JPH02308801A - Production of aqueous dispersion of silicone-containing resin - Google Patents

Abstract

PURPOSE:To obtain the subject dispersion having high surface tension and excellent water resistance without expanding properties in resultant emulsion by subjecting vinyl-based monomer to seed polymerization in the presence of aqueous emulsion comprising specific silicone-containing resin. CONSTITUTION:20-99.8wt.% vinyl-based monomer is subjected to seed polymerization in the presence of 0.2-80wt.% (solid component) aqueous emulsion having 0.001-0.2mu, preferably 0.001-0.05mu averaged particle diameter composed of silicone- containing resin containing 5-95wt.% monomer unit having organopolysiloxane group to afford the aimed dispersion. Besides, the aqueous emulsion is preferably obtained by copolymerizing vinyl monomer having organopolysiloxane group and capillary active vinyl monomer in alcoholic or ketone-based solvent, adding water and distilling off solvent.

Description

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

[Prior art and problems to be solved by the invention] Emulsions, which are so-called emulsions of various polymeric substances, use water as a solvent, so they are advantageous in terms of safety for the environment and the human body compared to solvent-based products. Paints, textile processing agents,
Currently widely used as adhesives, paper processing agents, etc.

In the production of emulsions, anionic surfactants, cationic surfactants, nonionic surfactants, and The surfactant alone or as a mixture is 0.5 to 5% of the raw material monomer.
% by weight used.

However, emulsions produced using the above-mentioned surfactants have a high foaming property, and therefore the bubbles may cause pinholes when coating the emulsion, and furthermore, since the surfactants are non-volatile, It remains in the film prepared from the emulsion and causes a decrease in the water resistance, adhesion, tensile strength, heat resistance, weather resistance, etc. of the film, and further reduces the water repellency, which is one of the characteristics of organopolysiloxane. It has also been pointed out that Therefore, efforts continue in the art to reduce the amount of active agent used as low as possible.

Furthermore, organopolysiloxane group-containing monomers are significantly more expensive than general monomers, and therefore it is important to exhibit their effects using the minimum necessary amount.

[Means to solve the problem]

The present inventors aim to reduce the amount of active agent used in such practical situations, or to maintain an appropriate polymerization rate even under conditions where no active agent is used, and furthermore, the resulting emulsion has no foaming property and has a high surface tension. As a result of extensive research into a manufacturing method for producing an aqueous silicone-containing resin dispersion that has good water resistance and sufficient organosiloxane characteristics even with a small content of monomers having organopolysiloxane groups, we have found that a specific aqueous silicone-containing resin dispersion has been developed. The present inventors have discovered that seed polymerization of vinyl monomers in the presence of an emulsion is extremely effective, and have completed the present invention.

That is, the present invention provides an aqueous emulsion of 0.2 to 80% by weight (with an average particle diameter of 0.001 to 0.2μ) consisting of a silicone-containing resin containing 5 to 95% by weight of monomer units having organopolysiloxane groups ( It is characterized by seed polymerization of 20 to 99.8% by weight of a vinyl monomer in the presence of (solid content), has low foaming, high surface tension, and excellent water resistance, and has a small content of organopolysiloxane groups. However, the present invention relates to a method for producing a silicone resin-containing aqueous dispersion having sufficient organosiloxane properties.

The particle size of the silicone-containing resin aqueous emulsion used in the present invention needs to be 0.001 to 0.2μ, preferably 0.001 to 0.05μ, and a silicone-containing resin aqueous emulsion with a large particle size is used. In this case, it is difficult to obtain a suitable polymerization rate, a long time is required to complete the emulsion polymerization, and the stability of the obtained silicone-containing resin aqueous dispersion is also deteriorated.

The content of monomer-equivalent units containing organopolysiloxane groups constituting the resin in the silicone-containing resin aqueous emulsion is 5 to 95% by weight, and if it is less than 5% by weight, the organopolysiloxane group concentration is too low and the organopolysiloxane group is The characteristics of siloxane, such as sliding properties, mold release properties, and water repellency, are not fully exhibited.

