JP2009209355A - Manufacturing method for inorganic composite water dispersion type resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide 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 hydrophilic inorganic compound having a specific shape. <P>SOLUTION: The bulk-like, needle-like, or plate-like hydrophilic inorganic compound is dispersed in water to prepare a water dispersion of the hydrophilic inorganic compound. The water dispersion, an ethylenic unsaturated monomer and a surfactant are formulated such that a formulation ratio of the hydrophilic inorganic compound 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 hydrophilic inorganic compound having a specific shape 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.
The object of the present invention is to use a hydrophilic inorganic compound having a specific shape on the surface of a water-dispersed resin as a practical material having excellent characteristics and suppressing the generation of aggregates. An object of the present invention is to provide an inorganic composite 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 dispersing a hydrophilic inorganic compound having a bulk shape, needle shape, or plate shape in water, and water of the hydrophilic inorganic compound. The step of preparing the dispersion and the water dispersion and the ethylenically unsaturated monomer are such that the blending ratio of the hydrophilic inorganic compound is 4 to 200 parts by weight with respect to 100 parts by weight of the ethylenically unsaturated monomer. And a step of preparing a monomer emulsion by emulsifying the ethylenically unsaturated monomer, and a surfactant in at least one of the water, the aqueous dispersion, the ethylenically unsaturated monomer, and the monomer emulsion. And a step of polymerizing the ethylenically unsaturated monomer in the monomer emulsion.

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.
In the method for producing an inorganic composite water-dispersed resin of the present invention, it is preferable that the maximum length of the hydrophilic inorganic compound is 1 to 400 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 monomer dispersion.

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, the maximum length of the hydrophobic inorganic compound is preferably 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 is 100 μm or less.

In the method for producing an inorganic composite water-dispersed resin of the present invention, a hydrophilic inorganic compound having a specific shape is dispersed in water to prepare an aqueous dispersion of the hydrophilic inorganic compound having a specific shape. 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 hydrophilic inorganic compound so that the hydrophilic inorganic compound 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 SEM photograph of the inorganic composite water dispersion type resin of Example 2 is shown. The image processing figure of the SEM photograph of the inorganic composite water dispersion type resin of Example 3 is shown. The image processing figure of the SEM photograph of the inorganic composite water dispersion type resin of Example 4 is shown. The image processing figure of the SEM photograph of the inorganic composite water dispersion type resin of Example 5 is shown. The image processing figure of the SEM photograph of the inorganic composite water dispersion type resin of Example 6 is shown. The image processing figure of the SEM photograph of the inorganic composite water dispersion type resin of Example 7 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 SEM 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 9 is shown. The image processing figure of the SEM photograph of the inorganic composite water dispersion type resin of Example 10 is shown. The image processing figure of the SEM photograph of the inorganic composite water dispersion type resin of Example 11 is shown. The image processing figure of the SEM photograph of the inorganic composite water dispersion type resin of Example 12 is shown. The image processing figure of the SEM photograph of the inorganic composite water dispersion type resin of Example 13 is shown. The image processing figure of the SEM photograph of the inorganic composite water dispersion type | mold resin of Example 14 is shown. The image processing figure of the SEM photograph of the inorganic composite water dispersion type | mold resin of Example 15 is shown. The image processing figure of the SEM photograph of the inorganic composite water dispersion-type resin of Example 16 is shown. The image processing figure of the SEM photograph of the inorganic composite water dispersion type resin of Example 17 is shown. The image processing figure of the SEM photograph of the inorganic composite water-dispersed resin of Example 18 is shown. The image processing figure of the SEM photograph of the inorganic composite water dispersion type resin of Example 19 is shown. The image processing figure of the TEM photograph of the inorganic composite water dispersion type resin of Example 20 is shown. The image processing figure of the TEM photograph of the inorganic composite water dispersion type resin of the comparative example 4 is shown. The image processing figure of the TEM photograph of the inorganic composite water dispersion type resin of the comparative example 5 is shown.

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

The hydrophilic inorganic compound has a bulk shape, a needle shape, or a plate shape (excluding a layer shape).
Examples of the hydrophilic inorganic compound having a bulk shape include a spherical inorganic shape, a rectangular parallelepiped shape, or an irregularly shaped hydrophilic inorganic compound thereof. Examples of the bulk-form hydrophilic inorganic compound include hydrophilic silica, calcium carbonate, titanium oxide, tin oxide (including antimony-doped tin oxide), alumina, magnesium hydroxide, barium titanate, zinc oxide, and nitride. Examples thereof include silicon, silicon carbide, carbon (diamond), and metal fine particles.

Examples of the needle-shaped hydrophilic inorganic compound include potassium titanate, wollastonite, sepiolite, acicular tin oxide, acicular magnesium hydroxide, and alumina.
The plate-shaped hydrophilic inorganic compound is a plate-shaped hydrophilic inorganic compound excluding a layer-shaped inorganic compound (hydrophilic inorganic compound) such as a layered clay mineral, such as boron nitride, plate-like calcium carbonate, plate And aluminum hydroxide.

