JP3454564B2 - Aqueous emulsion composition and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a coating material for various substrates formed of paper, plastic, fibers, inorganic materials, binders such as paints, metals such as metal foils, films, plastics, ceramics, wood, etc. The present invention relates to an aqueous emulsion composition useful as an adhesive and the like, a crosslinkable aqueous emulsion composition containing the composition, and a method for producing them.

[0002]

2. Description of the Related Art An aqueous emulsion is different from a solvent type in
Excellent in non-pollution, resource saving and workability. Therefore, aqueous emulsions are widely used as coating agents, binders, adhesives, and the like. However, the polymer of the aqueous emulsion exists in the form of particles and has a high molecular weight of generally 500,000 to 1,000,000. Therefore, not only the permeability to the base material, the adhesion to the base material is small, but the film forming property is inferior to that of the resin solution,
It is difficult to obtain a smooth and highly resistant coating film.

In order to improve the performance of these coating films, emulsions having crosslinkability are used, and in recent years,
Further, there is a demand for a crosslinkable emulsion that reacts at a low temperature and has high stability.

As the emulsion having such a crosslinking property, a two-component curable emulsion composition is generally used. However, in a two-component curable emulsion composition, two components must be mixed before use, so that the workability is reduced and the pot life of the composition is short. Therefore, a one-pack type emulsion having self-crosslinking property has been developed. However, since the one-pack type crosslinkable emulsion has functional groups that react with each other in the same particle, the crosslink reaction easily occurs during the polymerization process or during storage. Therefore, the pot life of the emulsion is shortened, and once the crosslinking reaction occurs, the film-forming property is deteriorated, and the heat resistance, solvent resistance and water resistance of the coating film cannot be expected.

In order to solve these problems, for example, JP-A-5-105799 discloses that dispersed particles of an emulsion have a phase of a copolymer having an epoxy group and a phase of a copolymer having a carboxyl group. And an emulsion composition containing a specific amount of sulfonate ions or sulfate ester ions with respect to epoxy groups.
However, in this emulsion composition, since the polymer particles have a two-phase structure of core-shell, the crosslinking reaction proceeds not only at the polymerization process but also at the time of storage at the phase interface.
Therefore, a monomer having a crosslinkable functional group cannot be effectively used in the crosslinking reaction. In addition, it is necessary to use a catalyst such as sulfonate ion, and to accelerate the crosslinking reaction, p
It is necessary to adjust H. Furthermore, since the polymerization is carried out in two steps, the manufacturing process is complicated and the productivity is low.

In JP-A-63-284280, a zinc ammonium carbonate aqueous solution or a zirconyl ammonium carbonate aqueous solution is added to a styrene-acrylic copolymer emulsion or (meth) acrylic polymer emulsion having a carboxyl group introduced. , An adhesive having a pH of 6.8 or higher has been proposed. However, in this emulsion composition, when the reactivity is increased, the storage stability and mechanical stability are decreased, and when the reactivity is decreased to increase the stability, a coating film having high water resistance cannot be formed at room temperature. Further, the smell of ammonia or amine becomes strong, which is not preferable in the working environment.

[0007]

Therefore, an object of the present invention is to provide an aqueous emulsion composition useful for obtaining a composition capable of forming a crosslinked coating film at room temperature, and a crosslinkable aqueous emulsion composition containing the composition. To provide things.

Another object of the present invention is to provide a crosslinkable aqueous emulsion composition which is excellent in storage stability and mechanical stability even if it is a one-pack type.

Still another object of the present invention is to provide a crosslinkable aqueous emulsion composition in which a functional group can be effectively utilized in a crosslinking reaction and which gives a crosslinked coating film having high heat resistance, solvent resistance and high water resistance. is there.

Still another object of the present invention is to provide a method for easily producing an aqueous emulsion composition having the above-mentioned excellent properties without using a special method.

[0011]

The present inventors have conducted extensive studies to achieve the above object, and as a result, have found that an aqueous emulsion containing polymer particles into which an oxocarboxylic acid acyl group has been introduced, and a compound having a plurality of amino groups in the molecule. The composition containing the compound has high storage stability and mechanical stability, and the cross-linking reaction proceeds smoothly even at room temperature due to evaporation of water to form a coating film excellent in heat resistance, solvent resistance, water resistance, etc. Then, they have completed the present invention.

That is, the crosslinkable aqueous emulsion composition of the present invention comprises an aqueous emulsion containing polymer particles having an oxocarboxylic acid acyl group such as acetoacetyl group introduced therein, and an amino compound having a plurality of amino groups in the molecule. A crosslinkable aqueous emulsion composition comprising: wherein the polymer particles are based on the entire polymerizable unsaturated monomer.
2.5-7.5% by weight of polymerizable unsaturated monomer having (A) oxocarboxylic acid acyl group and (B) oxocarboxylic acid
Non-Reactive Copolymerizable Polymers Inert to Acid Acyl Groups
Comprised of a copolymer with a compatible unsaturated monomer, the non-reaction
The polymerizable unsaturated monomer (B) is (B1) at least one hard monomer forming a polymer having a glass transition temperature of 50 ° C. or higher, and (B2) a polymer having a glass transition temperature of 25 ° C. or lower. At least one soft monomer to form, and polymerizable
Is composed of an unsaturated monomer having from 1 to 5% by weight of (B3) a carboxyl group or a salt thereof for the entire unsaturated monomer, before Symbol aqueous emulsion is neutralized with a neutralizing agent, wherein the amino compound There, Ri Oh in the dicarboxylic acid dihydrazide compound, however
However, the polymer particles are monomers forming the copolymer.
As the expression

[Chemical 6] (In the formula, R ¹ represents hydrogen or a methyl group, and R ² is a lower group.
Represents a alkylene group, and Y ¹ represents hydrogen or a lower alkyl group.
The above-mentioned aqueous emulsion containing no monomer represented by
The composition has a core (C) below and a shell (D) below.
Part of the copolymer particles, the core of the following (E), and
Crosslinking that does not include copolymer particles composed of the following (F) shell
Aqueous emulsion composition . (C) The following (c-1) to (c-3), (c-1) the monomer 60 to 100 represented by the following general formula (1)
weight%,

[Chemical 7] (However, in the formula, R ³ is hydrogen or a methyl group, and X is COO.
R ⁴ , OCOR ⁵ , an aryl group having 6 to 8 carbon atoms or CN
And R ⁴ is a straight chain or branched alkyl group having 1 to 18 carbon atoms.
Kill group, cycloalkyl group having 6 to 8 carbon atoms or carbon number
An aralkyl group of 7 to 12, R ⁵ is hydrogen or a carbon number of 1 to
12 straight chain or branched alkyl groups) (c-2) 0 to 20% by weight of acetoacetyl group-containing monomer, and
And (c-3) in addition to one radically polymerizable unsaturated group in the molecule,
A monomer having at least one functional group,
0 to 20% by weight of monomers other than the monomer (c-2), provided that
(C-1) to (c-3) total 100% by weight]
The glass transition point Tg _C is -60 to 80
C., and (D) the following (d-1) to (d-3), (d-1) the monomers 50 to 99. represented by the following general formula (1).
95% by weight,

