JPS62240303A - Production of fluorine-containing aqueous dispersion - Google Patents

Abstract

PURPOSE:To obtain a dispersion with high stability capable of forming film of outstanding water resistance and weatherabily, without using any surfactant, by polymerization in the presence of a specific dispersion stabilizer, of vinyl monomer(s) in a specific organic liquid followed by neutralization and addition of water. CONSTITUTION:Vinyl monomers made up of (A) 60-100wt% of a vinyl monomer with a solubility parameter ranging from that of methyl methacrylate to 19 and (B) 40-0wt% of a second vinyl monomer are polymerized in an organic liquid with a solubility to water >=5, number of hydrogen bonds -19-0, solubility parameter 9-13 (e.g. methyl alcohol), in the presence of a dispersion stabilizer consisting of a copolymer with a number-average molecular weight 1,000-100,000 and acid value 20-200, capable of solvation with said organic liquid, constituted essentially by a (meth)acrylic monomer of formula (R is H or CH3; n is 1-10; Rf is 3-12C perfluoroalkyl). hydroxyl group-contg. polymerizable unsaturated monomer and polymerizable unsaturated acid, followed by neutralization with a basic substance and adding water, and then, if needed, distilling off part or the whole of the organic liquid, thus obtaining the objective dispersion.

Description

[Detailed description of the invention] Star east upper fifth month! The present invention relates to a method for producing a fluorine-containing aqueous dispersion.

Although various studies have been made regarding methods for producing aqueous dispersions, most of them have been based on self-emulsification methods or emulsion polymerization methods. However, the self-emulsification method using a hydrophilic resin has the disadvantage that it is difficult to obtain an aqueous dispersion with high concentration and excellent stability. In addition, in the emulsion polymerization method, it is difficult to use large amounts of highly polar monomers to carry out the polymerization reaction in water, and the coating made using the aqueous dispersion obtained by this emulsion polymerization method is It has the disadvantage of poor water resistance, weather resistance, etc. due to the residual emulsifier (surfactant).

The present inventors have conducted extensive research in order to develop an aqueous dispersion that can form a film with excellent stability and good water resistance, weather resistance, etc. without using a surfactant. As a result, vinyl monomers are polymerized in a specific organic liquid in the presence of a specific dispersion stabilizer, and after neutralization, water is added, and if necessary, part or all of the organic liquid is removed. It has been found that by doing so, an aqueous dispersion that satisfies the above requirements can be obtained and the intended purpose of the present invention can be achieved. The present invention was completed based on this knowledge.

That is, the present invention has a solubility in water of 5 J.
In an organic liquid whose FSP value (hereinafter referred to as "FSP value") is 9 to 13,
The following general formula % Formula % [In the formula, R is a hydrogen atom or a methyl group, n is an integer of 1 to 10, and Rf represents a linear or branched perfluoroalkyl group having 3 to 21 carbon atoms. ) having a number average molecular weight of about 1,000 to about 100,000. In the presence of a dispersion stabilizer comprising a copolymer having an acid value of about 20 to about 200 and solvated in the organic liquid, (^)
The vinyl monomer is obtained by polymerizing 60 to 100% by weight ff1% of a vinyl monomer having an SP value of 1 to 1 as that of methyl methacrylate and (8) another vinyl monomer such as 40-0@13i%. After obtaining a dispersion of the polymer,
The present invention relates to a method for producing a fluorine-containing aqueous dispersion, which comprises neutralizing the dispersion with a basic substance, then adding water, and optionally distilling off part or all of the organic liquid.

In the present invention, perfluoroalkyl group-containing (
meth) Using a copolymer containing acrylic monomer (hereinafter also referred to as "fluorine monomer"), 1% water-containing polymerizable unsaturated monomer, and polymerizable unsaturated acid as essential components. It has particular characteristics.

Polymers containing a fluorine-based monomer as a constituent generally have the characteristics of being excellent in water repellency, oil repellency, and stain resistance, exhibiting non-stick properties, and being able to form a coating film with a low refractive index. ing. This polymer is usually synthesized by a solution polymerization method, but if it is blended with the fifth grade of fluorine-based monomer necessary to fully exhibit the properties such as water repellency, other coating properties such as heat resistance can be improved. Polymers with reduced thermal and mechanical properties such as hardness, weather resistance, adhesion, hardness, and impact resistance may be obtained. In other words, with fluoromonomer-containing polymers synthesized by solution polymerization, it is difficult to form a coating film that simultaneously has the performance that a coating film should have and the properties based on perfluoroalkyl groups. It is. Furthermore, fluorine-based monomers having a perfluoroalkyl group are significantly more expensive than general polymerizable vinyl-based monomers, so it is important to exhibit their effects with the minimum necessary amount. has been done.