These hydrophilic inorganic compounds can be used alone or in combination of two or more. Preferred examples include antimony-doped tin oxide, titanium oxide, tin oxide, alumina, zinc oxide, boron nitride, silicon nitride, silicon carbide, and carbon (diamond).
As such a hydrophilic inorganic compound, a general commercial product can be used. For example, more specifically, as antimony-doped tin oxide, for example, SN-100S, SN-100P, SN manufactured by Ishihara Sangyo Co., Ltd. -100D (water dispersion), as titanium oxide, for example, TTO series made by Ishihara Sangyo Co., Ltd., as zinc oxide, for example, SnO-310, SnO-350, SnO-410, made by Sumitomo Osaka Cement Co., as alumina For example, the NANOBYK series manufactured by Big Chemie Japan, the alumina sol series manufactured by Nissan Chemical Industries, Ltd., the silicon carbide, for example, the SiC series manufactured by Sumitomo Osaka Cement Co., and the diamond, for example, the diamond powder series, etc. Can be mentioned.

In the case of a hydrophilic inorganic compound having a bulk shape (spherical shape), the size of the hydrophilic inorganic compound is, for example, 1 to 400 nm, preferably 1 to 200 nm, more preferably 5 to 100 nm as the primary average particle diameter. It is. If it is larger than the above range, oil droplets with the desired particle size may not be obtained.
In the case of a needle-shaped hydrophilic inorganic compound or a plate-shaped hydrophilic inorganic compound, the maximum length is, for example, 1 to 400 nm, preferably 1 to 200 nm, and more preferably 5 to 200 nm. If it is larger than the above range, oil droplets with the desired particle size may not be obtained. Furthermore, these aspect ratios (in the case of needles, the major axis length / minor axis length or the major axis length / thickness are expressed. In the case of a plate shape, the diagonal length is also expressed. / Thickness or long side length / thickness) is, for example, 5 to 200, preferably 10 to 100.

The hydrophilic inorganic compound described above is present at the interface between water and the oil droplets of the ethylenically unsaturated monomer in the monomer emulsion preparation step, and is unevenly distributed on the surface of the water-dispersed resin after the polymerization step. Need to be supported as follows.
Therefore, if the hydrophilic inorganic compound is hydrophobic, it will be stably present in the oil phase in the monomer emulsion preparation process and cannot be present at the interface between water and oil droplets. Disappear. On the other hand, if the hydrophilicity of the hydrophilic inorganic compound is excessively high, it will exist stably in water, and again, it cannot exist at the interface between water and the oil droplets of the ethylenically unsaturated monomer. In some cases, it cannot be emulsified.

Therefore, when the hydrophilicity of the hydrophilic inorganic compound is excessively high and emulsification cannot be performed, the surface of the hydrophilic inorganic compound is partially surface-treated with a surface treatment agent as necessary.
Examples of the surface treatment agent include general surface modifiers such as coupling agents and fatty acids. 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, such as hexamethyldisilazane 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.
As the surface treatment with such a surface treatment agent, for example, a dry method in which an aqueous alcohol solution, an organic solvent solution or an aqueous solution of a surface treatment agent is added while stirring a hydrophilic inorganic compound in a mixer, for example, a hydrophilic inorganic compound. Examples include a wet method in which a compound is dispersed in an alcohol aqueous solution or an aqueous solution, and then a surface treatment agent is added, for example, a spray method in which a surface treatment agent is sprayed onto a hydrophilic inorganic compound.

In addition, as the hydrophilic inorganic compound having excessively high hydrophilicity, a commercially available product that has been surface-treated in advance can be used.
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) Lauryl acid), tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, 2-methylheptadecyl (meth) acrylate ( (Meth) acrylic acid isostearyl), (meth) acrylic acid octadecyl, (meth) acrylic acid 2-ethylhexadecyl and the like (meth) acrylic acid alkyl (C1-C18 linear or branched alkyl) ester. It is done.

Among these (meth) acrylic acid alkyl esters, preferably, butyl acrylate, methyl methacrylate, lauryl methacrylate, 2-ethylhexyl acrylate, isostearyl acrylate, and 2-ethylhexadecyl (meth) acrylate are used. Can be mentioned. 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-described hydrophilic inorganic compound and water are blended, and then these are stirred and mixed to disperse the hydrophilic inorganic compound in water. An aqueous dispersion is prepared (aqueous dispersion preparation step).

The blending ratio of the hydrophilic inorganic compound is, for example, 0.1 to 50 parts by weight, preferably 0.2 to 40 parts by weight, and more preferably 0.5 to 30 parts by weight with respect to 100 parts by weight of water. is there.
When the blending ratio of the hydrophilic inorganic compound exceeds the above range, the viscosity of the aqueous dispersion may be excessively increased or aggregation may occur in the polymerization process.
On the other hand, if the blending ratio of the hydrophilic inorganic compound is less than the above range, the content ratio of the hydrophilic inorganic compound in the inorganic composite water-dispersed resin becomes excessively low, and the hydrophilic inorganic compound is placed on the surface of the water-dispersed resin. In some cases, it cannot be uniformly supported.

