JPH02155956A - Cold-crosslinking cationic emulsion composition - Google Patents

Abstract

PURPOSE:To obtain the title composition of improved long-term storage stability by adding a polyhydrazide compound as a crosslinking agent to a cationic emulsion obtained by dispersing a carbonyl group containing copolymer in water. CONSTITUTION:A cationic emulsion (A) is obtained by emulsion-polymerizing 100pts.wt. mixture of 0.1-40wt.% carbonyl group containing copolymer as a monomer having at least one aldehyde or keto group and one radical- polymerizable double in the molecule with another ethylenically unsaturated monomer copolymerizable therewith in water in the presence of a radical polymerization initiator and 0.1-10pts.wt. cationic surfactant. A crosslinking agent (B) which is a polyhydrazide compound in an amount to give a ratio of the carbonyl groups of component A to the hydrazide groups of component B of (1-100)/(100-1), desirably (3-1)/(1-2) is added to component A.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a cold crosslinkable cationic emulsion composition.

(Prior art and its problems) Conventionally, organic solvent-based paints have been used because of their poor film-forming properties and coating performance.

However, organic solvent-based paints are unfavorable in terms of environmental protection and safety because the organic solvents in the paints are volatilized into the atmosphere during painting or drying. Various water-based emulsions have been developed to replace organic solvent-based paints and are now widely used.

Aqueous emulsions form a coating film by the volatilization of water and the fusion of emulsion particles, but the performance of the coating film is not sufficient. For this reason, when a higher level of coating performance is required, a method used in boat fishing is to introduce functional groups into the aqueous emulsion and utilize the functional groups during drying to form a crosslinked coating film.

As the aqueous emulsions that form the crosslinked coating, two types of aqueous emulsions have been developed: a one-component type in which a crosslinking agent is incorporated into the aqueous emulsion, and a two-component type in which a crosslinking agent is added before coating. This method is not commonly used because it has drawbacks such as the troublesome addition of a crosslinking agent and the need to consider the time (pot life) between adding the crosslinking agent and painting.

- For wave-shaped aqueous emulsions, a method of crosslinking using a combination of functional groups such as an oxirane group and an amino group or a carbonyl group and a hydrazide group has been carried out.

In the former aqueous emulsion, the reaction between oxirane groups and amino groups proceeds at room temperature, so the oxirane groups are introduced into the emulsion particles, and the amino groups are introduced into the aqueous phase by a crosslinking agent such as polyamine, so that the functional groups of both is separated in an aqueous system. However, this aqueous emulsion has the disadvantage that during long-term storage, self-reaction between oxirane groups within the particles and reactions between oxirane groups and amino groups gradually proceed, resulting in poor long-term storage stability.

Regarding the latter aqueous emulsion, research has been carried out and many reports have been made. , Japanese Patent Publication No. 58-10
4902, JP 61-136501, JP 62-72742, JP 63-17991
Publication No. 0 discloses that a copolymer of a carbonyl group-containing unsaturated monomer, an unsaturated carboxylic acid (or an amide group-containing monomer), and other monomers is used as an anionic and/or nonionic emulsifier. An aqueous emulsion in which a hydrazide compound (or hydrazide polymer) is added to an aqueous emulsion emulsified with is described. In these aqueous emulsions, the emulsion particles are uncharged or negatively charged by an anionic or nonionic emulsifier, and the hydrazide compound easily enters the particles (so that the reaction between the carbonyl group and the hydrazide group gradually progresses). The disadvantage is that the emulsion has poor storage stability.

Therefore, there is a drawback that the hydrazide compound easily enters the emulsion particles, resulting in poor emulsion storage stability. In addition, JP-A-55-147557 and JP-A-55-147,562 disclose an aqueous solution in which a copolymer of a carbonyl group-containing unsaturated monomer, an unsaturated carboxylic acid, and other monomers is emulsified with an emulsifier. Aqueous emulsions are described in which a hydrazide or hydrazone compound is added to the emulsion. As mentioned above, these aqueous emulsions have carboxyl groups in the emulsion particles, so the emulsion storage stability is poor, and although nonionic, anionic, and cationic surfactants are disclosed as emulsifiers, Nonionic and anionic surfactants are used, and these have the disadvantage of poor long-term storage stability of emulsions.

