JPH02167323A - Production of aqueous polysiloxane graft polymer - Google Patents

Abstract

PURPOSE:To obtain the subject dispersion capable of providing a coating film excellent in surface smoothness, heat resistance, weather resistance and water repellency by solution polymerizing a polymerizable silane, an unsaturated organic acid and a comonomer in the presence of a polysiloxane, subsequently adding a basic substance and water thereto respectively in a specified amount and stirring the resultant mixture. CONSTITUTION:In the presence of (A) 1-20wt.% terminal hydroxyl group- containing polysiloxane, (B) 0.05-10wt.% polymerizable silane compound, (C) 1-30wt.% unsaturated organic acid and (D) 40-97.95wt.% comonomer are polymerized in an organic solvent except alcohol-based organic solvents in which a water-soluble organic solvent occupies 30-100 pts.wt. of the total amount of the organic solvent to prepare a polysiloxane graft polymer solution. A basic compound and water are subsequently added thereto respectively in an amount equivalent to 20-200mol.% of the acid groups in the polymer and in an amount of 30-1000 pts.wt. based on 100 pts.wt. polymer and the resultant mixture is stirred, thus obtaining the objective aqueous polymer dispersion.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing an aqueous polysiloxane graft polymer dispersion. More specifically, the present invention relates to a method for producing an aqueous polysiloxane graft polymer dispersion that forms a film with excellent surface smoothness, heat resistance, weatherability, water repellency, water resistance, and migration resistance.

[Conventional technology and interstices]

Aqueous dispersions of polysiloxane graft polymers that have been proposed so far include producing a vinyl polymer having carboxyl groups and hydroxyl groups in a water-dilutable organic solvent, and then adding hydroxyl groups or alkoxyl groups to the vinyl polymer having carboxyl groups and hydroxyl groups. An aqueous dispersion obtained by reacting an organopolysiloxane and then diluting it with water (Japanese Patent Application Laid-Open No. 50-9538)
8), an aqueous dispersion obtained by emulsion polymerization of organopolysiloxane having a polymerizable unsaturated group and other vinyl monomers in an aqueous medium in the presence of an emulsifier (JP-A-5L-14FI5)
25) are known. However, in these methods, due to the low reactivity of organopolysiloxane,
Modification is often incomplete, and in some cases, phenomena such as separation and aggregation may easily occur during the reaction. Therefore, in order to stably obtain an aqueous polysiloxane graft polymer dispersion with the above-mentioned excellent performance, compositional restrictions must be met. The reality is that you will receive it.

On the other hand, the present inventors proposed in JP-A-61-200111 a method for producing a polysiloxane graft polymer, which comprises solution polymerizing a monomer mixture containing a polymerizable silane compound in the presence of a polysiloxane containing terminal hydroxyl groups. did. However, the polymer obtained by this production method is a solution of an organic solvent, which poses problems in terms of occupational hygiene and, depending on the composition of the polymer, may cause the inconvenience of gelation during long-term storage. [Means for solving the problem] In view of the current situation, the present inventors have conducted intensive research on a method for producing an aqueous polysiloxane graft polymer dispersion that solves the above problems, and have developed the present invention. invention has been achieved.

That is, in the present invention, a polymerizable silane compound (
B) 0.05-10% by weight, unsaturated organic acid (C) 1-
30% by weight and other polymerizable monomers (D) copolymerizable with these 40 to 97.95% by weight (However, (A),
The total of components CB), (C) and (I]) is 10
0% by weight. ) is polymerized in an organic solvent other than alcohol, and a jp basic compound and water are added to the solution to produce a polysiloxane graft polymer aqueous dispersion. The amount of the compound added is 20 to 200 mol % of the acid groups in the polysiloxane graft polymer, and the amount of water added is 30 to 1 part by weight based on ioo parts by weight of the polysiloxane graft polymer.
000 parts by weight, and the amount of water-soluble organic solvent in the liquid before or after addition of water is 30 to 100% by weight based on the total amount of organic solvent. The present invention relates to a method for producing an aqueous dispersion.

The terminal hydroxyl group-containing polysiloxane (A) used in the present invention can be used without any restriction as long as it is a linear or partially branched polysiloxane in which at least one terminal has a hydroxyl group. These are easily available and can be used depending on the purpose. Such terminal hydroxyl group-containing polysiloxane (A) is, for example, a monovalent hydrocarbon group which may be substituted with -(R1 and R2 are each independently), R3 is hydrogen, or an optionally halogen-substituted monovalent hydrocarbon group, where n is an integer of 1 or more. ), but partially branched polysiloxanes can also be suitably used.

