JP2688523B2 - Method for producing aqueous dispersion of silicone-containing resin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of use] The present invention relates to a method for producing an aqueous dispersion of a silicone-containing resin.

[Problems to be solved by conventional technology and invention]

Emulsions, which are so-called emulsions of various polymeric substances, use water as a solvent, so they are more advantageous than solvent-type products in terms of safety for the environment and the human body, and are used as paints, fiber processing agents, adhesives, and paper. It is currently widely used as a processing agent.

In the production of emulsions, anionic surfactants, cationic surfactants and nonionic surfactants are generally used to solubilize hydrophobic monomers in micelles to provide a place for polymerization and to stabilize the resulting emulsions. Surfactant alone or as a mixture is 0.5 to 5 with respect to the raw material monomer.
Used by weight percent.

However, the emulsion produced using the above-mentioned surfactant has a large foaming property, and therefore bubbles may cause pinholes when the emulsion is coated, and further, since the surfactant is non-volatile, Remains in the film prepared from the emulsion, water resistance of the film, adhesion,
It has been pointed out that it causes a decrease in tensile strength, heat resistance, weather resistance, and the like, and further reduces the water repellency, which is one of the characteristics of the organopolysiloxane. Therefore, efforts in the industry to keep the amount of active agent used as small as possible are continuing.

Further, the organopolysiloxane group-containing monomer is remarkably expensive as compared with general monomers, and therefore, it is important to exert its effect with a necessary minimum amount.

[Means for solving the problem]

The present inventors have made the amount of activator used in such a practical condition as small as possible, or have an appropriate polymerization rate even under conditions not containing these, and further, the obtained emulsion has no foaming property and high surface tension. In addition, it has been found that a water-soluble silicone-containing resin aqueous dispersion having sufficient organosiloxane characteristics even with a small amount of a monomer having an organopolysiloxane group is obtained. It was found that seed polymerization of a vinyl-based monomer in the presence of an emulsion is extremely effective, and completed the present invention.

That is, the present invention relates to an aqueous emulsion having an average particle size of 0.001 to 0.05 μ and comprising a silicone-containing resin containing 5 to 95% by weight of a monomer unit having an organopolysiloxane group and having an average particle size of 0.2 to 0.2.
Vinyl monomer 20-99.8 in the presence of 80% by weight (solid content)
Manufacture of an aqueous dispersion of a silicone-containing resin having a characteristic of an organosiloxane having less foaming, high surface tension, excellent water resistance, and sufficient organopolysiloxane group content, which is characterized by performing seed polymerization in a weight percentage. It is related to the method.

The particle size of the silicone-containing resin aqueous emulsion used in the present invention needs to be 0.001 to 0.05 μ, and when a silicone-containing resin aqueous emulsion having a large particle size is used, it is difficult to obtain an appropriate polymerization rate, It takes a long time to complete the emulsion polymerization, and the stability of the obtained silicone-containing resin aqueous dispersion also deteriorates.

The content of the monomer-equivalent unit containing the organopolysiloxane group that constitutes the resin in the silicone-containing resin aqueous emulsion is 5 to 95% by weight. If it is less than 5% by weight, the organopolysiloxane group concentration is too low and the organopolysiloxane group concentration is too low. The properties of siloxane, such as slidability, releasability and water repellency, are not sufficiently exhibited.

On the other hand, if it exceeds 95% by weight, the solubilization of the monomer may be hindered by the oil repellency in the subsequent seed polymerization, and the seed polymerization may not proceed smoothly. And other problems occur. (Meth) acrylate is generally used as a monomer to be copolymerized with the monomer having an organopolysiloxane group.

The mixing ratio of the silicone-containing resin aqueous emulsion and the vinyl-based monomer is 0.2 to 80% by weight (solid content) with respect to 99.8 to 20% by weight of the vinyl-based monomer. When the amount of the silicone resin-containing aqueous emulsion used is less than 0.2% by weight, it is difficult to maintain a proper polymerization rate and emulsion dispersion stability, and when it exceeds 80% by weight, the organopolysiloxane content increases and it is economically disadvantageous. is there.

