JPH09309906A - Manufacture of resin aqueous dispersion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin aqueous dispersion having both the properties of an aqueous resin and the properties of an emulsion resin and quite excellent in water resistance by polymerizing a radicalpolymerizable unsaturated monomer component in three specified steps. SOLUTION: A monomer component (A) comprising, as an essential component, a radical-polymerizable unsaturated monomer (hereinafter referred to as monomer) containing a carboxyl group, a sulfonic acid group, or a phosphoric acid group or an anionically functional groupcontaining monomer (A-1), i.e., the salt of the monomer is polymerized in water in the presence of a chain transfer agent to produce a copolymer aqueous product (A') (step 1), a monomer (B) containing a carboxyl group-containing monomer (B-1) and other monomer (B-2) in a weight ratio of (5-50)/(95-50) is polymerized in the presence of (A') and a chain transfer agent to produce a copolymer aqueous product (B') having a number-average molecular weight of 500 to 20,000 (step 2), and a monomer component (C) is polymerized in the presence of (B') (step 3) to obtain a resin aqueous dispersion.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an aqueous resin dispersion which has the characteristics of both a water-soluble resin and an emulsion resin and is more excellent in water resistance than conventional methods. The present invention provides a method for producing an aqueous resin dispersion useful as a fiber processing, civil engineering, building material, printing material, adhesive, ink and other various coating agents, binders and additives.

[0002]

2. Description of the Related Art In recent years, the demand for water-based resins has been increasing year by year because the improvement of the global environment has been rapidly promoted as a social issue due to laws and regulations.

Water-based resins can be roughly classified into water-soluble resins and water-dispersible resins. Those obtained by the former have advantages such as film-forming property, good gloss, no emulsifier, and fluidity characteristics close to solvent-based resins, but on the other hand, high non-volatile differentiation is difficult,
Since it is synthesized by solution polymerization, it has transfer emulsification and desolvation steps, so that it has drawbacks such as poor productivity and use of an organic solvent at the resin synthesis stage. On the other hand, a water-dispersible resin, so-called emulsion resin, is generally synthesized by emulsion polymerization, and thus has a high molecular weight and excellent physical strength and durability,
It has the advantages that it does not use organic solvents at all, does not have phase inversion emulsification and desolvation steps, and has a high polymerization rate and thus good productivity, but on the other hand, it uses an emulsifier and forms a film because it is in a particulate state. It has drawbacks such as poor properties and gloss. Further, the emulsion resin has a characteristic of having thixotropy, but this property serves as an advantage for the sauce, but on the other hand, thick coating property,
Leveling works as a drawback.

That is, although each of the water-soluble resin and the emulsion resin has its own characteristics, there are merits and demerits, and in the present situation, neither of them is sufficient in terms of conversion from a solvent resin to an aqueous resin. Therefore, various studies have been conducted on the development of a resin having both the characteristics of a water-soluble resin and an emulsion resin.

For example, JP-A-6-145262 discloses that an alkali-soluble polymer or an alkali-insoluble polymer is copolymerized with a monomer having a plurality of unsaturated groups, and the two polymers are crosslinked to obtain good durability. A technique for obtaining a water-based resin is disclosed.

Further, in JP-A-7-118544, a carboxyl group-containing polymer obtained by emulsion polymerization in the presence of a reactive emulsifier is used as a dispersant to contain a monomer containing a glycidyl group, an amino group or an amide group. There is disclosed a technique relating to an aqueous resin which has no coating unevenness by emulsion polymerization of a monomer and has good blocking resistance.

[0007]

However, Japanese Patent Application Laid-Open No.
Since it is difficult to stably leave the unsaturated group by the method described in JP-A-145262, the crosslinking efficiency between the alkali-soluble polymer and the alkali-insoluble polymer is extremely poor, and the water resistance of the resulting coating film is low. There was a problem that it was inferior to.

[0008] Further, in the patent, it is reported that the durability is improved by introducing an amino group into the alkali-insoluble polymer, but this method has a drawback that the selection of polymerization conditions is extremely difficult. However, the water resistance of the obtained resin was not improved even if it could be polymerized.

Further, in the method described in JP-A-7-118544, the water resistance is improved by using a reactive emulsifier. This method is expected to reduce free emulsifiers, but free emulsifiers will inevitably remain due to the polymerizability problem of reactive emulsifiers, and by copolymerizing reactive emulsifiers, hydrophilic groups can be added to the polymer main chain. However, there is a problem that sufficient water resistance cannot be obtained due to the reason that the water resistance of the polymer itself is rather deteriorated by introducing the above.

The problem to be solved by the present invention is to provide a method for producing an aqueous resin dispersion which has the characteristics of both an aqueous resin and an emulsion resin and is particularly excellent in water resistance as compared with conventional methods. .

[0011]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a radical-polymerizable monomer containing an anionic functional group-containing radical-polymerizable unsaturated monomer as an essential component is used. In the presence of an aqueous copolymer (A ') obtained by polymerizing a saturated monomer in water in the presence of a chain transfer agent,
Carboxyl group-containing radically polymerizable unsaturated monomer (B-
1) and other radically polymerizable unsaturated monomer (B-2)
And (B-1) / (B-2) weight ratio (5-50) /
The radically polymerizable unsaturated monomer component (B) contained at a ratio of (95 to 50) is polymerized in water in the presence of a chain transfer agent to give a copolymer aqueous product (B ′ having a number average molecular weight of 500 to 20,000). ) Is produced and then the radically polymerizable unsaturated monomer component (C) is polymerized in the presence of the resulting aqueous copolymer (B ′) to obtain a resin aqueous solution having better water resistance than the conventional method. It was found that a dispersion was obtained, and the present invention was completed.

That is, in the present invention, the radically polymerizable unsaturated monomer component (A) containing the anionic functional group-containing radically polymerizable unsaturated monomer (A-1) as an essential component is used in the presence of a chain transfer agent. To produce a copolymer aqueous product (A ') in water (step 1), and in the presence of the copolymer aqueous product (A'), a carboxyl group-containing radically polymerizable unsaturated monomer ( B-
1) and other radically polymerizable unsaturated monomer (B-2)
And (B-1) / (B-2) weight ratio (5-50) /
The radically polymerizable unsaturated monomer component (B) contained at a ratio of (95 to 50) is polymerized in water in the presence of a chain transfer agent to give an aqueous copolymer aqueous product having a number average molecular weight of 500 to 20,000. (B ') is produced (step 2), and then the radical polymerizable unsaturated monomer component (C) is added in the presence of the aqueous copolymer (A') and the aqueous copolymer (B '). It relates to a method for producing an aqueous resin dispersion, which comprises polymerizing (step 3).

The details of the invention will be described below.