[Chemical 8] (However, in the formula, R ³ and X are the same as above.) (D-2) acetoacetyl group-containing monomer 0.05 to 30 weight
%, And in addition to one radically polymerizable unsaturated group in the (d-3) molecule,
A monomer having at least one functional group,
Monomers other than the monomer (d-2) 0 to 20% by weight, provided that
the total of (d-1) to (d-3) is 100% by weight]
And its glass transition point Tg _D is -40 to +100.
C and higher than the Tg _{C of the} core (co) polymer ,
It consists of a shell that covers the core, and is compatible with 100 parts by weight of the core.
And (E) the following copolymer particles (e-1) to (e-4), wherein the shell part is 5 to 100 parts by weight.
Formed of a copolymer having a transition point Tg _E of −30 to + 70 ° C.
Core part (e-1) selected from monomers represented by the following general formula (2)
At least one (meth) acrylic acid ester monomer 3
0-99.9% by weight,

[Chemical 9] (However, in the formula, R ⁶ is hydrogen or a methyl group, and R ⁷ is a carbon number 1
~ E 20 straight or branched alkyl groups) (e-2) 0-20% by weight of acetoacetyl group-containing monomer, and
And (e-3) α, β-unsaturated mono- or di-carbon having 3 to 5 carbon atoms
-0.1 to 10% by weight of carboxylic acid, and 0 to 50 copolymerizable monomers other than (e-4) (e-1) to (e-3)
% By weight (however, the total of (e-1) to (e-4) above is 100% by weight
And (F) the following copolymers (f-1) to (f-4),
Transition point Tg _F is −40 to + 60 ° C., and Tg _F ≦ T
coating a core formed of a copolymer satisfying g _E
Shell part, (f-1) monomer represented by the following general formula (2) 30 to 99.
9% by weight,

[Chemical 10] (However, R ⁶ and X in the formula are the same as above.) (F-2) 0.1 to 20 weight of acetoacetyl group-containing monomer
%, (F-3) α, β-unsaturated mono- or di-carbon having 3 to 5 carbon atoms
0 to 10% by weight of carboxylic acid, and 0 to 50 copolymerizable monomers other than (f-4) (f-1) to (f-3)
% By weight [however, the total of (f-1) to (f-4) above is 100% by weight
And the weight ratio of the core / the shell is 95/5.
~ 50/50 copolymer particles

The polymer particles include (A) a polymerizable unsaturated monomer having an oxocarboxylic acid acyl group and (B) a non-reactive polymerizable unsaturated monomer which is inactive to the oxocarboxylic acid acyl group. mer, for example, but it may also be constituted by a copolymer of various monomers such as (meth) acrylic monomers, styrenic monomers.

The above aqueous emulsion composition is combined with a compound having a plurality of amino groups in the molecule,
It is useful for forming a crosslinkable aqueous emulsion composition.
As the amino compound, for example, etc. dicarboxylic acid dihydrazide compound can be used. The ratio of the oxo group of the polymer particles and the amino group of the amino compound can be appropriately selected within the range of, for example, amino group / oxo group (molar ratio) = 0.6 to 1.4.

[0015] The crosslinkable aqueous emulsion composition prior to
An aqueous Emarujo emissions containing serial oxo carboxylic acyl group is introduced polymer particles can be prepared by mixing the amino compound having a plurality of amino groups in the molecule. The aqueous emulsion is neutralized with a neutralizing agent,
Mix with amino compound. The aqueous emulsion composition
Is a polymer containing a monomer having an acyl oxocarboxylate group.
Emulsion polymerization of compatible unsaturated monomers in aqueous medium
You can get more.

In the present specification, "amino group" includes not only an amino group but also a hydrazino group, and compounds having such "amino group" are collectively referred to as "amino compound". Further, hereinafter, unless otherwise specified, acrylic monomers and methacrylic monomers are collectively referred to as (meth) acrylic monomers. Further, the “glass transition temperature” means a value calculated by the following Tobolsky formula.

1 / Tg = Wa / Tga + Wb / Tgb + [wherein Tg is the glass transition temperature (° K) of the copolymer, T
ga is the glass transition temperature (° K) of the homopolymer of monomer a, Tgb is the glass transition temperature (° K) of the homopolymer of monomer b, Wa is the weight fraction of monomer a, and Wb is the single Quantity b
In the aqueous emulsion composition of the present invention, oxocarboxylic acid acyl groups are introduced into the polymer particles.
The oxocarboxylic acid acyl group includes, for example, glyoxyloyl, pyruvoyl, methoxymesooxalyl, oxalacetyl, and 2-oxobutyryl groups having 2 to 14 carbon atoms.
Degree α-oxocarboxylic acid acyl group; carbon number 3 such as formylacetyl, acetoacetyl, 3-oxovaleryl, 3-oxohexanoyl, and 2-benzoylacetyl
A β-oxocarboxylic acid acyl group having about 14 to about 14; a γ-oxocarboxylic acid acyl group having about 4 to 14 carbon atoms such as a 4-oxovaleryl group. Among these,
A β-oxocarboxylic acid acyl group having about 3 to 14 carbon atoms is preferable, and a β-oxocarboxylic acid acyl group having about 3 to 9 carbon atoms, particularly a β-oxocarboxylic acid acyl group having about 3 to 6 carbon atoms (for example, , Acetoacetyl groups, etc.) are preferred.

The polymerizable unsaturated monomer having an oxocarboxylic acid acyl group is, for example, a hydroxyl group,
An ethylenically unsaturated compound having a functional group capable of introducing an oxocarboxylic acid acyl group such as an amino group, an amide group, a urethane group or a carboxyl group, and an oxocarboxylic acid acyl such as an oxocarboxylic acid ester, an oxocarboxylic acid halide or a diketene. It can be obtained by a reaction with a compounding reagent.

Examples of the ethylenically unsaturated compound having a hydroxyl group include 2-hydroxyethyl (meth)
Acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate,
1,3-butanediol mono (meth) acrylate,
1,4-butanediol mono (meth) acrylate, hexanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 3
Hydroxyalkyl (meth) acrylates such as chloro-2-hydroxypropyl (meth) acrylate; diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth ) Acrylate, tripropylene glycol mono (meth) acrylate, polyoxyalkylene glycol mono (meth) acrylate such as polypropylene glycol mono (meth) acrylate; glycerin mono (meth) acrylate, trimethylolpropane mono (meth) acrylate, pentaerythritol mono (Meth) acrylic acid ester of polyhydric alcohol such as (meth) acrylate; 2-hydroxypropyl 2 ′-(meth) acryl Examples thereof include hydroxyalkyl (meth) acryloyloxyalkyl phthalate such as liloyloxyethyl phthalate; N- (hydroxyalkyl) (meth) acrylamide such as N-methylol (meth) acrylamide and N-hydroxymethyl (meth) acrylamide. Among these, hydroxyalkyl (meth) acrylates (for example, hydroxy-
Preferred are (meth) acrylic acid esters having a hydroxyl group such as C _2-4 alkyl (meth) acrylate.

Examples of the ethylenically unsaturated compound having an amino group include 2-aminoethyl (meth) acrylate, 2- (methylamino) ethyl (meth) acrylate, 2-aminopropyl (meth) acrylate and 2-amino. Aminoalkyl (meth) acrylates such as butyl (meth) acrylate; N- (2-aminoethyl) (meth) acrylamide, N- (2-methylaminoethyl)
(Meth) acrylamide, N- (2-aminopropyl)
N- (aminoalkyl) such as (meth) acrylamide
(Meth) acrylamide etc. are mentioned. Among these, aminoalkyl (meth) acrylates such as amino-C _2-4 alkyl (meth) acrylate are preferable.

