JP2009209354A - Manufacturing method for inorganic composite water dispersion type resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method for an inorganic composite water dispersion type resin capable of being used as a practical material having excellent characteristic and suppressing generation of a coagulation body by carrying a surface of the water dispersion type resin with a laminar clay mineral. <P>SOLUTION: The hydrophilic laminar clay mineral is dispersed in water to prepare a water dispersion liquid of the laminar clay mineral. The water dispersion liquid, an ethylenic unsaturated monomer and a surfactant are formulated such that a formulation ratio of the laminar clay mineral becomes 4-200 pts.wt. based on 100 pts.wt. of the ethylenic unsaturated monomer, and the ethylenic unsaturated monomer is emulsified to prepare a monomer emulsion. The ethylenic unsaturated monomer in the monomer emulsion is polymerized. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for producing an inorganic composite water-dispersed resin, and more particularly to a method for producing an inorganic composite water-dispersed resin in which a layered clay mineral is composited.

It is widely known that water-dispersed resins are used in various industrial products. In recent years, mechanical properties of industrial products have been improved by adding various treatment agents to such water-dispersed resins.
For example, it has been proposed to blend montmorillonite clay with water to make a slurry, and then dissolve dodecyltrimethylammonium bromide as a swelling agent (hydrophobizing agent) to obtain a clay slurry. Then, a method for producing a polymer latex by adding a monomer solution containing isoprene and styrene to the obtained clay slurry, and then stirring (emulsifying) and heating (polymerizing) it has been proposed ( For example, see Patent Document 1.)

Special table 2001-518122 gazette

However, in the method for producing a polymer latex proposed in Patent Document 1, montmorillonite clay is hydrophobized and agglomerated with each other by blending dodecyltrimethylammonium bromide in the clay slurry. Therefore, when a monomer solution is added to the clay slurry, the monomer solution enters between the agglomerated montmorillonite clay.
When the monomer solution in the clay slurry is polymerized, the polymer latex partially encloses the montmorillonite clay.

For this reason, agglomerated aggregates of the composite are generated, which may be settled or a film cannot be formed. Industrial products obtained from polymer latex have the disadvantage that their mechanical properties are not sufficiently improved.
An object of the present invention is to provide an inorganic composite that can be used as a practical material having excellent properties and suppressing the generation of aggregates by supporting a layered clay mineral on the surface of a water-dispersed resin. The object is to provide a method for producing a water-dispersed resin.

  In order to achieve the above object, the method for producing an inorganic composite water-dispersed resin of the present invention comprises a step of dispersing a hydrophilic layered clay mineral in water to prepare an aqueous dispersion of the layered clay mineral; The aqueous dispersion and the ethylenically unsaturated monomer are blended so that the blending ratio of the layered clay mineral is 4 to 200 parts by weight with respect to 100 parts by weight of the ethylenically unsaturated monomer, and the ethylenic A step of emulsifying an unsaturated monomer to prepare a monomer emulsion, a step of blending a surfactant with at least one of the water, the aqueous dispersion, the ethylenically unsaturated monomer, and the monomer emulsion; and the monomer emulsion. And a step of polymerizing the ethylenically unsaturated monomer therein.

Moreover, it is preferable that the method for producing an inorganic composite water-dispersed resin of the present invention further includes a step of blending a hydrophobic compound into at least one of the ethylenically unsaturated monomer and the monomer emulsion.
Moreover, in the manufacturing method of the inorganic composite water dispersion type resin of this invention, it is suitable that the maximum length of each layer in the said layered clay mineral is 1-1000 nm.

  In the method for producing an inorganic composite water-dispersed resin of the present invention, in the step of preparing the monomer emulsion, a bulk, needle-like or plate-like hydrophobic inorganic compound is previously dispersed in the ethylenically unsaturated monomer. It is preferable to prepare a monomer dispersion of the hydrophobic inorganic compound, mix the monomer dispersion and the water dispersion, and emulsify the ethylenically unsaturated monomer.

In the method for producing an inorganic composite water-dispersed resin of the present invention, the blending ratio of the hydrophobic inorganic compound is 0.1 to 15 parts by weight with respect to 100 parts by weight of the ethylenically unsaturated monomer. Is preferred.
In the method for producing an inorganic composite water-dispersed resin of the present invention, it is preferable that the maximum length of the hydrophobic inorganic compound is 1 to 200 nm.

  Further, in the method for producing an inorganic composite water-dispersed resin of the present invention, in the step of preparing the monomer emulsion, the ethylenically unsaturated monomer is measured based on the volume of oil droplets measured by a laser diffraction particle size distribution analyzer. It is preferable to emulsify so that the median diameter thereof is 4 μm or less.

In the method for producing an inorganic composite water-dispersed resin of the present invention, a hydrophilic layered clay mineral is dispersed in water to prepare an aqueous dispersion of the hydrophilic layered clay mineral. A monomer emulsion is prepared by blending with a monomer, and an ethylenically unsaturated monomer is polymerized.
Therefore, the obtained water-dispersed resin can be composited with a layered clay mineral so that the layered clay mineral is unevenly distributed on the surface thereof.

  As a result, various industrial products in which the water-dispersed resin is used are excellent in various properties such as the generation of aggregates is suppressed and the liquid stability is good.

Sectional drawing of an example of the adhesive film using the inorganic composite water dispersion type resin obtained by the manufacturing method of the inorganic composite water dispersion type resin of this invention is shown. The image processing figure of the TEM photograph of the inorganic composite water dispersion type resin of Example 1 is shown. The image processing figure of the TEM photograph of the inorganic composite water dispersion type resin of Example 2 is shown. The image processing figure of the TEM photograph of the inorganic composite water dispersion type resin of Example 4 is shown. The image processing figure of the TEM photograph of the inorganic composite water dispersion type resin of Example 8 is shown. The image processing figure of the TEM photograph of the inorganic composite water dispersion type resin of Example 9 is shown. The image processing figure of the TEM photograph of the inorganic composite water dispersion type resin of Example 10 is shown. The image processing figure of the TEM photograph of the inorganic composite water dispersion type resin of Example 12 is shown. The image processing figure of the TEM photograph of the inorganic composite water dispersion type resin of the comparative example 7 is shown. The image processing figure of the TEM photograph of the inorganic composite water dispersion type resin of the comparative example 8 is shown. The image processing figure of the TEM photograph of the inorganic composite water dispersion type resin of the comparative example 9 is shown. The image processing figure of the TEM photograph of the inorganic composite water dispersion type resin of the comparative example 10 is shown.

  The method for producing an inorganic composite water-dispersed resin of the present invention comprises a step of dispersing a hydrophilic layered clay mineral in water to prepare an aqueous dispersion of the layered clay mineral (an aqueous dispersion preparing step), and an aqueous dispersion. And an ethylenically unsaturated monomer, emulsifying the ethylenically unsaturated monomer to prepare a monomer emulsion (monomer emulsion preparation step), water, aqueous dispersion, ethylenically unsaturated monomer and monomer emulsion A step of blending at least one of the surfactants (surfactant blending step) and a step of polymerizing the ethylenically unsaturated monomer in the monomer emulsion (polymerization step) are provided.

As a hydrophilic layered clay mineral, for example, a phyllosilicate mineral in which a plurality of layers extending in two dimensions is laminated, for example, smectite can be mentioned.
Smectite is a montmorillonite group mineral, for example, montmorillonite (montmorillonite), magnesia montmorillonite, tetsu montmorillonite, tectum magnesia montmorillonite, beidellite, aluminian beidelite, nontronite, aluminian non Examples include tronite, saponite (saponite), aluminian sapphire, hectorite, soconite, stevensite, and bentonite.

Examples of the layered clay mineral include vermiculite (vermiculite), halloysite, swellable mica, and graphite.
These layered clay minerals can be used alone or in combination of two or more.
As such a layered clay mineral, a general commercial product can be used. For example, more specifically, as a natural product, for example, Kunipia series (montmorillonite, manufactured by Kunimine Kogyo Co., Ltd.), Bengel series (bentonite, hojune) And somasif ME series (swellable mica, manufactured by Corp Chemical Co., Ltd.). As synthetic products, for example, smecton (saponite, manufactured by Kunimine Kogyo Co., Ltd.), Lucentite SWN series (produced by Hectorite, Corp Chemical Co., Ltd.) ), Laponite (hectorite, manufactured by Rockwood Holdings). Preferably, since the synthetic product generally has a maximum length smaller than that of the natural product, the synthetic product is mentioned from the viewpoint of obtaining small oil droplets.

As for the size of the layered clay mineral, the thickness of each layer is, for example, 0.5 to 2 nm, specifically about 1 nm, and the length (maximum length) of each layer is, for example, 1 to 1000 nm, preferably It is 20 to 800 nm, more preferably 30 to 700 nm. If it is larger than the above range, oil droplets with the desired particle size may not be obtained.
Examples of the ethylenically unsaturated monomer include (meth) acrylic acid alkyl ester.

