JPH10130387A - Hydrazine hydrate derivative composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a hydrazine hydrate derivative composition that contains a mixture of a polyhydrazine compound with a ketonic acid and/or its salt, has both high a low-temperature curability and high a storage stability, and provides a coating excelling in water and stain resistance, etc. SOLUTION: This hydrazine hydrate derivative composition contains a mixture of (A) a polyhydrazine compound having two or more hydrazine moieties, and (B) a ketonic acid and/or its salt, in which component (A) is preferably a semicarbazide derivative of the formula (R1 is polyisocyanate moiety which is derived from oligomers of from trimer to vicenimer and does not contain terminal isocyanate, or a triisocyanate moiety which is derived from a 2-20C alkylene diisocyanate and does not contain terminal isocyanate; R2 is H or a 1-20C alkyl; R3 is a 5-20C cycloalkylene, 6-10C arylene, etc.; (n) is 0 or 1; (1) and (m) are each 0 or a positive integer provided that (1)+(m) is 3-20).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a paint, a base material or a finishing material for building materials, an adhesive, a paper processing agent, or a woven fabric.
Compositions useful as nonwoven fabric finishing agents, etc., specifically, aqueous hydrazine derivative compositions and clear coats, top coats, paints, undercoats, cloth and paper impregnants, adhesives using the same The present invention relates to an excellent coating composition that can be used for various applications.

[0002]

2. Description of the Related Art In recent years, aqueous emulsions have attracted attention in the field of coating as a conversion material from an organic solvent type to an aqueous type. However, they are still insufficient in water resistance, stain resistance, hardness, etc. as compared with organic solvent type coating agents. It does not show proper physical properties. For the purpose of improving these properties, it is common practice to introduce a functional group into an aqueous emulsion to form a crosslinked coating film.

As an aqueous emulsion for forming a crosslinked coating film, there is a great demand for a one-part, room-temperature curing type from the viewpoint of workability, workability, and the like. Aqueous emulsions have attracted attention. For example,
No. 20053, JP-A-57-3850, JP-A-57-3857, JP-A-58-96643, JP-A-4-249587, WO96 / 012
In pamphlet No. 52 and the like, by adding a polyfunctional carboxylic acid hydrazide compound or a semicarbazide derivative having a specific structure as a curing agent to a carbonyl group-containing aqueous emulsion, it has both low-temperature curability and storage stability,
A coating composition excellent in hardness, stain resistance and the like has been proposed.

However, a polyfunctional carboxylic hydrazide compound as a curing agent has a disadvantage that it is difficult to control hydrophilicity. That is, when a compound having high hydrophilicity such as adipic acid dihydrazide is used as a curing agent, the resulting coating film has extremely poor water resistance. Conversely, low hydrophilic compounds such as sebacic acid dihydrazide,
It is difficult to use the aqueous emulsion as a curing agent.

Further, even when a semicarbazide derivative is used as a curing agent for an aqueous emulsion containing a carbonyl group, controlling the hydrophilicity of the semicarbazide derivative provides both low-temperature curability and storage stability, water resistance, stain resistance, This is the point of technology necessary for forming a film having excellent hardness and the like, but a technology capable of obtaining sufficient performance has not yet been developed.

[0006]

An object of the present invention is to provide an aqueous hydrazine derivative composition having both low-temperature curability and storage stability and capable of forming a film having excellent water resistance, stain resistance, hardness and the like. And a coating composition using them.

[0007]

Means for Solving the Problems The inventors have made intensive studies to solve the above-mentioned problems, and as a result, have reached the present invention. That is, a first aspect of the present invention is an aqueous hydrazine derivative composition containing a mixture of a polyhydrazine compound having two or more hydrazine residues in one molecule, and a ketone acid and / or a salt thereof.

A second aspect of the present invention is that the polyhydrazine compound is
The aqueous hydrazine derivative composition according to the first aspect of the present invention, which is a semicarbazide derivative composition represented by the formula (1).

[0009]

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Wherein R ¹ is a linear or branched alkylene diisocyanate having 2 to 20 carbon atoms, a cycloalkylene diisocyanate having 5 to 25 carbon atoms which may or may not have a substituent; Arylene diisocyanate having 6 to 20 carbon atoms which may or may not have a substituent,
And 8 to 20 carbon atoms which may or may not have a substituent
A polyisocyanate residue having no terminal isocyanate group, derived from at least one dimer to dimer oligomer of at least one diisocyanate selected from the group consisting of aralkylenediisocyanates, or R ¹ has ¹ carbon atom
Represents a triisocyanate residue having no terminal isocyanate group, which is derived from an alkylene diisocyanate having 2 to 20 carbon atoms which is substituted by an isocyanatoalkyl group having from 8 to 8 carbon atoms.

R ² represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. R ³ is a linear or branched C 1
Represents an alkylene group having 20 to 20 carbon atoms, a cycloalkylene group having 5 to 20 carbon atoms, or an arylene group having 6 to 10 carbon atoms which may or may not have a substituent. n represents 0 or 1. l and m each represent 0 or a positive integer. However, 20 ≧ (l + m) ≧ 3. A third aspect of the present invention is the aqueous hydrazine derivative composition according to the first or second aspect, wherein the ketone acid or a salt thereof is represented by the formula (2) or (4).

[0012]

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｛R ⁴ is a hydrogen atom, a phenyl group, an unsubstituted or a hydroxyl group or a group having 1 to 1 carbon atoms.
Represents a linear or branched alkyl group having 1 to 30 carbon atoms, which is substituted with an alkoxy group of 8; R ⁵ represents a linear or branched alkylene group having 1 to 30 carbon atoms which is substituted by or substituted or a hydroxyl group or an alkoxy group having 1 to 8 carbon atoms. p represents 0 or 1. X represents a hydrogen atom, an alkali metal, ammonium or a substituted ammonium represented by the formula (3).

HNR ⁶ R ⁷ R ⁸ (3) (R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom,
Or a linear or branched C1-C20 alkyl group which is not substituted or substituted with a hydroxyl group. R ⁶ and R ⁷ , R ⁷ and R ⁸ , R ⁶ and R
⁷ and R ⁸ may form a cyclic structure together. )｝

[0015]

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｛R ⁹ and R ¹⁰ are each independently unsubstituted or substituted with a hydroxyl group or an alkoxy group having 1 to 8 carbon atoms, which is linear or branched and has 1 to 30 carbon atoms. Represents an alkylene group. q and r each represent 0 or 1. Y and Z each independently represent a hydrogen atom, an alkali metal, ammonium or a substituted ammonium represented by the formula (3).

HNR ⁶ R ⁷ R ⁸ (3) (R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom,
Or a linear or branched C1-C20 alkyl group which is not substituted or substituted with a hydroxyl group. R ⁶ and R ⁷ , R ⁷ and R ⁸ , R ⁶ and R
⁷ and R ⁸ may form a cyclic structure together. The fourth aspect of the present invention is the aqueous hydrazine derivative composition according to any one of the first to third aspects of the present invention, which comprises alkenylsuccinic acid and / or a salt thereof.

A fifth aspect of the invention is a coating composition containing the aqueous hydrazine derivative composition according to any one of the first to fourth aspects of the invention and a polycarbonyl compound and / or a polyepoxy compound. A sixth aspect of the present invention is the coating composition according to the fifth aspect of the present invention, which comprises a monoketone represented by the formula (5).