The aqueous copolymer (A ') in step 1 can be produced in water, and the anionic functional group-containing radically polymerizable unsaturated monomer (A-1) is an essential component. . Anionic functional group-containing radical polymerizable unsaturated monomer (A-1) is a carboxyl group-containing radical polymerizable unsaturated monomer, sulfonic acid group-containing radical polymerizable unsaturated monomer, phosphoric acid group-containing radical A polymerizable unsaturated monomer or a salt thereof is meant, and as some of these specific examples, a carboxyl group-containing radically polymerizable unsaturated monomer is acrylic acid, methacrylic acid, maleic acid, fumaric acid, Itaconic acid, crotonic acid, itaconic acid half ester, maleic acid half ester, maleic anhydride, itaconic anhydride, 2-methacryloylpropionic acid, 2-methacryloyloxyethylphthalic acid and their sodium salts, potassium salts, ammonium salts, etc. Can be mentioned again
As the sulfonic acid group-containing radically polymerizable unsaturated monomer, vinyl sulfonic acid, styrene sulfonic acid, acrylamide tertiary butyl sulfonic acid, methacrylic acid polyoxyethylene sulfonic acid, polyoxyethylene alkenyl phenyl sulfonic acid and sodium salts thereof, Examples thereof include potassium salts and ammonium salts, and examples of the phosphoric acid group-containing radically polymerizable unsaturated monomer include mono 2- (methacryloyloxyethyl) acid phosphate and mono (2-
Examples thereof include acryloyloxyethyl) acid phosphate and their sodium, potassium and ammonium salts. Of course, it is possible to use these together.

In the present invention, the radical-polymerizable unsaturated monomer component (A) is used as the radical-polymerizable unsaturated monomer component (A), in addition to the monomer (A-1), and other radical-polymerizable unsaturated monomer components copolymerizable therewith. A saturated monomer (A-2) can be used. The other radically polymerizable unsaturated monomer (A-2) is not particularly limited as long as it can be generally used for radical polymerization reaction.

Specific examples of the radically polymerizable unsaturated monomer (A-2) include acrylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate; methacryl Methacrylic acid esters such as methyl acidate, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate; maleic acid, fumaric acid, itaconic acid esters; vinyl acetate, vinyl propionate, vinyl tertiary carboxylate, etc. Esters; Aromatic vinyl compounds such as styrene and vinyltoluene, Heterocyclic vinyl compounds such as vinylpyrrolidone; Vinyl chloride, acrylonitrile, vinyl ether, vinyl ketone, vinylamide, etc .; Vinylidene chloride, vinylidene fluoride and other vinylidene halide compounds; Ethylene, Professional Α-olefins such as lens; dienes such as butadiene; and, if desired, amides of α, β-ethylenically unsaturated acids such as acrylamide, methacrylamide, maleic acid amide; glycidyl methacrylate, allyl glycidyl ether, etc. Glycidyl group-containing monomer; 2-hydroxyethyl methacrylate and other hydroxyl group-containing monomer; dimethylaminoethyl methacrylate and other amino group-containing monomer; N-methylol acrylamide or methacrylamide, diacetone acrylamide and other unsaturated carboxylic acid substituted amides; γ
-Unsaturated bond-containing silane compounds such as methacryloxypropyltrimethoxysilane; monomers such as diallyl phthalate, divinylbenzene, allyl acrylate and trimethylolpropane trimethacrylate having two or more unsaturated bonds in one molecule. Can be mentioned. Of course, it is possible to use these together.

The ratio of the radically polymerizable unsaturated monomer (A-1) containing an anionic functional group to be used is not particularly limited, but in the radically polymerizable unsaturated monomer component (A). , The radical polymerizable unsaturated monomer (A-2) is
From the viewpoint of dispersion stability, it is preferably in the range of 50% by weight or less.

In the production of the aqueous copolymer (A ') in step 1, the use of a chain transfer agent is an essential condition. The chain transfer agent to be used is not particularly limited, and specific examples thereof include alkyl mercaptans such as n-octyl mercaptan, n-lauryl mercaptan, t-hexadecyl mercaptan, benzyl mercaptan, and alkyl such as dodecylbenzyl mercaptan. Benzyl mercaptans, thiocarboxylic acids such as thioglycolic acid, thiomalic acid or salts thereof, n-butyl thioglyconate, dodecyl-3-mercaptopropionate, octyl thioglycolate, thiobutyl carboxylic acid alkyl esters such as methoxybutyl thioglycolate , Nitrogen-containing thiols typified by monoethanolamine thioglycolate, reactive functional group-containing mercaptans typified by trimethoxysilylpropyl mercaptan, α-methylstyrene dimer, etc. Immersion-type chain transfer agents. In addition to these, organic amines such as triethylamine and tributylamine, alcohols such as n-butyl alcohol and i-propyl alcohol, organic solvents such as carbon tetrachloride and acetaldehyde, and the like can be mentioned. Of course, it is possible to use these together. The chain transfer agent is used in an amount of 0.1 to 50 parts by weight, preferably 1 to 20 parts by weight, per 100 parts by weight of the radically polymerizable unsaturated monomer component (A).

That is, when the amount is 0.1 parts by weight or more, it becomes easy to adjust the molecular weight of the obtained aqueous copolymer (A ') to an appropriate range, and when the amount is 50 parts by weight or less, the amount of the low molecular weight component is reduced. It can be suppressed, and water resistance and the like can be further improved.

The aqueous copolymer (A ') can be produced by radical polymerization in water, and the method is not particularly limited. For example, radically polymerizable unsaturated monomer component (A) 1
For each 100 parts by weight, 0.1 to 20 parts by weight of the radical polymerization initiator and 50 to 1000 parts by weight of the aqueous medium are used.
It can be polymerized at 90 ° C.

It is also possible to carry out redox polymerization using 0.1 to 20 parts by weight of the above initiator and a reducing agent.
At this time, a compound that generates a polyvalent metal salt ion such as iron ion or copper ion can be used together as an accelerator. Radical polymerization initiators that can be used in the above reaction include persulfates such as potassium persulfate, ammonium persulfate and sodium persulfate, azobisisobutyronitrile and its hydrochloride, 4,4′-azobis (4-cyano). Valeric acid), 2,2'-azobis (2-amidinopropane)
Examples thereof include azo-based initiators such as dihydrochloride, hydrogen peroxide, peroxide-based initiators such as tertiary butyl hydroperoxide and cumene hydroperoxide. Also,
Examples of reducing agents that can be used in combination with these radical initiators include sodium sulfoxylate formaldehyde, sodium pyrosulfite, and L-ascorbic acid. Also,
The radically polymerizable unsaturated monomer, the radical initiator, and the reducing agent can be added by a known technique such as batch charging, continuous dropping, and divided addition.

Next, in the present invention, in step 2, the aqueous copolymer (A ') obtained in step 1 is used as a dispersion stabilizer to polymerize the radically polymerizable unsaturated monomer component (B). ,
An aqueous copolymer (B ') is produced.

Here, the radical-polymerizable unsaturated monomer component (B) includes the carboxyl group-containing radical-polymerizable unsaturated monomer (B-1) and other radical-polymerizable unsaturated monomers ( B-2) is contained as an essential component.

As the carboxyl group-containing radically polymerizable unsaturated monomer (B-1) that can be used here, any one conventionally used in radical polymerization can be used without any particular problem. Specific examples include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, itaconic acid half ester, maleic acid half ester, maleic anhydride, itaconic anhydride,
2-methacryloyl propionic acid, 2-methacryloyl oxyethyl phthalic acid, etc. are mentioned. Of course, it is not limited to these, and it is also possible to use them together.