In order to stir and mix the water in which the hydrophilic compound is blended, for example, a known stirrer such as a disper or an ultrasonic homogenizer is used.
Moreover, in the above-described stirring and mixing, a partial surface treatment of the above-described hydrophilic inorganic compound can be performed.
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 hydrophilic inorganic compound 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. More preferably, it is 8 to 100 parts by weight.
If the blending ratio of the hydrophilic inorganic compound is less than the above range, in the monomer emulsion preparation process, a stable emulsion form cannot be obtained, and the coverage of the hydrophilic inorganic compound in the inorganic composite water-dispersed resin is excessive. Lower.

On the other hand, when the blending ratio of the hydrophilic inorganic compound exceeds the above range, the coverage of the hydrophilic inorganic compound in the inorganic composite water-dispersed resin becomes excessively high, the viscosity increases, and it may be necessary to adjust the viscosity. .
In the monomer emulsion step, a hydrophobic inorganic compound is previously dispersed in the ethylenically unsaturated monomer to prepare a monomer dispersion of the hydrophobic inorganic compound (monomer dispersion preparation step). It is also possible to emulsify a monomer dispersion of a functional inorganic compound. As a result, the hydrophobic inorganic compound can be encapsulated in the inorganic composite water-dispersed resin.

The hydrophobic inorganic compound has 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. As the surface treatment agent, the same ones as described above are used, and examples thereof include metal hydroxides such as aluminum hydroxide, and metal oxides such as zirconium oxide. The surface treatment method is the same as described above.

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 average particle diameter 12 nm, hexamethyldisilazane treatment), Aerosil R104 (primary average particle diameter 12 nm, octamethylcyclotetrasiloxane treatment), Aerosil R974 (primary average particle diameter). 12 nm, dimethyldichlorosilane treatment), Aerosil R812 (primary average particle diameter 7 nm, hexamethyldisilazane treatment) and the like are used. Examples of the TTO series include TTO-51 (C) (primary average particle diameter of 10 to 30 nm, aluminum hydroxide / stearic acid treatment), TTO-55 (C) (primary average particle diameter of 30 to 50 nm, hydroxylation). Aluminum / stearic acid treatment), TTO-55 (D) (primary average particle diameter 30 to 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.

In order to emulsify the ethylenically unsaturated monomer (or monomer dispersion), for example, an aqueous dispersion and an oil phase liquid containing the ethylenically unsaturated monomer are blended, and then these are emulsified, for example. To emulsify.
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.
The hydrophobic compound is a hydrophobic organic compound excluding the above-described hydrophobic inorganic compound, for example, higher alkanes having 8 to 30 carbon atoms such as dodecane, hexadecane, and octadecane, such as lauryl alcohol, cetyl alcohol, and stearyl alcohol. Higher alcohols having an alkyl group having 8 to 30 carbon atoms such as, for example, alkyl (meth) acrylates having an alkyl group having 8 to 30 carbon atoms such as lauryl (meth) acrylate, stearyl (meth) acrylate, etc. Examples thereof include 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, for example, 100 μm or less, preferably 40 μm or less, more preferably 4 μm or less, and usually 0.05 μm or more.
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 hydrophilic inorganic compound.
When blending the surfactant in water, in the aqueous dispersion preparation step, water before the hydrophilic inorganic compound is blended, or water before the hydrophilic inorganic compound is blended and dispersed, Add surfactant. Preferably, a dispersant is blended. By blending the surfactant with water, the primary particles of the hydrophilic inorganic compound that aggregates can be dispersed.

  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 hydrophilic inorganic compound in the aqueous dispersion is improved, the viscosity of the aqueous dispersion is reduced, 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.

Moreover, when preparing a monomer emulsion from a monomer dispersion liquid, surfactant is mix | blended with at least any one of water, an aqueous dispersion liquid, an ethylenically unsaturated monomer, a monomer dispersion liquid, and a 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 the inorganic composite water-dispersed resin is, for example, 100 μm or less, preferably 40 μm or less, more preferably 4 μm or less, and usually 0.05 μm or more. It is almost the same as the volume-based median diameter of the droplet.
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 hydrophilic inorganic compound is reduced in hydrophilicity and the dispersibility in the aqueous dispersion is lowered, and is not uniformly supported on the surface of the water-dispersed resin.
In the method for producing an inorganic composite water-dispersed resin of the present invention, a hydrophilic inorganic compound is dispersed in water to prepare an aqueous dispersion of the hydrophilic inorganic compound, and the aqueous dispersion, the ethylenically unsaturated monomer, Is added to prepare a monomer emulsion, and an ethylenically unsaturated monomer is polymerized.

Therefore, the obtained water-dispersed resin can be composited with a hydrophilic inorganic compound so that the hydrophilic inorganic compound is unevenly distributed on the surface thereof. That is, the inorganic composite water-dispersed resin can carry the hydrophilic inorganic compound on the outer surface without encapsulating the hydrophilic inorganic compound.
As a result, the inorganic composite water-dispersed resin of the present invention can form a path in which the hydrophilic inorganic compound is continuous in the water-dispersed resin, and is therefore 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, a hydrophilic inorganic compound is formed on the outer surface while encapsulating the hydrophobic inorganic compound, not the hydrophilic inorganic compound, in the resulting inorganic composite water-dispersed resin. Can be composited so as to carry (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. Preferably, polyethylene is used.