R ¹¹ R ¹² C ＝ O (5) wherein R ¹¹ and R ¹² are each a hydrogen atom, a linear or branched aliphatic residue having 2 to 20 carbon atoms,
It represents at least one selected from an alicyclic residue having 20 carbon atoms and an aromatic residue which may or may not have a substituent. R ¹¹ and R ¹² may form a cyclic structure. Hereinafter, the present invention will be described in detail.

In the present invention, the polyhydrazine compound having two or more hydrazine residues in one molecule refers to a compound having two or more hydrazine residues represented by the formula (6) in one molecule. —NR ² NH ₂ (6) (wherein, R ² represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.) A monohydrazine compound having only one hydrazine residue in one molecule will be described later. It is not preferable because it has no or very small cross-linking ability for the polycarbonyl compound and the like described above.

In the present invention, hydrazine is regarded as a category of monohydrazine compounds. Examples of the polyhydrazine compound include a polyhydrazide compound, a polysemicarbazide compound, and a carbonated polyhydrazide represented by the formula (7).

[0022]

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(In the formula, x represents an integer of 0 to 20.) Specific examples of the polyhydrazide compound include oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide,
Glutaric acid dihydrazide, adipic acid dihydrazide, pimelic acid dihydrazide, suberic acid dihydrazide, azelaic acid dihydrazide, sebacic acid dihydrazide, dodecanediohydrazide, hexadecandiohydrazide,
1,4-cyclohexanedihydrazide, tartaric acid dihydrazide, malic acid dihydrazide, iminodiacetic acid dihydrazide, maleic acid dihydrazide, fumaric acid dihydrazide,
Itaconic dihydrazide, isophthalic dihydrazide,
Terephthalic dihydrazide, 2,6-naphthoic dihydrazide, 1,4-naphthoic dihydrazide, 4,4'-
Dicarboxylic acid dihydrazides such as bisbenzene dihydrazide and 2,6-pyridine dihydrazide; tricarboxylic acid trihydrazides such as 1,3,5-cyclohexanetricarboxylic acid trihydrazide, trimellitic acid trihydrazide, citric acid trihydrazide and nitriloacetic acid trihydrazide. , Pyromellitic acid tetrahydrazide, 1,4,5
Examples thereof include tetracarboxylic acid tetrahydrazides such as 8-naphthoic acid tetrahydrazide and ethylenediaminetetraacetic acid tetrahydrazide, and acid hydrazide polymers represented by the formula (8) and having a number average molecular weight of 500 to 500,000 or a combination thereof. Can be

[0024]

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Wherein X is a hydrogen atom or a carboxyl group, Y is a hydrogen atom or a methyl group, and A is a monomer selected from acrylamide, methacrylamide, acrylate, methacrylate and maleic anhydride. And B is a polymerized unit of a monomer copolymerizable with acrylamide, methacrylamide, acrylate, methacrylate, and maleic anhydride, and l, m and n are as follows: The following shows the mole fraction of each component that satisfies each of the equations.

2 mol% ≦ l ≦ 100 mol% 0 mol% ≦ m + n ≦ 98 mol% l + m + n = 100 mol% The acid hydrazide-based polymer may be a random copolymer or a block copolymer. Among the above polyhydrazide compounds, when a poorly water-soluble polyhydrazide compound is used as a curing agent for the coating composition, a film having excellent water resistance can be obtained, which is preferable. Here, poor water solubility means that the solubility in 100 g of water at 25 ° C. is 1 g or less.

Among the polyhydrazine compounds according to the present invention, polysemicarbazide compounds are most preferred because of their good hydrolysis resistance of hydrazine residues. Specific examples of the polysemicarbazide compound include a semicarbazide derivative represented by the formula (1), a bissemicarbazide represented by the formula (9), and the like.

[0028]

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Wherein R ¹ is a linear or branched alkylene diisocyanate having 2 to 20 carbon atoms, a cycloalkylene diisocyanate having 5 to 25 carbon atoms which may or may not have a substituent; Arylene diisocyanate having 6 to 20 carbon atoms which may or may not have a substituent,
And 8 to 20 carbon atoms which may or may not have a substituent
A polyisocyanate residue having no terminal isocyanate group, derived from at least one dimer to dimer oligomer of at least one diisocyanate selected from the group consisting of aralkylenediisocyanates, or R ¹ has ¹ carbon atom
Represents a triisocyanate residue having no terminal isocyanate group, which is derived from an alkylene diisocyanate having 2 to 20 carbon atoms which is substituted by an isocyanatoalkyl group having from 8 to 8 carbon atoms.

R ² represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. R ³ is a linear or branched C 1
Represents an alkylene group having 20 to 20 carbon atoms, a cycloalkylene group having 5 to 20 carbon atoms, or an arylene group having 6 to 10 carbon atoms which may or may not have a substituent. n represents 0 or 1.

L and m each represent 0 or a positive integer.
However, 20 ≧ (l + m) ≧ 3. )

[0032]

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(Wherein, R ¹³ is a linear or branched divalent aliphatic residue having 2 to 20 carbon atoms;
Divalent alicyclic residue, divalent aromatic residue having 6 to 25 carbon atoms which may or may not have a substituent, and carbon which may or may not have a substituent It represents a divalent aromatic alicyclic residue of the formulas 6 to 25. R ² represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. Among the above polysemicarbazide compounds, the semicarbazide derivative represented by the formula (1) is polyfunctional and has good compatibility with a polycarbonyl compound and the like described later when used as a curing agent for the coating composition. Therefore, it is very preferable because a film having high crosslinking ability, toughness, and excellent water resistance can be obtained.

The semicarbazide derivative represented by the formula (1) can be obtained by reacting a polyisocyanate compound having three or more —NCO groups in one molecule with a hydrazine derivative. Examples of the polyisocyanate compound having three or more -NCO groups in one molecule include oligomerization by forming a diisocyanate compound into a buret bond, a urea bond, an isocyanurate bond, a urethane bond, an allophanate bond, a uretdione bond, or the like. Polyisocyanate compounds, and combinations thereof.

Examples of the diisocyanate compound include alkylene diisocyanates such as hexamethylene diisocyanate (HDI), 4,4'-methylenebiscyclohexyl diisocyanate (hydrogenated MDI), isophorone diisocyanate (IPDI), and dimethylcyclohexane diisocyanate (hydrogenated). XDI), 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate and mixtures thereof (TDI), diphenylmethane-4,4'-diisocyanate (MDI), naphthalene-1,5-diisocyanate ( NDI), 3,3-dimethyl-4,4-
Biphenylene diisocyanate (TODI), crude TD
I, polymethylene polyphenyl diisocyanate, crude MDI, arylene diisocyanate such as phenylene diisocyanate, xylylene diisocyanate (XD
Aralkylenediisocyanates such as I) and the like, and combinations thereof.

Of these diisocyanate compounds, alkylene diisocyanate and cycloalkylene diisocyanate are preferred from the viewpoint of improving heat resistance yellowing, weather resistance and the like of a film using a composition containing the resulting semicarbazide derivative. Furthermore, in addition to the above-mentioned polyisocyanate compounds, alkylene diisocyanates having 2 to 20 carbon atoms and substituted with an isocyanatoalkyl group having 1 to 8 carbon atoms, such as 1,8-diisocyanato-4-isocyanatomethyloctane, etc. From the viewpoint of compatibility with a polycarbonyl compound described below, it is preferable to use the above-described polyisocyanate compound obtained by oligomerizing a diisocyanate compound.