  The (meth) acrylic acid alkyl ester is, for example, a (meth) acrylic acid alkyl ester (methacrylic acid alkyl ester and / or acrylic acid alkyl ester) having an alkyl group having 1 to 18 carbon atoms. ) Methyl acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl butyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, T-butyl (meth) acrylate, pentyl (meth) acrylate, neopentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, (meth) acrylic acid Octyl, 2-ethylhexyl (meth) acrylate, (meth) actyl Isooctyl oxalate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, (meth) acrylic Such as tridecyl acid, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, 2-ethylhexadecyl (meth) acrylate Examples include (meth) acrylic acid alkyl (linear or branched alkyl having 1 to 18 carbon atoms) ester. Among these (meth) acrylic acid alkyl esters, butyl acrylate, methyl methacrylate, and 2-ethylhexadecyl (meth) acrylate are preferable. These alkyl (meth) acrylates can be used alone or in combination of two or more.

Examples of the ethylenically unsaturated monomer include a copolymerizable polymer copolymerizable with (meth) acrylic acid alkyl ester.
Examples of the copolymerizable vinyl monomer include aromatic vinyl monomers such as styrene and vinyl toluene, such as cyclopentyl di (meth) acrylate, cyclohexyl (meth) acrylate, bornyl (meth) acrylate, and (meth) acrylic acid. (Meth) acrylic acid alicyclic hydrocarbon esters such as isobornyl, for example, (meth) acrylic aryl esters such as phenyl (meth) acrylate, such as methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate Alkoxy group-containing unsaturated monomers such as ethylene, propylene, isoprene, butadiene, isobutylene and other olefinic monomers, vinyl ether-based monomers such as vinyl ether, halogen atom-containing unsaturated monomers such as vinyl chloride, etc. For example, N-vinylpyrrolidone, N- (1-methylvinyl) pyrrolidone, N-vinylpyridine, N-vinylpiperidone, N-vinylpyrimidine, N-vinylpiperazine, N-vinylpyrazine, N-vinylpyrrole, N-vinylimidazole, N -Acrylic ester monomers containing halogen atoms such as fluorine atoms, such as vinyl group-containing heterocyclic compounds such as vinyl oxazole, N-vinyl morpholine, tetrahydrofurfuryl (meth) acrylate, for example, fluorine (meth) acrylate Etc.

  Examples of the copolymerizable vinyl monomer include functional group-containing vinyl monomers, for example, carboxyl group-containing monomers such as acrylic acid, methacrylic acid, fumaric acid, maleic acid, crotonic acid, and carboxyethyl (meth) acrylate. Carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate, for example, hydroxyl group-containing vinyl monomers such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-methylol (meta Acrylamide Amide group-containing unsaturated monomers such as N-methylolpropane (meth) acrylamide and N-vinylcarboxylic acid amide, such as aminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, (meth) Amino group-containing unsaturated monomers such as acrylic t-butylaminoethyl, for example, glycidyl group-containing unsaturated monomers such as glycidyl (meth) acrylate and methyl glycidyl (meth) acrylate, for example, cyano such as acrylonitrile and methacrylonitrile Group-containing unsaturated monomers, for example, isocyanate group-containing unsaturated monomers such as 2-methacryloyloxyethyl isocyanate, such as styrene sulfonic acid, allyl sulfonic acid, 2- (meth) acrylamide-2-methylpropane sulfonic acid, (meth) Acrylamide Pro Sulfonic acid group-containing unsaturated monomers such as sulfonic acid, sulfopropyl (meth) acrylate, (meth) acryloyloxynaphthalene sulfonic acid, such as N-cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, N-phenylmaleimide, etc. Maleimide monomers such as N-methyl itaconimide, N-ethyl itaconimide, N-butyl itaconimide, N-octyl itaconimide, N-2-ethyl hexylitaconimide, N-cyclohexyl leuconconimide, N-lauryl itaconimide Itaconic imide monomers such as N- (meth) acryloyloxymethylene succinimide, N- (meth) acryloyl-6-oxyhexamethylene succinimide, N- (meth) acryloyl-8-o Succinimide monomers such as cyoctamethylene succinimide, for example, glycol acrylics such as polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate An ester monomer etc. are mentioned.

Furthermore, a polyfunctional monomer is mentioned as an above-described functional group containing vinyl monomer.
Examples of the multifunctional monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and tetraethylene glycol di (meth) acrylate. (Mono or poly) alkylene glycol di (meth) such as (mono or poly) ethylene glycol di (meth) acrylate and (mono or poly) propylene glycol di (meth) acrylate such as propylene glycol di (meth) acrylate In addition to acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, pentaerythritol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol Examples include (meth) acrylic acid ester monomers of polyhydric alcohols such as tall tri (meth) acrylate and dipentaerythritol hexa (meth) acrylate, such as divinylbenzene. Examples of the polyfunctional monomer include epoxy acrylate, polyester acrylate, and urethane acrylate.

Furthermore, examples of the copolymerizable vinyl monomer include alkoxysilyl group-containing vinyl monomers. Examples of the alkoxysilyl group-containing vinyl monomer include silicone-based (meth) acrylate monomers and silicone-based vinyl monomers.
Examples of the silicone-based (meth) acrylate monomer include (meth) acryloyloxymethyl-trimethoxysilane, (meth) acryloyloxymethyl-triethoxysilane, 2- (meth) acryloyloxyethyl-trimethoxysilane, 2- ( (Meth) acryloyloxyethyl-triethoxysilane, 3- (meth) acryloyloxypropyl-trimethoxysilane, 3- (meth) acryloyloxypropyl-triethoxysilane, 3- (meth) acryloyloxypropyl-tripropoxysilane, 3 -(Meth) acryloyloxypropyl-triisopropoxysilane, (meth) acryloyloxyalkyl-trialkoxysilane such as 3- (meth) acryloyloxypropyl-tributoxysilane, for example, (meth) acryloyloxymethyl-methyl Dimethoxysilane, (meth) acryloyloxymethyl-methyldiethoxysilane, 2- (meth) acryloyloxyethyl-methyldimethoxysilane, 2- (meth) acryloyloxyethyl-methyldiethoxysilane, 3- (meth) acryloyloxypropyl -Methyldimethoxysilane, 3- (meth) acryloyloxypropyl-methyldiethoxysilane, 3- (meth) acryloyloxypropyl-methyldipropoxysilane, 3- (meth) acryloyloxypropyl-methyldiisopropoxysilane, 3- (Meth) acryloyloxypropyl-methyldibutoxysilane, 3- (meth) acryloyloxypropyl-ethyldimethoxysilane, 3- (meth) acryloyloxypropyl-ethyldiethoxysilane, 3- (meth) acryloyloxypropyl Ethyl dipropoxysilane, 3- (meth) acryloyloxypropyl-ethyldiisopropoxysilane, 3- (meth) acryloyloxypropyl-ethyldibutoxysilane, 3- (meth) acryloyloxypropyl-propyldimethoxysilane, 3- ( Examples include (meth) acryloyloxyalkyl-alkyl dialkoxysilanes such as (meth) acryloyloxypropyl-propyldiethoxysilane, and (meth) acryloyloxyalkyl-dialkyl (mono) alkoxysilanes corresponding to these.

  Examples of the silicone-based vinyl monomer include vinyltrialkoxysilanes such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinyltriisopropoxysilane, vinyltributoxysilane, and vinyl corresponding to these. Alkyldialkoxysilanes and vinyldialkylalkoxysilanes such as vinylmethyltrimethoxysilane, vinylmethyltriethoxysilane, β-vinylethyltrimethoxysilane, β-vinylethyltriethoxysilane, γ-vinylpropyltrimethoxysilane, γ -Vinylalkyl such as vinylpropyltriethoxysilane, γ-vinylpropyltripropoxysilane, γ-vinylpropyltriisopropoxysilane, γ-vinylpropyltributoxysilane Another trialkoxysilane, these correspond and (vinyl) alkyl dialkoxy silanes, and the like (vinyl alkyl) dialkyl (mono) alkoxysilanes.

These copolymerizable vinyl monomers can be used alone or in combination of two or more.
Of these copolymerizable vinyl monomers, an alkoxysilyl group-containing vinyl monomer is preferable.
By using an alkoxysilyl group-containing vinyl monomer as the copolymerizable vinyl monomer, an alkoxysilyl group is introduced into the polymer chain, and a cross-linked structure can be formed by a reaction between them.

Such a copolymerizable vinyl monomer can be optionally used in combination with a (meth) acrylic acid alkyl ester if necessary, or can be used alone.
When the copolymerizable vinyl monomer is used in combination with a (meth) acrylic acid alkyl ester, the blending ratio of the copolymerizable vinyl monomer is, for example, 40 parts by weight or less with respect to 100 parts by weight of the ethylenically unsaturated monomer. Preferably, it is 30 parts by weight or less, more preferably 20 parts by weight or less. When the copolymerizable vinyl monomer is an alkoxysilyl group-containing vinyl monomer, the blending ratio is, for example, 0.001 to 10 parts by weight with respect to 100 parts by weight of the (meth) acrylic acid alkyl ester, preferably 0.01 to 5 parts by weight.