(Means for Solving the Problems) The present inventors have conducted extensive research in order to solve the problems of the prior art as described above. As a result, they discovered that a cationic emulsion obtained by water dispersing a carbonyl group-containing copolymer that does not substantially have carboxyl groups has excellent long-term storage stability. 1. Completed the present invention. I ended up doing it.

That is, the present invention relates to a room-temperature crosslinking type cationic emulsion composition, which is characterized by adding a polyhydrazide compound as a crosslinking agent to a cationic emulsion obtained by dispersing a carbonyl group-containing copolymer in water.

In the composition of the present invention, the cationic emulsion to which the crosslinking agent is added is a carbonyl group-containing unsaturated monomer (A) and other ethylenically unsaturated monomers capable of radical copolymerization with the monomer (A). CB) by emulsion polymerization using a cationic surfactant in the presence of a radical initiator.

The carbonyl group-containing unsaturated monomer (A) is a monomer having at least one aldehyde group or keto group and one radically polymerizable double bond in one molecule, that is, a particularly polymerizable monomer. These are olefinically unsaturated aldehyde compounds and keto compounds. Typical specific examples include acrolein, diacetone acrylamide, diacetone methacrylamide, formylstyrene, acrylamide pivalaldehyde, methacrylamide pivalaldehyde, 3-acrylamidomethyl-anisaldehyde, diacetone acrylate, acetonyl acrylate, diacetone Examples include methacrylate, 2-hydroxypropyl acrylate acetylacetate, butanediol acrylate acetylacetate, vinyl alkyl ketone, and the like. Among the above compounds, keto compounds are preferred.

The monomer (A) is about 0.1 to 40% by weight, preferably about 2 to 3% by weight, based on the total amount of monomer (A) and monomer (B).
It can be blended in a proportion of 0% by weight, more preferably 5 to 20% by weight. If the proportion of monomer (A) is less than about 0.1% by weight, a sufficiently crosslinked coating film cannot be obtained;
) is more than about 40% by weight, the storage stability of the aqueous emulsion deteriorates.

Other ethylenically unsaturated monomers (B) are not particularly limited as long as they have a double bond that can radically polymerize with the monomer (A), depending on the required coating performance. It can be selected and used as appropriate. Specifically, for example, (1) methyl acrylate, methyl methacrylate,
Ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, tert
-butyl acrylate, tert-butyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, lauryl acrylate,
Alkyl or cycloalkyl esters of acrylic acid or methacrylic acid having 1 to 24 carbon atoms, such as lauryl methacrylate, stearyl acrylate, stearyl methacrylate, decyl acrylate, etc.: (2) Acrylic or cycloalkyl esters such as acrylamide, methacrylamide, dimethylacrylamide, etc. Methacrylamide; (3) Styrene, vinyltoluene, vinyl propionate, α-methylstyrene, vinyl acetate, acrylonitrile, methacrylonitrile, vinylpropionate, vinyl bivalate, beoba monomer (Shell Chemical Products),
Ethylenically unsaturated monomers such as ethylene, propylene, butylene, and pentene: (4) Diene compounds such as butadiene, isoprene, and chlorobrene, and the like.

The above monomers or compounds (1) to (4) can be used alone or in a mixture of two or more.

In addition to the monomers or compounds (1) to (4) described above, the following cationic vinyl monomers can be used. When the cationic vinyl monomer is used, a positively charged barrier layer is formed on the surface of the aqueous emulsion particles,
Since the approach of positively charged polyhydrazide compounds is prevented, the storage stability of the aqueous emulsion is improved. Furthermore,
The cationic vinyl monomer is bonded to the particles through chemical bonds and is more stable in the system than the cationic surfactant that is physically adsorbed to the particles, so this monomer is used. This makes it possible to obtain an aqueous emulsion with even better long-term storage stability. However, since the cationic vinyl monomer inhibits the reaction between the carbonyl group and the polyhydrazide group, in order to obtain a sufficiently crosslinked coating film, the amount of the cationic vinyl monomer is preferably about 10% by weight or less based on the total amount of monomers. It is necessary to blend it in an amount of 5% by weight or less.