In the present invention, the semicarbazide derivative synthesized using the polyisocyanate compound having three or more —NCO groups in one molecule is polyfunctional, and can provide a high crosslink density and a tough film. If the number of semicarbazide groups in one molecule is too large, the viscosity of the generated semicarbazide derivative becomes high and handling becomes difficult. Therefore, the number of -NCO groups in one molecule of the polyisocyanate compound used for the synthesis of the semicarbazide derivative is preferably 3 to 20.

Among these polyisocyanate compounds, the semicarbazide derivative derived therefrom has excellent compatibility with the polycarbonyl compound and the like described below, and the hardness of the film formed from the coating composition containing the semicarbazide derivative, Preferable ones in terms of chemical resistance, heat resistance and the like include, for example, those having an isocyanurate structure or a burette structure as a basic skeleton.
In addition, examples of those having excellent flexibility of a film obtained from a coating composition with a polycarbonyl compound or the like include those having a urethane structure as a basic skeleton.

Examples of the polyisocyanate compound having an isocyanurate structure as a basic skeleton include isocyanurate-type polyisocyanates of hexamethylene diisocyanate as described in JP-A-55-38380 and JP-A-57-78460. Copolymerized isocyanurate type polyisocyanate of isophorone diisocyanate and hexamethylene diisocyanate as described in JP-A-57-47321, and isocyanurate modified with a polyfunctional alcohol as described in JP-A-57-47321. Low-viscosity isocyanurate-type polyisocyanate as described in JP-A-64-33115.
A cyclic trimerization reaction of a diisocyanate compound in the presence of a catalyst, such as a highly branched isocyanurate-type polyisocyanate described in US Pat. %, Preferably 10 to 60% by weight, and a polyisocyanate compound having an isocyanurate structure obtained by removing and purifying an excess diisocyanate compound.

Examples of the polyisocyanate compound having a burette structure as a basic skeleton include, for example, those described in
No. 106797, JP-A-55-11452 and the like, hexamethylene diisocyanate-based bullet type polyisocyanate,
No. 95259, a copolymer of isophorone diisocyanate and hexamethylene diisocyanate represented by a burette-type polyisocyanate and the like. Agent / diisocyanate in an equivalent ratio of 1/2 to 1/100, preferably 1
After reacting at / 3 to 1/50, a polyisocyanate compound having a buret structure obtained by removing and purifying an excess diisocyanate compound is exemplified.

Examples of the polyisocyanate compound having a urethane structure as a basic skeleton include, for example, JP-A-61-2
No. 8518 and JP-A-4-50277, etc., after reacting polycaprolactone polyol and diisocyanate at an equivalent ratio of -NCO / -OH of 5 to 40, and removing and purifying excess diisocyanate. The resulting urethane-type polyisocyanate is exemplified. In particular, when the molecular weight is less than 2,000, in addition to flexibility, water resistance, heat resistance and the like are excellent, and high hardness can be exhibited.

Examples of the hydrazine derivative to be reacted with the polyisocyanate compound include hydrazine and its hydrates, monoalkylhydrazines such as methylhydrazine and ethylhydrazine, ethylene-1,2-dihydrazine, and the like.
Propylene-1,3-dihydrazine, butylene-1,4
Dihydrazine compounds such as dihydrazine, oxalic acid dihydrazide, malonic acid dihydrazide, succinic dihydrazide,
Dicarboxylic acid dihydrazides such as glutaric acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, maleic acid dihydrazide, fumaric acid dihydrazide, itaconic acid dihydrazide, isophthalic acid dihydrazide, phthalic acid dihydrazide, etc .; Examples include carbonic acid polyhydrazides represented by the following general formula (7), bissemicarbazides represented by the following general formula (9), and the like, and combinations thereof.

[0043]

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(Where x represents an integer of 0 to 20)

[0045]

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(Wherein R ¹³ is a linear or branched divalent aliphatic residue having 2 to 20 carbon atoms;
Divalent alicyclic residue, divalent aromatic residue having 6 to 25 carbon atoms which may or may not have a substituent, and carbon which may or may not have a substituent It represents a divalent aromatic alicyclic residue of the formulas 6 to 25. R ² represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. ) In producing the semicarbazide derivative, the equivalent ratio of the NCO groups of the polyisocyanate compounds described above, a group capable of being converted into a ₂ group or -NHNH ₂ group -NHNH in hydrazine derivatives, 1: 1.2 to 100, Preferably it is 1: 2-80, more preferably 1: 4-50.
When the equivalent ratio is less than 1: 1.2, the product has a high molecular weight and the increase in viscosity is not preferable. Also 1: 1
If it is larger than 00, unreacted hydrazine derivatives are undesirably present in large amounts.

After the production of the semicarbazide derivative, the excess hydrazine derivative can be removed by distillation, extraction or the like, if necessary. The semicarbazide composition can be produced without a solvent or in a solvent. Solvents which are inert to the NCO groups or less active than the reaction components can be used. The solvent may remain in the semicarbazide composition, but can also be distilled off by heating under normal pressure or reduced pressure.

Examples of the ketone acid in the present invention include monoketone monocarboxylic acids represented by the formula (10), monoketone dicarboxylic acids represented by the formula (11), and a combination thereof.

[0049]

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(R ⁴ is a hydrogen atom, a phenyl group, an unsubstituted or a hydroxyl group or a C 1 -C
Represents a linear or branched alkyl group having 1 to 30 carbon atoms, which is substituted with an alkoxy group of 8; R ⁵ represents a linear or branched alkylene group having 1 to 30 carbon atoms which is substituted by or substituted or a hydroxyl group or an alkoxy group having 1 to 8 carbon atoms. p represents 0 or 1. )

[0051]

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(R ⁹ and R ¹⁰ are each independently unsubstituted or substituted with a hydroxyl group or an alkoxy group having 1 to 8 carbon atoms, which is linear or branched and has 1 to 30 carbon atoms. And q and r each represent 0 or 1.) Specific examples of the monoketone carboxylic acids include, for example, pyruvic acid, levulinic acid, acetoacetic acid, trimethylpyruvic acid, propionylacetic acid, benzoylformic acid, and phenyl. Pyruvic acid, ketocapric acid, ketoundecanoic acid, ketostearic acid, ketoheneicosenoic acid, benzoylacetic acid, benzoylpropionic acid, ketoglyconic acid and the like.

Specific examples of the monoketone dicarboxylic acid include, for example, ketomalonic acid, acetone dicarboxylic acid and 2-ketone dicarboxylic acid.
Ketoglutaric acid, acetone diacetic acid, acetone dipropionic acid and the like can be mentioned. The salt of ketone acid can be obtained by neutralizing the above ketone acid with a base. As the base used for neutralization, for example, KOH, NaOH, LiOH
And the like, amines represented by the formula (3), and the like, and combinations thereof.

NR ⁶ R ⁷ R ⁸ (3) (R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom,
Or a linear or branched C1-C20 alkyl group which is not substituted or substituted with a hydroxyl group. Further, R ⁶ and R ^7, or R ⁶ , R ⁷ and R ⁸ may form a cyclic structure together. Specific examples of the above amines include, for example, ammonia, diethylamine, dipropylamine, dibutylamine, N
-Methylethanolamine, diethanolamine, dimethylcyclohexylamine, methyldiethanolamine, dimethylethanolamine, triethanolamine, triethylamine, pyrrolidine, piperidine, morpholine and the like.

In the present invention, an aqueous hydrazine derivative composition whose hydrophilicity can be largely controlled can be obtained by mixing the above-mentioned polyhydrazine compound with a ketone acid and / or a salt thereof. However, ketone acid used in the present invention, for example, ester derivatives such as vinyl levulinate,
An amide derivative such as trimethylpyruvamide is not preferred because the effect of controlling the hydrophilicity of the polyhydrazine compound is lost. Similarly, even if a carboxylic acid such as acetic acid or butyric acid having no carbonyl group of the ketone is used instead of the ketone acid, the hydrophilicity of the polyhydrazine compound cannot be controlled.

