JPH03163103A - Preparation of aqueous resin dispersion - Google Patents

Abstract

PURPOSE:To effectively prepare the title dispersion suitable for a coating material, adhesive, etc., by dissolving a radical-polymerizable macromonomer and an oil-sol. radical polymn. initiator in a vinyl monomer copolymerizable with the macromonomer, and emulsion polymerizing the resulting soln. in an aq. medium in the presence of a specific emulsifier. CONSTITUTION:An anionic surfactant comprising an alkali metal sulfosuccinate, or a surfactant consisting of 2-98wt.% anionic surfactant comprising an alkali metal sulfonate or alkali metal salt of sulfuric ester and 98-2wt.% nonionic surfactant having an HLB value of 10 or higher is prepd. Separately, a radical polymerizable macromonomer (e.g. a polystyrene macromonomer contg. a methacryloyl group) and an oil-sol. radical polymn. initiator are dissolved in a vinyl monomer (e.g. styrene) copolymerizable with the macromonomer. The resulting soln. is emulsified in an aq. medium in the presence of said surfactant, and heated to copolymerize the macromonomer with the monomer, thus giving the title dispersion.

Description

Detailed Description of the Invention (a) Object of the Invention [Field of Industrial Application] The present invention relates to a method for aqueous emulsion polymerization of radically polymerizable macromonomers and other radically polymerizable monomers. The resin dispersion is an emulsion consisting of fine resin particles with an average particle size of 1 μm or less, mainly composed of graft polymers produced by the macromonomer method, and is suitable for paints, adhesives, and the like.

[Conventional technology]

In recent years, graft polymers have been recognized for their usefulness as highly functional polymer materials, and have come to be widely used industrially.

Conventionally, graft polymers are produced by using a polymerization initiator such as a radical polymerization initiator, and in the presence of a polymer compound to be used as a backbone polymer, a monomer of a different type than the monomer that forms the polymer compound is synthesized. However, the graft polymers produced by such methods have a problem of low purity because they contain a large amount of non-grafted polymer. On the other hand, a method in which a high molecular weight monomer having a polymerizable group at the end of the molecule, that is, a macromonomer, is copolymerized with other copolymerizable monomers (hereinafter referred to as the macroheptanomer method) has a high grafting efficiency. Graft polymers can be produced and have recently attracted attention. The production of graft polymers using the macromonomer method has conventionally been carried out by solution polymerization, in which the macromonomer is dissolved in an organic solvent together with the monomer to be copolymerized with it, or by suspension polymerization in an aqueous medium. However, solution-based graft polymers could not meet the demands of the era of pollution-free and resource-saving. Graft polymers obtained by Q-turbidity polymerization phase separate into a liquid phase and a solid phase, so it is difficult to handle them in liquid form as an aqueous dispersion. Grafted polymers have been highly desired.

Regarding the method of producing a graft polymer by macromonomer method by aqueous emulsion polymerization, there are few methods, but
The following suggestions are available.

For example, Joseph P. Kennedy
．． Kennedy et al.
ymerBuiletin) 1 No. 3, 441-44
6 (1985), describes the following regarding a method for emulsion copolymerization of styrene and a polyisoptylene macromonomer having a p-vinyl phenyl group at one end.

That is, the above-mentioned polyisobutylene macromonomer is dissolved in styrene monomer, and this solution is emulsified in water with nonylphenoxypolyethoxyethanol sulfate sodium salt, and then micronized to an average particle size of about 0.24 μm. It is reported that a graft polymer could be obtained in high yield by adding oil-soluble abbisisobutyronitrile (hereinafter referred to as AIBN) as a polymerization initiator after the polymerization.

However, the average molecular weight of the graft polymer obtained by the method proposed by Kennedy et al. is as low as 6,000 to 50,000 in terms of number average molecular weight, which limits its practical use. According to the above, when using a macromonomer other than the polyisobutylene macromonomer, such as a polyacrylic acid ester macromonomer or a styrene/acrylic nitrile copolymer macromonomer, the above polymerization method generates a large amount of grid. Therefore, a good emulsified dispersion could not be obtained.