The aqueous silicone resin-containing emulsion used in the present invention can be produced by polymerizing an organopolysiloxane-based monomer alone or a mixture with another monomer by using a known emulsion polymerization method in the presence of a surfactant. .

At this time, by using a large amount of a carboxylic acid-based monomer such as acrylic acid or methacrylic acid, swelling with alkali, and applying high shearing force, an emulsion having a smaller particle size can be obtained. Further, instead of the emulsion polymerization method, a so-called phase inversion method in which an organopolysiloxane-based monomer containing an ionic monomer is polymerized by a solution polymerization method, water is added after neutralization, and the solvent is distilled off may also be produced. You can

As another emulsion, for example, a urethane prepolymer having an isocyanate group at the terminal and having an organopolysiloxane group is reacted with an excess amount of a polyalkylene polyamine to produce a polyurethane urea polyamine, and then this product is subjected to an aqueous acid solution. It is also possible to use a urethane resin emulsion obtained by mixing the above or further reacting with an acid anhydride, neutralizing with a basic substance, and then self-dispersing in water.

The silicone-containing resin aqueous emulsion thus obtained has a particle size of 0.001 to 0.05 μ, a milky white appearance with a particle size of 0.05 μ, and a transparent or translucent colloidal dispersion with a particle size of less than 0.05 μ, The Tyndall phenomenon is recognized by laser light irradiation.

Examples of the organopolysiloxane monomer used in the production of the silicone-containing resin aqueous emulsion in the present invention include compounds represented by the following formulas.

(In the formula, R is H or CH ₃ , an integer of n = 0 to 100, and R ′ is an alkyl group such as methyl, ethyl, propyl, and butyl, a phenyl group, a fluoroalkyl group, and the like. .) In addition to the (meth) acrylic acid derivative shown above as the radical-polymerizable group, compounds having a radical-polymerizable group such as an amide derivative, a styrene derivative and an olefin derivative may be mentioned.

Furthermore, Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltributoxysilane, vinyltris (β-methoxyethoxy) silane, allyltriethoxysilane,
Trimethoxysilylpropyl allylamine, γ- (meth) acryloxypropyltrimethoxysilane, γ-
(Meth) acryloxypropyltriethoxysilane, γ
-(Meth) acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxypropylmethyldiethoxysilane, γ- (meth) acryloxypropyltris (β-methoxyethoxy) silane, N-β- (N-vinylbenzyl) Amino) ethyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane, 2-styrylethyltrimethoxysilane, 3- (N-styrylmethyl-2-aminoethylamino) propyltrimethoxy Examples thereof include organic silicon compounds such as silane, (meth) acryloxyethyldimethyl (3-trimethoxysilylpropyl) ammonium chloride, vinyltriacetoxysilane, and vinyltrichlorosilane.

Further, macromonomers of the monomers shown above can also be used. The production of this macromonomer is easily synthesized by the formulation known in the art.

For example, radical polymerization of the above monomers with thioglycolic acid, 2-mercaptoethanol, etc. in the presence of an initiator, and reaction of the obtained reaction product with glycidyl (meth) acrylate, isocyanate ethyl (meth) acrylate, etc. , Can be obtained by introducing a radically polymerizable unsaturated bond at one end.

The number average molecular weight of the macromonomer is preferably 10,000 or less, and above this molecular weight, the solubility in the solvent used for producing the self-dispersion type silicone-containing resin aqueous emulsion is poor. The number average molecular weight is preferably 5,000 or less.

The same effect can be obtained by grafting the above-mentioned monomers.

In the production of the silicone-containing resin aqueous emulsion according to the present invention, a monomer copolymerizable therewith may be used in combination with the organopolysiloxane monomer. Examples of this type of monomer include ionic monomers. Known compounds such as, (meth) acrylate, vinyl ester, vinyl ether, malate, fumarate and α-olefin can be mentioned.

