding an aqueous colloid solution along with water in a process that can be commonly referred to as the tanning process. More specifically, the leather/fabric, colloidal aqueous solution and optional water are added to the drum, then the drum is rotated for several hours, then the water is drained from the drum, and the drum is The leather/fabric can be flame retarded by the operation of washing the leather/fabric by pouring water into it. When the base material is leather, the leather, colloidal aqueous solution and optional water are added to the drum, and after rotating the drum for several hours, an acid (pH 4 or less) is added. The water may be drained after rotating the drum for several minutes to several hours.

In addition, for example, it is also possible to apply a flame retardant treatment to the substrate as described above by using a colloidal aqueous solution by a coating method such as an ink jet method, without depending on the method as described above.

EXAMPLES The present invention will be specifically described below based on examples, but the present invention is not limited to these examples. In the following description, "%" and "parts" representing amounts are based on mass unless otherwise specified.
In addition, in a polymer produced by copolymerizing a plurality of types of monomers, the proportion of monomer units formed by polymerizing a certain monomer in the polymer is usually , coincides with the ratio (feed ratio) of the certain monomer to all the monomers used for the polymerization of the polymer.
In the examples, the melting point of the substance (A), the solubility of the substance (A) in water, the HLB value of the compound (b1), the water content of the component (B), the water dispersibility of the component (B), the opaque mixture The viscosity, the content of the oil component in the water solvent, the volume average particle size D90 of the colloidal particles, the weight average molecular weight, and the SP value were each measured as follows.

<Melting point of substance (A)>
Using a differential thermal analysis measuring device (DSC-60 manufactured by Shimadzu Corporation), alumina was used as a reference substance and measured. The temperature at which the endothermic curve of the endothermic curve indicated by the melting point of the substance (A) is maximum was defined as the melting point. When two or more maximum temperatures were observed, the highest temperature was adopted as the melting point of substance (A).
<Solubility of substance (A) in water>
The solubility in water (% by mass) was measured at 1 atm and 20°C.

<HLB value of compound (b1)>
Calculated according to Griffin's method (HLB value = 20 x sum of formula weights of hydrophilic moieties/molecular weight).
<Water content ratio of component (B)>
Measured according to JIS K 0068-2001 using a Karl Fischer moisture analyzer (manufactured by Mitsubishi Chemical Analytech, CA-310).
<Water dispersibility of component (B)>
0.5 g of each component (B) used in the examples was dispersed in 100 g of water at room temperature and heated to 80° C. with high speed stirring at 800 rpm. After performing high-speed stirring at 80° C. for 1 hour, the mixture was cooled to room temperature while performing high-speed stirring, and then allowed to stand still for 1 hour. The aqueous solution after standing was visually observed, and if no precipitate was observed, it was determined that the component (B) had water dispersibility.

<Viscosity of opaque mixture>
The opaque mixtures obtained in Examples were measured at 23° C. with a Brookfield viscometer (rotation speed: 100 rpm).

<Content ratio of oily component in water solvent>
The aqueous colloidal solution prepared in Examples was filtered to separate the colloid from the aqueous solvent, and the aqueous solvent was analyzed by gas chromatography (GCMS-TQ8050 manufactured by Shimadzu Corporation) to measure the content of oily components. .

<Volume average particle diameter D90 of colloidal particles>
The volume-average particle diameter D90 of the colloidal particles is measured using the colloidal aqueous solution prepared in the Examples and using a laser diffraction particle size distribution analyzer (manufactured by Shimadzu Corporation, "SALD-2300") in accordance with JIS Z8825. It was measured. In the obtained volume-based particle size distribution, the particle size at which the cumulative volume calculated from the small size side becomes 90% was determined as the volume average particle size D90 of the colloidal particles.

<Weight average molecular weight>
The weight average molecular weight (Mw) of compound (b1) blended in Examples was measured using gel permeation chromatography.
Specifically, using a gel permeation chromatograph (manufactured by Shimadzu Corporation, LC-20), using water as a developing solvent, the weight average molecular weight (Mw) of compound (b1) was determined as a standard polystyrene conversion value.
<SP value>
The SP value of the substance (A) and the SP value of the structural unit having the largest mass ratio in the entire component (B) were calculated using J-OCTA.