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)
20 parts by weight of hydrophilic boron nitride particles (BN-20, bulk shape, primary average particle size 20 nm) were added to 715 parts by weight of water, and this was treated with an ultrasonic homogenizer for 3 minutes to obtain an aqueous dispersion.
(Preparation of monomer emulsion)
Isostearyl acrylate 100 parts by weight, hexadecane 5 parts by weight, initiator (dimethyl 2,2′-azobis (2-methylpropionate), oil-soluble azo initiator, trade name: V-601, Wako Pure Chemical Industries, Ltd. (Manufactured) 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 with a high-pressure homogenizer (PANDA 2K) for 2 passes at a pressure of 100 MPa, and 20 wt% dispersant liquid (polymer dispersant, trade name: Charol AN-103P, Daiichi 5 parts by weight (manufactured by Kogyo Seiyaku Co., Ltd.) (1 part by weight in solid content) was added 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 an inorganic composite water-dispersed resin having a concentration of 20% was obtained.

Example 2
In the aqueous dispersion preparation step, a monomer emulsion was prepared in the same manner as in Example 1 except that the blending number of water was changed to 942 parts by weight and the blending number of boron nitride particles was changed to 60 parts by weight. This was polymerized to obtain an emulsion of an inorganic composite water-dispersed resin having a solid content concentration of 20%.

Example 3
(Water dispersion preparation process)
20 parts by weight of hydrophilic titanium oxide (TTO-55D, bulk shape, primary average particle size 30-50 nm, manufactured by Ishihara Sangyo Co., Ltd.) is added to 517 parts by weight of water, and this is treated with an ultrasonic homogenizer for 3 minutes to form titanium oxide. An aqueous dispersion was obtained.
(Preparation of monomer emulsion)
100 parts by weight of isostearyl 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 -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.

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% dispersant liquid (polymer dispersant, trade name: SN Dispersant 5045, manufactured by San Nopco) ) 25 parts by weight (5 parts by weight solids) 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 inorganic composite water-dispersed resin having a partial concentration of 20% was obtained.

Example 4
(Preparation of aqueous dispersion)
ATO (antimony-doped tin oxide) aqueous dispersion (SN-100S, solid concentration 17.9%, bulk shape, primary average particle size 20 nm, manufactured by Ishihara Sangyo Co., Ltd.) 84 parts by weight (15 parts by weight in solids) Then, 368 parts by weight of water and 4.5 parts by weight of 3-methacryloyloxypropyl-trimethoxysilane (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) were added and stirred at room temperature for 20 hours. This was adjusted to pH 4.0 with a 5% aqueous acetic acid solution to prepare an aqueous dispersion.
(Monomer emulsion preparation process)
In an aqueous dispersion, 100 parts by weight of methyl methacrylate, 3 parts by weight of hexadecane, 0.2 part by weight of initiator (azobisisobutyronitrile), 20% by weight emulsifier liquid (anionic non-reactive emulsifier, trade name: High Tenol LA-16, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.25 parts by weight (0.05 parts by weight in solids) was added, and 6000 (1 / min) for 1 minute using a TK homomixer (Primics). The mixture was stirred and forcedly emulsified to prepare a monomer pre-emulsion. Subsequently, this monomer pre-emulsion was subjected to one pass treatment at a pressure of 150 MPa using a high-pressure homogenizer (Nanomizer, manufactured by Yoshida Kikai Kogyo Co., Ltd.) 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 5
In the aqueous dispersion preparation step, the blending part of the ATO aqueous dispersion was changed to 50 parts by weight in solid content, the blending part of water was changed to 486 parts by weight, and 3-methacryloyloxypropyl-trimethoxysilane Except that the blending amount was changed to 9.1 parts by weight, an aqueous dispersion was prepared in the same manner as in Example 4, and then a monomer emulsion was prepared, followed by polymerization to obtain a solid content concentration. An emulsion of 18% inorganic composite water-dispersed resin was obtained.

Example 6
In the aqueous dispersion preparation step, the blending number of the ATO aqueous dispersion was changed to 70 parts by weight in solid content, the blending number of water was changed to 486 parts by weight, and the pH was adjusted to 4.0 with a 5% aqueous acetic acid solution. After that, 2.2 parts by weight of the dispersant liquid (polycarboxylic acid-based dispersant, trade name: Charol AN-103P, solid content concentration 45%, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) is added. Except for the above, an aqueous dispersion was prepared in the same manner as in Example 4 and then a monomer emulsion was prepared and then polymerized to obtain an inorganic composite water-dispersed resin having a solid content concentration of 18%. An emulsion was obtained.

Example 7
In the aqueous dispersion preparation step, after adjusting the pH to 4.0 with a 5% aqueous acetic acid solution, 5 parts by weight of a 20% by weight dispersant liquid (polymer dispersant, trade name: Charol AN-103P, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) (1 part by weight in solid content) was further added, and in the monomer emulsion preparation step, a monomer emulsion was prepared in the same manner as in Example 4 except that butyl acrylate was used instead of methyl methacrylate. Was polymerized to obtain a water-dispersed nanoparticle polymer composite composition having a solid content concentration of 20%.