Specific examples of these compounds include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, citraconic acid, styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, N, N- Ionic monomers such as esters of dimethylaminoethyl (meth) acrylate, vinylphosphonic acid, unsaturated carboxylic acid monomers and polyoxyalkylene glycol or polyoxyalkylene oxide adducts of lower alcohols, methyl acrylate, Ethyl acrylate,
Acrylic acid esters such as n-butyl acrylate and 2-ethylhexyl acrylate, methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, styrene, vinyltoluene , Styrene-based monomers such as 2-methylstyrene, 1-butylstyrene, chlorostyrene, hydroxyethyl acrylate,
Hydroxy group-containing monomer such as hydroxypropyl acrylate, N-methylol (meth) acrylamide, N
In addition to N-substituted (meth) acrylic monomers such as butoxymethyl (meth) acrylamide, epoxy group-containing monomers such as glycidyl acrylate and glycidyl methacrylate, perfluoroalkyl (meth) acrylates, and monomers such as acrylonitrile, There are macromonomers of the monomers listed above. The production of this macromonomer is easily synthesized by the formulation known in the art.

For example, thioglycolic acid and 2-mercaptoethanol and the like and the above monomers are radically polymerized in the presence of an initiator, and the obtained reaction product is reacted with glycidyl (meth) acrylate and isocyanate ethyl (meth) acrylate and the like, It can be obtained by introducing a radically polymerizable unsaturated bond at one end.

It is desirable that the number average molecular weight of the macromonomer be 10,000 or less, and if the molecular weight is higher than this, the viscosity becomes high during the production of the self-dispersion type silicone-containing resin aqueous emulsion, which hinders the phase inversion process. An aqueous resin emulsion cannot be obtained.

The monomer can be selected from one or more of these monomers shown above. The same effect can be obtained by grafting the above-mentioned monomers.

As the initiator used in the production of the silicone-containing resin aqueous emulsion having a particle size of 0.001 to 0.05 μ in the present invention, a known radical initiator is used, and examples thereof include peroxides such as potassium persulfate, ammonium persulfate, and hydrogen peroxide. Thing or 2,2'-azobis (2-amidinopropane)
Hydrochloride, azobis-based initiators such as azobiscyclohexanecarbonitrile are preferred representative examples,
If necessary, a water-soluble amine, pyrosulfurous acid, sodium bisulfite; sodium formaldehyde sulfoxylate or the like may be used in combination with a polymerization catalyst as an activator, or as a polymerization degree regulator, an organic halogen compound, a nitro compound,
Alkyl mercaptans, diisopropylxanthogenic acid and the like can also be used.

Another formulation of the silicone-containing resin aqueous emulsion in the present invention, having an isocyanate group at the terminal,
And a silicone group used in a method of obtaining an aqueous emulsion by reacting a urethane prepolymer having an organopolysiloxane with an excess amount of a polyalkylene polyamine to produce a polyurethane urea polyamine, and subsequently mixing the product with an aqueous acid solution. The following publicly known compounds can be mentioned as the contained compounds.

(In the formula, R'is methyl, ethyl, phenyl, fluoroalkyl group, etc., average molecular weight 500-6000) (Wherein, R 'is methyl, ethyl, phenyl, fluoroalkyl group and the like, the average molecular weight _{500~6000) H 2 NC 2 H 4} NHC 2 H 4 -Si (OCH 3) containing a silicone resin aqueous dispersion according to _three invention The product is obtained by seed-polymerizing a vinyl-based monomer in the presence of the silicone-containing resin aqueous emulsion obtained by the method as described above. ) Known compounds such as acrylates, vinyl esters and vinyl ethers can be mentioned.

Specific examples of these compounds include α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid and maleic acid,
Α, β-unsaturated carboxylic acid amides such as acrylamide, methacrylamide, maleic acid amide, and maleic acid imide, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate,
Butyl methacrylate, perfluoroalkylethyl (meth) acrylate, stearyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, 2-aminoethyl methacrylate hydrochloride, dimethylaminoethyl methacrylate, methoxymethyl methacrylate, chloromethyl methacrylate, dichlorotriazinylamino Ethyl methacrylate and maleic acid,
Fumaric acid, itaconic acid ester, etc., α, β-unsaturated carboxylic acid ester, methylol acrylamide, methylol methacrylamide, substituted amides of unsaturated carboxylic acid such as methoxymethyl acrylamide, α, acrylonitrile, methacrylonitrile, etc. Represented by nitriles of β-unsaturated carboxylic acids, vinyl acetate, vinyl chloride, vinyl chloroacetate, etc., divinyl compounds such as divinylbenzene, vinylidene compounds, aromatic vinyl compounds represented by styrene, vinylpyridine and vinylpyrrolidone. Heterocyclic vinyl compounds, vinyl ketone compounds, vinyl ether compounds, vinyl amide compounds, monoolefin compounds such as ethylene and propylene, conjugated diolefin compounds such as butadiene, isoprene and chloroprene, acrylic alcohol, vinegar Allyl compounds allyl, etc., as well as one or more monomers selected from the group of monomers represented by glycidyl methacrylate or the like is used.

