JPH06340798A - Modified silicone polymer emulsion and emulsifying dispersant - Google Patents

Abstract

PURPOSE:To provide a modified silicone polymer emulsion excellent in storage stability, and to provide an emulsifying dispersant. CONSTITUTION:The emulsion can be obtained by dispersing, in water through self-emulsification process, a polyoxyethylene or oxypropylene ether polymer each having in one molecule at least one reactive silicon group such as alkoxysilyl group at the end(s) of a polymer, and the other objective emulsifying dispersant consisting of the polymer.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to novel emulsions and modified emulsion dispersants of modified silicone polymers.

[0002]

2. Description of the Related Art Conventionally, as a method for dispersing a polymer having a reactive silicon group in water, Japanese Patent Publication No. 3-22905.
As described in Japanese Patent Publication No. JP-A-2003-187, forced emulsification was carried out using a surfactant. However, when the emulsion is forcibly emulsified with a surfactant, the storage stability is poor, and the surfactant has various drawbacks that affect physical properties. The resulting emulsion had coarse particles.

[0003]

DISCLOSURE OF THE INVENTION The present invention is intended to solve the above-mentioned drawbacks and provide a modified silicone polymer emulsion having excellent storage stability and fine particles.

[0004]

The present invention is directed to at least one reactive silicon group in a molecule at a side chain or terminal of a polymer.
A novel emulsion in which a polyether, a polyester, or a polycarbonate having an individual unit and a hydrophilic site in the molecule is dispersed in water by a self-emulsification method, and one molecule of a reactive silicon group at the side chain or terminal of the polymer. Having at least one in the molecule and having a hydrophilic site in the molecule,
The present invention relates to an emulsifying dispersant composed of polyether, polyester or polycarbonate.

Any known polyether, polyester or polycarbonate can be used in the present invention. As the polyether,-(R ¹ -O) _n
Having a main chain represented by (R ¹ has 1 to 8 carbon atoms
Is a divalent hydrocarbon group. Hereinafter, n represents an integer. ),
The _{^{polyester, - (R 2 -COO) n}} - or -
^{(CO-R 3 -COO-R} 4 -O) n - are those having a main chain represented by ^{(R 2, R 3, R} 4 is from 1 to 12 carbon atoms
Is a divalent hydrocarbon group. ), Polycarbonate is
^{- (R 5 -O-CO-} O) n - are those having a main chain represented by (R ⁵ represents a divalent hydrocarbon group having 1 to 12 carbon atoms.).

In order to introduce a reactive silicon group into a side chain or a terminal, a polyether polyol, a polyester polyol or a polycarbonate polyol having a hydroxyl group at the terminal is preferably used.

The hydrophilic portion may be either ionic or non-ionic. Examples of the ionic portion include ammonium salts and phosphonium salts for cations, and sulfonates, sulfate ester salts and carboxylates for anions. Examples of such nonionics include oxyethylene chains.

The polyether polyol is preferably a polyoxyalkylene polyol, which is obtained by adding an alkylene oxide to an initiator which is an active hydrogen compound having at least one active hydrogen.

As the active hydrogen compound used as an initiator, a hydroxy compound or a polyhydroxy compound is particularly preferable.

Specific examples of the hydroxy compound include monoalcohols such as methanol, ethanol, propanol and butanol. Examples of the polyhydroxy compound include dihydric alcohols such as ethylene glycol and propylene glycol, trihydric alcohols such as glycerin, trimethylolpropane and hexanetriol, and tetrahydric or higher alcohols such as pentaerythritol, diglycerin, dextrose, sorbitol and sucrose. And so on.

In addition, a compound having a phenolic hydroxyl group or a methylol group such as bisphenol A, resole or novolac, a compound having a hydroxyl group and another active hydrogen such as ethanolamine or diethanolamine, a polyhydroxy compound or another active hydrogen compound is compared. Active hydrogen compounds such as compounds obtained by adding a small amount of alkylene oxide can also be used. Two or more of these active hydrogen compounds can be used in combination.