In contrast, in the present invention, a copolymer containing a fluorine-based monomer is used as a dispersion stabilizer for an aqueous dispersion. This makes it possible to form a coating film that simultaneously has the performance that a coating film should have and the properties based on perfluoroalkyl groups.

That is, the continuous phase of the coating film formed from the aqueous dispersion of the present invention is mainly composed of the dispersion stabilizer (i.e., the copolymer containing a fluoromonomer), and therefore the coating surface is Characteristics mainly based on perfluoroalkyl groups, such as excellent water repellency, oil repellency, and stain resistance, are non-adhesive, and can form a coating film with a low refractive index. Moreover, the thermal and mechanical properties that the coating film must have are reinforced by the polymer particle portion of the aqueous dispersion. Furthermore, this perfluoroalkyl group only needs to be present in the continuous phase (dispersion stabilizer) and does not need to be present inside the polymer particles of the aqueous dispersion. Compared to a group-containing polymer resin solution, the same characteristics based on perfluoroalkyl groups can be exhibited even if the amount of fluoromonomer used is reduced. In other words, a coating film that is significantly advantageous in terms of price can be obtained.

The dispersion stabilizer used in the present invention includes a fluorine-based monomer (first component), a hydroxyl group-containing polymerizable unsaturated monomer, and a second component.
component) and a polymerizable unsaturated acid (third component) are copolymerized as essential components.

Further, the dispersion stabilizer used in the present invention includes the above-mentioned first component,
In addition to the second component and the third component, the fourth component may be a copolymerized product of another polymerizable unsaturated monomer that can be copolymerized with these components.

As the first component fluorine-based monomer, the above general formula (1) is used.
Any conventionally known materials can be used as long as they are included in the following. Among these, those in which n is an integer of 2 to 4 are preferred, and Rj is preferably a linear or branched perfluoroalkyl group having 6 to 10 carbon atoms. Specific examples of such fluoromonomers include 2-perfluorooctylethyl acrylate, 2-perfluorooctylethyl methacrylate, 2-perfluorooctylethyl acrylate, and 2-perfluoroinnonylethyl methacrylate-1- etc. can be exemplified. In the present invention, these may be used alone or in combination of two or more.

Examples of the hydroxyl group-containing polymerizable unsaturated monomer as the second component include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate-1., 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate,
Examples include 2-hydroxybutyl acrylate and 2-hydroxybutyl methacrylate. In the present invention, these may be used alone or in combination of two or more.

Examples of the polymerizable unsaturated acid as the third component include acrylic acid, methacrylic acid, and itaconic acid, which may be used alone or in combination of two or more.

Furthermore, as the fourth component, a wide variety of conventionally known monomers can be used as long as they are monomers other than the above-mentioned first to third components and are polymerizable unsaturated monomers that can be copolymerized with these monomers, such as methyl Acrylic acid or methacrylic acid such as acrylate, methyl methacrylate, ethyl acrylate, butyl methacrylate, butyl acrylate, butyl methacrylate, hexyl acrylate, hexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, lauryl acrylate, lauryl methacrylate, etc. Alkyl (1 to 22 carbon atoms) ester, glycidyl group-containing acrylate such as glycidyl acrylate, glycidyl methacrylate, styrene, vinyl acetate, acrylamide, methacrylamide, crotonamide, N-methylol acrylamide, N-methylol methacrylamide, N-1 toxy Examples include methylacrylamide, N-butoxymethylmethacrylamide, diacetone acrylamide, etc., which may be used singly or in combination.
It is used by mixing more than one species.

The composition ratio of the first to fourth components in the dispersion stabilizer of the present invention is not particularly limited and can be arbitrarily selected depending on the purpose. For example, the total weight of the first to fourth components (not including the fourth component) The first component is about 1 to 92% by weight, the second component is about 5 to 70% by weight (preferably 5 to 60% culm), and the third component is 3 to 30% by weight. (preferably about 3 to 25% by weight). Furthermore, based on the acid value, it is suitable to mix the above-mentioned components so that the acid value is about 20 to 200. In this dispersion stabilizer, the first component is a component necessary to achieve the above-mentioned effects of the present invention, the second component is a component necessary to stably disperse polymer particles described below, and The third component is a component necessary to make the dispersion stabilizer water-soluble. Therefore, if it deviates from the above range, there is a tendency that such effects cannot be expected to be expressed.