In the present invention, in the presence of a silicone-containing resin aqueous emulsion having a particle size of 0.001 to 0.05μ, as the polymerization catalyst used in the seed polymerization of the above vinyl-based monomer, potassium persulfate, ammonium persulfate, peroxide Hydrogen, peroxides such as p-methane hydroperoxide and tert-butyl perbenzoic acid, or 2,2'-azobis (2-
Representative examples of azobis-based initiators such as amidinopropane) hydrochloride and azobiscyclohexanecarbonitrile are preferred, and if necessary, water-soluble amine, pyrosulfite, sodium bisulfite, sodium formaldehyde sulfoxylate, etc. are activators. It is also possible to use in combination with a polymerization catalyst, or as a polymerization degree regulator, an organic halogen compound, a nitro compound, an alkyl mercaptan, diisopropylxanthogenic acid or the like.

The seed polymerization reaction according to the present invention is the particle size according to the present invention.
In the presence of 0.001-0.05μ of the silicone-containing resin aqueous emulsion, the above vinyl-based monomer, catalyst, catalyst activator, polymerization regulator, etc., appropriately and appropriately combined, by a known method,
It is implemented without any special measures.

Needless to say, conventionally known protective colloids and surfactants can be used within a range that does not adversely affect the physical properties of the resin produced for the purpose of improving the stability of the resulting silicone-containing resin aqueous dispersion. .

The method for producing the silicone-containing resin aqueous dispersion of the present invention is a method in which the silicone-containing resin aqueous emulsion is used as a seed, and various vinyl-based monomers are added to the emulsion for emulsion polymerization. It is considered that the particle surface of the silicone-containing resin aqueous dispersion thus obtained is still the silicone-containing resin. When the silicone-containing resin is copolymerized with a monomer having a strong hydrophilicity such as an anion type, a cation type, and a nonionic type, the silicone containing resin can exist on the emulsion particle surface more stably. preferable.

The aqueous silicone-containing resin dispersion thus produced is considered to be a two-layer structure emulsion having a silicone-containing resin in the shell. Therefore, even if the average proportion of silicone resin in the resin is small, the silicone resin is an emulsion. Since it is localized on the particle surface, it is considered that the slidability, releasability and water repellency of the emulsion coating film can maintain high performance.

It is also known that the silicone-containing resin easily moves under heating even in the coating film and collects on the substrate or the air interface. Therefore, it is also effective to perform cross-linking between the core and shell polymer of the two-layer structure emulsion or to add a cross-linking monomer such as divinylbenzene during emulsion polymerization to adjust the moving speed of the silicone-containing resin.

Furthermore, depending on the application in which the silicone-containing resin aqueous dispersion produced by the method of the present invention is used, a defoaming agent, a fungicide, a fragrance, a fluorescent brightening agent, an antioxidant, which is usually used,
UV absorbers, reinforcing agents, fillers, pigments, antistatic agents, antiblocking agents, flame retardants, plasticizers, lubricants, organic solvents, tackifiers, thickeners, foaming agents, colorants, etc. As the agent, an epoxy compound, a compound having a methylol group or an alkoxymethyl group, a catalyst and the like can be blended in the aqueous resin dispersion.

The silicone-containing resin aqueous dispersion produced by the method of the present invention has properties of organopolysiloxane, namely, heat resistance, weather (light) resistance, chemical resistance, non-adhesiveness and releasability, water repellency, and low friction coefficient. , High gas permeability, low surface tension, etc. can be used to advantage.