By mixing a polyhydrazine compound with a ketone acid, for example, when a monoketone monocarboxylic acid is used as the ketone acid, the following equilibrium reaction occurs, and a carboxyl group or a salt thereof is introduced into the polyhydrazine compound, thereby obtaining It is estimated that the hydrophilicity of the resulting aqueous hydrazine derivative composition can be controlled.

[0057]

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As can be seen from the above equilibrium equation, the aqueous system of the present invention
To control the hydrophilicity of the hydrazine derivative composition,
Along with the mixing ratio of polyhydrazine compound and ketone acid,
H in the hydrazine derivative composition_TwoO concentration greatly affects
You. That is, H_TwoWhen the O concentration is small, the above equilibrium equation is generated
System, the carboxyl group on the polyhydrazine compound
Or the amount of salt introduced increases, and as a result
The hydrophilicity of the gin derivative composition increases. Conversely, H_TwoO concentration
If the degree is large, the hydrophilicity of the aqueous hydrazine derivative composition will decrease.
Will be less. In the present invention, aqueous hydrazine induction
H in body composition _TwoThe O concentration was designed to control the hydrophilicity.
Can be set arbitrarily.

For example, when it is desired to increase the hydrophilicity of the aqueous hydrazine derivative composition in an aqueous solution, it is preferable to use an aqueous solution having a solid content of 0.1% or more. In the aqueous hydrazine derivative composition of the present invention, the mixing of the polyhydrazine compound and the ketone acid and / or a salt thereof can be performed at any ratio, but the mixing of the keto group in the ketone acid with respect to the hydrazine residue in the polyhydrazine compound. The ratio is preferably in the range of 0.001 to 10 in terms of the molar ratio of (keto group) / (hydrazine residue).

The mixing of the polyhydrazine compound and the ketone acid can be performed in an arbitrary temperature range without a solvent or in a solvent. Specific examples of the solvent include water,
alcohols such as t-butanol, isopropanol and 2-butoxyethanol; ether solvents such as dioxane, tetrahydrofuran and diethylene glycol dimethyl ether; amide solvents such as dimethylformamide and dimethylacetamide; lactam solvents such as N-methyl-2-pyrrolidone. , Sulfoxide solvents such as dimethylsulfoxide, ester solvents such as ethyl acetate and cellosolve acetate, aromatic hydrocarbon solvents such as toluene and xylene, aliphatic hydrocarbon solvents such as n-hexane and the like, and combinations thereof. .

The aqueous hydrazine derivative composition of the present invention comprises:
If necessary, a surfactant may be added. Surfactants that can be added include, for example, salts of higher fatty acids, resin acids, acidic fatty alcohols, sulfates, higher alkyl sulfonic acids, alkyl allyl sulfonates, sulfonated castor oil, sulfosuccinates, and alkenyl succinic acids. Surface active agents, or nonionic surfactants typified by known reaction products of ethylene oxide with long-chain fatty alcohols or phenols and phosphoric acids, and cationic interfaces containing quaternary ammonium salts and the like Activators, (partially saponified) polymer dispersion stabilizers such as polyvinyl alcohol, and the like, and combinations thereof.

Of the above surfactants, the addition of alkenyl succinic acid and / or a salt thereof (alkali metal salt or ammonium salt) can greatly improve the water solubility or water dispersibility of the aqueous hydrazine derivative composition. Therefore, it is preferable. Specific examples of these include, for example, Latemul AS
K, Latemul DSK (trade name) (manufactured by Kao Corporation) and the like.

The aqueous hydrazine derivative composition obtained in the present invention has good controllability such as dispersibility or solubility in water, and has reactivity with polycarbonyl compounds and polyepoxy compounds. Water resistance and various curing performances that could not be achieved by the above method. Therefore, the aqueous hydrazine derivative composition of the present invention is useful as a curing agent for a (particularly aqueous) polycarbonyl compound and / or polyepoxy compound.

Here, the polycarbonyl compound refers to a compound having two or more keto groups or ald groups in one molecule. The coating composition of the present invention comprises the above aqueous hydrazine derivative composition and a polycarbonyl compound and / or a polyepoxy compound. Among the coating compositions, the combination of the aqueous hydrazine derivative composition and the polycarbonyl compound has excellent storage stability and gives a film excellent in water resistance, stain resistance, hardness and the like at a relatively low temperature. This is particularly preferred because

As the polycarbonyl compound, for example, a copolymer containing a carbonyl group, JP-A-2-2380
No. 15, carbonyl group-containing polyurethanes using carbonyl group-containing mono- or polyalcohols such as hydroxyacetone as raw materials, acetoacetylated polyvinyl alcohol, acetoacetylated hydroxyalkylcellulose, and the like, and combinations thereof. Is mentioned.

Among these, preferred polycarbonyl compounds are carbonyl group-containing ethylenically unsaturated monomers (a)
And a carbonyl group-containing copolymer obtained by copolymerizing the monomer (A) with an ethylenically unsaturated monomer (B) copolymerizable with the monomer (A), and more preferably a polycarbonyl compound. Is 0.1 to 30% by weight of a carbonyl group-containing ethylenically unsaturated monomer (a) and an ethylenically unsaturated monomer (b) 7 copolymerizable with the monomer (a).
A carbonyl group-containing copolymer obtained by copolymerizing 0 to 99.9% by weight.

Examples of the carbonyl group-containing ethylenically unsaturated monomer (a) include diacetone acrylamide, diacetone methacrylamide, acrolein, vinyl methyl ketone, acetoacetoxyethyl methacrylate, acetoacetoxyethyl acrylate, formylstyrene, and the like. Combination is mentioned. Examples of the ethylenically unsaturated monomer (b) copolymerizable with the monomer (a) include acrylic acid esters, methacrylic acid esters, ethylenically unsaturated monomers having a carboxyl group, and ethylene having an epoxy group. Unsaturated monomers, acrylamide-based monomers, methacrylamide-based monomers, vinyl cyanides, and the like. Examples of (meth) acrylates include those having 1 to 18 carbon atoms in the alkyl portion. (Meth) acrylic acid alkyl ester, (meth) acrylic acid hydroxyalkyl ester having 1 to 18 carbon atoms in the alkyl part, 1 to 100 (poly) oxyethylene (meth) acrylate having 1 to 100 ethylene oxide groups, propylene (Poly) oxypropylene (meth) acrylate having 1 to 100 oxide groups and 1 to 100 ethylene oxide groups Poly) oxyethylene di (meth) acrylate. Specific examples of the (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, methyl (meth) acrylate Cyclohexyl, dodecyl (meth) acrylate and the like. Specific examples of the hydroxyalkyl (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate,
2-hydroxycyclohexyl (meth) acrylate,
Dodecyl (meth) acrylate and the like. (Poly)
Specific examples of oxyethylene (meth) acrylate include ethylene glycol (meth) acrylate, ethylene glycol methoxy (meth) acrylate, diethylene glycol (meth) acrylate, diethylene glycol methoxy (meth) acrylate, and tetramethyl (meth) acrylate. Examples include ethylene glycol and tetraethylene glycol methoxy (meth) acrylate. Specific examples of (poly) oxypropylene (meth) acrylate include:
Propylene glycol (meth) acrylate, propylene glycol methoxy (meth) acrylate, dipropylene glycol (meth) acrylate, dipropylene glycol methoxy (meth) acrylate, tetrapropylene glycol (meth) acrylate, methoxy (meth) acrylic Acid tetrapropylene glycol and the like. Specific examples of (poly) oxyethylene di (meth) acrylate include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, diethylene glycol methoxy (meth) acrylate, and di (meth) acrylate.
Examples include tetraethylene glycol acrylate.