Examples of the ethylenically unsaturated compound having an amide group include (meth) acrylamide. Examples of the ethylenically unsaturated compound having a urethane group include reaction products of the above ethylenically unsaturated compound having a hydroxyl group with isocyanates such as phenyl isocyanate and alkyl isocyanate.

Examples of the ethylenically unsaturated compound having a carboxyl group include acrylic acid, methacrylic acid,
Unsaturated monocarboxylic acids such as crotonic acid, itaconic acid,
Unsaturated polycarboxylic acids such as maleic acid, fumaric acid and maleic anhydride, monoesters of unsaturated polycarboxylic acids such as itaconic acid monoester, maleic acid monoester, fumaric acid monoester and the like. And so on.

The polymerizable unsaturated monomer having an oxocarboxylic acid acyl group is obtained by subjecting, for example, (i) an ethylenically unsaturated compound having the functional group and a corresponding oxocarboxylic acid ester to a transesterification reaction. Method (ii) It can be produced by a method of reacting the ethylenically unsaturated compound having the functional group with a corresponding oxocarboxylic acid halide. Further, of the oxocarboxylic acid acyl groups, the monomer having an acetoacetyl group can be produced by reacting (iii) an ethylenically unsaturated compound having a functional group with diketene.

In the method (i), the oxocarboxylic acid ester is a lower alkyl having about 1 to 4 carbon atoms, particularly 1 or 2 carbon atoms, such as methyl ester, ethyl ester and isopropyl ester of the corresponding oxocarboxylic acid. Esters and the like are preferably used. The transesterification reaction is carried out by a conventional method, for example, at room temperature to 1 while distilling an alcohol which produces the ethylenically unsaturated compound and the corresponding oxocarboxylic acid ester as necessary.
It can be carried out by a method of reacting at a temperature of about 50 ° C. The reaction may be carried out in the presence of a conventional transesterification catalyst.

In the above method (ii), as an oxocarboxylic acid halide, an acid chloride or acid bromide of the corresponding oxocarboxylic acid can be used. The reaction can be carried out at a temperature of about -10 to 100 ° C in the presence of a base such as triethylamine or pyridine, if necessary.

In the above method (iii), the reaction can be carried out in the presence or absence of a catalyst. Examples of the catalyst include tertiary amines (triethylamine etc.), acids (sulfuric acid etc.). , Basic salts of metals (such as sodium acetate), organometallic compounds and the like can be used. The reaction can be performed, for example, at a temperature of about -10 to 180 ° C.

The polymerizable unsaturated monomer may have a plurality of oxocarboxylic acid acyl groups in one molecule, but usually has one oxocarboxylic acid acyl group in one molecule. In many cases. Examples of the polymerizable unsaturated monomer having an oxocarboxylic acid acyl group include 2-pyruvoyloxyethyl (meth) acrylate, 2-acetoacetoxyethyl (meth) acrylate, and 2- (3-oxovaleryloxy). Ethyl (meth) acrylate, 2- (2
-Benzoylacetoxy) ethyl (meth) acrylate, 2-acetoacetoxypropyl (meth) acrylate, 2-acetoacetoxybutyl (meth) acrylate, 2-acetoacetoxy-3-phenoxypropyl (meth) acrylate, 2-acetoacetoxy-3 -Chloropropyl (meth) acrylate, 2- (4-oxovaleryloxy) ethyl (meth) acrylate and other oxocarboxylic acid acyloxyalkyl (meth) acrylates; glycerin mono (meth) acrylate and polyhydric alcohols such as diacetoacetate Mono (meth) acrylate oxocarboxylic acid ester; 2-acetoacetoxypropyl 2 '-(meth) acryloyloxyethyl phthalate and other oxocarboxylic acid acyloxyalkyl (meth) acryloyl esters Shi alkyl phthalates; 2
-(Pyruvoylamino) ethyl (meth) acrylate,
2- (acetoacetylamino) ethyl (meth) acrylate, 2- (benzoylacetylamino) ethyl (meth) acrylate, 2- (acetoacetylamino) propyl (meth) acrylate, 2- (acetoacetylamino) butyl (meth) Acrylate, N- [2- (acetoacetylamino) ethyl] (meth) acrylamide, N
-[2- (acetoacetylamino) propyl] (meth)
Acrylaminoalkyl (meth) acrylates such as acrylamide and 2- (4-oxovalerylamino) ethyl (meth) acrylate are included. These monomers can be used alone or in combination of two or more.

Among these monomers, (meth) acrylic acid ester having an oxocarboxylic acid acyl group such as oxocarboxylic acid acyloxyalkyl (meth) acrylate is preferable. More preferred monomers include
(Meth) acrylic acid ester having an oxocarboxylic acid acyl group having 3 to 9 carbon atoms [for example, (oxooxycarboxylic acid acyloxy) -C _2-4 alkyl (meth) having an oxocarboxylic acid acyl group having 3 to 9 carbon atoms Acrylate and the like], in particular, (meth) acrylic acid ester having an oxocarboxylic acid acyl group having 3 to 6 carbon atoms is included. In particular, a (meth) acrylic acid ester having an acetoacetyl group [eg, 2-acetoacetoxyethyl (meth)]
Acetoacetoxy-C _2-4 alkyl (meth) acrylates such as acrylates] and the like are preferable.

Introduction of an oxocarboxylic acid acyl group into polymer particles can be carried out by emulsion polymerization of a polymerizable unsaturated monomer having an oxocarboxylic acid acyl group. The polymer particles may be a homopolymer or a copolymer of the polymerizable unsaturated monomer having an oxocarboxylic acid acyl group, but the polymerizable unsaturated monomer having the (A) oxocarboxylic acid acyl group may be used. It is preferably a copolymer of a monomer and (B) a non-reactive copolymerizable polymerizable unsaturated monomer which is inactive to an oxocarboxylic acid acyl group.

The ratio of the polymerizable unsaturated monomer (A) having an oxocarboxylic acid acyl group to the entire polymerizable unsaturated monomer is, for example, 0.5 to 50% by weight, preferably 1 to
It is about 15% by weight, more preferably about 2 to 10% by weight. The content of the monomer (A) with respect to the entire polymerizable unsaturated monomer is often about 2.5 to 7.5% by weight. If the ratio is less than 0.5% by weight, the cross-linking effect is small and the water resistance, solvent resistance and heat resistance of the coating film may be insufficient. On the other hand, when the ratio exceeds 50% by weight, the cost becomes high, and the glass transition temperature Tg of the polymer particles is lowered, so that the hardness of the coating film may be lowered.

The copolymerizable polymerizable unsaturated monomer (B) is, for example, a (meth) acrylic monomer, a styrene monomer, a vinyl ester, or a monomer having a non-reactive functional group. Includes monomers and other non-reactive monomers. As these polymerizable monomers, one or more monomers of the same or different series can be used.