Furthermore, in JP-A No. 62-64814, a macromonomer is dissolved in a Ja-containing solvent such as toluene, an emulsifier is added thereto, an emulsified dispersion with a fine particle size is prepared in water, and then the emulsified dispersion is dissolved in the emulsified dispersion. A method has been proposed for producing an aqueous emulsion type graft polymer by adding a monomer to be copolymerized with a macromonomer to the macromonomer and carrying out radical copolymerization. However, in the above method, since the macromonomer is not cellulized separately from other monomers to be copolymerized, polymerization of the macromonomers and other monomers becomes predominant, and the graft polymerization There was a problem that the survival rate was inferior.

(B) Structure of the Invention [Means for Solving the Problems] As a result of intensive studies to solve the above problems, the present inventors used the following surfactants as emulsifiers and macro-contained oil-soluble radical polymerization initiators. By adopting a method of dissolving the lipophilic copolymerizable vinyl monomer together with the monomer and simultaneously emulsifying and dispersing them in an aqueous medium, even if the amount of emulsifier used is small, the macromonomer and copolymerizable vinyl monomer can be easily dissolved. The monomers can be easily emulsified and dispersed into highly stable minute micelles with an average particle diameter of 1 μm or less, and the graft efficiency of the graft polymer obtained by subsequently polymerizing the emulsified and dispersed monomers is extremely high. This led me to completely disclaim this invention. That is, in the present invention, a macromonomer having a radically polymerizable group and an oil-soluble radical polymerization initiator are dissolved in another vinyl monomer copolymerizable with the macromonomer, and the resulting solution is dissolved in an aqueous medium as follows. Surfactant (A) or (
A method for producing an aqueous resin dispersion characterized by emulsifying and dispersing the macromonomer in the presence of an emulsifier consisting of B) and then raising the temperature to copolymerize the macromonomer and other vinyl monomer. A); Sulfosuccinic acid alkali metal salt-based anionic surfactant.

Surfactant (B); consisting of an alkali metal sulfonic acid salt-based or alkali metal sulfate ester-based anionic surfactant other than the above (A), and a nonionic surfactant having an HLB value of 10 or more, and both Based on the total amount of
A surfactant containing 2 to 98% by weight of the former and 98 to 2% by weight of the latter.

and a coating material consisting of an aqueous resin dispersion obtained by the above production method, further comprising a macromonomer having a radically polymerizable group as shown in (a) below, and another vinyl monomer copolymerizable with the macromonomer. are (b) and (c) below
The copolymerization ratio of (a), (b) and (c) is (a): 1 to 50% by weight, (b): 1 to 30% by weight, and (c): 20 to 98% by weight. This is a coating consisting of an aqueous resin dispersion obtained by the above manufacturing method. (a
) A macromonomer having a radically polymerizable group and having Tg of 50″C or more (b) A carboxyl group-containing vinyl monomer and/or a hydroxyl group-containing vinyl monomer. (c) Vinyl other than the above (a) and (b) Monomer. The present invention will be explained in more detail below. [Macromonomer] The macromonomer in the present invention consists of a polymer portion and a radically polymerizable group bonded to this, and has a radically polymerizable group at one end of its molecular weight. has a number average molecular weight of 100
A high molecular weight monomer in the range of 0 to 100,000,
Preferably, the number average molecular weight is 2,000 to 50,000. If the number average molecular weight of the macromonomer is less than 1,000, the polymer in the resulting graft polymer will be too short and the physical properties specific to the graft polymer will not be expressed, while if it exceeds 10,000, the vinyl monomer to be copolymerized will The yield of graft polymer becomes low due to the lack of copolymer. Examples of the radically polymerizable group include an acryloyl group, a methacryloyl group, a styryl group, an allyl group,
Examples include vinylbenzyl group, vinyl ether group, vinylalkylsilyl group, vinyl ketone group, and isopenyl group. In addition, monomers constituting the polymer part of the macromonomer include methyl (meth)acrylate, ethyl (meth)acrylate,
Acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, tertiarybutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate
(such as acrylate, behenyl (meth)acrylate)
meth〉acrylic esters, (meth)acrylic acid, 2
-Hydroxyalkyl (meth)acrylates such as hydroxyethyl (meth)acrylate, hydroxybrobyl (meth)acrylate, and hydroxybutyl (meth)acrylate; ) Acrylic acid, polyfluoroacrylate,
Fluorine-containing acrylates such as perfluoroalkyl acrylates, silicone-containing acrylates such as acryloyloxyprobyltrimethoxysilane, styrene, alpha
- Styrenic compounds such as methylstyrene and p-methylstyrene, nitrile group-containing monomers such as (meth)acrylonitrile, vinylidene cyanide, and α-cyanoethyl acrylate, vinyl esters such as vinyl acetate and vinyl propionate, vinyl monochloride, and Vinyl halides such as vinylidene, vinylidene chloride, vinylidene fluoride,
Examples include olefin compounds such as butadiene, isoprene, and isobutylene, polyalkylene glycol (mono)methacrylates such as polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, vinylpyrrolidone, vinylpyridine, and maleic anhydride. These can be used alone or in combination of two or more.