If the amount exceeds 95% by weight, the solubilization of the monomer may be hindered due to oil repellency etc. in the subsequent seed polymerization, and the seed polymerization may not proceed smoothly. This results in disadvantages such as a decrease in properties.(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 monomer is 99.8 to 20% by weight of the vinyl monomer.
In contrast, the silicone-containing aqueous emulsion is 0.2
~80% by weight (solid content).

If the amount of the silicone resin-containing aqueous emulsion used is less than 0.2% by weight, it will be difficult to maintain a suitable polymerization rate and emulsion dispersion stability, and if it exceeds 80% by weight, the organopolysiloxane content will increase, making it uneconomical. It is disadvantageous.

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

At this time, an emulsion with a smaller particle size can also be obtained by using a large amount of a carboxylic acid monomer such as acrylic acid or methacrylic acid to cause alkali swelling and then applying a high shearing force.

In addition, instead of the emulsion polymerization method, it can also be produced using a so-called phase inversion method in which organopolysiloxane monomers containing ionic monomers are polymerized using a solution polymerization method, neutralized condensate is added, and the solvent is distilled off. I can do it.

As another emulsion, for example, a urethane prepolymer having terminal isocyanate groups and organopolysiloxane groups is reacted with an excess amount of polyalkylene polyamine to form a polyurethaneurea polyamine, and this product is then mixed with an acid aqueous solution. A urethane resin emulsion obtained by mixing or further reacting with an acid anhydride, neutralizing with a basic substance, and self-dispersing in water can also be used.

The silicone-containing resin aqueous emulsion thus obtained has a particle size of 0.001 to 0.2μ, and a particle size of 0.001 to 0.2μ.
When the particle size is 0.05 to 0.32μ, it appears milky white, and when the particle size is less than 0.05μ, it becomes a transparent or translucent colloidal dispersion.
Tyndall phenomenon is observed with laser light irradiation.

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

(In the formula, R is H or CH, n = an integer of O to 1.00, R.

is an alkyl group such as methyl, ethyl, propyl, butyl, a phenyl group, a fluoroalkyl group, etc. The same applies to the following formulas. ) It' □ R'-5i-R' □ R'-3i-R' □ R' In addition to the (meth)acrylic acid derivatives shown above as radical polymerizable groups, amide derivatives, styrene derivatives, olefin derivatives, etc. Examples include compounds with groups.

Furthermore, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltributoxysilane, vinyltris(β-methoxyethoxy)silane, allyltriethoxysilane, trimethoxysilylpropylallylamine, γ-(meth)
Acryloxypropyltrimethoxysilane, γ-(meth)acryloxypropyltriethoxysilane, T-(meth)acryloxypropylmethyldimethoxysilane, γ
-(meth)acryloxypropylmethyljethoxysilane, γ-(meth)acryloxypropyltris(β-methoxyethoxy)silane, β-(N-vinylbenzylamino)ethyl-γ-aminopropyltrimethoxy]
0 Silane, N-vinylbenzyl-T-aminopropyltriethoxysilane, 2-styrylethyltrimethoxysilane, 3-(N-styrylmethyl-2-aminoethylamino)propyltrimethoxysilane, (meth)acryloxyethyldimethyl (3-trimethoxysilylpropyl)
Examples include organic silicon compounds such as ammonium chloride, vinyltriacetoxysilane, and vinyltrichlorosilane.

Macromonomers of the monomers shown above can also be used. This macromonomer can be easily synthesized using a recipe known in the art.

For example, the above monomers are radically polymerized with thioglycolic acid, 2-mercaptoethanol, etc. in the presence of an initiator, and the resulting reaction product is reacted 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 desirably less than io, ooo, and if it exceeds this molecular weight, the solubility in the solvent used for producing the self-dispersing silicone-containing resin aqueous emulsion is poor. Preferably several thousand.

Evenly distributed hanging type 5,000 or less.

The same effect can also be obtained by grafting the monomers shown above.