Further, the other radically polymerizable unsaturated monomer (B-2) is not particularly limited, and any one generally used in radical polymerization can be used. For example, Acrylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate; methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate; maleic acid , Esters of fumaric acid and itaconic acid; vinyl esters such as vinyl acetate, vinyl propionate and tertiary vinyl carboxylate; aromatic vinyl compounds such as styrene and vinyltoluene; heterocyclic vinyl compounds such as vinylpyrrolidone ; Vinyl chloride, acrylonitrile, vinyl ether, Niruketon, vinyl amide, and the like;
Vinylidene halides such as vinylidene chloride and vinylidene fluoride; α-olefins such as ethylene and propylene; dienes such as butadiene, diallyl phthalate,
Examples thereof include monomers having two or more unsaturated bonds in one molecule such as divinylbenzene, allyl acrylate, and trimethylolpropane trimethacrylate.

Further, as the other radical-polymerizable unsaturated monomer (B-2), radical-polymerization having a reactive functional group other than the carboxyl group and having a reactive functional group which is non-reactive with the unsaturated group Radical Polymerizable Unsaturated Monomer (C-1), Which Will Be Described Later in Use of Organic Unsaturated Monomer (B-2-2)
And the crosslinking reaction with the functional group in (C-2) is preferable because the water resistance of the finally obtained resin aqueous dispersion can be remarkably improved.

The radical polymerizable unsaturated monomer (B-2-2) having a reactive functional group other than the carboxyl group and having a reactive functional group which is non-reactive with the unsaturated group is not particularly limited. Glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether and other radically polymerizable unsaturated monomers such as glycidyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, allyl alcohol, polyethylene Radical-polymerizable unsaturated monomers containing hydroxyl groups such as glycol monoacrylate and glycerol monomethacrylate: amino group-containing radicals such as aminoethyl methacrylate, N-alkylaminoethyl methacrylate and N, N-dialkylaminoethyl methacrylate Polymerizable unsaturated monomers: N- methylolacrylamide, N- alkoxymethyl alkylol amide group-containing radical polymerizable acrylamide unsaturated monomers: acrylamide, methacrylamide, N-
Amide group-containing radical-polymerizable unsaturated monomer such as alkylacrylamide: 2-acetoacetoxy group-containing radical-polymerizable unsaturated monomer such as 2-acetoacetoxyethyl methacrylate: vinyltrichlorosilane, vinyltrimethoxysilane, γ-methacryloxy Radical-polymerizable unsaturated monomers containing hydrolyzable silyl groups such as propyltrimethoxysilane and γ-methacryloylpropyldiethoxymethylsilane: acryloyl isocyanate, acryloyl isocyanate, radical polymerization of isocyanate adducts such as phenol adducts of ethyl Unsaturated monomer: acrolein, diacetone acrylamide, alkyl vinyl ketone, crotonaldehyde: carbonyl group-containing radical-polymerizable unsaturated monomer: glyceryl cyclocarbonate acrylate, glyceryl silane Glyceryl cyclocarbonate group-containing radical-polymerizable unsaturated monomers such as chlorocarbonate methacrylate: 2-isopropenyl-2-oxazoline, oxazoline-group-containing radical polymerizable unsaturated monomers such as 2-vinyl-2-oxazoline, and the like. To be

The amounts of the carboxyl group-containing radically polymerizable unsaturated monomer (B-1) and the other radically polymerizable unsaturated monomer (B-2) used are (B-1) :( B-2). = (5
To 50): (95 to 50), preferably (B-1): (B-2) = (5 to 30): (95 to 7).
0).

That is, (B-1) :( B-2) = 5 or more: 9
When it is 5 or less, the characteristics as an aqueous resin are good, and when (B-1) :( B-2) = 50 or less: 50 or more, the water resistance is remarkably excellent.

In the polymerization of the radically polymerizable unsaturated monomer component (B), the amount of the aqueous copolymer (A ') used is the total amount of the radically polymerizable unsaturated monomer (B). 1
The solid content is preferably 0.5 to 10 parts by weight, more preferably 1.5 to 8 parts by weight, per 100 parts by weight.

That is, if it is 0.5 parts by weight or more, the polymerization stability of the aqueous copolymer (B ') will be good, and if it is 10 parts by weight or less, the water resistance of the final emulsion obtained will be remarkably improved.

Also in step 2, the copolymer (B ')
A chain transfer agent is used as an essential component in order to control the number average molecular weight of 1 to 500 to 20,000. The chain transfer agent is not particularly limited, and examples thereof include alkyl mercaptans such as n-octyl mercaptan, n-lauryl mercaptan, and t-hexadecyl mercaptan; alkylbenzyl mercaptans such as benzyl mercaptan and dodecyl benzyl mercaptan; thioglycolic acid; Thiocarboxylic acids such as thiomalic acid or salts thereof, thiocarboxylic acid alkyl esters such as n-butyl thioglyconate, dodecyl-3-mercaptopropionate, octyl thioglycolate and methoxybutyl thioglycolate,
Nitrogen-containing thiols represented by monoethanolamine thioglycolate, mercaptans containing reactive functional groups represented by trimethoxysilylpropyl mercaptan, α
-A dimer type chain transfer agent such as methylstyrene dimer and the like. In addition, organic amines such as triethylamine and tributylamine, n-butyl alcohol,
Alcohols such as i-propyl alcohol, organic solvents such as carbon tetrachloride, acetaldehyde and the like are also included.

The amount of the chain transfer agent used varies depending on the type of the radically polymerizable unsaturated monomer component (B) and the type of the chain transfer agent, but is 0.5 per 100 parts by weight of the radically polymerizable unsaturated monomer. It is preferably about 50 parts by weight.

In the production of the aqueous copolymer (B ') in step 2, it is preferable to carry out soap-free emulsion polymerization without using an emulsifier from the viewpoint of water resistance, but it is unavoidable from the viewpoint of polymerization stability. In this case, an emulsifier may be used, but in that case, the amount of the emulsifier used must be minimized, and a reactive emulsifier is more preferable. There is no particular limitation on the emulsifier that can be used. Typical examples are sodium alkylbenzene sulfonate, sodium alkyl sulfate, sodium dialkyl sulfosuccinate, anionic emulsifiers such as alkylphenyl polyoxyethylene sulfate soda salt or ammonium salt,
Polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene
Examples thereof include nonionic emulsifiers such as polyoxypropylene block copolymers.

Specific examples of the reactive emulsifier include sodium vinyl sulfonate, sodium styrene sulfonate, polyoxyethylene ammonium sulfate acrylate, sodium polyoxyethylene sulfonate methacrylic acid, ammonium polyoxyethylene alkenyl phenyl sulfonate,
Anionic reactive emulsifiers such as polyoxyethylene alkenyl phenyl sulphate sodium, sodium allylalkyl sulfosuccinate, sodium methacrylic acid polyoxypropylene sulfonate, nonionic reactive emulsifiers such as polyoxyethylene alkenyl phenyl ether, polyoxyethylene methacryloyl ether, etc. Is mentioned.