Example 8
After adjusting the pH to 4.0 with 5% aqueous acetic acid in the aqueous dispersion preparation step, the aqueous dispersion was further stirred and mixed for 20 hours. In the monomer emulsion preparation step, butyl acrylate was used instead of methyl methacrylate. In the same manner as in Example 4, a monomer emulsion was prepared, and then polymerized to obtain an emulsion of an inorganic composite water-dispersed resin having a solid content concentration of 20%.

Example 9
(Preparation of aqueous dispersion)
ATO (antimony-doped tin oxide) aqueous dispersion (SN-100D, solid content concentration 29.7%, bulk shape, primary average particle size 20 nm, manufactured by Ishihara Sangyo Co., Ltd.) 168 parts by weight (50 parts by weight in solids) And 167 parts by weight of water and 3.8 parts by weight of 3-methacryloyloxypropyl-trimethoxysilane (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) were added, and the pH was adjusted to 4.0 with a 5% aqueous acetic acid solution. This was stirred at room temperature for 20 hours, and 15.0 parts by weight (3 parts by weight in solid content) of a 20% by weight dispersant solution (polymer dispersant, trade name: Charol AN-103P, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) Was added and mixed to obtain an aqueous dispersion.
(Monomer emulsion preparation process)
In an aqueous dispersion, butyl acrylate 100 parts by weight, hexadecane 3 parts by weight, initiator (azobisisobutyronitrile) 0.2 parts by weight, 20% by weight emulsifier liquid (anionic non-reactive emulsifier, trade name: High Tenol LA-16, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.25 parts by weight (0.05 parts by weight in solids) was added, and 6000 (1 / min) for 1 minute using a TK homomixer (Primics). The mixture was stirred and forcedly emulsified to prepare a monomer pre-emulsion. Subsequently, this monomer pre-emulsion was subjected to one pass treatment at a pressure of 150 MPa using a high-pressure homogenizer (Nanomizer, manufactured by Yoshida Kikai Kogyo Co., Ltd.) 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 35% was obtained.

Example 10
(Preparation of aqueous dispersion)
In the monomer emulsion preparation step, a monomer emulsion was prepared in the same manner as in Example 9 except that 100 parts by weight of 2-ethylhexyl acrylate was used instead of 100 parts by weight of butyl acrylate, and this was then polymerized. As a result, an emulsion of an inorganic composite water-dispersed resin having a solid content concentration of 35% was obtained.

Example 11
In the monomer emulsion preparation step, a monomer emulsion was prepared in the same manner as in Example 9 except that 100 parts by weight of lauryl methacrylate (dodecyl methacrylate) was used instead of 100 parts by weight of butyl acrylate. Was polymerized to obtain an emulsion of an inorganic composite water-dispersed resin having a solid concentration of 35%.

Example 12
In the monomer emulsion preparation step, the monomer emulsion was prepared in the same manner as in Example 9, except that 100 parts by weight of isostearyl acrylate (2-methylheptadecyl acrylate) was used instead of 100 parts by weight of 2-ethylhexyl acrylate. This was then polymerized to obtain an inorganic composite water-dispersed resin emulsion having a solid content of 35%.

Example 13
In the aqueous dispersion preparation step, the blending number of 3-methacryloyloxypropyl-trimethoxysilane (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) was changed to 15.2 parts by weight, and the blending number of water was changed to 111 parts by weight. In the same manner as in Example 9, an aqueous dispersion was prepared, and then a monomer emulsion was prepared, followed by polymerization to obtain an emulsion of an inorganic composite water-dispersed resin having a solid content concentration of 35%. Obtained.

Example 14
(Preparation of aqueous dispersion)
Titanium oxide aqueous dispersion (TTO-W-5, solid content concentration 30.7%, bulk shape, primary average particle size 50 nm, manufactured by Ishihara Sangyo Co., Ltd.) 163 parts by weight (solid content 50 parts by weight) and water 172 Part by weight and 3.8 parts by weight of 3-methacryloyloxypropyl-trimethoxysilane (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) were added, and the pH was adjusted to 4.0 with a 5% aqueous acetic acid solution. This was stirred at room temperature for 20 hours, and 15.0 parts by weight (3 parts by weight in solid content) of a 20% by weight dispersant solution (polymer dispersant, trade name: Charol AN-103P, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) Was added to prepare an aqueous dispersion.
(Monomer emulsion preparation process)
In an aqueous dispersion, butyl acrylate 100 parts by weight, hexadecane 3 parts by weight, initiator (azobisisobutyronitrile) 0.2 parts by weight, 20% by weight emulsifier liquid (anionic non-reactive emulsifier, trade name: High Tenol LA-16, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.25 parts by weight (0.2 parts by weight in solids) is added, and TK (1 / min) is used for 1 minute using a TK homomixer (manufactured by Primics). The mixture was stirred and forcedly emulsified to prepare a monomer pre-emulsion. Subsequently, this monomer pre-emulsion was subjected to one pass treatment at a pressure of 150 MPa using a high-pressure homogenizer (Nanomizer, manufactured by Yoshida Kikai Kogyo Co., Ltd.) 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 35% was obtained.