In order to obtain a resin dispersion used for coating materials such as paints, T
It is necessary to use a macromonomer in which g is 50° C. or higher, and examples of the cough macromonomer include macromonomers having a skeleton of polymethyl methacrylate or polystyrene. If a macroheptanomer having a Tg of less than 50°C is used, the gloss and blocking resistance of the coating film will be poor.

Macromonomers can be produced by various known methods, and a typical production method is, for example, to form a monofunctional living polymer by solution polymerization using an anionic polymerization initiator, and to obtain a desired molecular weight. A method of reacting with a terminator having a radically polymerizable group such as a vinyl group (Japanese Unexamined Patent Publication No. 125186/1986)
Alternatively, in the presence of a merkabutane radical chain transfer agent having a carboxyl group, etc., a polymer having a carboxyl group, etc. at the molecular end obtained by polymerizing a radically polymerizable monomer is reacted with glycidyl (meth)acrylate, etc. (Japanese Patent Publication No. 43-11224), and group transfer polymerization method (Japanese Patent Publication No. 11224/1983).
2-62801), iniferter polymerization method, etc. can also be used.

To the present invention. In this case, it is preferable to use a macromonomer having a highly radically polymerizable (meth)acryloyl group introduced into the terminal group of a polymer skeleton produced by a radical polymerization method or an anionic polymerization method.

In the present invention, the macromonomer must be emulsified and dispersed in an aqueous medium in a state in which it is dissolved in the vinyl monomer to be copolymerized with the macromonomer, together with the oil-soluble radical polymerization initiator described later. By adopting the above means, it is possible to form micelles that contain a macromonomer, a comonomer, and a polymerization initiator in each emulsified fine particle, that is, a micelle, and therefore it is easy to control the concentration of the polymerization initiator in the micelles. In addition, since the macromonomer and the copolymerized vinyl monomer coexist in one micelle from the beginning, their copolymerization is likely to occur.
Therefore, according to the present invention, an excellent effect is achieved in that the production efficiency of the graft polymer is higher than that of the conventional emulsion polymerization method of macromonomers.

In addition, when dissolving the macromonomer and oil-soluble radical polymerization initiator in the vinyl monomer, an appropriate amount of an organic solvent such as toluene, xylene, methyl isobutyl ketone, and ethyl acetate may be used in combination to increase solubility. .

[Comonomer] In the present invention, the monomer to be copolymerized with the macromonomer is a hydrophobic vinyl monomer or vinyl monomer mixture that can be emulsified in an aqueous medium, and is a vinyl monomer that is liquid at room temperature. A vinyl monomer mixture containing the vinyl monomer as a main component is preferred.

Hydrophobic vinyl monomers that can be copolymerized with macromonomers and are liquid at room temperature include methyl methacrylate, ethyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, and tert-butyl (meth)acrylate. Acrylate, 2-ethylhexyl (meth)
(such as acrylate, lauryl (meth)acrylate)
meth)acrylic acid esters, polyfluoroacrylates, fluorine-containing acrylates such as perfluoroalkyl acrylates, silicone-containing acrylates such as acryloyloxypropyltrimethoxysilane, styrene,
Styrenic compounds such as α-methylstyrene and p-methylstyrene, (meth)acrylonitrile, vinyl acetate,
Examples include vinyl esters such as vinyl propionate. Other vinyl monomers that can be used with the above vinyl monomers in the hydrophobic liquid include methyl acrylate, 2-hydroxyethyl (meth)acrylate, hydroxyprobyl (meth)acrylate, (meth)acrylamide, N- Hydrophilic vinyl monomers such as methylol(meth)acrylamide, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, (meth)acrylic acid, vinylpyrrolidone and vinylbilidine, divinylbenzene, diallyl phthalate and diethylene glycol di Polyfunctional vinyl monomers such as acrylates and stearyl (meth)
Examples include acrylate, behenyl (meth)acrylate, maleic anhydride, butadiene, isoprene, and vinylidene chloride.

