JP2012107079A - Organic inorganic composite composition-emulsified dispersion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic-inorganic composite composition emulsified dispersion that is excellent in stability, transparent, free from cracks, tough and tough.
An organic-inorganic composite composition emulsification comprising a soap-free emulsified dispersion (A) containing a polymer obtained by polymerizing radically polymerizable monomers and an aqueous medium, and an inorganic aqueous dispersion. An organic / inorganic dispersion, wherein the monodispersed fine particles contained in the emulsified dispersion (A) have a particle size of 50 to 300 nm and do not contain a dispersion stabilizer and a surfactant. A composite composition emulsified dispersion is provided.
[Selection] Figure 1

Description

  The present invention relates to a soap-free emulsified dispersion containing monodispersed fine particles of 300 nm or less and containing no dispersion stabilizer or surfactant, and a composition emulsified dispersion comprising an inorganic component.

  As organic / inorganic composites, there are many known examples of blending inorganic components such as colloidal silica and layered silicate with organic acrylic emulsion polymers, etc., and colloidal silica particles in advance rather than direct blending. A composite emulsion in which the surface is covered with colloidal silica by emulsion polymerization or the like in the presence of is known. (For example, Patent Document 1, Patent Document 2, Non-Patent Document 1) However, when an acrylic emulsion and an inorganic component are blended, there is a problem that the system is often separated and the stability is poor. There was a problem that physical properties such as flexibility were impaired.

  In recent years, a drastic review of the manufacturing method of chemical products has been urged due to soaring petroleum energy. In this context, interest in microreactors has increased. A microreactor is a device that performs a reaction in a narrow space, and it is not necessary to introduce a large-scale device, and it is expected to reduce investment costs and manufacturing costs. Further, it is known that the microreactor has a feature that the reaction surface temperature is easy because the reaction is performed in a narrow space, and the specific surface area per unit volume is large.

JP-T-2005-281626 JP 2007-211075 A

Miyako Horie, Shinya Sakaguchi, Ryuichi Aoki, DNT Coating Technical Report, 8, 9-17, 2008

  An object of the present invention is to provide an organic-inorganic composite composition emulsified dispersion which is excellent in stability, transparent, free from cracks, and capable of obtaining a tough and tenacious film.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the reaction rate of the radical polymerizable monomer is 0.1 to 50% in the presence of the water-soluble radical initiator in the microtubular channel. After emulsion polymerization, the obtained emulsion polymerization solution is reacted in a reaction kettle equipped with a stirring blade to a reaction rate of 95% or more. A water dispersion characterized by comprising an emulsified dispersion containing monodisperse fine particles and an inorganic aqueous dispersion that are stable without containing a surfactant. It is excellent in stability, transparent, crack-free, tough and tough. The inventors have found that a film can be obtained and have completed the present invention.

  That is, the present invention provides an organic / inorganic composite composition comprising a soap-free emulsified dispersion (A) containing a polymer obtained by polymerizing radically polymerizable monomers and an aqueous medium, and an inorganic aqueous dispersion. An organic-inorganic composite composition emulsified dispersion, wherein the monodispersed fine particles contained in the emulsified dispersion (A) have a particle size of 50 to 300 nm.

  According to the emulsified dispersion of the organic-inorganic composite composition of the present invention, an emulsification that is obtained without using a protective colloid such as a water-soluble polymer or a surfactant, obtained by combining a microreactor and a batch reaction kettle. An organic / inorganic composite composition emulsified dispersion using a dispersion and an inorganic water dispersion can be produced with high production efficiency and has excellent stability. Furthermore, since the emulsified dispersion is composed of monodispersed fine particles, and no emulsifier or stabilizer is used during the preparation of the emulsified dispersion, when the polymer particles and inorganic particles are fused together to form a film, Since the diameters are uniform and are not affected by emulsifiers, stabilizers, etc., it is possible to obtain a film that is tough and sticky without cracks, and that the resulting film and the resulting coating film are homogeneous and transparent. .

It is a disassembled perspective view which shows three types of plate structures of the chemical reaction device 1 used for this invention. It is a perspective view which shows the plate structure of the chemical reaction device 1 in FIG. It is a horizontal sectional view showing the whole schematic diagram composition including the joint part of chemical reaction device 1 used for the present invention. It is a disassembled perspective view which shows two types of plate structures of the chemical reaction device 2 used for the manufacturing method of this invention. It is a perspective view which shows the plate structure of the chemical reaction device 2 in FIG. It is a horizontal sectional view showing the whole schematic diagram composition including the joint part of chemical reaction device 2 used for the present invention. It is a perspective view which shows the plate structure of the chemical reaction device 3 used for this invention. It is a horizontal sectional view showing the whole schematic diagram composition including the joint part of chemical reaction device 3 used for the present invention. It is a disassembled perspective view which shows two types of plate structures of the chemical reaction device 1 in FIG. It is a schematic block diagram which shows typically the manufacturing apparatus used in the Example. The figure which shows the transparency of the cast film created in Example 4-6 The figure which shows the crack of the cast film created in Comparative Example 2-4

Next, details necessary for carrying out the present invention will be described in detail.
As the inorganic aqueous dispersion in the present invention, an inorganic colloidal dispersion is preferably used.
Examples of the inorganic colloid dispersion include Li, Na, Cu, Ca, Sr, Ba, Zn, B, Al, Ga, Y, Si, Ge, Pb, P, Sb, V, Ta, W, La, Nd, Examples thereof include metals such as Si, Ti, and Zr, colloidal dispersions such as glass powder, mica, talc, clay, and amorphous substance colloids such as allophane.

Among these, metal colloids include metal oxide colloids. Specifically, silica (Si) colloid, aluminum (Al) colloid, titanium (Ti) colloid, zirconium (Zr) are commercially available. ) Colloid and the like.
Here, as the metal oxide colloid, metal oxide fine particles synthesized by a sol-gel method are used as a dispersoid, and a metal oxide colloid having an average primary particle diameter of 10 nm to 1 μm is preferable. Among such metal oxide colloids, silica colloids (colloidal silica) include silica dol (registered trademark) manufactured by Nippon Chemical Industry Co., Ltd., Adelite (registered trademark) AT manufactured by ADEKA Co., Ltd., and catalyst chemical industry. Examples include Cataloid (registered trademark) manufactured by Co., Ltd., Snowtex (registered trademark) manufactured by Nissan Chemical Industries, Ltd., and the like. Examples of the titanium colloid include titanium oxide manufactured by Ishihara Sangyo Co., Ltd. and titanium oxide manufactured by Teika Co., Ltd. Furthermore, examples of the aluminum colloid include alumina sol manufactured by Kawaken Fine Chemical Co., Ltd., alumina sol manufactured by Nissan Chemical Industries, Ltd., and the like. Examples of the zirconia colloid include Nano Youth (registered trademark) manufactured by Nissan Chemical Industries, Ltd.

  As the clay mineral, those having dispersibility in water, preferably those having a property of swelling between layers by water are used. More preferably, it is a layered clay mineral that can be at least partially exfoliated and dispersed in layers in water, and particularly preferably a lamellar clay mineral that can be exfoliated and dispersed uniformly in water with a thickness of 1 to 10 layers. For example, water-swellable smectite or water-swellable mica is used. More specifically, water-swellable hectorite containing sodium as an interlayer ion, water-swellable montmorillonite, water-swellable saponite, water-swellable synthetic mica, etc. Is mentioned.

  The emulsified dispersion (A) used in the present invention is a soap-free emulsified dispersion and does not contain a dispersion stabilizer and a surfactant. For example, in a microtubule, a water-soluble radical initiator In the presence, the radical polymerizable monomer can be emulsion-polymerized to a reaction rate of 0.1 to 50%, and then reacted in a reaction kettle equipped with a stirring blade to a reaction rate of 95% or more.

