JPS636009A - Emulsion-polymerized composition - Google Patents

Abstract

PURPOSE:To obtain the title emulsifier-free composition containing stable ultrafine resin particles in a high solid concentration and being useful for a water-based paint, by emulsion-polymerizing three specified reactive vinyl monomers. CONSTITUTION:1-25wt% hydroxyl group-terminated reactive vinyl monomer (A) of the formula is copolymerized with 1-25wt% reactive vinyl monomer (B) having a basic group selected from among an amino group, a ring nitrogen and their onium structures in the molecule (e.g., vinylpyridine) and 98-50wt% reactive vinyl monomer (C) selected from among alpha,beta-ethylenically unsaturated compounds (e.g., 2-hydroxylethyl acrylate) in an aqueous medium in the presence of a polymerization initiator (e.g., benzoyl peroxide) and, optionally, a chain transfer agent, a surfactant, an emulsifier, etc. to obtain an emulsion-polymerized composition emulsion of a nonvolatile content of 30-40wt% and particle diameter of 0.01-0.1mu.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical field The present invention relates to a milk (hyperoxygenate) polymerization composition, more specifically, to stabilize ultrafine resin particles at a high solid content concentration that do not contain surfactants or emulsifiers and are useful for water-based paints. The present invention relates to an emulsion polymerization composition contained in the present invention.

Prior Art An emulsion obtained by emulsion polymerization of an ethylenically unsaturated compound in an aqueous medium is generally obtained as a dispersion of fine resin particles, and is widely used in water-based paints and the like. However, when producing such emulsions, it is usually necessary to use surfactants and emulsifiers, which remain in the emulsion and have a negative effect on the water resistance of the coating film, so great efforts have been made to find a solution. ing.

As emulsion polymerization without using surfactants or emulsifiers, the so-called soap-free polymerization method, for example, synthesis of amphoteric latex is possible by simultaneously copolymerizing a monomer having an amino group in the molecule and a monomer having a carboxyl group such as acrylic acid or methacrylic acid. It has been proposed by Homola et al. and has attracted attention (A. Homola.

R, 0, James, J, Co11oid, Int.
erface Sci, 59.123~+34 (+
977)). However, in this soap-free polymerization method, since no surfactant is used during synthesis, the dispersion stability of latex particles is not sufficient, and therefore, it is not possible to increase the latex solid content concentration. The diameter of the produced particles is also on the order of several hundred microns, and it is technically difficult to obtain particles smaller than that. Incidentally, the solid content concentration of the latex obtained in the research of Homora et al. is 10% or less, and the particle size is also 0.1 μ or more.

Problems to be Solved by the Invention Therefore, in the synthesis of amphoteric latex by soap-free polymerization, if a latex containing fine resin particles at a higher concentration and more stably than before can be obtained, it would not only be advantageous in terms of production such as improved reaction yield. This contributes greatly to paint performance, and it is an object of the present invention to find such a solution.

Means for Solving the Problems According to the present invention, the above object is (in the formula, R1 is hydrogen or a methyl group; R2 is an aliphatic hydrocarbon having 2 to 10 carbon atoms which may have a substituent;
Alicyclic hydrocarbons having 6 to 7 carbon atoms, aromatic hydrocarbons having 6 carbon atoms; A is R9 is ethylene or propylene; R4 is alkylene having 2 to 7 carbon atoms, which may have a substituent; R5
is an alkylene having 2 to 5 carbon atoms which may have a substituent: m and n are the average values of the number of repeating units, and m is 1 to 5.
10 or n is 2 to 50; however, the terminal carboxyl group may be neutralized with an inorganic or organic base). (B) 1 to 25% by weight of at least one reactive vinyl monomer having an amino group, a cyclic nitrogen atom, or a basic group with an onium structure in the molecule, and (C) other reactions. 98% of at least one type of vinyl monomer
This is achieved by a milk polymerization composition obtained by emulsion polymerization of ~50% by weight in an aqueous medium.