The preferred copolymerization ratio of the macro-heptanomer and the comonomer is 1 to 50% by weight of the macromonomer and 50 to 99% by weight of the comonomer. The proportion of macromonomer is 50
Exceeding this weight percentage tends to cause gelation during polymerization. Further, when a polyfunctional vinyl monomer is used as a part of the comonomer, the preferred amount of the polyfunctional vinyl monomer used is 5% by weight based on the total amount of all monomers. It is as follows. In order to obtain a resin dispersion for a coating material, the presence of a carboxyl group copolymer-containing vinyl monomer and/or a hydroxyl group-containing vinyl monomer is required as a comonomer copolymerized with the macromonomer. In this case, the copolymerization ratio of each component is 1 to 50% by weight of macromonomer, 1 to 30% by weight of carboxyl group-containing vinyl monomer and/or hydroxyl group-containing vinyl monomer, and 20% by weight of other copolymerizable vinyl monomers. ~98% by weight
It is. The ratio of carboxyl group-containing vinyl monomer and/or hydroxyl group-containing vinyl monomer is 1! If it is less than tffi%, the adhesion to the base material will be poor.

〔emulsifier〕

In the present invention, a monomer is prepared by dissolving a macromonomer and an oil-soluble radical polymerization initiator in a comonomer using an emulsifier consisting of a surfactant (A) or a surfactant (B) as an emulsifier. It is necessary to emulsify and disperse the solution into micromicelles in an aqueous medium.

Emulsified dispersion contains 0 emulsifier per 100 parts by weight of monomer solution.
．． This can be carried out by using 3 to 5 parts by weight of water and 30 to 100 parts by weight of water, and stirring the mixture with a homogenizer, homogenizer, ultrasonic wave, or the like.

The particle size of the micelles of the emulsified dispersion prepared by the above method is:
It is preferable that the particle size is as small as possible, and specifically, the average particle size is 1 μm or less, and even 0.5 μm or less. It is preferably 5 μm or less. If the particle size of the micelles is larger than lIlm, the resin particle size in the resulting resin dispersion exceeds lμm, resulting in poor film-forming properties, making it difficult to apply the resin dispersion as a coating agent, adhesive, etc. The uses of the body are limited.

In addition, the smaller the amount of emulsifier used in the emulsification and dispersion, the better the physical properties such as water resistance of the resulting resin dispersion, and the preferred amount used in the present invention is 0.0000.
It is 3 to 3 parts by weight.

The obtained emulsified dispersion may be polymerized by raising the temperature as it is, but since it is easier to control the heat generation during polymerization, it is possible to polymerize the emulsified dispersion while dropping the emulsified dispersion into a heated aqueous medium. It is preferable to polymerize so as to finally obtain an aqueous resin dispersion having a solid content of 20 to 70% by weight. As the polymerization temperature, temperatures conventionally generally applied in emulsion polymerization methods can be used, and specifically, 50 to 90°C is preferable.

Next, the surfactant (A) used as an emulsifier in the present invention and the surfactant in the surfactant mixture (B) will be explained in more detail.

As mentioned above, the surfactant (A) is an anionic surfactant based on an alkali metal sulfosuccinate, and specific examples of such anionic surfactants include ';-2-ethylhexyl sodium sulfosuccinate; Examples include polycyclic phenylbolythoxysodium sulfosuccinate, polyoxyethylene alkyl allyl ether sulfosuccinic acid monoester sodium, and polyoxyethylene lauryl ether sodium sulfosuccinate.

The above surfactant (A) can be used alone as an emulsifier, but when used in combination with a nonionic surfactant having an HLB value of 10 or more, the emulsion stability of the aqueous emulsion dispersion during polymerization can be improved. can be further improved. As a specific example of such a nonionic surfactant, in the description of the surfactant (B) below, the surfactant (
Examples of the nonionic surfactant having the function of structure B) include nonionic surfactants and the like.