Examples of the surfactant include known surfactants (surfactants listed in “Surfactant Physical Properties / Performance Manual, Noboru Moriyama, published by the Technical Information Society”), such as liquid and Dispersants that mainly act on the interface between the solids, for example emulsifiers that act mainly on the interface between the liquid and the liquid.
Examples of the dispersant include a phosphoric acid dispersant and a carboxylic acid dispersant. Examples of the phosphate dispersant include sodium orthophosphate, sodium pyrophosphate, sodium tripolyphosphate, sodium tetraphosphate, sodium hexametaphosphate, and trisodium phosphate. Examples of the carboxylic acid-based dispersant include polymer dispersants such as polyacrylic acid-based, polymethacrylic acid-based, acrylic acid / maleic acid copolymer system, and styrene / maleic acid copolymer system.

  As the polymer dispersant, a general commercial product can be used. For example, Aquaric series (polyacrylic acid type or acrylic acid / maleic acid copolymer system, manufactured by Nippon Shokubai Co., Ltd.), Aron series (polyacrylic acid type). Series, manufactured by Toagosei Co., Ltd., Charol series (polyacrylic acid, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Poise series (acrylic acid / maleic acid copolymer system, manufactured by Kao Corporation), SN Dispersant Series (polycarboxylic acid Copolymer system, manufactured by San Nopco).

  Examples of the emulsifier include sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, polyoxyethylene sodium lauryl sulfate, polyoxyethylene alkyl ether sodium sulfate, polyoxyethylene alkyl phenyl ether ammonium sulfate, and polyoxyethylene alkyl phenyl ether. Anionic emulsifiers such as sodium sulfate and sodium polyoxyethylene alkyl sulfosuccinate, for example, nonionic emulsifiers such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, polyoxyethylene polyoxypropylene block polymer Etc.

Examples of the emulsifier include radical polymerizable (reactive) emulsifiers in which radical polymerizable functional groups (reactive groups) such as propenyl groups and allyl ether groups are introduced into these anionic emulsifiers and nonionic emulsifiers. .
These surfactants can be used alone or in combination of two or more.
In the present invention, for example, first, the above lamellar clay mineral and water are blended, and then these are stirred and mixed to disperse the hydrophilic lamellar clay mineral in water. An aqueous dispersion is prepared (aqueous dispersion preparation step).

The mixing ratio of the layered clay mineral is, for example, 0.1 to 11 parts by weight, preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of water.
If the blending ratio of the layered clay mineral exceeds the above range, the viscosity of the aqueous dispersion becomes excessively high, and the fluidity of the aqueous dispersion is excessively lowered, so that the layered clay mineral can be uniformly and sufficiently swollen. There are cases where it is not possible. Further, in the monomer emulsion preparation step, it is necessary to reduce the viscosity of the monomer emulsion, and in the polymerization step, the solid content concentration of the resulting polymer needs to be within a certain range, which may be complicated.

On the other hand, if the mixing ratio of the layered clay mineral is less than the above range, the content of the layered clay mineral in the inorganic composite water-dispersed resin becomes excessively low, and the layered clay mineral is uniformly supported on the surface of the water-dispersed resin. It may not be possible to
In order to stir and mix the water mixed with the layered clay mineral, for example, a known stirrer such as a disper or an ultrasonic homogenizer is used. Moreover, before the stirring and mixing, the water in which the layered clay mineral is blended can be allowed to stand in advance, for example, for 12 to 48 hours, preferably 24 to 36 hours. By allowing the water mixed with the layered clay mineral to stand, for example, the layered clay mineral can be swollen in water, and then the layered clay mineral is peeled off and reliably dispersed in water by subsequent stirring and mixing. Can be made.

Next, for example, an aqueous dispersion and an ethylenically unsaturated monomer are blended, followed by stirring and mixing to emulsify the ethylenically unsaturated monomer to prepare a monomer emulsion (monomer emulsion preparation step).
In the blending of the aqueous dispersion and the ethylenically unsaturated monomer, the blending ratio of the layered clay mineral is 4 to 200 parts by weight, preferably 5 to 150 parts by weight, based on 100 parts by weight of the ethylenically unsaturated monomer. Preferably, it is 8-100 weight part.

If the blending ratio of the layered clay mineral is less than the above range, a stable emulsion form cannot be obtained in the monomer emulsion preparation step, and the coverage of the layered clay mineral in the inorganic composite water-dispersed resin becomes excessively low. .
On the other hand, if the blending ratio of the layered clay mineral exceeds the above range, the coverage of the layered clay mineral in the inorganic composite water-dispersed resin becomes excessively high, the viscosity increases, and it may be necessary to adjust the viscosity.

  Further, in the monomer emulsion preparation step, the hydrophobic inorganic compound is previously dispersed in the above-mentioned ethylenically unsaturated monomer to prepare a monomer dispersion of the hydrophobic inorganic compound (monomer dispersion preparation step), and thus obtained. A monomer dispersion and an aqueous dispersion can be blended to emulsify the ethylenically unsaturated monomer. As a result, the hydrophobic inorganic compound can be encapsulated in the inorganic composite water-dispersed resin.

The hydrophobic inorganic compound is a hydrophobic inorganic compound having a bulk shape, a needle shape, or a plate shape (excluding a layer shape).
The bulk-form hydrophobic inorganic compound includes, for example, a spherical inorganic shape, a rectangular parallelepiped shape, or a hydrophobic inorganic compound having an irregular shape thereof. Examples of the bulk-form hydrophobic inorganic compound include silica, calcium carbonate, titanium oxide, tin oxide (including antimony-doped tin oxide), alumina, magnesium hydroxide, barium titanate, zinc oxide, silicon nitride, and metal fine particles. Etc.

Examples of the needle-shaped hydrophobic inorganic compound include potassium titanate, wollastonite, sepiolite, acicular tin oxide, acicular magnesium hydroxide, and the like.
The plate-shaped hydrophobic inorganic compound is a plate-shaped hydrophobic inorganic compound excluding the layer-shaped hydrophobic inorganic compound, and examples thereof include boron nitride, plate-like calcium carbonate, and plate-like aluminum hydroxide.

These hydrophobic inorganic compounds can be used alone or in combination of two or more.
Preferably, silica, titanium oxide, antimony-doped tin oxide, zinc oxide, boron nitride, and silicon nitride are used.
Moreover, as a hydrophobic inorganic compound, the hydrophobic inorganic compound hydrophobized by surface-treating using a surface treating agent can also be used.

Examples of the surface treatment agent include general surface modifiers, and examples include coupling agents, fatty acids, metal hydroxides, and metal oxides.
Examples of the coupling agent include a silane coupling agent, a titanium coupling agent, and an aluminum coupling agent.
Examples of the silane silane coupling agent include 3-methacryloxypropyl-trimethoxysilane, 3-acryloxypropyl-trimethoxysilane, 3-methacryloxypropyl-triethoxysilane, and 3-acryloxypropyl-triethoxysilane. 3-methacryloxypropylmethyl-dimethoxysilane, 3-acryloxypropylmethyl-dimethoxysilane, 3-methacryloxypropylmethyl-diethoxysilane, 3-acryloxypropylmethyl-diethoxysilane, vinyltrimethoxysilane, vinyltri Ethoxysilane, 4-vinylbutyltrimethoxysilane, 4-vinylbutyltriethoxysilane, 8-vinyloctyltrimethoxysilane, 8-vinyloctyltriethoxysilane, 10-metac Ruoxydecyltrimethoxysilane, 10-acryloxydecyltrimethoxysilane, 10-methacryloxydecyltriethoxysilane, 10-acryloxydecyltriethoxysilane, methyltrimethoxysilane, butyltrimethoxysilane, hexyltrimethoxysilane, decyl Trimethoxysilane, hexadecyltrimethoxysilane, octadecyldimethylmethoxysilane, tetramethoxysilane, tetraethoxysilane, dimethoxydimethylsilane, methoxytrimethylsilane, diethoxydimethylsilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane , Phenyltriethoxysilane, dimethoxydiphenylsilane, diphenylethoxymethylsilane, dimethoxymethylphenylsilane Emissions, hexamethyldisilazane, octamethylcyclotetrasiloxane, dimethyl dichlorosilane, and the like.

  Examples of titanium coupling agents include isopropyl triisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditridecyl phosphite). ) Titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltri (dioctylphosphate) Titanate, isopropyl tricumylphenyl titanate, isopropyl tri (N-amidoethyl acetate) Aminoethyl) such as titanate, and the like.