In the production of the silicone-containing resin aqueous emulsion in the present invention, in addition to the organopolysiloxane monomer, monomers that copolymerize therewith may be used in combination. Examples of this type of monomer include ionic monomers. , (meth)acrylate,
Known compounds such as vinyl esters, vinyl ethers, malates, fumarates, and α-olefins 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-methylpropanesulfonic acid,
N,N-dimethylaminoethyl (meth)acrylate,
Vinylphosphonic acid, ionic monomers such as esters of unsaturated carboxylic acid monomers and polyoxyalkylene oxide adducts of polyoxyalkylene glycol or lower alcohols, methyl acrylate, ethyl acrylate, n-acrylic acid Butyl, acrylic esters such as 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n methacrylate
- Methacrylic acid esters such as butyl and isobutyl methacrylate, styrene monomers such as styrene, vinyltoluene, 2-methylstyrene, 1-butylstyrene, and chlorostyrene, and hydroxyl groups such as hydroxyethyl acrylate and hydroxypropyl acrylate Monomers, N-substituted (such as N-methylol (meth)acrylamide, N-butoxymethyl (meth)acrylamide, etc.
meth)acrylic monomers, epoxy group-containing monomers such as glycidyl acrylate, glycidyl methacrylate,
In addition to monomers such as perfluoroalkyl (meth)acrylate and acrylonitrile, there are also macromonomers of the monomers listed above. This macromonomer can be easily synthesized using a recipe known in the art.

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

The number average molecular weight of the macromonomer is desirably 10.000 or less; if the molecular weight is higher than this, the self-dispersed silicone-containing resin aqueous emulsion will have a high viscosity during production, which will interfere with the phase inversion process, and the self-dispersed type will be stable at high concentrations. A silicone resin-containing aqueous emulsion cannot be obtained.

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

Particle size in the present invention is 0. Known radical initiators are used as initiators for producing silicone-containing resin aqueous emulsions with an OQ of 1 to 0.2μ, such as potassium persulfate, ammonium persulfate, peroxides such as hydrogen peroxide, or .2゛-Azobis(2-amidinopropane) hydrochloride, azobis-based initiators such as abbiscyclohexanecarbonitrile are preferred representative examples, and if necessary, water-soluble amines, trisulfite, sodium bisulfite; sodium Formaldehyde sulfoxylate and the like can be used as an activator in combination with a polymerization catalyst, and organic halogen compounds, nitro compounds, alkyl mercaptans, diisopropyl xanthate, etc. can also be used as polymerization degree regulators.

Another formulation of the silicone-containing aqueous emulsion of the present invention is to react an excess amount of polyalkylene polyamine with a urethane prepolymer having an isocyanate group at the terminal and organopolysiloxane to produce a polyurethaneurea polyamine. The following known silicone group-containing compounds can be used in the method of obtaining an aqueous emulsion by subsequently mixing this product with an aqueous acid solution.

(In the formula, R' is a methyl, ethyl, phenyl, fluoroalkyl group, etc., with an average molecular weight of 500 to 6000) (In the formula, R
' is a methyl, ethyl, phenyl, fluoroalkyl group, etc., average molecular weight 500-6000)t12NcJ4Ntl
czl14Si (OCIIs)sThe silicone-containing resin aqueous dispersion according to the present invention is prepared by:
Although obtained by seed polymerizing a vinyl monomer, examples of the vinyl monomer used in the present invention include known compounds such as (meth)acrylate, vinyl ester, and vinyl ether.

Specific examples of these compounds include α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, and maleic acid, acrylamide, methacrylamide, maleic acid amide,
α,β-unsaturated carboxylic acid amides such as maleic acid imide, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, perfluoroalkylethyl (meth)
acrylate, stearyl methacrylate-1-, hydroxyethyl acrylate, hydroxypropyl acrylate, 2-amino F-6 methyl methacrylate methyl methacrylate-I, methoxymethyl methacrylate-1
-, chloromethyl methacrylate, dichlorotriazinyl aminoethyl methacrylate, esters of maleic acid, fumaric acid, itaconic acid, etc., esters of α,β-unsaturated carboxylic acids, methylolacrylamide, methylolmethacrylamide, methoxymethylacrylamide, etc. α. Substituted amides of unsaturated carboxylic acids, acrylonitrile, methacrylaterile, etc. In addition to β-unsaturated carboxylic acids such as nitriles, vinyl acetate, vinyl chloride, and vinyl chloroacetate, divinyl compounds such as divinylbenzene, vinylidene compounds, aromatic vinyl compounds such as styrene, and vinylpyridine and vinylpyrrolidone are also included. Heterocyclic vinyl compounds, vinyl ketone compounds, vinyl ether compounds, vinylamide compounds, monoolefin compounds such as ethylene and propylene, conjugated diolefin compounds such as butadiene, isoprene and chlorobrene, allyl compounds such as allyl alcohol and allyl acetate, and glycidyl One or more monomers selected from the group of monomers represented by methacrylate and the like are used.