  There are no particular restrictions on the water-soluble radical initiator used in the present invention, and various types of water-soluble radical polymerization initiators conventionally used in radical polymerization can be used depending on the type of raw material radical polymerizable monomer. It can be selected and used accordingly. As such a water-soluble initiator, for example, water-soluble organic peroxides, water-soluble azo compounds, redox initiators, persulfates and the like are preferably used.

  Examples of the water-soluble organic peroxide include t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 1,1 , 3,3-tetramethyl hydroperoxide and the like. Examples of water-soluble azo compounds include 2,2′-diamidinyl-2,2′-azopropane monohydrochloride, 2,2′-diamidinyl-2,2′-azobutane monohydrochloride, 2,2 Examples include '-diamidinyl-2,2'-azopentane monohydrochloride and 2,2'-azobis (2-methyl-4-diethylamino) butyronitrile hydrochloride.

  Furthermore, examples of the redox initiator include a combination of hydrogen peroxide and a reducing agent. In this case, as the reducing agent, divalent iron ions, copper ions, zinc ions, cobalt ions, vanadium ions and other metal ions, ascorbic acid, reducing sugars and the like are used. Examples of the persulfate include ammonium persulfate and potassium persulfate.

  One of these water-soluble radical polymerization initiators may be used alone, or two or more thereof may be used in combination.

The radical polymerizable monomer used in the method for producing an emulsified dispersion used in the present invention is not particularly limited as long as it is a compound having a radical polymerizable unsaturated group. For example, methyl (meth) Acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, lauryl (meth) Acrylic unsaturated monomers of alkyl (meth) acrylates having 1 to 30 carbon atoms such as acrylate and stearyl (meth) acrylate;
For example, alkyl styrene such as styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, triethyl styrene, propyl styrene, butyl styrene, hexyl styrene, heptyl styrene and octyl styrene; fluorostyrene, chlorostyrene, bromostyrene, Halogenated styrene such as dibromostyrene and chloromethylstyrene; Styrenic unsaturated monomers such as nitrostyrene, acetylstyrene, methoxystyrene, α-methylstyrene, vinyltoluene;
Carboxylic acid group-containing unsaturated compounds such as (meth) acrylic acid, itaconic acid or its monoester, maleic acid or its monoester, fumaric acid or its monoester, itaconic acid or its monoester, crotonic acid, p-vinylbenzoic acid Monomers and salts thereof; 2- (meth) acrylamide-2-methylpropanesulfonic acid, vinylsulfonic acid, styrenesulfonic acid, (meth) allylsulfonic acid, sulfoethyl (meth) acrylate, sulfopropyl (meth) acrylate, sulfonic acid group-containing unsaturated monomers such as α-methylstyrene sulfonic acid and salts thereof;

Dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, vinylpyrrolidone, N-methylvinylpyridium chloride, (meth) allyltriethylammonium chloride, 2-hydroxy-3- (meth) acryloyloxypropyltrimethylammonium chloride, etc. A tertiary or quaternary amino group-containing unsaturated monomer; a hydroxyl-containing unsaturated monomer such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, or polyethylene glycol mono (meth) acrylate; ) Amide-containing unsaturated monomers such as acrylamide, N-hydroxyalkyl (meth) acrylamide, N-alkyl (meth) acrylamide, N, N-dialkyl (meth) acrylamide, vinyl lactams
Unsaturated dibasic acid diesters such as maleic acid, fumaric acid, itaconic acid, aromatic unsaturated monomers such as styrene, p-methylstyrene, α-methylstyrene, p-chlorostyrene, chloromethylstyrene, vinyltoluene Nitrile unsaturated monomers such as acrylonitrile and methacrylonitrile; conjugated diolefin unsaturated monomers such as butadiene and isoprene;
Multifunctional unsaturation such as divinylbenzene, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, allyl methacrylate, diallyl phthalate, trimethylolpropane triacrylate, glyceryl diallyl ether, polyethylene glycol dimethacrylate, polyethylene glycol diacrylate Monomer;

Vinyl unsaturated monomers such as ethylene, propylene and isobutylene;
Vinyl ester unsaturated monomers such as vinyl acetate, vinyl propionate, octyl vinyl ester, Veova 9, Veova 10, Veova 11 [Beova: Shell Chemical Company, Ltd.]; ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, cyclohexyl Vinyl ether unsaturated monomers such as vinyl ether; allyl ether unsaturated monomers such as ethyl allyl ether;
Halogen-free products such as vinyl chloride, vinyl bromide, vinylidene chloride, vinylidene fluoride, chlorotrifluoroethylene, tetrafluoroethylene, hexafluoropropylene, pentafluoropropylene, perfluoro (propyl vinyl ether), perfluoroalkyl acrylate, and fluoromethacrylate Saturated monomers, etc .;
Epoxy group-containing unsaturated monomers such as glycidyl acrylate and glycidyl methacrylate; vinyl silanes such as vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, and γ-methacryloxypropyltrimethoxysilane Unsaturated monomers;

Examples thereof include carbonyl group-containing unsaturated monomers such as acrolein, diacetone acrylamide, vinyl methyl ketone, vinyl butyl ketone, diacetone acrylate, acetonitrile acrylate, acetoacetoxyethyl (meth) acrylate, vinyl acetophenone and vinyl benzophenone.
Here, the weight ratio of the solid content of the emulsified dispersion and the inorganic water dispersion is preferably in the range of 99/1 to 50/50. Clay minerals and the like can obtain a film having excellent stability and transparency, no cracking, toughness and tenacity as long as it is within the range of 99/1 to 50/50, since the properties can be obtained even at a low addition rate. It becomes possible to provide an aqueous dispersion.

The emulsion dispersion used in the present invention is a reaction comprising a stirring blade after emulsion polymerization of a radical polymerizable monomer to a reaction rate of 0.1 to 50% in the presence of a water-soluble initiator in a microtubule. It can manufacture by making it react to 95% or more of reaction rates in a kettle.
More specifically, the emulsified dispersion used in the present invention uses a micromixer having a microtubular channel formed therein and a reaction vessel having a microtubular channel formed therein, and the presence of a water-soluble radical initiator. Then, after emulsion polymerization to a reaction rate of 0.1 to 50% of the radical polymerizable monomer, it can be produced by reacting to a reaction rate of 95% or more in a reaction kettle equipped with a stirring blade.

  More specifically, the emulsified dispersion used in the present invention uses a micromixer in which a microtubular channel is formed and a reaction vessel in which a microtubular channel is formed. By mixing the fluid of an aqueous medium containing a water-soluble radical initiator and a medium containing a radical polymerizable monomer with a micromixer with a path formed, oil droplets of the radical polymerizable monomer are converted into water-soluble radical initiators. After being formed in an aqueous medium containing an agent, the radically polymerizable monomer partially dissolved in the aqueous medium is polymerized by decomposition of the water-soluble radical initiator in a reaction vessel in which a microtubular channel is formed. From the oil droplets of radically polymerizable monomers finely dispersed in the aqueous phase to the surface of the particle nuclei. Monomer supplied The polymerization proceeds, the emulsion polymerization is carried out to a reaction rate of 0.1 to 50% of the radical polymerizable monomer, and then the reaction rate is 95% or more in a reaction vessel equipped with a stirring blade. be able to.

  In general, polymer particles obtained by soap-free emulsion polymerization as described above are stabilized by repulsion due to the charge of the radical initiator segment and adsorption of the oligo soap produced as a by-product to the particle surface. Generation of and stabilization of fine particle nuclei is promoted by decomposing more radical initiators in a reaction vessel in which uniform oil droplets are formed and microtubular channels are formed inside. Nucleation and growth of monodisperse fine particles having a smaller particle diameter obtained in (1) can be realized.