Examples of (meth) acrylic monomers include:
An alkyl group having about 1 to 20 carbon atoms, a cycloalkyl group,
A (meth) acrylate having an aryl group or an aralkyl group is included. More specifically, examples of the (meth) acrylic monomer include methyl (meth) acrylate,
Ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, amyl (meth) Acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, isoheptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) Alkyl (meth) acrylates such as acrylate and stearyl (meth) acrylate; Cycloalkyl (meth) acrylates such as cyclohexyl (meth) acrylate, phenyl (meth) acrylate Aryl, such as (meth) acrylate, an aralkyl (meth) acrylates such as benzyl (meth) acrylate. These (meth) acrylic monomers can be used alone or in combination of two or more. Among the (meth) acrylic monomers, the number of carbon atoms is 1 to 1.
2, (meth) acrylate having a linear or branched alkyl group of about 1 to 10 is preferable.

The styrene-based monomer includes, for example, styrene, α-methylstyrene, p-methylstyrene, vinyltoluene, t-butylstyrene, chlorostyrene, vinylanisole, vinylnaphthalene, divinylbenzene and the like. The preferred styrenic monomer includes styrene. Examples of the vinyl ester include vinyl acetate, vinyl caproate, vinyl propionate, vinyl versatate (VeoVa, etc.) and the like.
Styrene-based monomers and vinyl esters may be used alone or in combination of two or more.

Examples of the monomer having a non-reactive functional group include ethylenically unsaturated compounds having the above-mentioned hydroxyl group, amide group and carboxyl group; ethylenically unsaturated compounds having a glycidyl group, for example, glycidyl (Meth) acrylate and the like; ethylenically unsaturated sulfonic acids such as sodium styrene sulfonate, sodium vinyl sulfonate and the like are included. Monomers having these functional groups may be used alone or in combination of two or more.

Other non-reactive monomers include, for example, fumaric acid esters and their corresponding maleic acid esters (eg, diethyl fumarate, dipropyl fumarate, dibutyl fumarate, di (2-ethylhexyl) fumarate). Etc.), (meth) acrylonitrile, vinyl chloride, vinylidene halide (eg, vinylidene chloride, vinylidene fluoride, etc.), chloroprene, olefin (eg, ethylene, propylene, isoprene, butadiene, etc.), vinylamides, vinylpyrrolidone,
N-substituted (meth) acrylamides [for example, N- (2
-N- (disubstituted aminoalkyl) (meth) acrylamides such as dimethylaminoethyl) (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N
-N-alkoxyalkyl (meth) acrylamides such as ethoxymethyl (meth) acrylamide; diacetone (meth) acrylamide and the like], (meth) acrylic acid di-substituted aminoalkyl ester (for example, dimethylaminoethyl (meth) acrylate, diethylaminoethyl) (Meth) acrylate, etc., monovinyl pyridines (eg, vinyl pyridine, etc.), vinyl ethers (eg, di-substituted aminoalkyl vinyl ethers such as dimethylaminoethyl vinyl ether, etc.) and the like. Other monomers may be used alone or in combination of two or more.

Examples of preferable non-reactive polymerizable unsaturated monomer (B) include (1) (meth) acrylic monomers (for example, one or more kinds of (meth) acrylic acid alkyl ester). , (Meth) acrylic acid-based monomer-based monomers such as a mixture of (meth) acrylic acid alkyl ester and styrene-based monomer, and (2) styrene-based monomer (eg, styrene) , Styrene and monomers containing styrene-based monomers such as (meth) acrylic acid alkyl esters as main components), (3) vinyl esters (for example, a mixture of vinyl acetate and (meth) acrylic-based monomers, Such as a mixture of vinyl acetate and Veova). The preferred polymerizable unsaturated monomer (B) includes at least one monomer selected from the above (1) (meth) acrylic monomer and (2) styrene monomer.

In the more preferred non-reactive polymerizable unsaturated monomer (B), a plurality of unsaturated monomers, for example,
(B1) Glass transition temperature of 50 ° C. or higher, preferably 60 to
At least one hard monomer forming a hard polymer at 120 ° C., more preferably about 70 to 110 ° C.,
(B2) Glass transition temperature 25 ° C or lower, preferably -10
It is preferable to combine with at least one soft monomer forming a soft polymer at 0 ° C to 0 ° C, more preferably about -10 to -100 ° C.

The hard monomer (B1) is, for example, an alkyl methacrylate having about 1 to 6 carbon atoms (for example, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, t-butyl methacrylate). ), Styrenic monomer (for example,
Styrene), acrylonitrile and the like. Preferred hard monomers include methyl methacrylate, ethyl methacrylate, styrene, acrylonitrile.

Examples of the soft monomer (B2) include acrylic acid ester having an alkyl group having about 1 to 12 carbon atoms and methacrylic acid ester having an alkyl group having about 4 to 12 carbon atoms (eg, ethyl acrylate). , Butyl acrylate, Octyl acrylate, Acrylic acid-2-
Ethylhexyl, n-hexyl methacrylate, lauryl methacrylate, etc.) and the like. A preferred soft monomer includes an acrylate ester having an alkyl group having about 2 to 10 carbon atoms.

Hard monomer (B1) and soft monomer (B2)
And the ratio of hard monomer / soft monomer = 20 to 80/8
0 to 20% by weight, preferably 25 to 70/75 to 30% by weight, more preferably 30 to 60/70 to 40% by weight
It is a degree. When the amount of the hard monomer (B1) used is less than 20% by weight, the smoothness and gloss of the coating film deteriorate, and when it exceeds 80% by weight, the water resistance tends to decrease.

The polymerizable unsaturated monomer (B) has a glass transition temperature of -60 ° C to 50 ° C, preferably -50 ° C to 40 ° C.
C., more preferably about -40.degree. C. to 30.degree. C., composed of unsaturated monomers forming a homopolymer or a copolymer, particularly a plurality of unsaturated monomers forming a copolymer having the above glass transition temperature. Is preferred. The copolymer having such a glass transition temperature can be formed by polymerizing the hard monomer (B1) and the soft monomer (B2) in combination.

In order to improve the adhesion and the stability of the emulsion, the polymerizable unsaturated monomer (B) is further an acidic monomer, preferably an unsaturated monomer (B3) having a carboxyl group or a salt thereof, In particular, it preferably contains α, β-ethylenically unsaturated monocarboxylic acid or a salt thereof. Preferred α, β-ethylenically unsaturated monocarboxylic acids include (meth) acrylic acid. The stability of the emulsion can be further enhanced by neutralizing the carboxyl group of the α, β-ethylenically unsaturated carboxylic acid with a basic substance such as ammonia or amines.

The ratio of the unsaturated monomer (B3) having a carboxyl group or its salt to the whole polymerizable unsaturated monomer is, for example, 0.1 to 10% by weight, preferably 0.5 to.
It is about 7% by weight, more preferably about 1 to 5% by weight.
If the amount of the unsaturated monomer (B3) is out of the above range, the polymerization stability may decrease.

A preferable combination of the polymerizable unsaturated monomers is a (meth) acrylic ester having an oxocarboxylic acid acyl group (particularly, an acetoacetyl group) and a (meth) acrylic ester.
A combination with a polymerizable vinyl monomer which forms a polymer having a glass transition temperature of −50 ° C. to 40 ° C., which is selected from an acrylic monomer and a styrene monomer, is included. In the copolymer composed of this combination of monomers, the proportion of the (meth) acrylic acid ester having the acetoacetyl group is about 2 to 10% by weight, and the proportion of the (meth) acrylic monomer and the styrene monomer is The proportion of the polymerizable vinyl monomer selected and forming a polymer having a glass transition temperature of -50 ° C to 40 ° C is about 98 to 90% by weight.