(Example 1)
<Preparation of compound (b1-1)>
228 parts (1 mol) of bisphenol A as a phenolic resin and 24.2 parts (0.04 mol) of "Kyoward 500" as an ion scavenger were charged into a stainless steel autoclave equipped with stirring and temperature control functions. , under reduced pressure (1 to 5 mmHg), at 160° C. for 3 hours. Then, 110 parts (2.5 mol) of ethylene oxide (EO) was introduced at 180° C. to a gauge pressure of 1 to 3 kgf/cm ² . The time required for the addition polymerization reaction of EO was 3.5 hours. The weight-average molecular weight and water content of the obtained compound (b1-1), ie, the bisphenol A ethylene oxide adduct, were measured in the same manner as described above. Table 1 shows the results. Further, the SP value of the bisphenol A-derived structural unit of compound (b1-1), which is the structural unit having the largest mass ratio in the entire component (B), was calculated by OCTA. Table 1 shows the results.
<Production of Colloidal Aqueous Solution>
<< Heating and mixing process >>
Phosphazene-based flame retardant (manufactured by Otsuka Chemical Co., Ltd., SPB-100) as the substance (A) (abbreviated as "PZ" in Table 1, the same applies to the following examples. SP value calculated by OCTA: 19.5 ( MPa) ^1/2 ) and 100 parts of the compound (b1-1) obtained above, which constitutes the component (B), were dispensed into a 500 ml stainless steel beaker and heated to 100°C. heated with When the mixture was left at 100° C. for 3 minutes, the substance (A) dissolved in the component (B), so the mixture was stirred for 10 minutes (800 rpm) with a laboratory mixer. After the stirring was over, the beaker was heated again with the heater, and the entire contents became transparent in about 1 minute, and a transparent heated mixture was obtained.
<<Cooling process>>
The heating of the beaker by the heater was stopped, and the beaker was allowed to stand at room temperature to cool. The heated mixture was allowed to stand until the temperature reached 70° C. to obtain a cooled mixture.
<<Hydration process>>
3000 ml of water (temperature: 30° C.) was put into the mixer and high speed stirring (400 rpm) was started. 200 ml of the cooled mixture obtained in the above cooling step was added dropwise from a stainless steel beaker over 10 minutes. That is, the hydration step in this example was performed in one step. The water mixed in the hydration step was 15 times the volume of the cooling mixture.
Using the obtained colloidal aqueous solution, the amount of oil component in the aqueous medium (reference: total amount of colloidal particles) and the volume average particle diameter D90 of the colloidal particles were measured according to the above. Table 1 shows the results.

(Example 2)
<Preparation of compound (b1-3)>
As the compound (b1-3), "Naroacty (registered trademark) CL-70" manufactured by Sanyo Kasei Co., Ltd. was prepared. Various measurements similar to those in Example 1 were performed on the compound (b1-3). Table 1 shows the results.
<Production of Colloidal Aqueous Solution>
<< Heating and mixing process ~ Cooling process >>
In the heating and mixing step, 50 parts of SPB-100 as the substance (A) and 100 parts of the compound (b1-3) prepared above, which constitutes the component (B), were charged in a 500 ml stainless steel beaker. Except for this, the cooling process was carried out in the same manner as in Example 1.
<<Hydration process>>
- Opaque mixture formation process -
The cooled mixture cooled to 70° C. in the above cooling step was stirred at high speed (800 rpm) with a lab mixer, and 50 ml of water (temperature: 30° C.) was added dropwise over 1 minute. After dropping, the mixture was cooled to room temperature while stirring was continued for 30 minutes to obtain an opaque mixture that was opaque and milky white.
- Colloidal particle formation process -
2000 ml of water (temperature: 30° C.) was added to the mixer and high speed stirring (800 rpm) was started. Here, 200 ml of the opaque mixture obtained in the above step was dropped from a stainless steel beaker over 10 minutes.
Various measurements similar to those in Example 1 were performed on the obtained colloidal aqueous solution. Table 1 shows the results.