For example, water-repellent and antifouling applications, resin surface modifiers, positive photoresists, optical fibers, waterless planographic printing plates, contact / optical lenses, paints and ink applications, medical polymer materials, releasability applications, magnetic tape / It can be used in the fields of magnetic disk coating and slidability applications, cosmetics, recording materials, thermal recording paper, sizing agents, paper processing, OP varnishes, flooring agents, anti-caking agents, antifungal agents, etc. , Paper, leather, rubber, wood, metal, asphalt, concrete,
It can be used by impregnating gypsum, ALC plate, ceramic siding material, glass, glass fiber and plastics, or by coating and drying them.

〔Example〕

Next, the present invention will be specifically described with reference to Reference Examples and Examples, but it goes without saying that the present invention is not limited thereto. All parts and% in the examples are on a weight basis unless otherwise specified.

Reference example 1 formula With a compound (hydroxyl value 112) of 1000 parts, methyl ethyl ketone 578 parts and 2,4-tolylene diisocyanate and 2,
348 parts of an 80:20 mixture of 6-tolylene diisocyanate were placed in a round-bottomed flask equipped with a stirrer and a thermometer, and the mixture was stirred at 75 ° C for 4 hours.
After reacting for a period of time, a urethane prepolymer solution (A) containing 4.36% of free isocyanate groups was obtained.

Further, 400 parts of methyl ethyl ketone and 7.63 parts of diethylenetriamine were put into another flask and mixed uniformly, and 100 parts of the above urethane prepolymer solution (A) was added thereto.
It takes 1 hour to gradually add it from the dropping funnel with stirring,
The reaction was carried out at 50 ° C. for 30 minutes to obtain a polyurethaneurea polyamine solution (B).

Infrared absorption spectrum of one drop of this solution was measured and found to be 2250 cm based on free isocyanate groups.
^No absorption of ^-1 was observed.

Next, 10.9 parts of epichlorohydrin was added to this solution, and 50
The reaction was carried out at 90 ° C. for 90 minutes to obtain a polyurethaneurea polyamine solution (C).

Subsequently, 12.9 parts of 70% hydroxyacetic acid was added to this solution, then 550 parts of water was added, and methyl ethyl ketone was distilled off under reduced pressure.

Next, water was added to adjust the concentration to obtain a uniform and stable low-viscosity polyurethane emulsion having a resin content of 15%.

The obtained polyurethane emulsion is transparent and has a Tyndall phenomenon when irradiated with a laser beam, and the particle size is 0.
It was 026μ.

The particle size is COULTER MOD made by COULTER ELECTRONICS INC.
Measured with EL N4.

Reference Examples 2 and 3 A urethane emulsion was synthesized according to Reference Example 1 except that the amounts of diethylenetriamine and 70% hydroxyacetic acid shown in Table 1 were used. The particle size of the obtained emulsion is also shown in Table 1.

Reference Example 4 A reactor equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer, and a nitrogen introduction tube was provided with 320 parts of methyl ethyl ketone, 20 parts of methyl methacrylate, and a formula. 50 parts of the compound represented by and 10 parts of acrylic acid are charged, and nitrogen gas is flowed to remove dissolved oxygen.

On the other hand, 80 parts of methyl ethyl ketone from which dissolved oxygen has been removed, 20 parts of methyl methacrylate and 0.04 part of azobisisobutyronitrile are charged into the dropping funnel.

After heating the reactor to 83 ± 3 ° C., 0.16 parts of azobisisobutyronitrile dissolved in 2 parts of methyl ethyl ketone is added, and a monomer is added dropwise from a dropping funnel according to the consumption rate of methyl methacrylate.

After dropping the monomer, azobisisobutyronitrile
A solution prepared by dissolving 0.2 parts in 3 parts of methyl ethyl ketone was added, and the mixture was aged for 2 hours, and again azobisisobutyronitrile.
A solution prepared by dissolving 0.1 part in 2 parts of methyl ethyl ketone was added every 2 hours, and the reaction was continued for a total of 16 hours to obtain a homogeneous copolymer.

Next, 14.0 parts of triethylamine was added to the copolymer for neutralization, 610 parts of ion-exchanged water was subsequently added, and then methyl ethyl ketone was distilled off under reduced pressure to obtain a self-dispersion type silicone-containing resin aqueous emulsion having a particle size of 0.011μ. Got

Reference Example 5 320 parts of isopropyl alcohol in a reactor equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer, and a nitrogen introducing tube,
20 parts of methyl methacrylate, formula 50 parts of the compound represented by the formula, 10 parts of 2-acrylamido-2-methylpropanesulfonic acid and 7.5 parts of water are charged and nitrogen gas is flowed to remove dissolved oxygen.