Examples of the aluminum coupling agent include acetoalkoxyaluminum diisopropylate.
Examples of the fatty acid include stearic acid, oleic acid, linoleic acid, linolenic acid, and eleostearic acid.
Examples of the metal hydroxide include aluminum hydroxide.

Examples of the metal oxide include zirconium oxide.
These surface modifiers can be used alone or in combination.
As the surface treatment with such a surface treating agent, for example, an alcohol solution of the surface treating agent, an organic solvent (an organic solvent excluding alcohol) while stirring an inorganic compound in a bulk shape, needle shape or plate shape in a mixer. For example, a dry method in which a solution or an aqueous solution is added, for example, a wet method in which an inorganic compound having a bulk shape, a needle shape, or a plate shape is dispersed in an alcohol aqueous solution or an aqueous solution, and then a surface treatment agent is added. Examples thereof include a spray method in which a surface treatment agent is sprayed on an inorganic compound having a bulk shape, a needle shape, or a plate shape.

As such a hydrophobic inorganic compound, a general commercial product can be used. For example, as silica, Aerosil series (manufactured by Nippon Aerosil Co., Ltd.), for example, as titanium oxide, TTO series (manufactured by Ishihara Sangyo Co., Ltd.), etc. Can be mentioned.
Examples of the Aerosil series include Aerosil R8200 (primary particle diameter 12 nm, hexamethyldisilazane treatment), Aerosil R104 (primary particle diameter 12 nm, octamethylcyclotetrasiloxane treatment), Aerosil R974 (primary particle diameter 12 nm, dimethyl). Dichlorosilane treatment), Aerosil R812 (primary particle diameter 7 nm, hexamethyldisilazane treatment) and the like are used. Examples of the TTO series include TTO-51 (C) (primary particle diameter of 10 to 30 nm, aluminum hydroxide / stearic acid treatment), TTO-55 (C) (primary particle diameter of 30 to 50 nm, aluminum hydroxide / Stearic acid treatment), TTO-55 (D) (primary particle diameter 30-50 nm, aluminum hydroxide / zirconium oxide treatment), and the like.

  The size of the hydrophobic inorganic compound is, for example, 1 to 200 nm, preferably 5 to 150 nm, more preferably 5 to 100 nm, as a primary average particle diameter (maximum length in the case of needles or plates). Preferably, it is 5 to 50 nm. If the primary average particle size of the hydrophobic inorganic compound is larger than the above range, the hydrophobic inorganic compound may not be encapsulated in oil droplets having a desired particle size and may aggregate during polymerization.

In order to prepare the monomer dispersion liquid, the hydrophobic inorganic compound and the ethylenically unsaturated monomer are blended, and the mixture is stirred and mixed with the above-described known stirrer, whereby the hydrophobic inorganic compound is mixed with the ethylenically unsaturated monomer. To disperse.
The blending ratio of the hydrophobic inorganic compound is, for example, 0.1 to 15 parts by weight, preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the ethylenically unsaturated monomer. When the blending ratio of the hydrophobic inorganic compound exceeds the above range, the hydrophobic inorganic compound may not be completely encapsulated in the oil droplets and may aggregate during the polymerization.

And an aqueous dispersion and the oil phase liquid containing an ethylenically unsaturated monomer (or monomer dispersion) are mix | blended, for example, these are emulsified with an emulsification apparatus.
The oil phase liquid contains, for example, an ethylenically unsaturated monomer as an essential component, and an initiator and a hydrophobic compound (or a hydrophobic inorganic compound) as an optional component as necessary.
As the initiator, for example, a polymerization initiator usually used for emulsion polymerization is used, and for example, an oil-soluble initiator or a water-soluble initiator is used.

  Examples of the oil-soluble initiator include oil-soluble peroxide-based initiators such as benzoyl peroxide and lauroyl peroxide, such as dimethyl 2,2′-azobis (2-methylpropionate) (commercially available products such as V-601, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyldimethylvaleronitrile), 2,2′-azobis (2-methyl-butyronitrile), 1,1′-azobis (cyclohexane-1-carbononitrile), 2,2′-azobisisobutyronitrile (AIBN), azobis (2-methyl) And oil-soluble azo initiators such as butyronitrile).

  Examples of the water-soluble initiator include 2,2′-azobis (2-methylpropionamidine) disulfate, 2,2′-azobis (2-methylpropionamidine) dihydrochloride, 2,2′-azobis ( 2-Amidinopropane) dihydrochloride, 2,2′-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate, 2,2′-azobis (N, N′-dimethyleneisobutyl) Azo initiators (excluding oil-soluble azo initiators) such as amidine), 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, such as potassium persulfate, Persulfate-based initiators such as ammonium persulfate, for example, t-butyl hydroperoxide, peroxide-based initiators such as hydrogen peroxide (excluding oil-soluble peroxide-based initiators), such as phenyl Substituted ethane initiators such as substituted ethanes, for example, carbonyl initiators such as aromatic carbonyl compounds, for example, redox systems such as combinations of persulfate and sodium bisulfite, peroxides and sodium ascorbate An initiator etc. are mentioned.

These initiators are suitably used alone or in combination. Of the initiators, an oil-soluble initiator is preferably used, and an oil-soluble azo initiator is more preferably used.
The mixing ratio of the initiator is appropriately selected, and is, for example, 0.005 to 1 part by weight with respect to 100 parts by weight of the ethylenically unsaturated monomer.
Examples of the hydrophobic compound include hydrophobic organic compounds other than the above-described hydrophobic inorganic compounds, for example, higher alkanes having 8 to 30 carbon atoms such as dodecane, hexadecane, and octadecane, such as lauryl alcohol, cetyl alcohol, and stearyl. Higher alcohols having an alkyl group having 8 to 30 carbon atoms such as alcohol, for example, alkyl (meth) acrylates having an alkyl group having 8 to 30 carbon atoms such as lauryl (meth) acrylate, stearyl (meth) acrylate, etc. Thiols having an alkyl group having 8 to 30 carbon atoms, such as lauryl mercaptan, cetyl mercaptan, stearyl mercaptan, and polymers such as polystyrene and polymethyl (meth) acrylate. These hydrophobic compounds can be used alone or in combination of two or more. Preferably, higher alkanes are used. In addition, when using an alkyl (meth) acrylate having an alkyl group having 8 to 30 carbon atoms as the ethylenically unsaturated monomer, the alkyl (meth) acrylate may function as a hydrophobic compound. , There is a case where it is not necessary to blend.

The blending ratio of the hydrophobic compound is, for example, 1 to 80 parts by weight, preferably 1 to 60 parts by weight with respect to 100 parts by weight of the ethylenically unsaturated monomer.
If a hydrophobic compound is added to the oil phase liquid, the oil droplets in the monomer emulsion can be maintained at a median diameter in a specific range.
In order to include an optional component in the oil phase liquid, an initiator and a hydrophobic compound are added to the ethylenically unsaturated monomer and dissolved.

In the above description, the optional component is blended in the oil phase liquid, but it can also be added directly to the monomer emulsion, for example.
Examples of the emulsifier include an ultrasonic homogenizer, a high-pressure homogenizer (PANDA 2K, manufactured by NIRO-SOAVI), a microfluidizer (manufactured by Microfluidics), a nanomizer (manufactured by Yoshida Kikai Kogyo Co., Ltd.), and a TK homomixer (manufactured by Primics). TK film mix (manufactured by Primics) is used.

In the ultrasonic homogenizer, the frequency of the ultrasonic wave used is not particularly limited, and is, for example, 20 to 40 kHz. In the ultrasonic homogenizer, the oil droplets of the ethylenically unsaturated monomer are refined to the above-mentioned median diameter by the cavitation effect by ultrasonic irradiation.
In the high-pressure homogenizer, microfluidizer, and nanomizer, the pressure applied is not particularly limited, and is, for example, 10 to 300 MPa. In high-pressure homogenizers, microfluidizers and nanomizers, while the dispersion is pressurized, it is ejected from the micropores, and the oil droplets are refined to the above-mentioned median diameter by the addition of the high shearing force generated in such ejection. The

The TK homomixer and the TK fill mix are emulsifiers that utilize the high-speed rotation of the rotating body. When the rotating body rotates at a high speed in the mixed solution, a high shear force is added to the mixed solution, and oil droplets are generated. It is miniaturized to the median diameter described above.
These emulsifiers can be used alone or in combination of two or more.

Thereby, the volume-based median diameter of the oil droplets of the ethylenically unsaturated monomer to be emulsified is preferably 4 μm or less, more preferably 1 μm or less, particularly preferably 0.5 μm or less, usually 0.05 μm or more. It is.
If the median diameter of the oil droplets exceeds the above range, aggregates may be generated in the polymerization step.

  The volume-based median diameter of oil droplets in this monomer emulsion is measured with a laser diffraction particle size distribution measuring device. As the laser diffraction type particle size distribution measuring device, a general commercial product is usually used, and specifically, LS13 320 (manufactured by Beckman Coulter, Inc.) or the like is used, and the measurement condition is that the laser light source is a laser diode and a tungsten lamp. And the wavelength is 450 to 900 nm.