  A commercially available micromixer can be used as the micromixer having a microtubular channel formed therein. For example, a microreactor having an interdigital channel structure, an institute, a fool, a microtechnique, a mainz ( IMM) single mixer and caterpillar mixer; Microglass microglass reactor; CPC Systems Cytos; Yamatake YM-1, YM-2 mixer; Shimadzu GLC mixing tee and tee (T-shaped connector) ); IMT chip reactor manufactured by Micro Chemical Engineering Co., Ltd .; Toray Engineering developed product, Micro High Mixer, etc., and any of them can be used in the present invention.

  Furthermore, as a preferred form of the micromixer system, an aqueous medium containing a water-soluble radical initiator and a radical polymerizable monomer are circulated in separate flow paths and mixed at the outlets of both the flow paths. After mixing using a micromixer, a micromixer that further promotes mixing by supplying and flowing to a flow path whose flow path cross-sectional area is reduced in the flow direction is preferable. Mixing can be further promoted by a turbulent flow effect caused by further contracting the flow path.

  After mixing using a micromixer that mixes at the outlets of both the flow paths, mixing is promoted by supplying the flow to a flow path whose flow path cross-sectional area is reduced in the flow direction. By using a micromixer, it becomes possible to promote dispersion of a radical polymerizable monomer in an aqueous medium containing a water-soluble radical initiator.

After mixing using a micromixer that is mixed at the outlets of both of the above-mentioned channels, the mixing is promoted by supplying it to a channel whose channel cross-sectional area is reduced in the flow direction while being circulated. A micromixer microtubular channel may be a tube or pipe-shaped channel that combines at least two members and uses a space formed between the members as a channel. You may use as a flow path.
Hereinafter, the chemical reaction device 1 and the chemical reaction device 2 provided with a flow path in a preferable form used as a method for producing an emulsified dispersion used in the present invention will be described in detail. FIG. 1 shows a plate in which a microtubular channel through which a fluid containing a radical polymerizable monomer passes, a plate in which a microtubular channel through which a fluid containing a water-soluble radical initiator passes, and heat exchange are performed. It is a schematic structural example of the reaction apparatus formed by laminating | stacking the plate which installed the flow path through which a fluid flows. FIG. 2 shows a chemical reaction device 1 formed by laminating a plate on which microtubular channels for flowing the mixed liquid in the device of FIG. 1 are arranged and a plate on which a channel for flowing a fluid for heat exchange is installed. This is a schematic configuration example.
The chemical reaction device 1 includes, for example, a plurality of first plates (5 in FIG. 1) and second plates (8 in FIG. 1) alternately formed in the same rectangular plate shape in FIG. Configured. Further, as required, a third plate (3 in FIG. 1) is laminated as shown in FIG. Each one first plate is provided with a flow path through which a fluid containing a radical polymerizable monomer passes. The second plate is provided with a flow path (hereinafter referred to as a reaction flow path) through which a fluid containing a water-soluble radical initiator passes (hereinafter, the plate provided with the reaction flow path is referred to as a process plate). The third plate is provided with a flow channel for temperature control fluid (hereinafter referred to as a temperature control channel) (hereinafter, the plate provided with the temperature control channel is referred to as a temperature control plate).

  As shown in FIG. 3, these supply ports and discharge ports are dispersed and arranged in each region of the end faces 15b, 15c and side surfaces 15d, 15e of the chemical reaction device 1, and a water-soluble radical initiator is placed in these regions. Fluid containing δ (in FIG. 2 indicates a fluid flow of a fluid containing a water-soluble radical initiator), fluid containing a radical polymerizable monomer (ε in FIG. 2 is a fluid flow of a fluid containing a radical polymerizable monomer) , And a joint portion 32 composed of a connector 30 and a joint portion 31 for flowing a temperature control fluid (γ in FIG. 2 indicates the flow of the temperature control fluid). Further, the outlet mixing is achieved by the fluid containing the radical polymerizable monomer and the fluid containing the water-soluble radical initiator joining in the space 33 formed by the end face 15c of the chemical reaction device 1 and the connector 30. .

Via these joints, a fluid containing a radical polymerizable monomer and a fluid containing a water-soluble radical initiator are supplied from the end face 15b, discharged to the end face 15c, and a temperature-controlled fluid is supplied from the side face 15d. It is discharged to the side surface 15e.
The planar view shape of the device for chemical reaction 1 is not limited to the rectangular shape as shown in the figure, and may be a square shape or a rectangular shape with the side surfaces 15d and 15e longer than between the end surfaces 15b and 15c. Therefore, in accordance with the illustrated shape, the direction from the end face 15b to the end face 15c is referred to as the longitudinal direction of the process plate and the temperature control plate of the chemical reaction device 1, and the direction from the side face 15d to the side face 15e is referred to as the chemical reaction device. This is referred to as the short direction of the process plate 1 and the temperature control plate.
The chemical reaction device 2 includes, for example, a fourth plate (14 in FIG. 4) having the same rectangular plate shape in FIG. 4, and a temperature control plate (3 in FIG. 4) in FIG. As shown, they are stacked. Each one fourth plate is provided with a flow path through which the fluid mixed in the chemical reaction device 1 passes.
Then, as shown in FIG. 6, these supply ports and discharge ports are distributed and arranged in each region of the end surfaces 16b, 16c, and side surfaces 16d, 16e of the chemical reaction device 2, and in these regions, radically polymerizable single molecules are disposed. For flowing a fluid containing a mer and a fluid containing a water-soluble radical initiator (α in FIG. 5 indicates a liquid fluid) and, if necessary, a temperature adjusting fluid (γ indicates a temperature adjusting fluid in FIG. 5) A joint part 32 composed of a connector 30 and a joint part 31 is connected to each other.

Through these joint portions, a fluid containing a fluid containing a radical polymerizable monomer and a fluid containing a water-soluble radical initiator is supplied from the end face 16b, discharged to the end face 16c, and the temperature control fluid is discharged from the side face 16e. It is supplied and discharged to the side surface 16d.
The shape of the chemical reaction device 2 in plan view is not limited to the rectangular shape shown in the figure, and may be a square shape or a rectangular shape with the side surfaces 16d and 16e longer than between the end surfaces 16b and 16c. Therefore, in accordance with the illustrated shape, the direction from the end face 16b to the end face 16c is referred to as the longitudinal direction of the process plate and the temperature control plate of the chemical reaction device 2, and the direction from the side face 16d to the side face 16e is referred to as the chemical reaction device. The short direction of the process plate 2 and the temperature control plate will be referred to.

  As shown in FIG. 1, the temperature control plate is provided with a temperature control flow path 6 having a concave groove shape on one surface 3 a at a predetermined interval. The cross-sectional area of the temperature control channel 6 is not particularly limited as long as heat can be transferred to the reaction channel, but is approximately in the range of 1 × 10 −2 to 2.5 × 102 (mm 2). More preferably, it is 0.32-4.0 (mm2). The number of the temperature control flow paths 6 can adopt an appropriate number in consideration of heat exchange efficiency, and is not particularly limited, but is, for example, 1 to 1000, preferably 10 to 100 per plate. It is.

As shown in FIGS. 1 and 4, the temperature control channel 6 flows in a plurality of main channels 6 a arranged along the longitudinal direction of the temperature control plate, and upstream and downstream ends of the main channel 6 a, respectively. You may provide the supply side flow path 6b and the discharge side flow path 6c which are arrange | positioned substantially orthogonally to the path | route 20, and are connected to each main flow path 6a. In FIGS. 1 and 4, the supply-side flow path 6b and the discharge-side flow path 6c are bent at right angles twice and open to the outside from the side surfaces 3d and 3e of the temperature control plate. As for the number of each temperature control channel 6, only the main channel 6 a portion of the temperature control channel 6 is arranged, and the supply side channel 6 b and the discharge side channel 6 c are each composed of one. .
The emulsified dispersion used in the present invention is a reaction vessel in which a radical polymerizable monomer is finely dispersed in an aqueous medium containing a water-soluble radical initiator by the micromixer, and then a microtubular channel is formed therein. The emulsion can be produced by emulsion polymerization to a reaction rate of 0.1 to 50% of the radical polymerizable monomer, and then reacting to a reaction rate of 95% or more in a reaction kettle equipped with a stirring blade.