On the other hand, 80 parts of methyl ethyl ketone from which dissolved oxygen has been removed, 20 parts of methyl methacrylate and 0.04 part of azobisisobutyronitrile are charged into the dropping funnel.

After heating the reactor to 83 ± 3 ° C., 0.16 parts of azobisisobutyronitrile dissolved in 2 parts of methyl ethyl ketone is added, and a monomer is added dropwise from a dropping funnel according to the consumption rate of methyl methacrylate.

Azobisisobutyronitrile 0.
Add 2 parts dissolved in 3 parts methyl ethyl ketone,
Aged for another 2 hours, again using azobisisobutyronitrile 0.1
One part dissolved in 2 parts of methyl ethyl ketone was added every 2 hours and the reaction was continued for a total of 16 hours to obtain a homogeneous copolymer.

Next, 4.9 parts of triethylamine was added to the copolymer for neutralization, and then 610 parts of ion-exchanged water was added, and then isopropyl alcohol was distilled off under reduced pressure to obtain a self-dispersion type silicone-containing resin aqueous solution having a particle size of 0.015μ. An emulsion was obtained.

Reference Example 6 A reactor equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer, and a nitrogen introducing tube, was provided with 320 parts of methyl ethyl ketone, 20 parts of methyl methacrylate, and a formula. 50 parts of the compound represented by and N, N-dimethylaminoethylmethacrylate 10 parts are charged, and nitrogen gas is flowed to remove dissolved oxygen.

On the other hand, 80 parts of methyl ethyl ketone from which dissolved oxygen has been removed, 20 parts of methyl methacrylate and 0.04 part of azobisisobutyronitrile are charged into the dropping funnel.

After heating the reactor to 83 ± 3 ° C., 0.16 parts of azobisisobutyronitrile dissolved in 2 parts of methyl ethyl ketone is added, and a monomer is added dropwise from a dropping funnel according to the consumption rate of methyl methacrylate.

After dropping the monomer, azobisisobutyronitrile
A solution prepared by dissolving 0.2 parts in 3 parts of methyl ethyl ketone was added, and the mixture was aged for 2 hours, and again azobisisobutyronitrile.
A solution prepared by dissolving 0.1 part in 2 parts of methyl ethyl ketone was added every 2 hours, and the reaction was continued for a total of 16 hours to obtain a homogeneous copolymer.

Next, 7.7 parts of 70% glycolic acid was added to the copolymer to neutralize it, and then 610 parts of ion-exchanged water was added, and then methyl ethyl ketone was distilled off under reduced pressure to obtain a self-dispersion type silicone-containing silicone having a particle size of 0.038μ. A resin emulsion was obtained.

Reference Example 7 320 parts of methyl ethyl ketone, 20 parts of methyl methacrylate, 35 parts of n-butyl acrylate, in a reactor equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer, and a nitrogen introduction tube,
formula 15 parts of the compound represented by and 10 parts of acrylic acid are charged, and nitrogen gas is flowed to remove dissolved oxygen.

On the other hand, 80 parts of methyl ethyl ketone from which dissolved oxygen has been removed, 20 parts of methyl methacrylate and 0.04 part of azobisisobutyronitrile are charged into the dropping funnel.

After heating the reactor to 83 ± 3 ° C., 0.16 parts of azobisisobutyronitrile dissolved in 2 parts of methyl ethyl ketone is added, and a monomer is added dropwise from a dropping funnel according to the consumption rate of methyl methacrylate.

After dropping the monomer, azobisisobutyronitrile
A solution prepared by dissolving 0.2 parts in 3 parts of methyl ethyl ketone was added, and the mixture was aged for 2 hours, and again azobisisobutyronitrile.
A solution prepared by dissolving 0.1 part in 2 parts of methyl ethyl ketone was added every 2 hours, and the reaction was continued for a total of 16 hours to obtain a homogeneous copolymer.