The monomer emulsion is then polymerized, for example, by heating, to polymerize the ethylenically unsaturated monomer in the monomer emulsion.
The heating temperature (polymerization temperature) is set to 40 to 90 ° C., for example, and the polymerization time is set to 1 to 1, for example
Set to 10 hours.
In addition, the monomer emulsion can be polymerized at a time under the reaction conditions described above, and after the polymerization of a part of the monomer emulsion, the remaining monomer emulsion can be polymerized, for example, dropwise, and further, the reaction It is also possible to charge water in advance in a container and raise the temperature to the above-described temperature, and then add the monomer emulsion dropwise or dividedly.

Moreover, in this invention, surfactant is mix | blended with surfactant in at least any one of water, an aqueous dispersion, an ethylenically unsaturated monomer, and a monomer emulsion. The compounding ratio of the surfactant is, for example, 0.01 to 20 parts by weight, preferably 0.05 to 15 parts by weight with respect to 100 parts by weight of the layered clay mineral.
When the surfactant is blended with water, in the aqueous dispersion preparation step, the surface activity is added to the water before the layered clay mineral is blended or the water before the layered clay mineral is blended and dispersed. Add agent. Preferably, a dispersant is blended. By blending the surfactant with water, peeling between the layered clay minerals can be promoted.

  In addition, when the surfactant is added to the aqueous dispersion, the surfactant is added to the prepared aqueous dispersion in the monomer emulsion preparation step (after the aqueous dispersion preparation step). Preferably, a dispersant is added. By adding a surfactant to the aqueous dispersion, the dispersibility of the layered clay mineral in the aqueous dispersion is improved, the viscosity of the aqueous dispersion is lowered, and the solid content concentration of the resulting emulsion is easily within a certain range. Can be adjusted.

Moreover, when mix | blending surfactant with an oil phase liquid, in a monomer emulsion preparation process, surfactant is added to the prepared oil phase liquid (specifically ethylenically unsaturated monomer). Preferably, an emulsifier is blended. By blending the surfactant into the oil phase liquid, a stable emulsion form of the monomer emulsion can be obtained.
Moreover, when mix | blending surfactant with a monomer emulsion, surfactant is added to the prepared monomer emulsion in a superposition | polymerization process. Preferably, an emulsifier is blended. By blending the surfactant into the monomer emulsion, high polymerization stability can be obtained.

In addition, in the monomer emulsion preparation step, when the above-described monomer dispersion and water dispersion are blended to emulsify the ethylenically unsaturated monomer, the surfactant is water, water dispersion, ethylenically unsaturated. A surfactant is blended in at least one of the monomer, the monomer dispersion, and the monomer emulsion.
By adding the surfactant to the monomer dispersion, a stable emulsion form of the monomer emulsion can be obtained.

An emulsion of an inorganic composite water-dispersed resin can be obtained by such polymerization.
In addition, the solid content concentration of the emulsion of this inorganic composite water-dispersed resin is, for example, 5 to 50% by weight, preferably 6 to 45% by weight, and more preferably 8 to 40% by weight. When the solid content concentration of the emulsion exceeds the above range, the viscosity of the emulsion in the polymerization step becomes excessively high, handling properties may be lowered, and control of the polymerization temperature may be difficult. If the solid content concentration of the emulsion is less than the above range, productivity may be reduced.

The volume-based median diameter of the water-dispersed resin of this inorganic composite water-dispersed resin is, for example, 4 μm or less, preferably 1 μm or less, more preferably 0.5 μm or less, usually 0.05 μm or more. This is almost the same as the volume-based median diameter of the oil droplets.
Furthermore, for inorganic composite water-dispersed resins, for example, if necessary, a pH adjuster (such as an acetic acid aqueous solution), a crosslinking agent (isocyanate-based, epoxy-based, oxazoline-based, aziridine-based, metal chelate-based), chain transfer agent. Add additives such as (thiols), viscosity modifiers, release modifiers, plasticizers, softeners, fillers, colorants (pigments, dyes, etc.), anti-aging agents, surfactants, etc. can do. These additives may be added after the polymerization step, or may be added to each liquid in the aqueous dispersion preparation step, the monomer dispersion preparation step, the monomer emulsion preparation step, and the polymerization step.

  In the present invention, an aqueous dispersion is prepared so that a hydrophobizing agent such as a swelling agent (specifically, dodecyltrimethylammonium bromide or the like) is not added to the aqueous dispersion. When the hydrophobizing agent is added, the lamellar clay mineral is reduced in hydrophilicity, the dispersibility in the aqueous dispersion is lowered, and the delamination of the lamellar clay mineral is not promoted smoothly. Aggregates.

In the method for producing an inorganic composite water-dispersed resin of the present invention, a hydrophilic layered clay mineral is dispersed in water to prepare an aqueous dispersion of the hydrophilic layered clay mineral. A monomer emulsion is prepared by blending with an unsaturated monomer, and the ethylenically unsaturated monomer is polymerized.
Therefore, the obtained water-dispersed resin can be composited with a layered clay mineral so that the layered clay mineral is unevenly distributed on the surface thereof. That is, the inorganic composite water-dispersed resin can carry the layered clay mineral on the outer surface without encapsulating the layered clay mineral.

As a result, the inorganic composite water-dispersed resin of the present invention can form a path in which the layered clay mineral is continuous in the water-dispersed resin, and thus is suitable as a heat-dissipating material or a conductive material in various industrial fields. Can be used.
Moreover, since it is excellent in adhesiveness, it can be used suitably also as an adhesive layer of an adhesive film.

  In particular, when a monomer dispersion of a hydrophobic inorganic compound is used, the resulting inorganic composite water-dispersed resin supports the layered clay mineral on the outer surface while encapsulating the hydrophobic inorganic compound instead of the layered clay mineral. It can be composited so as to be (unevenly distributed). Therefore, a pressure-sensitive adhesive layer in which such a hydrophobic inorganic compound exists uniformly is obtained, and the mechanical strength of the pressure-sensitive adhesive layer can be improved.

FIG. 1 shows a cross-sectional view of an example of an adhesive film using an inorganic composite water-dispersed resin obtained by the method for producing an inorganic composite water-dispersed resin of the present invention.
Next, an example of a method for producing an adhesive film using the inorganic composite water dispersion obtained by the method for producing an inorganic composite water dispersion resin of the present invention will be described.
In this method, first, a substrate 1 is prepared.

  Examples of the material for forming the substrate 1 include polyolefin films such as polyethylene, polypropylene, and ethylene / propylene copolymers, polyester films such as polyethylene terephthalate, plastic films such as polyvinyl chloride, kraft paper, and Japanese paper. Examples thereof include papers, cotton cloths, cloths such as soft cloths, textiles such as polyester nonwoven fabrics and vinylon cloths, and metal foils.

The base material 1 is formed in a sheet (film) shape or a tape shape, for example.
The base material 1 can be subjected to known processes such as undercoating, sealing, corona and back processes, if necessary.
The thickness of the base material 1 is suitably selected according to the use and purpose, and is, for example, 20 to 150 μm, preferably 30 to 100 μm.

Next, the pressure-sensitive adhesive layer 2 is laminated on one side of the substrate 1.
In order to provide the pressure-sensitive adhesive layer 2, for example, the above-mentioned inorganic composite water-dispersed resin emulsion is directly applied to one side of the substrate 1 by a known coating method such as roll coating, screen coating, gravure coating, and the like. For example, it heats and drys at 50-180 degreeC.
Further, the pressure-sensitive adhesive layer 2 can be transferred to the substrate 1 from the release sheet on which the pressure-sensitive adhesive layer 2 is laminated.

  The release sheet laminated with the pressure-sensitive adhesive layer 2 is, for example, an inorganic composite water-dispersed resin emulsion is directly applied to a known release sheet by a known application method, and dried by heating. Formed by forming layer 2. In order to transfer the pressure-sensitive adhesive layer 2, a release sheet on which the pressure-sensitive adhesive layer 2 is laminated is bonded to the base material 1 so that one side of the base material 1 and the pressure-sensitive adhesive layer 2 are in contact with each other. Then, the release sheet is peeled off from the pressure-sensitive adhesive layer 2.

The thickness of the pressure-sensitive adhesive layer 2 thus formed (thickness after drying) is appropriately selected according to its use and purpose, and is, for example, in the range of about 1.0 to 100 μm, preferably about 3.0 to 50 μm. Set to
In the above description shown in FIG. 1, the pressure-sensitive adhesive layer 2 is provided on one side of the substrate 1, but it can also be provided on both sides of the substrate 1, for example.