The reactive vinyl monomer having a terminal carboxyl group represented by the formula [■] used in the present invention is as follows: (wherein R1 is hydrogen or a methyl group; R3 is ethylene or propylene; R
4 is alkylene having 2 to 7 carbon atoms which may have a substituent; R5 is alkylene having 2 to 5 carbon atoms which may have a substituent; m and n are the average values of the number of repeating units , m is 1 to 10, n is 2 to 50) A (meth)acrylate having a terminal hydroxyl group represented by
-10 aliphatic hydrocarbons, alicyclic hydrocarbons having 6 to 7 carbon atoms, aromatic hydrocarbons having 6 carbon atoms), preferably in the presence of a radical polymerization inhibitor. It is a compound. The present inventors have demonstrated that this reactive vinyl monomer having a terminal carboxyl group has excellent surfactant ability in a base-neutralized form, and has demonstrated that it is possible to emulsify α,β-ethylenically unsaturated compounds in an aqueous medium. He discovered that it was extremely useful as a reactive surfactant in polymerization and filed a patent application as Japanese Patent Application No. 1983-1900 (filed on January 8, 1986). The present invention is a further development of the above invention, but is novel in that the reactive vinyl monomer itself having a terminal carboxyl group is used in combination with a basic monomer to synthesize an amphoteric latex by soap-free polymerization. and has an inventive step.

Examples of (meth)acrylates having a terminal hydroxyl group represented by the formula [■] include hydroxyethyl (meth)acrylate or hydroxypropyl (meth)acrylate, β-propiolactone, δ-valerolactone, δ-caprolactone, and ε-caprolactone. This refers to compounds to which cyclic esters such as ethylene oxide, propylene oxide, and tetrahydrofuran are added.

An example of a commercially available product that is equivalent to this is Plaxel (FM-1) FA, which has hydroxyethyl (meth)acrylate and ε-caprolactone added to it.
-1 (1:1 adduct], (FM-3) FA-3 [1
: 3 adduct), (FM-5) FA-5C1: 5 adduct] (all of the above are registered trademarks of Daicel Chemical), or Blenmer PE, Blenmer PP (all of which are Daicel Chemical, registered trademarks), or Blenmer PE or Blenmer PP (which is obtained by adding ethylene oxide or propylene oxide to methacrylic acid). Nippon Oil & Fats, Inc. (registered trademark), etc., and also includes those that can be easily produced by those skilled in the art based on similar reactions.

On the other hand, examples of the acid anhydride represented by formula (1) include succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, het's acid anhydride, and Himic anhydride. Acid, adipic anhydride, azelaic anhydride, sebacic anhydride or substituted derivatives thereof are used.

The reaction proceeds easily by simply heating and stirring these raw materials, but it is preferable to carry out the reaction in the presence of a radical polymerization inhibitor, such as hydroquinone monomethyl ether, to protect the terminal vinyl group, and such polymerization inhibitors are usually 50
00 ppm or less, more preferably about 500 ppm or less.

Further, the hydroxy group-containing (meth)acrylate and the acid anhydride are usually used in a weight ratio of 9:10 to 11:10.

The above reactive monomer having a terminal carboxyl group is R2
, A The introduction of an alkylene chain allows the balance between hydrophilic and hydrophobic parts to be freely changed, and thereby provides the reactive monomer with excellent surface activity.

In the invention of Japanese Patent Application No. 61-1900, the above-mentioned reactive monomer was neutralized with an inorganic or organic base and used as a reactive monomer and surfactant in emulsion polymerization. However, in the present invention, the above-mentioned reactive monomer is used in combination with a reactive vinyl monomer having a basic group and is neutralized by the monomer, so neutralization of the terminal carboxyl group is unnecessary. It is. However, depending on the ratio of the reactive monomer having a carboxyl group and the reactive vinyl monomer having a basic group, or the type of reactive vinyl monomer having a basic group, the amount of monomer (A) It is preferable to neutralize the terminal carboxyl group with an inorganic or organic base.