The preferred mixing ratio of the surfactant (A) and the nonionic surfactant is 10 to 90% by weight to 90 to 10% by weight.
and more preferably 10 to 40% by weight to 90 to 6% by weight.
It is 0% by weight.

Next, among the anionic surfactants to be avoided as surfactant (B), examples of sulfonic acid alkali metal salt-based anionic surfactants other than (A) include alkylbenzene sulfones such as sodium dodecylbenzenesulfonate. Examples include acid alkali metal salts, sodium alkylnaphthalene sulfonates, sodium alkyl diphenyl ether disulfonates, and alkali metal salts of naphthalene sulfonic acid formalin condensates. Examples of sulfate ester alkali metal salt-based anionic surfactants include lauryl Examples include alkali metal salts of alkyl sulfates such as sodium sulfate and sodium stearyl sulfate, sodium polyoxyethylene alkylene ether sulfates such as sodium polyoxyethylene lauryl ether sulfate, and sodium polyoxyethylene octylphenyl ether sulfate.

As a nonionic surfactant with an HLB value of 10 or more, which is considered a surfactant (B), commercially available Emulgen 91
0°, Emulgen 9301 Emulgen 938 [manufactured by Kao ■]; Newcol 5 6 3, Newcol
5 6 6 (manufactured by Nippon Nyukazai ■); Nonal 2
Polyoxyethylene nonyl phenyl ether such as 10 (manufactured by Toho Chemical), Emulgen 810, Emulgen 840
S (manufactured by Kao ■); Newco1 8 60,
Newcol 8 0 4 (manufactured by Nippon Nyukazai)
; Polyoxyethylene octyl phenyl ether such as Nonal 210 [manufactured by Toho Chemical Co., Ltd.], Rheodol TW-L2
0, Leo. Doll TW-3120C or higher (manufactured by Kao ■)
; Newco! 2 5, Newcol 6 5 (
Examples include polyoxyethylene sorbitan monoalkylate, polyethylene glycol distearate, and polyoxyethylene cetyl ether such as Sorbon T-20 and Sorbon T-60 (manufactured by Toho Chemical).

If a nonionic surfactant with an HLB value of less than 1O is used as a component of the surfactant (B), the stability of the aqueous emulsion dispersion during polymerization will be poor and smooth emulsion polymerization will not be possible. Further, the preferred ratio of anionic surfactant to nonionic surfactant in surfactant (B) is 10
-90% by weight to 90-10% by weight, more preferably 10-40% by weight to 90-60% by weight.

Note that the emulsifier used may contain surfactants other than the above surfactants.

[Polymerization initiator]

The polymerization initiator used in the present invention is an oil-soluble radical polymerization initiator whose solubility in water at 20°C is 10% by weight or less. Among the azo-based initiators, preferred polymerization initiators include AIBN, i.e., 2. 2゜-azobisisobutyronitrile, 2,2゛azobis-2,4-dimethylvaleronitrile, 1-azobis-■-cyclohexane luponitrile, dimethyl-2.2"-azobisisobutyrate, 4,4゜- Azobis-4-cyanovaleric acid, etc.; organic peroxides include lauroyl peroxide, penzoyl peroxide, dicumyl peroxide, cyclohexanone peroxide, di-n-propyl peroxydicarbonate, t-butyl peroxypiparate 20°C such as
Examples include radical polymerization initiators having a solubility in water of 1% by weight or less.

The amount of the polymerization initiator used is preferably 0.1 to 10% by weight based on the total amount of the macromonomer and comonomer, and 0.1 to 10% by weight is preferable.
．． More preferably 5 to 5% by weight. Polymerization initiator amount is 0.1
If it is less than 1% by weight, it is difficult for emulsion polymerization to proceed smoothly, macromonomers and comonomers tend to remain unreacted, and
If it exceeds 0% by weight, the molecular weight of the resulting graft polymer will become small, limiting the uses of the resulting aqueous dispersion. In the present invention, the polymerization initiator is added to the polymerization system in an emulsified and dispersed state together with the macromonomer and the comonomer as described above, but it may be added to the polymerization system in other ways, such as adding it alone to the polymerization system afterwards. According to the above, the resulting aqueous resin dispersion contains a large amount of unreacted macromonomer and unreacted comonomer. [How to use it as a coating agent] When the aqueous resin dispersion obtained by the present invention is used as a coating agent, a film forming aid, a pigment, a filler, etc. can be added as necessary. As a film forming aid,
Plasticizer-type coalescents such as dioctyl phthalate, tricresyl phosphate and dibutyl phthalate, and coalescents such as butylcellosolve, butylcellosolve acetate, carbitol, carbitol acetate and butylcarbitol acetate can be used and are preferred. The amount is 0.0% relative to the aqueous resin dispersion. 1-10% by weight.