As the alkylene oxide, a monoepoxide having 2 or more carbon atoms, that is, propylene oxide, 1,
Alkylene oxides having 4 or less carbon atoms such as 2-butylene oxide and epichlorohydrin are preferable, and they are used alone or in combination of two or more thereof or with other epoxy group-containing compounds such as styrene oxide and glycidyl ether. You can also do it.

In the case of using two or more kinds of alkylene oxides or the use of alkylene oxides and other epoxy-containing compounds, they may be mixed and added or sequentially added to form a random polymer chain or a block polymer chain. it can.

In this addition reaction, most commonly, an alkali metal hydroxide such as potassium hydroxide or sodium hydroxide is used as a catalyst, and further boron trifluoride or 3 is used.
The use of catalysts such as primary amines has also been proposed. In addition, as a synthesis catalyst for low by-products and high molecular weight polyethers,
A complex metal cyanide complex is effective.

The structure of the polyether polyol used in the present invention can be obtained by block or random copolymerization of the above-mentioned initiator with an alkylene oxide or another epoxy group-containing compound. Furthermore, a polyether polyol obtained by addition-polymerizing tetrahydrofuran with the above initiator and a polyether polyol obtained by adding an alkylene oxide using the above as an initiator can also be used.

Preferred polyester polyols include polyesters having a polyvalent carboxylic acid residue and a polyhydric alcohol residue, or a polyester polyol having a ring-opening polymer chain of a cyclic ester or a hydroxycarboxylic acid polymer chain.

The former is a polyester polyol having a divalent carboxylic acid residue and a dihydric alcohol residue, and in some cases, a small amount of a trivalent or higher polyvalent carboxylic acid residue or a polyhydric alcohol residue. There are two or more kinds of these residues. Examples of polycarboxylic acids include adipic acid, sebacic acid, azelaic acid,
Aliphatic dicarboxylic acids such as succinic acid are preferable, and aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid can be used together therewith. As the polyhydric alcohol, ethylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol and the like are preferable, and trihydric or higher alcohols such as glycerin, trimethylolpropane and pentaerythritol are preferable. Polyhydric alcohol can be used together.

As the latter polyester polyol, ε-caprolactone, γ-butyrolactone, δ-valerolactone, other cyclic ester, or hydroxycarboxylic acid such as 6-hydroxyhexanoic acid is added to an initiator such as polyhydric alcohol. There is a polyester-based polyol obtained by the above. In particular, a polyester polyol obtained by adding ε-caprolactone to an initiator such as a polyhydric alcohol is preferable. As the initiator, the polyhydric alcohol having 2 to 8 valences described in the item of the polyether polyol is suitable, and the alcohol having 2 to 4 valences is particularly preferable.

Examples of polycarbonate polyols include polyhexamethylene carbonate.

The nonionic hydrophilic site can be provided by polymerizing ethylene oxide with the above polyether polyol, polyester polyol or polycarbonate polyol. Alternatively, ethylene oxide may be copolymerized with the alkylene oxide during the production of the polyether polyol. Also, a hydrophilic site can be provided by reacting a reactive silicon group with an oxyethylene chain-containing alcohol.

As the ionic hydrophilic site, an ionic compound having active hydrogen reactive with isocyanate can be introduced into the polyol via the polyisocyanate compound. Examples of isocyanate-reactive carboxylic acids include dimethylolpropionic acid and amino acids.

The hydrophilic portion is 10 to 90% by weight, preferably 30 to 90% by weight, in one molecule for nonionic ones, and 0.3 to 5% by weight in the polymer as a carboxyl group for ionic ones. , Preferably 0.5 to 3% by weight. These ionic compounds are preferably neutralized with an acid or a base during emulsification.

At least one reactive silicon group must be present at the molecular end or side chain of the polyether, polyester or polycarbonate, and the reactive silicon group is preferably the group represented by Chemical formula 1.