Specific examples of the ethylenically unsaturated monomers having a carboxyl group include acrylic acid, methacrylic acid,
There are itaconic acid, fumaric acid, maleic acid, maleic acid half ester, crotonic acid and the like. Examples of (meth) acrylamide monomers include (meth) acrylamide, N-methylol (meth) acrylamide, N-butoxy Examples include methyl (meth) acrylamide, and examples of vinyl cyanides include (meth) acrylonitrile.

Specific examples of the ethylenically unsaturated monomers having an epoxy group include glycidyl (meth) acrylate,
(Meth) acrylic acid 2,3-cyclohexene oxide, allyl glycidyl ether and the like can be mentioned. Specific examples other than the above include, for example, olefins such as ethylene, propylene and isobutylene, dienes such as butadiene, haloolefins such as vinyl chloride and vinylidene chloride, vinyl acetate, vinyl propionate, n-vinyl butyrate, and benzoic acid. Vinyl acid, vinyl pt-butyl benzoate,
Vinyl carboxylate esters such as vinyl pivalate, vinyl 2-ethylhexanoate, vinyl versatate and vinyl laurate; carboxylate isopropenyl esters such as isopropenyl acetate and isopropenyl propionate; ethyl vinyl ether, isobutyl vinyl ether and cyclohexyl Vinyl ethers such as vinyl ether; aromatic vinyl compounds such as styrene and vinyl toluene; allyl esters such as allyl acetate and allyl benzoate; allyl ethers such as allyl ethyl ether and allyl phenyl ether; and γ- (meth) acryloxy Propyltrimethoxysilane, 4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloyloxy-1,2,2,
6,6, -pentamethylpiperidine, perfluoromethyl (meth) acrylate, perfluoropropyl (meth) acrylate, perfluoropropyromethyl (meth) acrylate, vinylpyrrolidone, trimethylolpropane tri (meth) acrylate, (meth) Examples include allyl acrylate and the like, and combinations thereof.

The polycarbonyl compound is preferably obtained by suspension polymerization, emulsion polymerization or solution polymerization, more preferably a latex obtained by emulsion polymerization. The polycarbonyl compound is an anionic ethylenically unsaturated monomer selected from the group consisting of ethylenically unsaturated monomers having a sulfonic acid group or a sulfonate group, ethylenically unsaturated monomers having a sulfate group, and mixtures thereof. It is preferably obtained by copolymerization in the presence of the monomer (c).

The ethylenically unsaturated monomer having a sulfonic acid group or a sulfonate group has a radically polymerizable double bond and is partially formed by a group which is an ammonium salt, a sodium salt or a potassium salt of a sulfonic acid group. A group consisting of an alkyl group having 1 to 20 carbon atoms, an alkyl ether group having 2 to 4 carbon atoms, a polyalkyl ether group having 2 to 4 carbon atoms, an aryl group having 6 or 10 carbon atoms and a succinic acid group, A compound having a substituent selected from
It is a vinyl sulfonate compound having a vinyl group to which an ammonium salt, a sodium salt or a potassium salt of a sulfonic acid group is bonded.

The ethylenically unsaturated monomer having a sulfate group has a radically polymerizable double bond and is partially substituted by a group which is an ammonium, sodium or potassium salt of a sulfate group. Has 1-2 carbon atoms
0 alkyl group, alkyl ether group having 2 to 4 carbon atoms,
It is a compound having a substituent selected from the group consisting of a polyalkyl ether group having 2 to 4 carbon atoms and an aryl group having 6 or 10 carbon atoms.

As a specific example of the compound having a succinic acid group partially substituted by a group which is an ammonium salt, a sodium salt or a potassium salt of a sulfonic acid group, an allyl sulfosuccinic acid salt such as those represented by formulas (12) and (13) ), (1)
4) and (15).

[0074]

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[0075]

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[0076]

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[0077]

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In the formulas 12 to 15, R ^{1 ′} is hydrogen or a methyl group, R ^{2 ′} is a cycloalkyl group having 5 to 12 carbon atoms, an aryl group having 5 to 10 carbon atoms, A hydrocarbon group such as an aralkyl group, or a group in which a part thereof is substituted with a hydroxyl group, a carboxylic acid group, or the like, or a polyoxyalkylene alkyl ether group (where the alkyl portion has 0 to 20 carbon atoms and the alkylene portion has 2 carbon atoms. To 4), a polyoxyalkylene alkylphenyl ether group (where the alkyl moiety has 0 to 20 carbon atoms and the alkylene moiety has 2 carbon atoms)
Organic group containing an alkylene oxide compound such as A is an alkylene group having 2 to 4 carbon atoms or a substituted alkylene group. n is an integer of 0 to 200.
M is ammonium, sodium, or potassium.と し て As a compound containing the above formulas (12) and (13), for example, Eleminor JS-2 (trade name) (Sanyo Chemical Co., Ltd.)
And those containing the above formulas (14) and (15) include, for example, Latemul S-120, S-180A or S-180 (trade name) (manufactured by Kao Corporation).

An alkyl ether group having 2 to 4 carbon atoms or a C 2 to C 4 partially substituted with a group which is an ammonium salt, a sodium salt or a potassium salt of a sulfonic acid group.
Examples of the compound having a polyalkyl ether group of 4 include a compound represented by the formula (16) or (17).

[0080]

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(Wherein each of R ^{3 ′} and R ^{4 ′} is independently an alkyl group, alkenyl group or aralkyl group having 6 to 18 carbon atoms, and R ^{5 ′} is hydrogen or propenyl group. Is an alkylene group having 2 to 4 carbon atoms, and n is 1 to
It is an integer of 200. M is ammonium, sodium or potassium. )

[0082]

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(Wherein, R ^{6 ′} is hydrogen or a methyl group, R ^{7 ′} is an alkyl group or an acyl group having 8 to 24 carbon atoms, and A is an alkylene group having 2 to 4 carbon atoms. Is an integer of 0 to 20, n is an integer of 0 to 50. M
Is ammonium, sodium or potassium. As the alkylphenol ether-based compound represented by the above formula (16), for example, there is Aqualon HS-10 (trade name) (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), and the above formula (17)
As a compound represented by, for example, Adecaria Soap SE
-1025N (trade name) (manufactured by Asahi Denka Kogyo KK).

Other specific examples of compounds having an aryl group partially substituted by a sulfonate group include p-
Ammonium, sodium and potassium salts of styrene sulfonic acid. Examples of the vinyl sulfonate compound having a vinyl group to which a group which is an ammonium salt, a sodium salt or a potassium salt of a sulfonic acid group is bonded include, for example, alkylsulfonic acid (meth) acrylate such as 2-sulfoethylacrylate and methylpropanesulfonic acid And ammonium salts such as (meth) acrylamide and allylsulfonic acid, sodium salts and potassium salts.

Examples of the compound having an alkyl ether group having 2 to 4 carbon atoms or a polyalkyl ether group having 2 to 4 carbon atoms, which is partially substituted by an ammonium salt, a sodium salt or a potassium salt of a sulfate ester group, include: And a compound having an alkyl ether group partially substituted with a sulfonate group, represented by the formulas (16) and (17).