Specific examples of the cationic vinyl monomer include dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, and adducts with dimethylaminepropylamine. Furthermore, a salt obtained by neutralizing the cationic group of the above-mentioned cationic vinyl monomer with an acid or a quaternized salt may also be used.

Furthermore, in addition to the above monomers, hydrophilic monomers such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and polyethylene glycol (meth)acrylate may also be used depending on the required coating performance. Polyfunctional monomers such as acrylates can be used in combination with the above monomers.

The radical polymerization initiator used for copolymerizing the monomer (A) and monomer (B) can be used without any particular restrictions. Specifically, for example, l-[1-cyano-methylethyl)azo]formamide, 2.2'-
Azo initiators such as azobis(2-methyl-N-[1,1-bis(hydroxymethyl)ethyl]propionamide), azobisisobutyronitrile, etc.: hydrogen peroxide,
Nonionic initiators such as peroxide initiators such as tert-butyl hydroperoxide, cumene hydroperoxide, etc.: 2.2'-azobis(2-methylpropionamidine) dihydrochlorite, 2.2 ′−
Azobis(2-(5-methyl-2-imidacyline-2-
yl)propane] dihydrochloride, 2.2゛-azobis[2-(2-imidacillin-2-yl)-propane] dihydrochloride, 2.2゛-azobis[2-
Cationic azo initiators such as (4,5,6,7-tetrahydro IH-1,3-diazepin-2-yl)propane]dihydrochloride and the like can be suitably used.

As the cationic surfactant used in the copolymerization reaction of the monomer (A) and monomer (B), conventionally known ones can be used. Specifically, for example, octadecyltrimethylammonium chloride, dodecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, dioctadecyldimethylammonium chloride, didodecylmethylammonium chloride, dodecylbenzyldimethylammonium chloride, tetradecylbenzyldimethyl...ammonium chloride, occudecylbenzyldimethylammonium chloride, tetradecyltrimethylammonium chloride, dioctadecyldimethylammonium chloride, dioctadecyldimethylammonium chloride, hexadecylbenzyldimethylammonium chloride, palmityltrimethylammonium chloride, oleyltrimethylammonium chloride, civalmitylbenzyltrimethylammonium chloride, Dioleylbenzyltrimethylammonium chloride, decyl ammonium methyl sulfate, N-ethyldodecylammonium bromide, cetyl ammonium bromide, N chloride
, N-dimethyldodecyl ammonium, N,N-dimethylstearylammonium chloride, laurylpyridinium chloride, polyoxyethylene dodecylamine, polyoxyethylene hexadecylamine, polyoxyethylene octadecylamine, dodecylamine acetate, tetradodecylamine acetate, octadecyl Compounds such as amine hydrochloride, dodecylamine hydrochloride, tetradecylamine hydrochloride, octadecylamine hydrochloride, and hardened beef tallow amine acetate are mentioned. In addition to those mentioned above, cationic polymers containing the cationic vinyl monomer as an essential component, cationic polyvinyl alcohol, reactive emulsifiers, etc. can also be used. The above-mentioned cationic surfactants may be one or two types.
Can be used by mixing more than one species. Furthermore, the cationic surfactant described above and the nonionic surfactant described below can be used in combination.

The blending ratio of the cationic surfactant is approximately 0 per 100 parts by weight of the monomer (A) and monomer (B) in terms of storage stability of the aqueous emulsion and curability of the coating film. .1 to 10 parts by weight, preferably about 0.5 to 5 parts by weight.

The emulsion polymerization method using the monomer, initiator, and cationic surfactant can be carried out by a conventionally known emulsion polymerization method.

In addition to the above, the cationic emulsion used in the composition of the present invention may also include (1) the carbonyl group-containing unsaturated monomer (A) and the cationic vinyl monomer as essential monomers. (2) the carbonyl group-containing unsaturated monomer, in which the component monomer is polymerized in the presence of the nonionic radical initiator, or further polymerized using a cationic and/or nonionic surfactant; (A) and the other ethylenically unsaturated monomer (B) are polymerized in the presence of an initiator containing a cationic initiator as an essential component, or further polymerized using a nonionic surfactant. Those obtained by can also be used.