More specifically, examples include dialkylpolysiloxanes such as dimethylpolysiloxane and methylethylpolysiloxane, methylphenylborylbolysiloxane, and one selected from these groups.
Species or mixtures of two or more species can be used. Among these, linear or partially branched dimethylpolysiloxanes having at least one hydroxyl group at the end are preferred and used because they are available at low cost and can yield polysiloxane graft polymers with excellent performance. The average molecular weight of polysiloxane (A) is in the range of 5,000,000 to 1,500,000, preferably 5,000 to 150,000.
A range of 10,000, more preferably 20,000 to 1,500,000 is desirable.

If the average molecular weight is less than 500, the resulting aqueous dispersion may not fully exhibit the desired surface properties, and if the average molecular weight exceeds 1.5 million, it will have a high viscosity, making handling and polymerization operations difficult.

The amount of the terminal hydroxyl group-containing polysiloxane (A) to be used can be determined as appropriate within the range of 1 to 20% by weight, depending on the degree of surface properties. If the amount is less than 1% by weight, the surface properties will not be sufficient, and if it exceeds 20% by weight, the adhesion to the substrate will decrease, which is not desirable.

The polymerizable silane compound CB) used in the present invention is a compound having at least one polymerizable unsaturated group and at least one group capable of condensation reaction with the polysiloxane in the molecule, for example, vinyl trisilane. Methoxysilane, vinyltriethoxysilane, vinyltributoxysilane, vinyltris(β-methoxyethoxy)silane, allyltriethoxysilane, γ-(meth)acryloxypropyltrimethoxysilane, γ-(meth)acryloxypropyltriethoxysilane , γ-(meth)acryloxypropylmethyldimethoxysilane, γ-(meth)acryloxypropylmethylethoxysilane, γ-(meth)acryloxypropyltris(β-methoxyethoxy)silane,
Examples include 2-styrylethyltrimethoxysilane, (meth)acryloxyethyldimethyl(3-trimethoxysilylpropyl)ammonium chloride, vinyltriacetoxysilane, vinyltrichlorosilane, and one or more selected from these groups. Mixtures of two or more can be used.

The amount of the polymerizable silane compound (B) to be used can be determined as appropriate within the range of 0.05 to 10% by weight.

At an unlayered amount of 0.05% by weight, polysiloxane (A
) and the polymer consisting of the polymerizable silane compound (B), unsaturated organic acid (C), and polymerizable monomer (D) components are insufficient, and an effective amount of graft reaction does not occur, resulting in an aqueous dispersion. After this, unreacted polysiloxane tends to cause layer separation. Moreover, in a range exceeding 1 offi amount %, stability becomes poor and gelation tends to occur during polymerization.

The unsaturated organic acid (C) used in the present invention has the effect of inducing a bond between the polysiloxane (A) and the polymer to smoothly proceed with the grafting reaction, as well as improving the stability of the resulting aqueous dispersion. It increases the adhesion to the substrate, for example, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, itaconic acid, vinyl sulfonic acid, sulfoethyl methacrylate, 2-acrylamido-2-methylpropanesulfonic acid, etc. Examples include unsaturated sulfonic acids, and one or a mixture of two or more of these can be used.

The amount of the unsaturated organic acid (C) to be used can be determined as appropriate within the range of 1 to 30% by weight, preferably 3 to 20% by weight. At usage levels below 1% by weight, stable h-khbAK&t
-fis(r+A<'kl-do-kof-"lnmMk%) In the range exceeding Mk%, the resulting polymer becomes too woody, making it difficult not only to achieve stable water dispersion but also to achieve excellent water resistance. No polymer is obtained.