These anionic ethylenically unsaturated monomers (c) exist in the emulsion as a copolymer obtained by radical polymerization on the emulsion particles, or are adsorbed to the emulsion particles as unreacted substances, or the emulsion aqueous phase It is present in the emulsion particles, or is adsorbed to emulsion particles as a copolymer with a water-soluble monomer or a copolymer of monomers, or is present in an emulsion aqueous phase.

By increasing the ratio of the particular states, the water resistance of the film obtained from the emulsion can be improved. Further, the anionic ethylenically unsaturated monomer (c) is obtained by pyrolysis gas chromatogram mass spectrometry (Py-GC) of a film obtained from the emulsion.
-MS) or pyrolysis mass spectrometry (Py-MS). Another method is to separate the aqueous phase component of the emulsion and then use fast atom bombardment mass spectrometry (FAB).
Mass spectrum).

In the present invention, a normal surfactant can be used in addition to the anionic ethylenically unsaturated monomer (c). For example, fatty acid soaps, alkyl sulfonates,
Anionic surfactants such as alkyl sulfosuccinates, polyoxyethylene alkyl sulfates, and polyoxyethylene alkyl aryl sulfates; and non-ionic surfactants such as polyoxyethylene alkyl aryl ethers, polyoxyethylene sorbitan fatty acid esters, and oxyethylene oxypropylene block copolymers Reactive nonionic surfactant, α-
[1-[(allyloxy) methyl] -2- (nonylphenoxy) ethyl] -ω-hydroxypolyoxyethylene (trade names: Adecaria Soap NE-20, NE-30,
NE-40, etc., manufactured by Asahi Denka Kogyo Co., Ltd.), polyoxyethylene alkylpropenyl phenyl ether (trade names: AQUALON RN-10, RN-20, RN-30, RN-
Nonionic surfactants copolymerized with an ethylenically unsaturated monomer called reactive nonionic surfactants such as No. 50 manufactured by Daiichi Pharmaceutical Co., Ltd. are used.

In the present invention, in order to obtain a polycarbonyl compound, a radical polymerization catalyst, which is radically decomposed by heat or a reducing substance to cause addition polymerization of an ethylenically unsaturated monomer, is used. Soluble persulfates, peroxides, azobis compounds and the like are used. Examples thereof include potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, t-butyl hydroperoxide, t-butyl peroxybenzoate, 2,2-azobisisobutyronitrile, 2,2
-Azobis (2-diaminopropane) hydrochloride, 2,2-azobis (2,4-dimethylvaleronitrile) and the like, and the amount thereof is usually 0.1 to 1 weight based on the ethylenically unsaturated monomer. %. Usually, it is preferably carried out at a polymerization temperature of 65 to 90 ° C. under normal pressure, but it can be carried out under a high pressure according to the characteristics such as vapor pressure at the polymerization temperature of the monomer. When acceleration of the polymerization rate and low-temperature polymerization at 70 ° C. or lower are desired, it is advantageous to use a reducing agent such as sodium bisulfite, ferrous chloride, ascorbate, or Rongalite in combination with a radical polymerization catalyst. It is. In order to further control the molecular weight, a chain transfer agent such as dodecyl mercaptan can be optionally added.

In the present invention, in order to keep the polycarbonyl compound stable for a long period of time, it is preferable to adjust the pH to the range of 5 to 10, and if necessary, amine such as ammonia, sodium hydroxide, potassium hydroxide, dimethylaminoethanol and the like. And acids such as hydrochloric acid, sulfuric acid, acetic acid and lactic acid. The polyepoxy compound that can be used in the coating composition of the present invention includes, for example, an epoxy group-containing ethylenically unsaturated monomer such as glycidyl (meth) acrylate as an essential component and another unsaturated monomer. Epoxy-containing copolymers obtained by copolymerization by bulk polymerization, suspension polymerization, emulsion polymerization, solution polymerization, etc., bisphenol A epoxy resins, bisphenol F epoxy resins, and cyclic fats An epoxy resin such as a group-based epoxy resin, a glycidyl ester-based epoxy resin, a glycidylamine-based epoxy resin, a hydantoin-type epoxy resin, and a triglycidyl isocyanurate dispersed in water, and a combination thereof.

The coating composition containing the aqueous hydrazine derivative composition (A) of the present invention and the polycarbonyl compound (B) and / or the polyepoxy compound (C) has a solid content weight ratio of (A) / ( (B) + (C)) = 0.1 / 9
It is preferably in the range of 9.9 to 90/10. This combines low temperature curability and storage stability, water resistance,
A film excellent in stain resistance, hardness and the like can be provided.
If the ratio is less than 0.1 / 99.9, the crosslinking density is low, and the effect of crosslinking is not exhibited, which is not preferable. If it exceeds 90/10, the resulting film becomes very brittle, which is not preferable.

The aqueous hydrazine derivative composition of the present invention comprises:
For the purpose of controlling the reactivity with a polycarbonyl compound or a polyepoxy compound, a monoketone represented by the formula (5) can be mixed. R ¹¹ R ¹² C ＝ O (5) (wherein R ¹¹ and R ¹² are each a hydrogen atom, a linear or branched aliphatic residue having 2 to 20 carbon atoms,
It represents at least one selected from an alicyclic residue having 20 carbon atoms and an aromatic residue which may or may not have a substituent. R ¹¹ and R ¹² may form a cyclic structure. The monoketones represented by the formula (5) include 30 to
Those having a relatively low boiling point of 200 ° C. (for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.) are preferred because the reactivity can be easily controlled.

The coating composition of the present invention may contain, if necessary, components usually added to paints and the like, for example, pigments, fillers, dispersants, light stabilizers, wetting agents, thickeners, rheology control agents, defoamers. Agents, plasticizers, film-forming assistants, rust inhibitors, dyes, preservatives, and the like can be selected and combined according to the respective purposes. Further, the coating composition of the present invention is a paint, a base material or a finishing material for building materials, an adhesive, an adhesive,
It is useful as a paper processing agent or a finishing material for woven or nonwoven fabric, a binder for aqueous inks, and the like. Examples of the paint, a base material for a building material or a finishing material include concrete, cement mortar, slate board, calcite board, gypsum board, extruded board, inorganic building materials such as foamable concrete, and building materials based on woven or nonwoven fabric. , Paint or architectural finishing materials for various bases such as metal building materials, furthermore, main materials and top coats for multi-layer finishing coating materials, thin finishing coating materials, thick finishing coating materials, stone finish finishing materials, gloss paint, etc. Synthetic resin emulsion paint, metal paint, wood paint,
Tile coatings and the like.

Examples of the adhesive include wet adhesives for metals, plastics, wood, slate, paper, cloth, etc., which are used as, for example, adhesives for automobile interiors, adhesives for building members, and laminating adhesives for various films. An adhesive and the like can be mentioned. Examples of the pressure-sensitive adhesive include a permanent pressure-sensitive adhesive, a removable pressure-sensitive adhesive, and the like used for a single-sided tape, a double-sided tape, a label, an album, and the like.

[0095]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Parts in the examples mean parts by weight. The methods for measuring various physical properties used in the examples are as follows. Molecular weight distribution: It was determined from a calibration curve of a polystyrene standard using gel permeation chromatography.

(Equipment used) · Equipment: HLC-8020 manufactured by Tosoh Corporation · Column: TSKgel G-5000 HXL TSKgel G-4000 HXL TSKgel G-2000 HXL manufactured by Tosoh Corporation · Data processing: manufactured by Tosoh Corporation SC8010 • Carrier: tetrahydrofuran The infrared absorption spectrum is FT / IR-5300.
(Manufactured by JASCO Corporation). Appearance of Film The appearance of the film obtained in each Example or Comparative Example was determined as follows.