Next, 14.0 parts of triethylamine was added to the copolymer for neutralization, and then 610 parts of ion-exchanged water was added, and then methyl ethyl ketone was distilled off under reduced pressure to obtain a self-dispersion type silicone-containing resin aqueous emulsion having a particle size of 0.018μ. Got

Reference Example 8 320 parts of methyl ethyl ketone, 20 parts of methyl methacrylate, 48 parts of n-butyl acrylate, in a reactor equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer, and a nitrogen introduction tube,
formula 2 parts of the compound represented by and 10 parts of acrylic acid are charged, and nitrogen gas is flowed to remove dissolved oxygen.

Meanwhile, a dropping funnel is charged with 80 parts of methyl ethyl ketone from which dissolved oxygen is removed, 20 parts of methyl methacrylate, and 0.04 g part of azobisisobutyronitrile.

After heating the reactor to 83 ± 3 ° C., 0.16 parts of azobisisobutyronitrile dissolved in 2 parts of methyl ethyl ketone is added, and a monomer is added dropwise from a dropping funnel according to the consumption rate of methyl methacrylate.

After dropping the monomer, azobisisobutyronitrile
A solution prepared by dissolving 0.2 parts in 3 parts of methyl ethyl ketone was added, and the mixture was aged for 2 hours, and again azobisisobutyronitrile.
A solution prepared by dissolving 0.1 part in 2 parts of methyl ethyl ketone was added every 2 hours, and the reaction was continued for a total of 16 hours to obtain a homogeneous copolymer.

Next, 14.0 parts of triethylamine was added to the copolymer for neutralization, 610 parts of ion-exchanged water was subsequently added, and then methyl ethyl ketone was distilled off under reduced pressure to obtain a self-dispersion type silicone-containing resin aqueous emulsion having a particle size of 0.015μ. Got

Reference Example 9 A reactor equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer, and a nitrogen introduction tube was provided with 320 parts of methyl ethyl ketone, 28 parts of methyl methacrylate, 50 parts of the compound represented by and 2 parts of acrylic acid are charged, and nitrogen gas is flowed to remove dissolved oxygen.

On the other hand, 80 parts of methyl ethyl ketone from which dissolved oxygen has been removed, 20 parts of methyl methacrylate and 0.04 part of azobisisobutyronitrile are charged into the dropping funnel.

After heating the reactor to 83 ± 3 ° C., 0.16 parts of azobisisobutyronitrile dissolved in 2 parts of methyl ethyl ketone is added, and a monomer is added dropwise from a dropping funnel according to the consumption rate of methyl methacrylate.

After dropping the monomer, azobisisobutyronitrile
A solution prepared by dissolving 0.2 parts in 3 parts of methyl ethyl ketone was added, and the mixture was aged for 2 hours, and again azobisisobutyronitrile.
A solution prepared by dissolving 0.1 part in 2 parts of methyl ethyl ketone was added every 2 hours, and the reaction was continued for a total of 16 hours to obtain a homogeneous copolymer.

Next, 2.8 parts of triethylamine was added to the copolymer for neutralization, and then 610 parts of ion-exchanged water was added, and then methyl ethyl ketone was distilled off under reduced pressure to give a milky white self-dispersion type silicone-containing resin having a particle size of 0.3 μm. An aqueous emulsion was obtained.

Reference Example 10 100 parts of ion-exchanged water, with a homomixer stirring in an activator aqueous solution consisting of 3 parts of Perex SS-L, A mixture consisting of 30 parts of the compound represented by the formula, 35 parts of styrene, 32 parts of n-butyl acrylate, and 3 parts of acrylic acid was gradually added and emulsified. 10% of this emulsion was charged together with 30 parts of ion-exchanged water into a reactor equipped with a N ₂ introduction tube, a stirrer, and a thermometer, and the temperature was raised to 80 ° C. after N ₂ substitution. Potassium persulfate (0.1
Part) An aqueous solution was added to initiate polymerization, and 20 minutes later, the remaining emulsion was added dropwise over 3 hours. Thereafter, an aqueous solution of potassium persulfate (0.1 part) was further added, and the mixture was aged at 85 ° C. for 2 hours and neutralized by adding 4 parts of triethylamine to obtain an emulsion having a particle size of 0.15 μm.