In the present invention, the polymerization catalyst used in the seed polymerization of the above-mentioned vinyl monomer in the presence of a silicone-containing resin aqueous emulsion with a particle size of 0.001 to 0.2 μm includes potassium persulfate, ammonium persulfate, etc. , hydrogen peroxide, p-methane hydroperoxide, tert-
Preferred representative examples include peroxides such as butyl perbenzoic acid, or azobis-based initiators such as 2,2'-azobis(2-amidinopropane) hydrochloride and azobiscyclohexanecarbonitrile. Water-soluble amines, pyrosulfite, sodium bisulfite; sodium formaldehyde sulfoxylate, etc. are used as activators in combination with polymerization catalysts, and as polymerization degree regulators, organic halogen compounds, nitro compounds, alkyl mercaptans, diisopropyl xanthate, etc. etc. can also be used.

The seed polymerization reaction according to the present invention is performed using a particle size of 0 according to the present invention.
In the presence of a silicone-containing resin aqueous emulsion of 0.001 to 0.2μ, the above-mentioned vinyl monomer, catalyst, catalyst activator, polymerization regulator, etc. are appropriately combined, and a special It will be implemented without any ingenuity.

It goes without saying that for the purpose of improving the stability of the silicone-containing resin aqueous dispersion produced, conventionally known protective colloids and surfactants can be used as long as they do not adversely affect the physical properties of the produced resin. .

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, various vinyl monomers are added thereto, and emulsion polymerization is carried out. It is considered that the particle surface of the silicone-containing resin aqueous dispersion obtained in this manner still contains a silicone-containing resin. Note that if this silicone-containing resin is copolymerized with an anionic, cationic, or nonionic monomer that exhibits strong hydrophilicity, this silicone-containing resin can exist more stably on the surface of the emulsion particles. preferable.

The silicone-containing resin aqueous dispersion produced in this way is considered to be a two-layered emulsion with a silicone-containing resin in the shell, and therefore, even if the average proportion of silicone resin in the resin is small, the silicone resin is Since it is localized on the particle surface, it is thought that the emulsion coating film can maintain high performance in sliding properties, mold release properties, and water repellency.

Furthermore, it is known that silicone-containing resins easily move during heating even in the coating film and collect on the substrate or air interface. Therefore, it is also effective to adjust the movement speed of the silicone-containing resin by crosslinking between the core and shell polymers of the two-layer emulsion or by adding a crosslinking monomer such as divinylbenzene during emulsion polymerization, if necessary.

Furthermore, depending on the use of the silicone-containing resin aqueous dispersion produced by the method of the present invention, commonly used antifoaming agents, antifungal agents, fragrances, fluorescent whitening agents, antioxidants, and ultraviolet rays may be added. Absorbents, reinforcing agents, fillers, pigments, antistatic agents, anti-blocking agents, flame retardants, plasticizers, lubricants, organic solvents, tackifiers, thickeners, blowing agents, colorants, etc., as well as crosslinking agents. As such, an epoxy compound, a compound having a methylol group or an alkoxymethyl group, a catalyst, etc. can be blended into the aqueous resin dispersion.

The silicone-containing resin aqueous dispersion produced by the method of the present invention has the characteristics of organopolysiloxane, that is, heat resistance,
It can be advantageously used in fields that take advantage of weather resistance, chemical resistance, non-adhesion and mold releasability, water repellency, low friction coefficient, high gas permeability, low surface tension, etc.

For example, 1. Water and stain-proofing applications, resin surface modifiers, positive photoresists, optical fibers, waterless planographic printing plates, contact/optical lenses, paint and ink applications, medical polymer materials, mold release applications, and magnetism. Can be used in fields such as tape/magnetic disk coating and sliding properties, cosmetics, recording materials, thermal recording paper, sizing agents, paper processing, op varnishes, powders, anti-caking agents, anti-mold agents, etc., and fiber materials. , non-woven fabric, paper, leather, rubber, wood, metal, asphalt, concrete,
It can be used by impregnating plaster, ALC boards, ceramic siding materials, glass, glass fibers, plastics, etc., or by applying it to these surfaces and drying it.