The reactive monomer having a basic group used in combination with the above-mentioned reactive monomer (A) in the present invention is a reactive monomer having an amino group, a cyclic nitrogen atom, or a basic group having an onium structure thereof in the molecule. Any of the vinyl monomers is 1
It can be advantageously used as a species or in combination of two or more species.

Such reactive monomers (B) are more specifically classified into the following compound groups.

(In the formula, R1 is hydrogen or a methyl group; R6 and R7 are hydrogen or have a carbon number of 1 to 4, which may have a substituent.
an alkyl group; B is Oo 11I CO-(CH2)! -1CN -(CH2)k-1 R8 is hydrogen or an alkyl group having 1 to 4 carbon atoms; k,! and m is an integer of 2 to 6, respectively) having an amino group 9 For example, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, N-methyl-N-dimethylaminoethyl -(meth)acrylamide.

Dimethylaminostyrene, diethylaminoethylstyrene, dimethylaminovinylpyridine, etc., R (wherein R1, R6, R7, B are respectively as described above;
is an alkyl having 1 to 12 carbon atoms which may have a substituent; Ammonium propyl (meth)acrylamide, trimethylammonium P-phenylene (meth)acrylamide, etc.

R (in the formula, R1, R6, R7, B are each as described above: R1
゜ is a carbon number 2-6) which may have a substituent
/l, kylene; D is -5o3, -coo, or -P) A reactive vinyl monomer having a quaternary ammonium H ram structure. For example, N-(3
-Sulfopropyl-N-methacryloxyethyl-N,N
-dimethylammonium betaine, N-(3-sulfopropyl)-N-methacrylamidopropyl-N.

N-dimethylammonium betaine, N-(3-phosphopropyl)-N-methacryloxyethyl-N,N-dimethylammonium betaine, N-(2-carboxyethyl)-N-methacrylamidopropyl-N,N-dimethylammonium Betain et al.

4) Formula R1 ++2C=C-E ...(V) R11 is an alkyl group; X is an acid residue; R1□ is an alkylene having 2 to 6 carbon atoms which may have a substituent; D is - A reactive vinyl monomer having a cyclic nitrogen atom represented by S○, , -COO or -P or its H onium structure. For example, vinylpyridine, vinyltriazine, 2-vinyl-■-methylpyridinium chloride 1-(2-carboxyethyl)-2-vinylpyridinium betaine, 1-(3-sulfopropyl)-2-vinylpyridinium betaine, and the like.

In the present invention, the above-mentioned reactive vinyl monomer (A) having a terminal carboxyl group and reactive vinyl monomer (B) having a basic group are each used in an amount of 1 to 25% by weight based on the total monomers. %, and the remaining 98 to 50 weight percent can be selected from any α,β-ethylenically unsaturated compounds used in conventional vinyl resin production. Such unsaturated compounds have one α,β-ethylenically unsaturated bond in the molecule: 1) Carboxyl group-containing monomers such as acrylic acid, methacrylic acid, chloro-aconic acid, itaconic acid, maleic acid , fumaric acid, etc., 2) Hydroxyl group-containing monomers such as 2-hydroxyethyl acrylate, hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, allyl alcohol, methalyl alcohol, etc. 3) Nitrogen-containing alkyl acrylates or methacrylates, such as dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, etc., 4) Polymerizable amides, such as acrylamide, methacrylic acid amide, etc., 5) Polymerizable nitriles, such as acrylonitrile, methacrylateril, etc. 6) Alkyl acrylate or methacrylate such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, etc. 7) Polymerizable aromatic compounds such as styrene, α-methyl Styrene, vinyltoluene, t-butylstyrene, etc.; 8) α-olefins, such as ethylene, propylene, etc.; 9) Vinyl compounds, such as vinyl acetate, vinyl propionate, etc.;
10) Diene compounds such as butadiene, isoprene, etc. 11) Polymerizable unsaturated monocarboxylic acid esters of polyhydric alcohols; polymerizable unsaturated alcohols of polybasic acids ester;
Aromatic compounds substituted with two or more vinyl groups such as ethylene glycol acrylate, ethylene glycol methacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, trimethylolpropane triacrylate, Methylolpropane trimethacrylate, 1,4-butanediol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythridota acrylate, glycerol dimethacrylate, glycerol diacrylate,
Glycerol allyloxy dimethacrylate, 1.1.1
-trishydroxymethylethane diacrylate, 1,
1゜1-trishydroxymethylethane triacrylate, 1,1.1-trishydroxymethylethane dimethacrylate, 1,1.1-)lishydroxymethylethane trimethacrylate, 1,1゜1-trishydroxymethylpropane diacrylate , 1,1.1-1 lishydroxymethylpropane triacrylate, 1,1.1
-) lishydroxymethylpropane dimethacrylate,
1.1.1-Trishydroxymethylpropane trimethacrylate, triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate diallyl terephthalate, diallyl phthalate, divinylbenzene, etc. These monomers may be used alone or in combination. Emulsion polymerization is carried out according to conventional methods.