Examples of the polymerizable monomer (D) used in the present invention include acrylic esters such as butyl acrylate and 2-ethylhexyl acrylate;
(meth)acrylic acid hydroxyalkyl esters such as hydroxyethyl and 2-hydroxypropyl (meth)acrylate; methacrylic acid esters such as methyl methacrylate and butyl methacrylate; vinyl esters such as vinyl acetate and vinyl propionate; Aromatic vinyls such as styrene and vinyltoluene; unsaturated nitriles such as acrylonitrile and methacrylaterile; niacrylamide, N-
Unsaturated amides such as methylol acrylamide; α-olefins such as ethylene, propylene, and inbutylene;
Vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, t-butyl vinyl ether; vinyl chloride,
1. Yuru I/-II; Chino -9-Ruzo+1-
Halogen-containing α, β-unsaturated monomers such as L-, L-Levylidene; trifluoroethyl (meth)acrylate, 2゜2.3.3-tetrafluoropropyl acrylate, I
Fluorine-containing (meth)acrylic acid esters such as H, IH, 2H, 2H-heptadecafluorodecyl acrylate, IH, IH, 5H-octafluoropentyl acrylate; 2,3,5.6-titrafluorophenyl acrylic acid ester, z, 3,4. Examples include aromatic fluorine-containing (meth)acrylic esters such as s, 6-pentafluorophenyl methacrylic ester, and one type or a mixture of two or more of these can be used.

The amount of the polymerizable monomer (D) to be used can be appropriately determined within the range of 40 to 97.95% by weight. In the portion where the amount is less than 40% by weight or more than 97.95% by weight, the above-mentioned polysiloxane (A), ffi-compatible silane compound (
If the amount of B) or the unsaturated organic acid (C) used is too much or too little than the above-mentioned range, the above-mentioned drawbacks will occur, which is undesirable.

The method for producing the polysiloxane graft polymer aqueous dispersion of the present invention comprises a polysiloxane containing terminal hydroxyl groups (
A) in the presence of a polymerizable silane compound (B), an unsaturated organic acid (C), and other polymerizable monomers copolymerizable therewith (
A solution of a polymer obtained by polymerizing D) in an organic solvent other than alcohol.

A water-soluble organic solvent is obtained by adding a specific amount of a basic compound and a specific amount of water, and stirring a liquid containing a specific ratio of organic solvent to form an aqueous dispersion.

As the organic solvent that can be used during polymerization, any organic solvent that does not have an alcoholic hydroxyl group can be used without any restriction, such as toluene, xylene, benzene, hexane, cyclohexane, trichloroethane,
Methyl ethyl ketone, ethyl acetate, dioxane, selonlube acetate, etc. can be mentioned, and one type or a mixture of two or more of these can be used, but toluene and xylene are particularly preferred from the viewpoint of polymer solubility, boiling point, etc.

Alcohol-based solvent-saving solvents with alcoholic hydroxyl groups, such as methyl alcohol, ethyl alcohol,
Alcohols such as isopropyl alcohol, cellosolves such as methyl cellosolve, ethyl cellosolve, etc. are made from polysiloxane (A), a polymerizable silane compound (B), an unsaturated organic acid (C), and a polymerizable monomer (D). Since it suppresses the graft reaction with the polymer, it cannot be used from the initial stage of polymerization, but it can be added and used after the graft reaction has sufficiently progressed.

Examples of the polymerization initiator include common radical polymerization initiators such as azobisin butyronitrile and benzoyl peroxide.

The reaction temperature is room temperature to 200°C, preferably 40 to 120°C.
The monopolymerization concentration ranges from 30 to 70% by weight, preferably from 40 to 60% by weight.

The basic compound added to the polymer solution can be any one that has been conventionally used for neutralizing acidic substances, such as sodium hydroxide, potassium hydroxide, calcium hydroxide, etc. , ammonia, trimethylamine, triethylamine, methyldiethylamine, dimethylethylamine, monomethyloldimethylamine,
Monomethylol diethylamine, dimethylolmethylamine, dimethylolethylamine, etc. can be mentioned,
One or more of these can be used. The basic compound is used to disperse the above polymer in an aqueous medium, and is used in an amount corresponding to 20 to 200 mol% of the acid groups of the polymer.

If the amount is less than 20 mol%, it will be difficult to disperse in an aqueous medium. In particular, in order to obtain a polysiloxane graft polymer aqueous dispersion that maintains a good dispersion state even during storage and does not have the disadvantages caused by basic compounds, such as decreased water resistance and discoloration, It is preferable to add it in an amount corresponding to 50 to 100 mol% of the acid groups in the coalescence. At this time, if a high degree of dispersion stability is required, an appropriate traverse agent and/or protective colloid are used in combination. You can also do that. However, in consideration of the various performances of the obtained polysiloxane graft polymer aqueous dispersion, it is preferable that the amount used be as small as possible, and it is most preferable that it is not used.