As a flow path used as a manufacturing method of the emulsified dispersion used in the present invention, any micro tubular flow path can be used, and other requirements are not particularly limited. A simple pipe or pipe shape may be used as the reaction channel. In addition, a space formed between the members can be used as a reaction channel by combining at least two members.
The emulsified dispersion used in the present invention promotes the generation and stabilization of fine particle nuclei by emulsion polymerization of a radical polymerizable monomer in a temperature range of 70 ° C. to 200 ° C. Nucleation and growth of monodispersed fine particles of smaller particle size usually obtained by batch reaction can be realized.

  Usually, when preparing an emulsified dispersion containing fine polymer particles only in a batch reaction kettle, the reaction temperature is set to 50 ° C to 90 ° C. This is set together with the 10-hour half-life temperature of persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate that are usually used in soap-free emulsion polymerization. This may lead to runaway of the water, and the boiling point of water may exceed 100 ° C. Therefore, it is very dangerous except for batch reactors with special measures such as pressure resistance setting. On the other hand, in the microreactor, it is possible to increase the temperature and pressure safely and easily by providing a pressure adjusting valve at the outlet of the flow path. For this reason, no problem occurs even when the temperature of the aqueous medium exceeds 100 ° C.

  In general, the radical decomposition rate constant of the radical polymerization initiator can be obtained by the following formula.

k: radical decomposition rate constant (h-1) of polymerization initiator, A: frequency factor (h-1),
E: activation energy (J / mol), R: gas constant (= 8.314 J / mol · K)
T: Absolute temperature (K)

As is apparent from the above calculation formula, radical decomposition increases exponentially with increasing temperature. In a reaction vessel having a microtubular channel formed therein, the fluid temperature is increased to a range of 70 ° C. to 200 ° C., thereby rapidly increasing the amount of initiator slices that contribute to the nucleation and stability of fine particles. be able to. Compared to ordinary batch reaction kettles, it is safe, convenient, efficient, monodisperse fine particles with extremely high dispersion stability and small particle size without the addition of protective colloids such as water-soluble polymers and surfactants. Can also be generated.
The reaction temperature is preferably 70 ° C to 200 ° C, more preferably 90 ° C to 180 ° C, and most preferably 110 ° C to 160 ° C. When the temperature is 70 ° C. or lower, there is no difference from the batch, and when the temperature is 200 ° C. or higher, the initiator is decomposed too quickly, so there is almost no difference in effect. The above-mentioned effect can be most obtained at 70 ° C. to 200 ° C.

The ratio of the fluid containing the water-soluble radical initiator and the fluid containing the radical polymerizable monomer in the microtubule depends on the polymer fine particle concentration of the target emulsified dispersion. In order to promote the generation and stabilization of fine particle nuclei in the flow path, it is possible to obtain an emulsified dispersion having a smaller particle size and a higher solid content concentration than in a normal batch reaction. The ratio of the fluid containing the radical polymerizable monomer in the fluid containing the water-soluble radical initiator in the microtubule is usually 5-60%, preferably 10-50%, more preferably 15-40%. is there. If it exceeds 60%, there is a high possibility that the particles will aggregate and settle even by the method of the emulsion polymer used in the present invention. It becomes possible to obtain a stable emulsified dispersion by setting the ratio of the fluid containing the radical polymerizable monomer in the fluid containing the water-soluble radical initiator to 5-60%.
As a reaction apparatus used as a method for producing an emulsified dispersion used in the present invention, a reaction apparatus in which a flow path is installed in a heat transfer reaction vessel is preferable. Is preferable because it is possible. The microtubular channel is preferably of a size that can adjust the time to reach the polymerization reaction temperature in a short time and is sufficiently large to prevent clogging, and has a fluid cross-sectional area of 0.1 to 4 A flow path having a gap size of 0.0 mm 2 is preferable because it is easy to adjust the time to reach the polymerization reaction temperature in a short time and is sufficiently large to prevent clogging. In the present invention, “cross section” means a cross section perpendicular to the flow direction in the flow path, and “cross section” means the cross section.

  The cross-sectional shape of the channel is a square, a rectangle including a rectangle, a polygon including a trapezoid, a parallelogram, a triangle, a pentagon, etc. (a shape with rounded corners, a high aspect ratio, ie including a slit shape) It may be a star shape, a semicircle, a circle including an ellipse, or the like. The cross-sectional shape of the channel need not be constant.

  The method of forming the reaction channel is not particularly limited, but generally, the member (X) having a groove on the surface thereof is laminated, bonded, or the like on the surface having the groove. It is fixed and formed as a space between the member (X) and the member (Y).

  The channel may further be provided with a heat exchange function. In that case, for example, a groove for flowing the temperature adjusting fluid is provided on the surface of the member (X), and another member is bonded or laminated on the surface provided with the groove for flowing the temperature adjusting fluid. What is necessary is just to adhere. In general, a member (X) having a groove on the surface and a member (Y) provided with a groove for flowing a temperature-controlled fluid include a surface provided with a groove, and a surface provided with a groove of another member. A flow path may be formed by fixing the opposite surface, and a plurality of these members (X) and members (Y) may be fixed alternately.

  At this time, the groove formed on the member surface may be formed as a so-called groove lower than the peripheral portion thereof, or may be formed between the walls standing on the member surface. The method of providing the groove on the surface of the member is arbitrary, and for example, methods such as injection molding, solvent casting method, melt replica method, cutting, etching, photolithography (including energy beam lithography), and laser ablation can be used.

  The layout of the flow paths in the member may be in the form of a straight line, a branch, a comb, a curve, a spiral, a zigzag, or any other arrangement according to the purpose of use.

The outer shape of the member need not be particularly limited, and can take a shape according to the purpose of use. The shape of the member may be, for example, a plate shape, a sheet shape (including a film shape, a ribbon shape, etc.), a coating film shape, a rod shape, a tube shape, and other complicated shapes. External dimensions such as thickness are preferably constant. The material of the member is arbitrary, and may be, for example, a polymer, glass, ceramic, metal, semiconductor, or the like.
The reaction vessel having a microtubular channel formed therein for obtaining an emulsified dispersion used in the present invention has a structure in which a heat conductive plate-like structure having a plurality of grooves formed on the surface is laminated. A reactor can be used.
As a reaction vessel in which a microtubular channel is formed, a void having a heat exchange function and having a fluid cross-sectional area of 0.1 to 4.0 mm2 flowing in a liquid-tight manner in the microtubular channel Those having a microtubular channel having a size are preferable, and other requirements are not particularly limited. Examples of such a reaction container include a reaction container in which the channel (hereinafter, simply referred to as “microchannel”) is provided in a member used as a chemical reaction device.
Hereinafter, the reaction vessel having a microtubular channel formed therein will be specifically described. FIG. 7 shows a reaction vessel in which a plate provided with a microtubular flow channel for flowing a mixed solution and a plate provided with a flow channel for flowing a fluid that exchanges heat between the mixed solution are alternately stacked. A schematic configuration example of a reaction vessel (chemical reaction device 3) having a microtubular channel having a void size with a fluid cross-sectional area of 0.1 to 4.0 mm2 flowing in a liquid-tight manner in the microtubular channel. is there.