[0024]

[Chemical 1]

In the chemical formula 1, m is an integer of 0 to 18, a is 1 to 3 and b is 0 to 2. However, different values may be taken for each of the m siloxy groups in parentheses. X is a hydride group, a hydroxyl group, an alkoxy group (-OR:
R is a monovalent hydrocarbon group having 1 to 20 carbon atoms), one of which is
One is preferably an alkoxy group. However, a +
The mb groups represented by X may be different from each other.
It is necessary that at least one group represented by X in Chemical formula 1 be present. R ⁶ is 1 having 1 to 20 carbon atoms
It is a valent hydrocarbon group. However, (3-a) + m (2-
b) The groups represented by R ⁶ may be different from each other. Note that m is preferably 0.

The group represented by Chemical formula 2 is preferable as the one in which the hydrophilic moiety is directly bonded to the silicon group.

[0027]

[Chemical 2]

In the chemical formula 2, X is a hydride group, a hydroxyl group,
It is desirable that an alkoxy group (-OR: R is a monovalent hydrocarbon group having 1 to 20 carbon atoms), one of which is an alkoxy group. R ⁷ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and p is different depending on the type of polyol to be used so that the ratio of the hydrophilic moiety is within the above range.

Various methods can be adopted to introduce such a reactive silicon group into the side chain or terminal of a polyether, polyester or polycarbonate. Generally, the above-mentioned hydrophilic polyether having a hydroxyl group at the terminal. There are a method of introducing directly or via a polyisocyanate compound into a polyol, a hydrophilic polyester polyol, a hydrophilic polycarbonate polyol, and a method of reacting a silicon compound having a hydrophilic moiety with a polyether, polyester or polycarbonate.

For the method of introducing directly, the isocyanate silane compound represented by Chemical formula 3 can be used.

[0031]

[Chemical 3]

In Chemical Formula 3, m, X and R ⁶ are the same as defined above, and R ⁸ is a divalent hydrocarbon group having 1 to 20 carbon atoms.

Specific examples include .gamma.-isocyanatopropyldimethoxymethylsilane, .gamma.-isocyanatobutyltriethoxysilane and .gamma.-isocyanatopentyldiethoxymethylsilane.

As a method of introducing via a polyisocyanate compound, an isocyanate compound such as toluene diisocyanate or diphenylmethane diisocyanate, and a reactive silicon compound having active hydrogen reactive with an isocyanate group can be used. As such a reactive silicon compound, one having an amino group, a thiol group or a hydroxyl group is preferable.

As a compound having an amino group, an aminosilane compound represented by Chemical formula 4 can be used.

[0036]

[Chemical 4]

In the chemical formula 4, m, X, R ⁶ and R ⁸ are the same as defined above.

Specifically, γ-aminopropyltrimethoxysilane, γ-aminobutyldiethoxymethylsilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-amino Examples include propylmethyldimethoxysilane.

As a compound having a thiol group, a mercaptosilane compound represented by Chemical formula 5 can be used.

[0040]

[Chemical 5]

In the chemical formula 5, m, X, R ⁶ and R ⁸ are the same as defined above.

Specific examples include γ-mercaptopropyltrimethoxysilane, γ-mercaptobutylmethyldimethoxysilane and γ-mercaptopropyltriethoxysilane.

Further, a reactive silicon group can be introduced by introducing an unsaturated bond at the end of the polyol and reacting it with the hydrosilyl compound represented by Chemical formula 6. An allyl group is most preferably used as the unsaturated bond.

[0044]

[Chemical 6]

In the chemical formula 6, m, X and R ⁶ are the same as defined above.

Specific examples thereof include methyldimethoxysilane, ethyldimethoxysilane, triethoxysilane and butyldiethoxysilane.

Polyethers, polyesters and polycarbonates having reactive silicon groups obtained as described above (these are collectively referred to as modified silicone polymers)
Any molecular weight can be used, but in view of the physical properties of the cured film obtained from the emulsion or the effect as an emulsifying dispersant, the molecular weight is preferably from 1,000 to 50,000.

Since the modified silicone polymer of the present invention has a self-emulsifying property, the modified silicone polymer and water may be mixed and stirred for emulsification. The emulsion thus obtained exhibits room temperature curability when formed into a film.

The emulsion of the present invention is reactive at room temperature, but it is preferable to use a silanol condensation catalyst in combination in order to accelerate the condensation reaction of the modified silicone polymer to a high molecular weight at room temperature. The emulsion of the present invention is stable not only when the catalyst is not added, but also when the catalyst is added.