The aqueous resin dispersion for coating can be applied to the substrate as it is or after being thickened by a known method, using a roll coater, spraying, or the like.

(C) Effects of the Invention According to the present invention, macromonomers can be stably emulsified and dispersed into minute micelles by using a small amount of emulsifier, so it is possible to obtain an aqueous resin dispersion with a low emulsifier content, and also to obtain the resin dispersion. Excellent effects are achieved in that the content of the graft polymer in the dispersion is high and the amount of unreacted macroheptanomer is small.

Therefore, the aqueous resin dispersion obtained by the method of the present invention is
It is suitably used in a very wide range of applications, including adhesives, adhesives, coatings such as paints and coatings, dispersion improvers for pigments and fillers, antistatic agents, and resin modifiers.

In particular, a coating material made of an aqueous resin dispersion obtained by copolymerizing a specific monomer that essentially contains the above-mentioned carboxyl group-containing vinyl monomer and/or hydroxyl group-containing vinyl monomer, It has the effect of creating a coating film with excellent gloss and anti-blocking properties.

(Example〕 Hereinafter, the present invention will be explained in more detail with reference to Examples.

Note that "parts" in each example means "parts by weight."

Example 1 A mixture of 160 parts of methyl methacrylate (hereinafter referred to as MMA) and 40 parts of butyl acrylate (hereinafter referred to as BA) was added with an unended methacryloyl group type styrene/acrylonitrile copolymer macromonomer (Toa Goka Kagaku Kogyo Co., Ltd.).
AN-6, number average molecular weight Mn approximately 6000) 50 parts and A
Dissolve 3 parts of IBN and add 5 parts of sodium di-2-ethylhexylsulfosuccinate (total monomer: 10
(corresponding to 2 parts per 0 parts) was used as an emulsifier and was emulsified in 90 parts of deionized water using a homomixer to prepare an aqueous emulsified dispersion (hereinafter referred to as pre-emulsion). The particle size of the obtained pre-emulsion was measured using a laser diffraction particle size distribution measuring device (Horiba, Ltd., LA-500), and the average particle size was 0.44 μm, and the pre-emulsion did not separate for more than 1 day. It was stable. Using the entire amount of the above pre-emulsion, polymerization was carried out by the following method. In a 1 liter flask equipped with a stirrer, thermometer, and condenser, add 250 parts of deionized water and 1. Add 5 parts and keep the internal temperature at 80±VC while bubbling nitrogen. Then add the remaining pre-emulsion 3 4 6 while stirring.
．． After 5 parts were added dropwise over 4 hours, the reaction was continued for an additional 2 hours to complete the polymerization.

Apart from a slight amount of aggregate adhering to the wall of the flask during polymerization,
There was no separation or blocking, and the situation was mutual.

When the obtained emulsion polymer was filtered through a 200 mesh net, the amount of grid was 0. It was less than 1 copy. The total amount of unreacted monomers detected by gas chromatography was less than 1%, and the number average of the bioactive polymer in terms of bolystyrene determined by Kölpermeation chomatography was 10. ．． 80,000,
The weight average molecular weight Mw was 1,057,000, and the conversion rate of macroheptanomer was 66%. The average particle diameter of the obtained polymer was 0.42 μm, and its distribution was narrow. The conversion rate of macromonomer refers to the amount of macromonomer actually polymerized out of the amount of macromonomer subjected to polymerization. It represents the proportion of the amount of macromonomers and can be determined by Gelper ξ Acegonk stomatography.