Furthermore, it is advantageous for the dispersion stabilizer used in the present invention to have a polymerizable double bond introduced into its molecule.

The introduction of this polymerizable double bond is carried out by adding a glycidyl group-containing unsaturated monomer (e.g. glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, etc.). In addition, in the polymer containing the above first to third components, hydroxyl groups and (
Or) A polymerizable double bond can also be introduced by containing a mercapto group and then adding a compound having a polymerizable double bond and a functional group selected from a carboxyl group, an acid anhydride group, and an incyanate group. It is possible. The general conditions under which addition reactions occur between such combinations of reactive groups are well known, and the temperatures at which these reactions occur depend on the particular combination of reactive groups chosen and can be controlled by the use of catalysts. It goes without saying that words can be changed.

It is desirable to introduce, on average, at least 0.1 polymerizable double bond into each 1' molecule of the dispersion stabilizer through the above reaction. When a polymerizable double bond is introduced into the dispersion stabilizer, a covalent bond is formed between the polymer forming the dispersed particles and the dispersion stabilizer during emulsion polymerization, and as a result, the resulting aqueous dispersion is The effect is that storage stability, mechanical stability, etc. can be further improved.

The molecular weight of the dispersion stabilizer used in the present invention is conveniently within the range of about 1,000 to about 100,000, preferably about 5,000 to about 50,000 on a number average molecular weight scale. If the molecular weight is less than about 1,000, the stabilization of the dispersed particles in the resulting aqueous dispersion is insufficient, making it easy to cause agglomeration and sedimentation.On the other hand, if the molecular weight exceeds about 100,000, The viscosity of the dispersion becomes extremely high, making it difficult to handle, which is undesirable.

Further, the acid value of the dispersion stabilizer used in the present invention is conveniently about 20 to about 200.

When the acid value is less than about 20, it becomes difficult to water-solubilize the dispersion stabilizer, while when the acid value is more than about 200, the properties such as water resistance and weather resistance of the coating film obtained from the aqueous dispersion decrease. This is not desirable because it becomes a tendency.

The dispersion stabilizer of the present invention has, for example, a water solubility of 5 or more, a hydrogen bond number of -19 to 0, and a 5P (tlli of 9 to 0).
It can be obtained by copolymerizing predetermined amounts of each of the above components in an organic liquid of No. 13 in the presence of a polymerization initiator. As a polymerization initiator, for example, 2,2'-azobis(2
, 4-dimethylvaleronitrile), lauryl peroxide, benzoyl peroxide, t
Examples include peroxide-based polymerization initiators such as ert-butyl peroctoate. Ia of such a polymerization initiator
The degree is 0.5 to 100 parts by weight of the total amount of each component.
The amount is preferably about 10 parts by weight.

The dispersion stabilizer used in the present invention may be used alone or in combination of two or more types with different copolymer compositions or molecular weights, and if necessary, other water-soluble stabilizers may be used. It can also be used in combination with small amounts of resins that can be oxidized, such as water-soluble or water-dispersible methylolmelamine resins, alkyl etherified melamine resins, acrylic resins, etc.

The organic liquid used in the present invention has a solubility in water of 5
The above examples have a hydrogen bond number of -19 to 0 and an SP value of 9 to 13. Here, the solubility of the organic liquid in water is the parts by weight of the organic liquid that can be dissolved in 100 parts by weight of water at 20°C.

In addition, the number of hydrogen bonds and SP value of organic liquids are
Op Paint Technology, ±2°550.644
-652 (1970). Specifically, such organic liquids include methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol,
tert-butyl alcohol, 5ec-butyl alcohol, tert-7yl alcohol, 3-pentanol,
Examples include alcohols such as octyl alcohol, ether alcohols such as methyl cellosolve, cellosolve, isopropyl cellosolve, butyl cellosolve, and diethylene glycol monobutyl ether. These organic liquids can be used alone or in combination of two or more.

Even if the organic liquid has a hydrogen bond number and S and P values outside the above range, it must be a hydrophilic solvent with a water solubility of 5 or more, and the hydrophilic solvent can be used with the above alcohols or ether alcohols. Any solvent whose hydrogen bond number and SP value fall within the above ranges when mixed can be used as the organic liquid of the present invention by mixing with the above alcohols and ether alcohols. Examples of such solvents include ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, and esters such as ethyl acetate, cellosolve acetate, n-butyl acetate, inbutyl acetate, methyl cellosolve acetate, and carbitol acetate. .