  The chemical reaction device 3 includes, for example, a first plate (process plate) (2 in FIG. 7) and a second plate (temperature control plate) (in FIG. 7) having the same rectangular plate shape in FIG. And 3) are alternately stacked. Each one first plate is provided with a reaction channel. The second plate is provided with a temperature control channel.

  As shown in FIG. 8, these supply ports and discharge ports are dispersed and arranged in each region of the end surfaces 1b, 1c, side surfaces 1d, 1e of the chemical reaction device 3, and in these regions, radical polymerizable monomers are arranged. The joint part 32 including the connector 30 and the joint part 31 for flowing the fluid containing the water-soluble radical initiator and the temperature control fluid is connected to each other.

  Via these joint portions, a fluid containing a radical polymerizable monomer and a water-soluble radical initiator is supplied from the end surface 1b and discharged to the end surface 1c, and a temperature-controlled fluid is supplied from the side surface 1e to the side surface 1d. It is supposed to be discharged.

  The shape of the chemical reaction device 3 in plan view is not limited to the rectangular shape shown in the figure, and may be a square shape or a rectangular shape with the side surfaces 1d and 1e longer than between the end surfaces 1b and 1c. Therefore, in accordance with the illustrated shape, the direction from the end surface 1b to the end surface 1c is referred to as the longitudinal direction of the process plate and temperature control plate of the chemical reaction device 1, and the direction from the side surface 1d to the side surface 1e is referred to as the chemical reaction device. 3 is referred to as the short direction of the process plate and the temperature control plate.

  As shown in FIG. 9, the process plate is formed by extending a flow path 4 having a concave groove shape in one surface 2a in the longitudinal direction of the process plate and arranging a plurality of the process plates at a predetermined interval p0 in the short direction. It is. Let L be the length of the flow path 4. The cross-sectional shape is a width w0 and a depth d0.

  The cross-sectional shape of the flow path 4 can be appropriately set according to the type of fluid containing the radical polymerizable monomer and the water-soluble radical initiator, the flow rate, and the flow path length L. In order to ensure uniformity, the width w0 and the depth d0 are set in the range of 0.1 to 500 [mm] and 0.1 to 5 [mm], respectively. In addition, description of a width | variety and a depth is a case where a drawing is referred, Comprising: This value can be interpreted suitably so that it may become a wide value with respect to a heat transfer surface. Although it does not specifically limit, For example, 1-1000 pieces per plate, Preferably it is 10-100 pieces.

  The fluid containing the radical polymerizable monomer and the water-soluble radical initiator is caused to flow into each flow path 4 and is supplied from one end face 2b side as indicated by an arrow in FIGS. It is discharged to the end face 2c side.

  The plurality of process plates and temperature control plates are stacked by alternately stacking process plates and temperature control plates in the same direction, and are fixed to each other and stacked.

  Therefore, in the form of the chemical reaction device 3, each flow path 4 and the temperature control flow path 6 are covered with a lower surface of a plate on which the opening surface of the groove is laminated, and a tunnel shape having a rectangular cross section with both ends opened. It is said.

  Each process plate and temperature control plate can be made of an appropriate metal material. For example, a flow path 4 and a temperature control path 6 are formed by etching a stainless steel plate, and the flow path surface is changed. It can be manufactured by electrolytic polishing finish.

  As an apparatus having a chemical reaction device provided with a flow path used as a method for producing the emulsified dispersion used in the present invention, for example, a production apparatus shown in FIG. 10 can be exemplified.

  In FIG. 10, the fluid containing the radical polymerizable monomer is composed of the outlet of the tank 62 (first tank) into which the fluid (61) containing the radical polymerizable monomer and the inlet of the plunger pump 65 are placed. An outlet of a tank 64 (first tank) for containing a fluid containing a water-soluble radical initiator and an inlet of a plunger pump 66 are connected to each other through a piping that passes through the water-soluble radical initiator. It is connected via a pipe through which the fluid (63) it contains passes. Pipes through which a fluid containing a radical polymerizable monomer or a fluid containing a water-soluble radical initiator passes from the outlet of the plunger pump 65 and the outlet of the plunger pump 66 through the plunger pump 65 or the plunger pump 66, respectively. These pipes are connected to the inlet of the micromixer 67 which mixes at the junction provided at the outlet of the flow path exemplified as the chemical device 1 shown in FIGS. 1, 2, and 3. It is connected.

  In this micromixer 67, a fluid (61) containing a radical polymerizable monomer and a fluid (63) containing a water-soluble radical initiator are mixed, and the chemical device 2 shown in FIGS. The fluid is mixed with the radical polymerizable monomer and the water-soluble radical initiator by being guided to the micromixer 73 that promotes mixing by the flow path whose flow path cross-sectional area is reduced in the illustrated flow direction. . This fluid moves through the pipe connected to the outlet of the micromixer 73 to the inlet 1b of the reaction vessel 40 exemplified as the chemical device 3 shown in FIGS. A temperature control device 68 is connected to the reaction vessel 40. The radical polymerizable monomer is finely dispersed in the aqueous medium containing the water-soluble radical initiator by moving through the micro flow path in the reaction vessel 40 and dissolved in the aqueous medium by the decomposition of the water-soluble radical initiator. The core of fine particles is formed by polymerization precipitation of the radically polymerizable monomer, and the radically polymerizable monomer is supplied to the surface of the particle core from the oil droplets of the radically polymerizable monomer finely dispersed in the aqueous phase. Polymerization proceeds, moves through the micro flow path in the reaction vessel 40, and reaches the outlet 1 c of the reaction vessel 40. Then, it moves to the inflow port of the cooling heat exchanger 70 through the pipe connected to the outflow port. In the reaction container 40 of the manufacturing apparatus of FIG. 10, the residence time can be controlled by connecting several chemical devices 3 described in FIGS. 7, 8 and 9 as a part of the reaction container through the flow path. .

  As for the residence time, the reaction rate at the outlet of the reaction vessel is suitably 0.1 to 50%, more preferably 0.5 to 30%, depending on the reaction temperature and flow rate. When the reaction rate is lower than 0.1%, the monodispersity of the particles cannot be obtained, and in order to react more than 50%, it is necessary to lengthen the flow path. There is a risk of clogging the flow path due to adhesion of the polymer component. By controlling the content to 0.1 to 50%, an emulsified dispersion containing fine particles with high monodispersibility can be obtained, and the flow path can be stably blocked without clogging.

  Such a residence time depends on the reaction temperature, flow rate, and the type of water-soluble radical initiator used, but when using a persulfate as the water-soluble radical initiator, 0.1 to 30 minutes, preferably Is 0.2 to 20 minutes, more preferably 0.5 to 15 minutes.

  The emulsified dispersion obtained from the outlet of the flow path can be polymerized to a reaction rate of 95% or more in an ordinary batch reaction kettle equipped with a stirrer by adding a water-soluble radical initiator as necessary.

  As the water-soluble radical initiator to be added, the aforementioned water-soluble organic peroxides, water-soluble azo compounds, redox initiators, persulfates and the like are preferably used.

In this case, a radical polymerizable monomer may be added for the purpose of introducing a functional group that interacts with the inorganic material on the particle surface.
Specific examples of the radical polymerizable monomer having these functional groups include radical polymerizable monomers having an amide group, amino group, hydroxyl group, tetramethylammonium group, silanol group, epoxy group, and the like. Of these, a radical polymerizable monomer having an amide group is preferred.
Specific examples of the radical polymerizable monomer having an amide group include acrylamides such as N-alkylacrylamide, N, N-dialkylacrylamide, and acrylamide, or N-alkylmethacrylamide, N, N-dialkylmethacrylamide, And methacrylamides such as methacrylamide.
Specific examples of the radically polymerizable monomer having a silanol group include γ-methacryloxypropyltrimethoxysilane and γ-methacryloxypropylmethyldimethoxysilane used by changing the alkoxyl group to a silanol group by hydrolysis with water. be able to.
Furthermore, epoxy group-containing unsaturated monomers such as glycidyl (meth) acrylate and glycidyl methacrylate; dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, vinylpyrrolidone, N-methylvinylpyridinium chloride, ( Tertiary or quaternary amino group-containing unsaturated monomers such as (meth) allyltriethylammonium chloride and 2-hydroxy-3- (meth) acryloyloxypropyltrimethylammonium chloride; hydroxyethyl (meth) acrylate, hydroxypropyl ( Examples thereof include hydroxyl group-containing unsaturated monomers such as (meth) acrylate and polyethylene glycol mono (meth) acrylate.