[Example] Next, the present invention will be specifically explained with reference to Reference Examples and Examples, but it goes without saying that the present invention is not limited to these.

In addition, all parts and percentages in the examples are based on weight unless otherwise specified.

Reference Example 1 1000 parts of the compound represented by the formula (hydroxyl value 112), 578 parts of methyl ethyl ketone, and 80 parts of 2.4-)lylene diisocyanate and 2.6-lylene diisocyanate
4. Pour 348 parts of the mixture of 20 into a round bottom flask equipped with a stirrer and a thermometer and react at 75°C for 4 hours.
A urethane prepolymer solution (A) containing 36% of free isocyanate groups was obtained.

Furthermore, 400 parts of methyl ethyl ketone and 7.63 parts of diethylene triamine were placed in another flask and mixed uniformly, and the above urethane prepolymer solution (A) was added to this 10 parts.
0 part was gradually added over 1 hour from the dropping funnel with stirring, and the mixture was reacted at 50°C for 30 minutes to obtain a polyurethaneurea polyamine solution (B).

An infrared absorption spectrum was measured using a drop of this solution, and it was determined that <225
No absorption at 0 cm-' was observed.

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

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

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

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

In addition, the particle size is C0ULTERl! LECTRONICS
It was measured with COULTERMODEL N4 manufactured by INC.

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

Table 1 Reference Example 4 In a reactor equipped with a stirrer, reflux condenser, dropping funnel, thermometer, and nitrogen introduction tube, 320 parts of methyl ethyl ketone, 1.20 parts of methyl methacrylate, 50 parts of the compound represented by the formula, 10 parts of acrylic acid was charged, and nitrogen gas was introduced to remove dissolved oxygen.

On the other hand, 80 parts of methyl ethyl ketone from which dissolved oxygen had been removed, 1.20 parts of methyl methacrylate, and 0.04 part of azobisisobutyronitrile were charged into a dropping funnel 1-.

After heating 83 parts of the reactor to 3°C, 0.16 part of abbisisobutyronitrile dissolved in 2 parts of methyl ethyl ketone was added, and the monomer was added from the dropping funnel according to the consumption rate of methyl methacrylate-1. Drip.

After dropping the monomer, azobisisobutyronitrile 0
．． A solution of 2 parts dissolved in 3 parts of methyl ethyl ketone was added, and the mixture was further aged for 2 hours.
．． A solution of 1 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, 14.0 parts of triethylamine was added to this copolymer to neutralize it, and then 610 parts of ion-exchanged water was added, and the methyl ethyl ketone was distilled off under reduced pressure.
A self-dispersing silicone-containing resin aqueous emulsion was obtained.

Reference Example 5 320 parts of isopropyl alcohol was placed in a reactor equipped with a stirrer, reflux condenser, dropping funnel, thermometer, and nitrogen introduction tube.
20 parts of methyl methacrylate, 50 parts of the compound represented by the formula
80 parts of methyl ethyl ketone and 20 parts of methyl methacrylate were charged with 10 parts of 2-acrylamido-2-methylpropanesulfonic acid and 7.5 parts of water, and nitrogen gas was passed through to remove dissolved oxygen. and 0.04 part of azobisisobutyronitrile.

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

After completing the monomer dropwise addition, add 0.0% azobisisobutyronitrile.
Add 2 parts dissolved in 3 parts of methyl ethyl ketone,
Aging for another 2 hours, then adding 0.0% azobisisobutyronitrile again.
A solution of 1 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 this copolymer to neutralize it, followed by 610 parts of ion-exchanged water, and the isopropyl alcohol was distilled off under reduced pressure.
A self-dispersing silicone-containing resin aqueous emulsion was obtained.

Reference Example 6 320 parts of methyl ethyl ketone, 20 parts of methyl methacrylate, 50 parts of the compound represented by the formula,
10 parts of N,N-dimethylaminoethyl methacrylate were charged, and nitrogen gas was introduced to remove dissolved oxygen.