The above-mentioned organic liquid functions as a dispersion medium, and by controlling the number of hydrogen bonds to -19 to O and the SP value to a value of 9 to 13, the organic liquid functions as a dispersion stabilizer that is solvated by the dispersion medium (i.e., By fully exerting the function of stably dispersing particles) and polymerizing in the presence of the dispersion stabilizer, it becomes possible to produce 1 q of stably dispersed particles of vinyl polymer. When the solubility in water, the number of hydrogen bonds, and the SP value deviate from the above ranges, for example, when the number of hydrogen bonds is -19 or the SP value is less than 9, dispersed particles will precipitate, whereas when the number of hydrogen bonds is O or the SP value is If it is larger than 13, the vinyl polymer to be dispersed particles will be dissolved or almost dissolved in the organic liquid, making it impossible to obtain stable dispersed particles.

Further, if the solubility in water is less than 5, the dispersion state becomes unstable and storage stability becomes poor.

In the method of the present invention, a vinyl monomer is first polymerized in the organic liquid in the presence of the dispersion stabilizer to obtain a dispersion in which a polymer of the vinyl monomer is stably dispersed. The vinyl monomer is composed of (A) 60 to 100% by weight of a monomer having an SP value of 19 to 19% as that of methyl methacrylate, and (B) 40-0% by weight of another monomer.

As the component (A), which has an SP value of 19 to methyl methacrylate, a wide range of conventional vinyl methacrylates can be used, such as methyl methacrylate (SP
Value: 9.1-9.5, SP value as a homopolymer, Journal of Paint Technology, Jdan (
492).

Calculations were made based on the description in January 43-57, 1966. (same below), acryloni-1-lyl (12
, 75-15.4), methyl acrylate (9,7-1
0.1>, ethyl acrylate (9,2-9.4>, methacrylate tolyl (10,7>, ethyl methacrylate (8,95-9.1>), acrylic acid (about 13), methacrylic acid (about 13) , 2-hydroxyethyl acrylate (approximately 10>), 2-hydroxypropyl acrylate (approximately 10), 2-hydroxyethyl methacrylate (approximately 10
>, 2-hydroxypropyl methacrylate (approximately 10)
, acrylamide (16-19), methacrylamide (
16-19), N-methylolacrylamide (13-
14), N-methylol methacrylamide (11-12
>, N-11~xymethylacrylamide (10~11
), N-butoxymethyl methacrylamide (10-11
), styrene (approximately 9.1), and the like.

Among these, acrylamides are particularly desirable from the viewpoint of curability. In the present invention, these may be used alone or in a mixture of two or more. If the SP value of the monomer is smaller than that of methyl methacrylate, it becomes difficult for the resulting polymer to form stable particles. On the other hand SP
Vinyl monomers with a value greater than 19 are difficult to obtain industrially and are not practical.

In addition, as the vinyl monomer which is the component (8), the above (
Any conventionally known vinyl monomer other than component A) and copolymerizable with component (A) can be used, such as butyl acrylate, 2-ethylhexyl acrylate, butyl methacrylate, and 2-ethyl. Examples include hexyl methacrylate, lauryl methacrylate, and glycidyl methacrylate. These monomers may be used alone or in combination of two or more.

The mixing ratio of the (^) monomer and the (B) monomer is usually the former: the latter = 60-100% by weight: 40-0% by weight, preferably the former: the latter = 70-100% by weight: 30-0@
However, it is %. If the proportion of the (^) monomer in the total amount of the (^) monomer and (B) monomer is less than 60% by weight, it is not preferable because it becomes difficult to form stable polymer particles.

Polymerization of the above-mentioned vinyl monomers is usually carried out in the presence of a polymerization initiator. As a polymerization initiator, for example, 2,2'-azobisisobutyronitrile, 2°2'-azobis(2,
azo polymerization initiators such as 4-dimethylvaleronitrile),
lauryl peroxide, benzoyl peroxide, te
Examples include peroxide-based polymerization initiators such as rt-butyl peroctoate. The concentration of such a polymerization initiator is preferably about 0.5 to 10 parts by weight per 100 parts by weight of vinyl monomer.