  There is no particular limitation on the reaction temperature, but when using a persulfate as a water-soluble radical initiator and a batch reaction kettle used under normal atmospheric pressure, 50-90 ° C., more preferably 60 ° C.-85 ° C is preferred.

  Although the reaction time depends on the temperature, it is usually 0.5 hours to 10 hours. In the present invention, as described above, in the microtubular channel, the radical polymerizable monomer is emulsion-polymerized to a reaction rate of 0.1 to 50% in the presence of a water-soluble radical initiator, and then provided with a stirring blade. By reacting to a reaction rate of 95% or more in the reaction kettle, the particle size of the monodispersed fine particles contained is 300 nm or less, the coefficient of variation CV of the particle size distribution is 15% or less, and the solid content of the monodispersed fine particles is An emulsified dispersion containing 15% or more and having a residual monomer amount of 500 ppm or less and containing no dispersion stabilizer or surfactant can be obtained.

  In general, polymer particles obtained by soap-free emulsion polymerization as described above are stabilized by repulsion due to the charge of radical initiator segments and adsorption of by-product oligosoap to the particle surface. In the reaction, in order to obtain fine particles of 300 nm or less, it was necessary to carry out under very dilute conditions or the system became unstable. However, as described above, the emulsified dispersion in the present invention is fine particles in the microtubular channel. In order to promote the generation and stabilization of nuclei, it is possible to use an emulsified dispersion that does not contain a dispersion stabilizer or a surfactant having a smaller particle size and a higher solid content than a normal batch reaction.

  The polymer particles obtained by the soap-free emulsion polymerization as described above are colloidally dispersed by the repulsion due to the charge of the radical initiator segment and the adsorption of the by-product oligo soap to the particle surface as described above. It is considered that it is less affected by the blend of the above, and is more likely to be mixed more uniformly than a general acrylic emulsion or dispersion and a blend of inorganic components. For this reason, when the polymer particles and the inorganic particles are fused to form a film by drying, the particle diameters are uniform, and it is obtained in combination with being unaffected by emulsifiers and stabilizers. It is possible to obtain a film that is tough and tough even when the film and the resulting coating film are homogeneous and transparent, without cracks.

  The organic-inorganic composite composition emulsified dispersion of the present invention is obtained by mixing the above-mentioned emulsion polymer with the above-mentioned inorganic water dispersion. Even when the emulsion polymer and the inorganic water dispersion are mixed, there is a special case. It is possible to prepare a composition that can be mixed without a mixing device and has good stability.

Hereinafter, the present invention will be described in more detail by way of examples. In the examples,% and weight are based on weight unless otherwise specified.
<Micromixer used for production of emulsified dispersion used in Examples>
In this embodiment, the process plates 5 and 8 having the structure shown in FIG. 1 were used as the micromixer as a micromixer for mixing at the junction provided at the outlet of the flow path. Further, as a micromixer that promotes mixing by a flow path whose flow path cross-sectional area is reduced in the flow direction, a process plate 14 having a structure shown in FIG. 4 was used as the micromixer. The structure of the micromixer includes a chemical reaction device in which the temperature control plate 3 is stacked on the top and bottom of the micromixer laminate in which the plate 5 is stacked on the plate 8, and a chemistry in which the temperature control plate 3 is stacked on the top and bottom of the plate 14. A structure in which a reaction device was connected in series was used. Specifically, an aqueous fluid in which a water-soluble radical initiator was dissolved was introduced into the flow channel 20 of the plate 5 into the flow channel 21 of the radical polymerizable monomer plate 8, and the respective fluids were united at the plate outlet. Thereafter, the radical polymerizable monomer was further finely dispersed in an aqueous fluid in which a water-soluble radical initiator was dissolved by passing through the flow path 22 of the plate 14. The process plates 5, 8, and 14 and the temperature control plate 3 are made of SUS304, and the plate thicknesses of the plates 5 and 14 are 0.4 mm and the plate 8 is 1 mm. The cross-sectional dimension of the reaction channel 21 is 1.0 mm wide × 0.5 mm deep, the cross-sectional dimension of the temperature control channel 6 is 1.2 mm wide × 0.5 mm deep, and the cross-sectional dimension of the reaction channel 20 is 6 mm wide × The depth is 0.2 mm, and the cross-sectional dimension of the reaction channel 22 is 4 mm wide × 0.2 mm deep at the wide portion and 0.2 mm wide × 0.2 mm deep at the contracted portion.
<Device for reaction vessel used for production of emulsified dispersion used in Examples>
In this example, a reaction vessel device having the structure shown in FIG. 7 was used. As a structure, the process plate 2 and the temperature control plate 3 are alternately laminated. A flow path 4 is formed in the process plate, and a temperature control flow path 6 is formed in the temperature control plate.
The reaction vessel device is formed by alternately laminating three temperature control plates with five temperature control channels 6 formed by etching, as well as two process plates with five reaction channels 4 formed by dry etching. Yes. The material of the process plate 2 and the temperature control plate 3 is SUS304, and the plate thickness is 1 mm. The cross-sectional dimensions of the reaction channel 4 and the temperature control channel 6 are both width 1.2 mm × depth 0.5 mm.
<Measurement method of solid content of emulsion dispersion polymer>
1 g of the emulsified dispersion was weighed in a metal petri dish with a precision balance, diluted with 1 g of ion-exchanged water, and then dried for 2 hours in a dryer set at 110 ° C. The polymer solid content in the emulsified dispersion was measured from the resin solid content remaining in the petri dish after drying and the amount of the emulsified dispersion initially weighed.
<Measuring method of particle size>
Measurement was performed using a Nikkiso Co., Ltd. Microtrac particle size distribution analyzer UPA-ST150. The blended solution of the emulsified dispersion and the inorganic material was diluted about 100 times and placed in a cell for measurement. The coefficient of variation (CV) of the particle size distribution of the monodisperse fine particles according to the present invention is defined by the following equation in the average particle size (d) and standard deviation (SD) of the particle size distribution obtained by measurement. For example, it is obtained by the measurement of the particle size distribution meter.

<Measurement method of film state and film strength>
Pour 18 g of NV10% emulsified dispersion and inorganic material mixture onto a substrate (a glass plate with a PET film with a thickness of 350 μm and a frame with a length of 10 cm and a width of 6 cm) and dry at room temperature for 2 days. Then, a cast film having a film thickness of 100 to 200 μm was prepared by thermally drying at 140 ° C. for 1 minute. As for the film state, the cast film was peeled off from the substrate, and the transparency and cracking were judged by visual observation.
When there was no crack, the film strength was measured. The film strength was measured with an autograph AGS-1kNG manufactured by Shimadzu Corporation after processing the cast film into a width of 5 mm and a length of 7 cm.
<Measurement method of film oxygen permeability>
By applying a 10% NV coater to a PET film having a film thickness of 50 μm that has been subjected to corona treatment with a 10% NV emulsion dispersion and an inorganic material, the film is calculated to have a film thickness of 1.2 μm by drying at 80 ° C. for 5 minutes. It was created. The oxygen permeability (cc / m ² · day · atm) was measured using a film barrier property evaluation apparatus (DELTATAPERM) under the conditions of a temperature of 30 ° C. and a humidity of 0%.
<Production Example 1 of soap-free emulsified dispersion used in Examples>
Two syringe pumps and a 2.17 mm tube were connected to the outlet of each syringe via a pressure gauge, a safety valve, a filter, and a check valve. Similarly, a micromixer that mixes each tube at a junction provided at the outlet shown in FIG. 1, and a device for a reaction vessel shown in FIG. 7 through a flow path with a reduced cross-sectional area shown in FIG. Were connected to 10 reaction vessels linked together. A 150 ° C. heating medium was fed into the reaction vessel device for temperature control. In addition, a cooling device was connected. Water was sent to the temperature control plate of the cooling device so that it could be cooled. Finally, a back pressure valve was connected so that the discharged reaction mixture could be received in a container.