Examples of the catalyst used in the present invention include dibutyltin dilaurate, alkyl titanates, organosilicon titanates, tin octylate, dibutyltin maleate and dibutylamine-2-ethylhexoate. The amount of condensation catalyst used is 0.01 to 10 with respect to the amount of polymer.
% By weight, preferably 0.5-5% by weight.

In the present invention, the catalyst may be emulsified separately, but it is also possible to emulsify the modified silicone polymer to which the catalyst is added or to add the catalyst to the emulsion of the modified silicone polymer.

Since the emulsion of the present invention is a one-pack type which can coexist with a catalyst and has a room temperature curability, it has a strong chemical resistance at room temperature without using a crosslinking agent or the like. Excellent film formation can be achieved.

Further, in the case of a normal reactive emulsion, the particles themselves are solid, whereas in the emulsion of the present invention, the particles are in a liquid state. Therefore, when the emulsion is broken, the particles are fused well. In addition, in the case of a normal reactive emulsion, it is necessary to preliminarily contain a solvent in order to improve the fusion property between particles when the emulsion is broken, but since the emulsion of the present invention does not need to use a solvent, It also has the feature that it can increase its concentration.

The emulsion of the present invention is characterized in that it has better storage stability than the emulsion forcibly emulsified with a surfactant, the emulsion particles are fine, and a smooth film can be easily obtained.

In the emulsion of the present invention, various additives, fillers and the like can coexist in the aqueous phase. For example,
As a stabilizer of emulsion, sodium carboxymethyl cellulose, polyvinyl alcohol, polyacrylic acid, polymaleic acid, polyacrylpyrrolidone, polyacrylamide, synthetic polymer dispersants and thickeners such as polyethylene glycol, casein, starch, glue,
Examples thereof include natural polymers such as egg white and rubber, and inorganic substances such as bentonite and activated clay.

Since the modified silicone polymer emulsion obtained in the present invention is reactive, the resulting film is polymerized by chain extension or cross-linking, so that a coating material, a spray material, an adhesive or a sealing agent is obtained. It can be used as a binder, an adhesive, an antifogging material, a surface treatment agent for various resins, and the like.

The modified silicone polymer in the present invention can also be used as an emulsifying dispersant for emulsifying other resins. The emulsifying dispersant of the present invention can be used for emulsifying acrylic resins, polyurethane resins, vinyl acetate resins, reactive silicon group-containing polymers having no hydrophilic site, and the like.

Particularly, it is preferably used as an emulsifying dispersant for a reactive silicon group-containing polymer having no hydrophilic portion. The reactive silicon group-containing polymer having no hydrophilic site has the above-mentioned reactive silicon at the terminal or side chain,
Examples thereof include polymers having a polyoxypropylene chain as the main chain and vinyl resins having a reactive silicon group.

Since the effect as an emulsifying dispersant can be controlled by the introduction ratio of the hydrophilic site, the effect is exhibited even with a small amount, but an excellent effect is obtained by using 0.1% by weight or more with respect to the resin which is usually emulsified. . The emulsifying dispersant of the present invention effectively functions for emulsifying and dispersing, and there is almost no foaming which is a problem during working.

In the resin film obtained by using the reactive emulsifying dispersant of the present invention, the emulsifying dispersant does not bleed out, so that the surface does not become sticky and the adhesive force to the substrate or the adhesive force even when coated is increased. Does not decrease. Further, since the emulsifying dispersant has a reactive terminal, it is more excellent in water resistance than when a non-reactive emulsifying dispersant is used, and a strong resin film can be obtained.

[0061]

【Example】

[Modified Silicone Polymer Production Example] (Example 1) 90 wt% of all terminals were allylated, 60 wt% of ethylene oxide and 40 wt% of propylene oxide.
500 g of a trifunctional polyoxyalkylene polyol having a molecular weight of 20,000 and methyldimethoxysilane 9.
0 g of platinum chloride catalyst (5 ppm) was added, the mixture was allowed to react at 70 ° C. for 5 hours, and then deaerated for 2 hours to remove unreacted substances, to synthesize a polyether having a reactive silicon group at 85% by weight of all terminals.