In the above polymerization reaction, the amount of the dispersion stabilizer is as follows:
3 to 70% by weight in the total amount of vinyl monomer and dispersion stabilizer
It is preferable to use it to the extent that If the amount of the dispersion stabilizer used is less than 3% by weight, the stability of the resulting dispersion may decrease, which is not preferable. Further, if the amount of the dispersion stabilizer used is more than 70% by weight, the dispersion system may turn into a solution and the characteristics of the dispersion system (high solids content, low viscosity) may be lost, which is also undesirable. In the present invention,
It is particularly preferable to use the dispersion stabilizer in an amount of about 10 to 50% by weight in the total amount of the vinyl monomer and the dispersion stabilizer. The total concentration of the vinyl monomer and dispersion stabilizer in the dispersion is usually about 30 to 70%, preferably 30 to 70%.
It is best to adjust the weight to about 60% to 60%. The above polymerization reaction is usually carried out at a temperature of 60 to 160°C.

More specifically, the above polymerization reaction is carried out by charging the above organic liquid (dispersion ts), dispersion stabilizer, the entire amount of vinyl monomer, and a polymerization initiator in a reaction vessel, and carrying out a type polymerization reaction for a period of 7 to 15 hours. It is also possible to obtain a stable dispersion, but it is possible to obtain a stable dispersion by mixing a mixture of a vinyl monomer (a dispersion stabilizer may be partially or partially mixed with the vinyl monomer) and a polymerization initiator. A stable dispersion can also be obtained by dropping the solution over a period of ~7 hours and then continuing the reaction for 2 to 7 hours.

In the present invention, the dispersion thus obtained is neutralized with a basic substance, then water is added, and if necessary, part or all of the organic liquid is distilled off.

By treating with a basic substance, the dispersion stabilizer in the dispersion is mainly neutralized. Examples of the basic substances used include ammonia, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, dimethylethanolamine, diethylethanolamine, jetanolamine, triethanolamine, etc. It is used in such a manner that about 50 parts or more, preferably about 70 parts or more of the free carboxyl groups contained in the compound are neutralized.

In the present invention, water is then added to the neutralized dispersion to dilute it to a desired concentration, for example, about 20 to 60% by weight, and if necessary, the organic matter contained in the dispersion is The liquid is distilled off under normal pressure or reduced pressure. In the present invention, from the viewpoint of pollution control, it is particularly desirable to distill off the organic liquid until the amount of organic liquid is less than 10% by weight relative to the amount of water in the dispersion.

The aqueous dispersion thus obtained can be suitably used for applications such as paints, molded products, adhesives, and fillers.

The aqueous dispersion of the present invention can be used as it is, but if necessary, colorants, plasticizers, curing agents, etc. can be mixed therein. Here, examples of the coloring agent include dyes, organic pigments, and inorganic pigments. Examples of the plasticizer include conventionally known ones, such as low molecular weight plasticizers such as dimethyl phthalate and dimethyl phthalate, and high molecular weight plasticizers such as vinyl polymer plasticizers and polyester plasticizers. These can be mixed in and used after producing the aqueous dispersion of the present invention, but they can also be dissolved in the vinyl monomer and distributed into the dispersed particles of the produced dispersion during the production of the aqueous dispersion. can. In addition, as a hardening agent, water-soluble or water-dispersible 7
Examples include crosslinking agents such as mino resin and epoxy resin.

The aqueous dispersion produced by the method of the present invention has good dispersion stability, and when it is mixed with a curing agent and cured, the finish and smoothness of the coating film are excellent, and no skin irritation occurs. The physical properties of the coating film are also excellent.

EXAMPLES The present invention will be further clarified with reference to Examples and Comparative Examples below. In the following, "parts" simply means "parts by weight."

Example 1 (1) Synthesis of dispersion stabilizer 100 parts of isopropyl alcohol was placed in a flask,
While refluxing, the following monomers and polymerization initiators were added dropwise for 3 hours, and after the dropwise addition was completed, aging was carried out for 2 hours.

2-perfluorooctylethyl 47 parts methacrylate 2-hydroxyethyl methacrylate 1 to 50 parts Acrylic wi 3 parts Benzoyl peroxide 5 parts The obtained liquid was transparent, had a non-volatile content of 50% by weight, and had a Gardner viscosity (25%). ℃)
was S.

The number average molecular weight of this polymer is approximately 7000. The acid value was 24.

(2) Synthesis of aqueous dispersion The mixture of (f) 86 parts of the dispersion stabilizer and 100 parts of isopropyl alcohol was kept at the reflux temperature of isopropyl alcohol, and the following 7-mer and polymerization initiator were added
The solution was added dropwise over a period of time, and aged for 2 hours after completion of the addition.