Example 15
(Preparation of aqueous dispersion)
100 parts by weight of alumina aqueous dispersion (NANOBYK-3600, alumina solid content concentration 50%, bulk shape, primary average particle size 40 nm, manufactured by Big Chemie Japan Co., Ltd.) and 235 parts by weight of water , 3-methacryloyloxypropyl-trimethoxysilane (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.), 3.8 parts by weight, was added to adjust the pH to 4.0 with a 5% aqueous acetic acid solution. This was stirred at room temperature for 20 hours, and 15.0 parts by weight (3 parts by weight in solid content) of a 20% by weight dispersant solution (polymer dispersant, trade name: Charol AN-103P, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) Was added to prepare an aqueous dispersion.
(Monomer emulsion preparation process)
In an aqueous dispersion, butyl acrylate 100 parts by weight, hexadecane 3 parts by weight, initiator (azobisisobutyronitrile) 0.2 parts by weight, 20% by weight emulsifier liquid (anionic non-reactive emulsifier, trade name: High Tenol LA-16, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.25 parts by weight (0.2 parts by weight in solids) is added, and TK (1 / min) is used for 1 minute using a TK homomixer (manufactured by Primics). The mixture was stirred and forcedly emulsified to prepare a monomer pre-emulsion. Subsequently, this monomer pre-emulsion was subjected to one pass treatment at a pressure of 150 MPa using a high-pressure homogenizer (Nanomizer, manufactured by Yoshida Kikai Kogyo Co., Ltd.) 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 35% was obtained.

Example 16
(Preparation of aqueous dispersion)
285 parts by weight of alumina aqueous dispersion (alumina sol 100, alumina solid content concentration 10.3%, needle shape, maximum length 300 nm, manufactured by Nissan Chemical Industries, Ltd.), 67 parts by weight of water, 15.3 parts by weight of 3-methacryloyloxypropyl-trimethoxysilane (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) was added, and the pH was adjusted to 4.0 with a 5% aqueous acetic acid solution. This was stirred at room temperature for 20 hours, and 15.0 parts by weight (3 parts by weight in solid content) of a 20% by weight dispersant solution (polymer dispersant, trade name: Charol AN-103P, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) Was added and mixed to prepare an aqueous dispersion.
(Monomer emulsion preparation process)
In an aqueous dispersion, butyl acrylate 100 parts by weight, hexadecane 3 parts by weight, initiator (azobisisobutyronitrile) 0.2 parts by weight, 20% by weight emulsifier liquid (anionic non-reactive emulsifier, trade name: High Tenol LA-16, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.25 parts by weight (0.2 parts by weight in solids) is added, and TK (1 / min) is used for 1 minute using a TK homomixer (manufactured by Primics). The mixture was stirred and forcedly emulsified to prepare a monomer pre-emulsion. Subsequently, this monomer pre-emulsion was subjected to one pass treatment at a pressure of 150 MPa using a high-pressure homogenizer (Nanomizer, manufactured by Yoshida Kikai Kogyo Co., Ltd.) 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 inorganic composite water-dispersed resin emulsion having a partial concentration of 35% was obtained. EXAMPLE 17
(Preparation of aqueous dispersion)
Alumina aqueous dispersion (NANOBYK-3600, alumina solid content concentration 50%, bulk shape, primary average particle size 40 nm, manufactured by Big Chemie Japan) 100 parts by weight (solid content 50 parts by weight) and alumina water dispersion (alumina sol 100, alumina solid content concentration 10.3%, needle shape, maximum length 300 nm, manufactured by Nissan Chemical Industries, Ltd.) 485 parts by weight (50 parts by weight solids), water 70 parts by weight, 3-methacryloyloxypropyl- 16.2 parts by weight of trimethoxysilane (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) was added, and the pH was adjusted to 4.0 with a 5% aqueous acetic acid solution. This was stirred at room temperature for 20 hours, and 15.0 parts by weight (3 parts by weight in solid content) of a 20% by weight dispersant solution (polymer dispersant, trade name: Charol AN-103P, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) Was added and mixed to prepare an aqueous dispersion.
(Monomer emulsion preparation process)
In an aqueous dispersion, butyl acrylate 100 parts by weight, hexadecane 3 parts by weight, initiator (azobisisobutyronitrile) 0.2 parts by weight, 20% by weight emulsifier liquid (anionic non-reactive emulsifier, trade name: High Tenol LA-16, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.25 parts by weight (0.2 parts by weight in solids) is added, and TK (1 / min) is used for 1 minute using a TK homomixer (manufactured by Primics). The mixture was stirred and forcedly emulsified to prepare a monomer pre-emulsion. Subsequently, this monomer pre-emulsion was subjected to one pass treatment at a pressure of 150 MPa using a high-pressure homogenizer (Nanomizer, manufactured by Yoshida Kikai Kogyo Co., Ltd.) 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 35% was obtained.