Example 2 60% by weight of ethylene oxide and 40% by weight of propylene oxide and having an average molecular weight of 1
0000 trifunctional polyoxyalkylene polyol 10
5.7 g of γ-isocyanatopropyldimethoxymethylsilane was reacted with 0 g at 80 ° C. using tin octylate as a catalyst until the reaction rate reached 98% by weight or more to synthesize a polyether having a reactive silicon group at the end.

Example 3 70% by weight of ethylene oxide and 30% by weight of propylene oxide, having an average molecular weight of 5
000 trifunctional polyoxyalkylene polyol 100
g-γ-isocyanatopropyltriethoxysilane 1
4.8 g of tin octylate was used as a catalyst at 80 ° C. for a reaction rate of 9
The reaction was performed until the content became 8% by weight or more, and a polyether having a reactive silicon group at the end was synthesized.

Example 4 300 g of bifunctional polybutylene adipate having an average molecular weight of 2000, 11.2 g of dimethylolpropionic acid and 3 of diphenylmethane diisocyanate.
8.9 g of tin octylate as a catalyst at 80 ° C.
Reacted for hours. It was confirmed by titration that there was no residual NCO, and a polyester having a carboxylic acid in the molecule at the terminal hydroxyl group was obtained. Furthermore, 38.8 g of γ-isocyanatopropyltriethoxysilane was added, and the reaction rate was 9 at 80 ° C.
The reaction was carried out until the amount became 8% by weight or more to obtain an ionic polymer having a reactive silicon group.

[Example of Emulsion Production] (Example 5) To the polymer of Example 1, 5.1 g of dibutyltin dilaurate, which is a silanol condensation catalyst, was added. Ion-exchanged water was added thereto so that the solid content was 30% by weight to obtain an emulsion. When the obtained emulsion was formed into a film, a cured film was obtained after being dried at room temperature for 1 day. Also,
This emulsion was stable with no aggregation of particles when observed at room temperature for 1 month.

Example 6 To the polymer of Example 2 was added 2 g of dibutyltin dilaurate as a catalyst. And solid content 50
Ion-exchanged water was added to the mixture so that the weight of the emulsion became an emulsion. The resulting emulsion was formed into a film and cured by leaving it at room temperature overnight. Also, this emulsion was stable without agglomeration of particles even when observed at room temperature for 1 month or more.

Example 7 4.6 g of dibutyltin dilaurate was added to the polymer of Example 3, and ion-exchanged water was added so that the solid content was 40% by weight to obtain an emulsion. The resulting emulsion was formed into a film and cured by leaving it at room temperature overnight. Also, this emulsion was stable without agglomeration of particles even when observed at room temperature for 1 month or more.

Example 8 To the polymer of Example 4 was added 3.9 g of dibutyltin dilaurate. 40% solids by weight
Ion-exchanged water was added to the mixture so as to be neutralized and neutralized with triethylamine while stirring to obtain an emulsion. The resulting emulsion was formed into a film and cured by leaving it at room temperature overnight. Also, this emulsion was stable without agglomeration of particles even when observed at room temperature for 1 month or more.

Comparative Example (Example 9) 9.0 g of methyldimethoxysilane and 5 ppm of a platinum chloride catalyst were added to 500 g of a trifunctional polyoxypropylene polyol having a molecular weight of 20,000, in which 90% by weight of all terminals were allylated and did not contain ethylene oxide. , 70 ° C
At room temperature for 5 hours, followed by degassing for 2 hours to remove unreacted materials and synthesize a polyether having a reactive silicon group at 85% by weight of all terminals.

5.1 g of dibutyltin dilaurate which is a silanol condensation catalyst was added thereto, and 20 g of polyoxyethylene nonifulphenol ether which was a nonionic surfactant was further added thereto so that ion-exchanged water had a solid content of 30% by weight. In addition to 10000 rp with a homomixer
The emulsion was obtained by stirring for 10 minutes. When the obtained emulsion was left at room temperature for several days, aggregation was observed, and the particles were coarser than those of Example 5.