Further, generally commercially available reactive emulsifiers such as Aqualon HS-10, New Frontier A-229E (all manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), Adecaria Soap SE-3N, SE-5N, SE-10N, SE
-20N, SE-30N (all manufactured by Asahi Denka Co., Ltd.),
Antox MS-60, MS-2N, RA-1120,
RA-2614 (manufactured by Nippon Emulsifier Co., Ltd.), Eleminol JS-2, RS-30 (manufactured by Sanyo Chemical Industry Co., Ltd.)
Manufactured), Latemur S-120A, S-180A, S-18
0 (above Kao Co., Ltd.) and other anionic reactive surfactants, Aqualon RN-20, RN-30, RN-50,
New Frontier N-177E (all manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), ADEKA REASOAP NE-10, NE-2
0, NE-30, NE-40 (above Asahi Denka Co., Ltd.)
Manufactured), RMA-564, RMA-568, RMA-11
14 (all manufactured by Nippon Emulsifier Co., Ltd.), NK ester M-2
Nonionic reactive surfactants such as 0G, M-40G, M-90G and M-230G (all manufactured by Shin-Nakamura Chemical Co., Ltd.) as long as they are generally used in emulsion polymerization reaction. It can be used without any problems. Of course, it is also possible to use a commercially available reactive surfactant other than these.

In the production of the aqueous copolymer (B '), the reaction can be carried out by a commonly used emulsion polymerization method except that the aqueous copolymer (A') is used as the dispersion stabilizer. it can. That is, 0.1 parts by weight of the radical polymerization initiator per 100 parts by weight of the radically polymerizable unsaturated monomer component (B).
Polymerization can be carried out at 40 to 90 ° C. using 10 to 10 parts by weight and 50 to 1000 parts by weight of an aqueous medium. It can also be carried out by redox polymerization in which 0.1 to 10 parts by weight of the above-mentioned initiator is used in combination. At this time, a compound that generates a polyvalent metal salt ion such as iron ion or copper ion can be used together as an accelerator. As the radical polymerization initiator that can be used in the above reaction, potassium persulfate, ammonium persulfate, persulfates such as sodium persulfate,
Azobisisobutyronitrile and its hydrochloride, 2,2 '
-Azobis (2-amidinopropane) dihydrochloride, 4,
Examples thereof include azo initiators such as 4′-azobis (4-cyanovaleric acid), peroxide initiators such as hydrogen peroxide, tertiary butyl hydroperoxide and cumene hydroperoxide. Examples of reducing agents that can be used in combination with these radical initiators include sodium sulfoxylate formaldehyde, sodium pyrosulfite, and L-ascorbic acid. The radical-polymerizable unsaturated monomer, the radical initiator, and the reducing agent can be added by a known technique such as batch charging, continuous dropping, and divided addition.

The aqueous copolymer (B ') thus obtained has a number average molecular weight of 500 to 200 as described above.
It must be in the range of 00. That is, when it is 500 or less, the characteristics as an aqueous resin may not be exhibited in some cases, and when it is 20,000 or more, polymerization of the aqueous copolymer (C ′) may not be successful.

Next, in the present invention, as step 3, the radically polymerizable unsaturated monomer component (C) is added in the presence of the aqueous copolymer (A ') and the aqueous copolymer (B'). By polymerizing, the desired resin aqueous dispersion can be obtained.

The radical-polymerizable unsaturated monomer component (C) that can be used is not particularly limited, and any of those generally used for radical polymerization can be used. Specific examples include acrylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate;
Methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate; maleic acid, fumaric acid, itaconic acid esters; vinyl acetate, vinyl propionate, tertiary carboxylate vinyl, etc. Vinyl esters; aromatic vinyl compounds such as styrene and vinyltoluene, heterocyclic vinyl compounds such as vinylpyrrolidone; vinyl chloride, acrylonitrile, vinyl ether, vinyl ketone, vinylamide, etc .; vinylidene chloride, vinylidene fluoride, and other vinylidene halide compounds; ethylene. , Α-olefins such as propylene; dienes such as butadiene; and, if desired, amides of α, β-ethylenically unsaturated acids such as acrylamide, methacrylamide, maleic acid amide; Glycidyl group-containing monomers such as acrylate and allyl glycidyl ether; hydroxyl group-containing monomers such as 2-hydroxyethyl methacrylate; amino group-containing monomers such as dimethylaminoethyl methacrylate; unsaturated carboxylic acids such as N-methylol acrylamide or methacrylamide, diacetone acrylamide Substituted amide of acid; unsaturated bond-containing silane compound such as γ-methacryloxypropyltrimethoxysilane; two or more unsaturated bonds in one molecule such as diallyl phthalate, divinylbenzene, allyl acrylate and trimethylolpropane trimethacrylate. Having monomers, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, itaconic acid half ester, maleic acid half ester, maleic anhydride, anhydride Taconic acid,
Examples thereof include acid monomers such as 2-methacryloyl propionic acid and 2-methacryloyloxyethyl phthalic acid. Of course, it is not limited to these, and it is also possible to use them together.

The amount of the aqueous copolymer (A ') and the aqueous copolymer (B') used in step 3 is not particularly limited, but the radically polymerizable unsaturated monomer component is used. The total solid content of the aqueous copolymer (A ') and the aqueous copolymer (B') per 100 parts by weight of (C) is preferably in the range of 10 to 1000 parts by weight. That is, when it is 10 parts by weight or more, the characteristic as an aqueous resin becomes remarkable, and when it is 1000 parts by weight or less, the property as an emulsion resin becomes remarkable.

In step 3, except that the aqueous copolymer (A ') and the aqueous copolymer (B') are used as the dispersion stabilizer, the reaction is carried out by a commonly used emulsion polymerization method. You can That is, per 100 parts by weight of the radically polymerizable unsaturated monomer component (C), 0.1 to 10 parts by weight of a radical polymerization initiator is used, and 50 to 1000 parts by weight of an aqueous medium is used to perform polymerization at 40 to 90 ° C. Can be done. Also,
It can also be carried out by redox polymerization using 0.1 to 10 parts by weight of the above initiator and a reducing agent. At this time, a compound that generates a polyvalent metal salt ion such as iron ion or copper ion can be used together as an accelerator. As the radical polymerization initiator that can be used in the above reaction, any of those exemplified in step 2 can be used. The radical-polymerizable unsaturated monomer component (C), the radical initiator, and the reducing agent can be prepared by a known technique such as batch charging, continuous dropping, and divided addition.

In the present invention, the pH is neutralized at any stage.
By setting it to> 7, the properties as an aqueous resin become more remarkable. If the final pH is 7 or more, the neutralization step can be performed at any stage, for example, before step 2, during step 2, after step 2 after step 3, before step 3, during step 3, After the end of 3, any step may be used. Further, among these, it may be divided into several stages for neutralization, or may be neutralized by continuously adding a neutralizing agent.

At this time, the neutralizing agent that can be used is not particularly limited, and any commonly used neutralizing agent can be used. Specific examples include inorganic bases such as sodium hydroxide, potassium hydroxide and borax, alkylamines such as methylamine, isobutylamine and triethylamine, alkanolamines such as dimethylethanolamine, ammonia and the like. Of course, it is not limited to these, and plural kinds of these may be used in combination.