Example 18
(Preparation of aqueous dispersion)
50 parts by weight of silicon carbide powder (β-SiC, bulk shape, primary average particle size 30 nm, manufactured by Sumitomo Osaka Cement Co., Ltd.), 282 parts by weight of water, and 20% by weight dispersant liquid (polymer dispersant, trade name) : Charol AN-103P, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 15.0 parts by weight (3 parts by weight in solids), treated with an ultrasonic homogenizer for 5 minutes, and then 3-methacryloyloxypropyl-trimethoxysilane (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) 1.9 parts by weight was added, and the pH was adjusted to 4.0 with a 5% aqueous acetic acid solution. This was stirred for 20 hours at room temperature to prepare an aqueous dispersion.
(Monomer emulsion preparation process)
In an aqueous dispersion, butyl acrylate 100 parts by weight, hexadecane 3 parts by weight, initiator (azobisisobutyronitrile) 0.2 parts by weight, 20% by weight emulsifier liquid (anionic non-reactive emulsifier, trade name: High Tenol LA-16, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.25 parts by weight (0.2 parts by weight in solids) is added, and TK (1 / min) is used for 1 minute using a TK homomixer (manufactured by Primics). The mixture was stirred and forcedly emulsified to prepare a monomer pre-emulsion. Subsequently, this monomer pre-emulsion was subjected to one pass treatment at a pressure of 150 MPa using a high-pressure homogenizer (Nanomizer, manufactured by Yoshida Kikai Kogyo Co., Ltd.) 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 35% was obtained.

Example 19
(Preparation of aqueous dispersion)
50 parts by weight of diamond powder (trade name: HHM-A-1 / 10 μm, bulk shape, primary average particle size 100 nm, manufactured by Techno Rise), 279 parts by weight of water, and 20% by weight dispersant liquid (polymer dispersion) Agent, trade name: Charol AN-103P, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 15.0 parts by weight (3 parts by weight in solids), treated with an ultrasonic homogenizer for 5 minutes, and then 3-methacryloyloxypropyl -0.5 part by weight of trimethoxysilane (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) was added, and the pH was adjusted to 4.0 with a 5% aqueous acetic acid solution. This was stirred for 20 hours at room temperature to prepare an aqueous dispersion.
(Monomer emulsion preparation process)
In an aqueous dispersion, butyl acrylate 100 parts by weight, hexadecane 3 parts by weight, initiator (azobisisobutyronitrile) 0.2 parts by weight, 20% by weight emulsifier liquid (anionic non-reactive emulsifier, trade name: High Tenol LA-16, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.25 parts by weight (0.2 parts by weight in solids) is added, and TK (1 / min) is used for 1 minute using a TK homomixer (manufactured by Primics). The mixture was stirred and forcedly emulsified to prepare a monomer pre-emulsion. Subsequently, this monomer pre-emulsion was subjected to one pass treatment at a pressure of 150 MPa using a high-pressure homogenizer (Nanomizer, manufactured by Yoshida Kikai Kogyo Co., Ltd.) 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 35% was obtained.

Example 20
(Preparation of aqueous dispersion)
ATO (antimony-doped tin oxide) aqueous dispersion (SN-100D, solid content concentration 29.7%, bulk shape, primary average particle size 20 nm, manufactured by Ishihara Sangyo Co., Ltd.) 168 parts by weight (50 parts by weight in solids) And 183 parts by weight of water and 3.8 parts by weight of 3-methacryloyloxypropyl-trimethoxysilane (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) were added, and the pH was adjusted to 4.0 with a 5% aqueous acetic acid solution. This was stirred at room temperature for 20 hours, and 15.0 parts by weight (3 parts by weight in solid content) of a 20% by weight dispersant solution (polymer dispersant, trade name: Charol AN-103P, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) Was added and mixed to prepare an aqueous dispersion.
(Monomer dispersion preparation process)
Aerosil R8200 (fumed silica, primary average particle size of 12 nm, hexamethyldiethyl) was added to a solution in which 100 parts by weight of butyl acrylate, 3 parts by weight of hexadecane, and 0.2 part by weight of an initiator (azobisisobutyronitrile) were mixed. 5 parts of silazane treatment (manufactured by Nippon Aerosil Co., Ltd.) was added, and this was stirred and mixed with an ultrasonic homogenizer for 3 minutes to obtain an oil phase liquid containing a monomer dispersion.
(Monomer emulsion preparation process)
Subsequently, the prepared oil phase liquid and 20% by weight of an emulsifier liquid (anionic non-reactive emulsifier, trade name: Hytenol LA-16, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.25 parts by weight (0.05% by solid content) Part by weight) was added to the above-described aqueous dispersion, and the mixture was stirred and forcibly emulsified at 6000 (1 / min) for 1 minute using a TK homomixer (manufactured by Primics) to prepare a monomer pre-emulsion. Subsequently, this monomer pre-emulsion was subjected to one pass treatment at a pressure of 150 MPa using a high-pressure homogenizer (Nanomizer, manufactured by Yoshida Kikai Kogyo Co., Ltd.) 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 35% was obtained.