Examples of the nonionic surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether and polyoxyethylene lauryl ether:
Polyoxyethylene alkylphenyl ethers such as polyoxyethylene nonylphenyl ether and polyoxyethylene octylphenyl ether; polyoxyethylene alkyl esters such as polyoxyethylene monolaurate and polyoxyethylene monostearate; sorbitan monolaurate and sorbitan. Sorbitan esters such as monostearate; sorbitan ester ethers such as polyoxyethylene sorbitan monolaurate; polyoxyethylene oxybrobylene block polymer, polyethylene glycol, and the like.

Also, dimethylalkyl betaine, lauryl betaine,
Amphoteric surfactants such as stearyl betaine can also be used in combination.

These polymerizations can be carried out according to conventionally known polymerization methods.

In the composition of the present invention, the polyhydrazide compound as a crosslinking agent added to the cationic emulsion is not particularly limited as long as it has two or more hydrazide groups I (-C-NH-NH2) in one molecule. Can be used. Specifically, aliphatic carboxylic acid dihydrazide having 2 to 10 carbon atoms, such as oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide and/or sebacic acid dihydrazide, etc.: carbonic acid polyhydrazide For example, λ carbonic acid dihydrazide and a compound represented by the general formula % formula % (in the formula, X means a number from 1 to 5, preferably 1 to 3): bissemicarbazide, especially the general formula % formula % (in the formula the group -R- is a linear or branched aliphatic residue having 2 to 7 carbon atoms or a carbocyclic residue having 6 to 8 carbon atoms, such as 〇-m- or p-phenylene group, toluylene group, cyclohexylidene group or methylcyclohexylidene group); polyhydrazides of aromatic polycarboxylic acids, such as dihydrazides of phthalic acid, terephthalic acid or isophthalic acid; and dihydrazide, trihydrazide or tetrahydrazide of pyromellitic acid: polyhydrazide of polyacrylic acid having at least 2, often 20 to 100 hydrazide groups in one molecule ditrihydrazide, for example nitrilotriacetic acid trihydrazide Or a tetrahydrazide such as ethylenediaminetetraacetic acid tetrahydrazide.

Further examples of the hydrazides that can be used include the following. or trihydrazine-triazine,
Thiocarbohydrazide or N,N'-diaminoguanidine, as well as hydrazine-pyridine derivatives such as 2-
hydrazinopyridine-5-carboxylic acid hydrazide, 3-
Chlor-2-hydrazinopyridine-5-carboxylic acid hydrazide, 6-chloro-2-hydrazinopyridine-4-carboxylic acid hydrazide or 2,5-dihydrazinopyridine-4-carboxylic acid, etc. and bis-thiosemicarbazide,
and bishydrazines of alkylene bisacrylamides, hydrazine alkanes and dihydrazines of aromatic hydrocarbons, such as 1,4-dihydrazinobenzole, 1.3
- dihydrazinobenzole, 2,3-dihydrazine naphthalene, and dihydrazides of monoolefinically unsaturated dicarboxylic acids, such as maleic dihydrazide, fumaric acid dihydrazide and itaconic acid dihydrazide.

If the above-mentioned polyhydrazide compound itself is too hydrophilic, the emulsion storage stability will be poor, and on the other hand, if it is too hydrophobic, water dispersion will be difficult and a uniform crosslinked coating film will not be obtained. It is preferable to use a compound with a relatively low molecular weight (approximately 300 or less) that has hydrophilic properties. 04-1, such as succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, sepatic acid dihydrazide, etc.
The dihydrazide compound of dicarboxylic acid No. 2 is mentioned.

The amount of the polyhydrazide compound to be added is such that the ratio of the number of hydrazide groups in the polyhydrazide compound to the carbonyl groups in the aqueous emulsion is 1.
/100-100/1, preferably l/l O-10/
1, more preferably 3/1 to 1/2.

A crosslinked coating film can be obtained from the composition of the present invention by drying at room temperature, but it can also be heated if necessary.

Pigments, dyes, organic solvents, plasticizers, preservatives, coating surface conditioners, etc. can be added to the composition of the present invention as required.

The composition of the present invention is useful for paints, lining materials, sealing materials, fiber processing, adhesives, and the like.