In addition, during emulsion polymerization, the combination itself of the above monomer CI) and a monomer having a basic group, or the above formula [■
] Since the monomer itself has surfactant ability, there is no need to use a separate surfactant or emulsifier, but if the amount of monomer CI) and the monomer having a basic group is small, It is preferred to use small amounts of commonly used types of surfactants and emulsifiers. Particularly preferable examples include, for example, Japanese Patent Application No. 54-11Q1165:55-560411:5
5-116293:53-123899:55-476
52;56-71864:57-13053 and the like. Examples of polymerization initiators include organic peroxides such as benzoyl peroxide, t-butyl oxide, and cumene hydroperoxide; azobiscyanovaleric acid, azobisisobutyronitrile, azobis(2,4
- organic azo compounds such as dimethyl)valeronitrile, azobis(2-amidinopropane) hydrochloride;
Inorganic water-soluble radical initiators such as potassium persulfate, ammonium persulfate, sodium persulfate, and hydrogen peroxide; redox initiators are preferably used, and chain transfer agents include, for example, ethyl mercaptan, butyl mercaptan, and dodecyl. Mercaptans such as mercaptan; halogenated carbons such as carbon tetrabromide and carbon tetrachloride can be used. The proportions of the surfactant, emulsifier, polymerization initiator, chain transfer agent aqueous medium, polymerization method, etc. that are used as desired can all be determined by conventional techniques.

The emulsion polymerization composition of the present invention obtained in this manner does not contain an external emulsifier or only uses a very small amount of the external emulsifier. A low molecule that solubilizes the film even after being immersed in water! Since there are almost no IJ penetrations, the water resistance of the paint film is greatly improved compared to conventional emulsion paints.

Furthermore, in the present invention, it is possible to obtain an emulsion with extremely fine particles of, for example, 0.01 to 0.1B, compared to conventional research by Homora et al., and the non-volatile content is also 30 to 0.1B.
It is possible to obtain a stable emulsion with an extremely high concentration of up to 40% by weight, and when used in water-based paints, it improves coating performance and film forming properties due to particle miniaturization, and improves the mechanical strength of the coating film. 9 The present invention will be explained below with reference to Examples and Comparative Examples.

Parts and percentages are by weight unless otherwise specified.

Reference Example 1 150 parts of succinic anhydride, 385 parts of Plaxel FM-1 (ε caprolactone and 2-hydroxyethyl methacrylate No. 1:
1 mol adduct, Daicel Chemical Co., Ltd.> and 500 ppm of hydroquinone monomethyl ether based on the total amount charged were charged at once, and then the mixture was stirred at an internal temperature of 150°C for 40 minutes while sucking air through the inlet tube. The reaction was carried out. After the reaction is completed, when the product is cooled to room temperature, a small amount of unreacted acid anhydride crystals precipitate, which are removed by filtration to obtain the desired reaction composition.