As the radical-polymerizable unsaturated monomer component (C) used in step 3, a radical-polymerizable unsaturated monomer (C-1) having a functional group reactive with a carboxyl group is used. By introducing and making it a self-crosslinking type, it becomes possible to provide a resin aqueous dispersion having more excellent durability.

Examples of the radical-polymerizable unsaturated monomer (C-1) having a functional group reactive with a carboxyl group include glycidyl group-containing radical-polymerizable unsaturated monomers such as glycidyl acrylate, glycidyl methacrylate and allyl glycidyl ether. Polymer: 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-
Hydroxyl radical-containing unsaturated monomers such as hydroxypropyl methacrylate, allyl alcohol, polyethylene glycol monoacrylate, glycerol monomethacrylate: N-methylol acrylamide, N-
Radical-polymerizable unsaturated monomers containing alkylolamide groups such as alkoxymethyl acrylamide: Acryloyl isocyanate, radical-polymerizable unsaturated monomers containing isocyanate groups such as phenol adducts of acryloyl isocyanate ethyl: acrolein, diacetone Carbonyl group-containing radically polymerizable unsaturated monomer such as acrylamide, alkyl vinyl ketone, crotonaldehyde: Glyceryl cyclocarbonate acrylate, glyceryl cyclocarbonate group-containing radically polymerizable unsaturated monomer: 2-iso Examples include radical-polymerizable unsaturated monomers containing an oxazoline group such as propenyl-2-oxazoline and 2-vinyl-2-oxazoline. Among these, the glycidyl group-containing radically polymerizable unsaturated monomer is particularly preferable.

At this time, the radical-polymerizable unsaturated monomer (C-1) having a functional group reactive with a carboxyl group
Is used in an amount of 0.1 to 50 parts by weight, preferably 0.2 to 1 per 100 parts by weight of the radically polymerizable unsaturated monomer (C).
0 parts by weight is preferred. That is, when the amount is 0.1 parts by weight or more, the crosslinking effect is sufficiently exhibited, and when the amount is 50 parts by weight or less, the polymerization stability becomes good.

Further, as described above, in order to further increase the crosslinking efficiency, the radical polymerizable unsaturated monomer component (B-2) is used.
As a reactive functional group other than a carboxyl group,
Introducing a radical-polymerizable unsaturated monomer (B-2-2) having a reactive functional group that is non-reactive with an unsaturated group, (C-1)
It is also possible to increase the crosslink density by crosslinking with. Here, as a specific example of a preferable combination of (B-2-2) and (C-1), when a glycidyl group-containing radically polymerizable unsaturated monomer is used as (B-2-2), a glycidyl group is used. Examples of the radical-polymerizable unsaturated monomer (C-1) having a functional group capable of reacting with: an alkylolamide group-containing radical-polymerizable unsaturated monomer, a hydroxyl-group-containing radical-polymerizable unsaturated monomer, glycidyl Examples thereof include a radical-containing unsaturated monomer having a group.

When a radically polymerizable unsaturated monomer containing a hydroxyl group is used as (B-2-2), the radically polymerizable unsaturated monomer (C-1) having a functional group capable of reacting with a hydroxyl group.
As the alkylolamide group-containing radical polymerizable unsaturated monomer, carbonyl group-containing radical polymerizable unsaturated monomer, isocyanate group-containing radical polymerizable unsaturated monomer, glycidyl group-containing radical polymerizable unsaturated monomer. And a glyceryl cyclocarbonate group-containing radically polymerizable unsaturated monomer, an oxazoline group-containing radically polymerizable unsaturated monomer, and the like.

When the radical polymerizable unsaturated monomer containing an alkylolamide group is used as (B-2-2), the radical polymerizable unsaturated monomer having a functional group capable of reacting with the alkylolamide group (C -1) is a radical-polymerizable unsaturated monomer containing an isocyanate group, a radical-polymerizable unsaturated monomer containing an alkylolamide group, a radical-polymerizable unsaturated monomer containing a hydroxyl group, a radical-polymerizable unsaturated monomer containing a glycidyl group. Examples thereof include saturated monomers and glyceryl cyclocarbonate group-containing radically polymerizable unsaturated monomers.

When a radical-polymerizable unsaturated monomer containing an acetoacetyl group is used as (B-2-2), the radical-polymerizable unsaturated monomer having a functional group capable of reacting with an acetoacetyl group (C-1 ) Is an alkylolamide group-containing radical-polymerizable unsaturated monomer, a glycidyl group-containing radical-polymerizable unsaturated monomer, an isocyanate group-containing radical-polymerizable unsaturated monomer, a glyceryl cyclocarbonate group-containing radical polymerization And unsaturated unsaturated monomers.

When a hydrolyzable silyl group-containing radical-polymerizable unsaturated monomer is used as (B-2-2), the radical-polymerizable unsaturated monomer having a functional group capable of reacting with a silyl group (C- Examples of 1) include a radical-polymerizable unsaturated monomer containing a hydroxyl group and a radical-polymerizable unsaturated monomer containing an alkylolamide group.

When a carbonyl group-containing radically polymerizable unsaturated monomer is used as (B-2-2), the radically polymerizable unsaturated monomer (C-1) having a functional group capable of reacting with a carbonyl group is used. Is a hydroxyl group-containing radically polymerizable unsaturated monomer.

When an amide group-containing radical-polymerizable unsaturated monomer is used as (B-2-2), the radical-polymerizable unsaturated monomer having a functional group capable of reacting with the amide group (C-
Examples of 1) include radically polymerizable unsaturated monomers containing an alkylolamide group.

When a radical-polymerizable unsaturated monomer containing an isocyanate group is used as (B-2-2), the radical-polymerizable unsaturated monomer (C-1) having a functional group capable of reacting with the isocyanate group is used. Examples of () include a hydroxyl group-containing radically polymerizable unsaturated monomer and an alkylolamide group-containing radically polymerizable unsaturated monomer.

When a radical-polymerizable unsaturated monomer containing an amino group is used as (B-2-2), the radical-polymerizable unsaturated monomer having a functional group capable of reacting with an amino group (C-
1) includes radically polymerizable unsaturated monomer containing glycidyl group, radically polymerizable unsaturated monomer containing isocyanate group, radically polymerizable unsaturated monomer containing glyceryl cyclocarbonate group, radical polymerization containing alkylolamide group And unsaturated carboxylic acid-containing radical polymerizable unsaturated monomers.

When a glyceryl cyclocarbonate group-containing radically polymerizable unsaturated monomer is used as (B-2-2), the radically polymerizable unsaturated monomer having a functional group capable of reacting with the glyceryl cyclocarbonate group (C Examples of -1) include radically polymerizable unsaturated monomers having an alkylolamide group and radically polymerizable unsaturated monomers having a hydroxyl group.

When a radical-polymerizable unsaturated monomer containing an oxazoline group is used as (B-2-2), the radical-polymerizable unsaturated monomer (C-1) having a functional group capable of reacting with the oxazoline group is used. Examples thereof include a hydroxyl group-containing radically polymerizable unsaturated monomer and the like.

Of these, a system using a glycidyl group-containing radically polymerizable unsaturated monomer as (C-1) is preferable from the viewpoint of polymerization stability and crosslinking efficiency.