The amount of water added is 10% of the polysiloxane graft polymer.
The amount is 30 to 1000 parts by weight relative to 0 parts by weight. If the amount is less than 30 parts by weight, water will not form a continuous phase and a stable aqueous dispersion cannot be obtained. On the other hand, if the amount exceeds 100 parts by weight, the polysiloxane graft polymer content will be diluted and this is not economically preferable.

In order to stir a liquid containing a polysiloxane graft polymer to form a stable aqueous dispersion, the amount of water-soluble organic solvent in the liquid should be 30 to 100% by weight based on the total amount of organic solvent.
It is necessary to do so.

If the amount of water-soluble organic solvent used is less than 30% by weight,
Sedimentation of the dispersed particles occurs, making it difficult to obtain a stable dispersion. The proportion of water-soluble organic solvents is 30% of the total organic solvents.
-100% by weight may be made before or after addition of water, but preferably before addition.

Water-soluble organic solvents include lower alcohols such as methyl alcohol, ethyl alcohol, and inpropyl alcohol, cyclic ethers such as tetrahydrofuran and dioxane, ketones such as acetone, and water-dilutable organic solvents such as cellosolves such as methyl cellosolve and methyl cellosolve. It is a solvent.

Considering the residual organic solvent preferably used in polymerization, the proportion of water-soluble organic solvent is 40 to 9Of the total organic solvent.
It is preferable to set it as i amount %.

The polysiloxane graft polymer aqueous dispersion thus obtained has excellent long-term storage stability and can form a film with excellent surface smoothness, heat resistance, weather resistance, water repellency, water resistance, and migration resistance, and can be used as is. Although it can be suitably used for various purposes, considering environmental protection during use, it is preferable to further remove the solvent. Solvent removal can be easily carried out by conventionally known methods, such as vacuum distillation or heated distillation. be able to. The amount of solvent to be removed should be determined as desired, but in order to maximize the characteristics of the present invention, it is preferable to remove an amount equivalent to 90% by weight or more contained in the dispersion. The polysiloxane graft polymer aqueous dispersion after solvent removal in this manner does not impair the stability of the dispersion or the properties of the film at all, and moreover, environmental protection is solved when used in various applications.

〔Effect of the invention〕

The polysiloxane graft polymer aqueous dispersion of the present invention can be used to form a film or film with excellent surface smoothness, heat resistance, weather resistance, water repellency, water resistance, and acid migration property simply by volatilizing the volatile components at room temperature or under heating conditions. Can be made into sheets or molded products.

In addition, the aqueous polysiloxane graft polymer dispersion of the present invention can be applied to a wide variety of applications, such as coating agents or adhesives for metals, plastics, wood, inorganic substrates, etc., and treatment agents for paper, fibers, etc. It is possible. At this time, those skilled in the art are free to add pigments, toners, crosslinking agents, viscosity modifiers, lubricants, plasticizers, rust preventives, antifoaming agents, antistatic agents, etc. known to those skilled in the art.

The reason why the polysiloxane graft polymer aqueous dispersion obtained by the production method of the present invention exhibits such excellent properties is not yet clear, but it is thought to be as follows. That is, terminal hydroxyl group-containing polysiloxane (A)
By polymerizing the monomer mixture containing the polymerizable silane compound (B) in the presence of the polymer, the resulting polymer chain containing silane compound units and polysiloxane are bonded to each other, and a polysiloxane graft polymer is obtained. When a polysiloxane graft polymer aqueous dispersion in which such a graft polymer is dispersed in an aqueous medium is applied to a substrate, the polysiloxane portion is on the air side and the polymer chain portion generated by polymerization is on the substrate side. It is thought that as a result of orientation, surface properties such as water repellency and surface smoothness are compatible with adhesion to the substrate. but.

There are no restrictions for this reason alone.

The production method of the present invention provides a method for easily obtaining a polysiloxane graft polymer aqueous dispersion having the above characteristics.According to the production method of the present invention, a polysiloxane graft polymer aqueous dispersion is produced. This is truly surprising considering the current state of the art in this field, as it can be stably obtained without using any special surfactants. Furthermore, surprisingly, the aqueous dispersion of the polysiloxane graft polymer thus obtained has significantly improved storage stability compared to the organic solvent solution before being dispersed in the aqueous medium, and this fact is a feature of the present invention. It was something that even people could not have predicted.

Therefore, the present invention makes it possible to significantly expand the range of applications of polysiloxane graft polymers.