This reaction composition had an acid value of 172 and a viscosity of 250 cP (25
℃). The reaction rate was determined to be 96% by measuring the acid value of the reaction composition.

Reference Example 2 In a reactor similar to Reference Example 1, 60 parts of succinic anhydride, 440 parts of Plaxel FM-5 (a 5:1 molar adduct of ε-cabrolactone and 2-hydroxymethacrylate,
(manufactured by Daicel Chemical) and 500 pp for the total amount of preparation
Hydroquinone monomethyl ether (m) was charged all at once. Next, while introducing air, the internal temperature was 150°C.
The reaction was carried out by stirring for 0 minutes. After the reaction was completed, the product was cooled to room temperature, and a small amount of unreacted acid anhydride crystals precipitated, which were removed by filtration to obtain the desired reaction composition.

This reaction composition is a semi-solid with an acid value of 70 (25°
C), and the reaction rate was measured in the same manner as in Reference Example 1 and was 96%.

Reference Example 3 In a reactor similar to Reference Example 1, 98 parts of maleic anhydride, 480 parts of Plaxel FM-3 (a 3:1 molar adduct of ε-caprolactone and 2-hydroxymethacrylate,
(manufactured by Daicel Chemical) and 500 pp for the total amount of preparation
Hydroquinone monomethyl ether (m) was charged all at once. Next, while introducing air, the internal temperature was 150°C.
The reaction was carried out by stirring for 0 minutes.

The reaction composition had an acid value of 103 and a viscosity of 350 cP (25°C
)Met. Moreover, when the reaction rate was measured by the same method as in Reference Example 1, it was 95%.

Reference Example 4 Using the same reaction apparatus as Reference Example 1, 154 parts of tetrahydrophthalic anhydride and 420 parts of Bremmer PE-350 were added.
(7-9:1 molar adduct of ethylene oxide and methacrylic acid, NOF layer) and 500 p for the total amount charged
pm of hydroquinone monomethyl ether was charged all at once. Next, while introducing air, the internal temperature was 150°C.
The reaction was carried out by stirring for 0 minutes.

The reaction composition had an acid value of 103 and a reaction rate of 96%.

Reference Example 5 Using a reaction apparatus similar to Reference Example 1, 148 parts of phthalic anhydride, 400 parts of Blenmar P P-1000 (5.5:1 molar adduct of propylene oxide and methacrylic acid, NOF layer) and 500 ppm for the total amount
of hydroquinone monomethyl ether were charged all at once. The reaction was then carried out by stirring at an internal temperature of 150° C. for 60 minutes while introducing air.

The reaction composition had an acid value of 108 and a viscosity of 300 cP (25°C).
Met. Moreover, the reaction rate was 95%.

Reference Example 6 166 parts of dimethylaminopropyl methacrylamide (Texac) were placed in a one-pronged glass reaction flask equipped with a stirrer, a Dimroth, and a thermometer.

Ch=manufactured by mica1) and 72 parts of β-propiolactone were charged. Then, the internal temperature was increased to 100°C.
The reaction was carried out by stirring for 0 hours.

Chemical analysis revealed that the main reaction product was a quaternary ammonium salt (95% yield) based on the addition reaction of dimethylaminopropylmethacrylamide and β-propiolactone.

Reference Example 7 Using the same reaction apparatus as in Reference Example 6, 105 parts of 2-vinylpyridine and 72 parts of β-propiolactone were charged. The reaction was then carried out by stirring for 10 hours at an internal temperature of 100''C.

Chemical analysis shows that the main reaction products are 2-vinylpyridine and β
- It was found to be a quaternary ammonium salt (yield 97%) based on the addition reaction of propiolactone.