Comparative Example 1
In the monomer emulsion preparation step, a monomer emulsion was prepared in the same manner as in Example 1 except that 20% by weight dispersant liquid (polymer dispersant, trade name: Charol AN-103P, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was not used. This was then polymerized to obtain an inorganic composite water-dispersed resin emulsion having a solid content of 20%.

Comparative Example 2
In the aqueous dispersion preparation step, an aqueous dispersion was prepared in the same manner as in Example 1 except that the blending number of boron nitride particles was changed to 250 parts by weight and the blending number of water was changed to 1438 parts by weight. A monomer emulsion was prepared and subsequently polymerized to obtain an emulsion of an inorganic composite water-dispersed resin having a solid content concentration of 20%.

Comparative Example 3
In the aqueous dispersion preparation step, an aqueous dispersion was prepared in the same manner as in Example 1, except that the blending number of boron nitride particles was changed to 3 parts by weight and the blending number of water was changed to 450 parts by weight. A monomer emulsion was prepared and subsequently polymerized to obtain an emulsion of an inorganic composite water-dispersed resin having a solid content concentration of 20%.

Comparative Example 4
(Monomer emulsion preparation process)
100 parts by weight of butyl acrylate, 3 parts by weight of hexadecane, 0.2 part by weight of initiator (azobisisobutyronitrile), 20% by weight emulsifier liquid (anionic non-reactive emulsifier, trade name: Haitenol LA-16, 1 part by weight (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 1 part by weight (0.2 part by weight in solids), 309 parts by weight of water, and 1 minute at 6000 (1 / min) using a TK homomixer (manufactured by Primex) A monomer pre-emulsion was prepared by stirring and forcibly emulsifying. Subsequently, this monomer pre-emulsion was subjected to one pass treatment at a pressure of 150 MPa using a high-pressure homogenizer (Nanomizer, manufactured by Yoshida Kikai Kogyo Co., Ltd.) to obtain a monomer emulsion.
(Polymerization process)
By charging the prepared monomer dispersion in 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 a water-dispersed resin having a solid content concentration of 23% was obtained.

Thereafter, 75 parts by weight of an aqueous dispersion (SN-100S, solid concentration 17.9%, manufactured by Ishihara Sangyo Co., Ltd.) is added to the emulsion and stirred to obtain an inorganic composite water-dispersed resin. An emulsion was obtained.
Comparative Example 5
(Water dispersion preparation process)
10 parts by weight of Lucentite SWN (layered clay mineral, manufactured by Co-op 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 20 and Comparative Examples 1 to 5, 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 5.

2) Median diameter of inorganic composite water-dispersed resin For the inorganic composite water-dispersed resins obtained in Examples 1 to 20 and Comparative Examples 4 and 5, 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 6.

3) Polymerization stability (aggregate rate)
The emulsion after the production of the inorganic composite water-dispersed resin obtained in Examples 1 to 20 and Comparative Examples 1 to 5 was filtered through a nylon mesh (# 80), and then 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 7.

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: Total weight of oil phase liquid component, hexadecane and clay mineral, hydrophilic inorganic compound and hydrophobic inorganic compound

4) SEM observation The emulsion of the inorganic composite water-dispersed resin obtained in Examples 2 to 7 and 9 to 19 was diluted with water, dropped onto a sample stage, and then dried at 30 ° C for 30 minutes. Subsequently, after performing Pt-Pd sputtering for 5 seconds, SEM observation was performed using FE-SEM (S-4800 made by HITACHI) having an acceleration voltage of 0.1 to 1 kV.

Image processing diagrams of these SEM photographs are shown in FIG. 2 to FIG. 7, FIG. 9, and FIG.
5) TEM observation The emulsion of the inorganic composite water-dispersed resin obtained in Examples 8, 9, 20, Comparative Example 4 and Comparative Example 5 was diluted with water, and one drop was dropped on the TEM sample stage with a carbon film. The sample was dried and then observed at an acceleration 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 Example 4 in an epoxy resin, it was dyed by treating in an aqueous 2% ruthenic acid solution for 3 hours. Ultracut S, manufactured by Leica Co., Ltd.) was cut to a thickness of about 80 nm, and then a cross section of the ultrathin section was observed using an Hitachi transmission electron microscope Hitachi H-7650 at an acceleration voltage of 100 kV.

  Image processing diagrams of these TEM photographs are shown in FIG. 8, FIG. 10, and FIG.

1 Base material 2 Adhesive layer

Claims (7)

A step of dispersing a hydrophilic inorganic compound in a bulk shape, needle shape or plate shape in water to prepare an aqueous dispersion of the hydrophilic inorganic compound;
The aqueous dispersion and the ethylenically unsaturated monomer are blended so that the blending ratio of the hydrophilic inorganic compound is 4 to 200 parts by weight with respect to 100 parts by weight of the ethylenically unsaturated monomer, and the ethylene A step of emulsifying the polymerizable 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 hydrophilic inorganic compound has a maximum length of 1 to 400 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 the monomer dispersion is blended with the aqueous dispersion to emulsify the monomer dispersion.   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 100 μm or less. A method for producing an inorganic composite water-dispersed resin according to claim 1.