Acrylonitrile 73 parts Glycidyl methacrylate 15 parts 2-hydroxyethyl methacrylate 10 parts Methacrylic M
2 parts 2.2'-7zobisisobutyronitrile 2 parts The obtained liquid was a milky white dispersion, which was neutralized in an equivalent amount with triethylamine, and after adding 214 parts of water, the isopropyl alcohol was distilled off under reduced pressure. Upon removal, a milky white aqueous dispersion containing no organic solvent was obtained. No sediment was observed in the aqueous dispersion even after it was left for two weeks. In addition, the nonvolatile content is 41% by weight, and the Gardner viscosity (2
5°C) was G. Furthermore, the surface energy (measured by the contact angle using water-paraffin, the same applies hereinafter) of the dry coating film applied to the glass plate was as low as 13 dyn crn-'.

To 100 parts of this aqueous dispersion, 10 parts of Cyme I #301 (manufactured by American Cyanamid), a type of water-soluble melamine resin, was mixed, applied to a glass plate, and baked at 150"C for 30 minutes. However, a glossy, transparent, hard film with excellent water resistance, weather resistance, etc. was obtained.

Example 2 (1) Synthesis of dispersion stabilizer 100 parts of ethyl alcohol was placed in a flask, and while refluxing, the following seven polymers and polymerization initiator were added dropwise for 3 hours, and after the dropwise addition was completed, aging was carried out for 2 hours. Ta.

2-perfluoroisononyl 30 parts ethyl methacrylate 2-hydroxyethyl acrylate 40 parts acrylic acid 8 parts methyl methacrylate 10 parts N-methylolacrylamide 10 parts styrene
2 parts 2.2'-Azobisisobutyronitrile 1.
The liquid obtained in 25 parts was transparent and had a Gardner viscosity (25° C.) of Z2 when the nonvolatile content was separated 50 times. This polymer had a number average molecular weight of about 15,000 and an acid value of 64. The obtained dispersion stabilizer is hereinafter referred to as "dispersion stabilizer A."

(2) Synthesis of dispersion stabilizer Glycidyl methacrylate 0.7 Part number stabilizer A 100 parts p-t
0.05 parts or more of ert-butylcatechol o, oi part fudimethylaminoethanol were reacted at 80°C to introduce about 0.7 active double bonds per molecule. The acid value of the dispersion stabilizer thus obtained (hereinafter referred to as "dispersion stabilizer B") was 61.

(3) Synthesis of aqueous dispersion 21.5 parts of dispersion stabilizer A obtained above, 8 parts of dispersion stabilizer
A mixture of 21.5 parts of ethyl alcohol and 100 parts of ethyl alcohol was maintained at the reflux temperature of ethyl alcohol, and the following monomers and polymerization initiators were added dropwise for 5 hours, and after the addition was completed, aging was carried out for 2 hours.

Acrylonitrile 35 parts Methyl methacrylate 30 parts Styrene
20 parts 2-hydroxyethyl methacrylate 10 parts methacrylic acid
5 parts 2.2'-Azobisisobutyronitrile 2
The obtained liquid was a milky white dispersion, which was neutralized by 0.7 parts with dimethylethanolamine, 214 parts of water was added, and the ethyl alcohol was distilled off under reduced pressure to form a milky white aqueous dispersion. A liquid was obtained. The aqueous dispersion had extremely good storage stability at room temperature. Further, the nonvolatile content was 39% by weight, and the Gardner viscosity (25°C) was O. Furthermore, the surface energy of the dry coating film applied to the glass plate was as low as 1 6 dyn cm-1.

To 100 parts of this aqueous dispersion, 10 parts of Cymel #301, a type of water-soluble melamine resin, was mixed, applied to a glass plate, and baked at 170°C for 20 minutes. A film with excellent properties such as hardness and weather resistance was obtained.

Example 3 (1) Synthesis of dispersion stabilizer 60 parts of ethyl alcohol and 40 parts of butyl cellosolve were placed in a flask, and while refluxing, the following seven polymers and polymerization initiator were added dropwise over a period of 4 hours. Time aging was performed.

2-Perfluorooctyl 28 parts Ethyl methacrylate (-2-hydroxypropyl methacrylate 30 parts Methacrylic acid 13 parts Methyl methacrylate 29 parts 2.2'-Azobis(2,
(4-2,5 parts dimethylvaleronitrile) The resulting liquid was transparent, had a nonvolatile content of 50% by weight, and had a Gardner viscosity (25° C.) of U.

The number average molecular weight of this polymer is about 12,000. Acid value is 86
I failed.