  In one syringe, an aqueous solution in which 0.075 g of sodium persulfate was dissolved in 100 g of ion-exchanged water was prepared and charged. The other syringe was charged with a mixed monomer solution of methyl methacrylate (MMA) and butyl acrylate (BA) (50/50). The reaction mixture was introduced into the reaction vessel device at a flow rate of 20 g / min (hereinafter referred to as g / min). The emulsified dispersion was produced by receiving the discharged liquid in a receiving container. At this time, the pressure in the pipe was adjusted to 2.0 MPa by the exhaust pressure valve.

The resulting emulsified dispersion was charged while introducing nitrogen into a 0.5 liter reaction kettle equipped with a stirrer, a nitrogen inlet tube, and a temperature sensor for measuring the temperature in the reaction kettle, and then 0.02 g of sodium persulfate. After adding an aqueous solution in which 2 g of ion exchange water was dissolved, the internal temperature of the reaction kettle was maintained at 80 ° C. for 2 hours.
When the obtained emulsified dispersion was analyzed, the particle size was 160 nm, the solid content was 18.6%, and CV = 8.0%.
<Production example 2 of soap-free emulsified dispersion used in Examples>
An emulsified dispersion was produced using the same apparatus as in Production Example 1. In one syringe, an aqueous solution in which 0.075 g of sodium persulfate was dissolved in 100 g of ion-exchanged water was prepared and charged. The other syringe was charged with a mixed monomer solution of methyl methacrylate (MMA) and butyl acrylate (BA) (50/50). The reaction mixture was introduced into the reaction vessel device at a flow rate of 20 g / min (hereinafter referred to as g / min). The emulsified dispersion was produced by receiving the discharged liquid in a receiving container. At this time, the pressure in the pipe was adjusted to 2.0 MPa by the exhaust pressure valve.

100 g of the resulting emulsified dispersion was charged while introducing nitrogen into a 0.5 liter reaction kettle equipped with a stirrer, a nitrogen inlet tube, and a temperature sensor for measuring the temperature in the reaction kettle, and then 0.1 g of dimethylacrylamide. An aqueous solution in which 1 g of ion exchange water was dissolved and an aqueous solution in which 0.02 g of sodium persulfate was dissolved in 1 g of ion exchange water were added, and the internal temperature of the reaction kettle was maintained at 80 ° C. for 2 hours.
When the obtained emulsified dispersion was analyzed, the particle size was 162 nm, the solid content was 17.8%, and CV = 8.5%.
(Example 1-3)
By adding a water-dispersible clay aqueous solution (Laponite XLS (Wilver Ellis) 6% aqueous solution) to the emulsified dispersion obtained in Production Example 1, polymer / clay = 90/10, 80/20, 70 / An emulsified dispersion having a solid content of 30 (solid content ratio) of 10% was prepared. When the particle size of each emulsified dispersion was measured, there was almost no change at 157 nm, 158 nm, and 165 nm.

  Furthermore, a film having a film thickness of 100 to 200 μm was prepared by casting the emulsified dispersion. The obtained film was almost transparent and had almost no cracks.

The yield point stresses of the respective films were 6.7 MPa, 14.0 MPa, and 16.3 MPa, and the elongations were 189%, 294%, and 163%, respectively, and strong and elongated films were obtained.
(Example 4-6)
By adding a water-dispersible clay aqueous solution (Laponite XLS (manufactured by Wilber Ellis Co., Ltd.) 6% aqueous solution, particle size = 9.3 nm) to the emulsified dispersion obtained in Production Example 2, polymer / clay = 90 / An emulsion dispersion having a solid content of 10% consisting of 10, 80/20 and 70/30 (solid content ratio) was prepared. When the particle size of each emulsified dispersion was measured, the changes were small, 176 nm, 189 nm, and 205 nm.

  Furthermore, a film having a film thickness of 100 to 200 μm was prepared by casting the emulsified dispersion. The obtained film was very transparent and had almost no cracks. FIG. 11 shows the transparency of the film.

The yield point stress of each film was 8.1 MPa, 12.7 MPa, and 14.5 MPa, and the elongation was 414%, 379%, and 187%.
In addition, the oxygen permeability of the calculated 1.2 μm thick film applied to the corona-treated 50 μm thick PET film with a No. 10 bar coater is 56.4%, 54.8% and 51.9%, respectively. It decreased with increasing blending amount. The expression of film barrier properties was confirmed by clay blending.
(Example 7-9)
By adding colloidal silica (Snowtex 20 (Nissan Chemical Co., Ltd.), particle size = 8.5 nm) to the emulsified dispersion obtained in Production Example 2, polymer / silica = 90/10, 80/20 , 70/30 (solid content ratio) and a 10% solid content emulsion dispersion was prepared. When the particle size of each emulsified dispersion was measured, there was almost no change at 160 nm, 156 nm, and 166 nm.

  Furthermore, a film having a film thickness of 100 to 200 μm was prepared by casting the emulsified dispersion. The obtained film was almost transparent and had almost no cracks.

The yield point stress of each film was 5.8 MPa, 7.9 MPa, and 14.1 MPa, and the elongation was 218%, 275%, and 233%, and a film having strength and elongation was obtained.
(Examples 10-12)
By adding an aqueous titanium oxide dispersion (STS-21 (manufactured by Ishihara Sangyo Co., Ltd.), particle size = 382 nm) to the emulsified dispersion obtained in Production Example 1, polymer / titanium oxide = 95/5, 90 / An emulsion dispersion having a solid content of 10% and a solid content ratio of 80/20 (solid content ratio) was prepared. When the particle size of each emulsified dispersion was measured, there was almost no change at 158 nm, 164 nm, and 160 nm.

  Furthermore, a film having a film thickness of 100 to 200 μm was prepared by casting the emulsified dispersion. The obtained film was hardly cracked.

The yield stresses of the respective films were 5.2 MPa, 6.0 MPa, and 6.0 MPa, and the elongations were 311%, 337%, and 320%.
(Comparative Example 1)
A film having a film thickness of 100 to 200 μm was prepared by casting the emulsified dispersion obtained in Production Example 2. The obtained film was very transparent and had almost no cracks.

The yield point stress of the film was 2.8 MPa, the elongation was 60%, the strength was weak, and the elongation was small.
Further, the oxygen permeability of the calculated film thickness of 1.2 μm applied to the corona-treated PET film of 50 μm thickness with a No. 10 bar coater was 58.1%.
(Production Example 3 of acrylic emulsion used in Comparative Example)
While introducing nitrogen into a 2 liter reaction vessel flask equipped with a stirrer, a nitrogen introduction tube, and a temperature sensor for measuring the temperature in the reaction kettle, 327 g of ion-exchanged water and New Coal 707SF [a solid product manufactured by Nippon Emulsifier Co., Ltd. 4.0 g of anionic emulsifier with 30% min.]. While flowing nitrogen gas, the temperature of the aqueous medium in the reaction vessel was raised to 80 ° C.