Examples 2-6 Example 1 except that the macromonomers listed in Table 1 were used.
Emulsion polymerization was carried out in the same manner as above to produce an aqueous resin dispersion.

The results are shown in Table 1.

The amount of grid in the table is 250% of the total monomer mixture consisting of macromonomers and comonomers subjected to emulsion polymerization.
This is the amount of grids generated per copy, and this point is the same for Tables 2 onwards.

Examples 7 to 8 and Comparative Examples 1 to 4 Emulsion polymerization was carried out in the same manner as in Example 1, except that the emulsifiers shown in Table 2 were used, and the results shown in Table 2 were obtained. In addition,
Both file manoresions had stability for more than 1 day.

Examples 9 to 12 Emulsion polymerization was carried out under the same conditions as in Example 1, except that 2 parts of the anionic emulsifier shown in Table 3 and 4 parts of a polyoxyethylene nonyl phenyl ether type nonionic emulsifier with a different HLB were used. The results shown in 3 were obtained. In these Examples, the stability of all preemulsions and the stability during polymerization were good.

Example 13 and Comparative Example 5 The above AN-6 was used as a macromonomer, and MMA, BA and methacrylic acid (hereinafter referred to as MAA) were used as comonomers.
), and emulsion polymerization was carried out using the following method at the copolymerization ratio shown below. AN-6/MMA/BA/MAA=1 00/100/
45/5 (Part) All conditions were the same as in Example 1 except that 3 parts of sodium nonylphenoxypolyethoxyethanol sulfate used by Joseph B. Kennedy et al. shown in the prior art section was used as an emulsifier. It was polymerized (Comparative Example 5).

On the other hand, as an emulsifier, HL B l 8 along with 3 parts of the above sodium nonylphenoxyboethoxyethanol sulfate
．． Polymerization was carried out in the same manner as in Example 1, except that 4 parts of polyoxyethylene nonylene phenyl ether of No. 5 was used in combination (Example 13). The properties of the aqueous resin dispersions obtained in Example 13 and Comparative Example 5 were as shown in Table 4. Table 4 Example 14 Lauroyl peroxide as a polymerization initiator 1. Emulsion polymerization was carried out in the same manner as in Example 1 except that 5% by weight was used. The properties of the obtained aqueous resin dispersion were as follows.

Grid amount (parts): 0.1 or less, macromonomer conversion rate (%): 73, average particle size of resin dispersion (μm): 0.3
6. Number average molecular weight M n = 2,500,000, weight average molecular weight Mw = 2,108,000 Example 15 70 parts of MMA, 130 parts of BA, 6 parts of methacrylic acid, and macromonomer AA-6 manufactured by Toa Gokai Chemical Industry ■; Polymerization was carried out in an aqueous medium in the same manner as in Example 1, except that 50 parts were used, to obtain an aqueous resin dispersion having an average particle size of 0.39 μm. The obtained aqueous resin dispersion was thickened with an alkali-soluble polyacrylic acid-based thickener, and then coated on a glass plate with a bar coater to a dry film thickness of 50 am, and dried. The paint film was made to look impressive. Next, the following physical properties were measured for the above coating film, and the results are shown in Table 5. Glossiness: 601 according to JIS K5400! Measure surface gloss. Blocking resistance: Place the coated surfaces on a glass plate together, apply a load of 150 g/ai, leave in an atmosphere of 45°C and 90% relative humidity for 24 hours, and then separate the test pieces. Based on the condition of the test piece when it was released, it was evaluated as follows. ◎: Does not adhere O: Adheres but the coating does not peel off from the glass surface ×: Adheres and the coating peels off in spots from the glass surface Scratch resistance: Using a drawing tester made by Ueshima Seisakusho, a weight was placed on the cargo tray. A continuous circle was drawn on the paint film using a steel needle attached to the paint without placing the paint on it, and the evaluation was made as follows. ◎: Hardly any needle marks left ○: Slight needle marks remain △: Part of the paint film falls off Adhesion: Condition of the paint film when sellotape is adhered to the paint film and quickly peeled off. Based on the above, the evaluation was as follows: ◎: The paint film surface and cellophane tape peeled off, and there was no change in the paint film ○: v1! Less than 10% of the coating surface adheres to the cellophane tape. ×: More than 10% of the coating surface adheres to the cellophane tape. Hardness: When applied to a surface-treated steel plate and dried in the same manner as a glass plate, Pencil hardness was measured.