(Functions and Effects) As described above, in the composition of the present invention, the emulsion particles are positively charged in the system and repel the positively charged hydrazide compound in the aqueous dispersion medium layer. Since it is possible to prevent infiltration into the water, it exhibits excellent long-term storage stability.

(Example) Next, the present invention will be described in more detail with reference to Examples. "Parts" and "%" in the production examples are based on weight.

Aqueous emulsion A = H production side Manufacturing example 1 2e Put the following into the flask.

Deionized water 170 parts V
-50 (manufactured by Wako Pure Chemical Industries, Ltd., trade name, 2.2°
-Azobis (2-methylpropiona
midin) dihydrochloride, hereinafter referred to as
(expressing the same meaning)
Prepare a pre-emulsion by thoroughly stirring the following formulation in 0.6 parts portions.

Deionized water 340 parts Cortamine 86P Conc (Kao Corporation, trade name, stearyltrimethylammonium chloride) 23 parts V-503, 5 parts Styrene 150 parts 2-
Ethylhexyl acrylate 300 parts Diacetone acrylamide 50 parts 2I2. After heating the contents of the flask to 80° C., the pre-emulsion is added dropwise over 2-3 hours to effect emulsion polymerization. 30 minutes after the completion of the dropping, the V-50 was heated to 0.
Add 5 parts dissolved in 10 parts deionized water.

Furthermore, after aging for 30 minutes at the same temperature, emulsion A was obtained by cooling. The characteristics of emulsion A are shown in Table 1.
It was shown to.

Manufacturing example 2 Put the following into a 2°C flask.

Deionized water 170 parts V
-50 Make a pre-emulsion by thoroughly stirring the following formulation in 0.6 parts portions.

Deionized water 340 parts Cortamine 86P Conc 15 parts Neugen EA130T (manufactured by Dai-Kogyaku Co., Ltd., trade name, polyoxyethylene nonylphenyl ether)
10 parts V-503, 5 parts styrene 150 parts 2-
A mixture of 300 parts of ethylhexyl acrylate and 50 parts of diacetone acrylamide was synthesized in the same manner as in Production Example 1 to obtain emulsion B. The characteristics of the emulsion B are shown in Table-1.

Manufacturing example 3 22 Put the following into the flask.

Deionized water 170 parts V
-50 Prepare a pre-emulsion by thoroughly stirring the following formulation in 0.6 parts.

Deionized water 435.7 parts Cortamine 86P Conc 23 parts V-5
03.5 parts Styrene 95 parts 2-ethylhexyl acrylate 370 parts Diacetone acrylamide 25 parts Dimethylaminopropylacrylamide 10 parts The above blend was synthesized in the same manner as in Production Example 1 to obtain Emulsion C. Ta. The characteristics of the emulsion C are shown in Table 1.

Production example 4 Put the following into a 2I2 flask.

Deionized water 170 parts V
-50 Make a pre-emulsion by thoroughly stirring the following formulation in 0.6 parts portions.

Deionized water 340 parts Cortamine 86P Conc 23 parts V-50
3.5 parts Styrene 150 parts 2-ethylhexyl acrylate 325 parts Diaseptone acrylamide 25 parts
Emulsion D was obtained by synthesis in the same manner as above.

The characteristics of the emulsion D are shown in Table 1.

Manufacturing example 5 2! ! Add the following to the flask.

Deionized water 170 parts V-
50 Prepare a pre-emulsion by thoroughly stirring the following formulation in 0.6 parts.

Deionized water 340 parts Cortamine 86P Conc 23 parts V-50
3.5 parts Styrene 150 parts 2-ethylhexyl acrylate 250 parts Diacetone acrylamide loo parts The above-mentioned formulation was synthesized in the same manner as in Production Example 1 to obtain Emulsion E. The characteristics of the emulsion E are shown in Table 1.

Manufacturing example 6 Add the following to a 2°C flask.

Make a pre-emulsion by stirring well the following formulation in 200 parts deionized water portions.