Example 1 After 230 parts of ion-exchanged water was charged in advance into a glass reaction flask equipped with a stirrer, a Dimroth, a thermometer, a dropping funnel, and a nitrogen introduction tube, Reference Example 1 was prepared.
4 parts of the reactive monomer synthesized in
) 2 parts, 30 parts of methyl methacrylate, 3 parts of styrene
A mixture of 0 parts and 40 parts of n-butyl acrylate was added dropwise to the flask using a dropping funnel while stirring at an internal temperature of 80°C for 2 hours. In addition, as an initiator, 1 part of 4.4'-azobis-4-cyanovaleric acid is neutralized with an alkali, and then dissolved in 20 parts of ion-exchanged water, which is added dropwise at the same time separately from the above mixed monomers. Emulsion polymerization was carried out by.

The solid content of the reaction product was 30% by weight, and the diameter of the emulsion particles was 80% by scanning transmission electron microscopy.
It was part m.

Example 2 In a reactor similar to Example 1, ion exchange water 2 was placed in advance.
After charging 40 parts, 6 parts of the reactive monomer synthesized in Reference Example 2, N-(3-sulfopropyl)-N-methacroyloxyethyl-dimethylammonium betaine (R
ASCHIG) 2 parts, methacrylamide propyltrimethylammonium chloride (Texaco C
Hemica1), 20 parts of 1,6-hexanethiol dimethacrylate, 10 parts of methyl methacrylate, 30 parts of styrene, and 40 parts of n-butyl acrylate were mixed using a dropping funnel to bring the internal temperature of the flask to 80.
The mixture was added dropwise while stirring at ℃ for 2 hours. Also, the initiator is 4
．． After 1 part of 4'-azobis-4-cyanovaleric acid was neutralized with an alkali, a solution dissolved in 20 parts of ion-exchanged water was simultaneously added dropwise to the mixture separately from the above mixed monomers, thereby carrying out emulsion polymerization.

The solid content of the reaction product was 30% by weight, and the emulsion particle diameter was 40% by scanning transmission electron microscopy.
It was part m.

Example 3 After charging 150 parts of ion-exchanged water in advance into a reaction apparatus similar to Example 1, 8 parts of the reactive monomer synthesized in Reference Example 2, 1-(3-sulfopropyl)- 2 parts of 2-vinylpyridinium betaine (RASCHIG), dimethylaminoneopentyl acrylate (BAS
A mixture of 4 parts (manufactured by Company F), 30 parts of methyl methacrylate, 30 parts of styrene, and 40 parts of n-butyl acrylate was added dropwise using a dropping funnel while stirring at an internal temperature of 80° C. for 2 hours. In addition, as an initiator, 1 part of 4,4'-azobis-4-cyanovaleric acid was mixed with 2 parts of ion-exchanged water.
Emulsion polymerization was carried out by simultaneously dropping a solution of 0 parts of the above-mentioned mixed monomers separately.

The solid content of the reaction product was 40% by weight, and the emulsion particle diameter was 25% by scanning transmission electron microscopy.
It was part m.

Example 4 In a reactor similar to Example 1, 24 ml of ion-exchanged water was placed in advance.
After charging 0 parts, 6 parts of the reactive monomer synthesized in Reference Example 2, 4 parts of Cibomer TBM (t-butylaminoethyl methacrylate, manufactured by Alcolac), 30 parts of methyl methacrylate, 30 parts of styrene, and n- A mixture of 40 parts of butyl acrylate was added dropwise to the flask using a dropping funnel while stirring at an internal temperature of 80° C. for 2 hours. In addition, as an initiator, 1 part of 4.4'-azobis-4-cyanovaleric acid is neutralized with an alkali, and then dissolved in 20 parts of ion-exchanged water, which is added dropwise at the same time separately from the above mixed monomers. Emulsion polymerization was carried out by.

The solid content of the reaction product was 30% by weight, and the emulsion particle diameter was 30% by scanning transmission electron microscopy.
It was part m.