Example 16 A solution obtained by mixing and dissolving 50 parts of macromonomer AS-6 manufactured by Toagosei Kagaku Kogyo ■ and 3 parts of AIBN in a mixed solution of 80 parts of MMA, 120 parts of BA, and 40 parts of 2-hydroxyethyl methacrylate was added to di-2-ethylhexyl sulfosuccinate. 4 parts of sodium hydroxide and H L B 1 B. Emulsion polymerization was carried out under the same conditions as in Example 1, except that 3 parts of the polyoxyethylene nonyl phenyl ether type nonionic emulsifier of No. 9 was used to form a pre-emulsion, and the average particle size was 0.36.
A stable aqueous resin dispersion of μm was obtained.

To the obtained dispersion, 10 parts of butylcellosolve was added as a film-forming agent, and after stirring sufficiently at room temperature, the dispersion was thickened in the same manner as in Example 16, and the physical properties of the coating film were determined.

Example 17 60 parts of styrene, 160 parts of butyl methacrylate, MAA
15 parts macromonomer AA-5; 30 parts and ATBN3
Examples except that a solution obtained by mixing and dissolving 1 part was pre-emulsified with 8 parts of a commercially available 40% aqueous solution of sodium nonylphenoxybolyethoxyethanol sulfate and 3 parts of polyoxyethylene nonylphenyl ether with an HLB of 17.2. Polymerized under the same conditions as 1, with an average particle size of 0.51
A stable aqueous resin dispersion of μm was obtained, and the physical properties of the coating film were measured in the same manner as in Example 16.

Comparative Example 6 Polymerization was carried out under the same conditions as in Example 16, except that 50 parts of styrene was used instead of the macromonomer AS-6. The average particle size of the obtained aqueous resin dispersion was 0.31 μm, Mn was 101,000, and Mw was 195,000.

To the above aqueous resin dispersion, 10 parts of butylcellosolve was added as a film forming aid, and after stirring sufficiently at room temperature, the physical properties of the coating film were measured in the same manner as in each of the above examples.

Comparative Example 7 Instead of macromonomer AA-6, MMA30
Polymerization was carried out under the same conditions as in Example 17, except that 10% of the polymer was used. The average particle size of the obtained aqueous resin dispersion was 0.44μ
m, Mn was 93,000, and Mw was 96,000.

Regarding the above aqueous resin dispersion, the physical properties of the coating film were measured in the same manner as in each of the above examples.

The measurement results of the physical properties of the coating films in Examples 15 to 17 and Comparative Examples 6 to 7 are shown in Table 5 below.

table 5 Anti-locking property Scratchability closeness 6il! Every time

Claims (1)

[Claims] 1. A macromonomer having a radically polymerizable group and an oil-soluble radical polymerization initiator are dissolved in another vinyl monomer copolymerizable with the macromonomer, and the resulting solution is dissolved in an aqueous medium. The macromonomer is emulsified and dispersed in the presence of an emulsifier consisting of the following surfactant (A) or (B), and then heated to copolymerize the macromonomer and another vinyl monomer. A method for producing an aqueous resin dispersion. Surfactant (A): anionic surfactant based on alkali metal sulfosuccinate. Surfactant (B); consisting of an alkali metal sulfonic acid salt-based or alkali metal sulfate ester-based anionic surfactant other than the above (A), and a nonionic surfactant having an HLB value of 10 or more, and both Based on the total amount of
A surfactant containing 2 to 98% by weight of the former and 98 to 2% by weight of the latter. 2. A coating comprising an aqueous resin dispersion obtained by the production method according to claim 1. 3. The macromonomer having a radically polymerizable group is as follows (
a), and the other vinyl monomer copolymerizable with the macromonomer consists of the following (b) and (c), (a), (b)
and (c) copolymerization ratio of (a): 1 to 50% by weight,
(b): 1-30% by weight and (c): 20-98% by weight
The coating material according to claim 2. (a) A macromonomer having a radically polymerizable group and having a Tg of 50°C or higher. (b) Carboxyl group-containing building monomer and/or hydroxyl group-containing vinyl monomer. (c) Vinyl monomers other than the above (a) and (b).