The reactive functional group-containing radically polymerizable unsaturated monomer (B-2-2) is used in an amount of 0.1 to 50 parts by weight per 100 parts by weight of the radically polymerizable unsaturated monomer (B). It is preferably 0.2 to 10 parts by weight. That is, when the amount is 0.1 parts by weight or more, the crosslinking effect becomes remarkable, while when it is 50 parts by weight or less, the polymerization stability becomes good.

In the present invention, a radically polymerizable unsaturated monomer (C-2) containing a reactive functional group which is non-reactive with a carboxyl group is introduced into the radically polymerizable unsaturated monomer (C),
(C-2) Functional group and radically polymerizable unsaturated monomer (B) Reactive functional group-containing radically polymerizable unsaturated monomer (B-2-2) It is also preferable to make it self-crosslinking by reacting with a functional group.

The radical-polymerizable unsaturated monomer (C-2) containing a reactive functional group which is non-reactive with the carboxyl group is not particularly limited, but 2-hydroxyethyl acrylate, 2 -Hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, allyl alcohol, polyethylene glycol monoacrylate, glycerol monomethacrylate and other hydroxyl group-containing radically polymerizable unsaturated monomers: aminoethyl methacrylate, N-alkylaminoethyl methacrylate, N, N
-Amino group-containing radical polymerizable unsaturated monomer such as dialkylaminoethyl methacrylate: 2-acetoacetoxy group-containing radical polymerizable unsaturated monomer such as 2-acetoacetoxyethyl methacrylate: vinyltrichlorosilane,
Hydrolyzable silyl group-containing radically polymerizable unsaturated monomers such as vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloylpropyldiethoxymethylsilane: acrylic acid, methacrylic acid,
Radical polymerization containing carboxyl group such as maleic acid, fumaric acid, itaconic acid, crotonic acid, itaconic acid half ester, maleic acid half ester, maleic anhydride, itaconic anhydride, 2-methacryloylpropionic acid, 2-methacryloyloxyethylphthalic acid And unsaturated unsaturated monomers.

Specific examples of the combination of these monomers and the radically polymerizable unsaturated monomer (B-2-2) include:

When a glycidyl group-containing radically polymerizable unsaturated monomer is used as (B-2-2), the radically polymerizable unsaturated monomer (C-2) having a functional group capable of reacting with the glycidyl group is used. Examples thereof include an acetoacetyl group-containing radically polymerizable unsaturated monomer, an amino group-containing radically polymerizable unsaturated monomer, and a carboxyl group-containing radically polymerizable unsaturated monomer.

When a radically polymerizable unsaturated monomer having a hydroxyl group is used as (B-2-2), the radically polymerizable unsaturated monomer (C-2) having a functional group capable of reacting with a hydroxyl group.
Examples thereof include a hydrolyzable silyl group-containing radically polymerizable unsaturated monomer and a carboxyl group-containing radically polymerizable unsaturated monomer.

When an alkylolamide group-containing radically polymerizable unsaturated monomer is used as (B-2-2), the radically polymerizable unsaturated monomer having a functional group capable of reacting with a methylolamide group (C- As 2), amide group-containing radically polymerizable unsaturated monomer, hydrolyzable silyl group-containing radically polymerizable unsaturated monomer, acetoacetyl group-containing radically polymerizable unsaturated monomer, carboxyl group-containing radically polymerizable monomer Examples thereof include unsaturated monomers and amino group-containing radically polymerizable unsaturated monomers.

When a radical-polymerizable unsaturated monomer containing an acetoacetyl group is used as (B-2-2), the radical-polymerizable unsaturated monomer having a functional group capable of reacting with an acetoacetyl group (C-2 Examples of) include radically polymerizable unsaturated monomers containing an amino group.

When a hydrolyzable silyl group-containing radical-polymerizable unsaturated monomer is used as (B-2-2), the radical-polymerizable unsaturated monomer having a functional group capable of reacting with a silyl group (C- Examples of 2) include radically polymerizable unsaturated monomers containing a hydrolyzable silyl group.

When a carbonyl group-containing radically polymerizable unsaturated monomer is used as (B-2-2), the radically polymerizable unsaturated monomer (C-2) having a functional group capable of reacting with the carbonyl group is used. Examples thereof include an amino group-containing radically polymerizable unsaturated monomer and a carboxyl group-containing radically polymerizable unsaturated monomer.

When a radical polymerizable unsaturated monomer containing an isocyanate group is used as (B-2-2), the radical polymerizable unsaturated monomer having a functional group capable of reacting with an isocyanate group (C-2 Examples of) include acetoacetyl group-containing radically polymerizable unsaturated monomers, carboxyl group-containing radically polymerizable unsaturated monomers, and amino group-containing radically polymerizable unsaturated monomers.

When a radical-polymerizable unsaturated monomer containing an amino group is used as (B-2-2), the radical-polymerizable unsaturated monomer having a functional group capable of reacting with an amino group (C-
Examples of 2) include radically polymerizable unsaturated monomers containing an acetoacetyl group.

When a glyceryl cyclocarbonate group-containing radically polymerizable unsaturated monomer is used as (B-2-2), the radically polymerizable unsaturated monomer having a functional group capable of reacting with the glyceryl cyclocarbonate group (C Examples of -2) include acetoacetyl group-containing radically polymerizable unsaturated monomer, amino group-containing radically polymerizable unsaturated monomer, and carboxyl group-containing radically polymerizable unsaturated monomer.

When the radical-polymerizable unsaturated monomer containing an oxazoline group is used as (B-2-2), the radical-polymerizable unsaturated monomer (C-2) having a functional group capable of reacting with the oxazoline group is used. Examples include a carboxyl group-containing radically polymerizable unsaturated monomer.

Among them, a radically polymerizable unsaturated monomer having a hydrolyzable silyl group is used as (B-2-2) from the viewpoints of polymerization stability, cross-linking effect, etc., particularly solvent resistance, and (C-
A system using a hydrolyzable silyl group-containing radically polymerizable unsaturated monomer as 2) is preferable.

The amount of the reactive functional group-containing radically polymerizable unsaturated monomer (C-2) to be used is not particularly limited, but per 100 parts by weight of the radically polymerizable unsaturated monomer (C). It is preferably 0.1 to 50 parts by weight, and more preferably 0.2 to 10 parts by weight. That is, when the amount is 0.1 parts by weight or more, the crosslinking effect becomes remarkable, and when it is 50 parts by weight or less, the polymerization stability becomes good.

The resin aqueous dispersion obtained through the above steps 1 to 3 is characterized in that it has a flow characteristic close to that of a solvent type resin, that is, the viscosity does not change even if the shear is changed. The preferable aqueous resin dispersion obtained in the present invention satisfies the following conditions.

[0077]

[Equation 1] 0.5 ≦ η (6) / η (60) ≦ 3.0 η (6): Viscosity at 6 revolutions in B type viscometer η (60): At 60 revolutions in B type viscometer viscosity

The resin aqueous dispersion obtained by the present invention is extremely useful in consideration of conversion from a solvent-based resin to an aqueous resin, and is used for paints, paper processing, textile processing, printing materials, adhesion,
It can be used as a binder or an additive for civil engineering, ink, and other coating applications.