(Example 3)
<Preparation of Component (B1) as Component (B)>
As the compound (b1-4), "Naroacty (registered trademark) CL-40" manufactured by Sanyo Kasei Co., Ltd. was prepared. Various measurements similar to those in Example 1 were performed on compound (b1-4). Table 1 shows the results. Then, 100 parts of the prepared compound (b1-4) and an acrylic polymer as the compound (b2) (manufactured by Soken Kagaku Co., Ltd., Actflow (registered trademark) UMM1001 (weight average molecular weight: 1000) 30 parts (room temperature, 1 atm and liquid) were stirred with a high-speed stirrer (800 rpm) to obtain a composition as component (B1).The moisture content of this composition was measured in the same manner as in Example 1. The results are shown in Table 1. shown in
<Production of Colloidal Aqueous Solution>
<< Heating and mixing process >>
50 parts of SPB-100 as the substance (A) and 130 parts of the component (B1) obtained above were placed in a 500 ml stainless beaker and heated with a heater set at 100°C. When left at 100° C. for 5 minutes, the substance (A) dissolved in the component (B1), so the mixture was stirred for 10 minutes (800 rpm) with a high-speed laboratory mixer. After the stirring was over, the beaker was heated again with the heater, and in about 1 minute, a translucent heated mixture was obtained in which the bottom of the stainless steel beaker was barely visible.
<<Cooling process>>
The heating of the beaker by the heater was stopped, and the beaker was allowed to stand at room temperature to cool. The heated mixture was allowed to stand until the temperature reached 70° C. to obtain a cooled mixture.
<<Hydration process>>
- Opaque mixture formation process -
The cooled mixture cooled to 70° C. in the above cooling step was stirred at high speed (800 rpm) with a lab mixer, and 20 ml of water (temperature: 30° C.) was added dropwise over 1 minute. After dropping, the mixture was cooled to room temperature while stirring was continued for 45 minutes to obtain an opaque mixture that was opaque and milky.
- Colloidal particle formation process -
2000 ml of water (temperature: 30° C.) was put into the mixer and high speed stirring (400 rpm) was started. Here, 200 ml of the opaque mixture obtained in the above step was dropped from a stainless steel beaker over 10 minutes.
Various measurements similar to those in Example 1 were performed on the obtained colloidal aqueous solution. Table 1 shows the results.

(Example 4)
<Preparation of Component (B2) as Component (B)>
130 parts of the same component (B1) as in Example 3 was placed in a 500 ml stainless steel beaker, and 10 parts of PET polymer was added thereto and heated to 100°C. The contents of the stainless steel beaker were stirred at high speed (800 rpm) with a laboratory mixer to make the entire contents into a uniform milky white liquid.
<< Heating and mixing process >>
30 parts of SPB-100 was added to the heated component (B2) obtained in the above step, and the mixture was stirred at high speed (800 rpm) for 10 minutes with a lab mixer. After the stirring was over, the beaker was heated again with the heater, and the entire content became translucent in about 5 minutes, and a translucent heated mixture was obtained.
<<Cooling process>>
The heating of the beaker by the heater was stopped, and the beaker was allowed to stand at room temperature to cool. The heated mixture was allowed to stand until the temperature reached 80° C. to obtain a cooled mixture.
<<Hydration process>>
- Opaque mixture formation process -
The cooled mixture cooled to 80° C. in the above cooling step was stirred at high speed (800 rpm) with a lab mixer, and 40 ml of water (temperature: 30° C.) was added dropwise over 1 minute. After dropping, the mixture was cooled to room temperature while stirring was continued for 30 minutes to obtain an opaque mixture that was opaque and milky white.
- Colloidal particle formation process -
3000 ml of water (temperature: 30° C.) was put into the mixer and high speed stirring (400 rpm) was started. 210 ml of the opaque mixture obtained in the above step was dropped from a stainless steel beaker over 10 minutes.
Various measurements similar to those in Example 1 were performed on the obtained colloidal aqueous solution. Table 1 shows the results.