〔Example〕

The present invention will be specifically explained below with reference to Examples, but the present invention is not limited in any way by these examples, and all numbers in the examples indicate parts by weight.

Example 1 A linear polysiloxane having an average molecular weight of 120,000 as a terminal hydroxyl group-containing polysiloxane was introduced into a four-necked flask equipped with a thermometer, a reflux condenser, a dropping funnel, a nitrogen inlet tube and a stirrer.
10 parts of a 30% by weight toluene solution of dihydroxydimethylpolysiloxane and 100 parts of toluene were charged, and the temperature was raised to 80°C under a nitrogen atmosphere. To this, 70 parts of methyl methacrylate, 20 parts of butyl acrylate, 5 parts of acrylic acid.
part, γ-methacryloxypropyltrimethoxysilane 5
1 part and 2 parts of azobisisobutyronitrile were added thereto, and the mixture was heated at 80°C for 30 minutes.
Initial polymerization was performed. Next, the remaining monomer homogeneous solution was added dropwise over 2 hours at the same temperature, and polymerization was carried out for 2 hours and 30 minutes after the addition was completed! ! At the end of the reaction, 10 parts of isopropyl alcohol was added to dilute the mixture. 1 while continuing to maintain the temperature at 80″C.
After stirring for 30 minutes to continue the polymerization reaction, the mixture was cooled to obtain a polysiloxane graft polymer solution (hereinafter referred to as 1 polymer solution (1)). After diluting 40 parts of the obtained polymer solution (1) by adding 60 parts of isopropyl alcohol, 3 parts of 28% ammonia water was added with stirring, and 1
After continuing stirring for 0 minutes, 237 parts of water was added to form a water dispersion. Subsequently, the internal temperature was raised to 60°C, 250 parts were distilled off by vacuum distillation to remove the solvent, and aqueous ammonia and water were added to adjust the pH to 9.0 and the concentration to 30%, and the polysiloxane A graft polymer aqueous dispersion (hereinafter referred to as aqueous dispersion (1)) was obtained. Obtained aqueous dispersion (1)
has a viscosity of 10 cps (25°C, B-type viscometer, SORP
In case of m), the emulsion remained stable without sedimentation of the dispersed particles or separation of the polysiloxane even after being allowed to stand for -week.

In addition, residual isopropyl alcohol and toluene were 90 ppm and 750 ppa+, respectively.

In order to check the storage stability of the liquid, it was stored at 50°C for 6 months, and the polymer solution (1) was gelatinized, but the aqueous dispersion (1) was stable without any change in viscosity.

Example 2 Example 1 was placed in a four-loaf flask similar to that used in Example 1.
33.3 parts of a 30% by weight toluene solution of the same terminal hydroxyl group-containing polysiloxane as used in the above and 100 parts of toluene were charged, and the temperature was raised to 80° C. under a nitrogen atmosphere.

To this, 50 parts of methyl methacrylate, 2 parts of butyl acrylate
0 parts, 20 parts of acrylonitrile, 5 parts of acrylic acid, γ-
Using a homogeneous monomer solution consisting of 5 parts of methacryloxypropyltrimethoxysilane and 2 parts of azobisisobutyronitrile, the same initial polymerization operation and dropping operation of the homogeneous monomer solution as in Example 1 were performed. When polymerization was continued for 30 minutes after the monomer homogeneous solution was added dropwise, ethyl alcohol 1
It was diluted by adding 0.00 parts. Further reaction at 80°C for 3 hours and 30 minutes! ! After that, the solution was cooled to obtain a polysiloxane graft polymer solution (hereinafter referred to as 1-polymer solution (2)). 28 to 200 parts of the obtained polymer solution (2)
The same operation as in Example 1 was performed except that the amount of aqueous ammonia was 2.5 parts to obtain a polysiloxane graft polymer aqueous dispersion (hereinafter referred to as aqueous dispersion (2)).

The resulting aqueous dispersion (2) had a viscosity of 70 cps (25'C
! , B-type viscometer, 60 rpm) The emulsion remained stable, with no sedimentation of the dispersed particles or separation of the polysiloxane, even when the emulsion was allowed to stand for a week. In addition, the remaining ethyl alcohol and toluene are 230 ppm and 870 PP, respectively.
It was I.

Example 3 Three parts of linear dihydroxydimethylpolysiloxane having an average molecular weight of 48,000 as a terminal hydroxyl group-containing polysiloxane and 100 parts of toluene were charged into a four-bottle flask similar to that used in Example 1, and the mixture was heated under a nitrogen atmosphere.
The temperature was raised to 80″C.