And in this adhesive film, the mechanical property of an adhesive, specifically, the adhesive force is excellent. The pressure-sensitive adhesive layer has a high loss elastic modulus G ″ and loss tangent tan δ obtained by dynamic viscoelasticity measurement. Therefore, it is presumed that the pressure-sensitive adhesive layer has excellent vibration damping properties.
Furthermore, since this adhesive film is excellent in the adhesive strength, heat resistance and moisture resistance of the pressure-sensitive adhesive layer, it is excellent in adhesive strength, heat resistance and moisture resistance.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to the following examples and comparative examples.
Example 1
(Water dispersion preparation process)
10 parts by weight of Lucentite SWN (hydrophilic layered clay mineral, maximum length of each layer: 50 nm, manufactured by Coop Chemical Co.) was added to 464 parts by weight of water and allowed to stand for 24 hours. This was stirred and mixed with an ultrasonic homogenizer for 3 minutes to obtain an aqueous dispersion.
(Monomer emulsion preparation process)
100 parts by weight of butyl acrylate, 5 parts by weight of hexadecane, initiator (dimethyl 2,2′-azobis (2-methylpropionate), oil-soluble azo-based initiator, trade name: V-601, manufactured by Wako Pure Chemical Industries, Ltd. ) 0.25 part by weight was mixed to prepare an oil phase liquid.

Subsequently, the oil phase liquid and the aqueous dispersion were mixed, and stirred and forcedly emulsified at 6000 (1 / min) for 1 minute using a TK homomixer (manufactured by Primex) to prepare a monomer pre-emulsion. Next, this monomer pre-emulsion was treated for 2 passes at a pressure of 100 MPa using a high-pressure homogenizer (PANDA 2K), and 20 wt% emulsifier liquid (anionic non-reactive emulsifier, trade name: Haitenol LA-16, Daiichi Kogyo Seiyaku Co., Ltd.) 5 parts by weight (solid content 1 part by weight) was added to obtain a monomer emulsion.
(Polymerization process)
The prepared monomer emulsion was charged into a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer, and a stirrer, and then the reaction vessel was purged with nitrogen, then heated to 70 ° C. and polymerized for 3 hours to form a solid. An emulsion of an inorganic composite water-dispersed resin having a partial concentration of 20% was obtained.

Example 2
Monomer emulsion as in Example 1, except that 0.03 parts by weight of 3-methacryloyloxypropyl-trimethoxysilane (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) was further added to the oil phase liquid in the monomer emulsion preparation step. Was then polymerized to obtain an inorganic composite water-dispersed resin emulsion having a solid content of 20%.

Example 3
In the monomer emulsion preparation step, 0.03 part by weight of 3-methacryloyloxypropyl-trimethoxysilane (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) is further added to the oil phase liquid, and Lucentite SWN (hydrophilic layered clay mineral) (Manufactured by Coop Chemical Co., Ltd.), the monomer emulsion was changed to 20 parts by weight, and the monomer emulsion was prepared in the same manner as in Example 1 except that the amount of water was changed to 504 parts by weight. Subsequently, this was polymerized. Thus, an emulsion of an inorganic composite water-dispersed resin having a solid content concentration of 20% was obtained.

Example 4
(Water dispersion preparation process)
5 parts by weight of Lucentite SWN (hydrophilic layered clay mineral, manufactured by Corp Chemical) was added to 631 parts by weight of water and allowed to stand for 24 hours. This was stirred and mixed with an ultrasonic homogenizer for 3 minutes to obtain an aqueous dispersion.
(Monomer emulsion preparation process)
100 parts by weight of butyl acrylate, 5 parts by weight of hexadecane, 0.03 part by weight of 3-methacryloyloxypropyl-trimethoxysilane (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.), initiator (dimethyl 2,2′-azobis (2- Methyl propionate), oil-soluble azo initiator, trade name: V-601, manufactured by Wako Pure Chemical Industries, Ltd.) 0.25 parts by weight were mixed to prepare an oil phase liquid.

Subsequently, the oil phase liquid and the aqueous dispersion were mixed, and stirred and forcedly emulsified at 6000 (1 / min) for 1 minute using a TK homomixer (manufactured by Primex) to prepare a monomer pre-emulsion. Next, this monomer pre-emulsion was treated for 2 passes at a pressure of 100 MPa using a high-pressure homogenizer (PANDA 2K), and 20 wt% emulsifier liquid (anionic non-reactive emulsifier, trade name: Haitenol LA-16, Daiichi Kogyo Seiyaku Co., Ltd.) 2.5 parts by weight (solid content 0.5 parts by weight) and 20% dispersant liquid (Charol AN-103P, polymer dispersant, Daiichi Kogyo Seiyaku Co., Ltd.) 5 parts by weight ( A monomer emulsion was obtained by adding 1 part by weight of solid content).
(Polymerization process)
The prepared monomer emulsion was charged into a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer, and a stirrer, and then the reaction vessel was purged with nitrogen, then heated to 70 ° C. and polymerized for 3 hours to form a solid. An emulsion of an inorganic composite water-dispersed resin having a partial concentration of 15% was obtained.

Example 5
In the monomer emulsion preparation process, 0.03 part by weight of 3-methacryloyloxypropyl-trimethoxysilane (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) is further added to the oil phase liquid, and the number of water blending parts is changed to 271 parts by weight. 20% by weight emulsifier liquid (anionic non-reactive emulsifier, trade name: Hytenol LA-16, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), 20% dispersant liquid (Charol AN-103P, polymer dispersant) A monomer emulsion was prepared in the same manner as in Example 1 except that Daiichi Kogyo Seiyaku Co., Ltd. was used, and was then polymerized to give an emulsion of an inorganic composite water-dispersed resin having a solid content concentration of 30%. Got.

Example 6
(Water dispersion preparation process)
50 parts by weight of Lucentite SWN (hydrophilic layered clay mineral, manufactured by Co-op Chemical) was added to 1056 parts by weight of water and allowed to stand for 24 hours. To this was added 12.5 parts by weight of a 20% dispersant solution (Charol AN-103P, polymer dispersant, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) (2.5 parts by weight in solid content), and 3 with an ultrasonic homogenizer. The mixture was stirred and mixed for a minute to obtain an aqueous dispersion.
(Monomer emulsion preparation process)
100 parts by weight of butyl acrylate, 5 parts by weight of hexadecane, 0.03 part by weight of 3-methacryloyloxypropyl-trimethoxysilane (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.), initiator (dimethyl 2,2′-azobis (2- Methyl propionate), oil-soluble azo initiator, trade name: V-601, manufactured by Wako Pure Chemical Industries, Ltd.) 0.25 parts by weight were mixed to prepare an oil phase liquid.

Subsequently, the oil phase liquid and the aqueous dispersion were mixed, and stirred and forcedly emulsified at 6000 (1 / min) for 1 minute using a TK homomixer (manufactured by Primex) to prepare a monomer pre-emulsion. Next, this monomer pre-emulsion was treated for 2 passes at a pressure of 100 MPa using a high-pressure homogenizer (PANDA 2K), and 20 wt% emulsifier liquid (anionic non-reactive emulsifier, trade name: Haitenol LA-16, 4 parts by weight (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) (0.8 parts by weight in solid content) was added to obtain a monomer emulsion.
(Polymerization process)
The prepared monomer emulsion was charged into a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer, and a stirrer, and then the reaction vessel was purged with nitrogen, then heated to 70 ° C. and polymerized for 3 hours to form a solid. An emulsion of an inorganic composite water-dispersed resin having a partial concentration of 13% was obtained.

Example 7
In the aqueous dispersion preparation step, the amount of water blended was changed to 2418 parts by weight, the amount of Lucentite SWN (hydrophilic layered clay mineral, manufactured by Corp Chemical) was changed to 100 parts by weight, and a 20% dispersant A monomer emulsion was prepared in the same manner as in Example 6 except that the amount of the liquid (Charol AN-103P, polymer dispersant, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was changed to 25 parts by weight (5 parts by solid). Subsequently, this was polymerized to obtain an emulsion of an inorganic composite water-dispersed resin having a solid content concentration of 8%.

Example 8
In the aqueous dispersion preparation step, the monomer emulsion was prepared in the same manner as in Example 1 except that the amount of water blended was changed to 658 parts by weight, and methyl methacrylate was used instead of butyl acrylate. This was polymerized to obtain an inorganic composite water-dispersed resin emulsion having a solid content concentration of 15%.

Example 9
In the aqueous dispersion preparation process, the amount of water blended is changed to 658 parts by weight, isostearyl acrylate is used in place of butyl acrylate, and hexadecane is not used in the monomer emulsion preparation process. Similarly, a monomer emulsion was prepared and subsequently polymerized to obtain an emulsion of an inorganic composite water-dispersed resin having a solid concentration of 15%.

Example 10
In the aqueous dispersion preparation process, the monomer emulsion was changed to 658 parts by weight, and a monomer emulsion was prepared in the same manner as in Example 1 except that styrene was used instead of butyl acrylate. Was polymerized to obtain an emulsion of an inorganic composite water-dispersed resin having a solid concentration of 15%.