Example 1 The amount of the urethane emulsion obtained in Reference Example 1 shown in Table 3 was placed in a reactor equipped with a nitrogen introduction tube, a stirrer, and a thermometer, and 500 parts of ion-exchanged water, styrene / n-butyl acrylate = 1 / 100 parts of 1 mixture was added, and the atmosphere was replaced with nitrogen at room temperature. Next, after adjusting the liquid temperature to 30 ° C, 2,2'-azobis (2-
An aqueous solution of amidinopropane) hydrochloride (0.1 part) (hereinafter abbreviated as an initiator) was added, and the reactor was immersed in an oil bath at 70 ° C. to initiate polymerization.

After 2 hours, an initiator (0.1 part) aqueous solution was added and the polymerization was continued. After 1 hour of polymerization, the mixture was cooled to obtain an emulsion with little monomer odor.

The storage stability, foaming, water resistance and slidability of the dried film of the obtained emulsion were measured by the methods described below.

 The above results are summarized in Table 3.

<Storage stability> The emulsion was placed in mayonnaise bottle and left in a thermostat at 50 ° C, and the state change was observed.

X mark: Sedimentation of coarse particles, thickening and gum-up are observed within 50 ° C x 1 week.

Δ mark: Sedimentation of coarse particles, thickening and gum-up are observed within 50 ° C. × 2 weeks.

○: Stable at 50 ℃ x 2 weeks or more.

◎: Stable at 50 ℃ x 2 months or more.

<Bubbling> 10 ml of the emulsion was put into a 30 ml test tube, shaken vigorously for 30 seconds, the total volume including bubbles was measured, and the increased volume was shown in%.

<Water resistance> The coating film obtained by coating the emulsion on a glass plate and drying it at 70 ° C overnight was set in tap water for one sunset, and the degree of whitening was visually determined according to the following criteria.

<Sliding property> Treat the obtained emulsion with an applicator OP
After being evenly coated on the P film, it was dried at 25 ° C. and 65% RH for 1 day, and the slidability was examined. The slidability was measured by making a test piece of 10 cm × 20 cm and using the method shown in FIG.

In the figure, 1 is a test piece, 2 is a load (120 g), 3
Is load cell, 4 is wire, 5 is φ20m rotating at 80 rpm
It is a chrome plated bar of m.

Examples 2 to 5 Emulsion polymerization was carried out according to Example 1 except that the seed emulsion and the initiator shown in Table 3 were used and the polymerization was carried out for the time shown in the table. The physical properties of the obtained emulsion are also summarized in the same table.

Examples 6 to 8 Emulsion polymerization was carried out according to Example 3 except that the monomer composition shown in Table 2 was used. The physical properties of the obtained emulsion are summarized in Table 3.

Example 9 Emulsion polymerization was carried out according to Example 3 except that the seed emulsion and the initiator shown in Table 3 were used and the polymerization was carried out for the time shown in the table. The physical properties of the obtained emulsion are also summarized in the same table.

Comparative Examples 1 to 5 Emulsion polymerization was carried out according to Example 1 except that the seed emulsion shown in Table 3 and the initiator were used for the time described in the same table. The physical properties of the obtained emulsion are also summarized in the same table.

[Brief description of the drawings]

 FIG. 1 is a schematic view of an apparatus used for measuring slidability. 1: Test piece 2: Load 3: Load cell 4: Wire 5: Chrome plated rod

Claims (3)

(57) [Claims] 1. In the presence of 0.2 to 80% by weight (solid content) of an aqueous emulsion comprising a silicone-containing resin containing 5 to 95% by weight of a monomer unit having an organopolysiloxane group and having an average particle size of 0.001 to 0.05 μ. Vinyl monomer 20 to 99.8% by weight
A method for producing an aqueous dispersion of a silicone-containing resin, comprising: 2. An aqueous emulsion is obtained by copolymerizing a vinyl monomer having an organopolysiloxane group and a vinyl monomer copolymerizable therewith in an alcohol or ketone solvent, and then adding water. The method according to claim 1, which is obtained by distilling off the solvent. 3. The method according to claim 1, wherein the aqueous emulsion is a urethane resin emulsion.