：: Transparent and smooth film △: Transparent but rough surface is observed ×: Opaque and rough surface is observed Film strength Tensilon tensile tester (RT manufactured by Orientec Co., Ltd.)
A-100) Measurement length: 300 mm, tensile speed: 50 m
It was measured under the condition of m / min. Solvent Resistance of Film After the film was put in a 200-mesh wire mesh bag and immersed in tetrahydrofuran at room temperature for 24 hours, the retention of the film weight was determined by (film weight after immersion in tetrahydrofuran). (Film weight before immersion in tetrahydrofuran) × 100. Water resistance of the film After immersing the film in water at room temperature for 6 days, the water absorption (%) of the film is calculated by ((film weight after water immersion) − (film weight before water immersion)) ÷ (film before water immersion) Weight) ×
It was determined as 100.

After the film was immersed in water at room temperature for 24 hours, the breaking strength and the strength at an elongation of 100% were measured. , (Strength after immersion in water)
(Strength before water immersion) × 100.

[0099]

Reference Example 1 Synthesis example of polyhydrazine compound (1). 222 parts of isophorone diisocyanate, 168 parts of hexamethylene diisocyanate, and 2.4 parts of water as a buret agent are dissolved in 130 parts of a 1: 1 (weight ratio) mixed solvent of ethylene glycol methyl ether acetate and trimethyl phosphate, and reacted. The reaction was performed at a temperature of 160 ° C. for 1.5 hours. The first reaction was performed using a thin-film distillation can to obtain 1.0 mm
The second time is 0.1 mmHg / 2 under the condition of Hg / 160 ° C.
Excess isophorone diisocyanate and hexamethylene diisocyanate and the solvent were distilled off and recovered by a two-stage treatment under the condition of 00 ° C.

The obtained polyisocyanate compound is a cobulet-type polyisocyanate of isophorone diisocyanate and hexamethylene diisocyanate, with 0.7% by weight of residual isophorone diisocyanate, 0.1% by weight of residual hexamethylene diisocyanate, -NCO
The content is 19.6% by weight and the viscosity is 20,000 (± 300
0) mPa · s / 40 ° C., number average molecular weight is about 800 (±
100) and the average -NCO functionality was about 3.7.

20 parts of hydrazine monohydrate was added at room temperature to 230 parts of isopropyl alcohol in a reactor having a reflux condenser, a thermometer and a stirrer. A solution prepared by dissolving 42 parts of the above-mentioned burette-type polyisocyanate in 168 parts of tetrahydrofuran was added at 40 ° C. over about 1 hour, and stirring was continued at 40 ° C. for 3 hours. The polyhydrazine compound (1) was obtained as a white solid by distilling off tetrahydrofuran, hydrazine, water and the like in the obtained reaction solution under heating and reduced pressure.

FIG. 1 shows the infrared absorption spectrum of this product.

[0103]

Reference Example 2 Synthesis example of polyhydrazine compound (2). 8.9 parts of hydrazine monohydrate was added at room temperature to 103 parts of isopropyl alcohol in a reactor having a reflux condenser, a thermometer and a stirrer. The isocyanurate-type polyisocyanate of isophorone diisocyanate (trade name: VE)
STANAT T-1890. Number average molecular weight is about 80
0, average number of NCO groups is about 3.2, NCO group content is 16.
4 wt% (100% pellet product). Made by Huls Japan K.K. ) 23 parts of tetrahydrofuran 92
The solution dissolved in the part was added at 10 ° C. over about 1 hour,
Stirring was further continued at 40 ° C. for 3 hours. Thereafter, 50 parts of butyl cellosolve was added while stirring the reaction system at 40 ° C. Tetrahydrofuran, hydrazine, isopropyl alcohol, butyl cellosolve and the like in the obtained reaction solution were distilled off under heating and reduced pressure to obtain a butyl cellosolve solution of the polyhydrazine compound (2) having a solid content of 50%.

[0104]

Reference Example 3 Synthesis example of polyhydrazine compound (3). Tetramethylammonium acetate 0.01 as an isocyanuration catalyst was added to 1000 parts of hexamethylene diisocyanate.
And reacted at 60 ° C. for 4 hours. Phosphoric acid 0.
After adding 2 parts and stopping the reaction, the mixture was further added at 90 ° C. for 1 hour.
After heating for an hour and cooling to room temperature, the deactivated catalyst was deposited as a solid. After removing this precipitate by filtration, the obtained reaction solution was first treated with a thin film distillation can at 1.0 mmH.
g / 160 ° C., the second time is 0.1 mmHg / 16
Excess hexamethylene diisocyanate and solvent were distilled off and recovered by two-stage treatment at 0 ° C.

The obtained polyisocyanate compound is an isocyanurate-type polyisocyanate of hexamethylene diisocyanate, having a residual hexamethylene diisocyanate of 0.1% by weight, a -NCO content of 23.4% by weight, and a viscosity of 1400 (± 200%). ) MPa. s / 25 °,
The number average molecular weight is about 580 (± 80), and the average-NC
The number of O functional groups was about 3.2.

16.3 parts of methylhydrazine were added at room temperature to 103 parts of tetrahydrofuran placed in a reactor having a reflux condenser, a thermometer and a stirrer. A solution prepared by dissolving 16 parts of the above polyisocyanate compound in 92 parts of tetrahydrofuran was added at 10 ° C. over about 1 hour, and stirring was continued at 40 ° C. for 3 hours. afterwards,
While stirring the reaction system at 40 ° C., butyl cellosolve 50
Parts were added. The tetrahydrofuran, hydrazine, isopropyl alcohol, butyl cellosolve, and the like in the obtained reaction solution are distilled off under reduced pressure by heating to obtain a solid content of 50%.
% Of a butyl cellosolve solution of the polyhydrazine compound (3).

[0107]

Reference Example 4 Preparation example of polycarbonyl compound. Reflux condenser, dripping tank,
In a reactor having a thermometer and a stirrer, 218 parts of ion-exchanged water and a surfactant (trade name: Adecaria Soap SE)
-1025N, 3.7 parts of a 25% aqueous solution of Asahi Denka Kogyo Co., Ltd.) was added, the temperature in the reaction vessel was raised to 80 ° C., and then 9 parts of methacrylic acid, 4.5 parts of styrene, and acrylic Butyl 234 parts, diacetone acrylamide 1
13. 3.5 parts, 189 parts of methyl methacrylate, 225 parts of ion-exchanged water, and Adecaria Soap SE-1025N.
A mixture of 4 parts, 10 parts of a 25% aqueous solution of polyoxyethylene nonylphenyl ether (trade name: Emulgen 950, manufactured by Kao Corporation) and 1 part of ammonium persulfate was allowed to flow into the reaction vessel from the dropping tank over 3 hours. Was. During the inflow, the temperature in the reaction vessel was kept at 80 ° C. After completion of the inflow, the temperature in the reaction vessel was kept at 80 ° C. and kept for 2 hours. Thereafter, the mixture was cooled to room temperature, the pH was adjusted to 8 by adding a 25% aqueous ammonia solution, and the mixture was filtered through a 100-mesh wire gauze.
An aqueous emulsion of 6.8% carbonyl group-containing copolymer having an average particle size of 1060 ° was obtained.