[0079]

The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following examples. In addition, all the following parts and% are values based on weight.

Further, each evaluation test in Examples and Comparative Examples is based on the following evaluation method.

[Evaluation method] Water resistance: 0.5 m in thickness prepared under room temperature and 7 days of drying conditions
The film of m was immersed in tap water for 7 days, and the water absorption and whitening degree of the film were evaluated.

Evaluation of degree of whitening of film ◯: No whitening at all. Δ: White and pale, but transparent.

X: Completely cloudy.

Solvent resistance: A 0.5 mm-thick film produced under a dry condition at room temperature for 7 days was immersed in acetone for 24 hours, and the weight percentage of insoluble matter was examined.

Structural Viscosity: The viscosity at 6 revolutions (η (6)) and the viscosity at 60 revolutions (η (60)) measured by a B-type viscometer were measured and calculated by the following formula. Structural viscosity = η (6) / η (60)

Number average molecular weight: measured in terms of polystyrene by GPC analysis

Reference Example 1 (Copolymer aqueous material (A '))
(B ′) Production Method 140 parts of butyl acrylate (hereinafter abbreviated as BA), 130 parts of methyl methacrylate (hereinafter abbreviated as MMA), 30 parts of methacrylic acid (hereinafter abbreviated as MAA), n-lauryl mercaptan (hereinafter L-). A mixture of 30 parts of SH (abbreviated as SH) was used as a monomer component (B).

A stirrer, a thermometer, and a cooler were attached.
A 2 liter reaction vessel was charged with 470 parts of ion-exchanged water, and the temperature inside the reaction vessel was raised to 80 ° C. while feeding nitrogen gas while stirring. After heating, 4.5 parts of MAA, 4.5 parts of sodium styrenesulfonate (hereinafter abbreviated as NaSS), L-S
Add 0.45 parts of H in order and hold for about 5 minutes, then add 1.5 parts of ammonium persulfate (hereinafter abbreviated as APS) and
The temperature was maintained at 80 ° C. with stirring for an hour to prepare an aqueous copolymer (A ′). After the production of the aqueous copolymer (A '),
Subsequently, the monomer component (B) prepared previously and a solution prepared by dissolving 1.5 parts of APS in 40 parts of ion-exchanged water were dropped into the system, respectively, and the aqueous copolymers (A ′) and (B ′) were obtained. Was prepared. The dropping time was 3 hours for the monomer mixed solution and 3 hours 30 minutes for the aqueous initiator solution. In addition, the inside of the system was maintained at 80 ° C. with stirring during the dropping. After the dropping was completed, the mixture was kept at 80 ° C. for 2 hours with stirring, cooled, and taken out.

The obtained emulsion has a nonvolatile content of 40.2.
%, Viscosity 8 cps, pH = 1.5. The number average molecular weight was 5,580.

Reference Examples 2 and 3 (Copolymer aqueous product (A '))
Production of (B ')) Production was carried out in the same manner as in Reference Example 1 except that the raw material composition was produced according to Table 1.

[0091]

[Table 1] 2EHA: 2-ethylhexyl acrylate A-174: γ-methacryloxypropyltrimethoxysilane

Comparative Reference Example 1 140 parts BA, 130 parts MMA, 30 parts MAA, L-S
H30 part, Aqualon HS-10 (Daiichi Kogyo Seiyaku Co., Ltd.)
A mixture of 1 part of reactive anionic emulsifier) and 150 parts of ion-exchanged water was used as a monomer mixture solution.

A stirrer, a cooler, and a thermometer were attached.
310 parts of ion-exchanged water was charged into a 2 liter reaction vessel, and the inside of the reaction vessel was heated to 80 ° C. while stirring while feeding nitrogen gas. After the temperature was raised, 1.5 parts of APS dissolved in 40 parts of ion-exchanged water were dropped into the container. The dropping time is 3 hours for the monomer mixture, APS
Aqueous solution for 3 hours and 30 minutes, stirring at 80 ℃ during dropping
Held. After completion of dropping, stirring at 80 ° C for 2 hours
It was then cooled and taken out. The obtained emulsion had a nonvolatile content of 40.1%, a viscosity of 11 cps, and a pH of 1.
It was 2. The number average molecular weight was 4,150.

Comparative Reference Examples 2 and 3 Production was carried out in the same manner as Comparative Reference Example 1 except that the raw materials shown in Table 2 were used.

[0095]

[Table 2] ALMA: Allyl methacrylate

Example 1 A mixture of 102 parts of BA, 102 parts of MMA and 6 parts of glycidyl methacrylate (hereinafter abbreviated as GMA) was used as a monomer mixture solution.

In a 1 liter reaction vessel equipped with a stirrer, a thermometer, and a cooler, 255 parts of ion-exchanged water and 225 parts of the composite copolymer aqueous substance (A ') and (B') produced in Reference Example 1 were added. Preparation and stirring were started. Next, 32 parts of a 7% aqueous ammonia solution was gradually charged, and after the charging was completed, the temperature was started to be raised to 80 ° C. After the temperature reached 80 ° C., 1.5 parts of ammonium persulfate was mixed with 3 parts of ion-exchanged water.
Each of those dissolved in 0 part was started to be dropped into the system.
The temperature in the system was maintained at 80 ° C. with stirring during the dropping, and the dropping time was 3 hours for the monomer mixture solution and 3 hours 30 minutes for the ammonium persulfate aqueous solution. After completion of the dropping, the mixture was kept for 2 hours under the same conditions, cooled, and taken out. The obtained emulsion has a nonvolatile content of 40.2%, a viscosity of 2300 cps, and a pH.
It was 8.8.

Examples 2 to 4 Production was carried out in the same manner as in Example 1 except that the raw materials shown in Table 3 were used.

[0099]

[Table 3]

Example 5 A mixture of 102 parts of BA, 102 parts of MMA and 6 parts of glycidyl methacrylate (hereinafter abbreviated as GMA) was used as a monomer mixture solution.

255 parts of ion-exchanged water in a 1 liter reaction vessel equipped with a stirrer, a thermometer, and a cooler, and the composite aqueous product 225 of (A ′) and (B ′) produced in Reference Example 1
A part was charged, stirring was started, and the temperature was raised to 80 ° C. 80 ℃
Monomer mixture, ammonium persulfate 1.5 after reaching
Each of the parts dissolved in 30 parts of ion-exchanged water was started to be dropped into the system. The temperature in the system is 80 ° C while stirring while dropping.
And the dropping time was 3 hours for the monomer mixture solution and 3 hours and 30 minutes for the ammonium persulfate aqueous solution. After completion of dropping, the mixture was kept for 2 hours under the same conditions and then cooled, 32 parts of 7% aqueous ammonia was added, and the mixture was taken out. The obtained emulsion had a nonvolatile content of 40.0%, a viscosity of 810 cps, and a pH of 9.
Was 3.

Comparative Example 1 (Production Method of Comparative Emulsion) A mixture of 102 parts of BA, 102 parts of MMA and 6 parts of GMA was used as a monomer mixture liquid.