  On the other hand, 75.0 g of ion-exchanged water, 21.0 g of New Coal 707SF, 242.5 g of butyl acrylate, 242.5 g of methyl methacrylate and 15.0 g of acrylic acid are charged into a 2 liter beaker, and the monomer emulsified premix is prepared by stirring and emulsifying. Was prepared. 29.8 g of the monomer emulsified premix prepared from the 2 liter beaker was extracted and added to the reaction vessel in which the temperature of the aqueous medium was maintained at 80 ° C.

  Initial polymerization was started by press-fitting a thermal polymerization initiator aqueous solution prepared by dissolving 0.25 g of potassium persulfate in 10.0 g of ion-exchanged water into the reaction vessel. After the initial polymerization was continued at 80 ° C. for 20 minutes, the remaining monomer emulsified premix was controlled at a constant temperature of 80 ° C. and added dropwise over 3 hours to carry out emulsion polymerization. After completion of dropping, the mixture was cooled to 80 ° C., kept at the same temperature for 2 hours, and then cooled to room temperature.

When the average particle diameter of the obtained emulsion polymer aqueous dispersion was measured, it was 135 nm and the solid content was 43.6%.
(Comparative Example 2-4)
By adding a water-dispersible clay aqueous solution to the acrylic emulsion obtained in Production Example 3, polymer / clay = 90.9 / 9.1, 87 / 13.0, 83.3 / 16.7 (solid content ratio) An emulsified dispersion having a solid content of 10% was prepared. When the particle size of each emulsified dispersion was measured, the particle size of the acrylic emulsion was increased by addition of clay to 193 nm, 377 nm, and 483 nm.

Furthermore, a film having a film thickness of 100 to 200 μm was prepared by casting the emulsified dispersion. Only the film with many cracks was obtained. The figure which shows the crack of a film is shown in FIG.
(Production Example 4 of Acrylic Dispersion Used in Comparative Example)
A 4-necked flask similar to Reference Example 1 was charged with 60 parts of diethylene glycol diethyl ether, heated to 125 ° C. under a nitrogen stream, and then mixed with 80 parts of BA, 87 parts of MMA, 4 parts of AA, and 14 parts of 2-HEMA. Then, a mixed solution composed of 20 parts of t-butylperoxy-2-ethylhexanoate and 1 part of t-butylperoxybenzoate was added dropwise over 5 hours. After the dropwise addition, the mixture was reacted at 125 ° C. for 5 hours, then cooled to 60 ° C., 5.6 parts of triethylamine was added, and the mixture was mixed at 60 ° C. for 30 minutes. And after adding 461 parts of ion-exchanged water over 2 hours, it cooled to 25 degreeC and obtained the acrylic dispersion of 30% of non volatile matter, and a particle size of 96 nm.
(Comparative Example 4-6)
By adding a water-dispersible clay aqueous solution to the acrylic dispersion, an emulsion dispersion having a solid content of 10% composed of polymer / clay = 90/10, 80/20, 70/30 (solid content ratio) was prepared. When the particle size of each emulsified dispersion was measured, 115 nm, 132 nm, and 192 nm, and the particle size of the acrylic dispersion increased with the addition of clay.

  Furthermore, a film having a film thickness of 100 to 200 μm was prepared by casting the emulsified dispersion. The obtained film was nearly transparent, but the 20% and 30% clay blends were very brittle.

  The yield point stress of each film was 2.0 MPa, 5.2 MPa, and 4.5 MPa, and the elongation was 372%, 8%, and 2%, and the film was weak and did not stretch.

δ: Fluid containing water-soluble radical initiator ε: Fluid containing radically polymerizable monomer
γ ... Temperature control fluid 5 .... 1st plate (process plate)
5a: the surface of the first plate 5b: the end surface of the first plate 5c: the end surface of the first plate 5d: the side surface of the first plate 5e: Side face of the first plate 3 .... Third plate (temperature control plate)
3a: the surface of the third plate 3b: the end surface of the third plate 3c: the end surface of the third plate 3d: the side surface of the third plate 3e: Side surface of third plate 6... Temperature control flow path with cross-sectional groove shape 6 a... Main flow path with cross-section groove shape 6 b.・ ・ ・ ・ ・ Drain-side channel with cross-sectional groove shape 8 ・ ・ ・ ・ ・ ・ Second plate (process plate)
8a: the surface of the second plate 8b: the end surface of the second plate 8c: the end surface of the second plate 8d: the side surface of the second plate 8e: Side of second plate 14 ... Fourth plate (process plate)
14a ... the surface of the fourth plate 14b ... the end surface of the fourth plate 14c ... the end surface of the fourth plate 14d ... the side surface of the fourth plate 14e ... the side surface of the fourth plate 15 ... Chemical reaction device 1
15b .... End face of the device 1 for chemical reaction 15c ... ... End face of the device 1 for chemical reaction 15d ... Side face of the device 1 for chemical reaction 15e ... Side face of the device 1 for chemical reaction 16 .... Chemical reaction device 2
16b... End surface of chemical reaction device 2 16c... End surface of chemical reaction device 2 16d... Side surface of chemical reaction device 2 16e. .... Chemical reaction device 3
1b... End surface of the chemical reaction device 1 1c... End surface of the chemical reaction device 3 1d... Side surface of the chemical reaction device 3 1e. .... First plate (process plate)
2a ... the first plate surface 2b ... the first plate end surface 2c ... the first plate end surface 2d ... the first plate side surface 2e ... the first plate side surface 3 ... 2nd plate (temperature control plate)
3a ··· surface of the second plate 3b ··· end surface of the second plate 3c ··· end surface of the second plate 3d ··· side surface of the second plate 3e ··· side surface of the second plate 4... Channel having a groove shape in cross section p0... Predetermined interval w0... Width d0... Depth L. ··· Connector 31 ··· Joint portion 32 ··· Joint portion 40 ··· Reaction vessel (chemical reaction device 3)
61. Compound (A) (fluid containing water-soluble radical initiator)
62... First tank 63... Compound (B) (fluid containing radical polymerizable monomer)
64 ... Second tank 65 ... Plunger pump 66 ... Plunger pump 67 ... Micromixer 68 ... Temperature controller 69 ... -Heat exchanger for cooling 70 ... Temperature controller 71 ... Exhaust pressure valve 72 ... Receptacle container 73 ... Micromixer 79 ... Used in the examples Schematic configuration diagram schematically showing the resin manufacturing equipment

Claims (4)

An organic / inorganic composite composition emulsion dispersion comprising a soap-free emulsion dispersion (A) containing a polymer obtained by polymerizing a radical polymerizable monomer and an aqueous medium, and an inorganic water dispersion. The organic-inorganic composite composition emulsion dispersion, wherein the monodisperse fine particles contained in the emulsion dispersion (A) have a particle size of 50 to 300 nm. The organic-inorganic composite composition emulsion dispersion according to claim 1, wherein the dispersion coefficient (CV) of the particle size distribution of the monodisperse fine particles contained in the emulsion dispersion (A) is 15% or less. The emulsified dispersion (A) was obtained after polymerizing the radical polymerizable monomer to a reaction rate of 0.1 to 50% in the presence of a water-soluble radical initiator in the microtubular channel. The organic-inorganic composite composition emulsion dispersion according to claim 1 or 2, which is an emulsion dispersion obtained by polymerizing the polymerization reaction liquid to a reaction rate of 95% or more using a reaction kettle equipped with a stirring device.   The organic-inorganic composite composition according to claim 1 or 2, wherein the inorganic water dispersion is at least one water dispersion selected from the group consisting of a colloidal dispersion of layered silicate, colloidal silica, and a titanium oxide aqueous dispersion. Emulsified dispersion.

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