Example 11
In preparation of the aqueous dispersion process, the amount of water blended was changed to 504 parts by weight, and instead of 10 parts by weight of Lucentite SWN (hydrophilic layered clay mineral, manufactured by Corp Chemical), Kunipia F (hydrophilic layered clay) Mineral, maximum length of each layer: 300 nm, 20 parts by weight of Kunimine Kogyo Co., Ltd., in the monomer emulsion preparation step, 20% by weight emulsifier liquid (anionic non-reactive emulsifier, trade name: Haitenol LA-16, No. 1) A monomer emulsion was prepared in the same manner as in Example 4 except that Ichi Kogyo Seiyaku Co., Ltd. was not used, and then polymerized to obtain an inorganic composite water-dispersed resin having a solid content concentration of 20%. An emulsion was obtained.

Example 12
(Water dispersion preparation process)
10 parts by weight of Lucentite SWN (hydrophilic layered clay mineral, manufactured by Co-op Chemical) was added to 279 parts by weight of water and allowed to stand for 24 hours. To this, 2.5 parts by weight of a 20% dispersant solution (Charol AN-103P, polymer dispersant, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) (0.5 parts by weight in solid content) was added, and this was added with an ultrasonic homogenizer. The mixture was stirred and mixed for a minute to obtain an aqueous dispersion.
(Monomer dispersion preparation process)
100 parts by weight of butyl acrylate, 5 parts by weight of hexadecane, 0.05 part by weight of 3-methacryloyloxypropyl-trimethoxysilane (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.), initiator (dimethyl 2,2′-azobis (2- Methyl propionate), oil-soluble azo initiator, trade name: V-601, manufactured by Wako Pure Chemical Industries, Ltd.) 0.25 parts by weight were mixed to prepare a mixed solution. To this was added 5 parts of Aerosil R8200 (fumed silica, plate-like hydrophobic silica, primary particle size 12 nm, hexamethyldisilazane treatment, manufactured by Nippon Aerosil Co., Ltd.), and this was stirred and mixed with an ultrasonic homogenizer for 3 minutes. An oil phase liquid containing a monomer dispersion was obtained.
(Monomer emulsion preparation process)
Subsequently, the oil phase liquid and the aqueous dispersion were mixed, and stirred and forcedly emulsified at 6000 (1 / min) for 1 minute using a TK homomixer (manufactured by Primex) to prepare a monomer pre-emulsion. Next, this monomer pre-emulsion was treated for 2 passes at a pressure of 100 MPa using a high-pressure homogenizer (PANDA 2K), and 20 wt% emulsifier liquid (anionic non-reactive emulsifier, trade name: Haitenol LA-16, Daiichi Kogyo Seiyaku Co., Ltd.) 2.5 parts by weight (solid content 0.5 parts by weight) was added to obtain a monomer emulsion.
(Polymerization process)
The prepared monomer emulsion was charged into a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer, and a stirrer, and then the reaction vessel was purged with nitrogen, then heated to 70 ° C. and polymerized for 3 hours to form a solid. An emulsion of an inorganic composite water-dispersed resin having a partial concentration of 30% was obtained.

Comparative Example 1
In the monomer emulsion preparation step, the same procedure as in Example 1 was carried out except that a 20% by weight emulsifier solution (anionic non-reactive emulsifier, trade name: Haitenol LA-16, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was not used. A monomer emulsion was prepared and subsequently polymerized to obtain an emulsion of an inorganic composite water-dispersed resin having a solid concentration of 20%.

Comparative Example 2
In the monomer emulsion preparation step, 0.03 part by weight of 3-methacryloyloxypropyl-trimethoxysilane (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) is further added to the oil phase liquid, and the monomer pre-emulsion is added to the high-pressure homogenizer (PANDA 2K). A monomer emulsion was prepared in the same manner as in Example 1 except that the emulsion was not stirred and mixed and was not emulsified. Subsequently, this was polymerized to obtain an inorganic composite water dispersion type having a solid content concentration of 20%. A resin emulsion was obtained.

Comparative Example 3
(Water dispersion preparation process)
250 parts by weight of Lucentite SWN (hydrophilic layered clay mineral, manufactured by Corp Chemical) was added to 4263 parts by weight of water and allowed to stand for 24 hours. To this was added 62.5 parts by weight of a 20% dispersant solution (Charol AN-130P, polymer dispersant, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) (12.5 parts by weight in terms of solid content), and 3 times with an ultrasonic homogenizer. The mixture was stirred and mixed for a minute to obtain an aqueous dispersion.
(Monomer emulsion preparation process)
100 parts by weight of butyl acrylate, 5 parts by weight of hexadecane, 0.03 part by weight of 3-methacryloyloxypropyl-trimethoxysilane (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.), initiator (dimethyl 2,2′-azobis (2 -Methylpropionate), oil-soluble azo initiator, trade name: V-601, manufactured by Wako Pure Chemical Industries, Ltd.) 0.25 parts by weight was mixed to prepare an oil phase solution.

Next, the oil phase liquid and the aqueous dispersion were mixed, and stirred and forcedly emulsified at 6000 (1 / min) for 1 minute using a TK homomixer (manufactured by Primex) to prepare a monomer pre-emulsion.
Next, this monomer pre-emulsion was treated for 2 passes at a pressure of 100 MPa using a high-pressure homogenizer (PANDA 2K), and 20 wt% emulsifier solution (anionic non-reactive emulsifier, trade name: Hanotenol LA-16, No. 1). 4 parts by weight (manufactured by Ichi Kogyo Seiyaku Co., Ltd.) (0.8 parts by weight in solid content) was added to obtain a monomer emulsion.
(Polymerization process)
By charging the prepared monomer emulsion into a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer and a stirrer, and then substituting the reaction vessel with nitrogen, the temperature was raised to 70 ° C., and polymerization was performed for 3 hours. An emulsion of an inorganic composite water-dispersed resin having a solid content concentration of 8% was obtained.

Comparative Example 4
Comparative Example, except that, in the aqueous dispersion preparation process, the blending part of Lucentite SWN (hydrophilic layered clay mineral, manufactured by Co-op Chemical) was changed to 3 parts by weight and the blending part of water was changed to 587 parts by weight. In the same manner as in Example 3, an emulsion of an inorganic composite water-dispersed resin having a solid content concentration of 15% was obtained.

Comparative Example 5
(Water dispersion preparation process)
To 106 parts by weight of water, add 20% by weight of an emulsifier solution (anionic non-reactive emulsifier, trade name: Haitenol LA-16, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 15 parts by weight (solid content concentration: 3 parts by weight) An aqueous dispersion was prepared.
(Monomer emulsion preparation process)
100 parts by weight of butyl acrylate, 5 parts by weight of hexadecane, 0.03 part by weight of 3-methacryloyloxypropyl-trimethoxysilane (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.), initiator (dimethyl 2,2′-azobis (2- Methyl propionate), oil-soluble azo initiator, trade name: V-601, manufactured by Wako Pure Chemical Industries, Ltd.) 0.25 parts by weight were mixed to prepare an oil phase liquid.

Next, the oil phase liquid and the aqueous dispersion were mixed, and the mixture was forcibly emulsified by stirring at 6000 (1 / min) for 1 minute using a TK homomixer (manufactured by Primics) to prepare a monomer pre-emulsion. . Next, this monomer pre-emulsion was treated for 2 passes at a pressure of 100 MPa using a high-pressure homogenizer (PANDA 2K) to obtain a monomer emulsion.
(Polymerization process)
Charge the prepared monomer emulsion into a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer and a stirrer, and then purge the reaction vessel with nitrogen, then raise the temperature to 70 ° C. and polymerize for 3 hours to solidify the solid content. An emulsion of a water-dispersed resin having a concentration of 50% was obtained.

Comparative Example 6
(Water dispersion preparation process)
90 parts by weight of water and 10 parts by weight of Lucentite SWN (hydrophilic layered clay mineral, manufactured by Co-op Chemical) were added to the container and allowed to stand for 24 hours. To this, sodium hexametaphosphate (dispersant, manufactured by Wako Pure Chemical Industries, Ltd.) adjusted to 10% was added so that the solid content concentration was 10% by weight with respect to Lucentite SWN. Next, the mixture was stirred and mixed for 3 minutes with an ultrasonic homogenizer to prepare an aqueous dispersion of 10% layered clay mineral.
(Monomer emulsion preparation process)
An aqueous dispersion of 10% layered clay mineral is added to an emulsion of a water-dispersed resin having a solid content concentration of 50% prepared in Comparative Example 1, and 10 parts by weight of the layered clay mineral with respect to 100 parts by weight of the aqueous dispersion resin. The resulting mixture was stirred and an emulsion of an inorganic composite water-dispersed resin was obtained.