(Example 10) 8 g of 5.7 g of γ-isocyanatopropyldimethoxymethylsilane was added to 100 g of trifunctional polyoxypropylene polyol having an average molecular weight of 10,000.
The reaction was carried out using tin octylate as a catalyst at 0 ° C. until the reaction rate reached 98% by weight or more, to synthesize a polyether having a reactive silicon group at the end.

2 g of dibutyltin dilaurate as a catalyst and 7 g of glycerol monostearate as a nonionic surfactant were added, ion-exchanged water was added so that the solid content became 50% by weight, and 1000 with a homomixer.
The mixture was stirred at 0 rpm for 10 minutes to obtain an emulsion. When the obtained emulsion was left at room temperature for several days, aggregation was observed, and the particles were coarser than those of the emulsion of Example 6.

Example 11 100 g of a trifunctional polyoxypropylene polyol having an average molecular weight of 5000 and 14.8 g of γ-isocyanatopropyltriethoxysilane were used as a catalyst with tin octylate at 80 ° C. to obtain a reaction rate of 98% by weight.
The reaction was performed until the above, and a polyether having a reactive silicon group at the end was synthesized.

To this, 5.1 g of tin octylate as a catalyst was added. Further, 5.5 g of polyoxyethylene oleyl ether, which is a nonionic surfactant, was added, and the mixture was stirred with a homomixer at 10,000 rpm for 10 minutes to obtain an emulsion. The obtained emulsion showed aggregation when left at room temperature for several days, and the particles were coarser than those of the emulsion of Example 7.

Example 12 74.1 g of γ-isocyanatopropyltriethoxysilane was added to 300 g of bifunctional polybutylene adipate having an average molecular weight of 2000, and the reaction rate was 98% by weight at 80 ° C. using tin octylate as a catalyst.
The reaction was performed until the above, and a polymer having a reactive silicon group was synthesized.

3.7 g of dibutyltin dilaurate as a catalyst was added thereto. Solid content of 40% by weight in this polymer
Ion-exchanged water was added thereto so that 26.2 g of sorbitan monolaurate which is a nonionic surfactant was added, and the mixture was stirred with a homomixer at 10,000 rpm for 10 minutes to obtain an emulsion. The obtained emulsion showed aggregation when left at room temperature for several days, and the particles were coarser than those of the emulsion of Example 8.

Physical properties of films obtained by forming the emulsions of Examples 5 to 8 (Examples) and Examples 9 to 12 (Comparative Examples), that is, 50% modulus [M ₅₀ (kg / cm ² )], breaking Table 1 shows the hour strength [T _S (kg / cm ² )] and the elongation at break [E (%)].

[Example of Production of Emulsifying Dispersant] (Example 13) 500 g of a bifunctional polyoxyalkylene polyol having a molecular weight of 8000, in which 90% by weight of all terminals are allylated and which contains 70% by weight of ethylene oxide and 30% by weight of propylene oxide. Methyldiethoxysilane 1
Add 5.1g and 5ppm chloroplatinic acid catalyst,
After reacting for a period of time, deaeration was performed for 2 hours to remove unreacted substances, and a polyether having a reactive silicon group at 85% by weight of all terminals was synthesized (emulsion dispersant A).

Example 14 Bifunctional polyoxyalkylene polyol 10 containing 80% by weight of ethylene oxide and 20% by weight of propylene oxide and having an average molecular weight of 5000.
7.56 g of γ-isocyanatopropyldimethoxymethylsilane was reacted with 0 g to synthesize a polyether having a reactive silicon group (emulsifying dispersant B).

Example 15 Bifunctional polyoxyalkylene polyol 10 containing 65% by weight of ethylene oxide and 35% by weight of propylene oxide and having an average molecular weight of 8000.
6.18 g of γ-isocyanatopropyltriethoxysilane was reacted with 0 g to synthesize a polyether having a reactive silicon group at its terminal (emulsifying dispersant C).