A particularly preferred combination of the polymerizable unsaturated monomers is (A) a polymerizable unsaturated monomer having an oxocarboxylic acid acyl group [particularly, a (meth) acrylic acid ester having an acetoacetyl group [for example, , Acetoacetoxy-C _2-4 alkyl (meth) acrylates such as 2-acetoacetoxyethyl (meth) acrylate]],
(B1) hard monomer, (B2) soft monomer and (B3)
) A combination with an unsaturated monomer having a carboxyl group or a salt thereof is included. In the copolymer composed of this combination of monomers, the proportion of each monomer is (A) 1 to 15% by weight, (B1) 20 to 80% by weight, (B2) 20 to 80% by weight, and ( B3) 0.1 to 10% by weight.

The introduction of the oxocarboxylic acid acyl group into the polymer particles was produced by emulsion-polymerizing a mixture of the ethylenically unsaturated compound having the functional group and the polymerizable unsaturated monomer (B). The oxocarboxylic acid acyl group may be introduced into the polymer particles by reacting the polymer particles with an oxocarboxylic acid acylating reagent, and the mixture is polymerized to obtain the polymer and the oxocarboxylic acid acylating reagent. The reaction may be carried out by introducing an acyl oxocarboxylate group and emulsifying the resulting polymer. The introduction of the oxocarboxylic acid acyl group into the polymer particles or the polymer can be performed according to the methods (i) to (iii).

The aqueous emulsion composition of the present invention can be manufactured by a conventional method. For example, it can be obtained by emulsion-polymerizing a polymerizable unsaturated monomer containing the monomer having an oxocarboxylic acid acyl group in an aqueous medium.

The emulsion polymerization can be carried out using a polymerization initiator. Examples of the polymerization initiator include persulfates such as potassium persulfate, sodium persulfate and ammonium persulfate, and water-soluble polymerization initiators such as hydrogen peroxide. The polymerization initiator may constitute a water-soluble redox type polymerization initiator system. The amount of the polymerization initiator used is not particularly limited, and for example, it is sufficient if it is used in an amount of 0.1 to 5% by weight, preferably 0.2 to 2% by weight, based on the entire polymerizable unsaturated monomer. .

In order to adjust the molecular weight of the polymer, various chain transfer agents, for example, alcohols such as catechols, thiols, mercaptans and the like may be used.
The amount of the chain transfer agent used is, for example, about 0.01 to 3 parts by weight, preferably about 0.05 to 2.5 parts by weight, based on 100 parts by weight of the total amount of the polymerizable unsaturated monomer.

In the emulsion polymerization, various emulsifiers,
For example, anionic surfactants (eg, sodium dodecylbenzene sulfonate, sodium alkyl diphenyl ether disulfonate, sodium alkyl naphthalene sulfonate, sodium lauryl sulfate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkylphenyl ether sulfate, dialkyl Sodium sulfosuccinate, etc., nonionic surfactants (eg, polyoxyethylene lauryl ether, polyoxyethylene oleyl phenyl ether,
Surfactants such as poly (ethyleneethylene nonylphenyl ether) and oxyethylene / oxypropylene block copolymers) and protective colloids such as polyvinyl alcohol and water-soluble polymers can be used. When using a reactive emulsifier having a polymerizable unsaturated group,
The emulsifier is not always necessary. The amount of the emulsifier used is, for example, 0.1 to 0.1 with respect to the entire polymerizable unsaturated monomer.
The amount is 10% by weight, preferably 0.5 to 7% by weight, more preferably 1 to 5% by weight.

The polymerization method can be carried out in accordance with a conventional emulsion polymerization method. For example, a method in which the polymerizable unsaturated monomers are charged all at once and polymerized, or the polymerizable unsaturated monomers are continuously added. Alternatively, there may be mentioned a method of intermittently supplying and polymerizing. Further, in the case of continuously supplying, a method of polymerizing while dropping a polymerizable unsaturated monomer, a pre-emulsion method of preliminarily emulsifying and polymerizing a monomer, a method of combining the above methods, etc. Can be adopted.

Furthermore, when a plurality of polymerizable unsaturated monomers are copolymerized, for example, the polymerizable unsaturated monomer (A) having an oxocarboxylic acid acyl group and the polymerizable unsaturated monomer (B ) With the monomer (A) is added in the latter part of the polymerization, or the concentration of the monomer (A) in the monomer added in the latter part of the polymerization is increased, the surface layer portion of the polymer particles The concentration of the oxocarboxylate acyl group may be increased. In such a method, it may be possible to reduce the amount of the polymerizable unsaturated monomer (A) having the oxocarboxylic acid acyl group. In addition, in emulsion polymerization, a conventional method such as a multistage polymerization method or a seed polymerization method can be employed.

The polymerization reaction can be selected according to the kind of the polymerization initiator and is usually 40 to 100 ° C., preferably 50 to 90.
C., more preferably about 60 to 85.degree. C., and the reaction time is usually 1 to 12 hours (for example, 2 to 10 hours).
Time).

When an acidic monomer is used, at a suitable stage from the start to the end of emulsion polymerization, or after emulsion polymerization,
When the pH is adjusted by adding a basic substance, the emulsion polymerization stability, freezing stability, mechanical stability, chemical stability and the like can be improved. The pH of the emulsion is
Although not particularly limited, for example, it is often 5 or more, preferably 6 or more, and more preferably about 6 to 9 in a neutral to weakly alkaline region. If the pH is less than 5, a sufficient cross-linking effect may not be obtained during coating film formation. Even if the pH exceeds 9, the cross-linking reaction proceeds at the time of forming the coating film, but the alkalinity becomes strong, so that care must be taken in handling.

Examples of the basic substance include organic bases (for example, chain amines such as monomethylamine, monoethylamine, dimethylamine, diethylamine, trimethylamine and triethylamine; cyclic amines such as morpholine and piperidine; monoethanolamine and dimethyl). Alkanolamines such as ethanolamine and triethanolamine; nitrogen-containing heterocyclic compounds such as pyridine) and inorganic bases (eg, ammonia, potassium hydroxide, sodium hydroxide) can be used.

In the above aqueous emulsion composition, the particle size of the polymer particles may be in the range that does not impair the film forming property, dispersion stability, mechanical stability, etc., and is, for example, 0.0
The thickness is 1 to 1 μm, preferably 0.01 to 0.5 μm, and more preferably 0.01 to 0.3 μm.

The crosslinkable aqueous emulsion composition of the present invention contains an amino compound having a plurality of amino groups in the molecule, in addition to the polymer particles into which the oxocarboxylic acid acyl group has been introduced.

In the amino compound, one of the hydrogen atoms bonded to the amino group may be substituted with a lower alkyl group such as methyl or ethyl group. Such amino compounds include, for example, diamines, polyamines,
Examples include hydrazines, dicarboxylic acid dihydrazides, carbonic acid polyhydrazides, and the like. These amino compounds may be used alone or in combination of two or more.