Example 5 In a reactor similar to Example 1, 2
After charging 30 parts, 4 parts of the reactive monomer synthesized in Reference Example 3, and the quaternary ammonium salt synthesized in Reference Example 6 (
reactive monomer) 2 parts, dimethylaminoethyl methacrylate (manufactured by Sanyo Chemical Industries) 2 parts, methyl methacrylate 3
0 parts, 30 parts of styrene and 40 parts of n-butyl acrylate
Using a dropping funnel, mix the flask to a temperature of 8.
The mixture was added dropwise while stirring at 0°C for 2 hours. In addition, as an initiator, 1 part of 4.4'-azobis-4-cyanovaleric acid is neutralized with an alkali, and then dissolved in 20 parts of ion-exchanged water, which is added dropwise at the same time separately from the above mixed monomers. Emulsion polymerization was carried out by.

The solid content of the reaction product was 30% by weight, and the emulsion particle diameter was 40% by scanning transmission electron microscopy.
It was part m.

Example 6 In a reactor similar to Example 1, 4 quarts of ion-exchanged water was added in advance.
After charging 20 parts, 6 parts of the reactive monomer synthesized in Reference Example 4, and the quaternary ammonium salt synthesized in Reference Example 7 (
reactive monomer) 2 parts, dimethylaminoethyl acrylate (manufactured by BASF) 2 parts, methyl methacrylate 30 parts,
Using a dropping funnel, add a mixture of 30 parts of styrene and 40 parts of n-butyl acrylate to a flask with an internal temperature of 80°C.
The mixture was added dropwise while stirring for 2 hours. In addition, as an initiator, after neutralizing 1 part of 4゜4'-azobis-4-cyanovaleric acid with an alkali, the initiator dissolved in 20 parts of ion-exchanged water is added dropwise at the same time separately from the above mixed monomers. Emulsion polymerization was carried out by.

The solid content of the reaction product was 20% by weight, and the emulsion particle diameter was 70% by scanning transmission electron microscopy.
It was part m.

Example 7 In a reactor similar to Example 1, 2
After charging 30 parts, a mixture of 5 parts of the reactive monomer synthesized in Reference Example 5, 2 parts of 4-vinylpyridine, 30 parts of methyl methacrylate, 30 parts of styrene, and 40 parts of n-butyl acrylate was added to the dropping funnel. The mixture was added dropwise with stirring for 2 hours at an internal flask temperature of 80°C. In addition, the initiator is 4゜4'-azobis-4-cyanomulelic R1
After 1 part was neutralized with alkali, a solution dissolved in 20 parts of ion-exchanged water was added dropwise at the same time separately from the above mixed monomers, thereby carrying out emulsion polymerization.

The solid content of the reaction product was 30% by weight, and the emulsion particle diameter was 60% by scanning transmission electron microscopy.
It was part m.

Comparative Example 1 After charging 230 parts of ion-exchanged water in advance into the same reaction apparatus as in Example 1, 4 parts of methacrylic acid, dimethylaminobrobyl methacrylamide (Texaco
Chemica 1) 2 parts, methyl methacrylate 3
0 parts, 30 parts of styrene and 4 parts of n-butyl acrylate
A mixture of 0 parts was added dropwise to the flask using a dropping funnel while stirring at an internal temperature of 80° C. for 2 hours. In addition, as an initiator, 1 part of 4.4'-azobis-4-cyanovaleric acid is neutralized with an alkali, and then dissolved in 20 parts of ion-exchanged water, which is added dropwise at the same time separately from the above mixed monomers. Emulsion polymerization was carried out by.

However, during the dropping of the mixed monomer and aqueous initiator solution, the emulsion agglomerated and the entire system became a gel.

Comparative Example 2 In a reactor similar to Example 1, 1 1/2 ion-exchanged water was placed in advance.
After charging 200 parts, add 4 parts of methacrylic acid and Sibomer T.
A mixture of 2 parts of B M (manufactured by Alcolac), 30 parts of methyl methacrylate, 30 parts of styrene, and 40 parts of n-butyl acrylate was added dropwise to the flask using a dropping funnel while stirring at an internal temperature of 80°C for 2 hours. .