A homogeneous monomer solution consisting of 30 parts of methyl methacrylate, 30 parts of styrene, 25 parts of vinyl acetate, 10 parts of acrylic acid, 5 parts of 2-styrylethyltrimethoxysilane and 2 parts of azobisisobutyronitrile was added to this. , Example 1
The same initial polymerization operation and dropwise addition operation of a homogeneous monomer solution were performed. When the polymerization was continued for 15 minutes after the dropwise addition of the homogeneous monomer solution, 100 parts of isopropyl alcohol was added to form a box. The polymerization reaction was further continued at 80° C. for 3 hours and 45 minutes, and then cooled to obtain a polysiloxane graft polymer solution (hereinafter referred to as polymer solution (3)). 28% ammonia water to 200 parts of the obtained polymer solution (3)
After stirring for 10 minutes, 238 parts of water was added and water-dispersed to form an aqueous polysiloxane graft polymer dispersion (hereinafter referred to as aqueous dispersion (3)).
) was obtained.

The resulting aqueous dispersion (3) had a viscosity of 750 cps (25°
C, Type B viscometer, 60 rpm) The emulsion remained stable without sedimentation of the dispersed particles or separation of the polysiloxane even after it was allowed to stand for a week.

Example 4 The amount of 7-crylonitrile in Example 2 was changed from 20 parts to 5 parts,
The same operation as in Example 2 was carried out except that the amount of acrylic acid was changed from 5 parts to 20 parts to obtain a polysiloxane graft polymer aqueous dispersion (hereinafter referred to as aqueous dispersion (4)).
I got it. The resulting aqueous dispersion (4) has a viscosity of 220 cps
(25°C, B-type viscometer, 60 rpm), -p
Even after standing for a while, the emulsion remained stable without sedimentation of the dispersed particles or separation of the polysiloxane. In addition, the remaining ethyl alcohol and toluene were each 300%
ppm, 1l 100pp.

Example 5 Instead of the terminal hydroxyl group-containing polysiloxane used in Example 1, a 30% by weight toluene solution of partially branched dimethylpolysiloxane having an average of 4 terminal hydroxyl groups and an average molecular weight of 260,000 was used. A polysiloxane graft polymer aqueous dispersion (hereinafter referred to as polysiloxane aqueous dispersion (5)) was obtained by carrying out the same operation as in Example 1 except for using the following. Obtained aqueous dispersion (5)
has a viscosity of 12 cps (25°C, B-type viscometer, 60 rpm)
The emulsion remained stable even after being allowed to stand for a week without causing any sedimentation of the dispersed particles or separation of the polysiloxane. In addition, residual inpropyl alcohol and toluene were 70 PPI and 800 ppm, respectively.

Comparative Example 1 A comparative polymer solution (hereinafter referred to as a comparative polymer solution (1
), we got ). Obtained comparative polymer solution (1)
After diluting by adding 60 parts of isopropyl alcohol to 140 parts, 3 parts of 28% ammonia water was added under stirring, and after stirring was continued for 10 minutes, 237 parts of water was added and water-dispersed to obtain an aqueous dispersion for comparison. ' body (hereinafter referred to as comparative aqueous dispersion (1
), we got ). Obtained comparative aqueous dispersion (1)
After standing for one night, the polysiloxane separated into an upper layer.

Comparative Example 2 The same terminal hydroxyl group-containing polysiloxane as used in Example 1 was added to 302 parts of a polymer solution obtained in the same manner as in Example 1, except that the polysiloxane containing terminal hydroxyl groups in Example 1 was not used. 10 parts of the containing polysiloxane was added as a 30% by weight toluene solution and mixed well to obtain a comparative polymer solution (hereinafter referred to as comparative polymer solution (2)). After diluting 140 parts of the obtained comparative polymer solution (2) with 60 parts of inbrovir alcohol, 3 parts of 28% ammonia water was added with stirring, and after continued stirring for 10 minutes, 237 parts of water was added. and water-dispersed to obtain a comparative aqueous dispersion (hereinafter referred to as comparative aqueous dispersion (2)). The resulting comparative aqueous dispersion (2) was left to stand for one night, and the polysiloxane was separated into an upper layer.