Examples of the diamines include polymethylenediamine such as ethylenediamine, N, N'-dimethylethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine and heptamethylenediamine. And o-xylylenediamine, m-xylylenediamine, p-xylylenediamine and the like having 2 carbon atoms
To about 20 aliphatic diamines; polyether glycol diamines such as ethylene glycol bis (2-aminoethyl) ether; alicyclic diamines having about 3 to 10 carbon atoms such as 1,2-cyclohexyldiamine and 1,4-cyclohexyldiamine. 1,2-phenylenediamine, 1,3-phenylenediamine, 1,4-phenylenediamine, 1,4
-Aromatic diamines having about 6 to 20 carbon atoms such as naphthylenediamine, 4,4'-diaminodiphenylmethane and 4,4'-diaminodiphenylsulfone.

Examples of the polyamines include polyalkylene polyamines having about 4 to 20 carbon atoms such as polyethylene polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine and pentaethylenehexamine; 1,2,3-triaminopropane and the like. Examples thereof include aliphatic triamines having about 3 to 20 carbon atoms; aromatic triamines having about 6 to 20 carbon atoms such as 1,2,3-aminobenzene.

Examples of hydrazines include hydrazine, 1,6-dihydrazinohexane, 1,4-dihydrazinobenzene, and 1,4-diaminopiperidine.

Examples of dicarboxylic acid dihydrazides include oxalic acid dihydrazide, malonic acid dihydrazide,
Saturated aliphatic dicarboxylic acid dihydrazide having about 2 to 14 carbon atoms such as succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide; maleic acid dihydrazide, fumaric acid dihydrazide,
Itaconic acid dihydrazide, citraconic acid dihydrazide,
Unsaturated aliphatic dicarboxylic acid dihydrazides having about 4 to 14 carbon atoms such as mesaconic acid dihydrazide; 1,4-cyclohexanedicarboxylic acid dihydrazide, phthalic acid dihydrazide, isophthalic acid dihydrazide, terephthalic acid dihydrazide, 1,5-naphthalenedicarboxylic acid dihydrazide, etc. Carbocyclic dicarboxylic acid dihydrazide; and heterocyclic dicarboxylic acid dihydrazide such as 3,5-pyridinedicarboxylic acid dihydrazide. Carbonic acid polyhydrazides include carbonic acid dihydrazide and the like.

Of these amino compounds, diamines, polyamines, hydrazines, dicarboxylic acid dihydrazides and the like are preferable. More preferable amino compounds include polymethylenediamine having about 2 to 12 carbon atoms such as tetramethylenediamine and hexamethylenediamine;
Preferred are polyethylene polyamines having about 4 to 16 carbon atoms such as diethylene triamine and triethylene tetramine; hydrazines; saturated aliphatic dicarboxylic acid dihydrazides having about 2 to 12 carbon atoms such as succinic acid dihydrazide and adipic acid dihydrazide.

The amino compound may be insoluble or sparingly soluble in the solvent system of the aqueous emulsion composition, but
Often soluble or dispersible. Such amino compounds usually include water-soluble or hydrophilic amino compounds.

In the crosslinkable aqueous emulsion composition of the present invention, the ratio of the amino group of the amino compound to the oxo group of the polymer particles is, for example, amino group / oxo group (molar ratio) = 0.6 to 1.4, preferably Is 0.8 to 1.2,
More preferably, it is about 0.9 to 1.1. When the ratio (molar ratio) of the amino group to the oxo group is less than 0.6, the unreacted oxo group remains, so that the oxo group cannot be effectively used in the crosslinking reaction, and when the ratio exceeds 1.4. Since the amino compound remains in the coating film, the water resistance of the coating film may decrease.

A particularly preferred crosslinkable aqueous emulsion is
Polymethylenediamine having 2 to 12 carbon atoms, 4 to 1 carbon atoms
6 polyethylene polyamine, hydrazines and at least one compound selected from saturated aliphatic dicarboxylic acid dihydrazides having 2 to 12 carbon atoms, and amino of amino compound with respect to oxo group (eg, acetoacetyl group) of polymer particles The ratio of the groups is amino group / oxo group (molar ratio) = 0.8 to 1.2, particularly 0.9 to 1.1.

In the crosslinkable aqueous emulsion composition of the present invention, as described above, the polymer particles having an oxo group in the molecule and the compound having a plurality of amino groups in the molecule coexist in an aqueous system. Therefore, the crosslinking reaction hardly progresses, and not only storage stability but also mechanical stability is remarkably high.
Since the aqueous emulsion composition has high miscibility and dispersion stability, the addition of the amino compound does not impair the storage stability and mechanical stability.

In the crosslinkable aqueous emulsion composition of the present invention, when the coating film is formed, the dehydration condensation reaction between the oxo group of the polymer particles and the amino group of the compound smoothly proceeds due to the evaporation of water, and the glycidyl group is formed. Cross-linking efficiency is higher than that of the cross-linking reaction between a carboxyl group and an amino group. Therefore, the polymer is crosslinked even at room temperature of about 10 to 40 ° C., and a crosslinked coating film having good heat resistance, solvent resistance and water resistance can be obtained. The crosslinkable aqueous emulsion composition of the present invention can be crosslinked by heating, if necessary. In addition, the crosslinkable aqueous emulsion composition of the present invention is a one-pack type and can be used in the neutral range, so that it is excellent in handleability.

The crosslinkable aqueous emulsion composition of the present invention can be prepared by simply mixing the aqueous emulsion composition containing the polymer particles having an acyl oxocarboxylate group introduced therein with the compound having a plurality of amino groups in the molecule. It can be obtained by simple operation. The aqueous emulsion and the amino compound are mixed by a conventional mixing method, for example, stirring,
It can be performed by an operation such as shaking. Upon mixing, the amino compound may be added directly to the aqueous emulsion composition or diluted with a diluent such as water or alcohol.

In the aqueous emulsion composition and the crosslinkable aqueous emulsion composition of the present invention, various additives, for example, a film forming aid, a dispersant such as a surfactant, an emulsifier, a surface conditioner, Antiseptic, antibacterial agent, antifoaming agent, color pigment, extender pigment, filler, thickener, plasticizer, rust preventive agent, organic solvent (for example, alcohols such as ethanol and isopropanol, cellosolves, carbitols) , Aliphatic,
Alicyclic or aromatic hydrocarbons, esters such as ethyl acetate, ketones such as acetone and methyl ethyl ketone, ethers, etc.) may be added.

The aqueous emulsion composition and the crosslinkable aqueous emulsion composition of the present invention can be used in a wide range such as coating agents, paints, printing inks, adhesives, paper processing, fiber processing, cement admixtures.

[0072]

EFFECTS OF THE INVENTION The aqueous emulsion composition of the present invention contains polymer particles into which an acyl group of oxocarboxylic acid has been introduced, and therefore, when used in combination with a compound having a plurality of amino groups in the molecule, a crosslinked coating film at room temperature is obtained. It is useful in obtaining a crosslinkable aqueous emulsion composition that forms

The crosslinkable aqueous emulsion composition also comprises
A crosslinked coating film can be easily formed at room temperature. This crosslinkable aqueous emulsion composition is excellent in storage stability and mechanical stability even if it is a one-pack type. Furthermore, it is possible to form a crosslinked coating film which is excellent in handleability, can effectively utilize the functional group in the crosslinking reaction, and has good heat resistance, solvent resistance, and water resistance.