(Example 5)
<Preparation of compound (b1-2)>
In place of bisphenol A, except for using 186 parts (1 mol) of 1-dodecanol, the same operation as in the preparation of compound (b1-1) in Example 1 was performed to obtain compound (b1-2). A dodecanol ethylene oxide adduct was obtained. Various measurements similar to those in Example 1 were performed on the compound (b1-2). Table 1 shows the results. In measuring the SP value of the component (B) according to the above method, the dodecanol-derived structural unit of the compound (b1-2) was used.
<Production of Colloidal Aqueous Solution>
<< Heating and mixing process >>
50 parts of SPB-100 as the substance (A) and 100 parts of the compound (b1-2) obtained above as the component (B) were placed in a 500 ml stainless steel beaker and heated to 100 ° C. Heated with the heater set. When left at 100° C. for 5 minutes, substance (A) dissolved in component (B), so the mixture was stirred for 10 minutes with a high-speed lab mixer (800 rpm). After the stirring was over, the beaker was heated again with the heater, and in about 1 minute, a translucent heated mixture was obtained in which the bottom of the stainless steel beaker was barely visible.
<<Cooling process>>
The heating of the beaker by the heater was stopped, and the beaker was allowed to stand at room temperature to cool. The heated mixture was allowed to stand until the temperature reached 70° C. to obtain a cooled mixture.
<<Hydration process>>
- Opaque mixture formation process -
The cooled mixture cooled to 70° C. in the above cooling step was stirred at high speed (800 rpm) with a lab mixer, and 100 ml of water (temperature: 30° C.) was added dropwise over 10 minutes. After the dropwise addition, the mixture was cooled to room temperature while stirring was continued for 5 minutes to obtain an opaque milky white opaque mixture.
- Colloidal particle formation process -
2000 ml of water (temperature: 30° C.) was put into the mixer and high speed stirring (400 rpm) was started. Here, 250 ml of the opaque mixture obtained in the above step was dropped from a stainless steel beaker over 10 minutes.
Various measurements similar to those in Example 1 were performed on the obtained colloidal aqueous solution. Table 1 shows the results.

(Example 6)
In this example, the colloidal aqueous solution obtained in Example 1 was used to give flame retardant treatment to leather (cowhide) as a base material. Specific operations were as follows.
400 g of cowhide was cut out and placed in a drum tank. 2000 ml of the aqueous colloidal solution obtained in Example 1 and 7000 ml of tap water were further added to the same drum, and the drum was rotated at 20 rpm for 3 hours. After 3 hours, 100 ml of an aqueous formic acid solution having a concentration of 20% was added to the drum, and the drum was further rotated under the same conditions as above for 30 minutes. Then, the cowhide was removed from the drum and the drum was washed. Again, 10,000 ml of tap water was put into the drum, the cowhide was put into the drum, and the drum was rotated for 30 minutes under the same conditions as described above. This washing operation was repeated twice, and the obtained flame retardant treated cowhide was dried in the shade for 2 days to obtain a dry cowhide. When dry cowhide was ignited with a lighter, it carbonized immediately after ignition. It was confirmed that the dried cowhide obtained in this way acquired self-extinguishing properties through the above flame retardant treatment.

(Example 7)
In this example, the colloidal aqueous solution obtained in Example 4 was used to give a flame retardant treatment to a polyester woven fabric as a base material. Specific operations were as follows.
A flame-retardant-treated polyester woven fabric was obtained in the same manner as in Example 6, except that a polyester woven fabric was used as the base material, no aqueous formic acid solution was added, and the washing operation was performed once. Then, the obtained flame-retardant-treated polyester woven fabric was dried in the sun for one day to obtain a dry polyester woven fabric. When the dry polyester woven fabric was ignited with a lighter, it carbonized immediately after the ignition. It was confirmed that the dry polyester woven fabric thus obtained acquired self-extinguishing properties through the flame retardant treatment.