In addition, as an initiator, 1 part of 4.4'-azobis-4-cyanovaleric acid is neutralized with an alkali, and then dissolved in 20 parts of ion-exchanged water, which is added dropwise at the same time separately from the above mixed monomers. Emulsion polymerization was carried out by.

The solid content of the reaction product was 8% by weight, and the emulsion particle diameter was 400% by scanning transmission electron microscopy.
It was part m.

Example 8 After adding a small amount of ethylene glycol monobutyl ether as a thickener to the emulsion varnishes of Examples 1 to 7 (excluding Example 2 for internally crosslinked particles) and Comparative Example 2, a glass plate was prepared using a doctor blade. expanded above.

After heating in an oven at 60° C. for 20 minutes, the film forming properties of the formed film were visually determined.

The results are shown in Table 1.

Chapter 1 Table Judgment results of emulsion film-forming properties patent application agent

Claims (4)

[Claims] (1) (A) Formula▲There are mathematical formulas, chemical formulas, tables, etc.▼...[I] (In the formula, R_1 is hydrogen or a methyl group; R_2 has 2 to 10 carbon atoms, which may have a substituent. aliphatic hydrocarbons, alicyclic hydrocarbons with 6 to 7 carbon atoms, aromatic hydrocarbons with 6 carbon atoms; repeating unit; R_3 is ethylene or propylene; R_4 is alkylene having 2 to 7 carbon atoms which may have a substituent; R
_5 is an alkylene having 2 to 5 carbon atoms which may have a substituent; m and n are the average values of the number of repeating units; m is 1 to 10 or n is 2 to 50; however, the terminal carboxyl group is an inorganic or neutralized with an organic base) 1 to 25% by weight of at least one reactive vinyl monomer having a terminal carboxyl group represented by (B) an amino group or a cyclic nitrogen atom in the molecule. Alternatively, 1 to 25% by weight of at least one of these reactive vinyl monomers having a basic group having an onium structure, and (C) 98% by weight of at least one of the other reactive vinyl monomers.
An emulsion polymerization composition obtained by emulsion polymerization of ~50% by weight in an aqueous medium. (2) The reactive vinyl monomer having an amino group or its onium structure has the formula ▲ Numerical formula, chemical formula, table, etc. ▼... (II) (In the formula, R_1 is hydrogen or a methyl group; R_6 and R_7
is hydrogen or an alkyl group with 1 to 4 carbon atoms which may have a substituent;
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ R_8 is hydrogen or an alkyl group with 1 to 4 carbon atoms; k, l, and m are each 2 to 6 (Integer number) or formula ▲ Numerical formula, chemical formula, table, etc. ▼... (II) (In the formula, R_1, R_6, R_7, and B are each as described above; R_9 is a carbon that may have a substituent. Number 1~
12 alkyl; alkylene having 2 to 6 carbon atoms, which may be present; D is -SO_3, -COO, or ▲a mathematical formula, a chemical formula, a table, etc.▼; the composition according to claim 1; . (3) A reactive vinyl monomer having a cyclic nitrogen atom or its onium structure has the formula ▲mathematical formula, chemical formula, table, etc.▼...(V) (In the formula, R_1 is hydrogen or a methyl group; E is ▲mathematical formula , chemical formulas, tables, etc. ▼, ▲ mathematical formulas, chemical formulas,
There are tables, etc. ▼, or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables etc. Represents ▼; R_1_1 is an alkyl group; There are chemical formulas, tables, etc. ▼) The composition according to claim 1. (4) Crosslinking in which the other reactive vinyl monomer is either a compound having two or more α,β-ethylenically unsaturated bonds or two types of reactive vinyl compounds each carrying functional groups that react with each other. 2. The composition according to claim 1, which comprises a monomer.