According to the method of the present invention, the aqueous emulsion composition and the crosslinkable aqueous emulsion composition having the above-mentioned excellent properties can be easily produced without any special method.

[0075]

EXAMPLES The present invention will be described in more detail below based on examples and comparative examples.

Reference Example 1 359.5 g of pure water was placed in a reactor (2 liter flask) equipped with a stirrer, a reflux condenser, a dropping device and a thermometer.
Then, 5 g of sodium polyoxyethylene nonylphenyl ether sulfate was charged, and the mixture was heated to a temperature of 80 ° C. under nitrogen atmosphere and 2.5 g of ammonium persulfate was added and dissolved while stirring.

Then, an emulsified mixture of 210 g of styrene, 240 g of n-butyl acrylate, 10 g of acrylic acid, 20 g of acetoacetoxyethyl methacrylate, 140 g of pure water and 13 g of sodium polyoxyethylene nonylphenyl ether sulfate was placed in the reactor for 3 hours. And continuously dripped. After the dropwise addition was completed, heating was continued for another hour, then cooled to room temperature, and ammonia water was added as a neutralizing agent to adjust the pH to 7. The obtained aqueous emulsion composition has a solid content of 49.8% by weight and a viscosity of 400 c.
ps (room temperature, the same applies hereinafter) and the average particle size was 143 nm.

Hexamethylenediamine (5.5 g) was added to the obtained aqueous emulsion composition to obtain a crosslinkable aqueous emulsion composition.

Reference Example 2 A reactor similar to that of Reference Example 1 was charged with 259.5 g of pure water and 8 g of sodium polyoxyethylene nonylphenyl ether sulfate, heated to a temperature of 80 ° C. under a nitrogen blanket, and stirred. 2.5 g of ammonium persulfate was added and dissolved.

Then, 200 g of methyl methacrylate,
250 g of 2-ethylhexyl acrylate, 10 g of methacrylic acid, 20 acetoacetoxyethyl methacrylate
g, 240 g of pure water, and 10 g of sodium polyoxyethylene nonylphenyl ether sulfate were continuously added dropwise into the reactor over 3 hours. After the dropping is completed,
After heating was continued for another hour, the temperature was cooled to room temperature, and aqueous ammonia was added as a neutralizing agent to adjust the pH to 7.
The obtained aqueous emulsion composition had a solid content of 49.9% by weight, a viscosity of 600 cps, and an average particle diameter of 126 nm.

Hexamethylenediamine (5.5 g) was added to the obtained aqueous emulsion composition to obtain a crosslinkable aqueous emulsion composition.

[0082] except for using adipic acid dihydrazide 8.2g instead Example 1 hexamethylenediamine 5.5 g, in the same manner as in Reference Example 1 to obtain a crosslinkable aqueous emulsion composition.

Reference Example 3 A crosslinkable aqueous emulsion composition was obtained in the same manner as in Reference Example 1 except that 10 g of acetoacetoxyethyl methacrylate was used. The solid content of the aqueous emulsion composition before the addition of hexamethylenediamine is 49.3% by weight,
The viscosity was 500 cps and the average particle size was 138 nm.

Comparative Example 1 A reference was made except that 20 g of glycidyl methacrylate was used instead of 20 g of acetoacetoxyethyl methacrylate.
An aqueous emulsion composition was prepared in the same manner as in Consideration 1. The solid content of this aqueous emulsion composition was 49.7% by weight, the viscosity was 390 cps, and the average particle size was 145 nm. Hexamethylenediamine was not added to this aqueous emulsion composition.

Comparative Example 2 To the aqueous emulsion composition obtained in the same manner as in Comparative Example 1, 5.5 g of hexamethylenediamine was added to obtain a crosslinkable aqueous emulsion composition.

Comparative Example 3 An aqueous emulsion composition was obtained in the same manner as in Reference Example 1 without using acetoacetoxyethylmethacrylate and hexamethylenediamine. This aqueous emulsion composition has a solid content of 48.8% by weight and a viscosity of 550c.
ps, average particle diameter was 129 nm.

The emulsion compositions obtained in the above-mentioned Examples , Reference Examples and Comparative Examples had film-forming properties, mechanical stability and storage stability, and heat resistance, water resistance and gel of the dried film of the above-mentioned aqueous emulsion compositions. The content rate was examined by the following test method.

(1) Film-forming property: The emulsion composition was coated on a glass plate [10 cm × 20 cm × 2 mm (thickness)] at a coating amount of 10 g / m ² after drying, dried at room temperature, and visually observed to the following criteria. The film forming property was evaluated by.

◯: A transparent and uniform coating can be obtained ×: Cracks are generated in the coating (2) Mechanical stability: Rotation speed 1 using a Maron type tester
A mechanical frictional force was applied to the emulsion composition under the conditions of 000 rpm, a load of 25 kg, and a rotation time of 15 minutes.
The generated coarse particles were filtered with a 100-mesh filter, the filter cake was dried, and the weight was measured to determine the amount of generated coarse particles (mg / kg) per 1 kg of the emulsion composition.

(3) Storage stability: The emulsion composition was placed in a closed container and stored at 50 ° C. for 1 month, and the change in viscosity was examined. The ratio (%) of the viscosity change to the initial viscosity was determined and evaluated according to the following criteria.

◯: ≦ ± 10% Δ: ± 10% to ± 20% ×: ≧ ± 20% (4) Heat resistance: The emulsion composition was applied to an aluminum foil using a bar coater No. The test piece was coated with No. 6 and laminated with high-quality paper and pressure-bonded with a rubber roller, followed by curing at room temperature for 7 days. This test piece was heat-sealed for 60 seconds with a heat-sealing tester, and the temperature at which abnormal appearance occurred was determined.

(5) Water resistance: The emulsion composition was coated on a Teflon plate and dried at room temperature for 7 days to give a thickness of about 1
A 0 μm film was prepared and used as a test piece. After the test piece was immersed in water for 3 days, the whitening state of the test piece was visually observed and evaluated according to the following criteria.

⊚: Transparent ◯: Slightly whitened Δ: Fairly whitened ×: Whitened (6) Gel content: After measuring the weight (W1) of the test piece prepared in the same manner as in (5) above, Was immersed in ethyl acetate for 3 days. The weight (W2) of the solid content dissolved in ethyl acetate was determined, and the gel content was calculated by the following formula.

Gel content (%) = [(W1−W2) / W1] × 100 The results are shown in the table. In addition, in the storage stability test of the emulsion compositions obtained in Comparative Examples 1 and 2, the viscosity was remarkably lowered. As is clear from the table, the aqueous emulsion compositions of Examples are superior to the aqueous emulsion compositions of Comparative Examples in film-forming property, mechanical stability and storage stability, and the heat resistance and water resistance of the obtained coating film are excellent. The properties and gel content are significantly improved.