Deionized water 285 parts Levelshile WZ (manufactured by Kao Corporation, trade name, sodium polyoxyethylene alkylphenyl ether sulfate) 58
parts ammonium persulfate 2.5 parts styrene 150 parts 2-ethylhexyl acrylate 300 parts diacetone acrylamide 5 parts additional production except that the catalyst used was 0.5 parts ammonium persulfate dissolved in 10 parts deionized water. Emulsion F was obtained by synthesis in the same manner as in Example 1. The characteristics of the emulsion F are shown below.
Shown in 1.

Manufacturing example 7 Add the following to the 2I2 flask.

Make a pre-emulsion by stirring well the following formulation in 200 parts deionized water.

Deionized water 285 parts Emal 2F needle (manufactured by Kao Corporation, trade name, sodium lauryl sulfate) 19 parts Ammonium persulfate 2.5 parts Styrene
150 parts 2-ethylhexyl acrylate 300 parts diacetone acrylamide
Emulsion G was obtained by synthesizing 50 parts of the above blend in the same manner as in Production Example 6. The emulsion G
The characteristics are shown in Table-1.

Production example 8 Add the following to the 2β flask.

Make a pre-emulsion by stirring well the following formulation in 200 parts deionized water.

Deionized water 285 parts Level W2 50 parts Ammonium persulfate 2.5 parts Styrene
90 parts 2-ethylhexyl acrylate 340 parts diacetone acrylamide 50 parts acrylic acid
10 parts acrylamide
Emulsion H was obtained by synthesis in the same manner as in Production Example 6. The characteristics are shown in Table-1.

Production Examples of Crosslinking Agents X and Y Production Example 1 174.2 parts of dimethyl adipate 100.1 parts of hydrazine (monohydrate) 224 parts of deionized water are placed in a 2β flask and heated to 80°C. Crosslinking agent X was obtained by continuing the reaction at the same temperature for 10 hours. The crosslinking agent forms a white solid crystal in water at room temperature, but becomes a homogeneous aqueous solution when heated.

Production Example 2 Dimethyl malonate 139 parts Hydrazine (l hydrate) 105 parts Deionized water 332 parts 2
The mixture was placed in a No. 12 flask and heated at 80° C. for 7 hours to obtain a crosslinking agent Y. The crosslinking agent forms a white solid crystal in water at room temperature, but becomes a homogeneous aqueous solution when heated.

Table-1 Examples and comparative examples Add crosslinking agent X to emulsion A-H obtained in Production Example.

Examples 1 to 1 were prepared by mixing Y in the combinations shown in Table 2 so that the compounding ratio was equivalent to carbonyl group and hydrazide.
Aqueous emulsions of O and Comparative Examples 1 to 6 were obtained.

The storage stability and properties of the crosslinked coating film are summarized in Table 2.

The medium particle size was measured by turbidity method.

The clear emulsion diluted with water was measured using a spectrophotometer, and the absorbance ratio was calculated using the following formula.
Industrial, Chemical, Re5
earth VoL, 42P145-152 (196
The average particle diameter was determined using the calibration curve described in [4]].

It was stored in a 225 cc mayonnaise bottle. The state of the emulsion after storage was visually evaluated.

○: No change, ◎: A lump is observed in a small part,
△: The viscosity is considerably thickened. ×: The whole is hardened.

Umbrella mixed solvent (dioxane/benzyl alcohol/
Methyl isobutyl ketone = 5/4.510°5) 100
An amount of emulsion having a solid content of 1 g was added to cc. The progress of the reaction during storage of the polymer in the emulsion particles was investigated from the solubility of the emulsion at that time. (The solubility of the emulsion before being left at room temperature for 1 day is ○ in both Examples and Comparative Examples.) O: Dissolved within 2 hours, ◎: Difficult to dissolve, △2 cloudy 5X
: Undissolved as lumps.

The umbrella** mixture was applied to a glass plate using a 25 mil doctor blade, and after drying at room temperature for 7 days, the coating film was immersed in acetone for 3 days and the residue was measured.

hand Continued Supplementary Positive 1 big Day (spontaneous)

Claims (2)

[Claims] (1) A room-temperature crosslinkable cationic emulsion composition, characterized in that a polyhydrazide compound is added as a crosslinking agent to a cationic emulsion obtained by dispersing a carbonyl group-containing copolymer in water. (2) The composition according to claim 1, wherein the carbonyl group-containing copolymer has substantially no carboxyl groups.