[Example of Emulsion Production] (Example 16) 15.2 g of difunctional polyoxypropylene polyol having a molecular weight of 8000 and 500 g of methyldiethoxysilane.
1g, chloroplatinic acid catalyst 5ppm was added, reacted at 70 ° C for 5 hours, and then degassed for 2 hours to remove unreacted materials,
A polyether having a reactive silicon group at 85% by weight of all terminals was synthesized. 3 g of the emulsifying dispersant A produced in Example 13 was added to 100 g of the reactive silicon group-terminated polyether.
After being added and thoroughly mixed with a homomixer, water was added with stirring to a solid content of 40% by weight.

Example 17 16.67 g of isophorone diisocyanate was added to 100 g of a bifunctional polyether polyol having a molecular weight of 2000, and the mixture was reacted at 100 ° C. for 4 hours, and 1 g of the emulsified dispersant B produced in Example 14 was added thereto. While cooling, a homomixer was used and agitated while adding water so that the solid content was 30% by weight. Thereafter, 1.5 g of ethylenediamine was reacted to obtain an emulsion.

Example 18 100 g of a bifunctional polyoxypropylene polyol having an average molecular weight of 8000 was reacted with 6.18 g of γ-isocyanatopropyltriethoxysilane to synthesize a polyether having a reactive silicon group at the end.
1 g of the emulsifying dispersant C produced in Example 15 was added to 100 g of the polyether having a reactive silicon group at the terminal, and after thoroughly mixing with a homomixer, water was added while stirring to a solid content of 30% by weight. .

Comparative Example (Example 19) An emulsion was obtained in the same manner as in Example 16 except that polyoxyethylene stearyl ether was used as the emulsifier.

Example 20 An emulsion was obtained in the same manner as in Example 17 except that polyoxyethylene lauryl ether was used as the emulsifier.

Example 21 In Example 18, as an emulsifier, (oxyethylene-oxypropylene-) having a molecular weight of 5000 was used.
An emulsion was obtained in the same manner except that the (oxyethylene) block copolymer was used.

The emulsions of Examples 16-18 prepared with the reactive emulsifying dispersant were similar to the emulsions of Examples 19-21 prepared with the non-reactive emulsifying dispersant even after one month. There was no change.

Next, Examples 16 to 18 (Examples) and Examples 19 to
The emulsion of No. 21 (Comparative Example) was formed into a film, and the strength of the obtained film at break [T _S (kg / cm ² )] and surface properties were evaluated (stickiness occurs when the emulsified dispersant bleeds out). The results are shown in Table 2. As can be seen from Table 2, when the emulsifying dispersant of the present invention is used, the emulsifier does not bleed out, so that the obtained film is less likely to change with time, and the strength of the obtained film is high.

[0089]

[Table 1]

[0090]

[Table 2]

[0091]

According to the present invention, it is possible to provide a modified silicone polymer emulsion having storage stability and fine particles. Further, the modified silicone polymer in the present invention can be used as an emulsifying dispersant for emulsifying another polymer. By using the modified silicone polymer as an emulsifying dispersant, a good emulsion is obtained, and even after the emulsion is cured, the emulsifying dispersant does not bleed out and a resin film having excellent physical properties and durability is obtained. .

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shigeyuki Ozawa 1150 Hazawa-machi, Kanagawa-ku, Yokohama, Kanagawa Prefecture Asahi Glass Co., Ltd. Central Research Laboratory

Claims (6)

[Claims] 1. A polyether, polyester or polycarbonate which has at least one reactive silicon group in a molecule at a side chain or terminal of a polymer and has a hydrophilic site in the molecule by a self-emulsification method. Emulsion dispersed in water. 2. The emulsion according to claim 1, wherein the reactive silicon group is an alkoxysilyl group. 3. The emulsion according to claim 1, which contains a silanol condensation catalyst. 4. The emulsion according to any one of claims 1 to 4, wherein the hydrophilic part is an oxyethylene chain. 5. An emulsifying dispersant comprising a polyether, polyester or polycarbonate, which has at least one reactive silicon group in one molecule in the side chain or terminal of the polymer and has a hydrophilic site in the molecule. . 6. The emulsifying dispersant according to claim 5, wherein the reactive silicon group is an alkoxysilyl group.