(Example 8)
In this example, the colloidal aqueous solution according to the present invention was used to give a flame retardant treatment to a polyester woven fabric as a base material according to the inkjet method. Specific operations were as follows.
<Preparation of Colloidal Aqueous Solution>
<< Heating and mixing process >>
50 parts of SPB-100 as the substance (A) and 100 parts of the compound (b1-3) obtained in the same manner as in Example 2 as the component (B) were placed in a 500 ml stainless steel beaker. , with a heater set at 100°C. When left at 100° C. for 5 minutes, the substance (A) dissolved in the component (B), so the mixture was stirred with a laboratory mixer (800 rpm) for 10 minutes. After the stirring was over, the beaker was heated again with the heater, and the entire contents became transparent in about 1 minute, and a transparent heated mixture was obtained.
<<Cooling process>>
The heating of the beaker by the heater was stopped, and the beaker was allowed to stand at room temperature to cool. The heated mixture was allowed to stand until the temperature reached 70° C. to obtain a cooled mixture.
<<Hydration process>>
- Opaque mixture formation process -
The mixture obtained in the above step was stirred at high speed (400 rpm) with a lab mixer, and 140 ml of water (temperature: 30° C.) was added dropwise over 10 minutes to obtain an opaque milky white opaque mixture.
- Colloidal particle formation process -
2000 ml of an acrylic polymer-containing aqueous solution with a water content of 60% (acrylic polymer: manufactured by Aica Kogyo Co., Ltd., Ultrasol (registered trademark) for textile printing) was placed in a stainless steel beaker, and high-speed stirring (400 rpm) was started. Here, 290 ml of the opaque mixture obtained in the above step was dropped over 1 hour.
Various measurements similar to those in Example 1 were performed on the obtained colloidal aqueous solution. Table 1 shows the results.
<Flame-retardant process>
The colloidal aqueous solution obtained as described above was placed in an ink bottle of an inkjet printer (Nassenger V, manufactured by Konica Minolta), and the colloidal aqueous solution was printed on the surface (one side) of the polyester woven fabric for coating. The coated polyester woven fabric was dried with a dryer at the outlet of the inkjet printer.
When the obtained flame-retardant-treated polyester fabric was ignited with a lighter, it melted immediately after the ignition. It was confirmed that the dry polyester woven fabric thus obtained acquired self-extinguishing properties through the flame retardant treatment.

According to the present invention, it is possible to provide a colloidal aqueous solution in which a water-insoluble substance is dispersed and which does not substantially contain an oily component.
Furthermore, according to the present invention, it is possible to provide a method for producing an aqueous colloidal solution, which can satisfactorily produce an aqueous colloidal solution in which a water-insoluble substance is dispersed and which does not substantially contain an oily component.
Furthermore, according to the present invention, it is possible to provide a method for imparting flame retardancy to a base material using the colloidal aqueous solution in which a flame retardant as a water-insoluble substance is dispersed.

Claims (6)

A method for producing a colloidal aqueous solution, comprising dispersing colloidal particles comprising a water-insoluble substance (A) having a melting point of 250° C. or less and a water-dispersible component (B) in an aqueous solvent,
The colloidal aqueous solution is
The content of the colloidal particles in the colloidal aqueous solution is 0.01% by mass or more and 30% by mass or less, and
The content of the oily component in the water solvent of the aqueous colloidal solution is 1% by mass or less, with the total mass of the colloidal particles being 100% by mass,
In producing the colloidal aqueous solution,
a heating and mixing step of heating and mixing the substance (A) and the component (B) at a heating temperature T ₁ ° C. of 40° C. or more and less than 280° C. to obtain a heated mixture;
a cooling step of obtaining a cooled mixture by setting the temperature of the heated mixture to a cooling temperature T ₂ ° C. or lower, which is 90 ° C. or lower and lower than the heating temperature T ₁ ° C.;
a water addition step of forming colloidal particles comprising the substance (A) and the component (B) by stirring and mixing the cooled mixture and water, and obtaining a colloidal aqueous solution in which the colloidal particles are dispersed in water;
including
The hydration step is
An opaque mixture forming step of adding water to the cooled mixture while stirring to obtain an opaque mixture (C) having a water content of 0.01% by mass or more and 50% by mass or less;
a colloidal particle-forming step of preparing water in an amount three times or more the amount of the opaque mixture (C) and stirring, while gradually adding the opaque mixture to the water to obtain a colloidal aqueous solution;
A method for producing a colloidal aqueous solution , comprising : The method for producing an aqueous colloidal solution according to claim 1 , wherein the opaque mixture (C) has a viscosity of 1 mPa·s or more and 10 ⁷ Pa·s or less. 3. The method for producing an aqueous colloidal solution according to claim 1 or 2 , wherein said component (B) contains at least one compound (b1) containing a hydrophilic portion and a hydrophobic portion. The method for producing a colloidal aqueous solution according to any one of claims 1 to 3 , wherein the colloidal particles have a volume average particle diameter D90 of 10 µm or less. 5. The method for producing an aqueous colloidal solution according to any one of claims 1 to 4 , wherein said substance (A) is a flame retardant. Using the colloidal aqueous solution produced according to the method for producing a colloidal aqueous solution according to claim 5 , the step of flame-retarding the base material,
Base material flame retardant processing method.