(2) Synthesis of aqueous dispersion 50 parts of the dispersion stabilizer obtained above, 9 parts of ethyl alcohol
A mixture of 0 parts of carpitol acetate and 10 parts of carpitol acetate was maintained at the reflux temperature of ethyl alcohol, and the following monomers and polymerization initiators were added dropwise over a period of 5 hours, and after the addition was completed, aging was carried out for 3 hours.

Acrylonitrile 20 parts Ethyl acrylate 40 parts Styrene
20 parts 2-hydroxyethyl methacrylate 10 parts N-methylolacrylamide
5 parts meth 1 naric acid
5 parts 2,2'-azobis(2,4-5 parts dimethylvaleroni-1-lyl) The obtained liquid was a milky white dispersion, which was neutralized in an equivalent amount with dimethylethanolamine, and 207 parts of water was added. After
A milky white aqueous dispersion was obtained by distilling off the ethyl alcohol under reduced pressure. The aqueous dispersion had very good storage stability at room temperature. The nonvolatile content was 38% by weight, and the Gardner viscosity (25°C) was H.

Also, the surface energy of a dry coating film applied to a glass plate is '
11 parts of HM-100 (manufactured by Sumitomo Chemical Co., Ltd.), a type of water-soluble melamine resin, was mixed with 100 parts of this aqueous dispersion and applied to a glass plate. When baked at 170° C. for 20 minutes, a glossy, transparent, hard film with excellent water resistance, weather resistance, etc. was obtained.

Example 4 (1) Synthesis of dispersion stabilizer 100 parts of methyl cellosolve was kept at reflux temperature, and the following monomers and polymerization initiator were added dropwise to it over a period of 4 hours, and aged for 3 hours after completion of the dropwise addition.

2-Perfluorooctyl 35 parts Ethyl methacrylate-1 ~ Methacrylic acid 20 parts 2-hydroxyethyl, methacrylate 5 parts n-butyl methacrylate 25 parts Ethyl acrylate
15 parts 2.2' - 2 parts of azobisisobutyronitrile The resulting liquid was clear and had a non-volatile content of 5
Gardner viscosity (25° C.) was N at 0% by weight.

The number average molecular weight of this polymer is approximately 13,000. M value is 13
It was 5.

(2) Synthesis of aqueous dispersion A mixture of 36 parts of the dispersion stabilizer obtained above and 100 parts of ethyl alcohol was kept at reflux temperature, and the following monomers and polymerization initiator were added dropwise for 5 hours. Aging was performed for 4 hours.

Acrylonitrile 30 parts Methyl methacrylate 35 parts Ethyl acrylate 10 parts Styrene
25 parts benzoyl peroxide
The liquid obtained in 2 parts was a milky white dispersion, which was neutralized with 0.75 equivalents of triethylamine, 145 parts of water was added, and the ethyl alcohol was distilled off under reduced pressure to obtain a milky white aqueous dispersion. It was done. The aqueous dispersion had extremely good storage stability at room temperature. The nonvolatile content was 42%, and the Gardner viscosity (25°C) was S. Furthermore, the surface energy of the dry coating film applied to the glass plate was as low as 15 dyn cm-'.

For 100 parts of this aqueous dispersion, add l-IM=100 to 100 parts.
When 0 parts were mixed and a coating film was baked on a glass plate at 150°C for 30 minutes, a glossy, transparent, hard film with excellent water resistance, weather resistance, etc. was obtained.

Example 5 (1) Synthesis of dispersion stabilizer 100 parts of inpropyl alcohol was kept at reflux temperature, and the following 7-mer and polymerization initiator were added dropwise to it for 4 hours, and aged for 3 hours after the dropwise addition was completed. Ta.

2-Perfluorooctyl 28 parts Ethyl methacrylate 1 to 10 parts of 2-hydroxyethyl acrylate N-butoxymethylacrylamide 30 parts Acrylic acid
12 parts ethyl acrylate
20 parts 2.2'-7 zobisisoputyronitrile 5 parts The resulting liquid was clear and had a non-volatile content of 5
Gardner viscosity (25° C.) was R at 0%.

The number average molecular weight of this polymer is approximately 7500. Acid value is 100
Met.

(2) Synthesis of aqueous dispersion 86 parts of the dispersion stabilizer obtained above, 9 parts of ethyl alcohol
A mixture of 0 parts of butyl cellosolve and 10 parts of butyl cellosolve was kept at reflux temperature, and the following monomers and polymerization initiators were added dropwise for 5 hours, and aged for 4 hours after completion of the addition.