Meanwhile, 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 83 parts of the reactor to 3°C, 0.16 part of azobisisobutyronitrile dissolved in 2 parts of methyl ethyl ketone is added, and the monomer is added dropwise from the dropping funnel in accordance with the consumption rate of methyl methacrylate.

After dropping the monomer, azobisisobutyronitrile 0
．． A solution of 2 parts dissolved in 3 parts of methyl ethyl ketone was added, and the mixture was further aged for 2 hours.
．． A solution of 1 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, 7.7 parts of 70% glycolic acid was added to this copolymer to neutralize it, and then 610 parts of ion-exchanged water were added, and methyl ethyl ketone was distilled off under reduced pressure. A mold-containing silicone resin emulsion was obtained.

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

-Methyl ethyl ketate from which dissolved oxygen has been removed in the recessive funnel [
- Charge 780 parts, 20 parts of methyl methacrylate I, and 0.04 part of azobisisobutyronitrile.

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

After dropping the monomer, add 0.2 parts of azobisisobutyronitrile dissolved in 3 parts of methyl ethyl ketone, age for another 2 hours, and dissolve 0.1 part of azobisisobutyronitrile in 2 parts of methyl ethyl ketone again. 2
The reaction was continued for a total of 16 hours, and a homogeneous copolymer was obtained.

Next, 14.0 parts of triethylamine was added to this copolymer to neutralize it, and then 610 parts of ion-exchanged water were added, and methyl ethyl ketone was distilled off under reduced pressure. Obtain a resin aqueous emulsion.

Reference Example 8 320 parts of methyl ethyl ketone, 20 parts of methyl methacrylate, and 1.4 parts of n-butyl acrylate were placed in a reactor equipped with a stirrer, reflux condenser, dropping funnel, thermometer, and nitrogen introduction tube.
8 parts, 2 parts of the compound represented by the formula, and 10 parts of acrylic acid were charged, and dissolved oxygen was removed by flowing nitrogen gas.

Meanwhile, 80 parts of methyl ethyl ketone from which dissolved oxygen has been removed, 1.20 parts of methyl methacrylate, and 0.04 part of azobisisobutyronitrile are charged into a dropping funnel.

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

After dropping the monomer, azobisisobutyronitrile 0
．． A solution of 2 parts dissolved in 3 parts of methyl ethyl ketone was added, and the mixture was further aged for 2 hours.
．． A solution of 1 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, 14.0 parts of triethylamine was added to this copolymer to neutralize it, and then 610 parts of ion-exchanged water were added, and methyl ethyl ketone was distilled off under reduced pressure. A resin aqueous emulsion was obtained.

Reference Example 9 50 parts of a compound represented by 320 parts of methyl ethyl ketone, 28 parts of methyl methacrylate,
Two parts of acrylic acid was charged, and nitrogen gas was introduced to remove dissolved oxygen.

- Methyl ethyl with dissolved oxygen removed in the funnel
80 parts of methyl methacrylate, 20 parts of methyl methacrylate, and 0.04 parts of azobisisobutyronitrile were charged.

After heating 83 parts of the reactor to 3°C, a solution of 0.16 parts of azobisisobutyronitrile dissolved in 2 parts of methyl ethyl ketone was added, and the monomer was added from the dropping funnel to match the consumption rate of methyl methacrylate-1. Drip.

After dropping the monomer, add abbisisobutyronitrile 0
．． 2 parts dissolved in 73 parts of methyl ethyl ketone was added and aged for another 2 hours, and again 0.1 part of azobisisobutyroni I dissolved in 2 parts of methyl ethyl ketone was added every 2 hours to give a total of 16 The reaction was continued for hours to obtain a homogeneous copolymer.

Next, 2.8 parts of triethylamine was added to this copolymer to neutralize it, and then 610 parts of ion-exchanged water were added, and methyl ethyl ketone was distilled off under reduced pressure. A silicone resin-containing aqueous emulsion was obtained.