Comparative Example 3 After diluting 140 parts of the polymer solution (1) obtained in Example 1 by adding 60 parts of inpropyl alcohol, 0.4 part of 28% ammonia water was added under stirring, and stirring was continued for 10 minutes. After that, 239 parts of water was added and water-dispersed to obtain a comparative aqueous dispersion (hereinafter referred to as aqueous dispersion (3)).

When the obtained comparative aqueous dispersion (3) was allowed to stand for a week, the particles settled and a transparent aqueous layer was separated in the upper layer.

Comparative Example 4 After diluting 140 parts of the polymer solution (1) obtained in Example 1 with 50 parts of toluene and 10 parts of isopropyl alcohol, 3 parts of 28% ammonia water was added with stirring, and 140 parts of the polymer solution (1) obtained in Example 1 was diluted.
Stir for 0 minutes! ! After stirring, 239 parts of water was added and water-dispersed to obtain a comparative aqueous dispersion (hereinafter referred to as comparative aqueous dispersion (4)). The comparative aqueous dispersion obtained (
When the sample 4) was allowed to stand for -1 week, the particles settled and a transparent water layer separated from the upper layer.

Comparative Example 5 The same operation as in Example 1 was carried out except that the amount of acrylic acid in Example 1 was changed from 5 parts to 0.5 parts, and a comparative polysiloxane graft polymer aqueous dispersion (hereinafter referred to as a comparative aqueous dispersion) was prepared. We obtained the body (5). When the obtained comparative aqueous dispersion (5) was allowed to stand for a week, the particles settled, and a transparent aqueous layer was separated in the upper layer.

Examples 6 to 1O The aqueous dispersions (1) to (5) obtained in Examples i to 5 were applied to a glass plate using a No. 6 barcoder, and the physical properties of the coating film after heating and drying at 150°C for 1 minute were evaluated. They are summarized in Table 1.

Comparative Examples 6 to 10 Comparative aqueous dispersions (1) to (5) obtained in Comparative Examples 1 to 5
Table 1 summarizes the physical properties of the coating film that was applied to a glass plate using an NO6 bar coater and dried by heating at 150° C. for 1 minute.

Table 1 Note) Test method for physical properties of the coating film Overview of the coating film: Observing the surface condition of the coating film after heating and drying at 150°C for 10 minutes Adhesion: ...After making 100 squares by making vertical and horizontal cuts in the paint film at 1-open intervals, apply Chiban cellophane tape No. 1800) to this surface and then peel it off to check the peeling state of the paint film. were scored using a 10-point scale.

Heat resistance...Temperature 250℃, load 1k
A stainless steel plate was pressed onto the surface of the coating film under conditions of g/cm 2 and left for 10 seconds, and then the peelability of the stainless steel plate and changes in the coating film were examined.

Coefficient of friction......Heidon-14 type surface property measuring machine, load 100g, moving speed 150m+o/
A Teflon-treated surface indenter (83
, 5 x 83.5 m + 11) was determined. The smaller the number, the better the surface and slipperiness.

Water repellency: A small amount of deionized water was dropped onto the paint film, and the contact angle between the water droplet and the paint film was determined using an optical mirror contact angle meter. A large angle indicates a high degree of yielding water.

Water resistance: Sample plates were immersed in deionized water for 3 days at room temperature, and changes in the coating film were examined.

Claims (1)

[Claims] 1. Polysiloxane containing terminal hydroxyl group (A) 1-
In the presence of 20% by weight, 0.0% of polymerizable silane compound (B)
5 to 10% by weight, unsaturated organic acid (C) 1 to 30% by weight, and other polymerizable monomers copolymerizable with these (D) 40
Polymer obtained by polymerizing ~97.95% by weight (however, the total of components (A), (B), (C) and (D) is 100% by weight) in an organic solvent other than alcohol-based When producing a polysiloxane graft polymer aqueous dispersion by stirring a liquid product obtained by adding a basic compound and water to the combined solution, the amount of the basic compound added is adjusted to 20 to 200% of the acid groups in the polysiloxane graft polymer. The amount of water added is equivalent to 10% by mole of the polysiloxane graft polymer.
30 to 1000 parts by weight relative to 0 parts by weight,
A method for producing a polysiloxane graft polymer aqueous dispersion, characterized in that the amount of water-soluble organic solvent in the liquid before or after addition of water is 30 to 100% by weight based on the total amount of organic solvent. . 2. The method for producing an aqueous polysiloxane graft polymer dispersion according to claim 1, further comprising removing the solvent after dispersing it in water.