A 1-liter reaction vessel equipped with a stirrer, a thermometer, and a cooler was charged with 255 parts of ion-exchanged water, Comparative Reference Example 1
Was charged with 225 parts of the aqueous copolymer aqueous product produced by, and after stirring was started, 25 parts of 7% ammonia water was charged.
The temperature was raised to 80 ° C. After the temperature was raised, the monomer mixture and 1.5 parts of ammonium persulfate dissolved in 30 parts of deionized water were added dropwise. The temperature in the system was maintained at 80 ° C. with stirring during the dropping, and the dropping time was 2 hours for the monomer mixture solution and 2 hours 30 minutes for the ammonium persulfate solution. After completion of dropping, the mixture was stirred for 2 hours, kept at 80 ° C., cooled, and taken out. The obtained emulsion had a nonvolatile content of 40.3%, a viscosity of 1100 cps and a pH of 8.7.

Comparative Examples 2 and 3 (Production Method of Comparative Emulsion) Production was carried out in the same manner as in Comparative Example 1 except that the raw materials shown in Table 4 were used.

[0105]

[Table 4] DMAEMA: Dimethylaminoethyl Methacrylate The following Table 5 shows the results of examining the water resistance, solvent resistance, film-forming property, and structural viscosity of the emulsions obtained in the above Examples and Comparative Examples.

[0106]

[Table 5]

[0107]

[Table 6]

[0108]

Industrial Applicability According to the present invention, it is possible to provide a method for producing an aqueous resin dispersion which has the characteristics of both an aqueous resin and an emulsion resin and is particularly excellent in water resistance as compared with conventional methods.

Therefore, the aqueous resin dispersion obtained in the present invention is extremely useful as a binder and an additive in paints, paper processing, fiber processing, adhesion, civil engineering, inks, printing materials and other coating applications.

Claims (15)

[Claims] 1. A radically polymerizable unsaturated monomer component (A) containing an anionic functional group-containing radically polymerizable unsaturated monomer (A-1) as an essential component in water in the presence of a chain transfer agent. Polymerization to produce an aqueous copolymer (A ′) (step 1), and in the presence of the aqueous copolymer (A ′), a carboxyl group-containing radically polymerizable unsaturated monomer (B-1 ) And another radically polymerizable unsaturated monomer (B-2) (B-1)
/ (B-2) weight ratio (5 to 50) / (95 to 50) contained radically polymerizable unsaturated monomer component (B)
Is polymerized in water in the presence of a chain transfer agent to produce an aqueous copolymer (B ') having a number average molecular weight of 500 to 20,000 (step 2), and then an aqueous copolymer (A' And a copolymer aqueous solution (B ′) in the presence of the radical-polymerizable unsaturated monomer component (C) (step 3). 2. The radical-polymerizable unsaturated monomer component (A) in step 1 comprises an anionic functional group-containing radical-polymerizable unsaturated monomer (A-1) and another radical-polymerizable unsaturated monomer. The monomer (A-2) and the latter are 50% in the component (A).
The manufacturing method according to claim 1, wherein the content is not more than wt%. 3. The anionic functional group in the anionic functional group-containing radically polymerizable unsaturated monomer (A-1) is a carboxyl group, a sulfonic acid group, a phosphoric acid group, or a salt thereof. The manufacturing method according to 1 or 2. 4. The use ratio of the radically polymerizable unsaturated monomer component (B) and the aqueous copolymer (A ′) in the step 2 is 100% by weight of the radically polymerizable unsaturated monomer component (B). The amount of the aqueous copolymer (A ') per part by solid content was 0.
The manufacturing method according to claim 1, 2 or 3, wherein 5 to 10 parts by weight is used. 5. The use ratio of each component in step 3 is such that the aqueous copolymer (A ′) and the aqueous copolymer (B ′) are used per 100 parts by weight of the radically polymerizable unsaturated monomer component (C). 5) is a range of 10 to 1000 parts by weight in terms of the total solid content of both, and the production method according to any one of claims 1 to 4. 6. The production method according to claim 1, wherein the neutralization is carried out at any stage of step 2 or step 3. 7. The radically polymerizable unsaturated monomer (C) is
The production method according to any one of claims 1 to 6, which comprises a radically polymerizable unsaturated monomer (C-1) having a functional group reactive with a carboxyl group. 8. A radically polymerizable unsaturated monomer component (B)
Other radically polymerizable unsaturated monomer (B-2) in
Has a radically polymerizable unsaturated monomer (B-2-2) having a reactive functional group other than a carboxyl group and having a reactive functional group that is non-reactive with the unsaturated group, and The radical-polymerizable unsaturated monomer (C-1) in the radical-polymerizable unsaturated monomer component (C) serves as a reactive functional group in the monomer (B-2-2) together with the carboxyl group. The production method according to claim 7, which has a reactive functional group. 9. Radical-polymerizable unsaturated monomer component (B)
In the radical polymerizable unsaturated monomer (B-2-2),
A radically polymerizable unsaturated monomer having a reactive functional group other than a carboxyl group and having a reactive functional group that is non-reactive with an unsaturated group, and also a radically polymerizable unsaturated monomer component (C) Is a radically polymerizable unsaturated monomer (B-2-2)
The production method according to any one of claims 1 to 6, which comprises a radically polymerizable unsaturated monomer (C-2) having a functional group reactive with a reactive functional group present therein. 10. The radical-polymerizable unsaturated monomer component (C) has a radical-polymerizable unsaturated monomer (C-1) and a radical-polymerizable unsaturated monomer (C-2). Cage,
The functional group in the radically polymerizable unsaturated monomer (C-2) is not reactive with a carboxyl group.
The manufacturing method as described. 11. The content of the carboxyl group-containing radically polymerizable unsaturated monomer (B-1) in the radically polymerizable unsaturated monomer component (B) is 5 to 50% by weight, and The content of the radical-polymerizable unsaturated monomer (B-2-2) having a reactive functional group other than the carboxyl group, which functional group does not react with the unsaturated group, is 0.1 to 50% by weight. The manufacturing method according to claim 8. 12. The content of the radically polymerizable unsaturated monomer (C-1) having a functional group reactive with a carboxyl group in the radically polymerizable unsaturated monomer component (C) is 0.1. %, 50% to 50% by weight.
2. The production method according to 1. 13. A radical-polymerizable unsaturated monomer having a functional group reactive with the functional group present in (B-2-2) in the radical-polymerizable unsaturated monomer component (B) ( The production method according to claim 9, 10 or 11, wherein the content of C-2) is 0.1 to 50% by weight. 14. A radical polymerizable unsaturated monomer (C-1) having a functional group reactive with a carboxyl group,
The production method according to claim 7, 8, 10, 11, or 12, which is a radically polymerizable unsaturated monomer having a glycidyl group. 15. A radically polymerizable unsaturated monomer (B-2-2) having a reactive functional group other than a carboxy group, which functional group does not react with an unsaturated group, contains a hydrolyzable silyl group. A radically polymerizable unsaturated monomer, and
Radical polymerizable unsaturated monomer (C-2) having a functional group having reactivity with the functional group present in (B-2-2)
Is a radically polymerizable unsaturated monomer containing a hydrolyzable silyl group, The production method according to claim 9, 10, 11, or 13.