Reference Example 1O To an aqueous activator solution consisting of 100 parts of ion-exchanged water and 3 parts of Pellex 5S-L, while stirring with a homomixer, 30 parts of the compound represented by: 35 parts of styrene, 3 parts of n-butyl acrylate
A mixture of 2 parts of acrylic acid and 3 parts of acrylic acid was gradually added and emulsified. 10% of this emulsion was charged into a reactor equipped with a N2 introduction pipe, a stirrer, and a thermometer together with 30 parts of ion-exchanged water, and after N2N exchange, the temperature was raised to 80'C. Potassium persulfate (0,
1 part) Aqueous solution was added to start polymerization, and 20 minutes later, the remaining emulsion was added dropwise over 3 hours. After that, an aqueous solution of potassium persulfate (0.1 parts) was further added, and the mixture was aged at 85°C for 2 hours, and 4 parts of triethylamine was added to neutralize it, and the particle size was 0.15μ.
An emulsion was obtained.

Example 1 The amount of the urethane emulsion obtained in Reference Example 1 listed 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 a /1 mixture was added thereto, and the atmosphere was replaced with nitrogen at room temperature. Next, after adjusting the liquid temperature to 30°C, an aqueous solution of 2.2”-azobis(2-amidinopropane) hydrochloride (0.1 part) (hereinafter referred to as initiator) was added, and the reactor was placed in a 70°C oil bath. to initiate polymerization.

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

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

The above results are summarized in Table 3.

<Storage Stability> The emulsion was placed in a mayonnaise bottle and left in a thermostat at 50'C, and changes in state were observed.

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

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

0 mark: Stable for 2 weeks or more at 50°C.

◎: 50'CX stable for more than 2 months.

Foaming> 10 mj of the emulsion was placed in a 30 ml test tube, shaken vigorously for 30 seconds, the total volume including foam was measured, and the volume increase was expressed in %.

<Water Resistance> The emulsion was applied onto a glass plate and dried overnight at 70"C. The obtained coating film was immersed in tap water for one day, and the degree of whitening was visually judged according to the following criteria.

<Slidability> Process the obtained emulsion using an applicator.
After uniformly coating on the P film, 25'C, 65χl
? ) After drying for one day in I, the sliding properties were examined.

A test piece measuring 10 cm x 20 cm was prepared and the slidability was measured using the method shown in FIG.

In addition, in the figure, 1 is the test piece, 2 is the load (120g),
3 is a code cell, 4 is a wire, and 5 is a 420 mm chrome-plated rod that rotates at 80 rpm.

Examples 2 to 6 Emulsion polymerization was carried out in accordance with Example 1, except that the seed emulcidin and 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 7 to 9 Example 3 except that the monomer composition was as shown in Table 2.
Emulsion polymerization was carried out according to the following procedure. The physical properties of the obtained emulsion are summarized in Table 3.

Table 2 Example 10 Emulsion polymerization was carried out in accordance with Example 3, except that the seed emulsion and initiator shown in Table 3 were used and the polymerization was carried out for the time specified in the table. The physical properties of the obtained emulsion are also summarized in the same table.

Comparative Examples 1 to 4 Emulsion polymerization was carried out in accordance with Example 1, except that the seed emulsions and initiators 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.

[Brief explanation of drawings]

FIG. 1 is a schematic diagram of the apparatus used for measuring sliding properties. 1: Test piece 2: Load 3: Load cell 4: Wire 5 Nichrome plating stick Outsourcing agent Kaoru Furutani Figure 1

Claims (1)

[Claims] 1. 5 to 5 monomer units having an organopolysiloxane group
An aqueous emulsion containing 95% by weight of a silicone-containing resin with an average particle size of 0.001-0.2μ 0.2-8
Vinyl monomer 20-9 in the presence of 0% by weight (solid content)
A method for producing a silicone-containing aqueous dispersion, comprising seed polymerizing 9.8% by weight. 2. The average particle diameter of the aqueous emulsion is 0.001-0.
The manufacturing method according to claim 1, wherein the particle size is 0.05μ. 3. An aqueous emulsion is obtained by copolymerizing a vinyl monomer having an organopolysiloxane group and a surface-active vinyl monomer in an alcohol-based or ketone-based solvent, then adding water and distilling off the solvent. The manufacturing method according to claim 1, which is obtained. 4. The manufacturing method according to claim 1, wherein the aqueous emulsion is a urethane resin emulsion.