[0095]

[Table 1]

─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP 61-197649 (JP, A) JP 61-78883 (JP, A) JP 5-148432 (JP, A) JP 7- 90154 (JP, A) JP-A-7-62191 (JP, A) JP-A-7-102218 (JP, A) JP-A-7-228786 (JP, A) International Publication 93/016133 (WO, A1) (JP 58) Fields surveyed (Int.Cl. ⁷ , DB name) C08L 101/02 C08L 33/04-33/14

Claims (7)

(57) [Claims] 1. An oxocarboxylic acid acyl group is introduced.
Aqueous emulsion containing polymer particles and multiple in the molecule
Crosslinkable aqueous solution containing amino compound having amino group
An emulsion composition, The polymer particles areFor all polymerizable unsaturated monomers
2.5-7.5% by weight(A) Acyl oxocarboxylate
Group-containing polymerizable unsaturated monomerAnd (B) oxocarvone
Non-Reactive Copolymerizable Polymers Inert to Acid Acyl Groups
Composed of a copolymer with a compatible unsaturated monomer, The non-reactive polymerizable unsaturated monomer (B) is , (B1)
At least to form a polymer having a glass transition temperature of 50 ° C. or higher
Also one hard monomer, (B2) glass transition temperature 25 ℃ or more
At least one soft monomer forming the polymer below,
And1 to 5% by weight based on the whole polymerizable unsaturated monomer
(B3) Unsaturated monomer having carboxyl group or salt thereof
In the bodyComposed, Previous The aqueous emulsion is neutralized with a neutralizing agent,
The compound is, JCarboxylic acid dihydrazideIn kindAh, However, the amount by which the polymer particles constitute the copolymer
Body as an expression [Chemical 1] (In the formula, R ¹ Represents hydrogen or a methyl group, and R ² Is lower
Represents a alkylene group, Y ¹ Is hydrogen or a lower alkyl group
Does not include a monomer represented by The aqueous emulsion composition has the following core part (C)
And (D) a copolymer particle comprising a shell part, and
Copolymer comprising core of (E) and shell of (F) below
Free of particles Crosslinkable aqueous emulsion composition.(C) The following (c-1) to (c-3), (c-1) Monomer 60-100 represented by the following general formula (1)
weight%, [Chemical 2] (However, in the formula R ³ Is hydrogen or a methyl group, X is COO
R ^Four , OCOR ^Five , An aryl group having 6 to 8 carbon atoms or CN
And R ^Four Is a linear or branched alkane having 1 to 18 carbon atoms
Kill group, cycloalkyl group having 6 to 8 carbon atoms or carbon number
7 to 12 aralkyl groups, R ^Five Is hydrogen or carbon number 1 to
12 straight or branched alkyl groups) (c-2) 0 to 20% by weight of acetoacetyl group-containing monomer, and
And (c-3) In addition to one radically polymerizable unsaturated group in the molecule,
A monomer having at least one functional group,
0 to 20% by weight of monomers other than the monomer (c-2), provided that
(C-1) to (c-3) total 100% by weight]
A glass transition point Tg _C Is -60 to 80
℃ is the core, and (D) The following (d-1) to (d-3), (d-1) Monomers 50 to 99. represented by the following general formula (1).
95% by weight, [Chemical 3] (However, in the formula R ³ And X are the same as above) (d-2) Acetoacetyl group-containing monomer 0.05 to 30 weight
%,as well as, (d-3) In addition to one radically polymerizable unsaturated group in the molecule,
A monomer having at least one functional group,
Monomers other than the monomer (d-2) 0 to 20% by weight, provided that
the total of (d-1) to (d-3) is 100% by weight]
And its glass transition point Tg _D Is -40 to +100
Tg of the core (co) polymer at 0 ° C _C taller than,
It consists of a shell that covers the core, and is compatible with 100 parts by weight of the core.
Copolymer particles in which the shell is 5 to 100 parts by weight, (E) The following copolymers (e-1) to (e-4), which are
Transition point Tg _E Formed of a copolymer of -30 to + 70 ° C
Core part, (e-1) selected from monomers represented by the following general formula (2)
At least one (meth) acrylic acid ester monomer 3
0-99.9% by weight, [Chemical 4] (However, in the formula R ⁶ Is hydrogen or a methyl group, R ⁷ Has 1 carbon
To 20 straight or branched alkyl groups) (e-2) 0 to 20% by weight of acetoacetyl group-containing monomer, and
And (e-3) C3 to C5 α, β-unsaturated mono- or di
-0.1 to 10% by weight of carboxylic acid, and (e-4) Copolymerizable monomer other than (e-1) to (e-3) 0 to 50
% By weight (however, the total of (e-1) to (e-4) above is 100% by weight
And] (F) The following copolymers (f-1) to (f-4), which are
Transition point Tg _F Is −40 to + 60 ° C., and Tg _F ≤T
g _E Coated with a core satisfying the requirements
Shell, (f-1) Monomers represented by the following general formula (2) 30 to 99.
9% by weight, [Chemical 5] (However, in the formula R ⁶ And X are the same as above) (f-2) Acetoacetyl group-containing monomer 0.1 to 20 weight
%, (f-3) α, β-unsaturated mono- or di-containing 3 to 5 carbon atoms
0 to 10% by weight of carboxylic acid, and (f-4) Copolymerizable monomer other than (f-1) to (f-3) 0 to 50
% By weight [however, the total of (f-1) to (f-4) above is 100% by weight
And the weight ratio of the core / the shell is 95/5.
~ 50/50 copolymer particles Wherein (A) having an acetoacetyl group-containing (meth) acrylic acid ester le 2.5 to 7.5 wt%, (B
1) Styrene-based monomer, (B2) acrylic acid ester having an alkyl group having 1 to 12 carbon atoms and 4 to 12 carbon atoms
At least one soft monomer selected from methacrylic acid esters having an alkyl group and (B3) a copolymer of 1 to 5 % by weight of (meth) acrylic acid, and a styrenic monomer (B1). ) And the soft monomer (B2), the ratio is styrene-based monomer / soft monomer = 20 to 80/8.
The content of the polymer particles is 0 to 20% by weight and dicarboxylic acid dihydrazide, and the ratio of the acetoacetyl groups of the polymer particles to the amino groups of the dicarboxylic acid dihydrazide is such that amino group / acetoacetyl group (molar ratio) = 0. 6 ~
The aqueous emulsion composition according to claim 1, which is 1.4. 3. The aqueous emulsion composition according to claim 1, wherein the oxocarboxylic acid acyl group is an acetoacetyl group. Wherein the amino compound is at least one compound in which claim 1 the crosslinkable aqueous emulsion composition according selected from saturated aliphatic dicarboxylic acid dihydrazide having a carbon number of 2-12. 5. The ratio of the oxo group of the polymer particles and the amino group of the amino compound is amino group / oxo group (molar ratio).
= 0.8-1.2, The crosslinkable aqueous emulsion composition according to claim 1. 6. A crosslinkable aqueous emulsion composition, which comprises mixing the aqueous emulsion containing the polymer particles having an oxocarboxylic acid acyl group introduced therein according to claim 1 and an amino compound having a plurality of amino groups in the molecule. a manufacturing method, the aqueous emulsion was neutralized with a neutralizing agent, di mosquito <br/> crosslinkable aqueous claim 1 admixed with at least one amino compound selected carboxylic acid dihydrazide compound or al Method for producing emulsion composition. 7. An aqueous emulsion composition obtained by emulsion-polymerizing a polymerizable vinyl monomer containing a polymerizable unsaturated monomer having an oxocarboxylic acid acyl group in an aqueous medium. The manufacturing method according to claim 6 .