Comparative Example 7
In the aqueous dispersion preparation step, an inorganic composite water-dispersed resin emulsion was prepared in the same manner as in Comparative Example 6 except that the solid content of sodium hexametaphosphate (dispersant, manufactured by Wako Pure Chemical Industries, Ltd.) was changed to 20 parts by weight. Obtained.
Comparative Example 8
In the aqueous dispersion preparation process, except for changing to Lucentite SPN (hydrophobic layered clay mineral, manufactured by Corp Chemical) instead of Lucentite SWN (hydrophilic layered clay mineral, manufactured by Corp Chemical), comparison In the same manner as in Example 6, a monomer emulsion was prepared, and then an emulsion of an inorganic composite water-dispersed resin having a solid content concentration of 50% was obtained.

Comparative Example 9
In the aqueous dispersion preparation process, instead of Lucentite SWN (hydrophilic layered clay mineral, manufactured by Corp Chemical), it was changed to Lucentite SPN (hydrophobic layered clay mineral, manufactured by Corp Chemical), and sodium hexametaphosphate. A monomer emulsion was prepared in the same manner as in Comparative Example 6 except that (dispersing agent, manufactured by Wako Pure Chemical Industries, Ltd.) was added so that the solid concentration with respect to Lucentite SWN was 20% by weight. An emulsion of an inorganic composite water-dispersed resin having a partial concentration of 50% was obtained.

Comparative Example 10
(Water dispersion preparation process)
10 parts by weight of Lucentite SWN (hydrophilic layered clay mineral, manufactured by Corp Chemical) was added to 372 parts by weight of water, allowed to stand for 24 hours, and further stirred for 24 hours to prepare an aqueous dispersion.
(Monomer emulsion preparation process)
14 parts by weight of dodecyltrimethylammonium bromide (hydrophobizing agent, manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 126 parts by weight of water, and this was added to the aqueous dispersion.

Next, an oil phase liquid in which 100 parts by weight of butyl acrylate and 0.5 parts by weight of azobisisobutyronitrile were mixed was added thereto and stirred at 23 ° C. for 24 hours to prepare a monomer emulsion.
(Polymerization process)
The prepared monomer emulsion was charged into a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer, and a stirrer, and then the reaction vessel was purged with nitrogen, then heated to 70 ° C. and polymerized for 3 hours to form a solid. An emulsion of an inorganic composite water-dispersed resin having a partial concentration of 20% was obtained.

(Evaluation)
1) Median diameter of oil droplets Regarding the monomer emulsions obtained in Examples 1 to 12 and Comparative Examples 1 to 10, a laser diffraction / scattering particle size distribution analyzer (LS13 320, laser light source: laser diode and tungsten lamp, wavelength 450 to 900 nm) , Manufactured by Beckman Coulter, Inc.), the volume-based average median diameter of the oil droplets was measured. The results are shown in Table 3.

2) Median diameter of inorganic composite water-dispersed resin For the inorganic composite water-dispersed resins obtained in Examples 1 to 12 and Comparative Examples 5 to 10, a laser diffraction scattering particle size distribution system (LS 13 320, laser light source: laser) The average median diameter was measured using a diode and a tungsten halogen lamp (wavelength 450 to 900 nm, manufactured by Beckman Coulter, Inc.). The results are shown in Table 4.

3) Polymerization stability (aggregate rate)
After filtering the emulsion after manufacture of the inorganic composite water-dispersed resin obtained in Examples 1 to 12 and Comparative Examples 1 to 10 with a nylon mesh (# 80), the aggregate remaining in the nylon mesh, the reaction vessel, and The total amount with the agglomerates adhering to the stirring blades was weighed, and the agglomerate rate was calculated by the following formula. The results are shown in Table 5.

Aggregate rate (%) = {(A + B) / C} × 100
A: Weight of aggregate remaining on nylon mesh B: Weight of aggregate adhered to reaction vessel and stirring blade C: Oil phase liquid component, hexadecane, clay mineral and inorganic compound (hydrophilic layered clay mineral and hydrophobic inorganic Total weight of compounds, etc.)

4) Haze On the release film (polyethylene terephthalate base material, Diafoil MRF38, manufactured by Mitsubishi Chemical Polyester Co., Ltd.), the emulsion of the inorganic composite water-dispersed resin obtained in Examples 1 to 7 and 12 and Comparative Examples 5 to 9 was used. The film after drying is coated to have a thickness of 25 μm and 100 μm, and then dried in a hot air circulation oven at 120 ° C. for 5 minutes to form a film made of an inorganic composite water-dispersed resin on the release film. Formed.

The haze was measured by using a haze meter HM-150 type (manufactured by Murakami Color Research Laboratory Co., Ltd.), which was obtained by stacking 4 pieces of this cut into 50 mm × 50 mm to 200 μm. The results are shown in Table 6.
In Comparative Examples 6 to 9, the layered clay mineral easily aggregates, and a smooth and transparent film could not be obtained when coated in a film (sheet) shape.

5) Adhesive strength After drying the emulsions of inorganic composite water-dispersed resins obtained in Examples 1 to 4 and 12, Comparative Examples 5, 7 and 8 on Lumirror S10 # 12 (polyester film, manufactured by Toray Industries, Inc.) And then dried in a hot air circulation oven at 120 ° C. for 5 minutes to form a composite film made of an inorganic composite water-dispersed resin on a polyethylene terephthalate substrate, This was used as an evaluation sample.

These samples were cut to a width of 25 mm, and this was attached to a glass plate (Corning # 1737, manufactured by Corning). It was left to stand in an autoclave for 15 minutes, then cooled to 25 ° C., and a 90 ° peel adhesive force (peel rate 300 mm / min) was measured (initial adhesive force).
In addition, after being left in an autoclave, it was further left for 24 hours in an atmosphere of 60 ° C. and 60 ° C./90% RH, then cooled to 25 ° C., and 90 ° peel adhesion (peel rate) 300 mm / min) was measured. The results are shown in Table 7.

  In addition, adhesiveness shows that it is so favorable that the value of peeling adhesive force is high.

6) TEM observation The emulsion of the inorganic composite water-dispersed resin obtained in Examples 1, 2, 4, 8 to 10, and Comparative Example 10 was diluted with water, and one drop of the emulsion was prepared as a TEM sample table with a carbon film. After being dropped and dried, it was observed at an accelerating voltage of 100 kV using a Hitachi transmission electron microscope Hitachi H-7650.

  Moreover, after embedding the emulsion of the inorganic composite water-dispersed resin obtained in Comparative Examples 7 to 9 in an epoxy resin, it was dyed by treating in an aqueous 2% ruthenic acid solution for 3 hours. A microtome (Ultracut S, manufactured by Leica Co., Ltd.) was used to cut the film to a thickness of about 80 nm, and then a cross section of the ultrathin section was observed using a Hitachi transmission electron microscope Hitachi H-7650 at an acceleration voltage of 100 kV.

  Image processing diagrams of these TEM photographs are shown in FIGS.

1 Base material 2 Adhesive layer

Claims (7)

A step of dispersing a hydrophilic layered clay mineral in water to prepare an aqueous dispersion of the layered clay mineral;
The aqueous dispersion and the ethylenically unsaturated monomer are blended so that the blending ratio of the layered clay mineral is 4 to 200 parts by weight with respect to 100 parts by weight of the ethylenically unsaturated monomer, and the ethylenic A step of emulsifying an unsaturated monomer to prepare a monomer emulsion;
Adding a surfactant to at least one of the water, the aqueous dispersion, the ethylenically unsaturated monomer, and the monomer emulsion;
And a step of polymerizing an ethylenically unsaturated monomer in the monomer emulsion. A method for producing an inorganic composite water-dispersed resin. The method for producing an inorganic composite water-dispersed resin according to claim 1, further comprising a step of blending a hydrophobic compound into at least one of the ethylenically unsaturated monomer and the monomer emulsion.   The method for producing an inorganic composite water-dispersed resin according to claim 1 or 2, wherein the maximum length of each layer in the layered clay mineral is 1-1000 nm.   In the step of preparing the monomer emulsion, a hydrophobic inorganic compound in bulk, needle or plate is dispersed in the ethylenically unsaturated monomer in advance to prepare a monomer dispersion of the hydrophobic inorganic compound, The method for producing an inorganic composite water-dispersed resin according to any one of claims 1 to 3, wherein a monomer dispersion and the aqueous dispersion are blended to emulsify the ethylenically unsaturated monomer.   The inorganic composite water-dispersed resin according to claim 4, wherein a blending ratio of the hydrophobic inorganic compound is 0.1 to 15 parts by weight with respect to 100 parts by weight of the ethylenically unsaturated monomer. Manufacturing method.   The method for producing an inorganic composite water-dispersed resin according to claim 4 or 5, wherein the maximum length of the hydrophobic inorganic compound is 1 to 200 nm.   In the step of preparing the monomer emulsion, the ethylenically unsaturated monomer is emulsified so that the volume-based median diameter of oil droplets measured with a laser diffraction particle size distribution analyzer is 4 μm or less. A method for producing an inorganic composite water-dispersed resin according to claim 1.