Acrylonitrile 30 parts N-butoxymethylacrylamide 15 parts Methyl methacrylate 30 parts Styrene
20 parts methacrylic M
5 parts 2.2' -Azobisisobutyronitrile
The liquid obtained in 2 parts was a milky white dispersion, which was neutralized in an equivalent amount with dimethylethanolamine, 214 parts of water was added, and the ethyl alcohol was distilled off under reduced pressure to obtain a milky white aqueous dispersion. Ta. The aqueous dispersion had extremely good storage stability at room temperature. Non-volatile content is 38
Weight % and Gardner viscosity (25°C) were Q.

Also, the surface energy of a dry coating film applied to a glass plate is 1
It was as low as 6 dyn cr'.

When this aqueous dispersion was applied to a glass plate and baked at 170° C. for 20 minutes, a glossy, transparent, hard film with excellent water resistance, weather resistance, etc. was obtained.

Comparative Example 1 (1) Synthesis of dispersion stabilizer Put 100 parts of isopropyl alcohol into a flask,
While refluxing, the following seven polymers and a polymerization initiator were added dropwise over a period of 3 hours, and after the dropwise addition was completed, aging was carried out for 2 hours.

2-Hydroxyethyl methacrylate 80 parts Acrylic acid 3 parts Styrene
17 parts benzoyl peroxide
5 parts The resulting liquid was clear and had a non-volatile content of 5
At 0% by weight, the Gardner viscosity (25°C) was V.

The number average molecular weight of this polymer was about 7,000.

(2) Synthesis of aqueous dispersion A mixture of 86 parts of the dispersion stabilizer obtained above and 100 parts of isopropyl alcohol was maintained at the reflux temperature of inpropyl alcohol, and the following monomers and polymerization initiator were added dropwise over 5 hours. After the completion of the dropwise addition, aging was carried out for 2 hours.

Acrylonitrile 88 parts 2-hydroxyethyl methacrylate 10 parts Methacrylic 1!2
Part 2.2' -7 Zobisisobutyronitrile 2 parts The obtained liquid was a milky white dispersion, which was neutralized in an equivalent amount with triethylamine, 214 parts of water was added, and the isopropyl alcohol was distilled off under reduced pressure. As a result, a milky white aqueous dispersion containing no organic solvent was obtained. No sediment was observed in the aqueous dispersion even after it was left for two weeks. Non-volatile content is 4
1% by weight, Gardner viscosity (25°C) was H.

In addition, the surface energy of the dry paint film applied to the glass plate is 3
8 dyn cm”.

When 10 parts of Cymel #301 was mixed with 10.0 parts of this aqueous dispersion and applied to a glass plate and baked at 150'C for 30 minutes, a glossy, transparent, hard coating film was obtained. Compared to the coating film obtained in Example 1, the water resistance and weather resistance were inferior.

Comparative Example 2 An equivalent amount of the dispersion stabilizer obtained in Example 1 was neutralized with triethylamine, 75 parts of water was added, and then the isopropyl alcohol was distilled off under reduced pressure to obtain an aqueous solution.

10 parts of Cymel #301 was mixed with 100 parts of this aqueous solution, and the mixture was applied to a glass plate and heated to 150°C.
When baked for 30 minutes, the surface energy was 13 d.
yn Cm-' was low, but the resulting coating film was inferior in water resistance, weather resistance, heat resistance, impact resistance, adhesion, etc.

(that's all)

Claims (1)

[Claims] (1) Solubility in water is 5 or more, number of hydrogen bonds is -19
~0 and the solubility parameter value is 9 to 13 in organic liquids, the following general formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, R is a hydrogen atom or a methyl group, n is an integer from 1 to 10, R_f represents a linear or branched perfluoroalkyl group having 3 to 21 carbon atoms. ] The perfluoroalkyl group-containing (meth)acrylic monomer, the hydroxyl group-containing polymerizable unsaturated monomer, and the polymerizable unsaturated acid are essential components, and the number average molecular weight is about 1000 to
100,000, an acid value of about 20 to about 200, and in the presence of a dispersion stabilizer consisting of a copolymer that is solvated in the above organic liquid, (A) has a solubility parameter value ranging from the same as that of methyl methacrylate to 19 After polymerizing a vinyl monomer consisting of 60 to 100% by weight of the vinyl monomer and 40 to 0% by weight of the other vinyl monomer (B) to obtain a dispersion of a polymer of the vinyl monomer, A method for producing a fluorine-containing aqueous dispersion, which comprises neutralizing the dispersion with a basic substance, then adding water, and optionally distilling off part or all of the organic liquid.