[0108]

Example 1 To 7.2 parts of levulinic acid was added 9.6 parts of a 10% aqueous ammonia solution, and the mixture was stirred at 30 ° C. for 30 minutes.
74 parts of the polyhydrazine compound (1) obtained in Reference Example 1 and 156 parts of water were added, and the mixture was further stirred at 30 ° C. for 1 hour to obtain a homogeneous and transparent aqueous hydrazine derivative composition aqueous solution.

FIG. 2 shows the infrared absorption spectrum of this product.

[0110]

Example 2 To 27 parts of the polyhydrazine compound (1) obtained in Reference Example 1, 2 parts of pyruvic acid and 58 parts of water were added to give 3 parts.
After stirring at 0 ° C. for 30 minutes, 3.6 parts of a 10% aqueous ammonia solution was added, and the mixture was further stirred at 30 ° C. for 1 hour to obtain a homogeneous and transparent aqueous hydrazine derivative aqueous solution.

[0111]

Example 3 To 33 parts of the polyhydrazine compound (1) obtained in Reference Example 1, 3 parts of α-ketoglutaric acid and 70 parts of water were added, and the mixture was stirred at 30 ° C. for 30 minutes. 4 parts were added, and the mixture was further stirred at 30 ° C. for 1 hour to obtain a uniform and transparent aqueous hydrazine derivative aqueous solution.

FIG. 3 shows the infrared absorption spectrum of this product.

[0113]

Example 4 9 parts of levulinic acid and 12 parts of a 10% aqueous ammonia solution were added to 95 parts of a 50% butyl cellosolve solution of the polyhydrazine compound (2) obtained in Reference Example 2, and
6 parts were added, and the mixture was stirred at 30 ° C. for 1 hour to obtain a uniform and transparent aqueous hydrazine derivative aqueous solution.

[0114]

Example 5 1.8 parts of levulinic acid and 2.4 parts of a 10% aqueous ammonia solution were added to 95 parts of a 50% butyl cellosolve solution of the polyhydrazine compound (2) obtained in Reference Example 2, and further, latemul ASK (solid content: 28%) ) (Trade name) (manufactured by Kao Corporation) 6.7 parts and water 52 parts were added,
The mixture was stirred for an hour to obtain a homogeneous and transparent aqueous hydrazine derivative aqueous solution.

[0115]

Example 6 After adding 25.5 parts of a 2N aqueous sodium hydroxide solution to 5 parts of pyruvic acid and stirring at 30 ° C. for 30 minutes, 50% butyl cellosolve of the polyhydrazine compound (3) obtained in Reference Example 3 was obtained. Add 40 parts of solution and add 3 more
The mixture was stirred at 0 ° C. for 1 hour to obtain a homogeneous and transparent aqueous hydrazine derivative aqueous solution.

[0116]

Example 7 To 14 parts of 1,3,5-cyclohexanetrihydrazide, 10 parts of levulinic acid and 108 parts of water were added.
By stirring at 30 ° C. for 1 hour, a homogeneous and transparent aqueous hydrazine derivative aqueous solution was obtained.

[0117]

EXAMPLE 8 23 parts of α-ketoglutaric acid and 94 parts of water were added to 18 parts of sebacic acid dihydrazide, and the mixture was added at 30 ° C. for 30 minutes.
After stirring for 10 minutes, 49 parts of a 10% aqueous ammonia solution was added, and the mixture was further stirred at 30 ° C. for 1 hour to obtain a homogeneous and transparent aqueous hydrazine derivative aqueous solution.

[0118]

Example 9 6.2 parts of an aqueous solution of the aqueous hydrazine derivative composition obtained in Example 2 was added to 100 parts of an aqueous emulsion of a carbonyl group-containing copolymer synthesized in Reference Example 4, and the resulting coating composition was mixed with glass. After forming a film on the plate at room temperature, the film was further dried at room temperature for one month to obtain a transparent and smooth coating film.

The physical properties of the coating film were measured. Table 1 shows the results.

[0120]

Example 10 To 100 parts of an aqueous emulsion of a carbonyl group-containing copolymer synthesized in Reference Example 4, 7.5 parts of an aqueous solution of the aqueous hydrazine derivative composition obtained in Example 4 was added, and the resulting coating composition was mixed with glass. After forming a film on a plate at room temperature,
Further drying was performed at room temperature for one month to obtain a transparent and smooth coating film.

The physical properties of the coating film were measured. Table 1 shows the results.

[0122]

Example 11 To 100 parts of an aqueous emulsion of a carbonyl group-containing copolymer synthesized in Reference Example 4, 7.5 parts of an aqueous solution of the aqueous hydrazine derivative composition obtained in Example 5 was added, and the resulting coating composition was mixed with glass. After forming a film on a plate at room temperature,
Further drying was performed at room temperature for one month to obtain a transparent and smooth coating film.

The physical properties of the coating film were measured. Table 1 shows the results.

[0124]

Example 12 To 100 parts of an aqueous emulsion of a carbonyl group-containing copolymer synthesized in Reference Example 4, 6.7 parts of an aqueous solution of the aqueous hydrazine composition obtained in Example 7 was added, and the mixed coating composition was mixed with a glass plate. After forming a film at room temperature on the above, it was further dried at room temperature for one month to obtain a transparent and smooth coating film.

The physical properties of the coating film were measured. Table 1 shows the results.

[0126]

Comparative Example 1 Example 2 except that pyruvic acid was not used.
The same operation as described above was performed, except that the polyhydrazine compound (1)
Remained solid and hardly soluble in water.

[0127]

Comparative Example 2 Example 4 except that levulinic acid was not used.
As a result of the same operation as described above, polyhydrazine compound (2) was deposited.

[0128]

Comparative Example 3 Example 6 except that pyruvic acid was not used.
As a result of the same operation as described above, polyhydrazine compound (2) was deposited.

[0129]

Comparative Example 4 Example 7 except that levulinic acid was not used.
However, 1,3,5-cyclohexanetrihydrazide remained solid and hardly dissolved in water.

[0130]

Comparative Example 5 The same operation as in Example 8 was carried out except that α-ketoglutaric acid was not used. However, sebacic acid dihydrazide remained solid and was hardly dissolved in water.

[0131]

Comparative Example 6 The same operation as in Example 2 was carried out except that pyruvic acid (7.2 parts) was replaced with acetic acid (4.9 parts). However, the polyhydrazine compound (1) remained solid, and almost no water was added. Did not dissolve.

[0132]

Comparative Example 7 The same operation as in Example 2 was carried out except that 7.2 parts of pyruvic acid was replaced with 4.9 parts of acetic acid and no aqueous ammonia solution was used, but the polyhydrazine compound (1) remained solid. And hardly dissolved in water.

[0133]

Comparative Example 8 A film was dried using the aqueous carbonyl group-containing copolymer alone synthesized in Reference Example 2 in the same manner as in Example 4 to obtain a coating film. The physical properties of this coating were measured.
Table 1 shows the results.

[0134]

Comparative Example 9 The same procedure as in Example 9 was carried out except that the aqueous solution of the aqueous hydrazine derivative composition obtained in Example 2 was replaced with 14.5 parts of a 5% aqueous solution of adipic dihydrazide (manufactured by Nippon Hydrazine Industry Co., Ltd.). It was blended by the method and dried to form a film. The physical properties of this coating were measured. Table 1 shows the results.

[0135]

[Table 1]

[0136]

The coating composition using the aqueous hydrazine derivative composition of the present invention as a curing agent has a high cross-linking density, and is capable of forming a tough film excellent in water resistance, chemical resistance, heat resistance, etc. at a relatively low temperature. Obtainable. Accordingly, the present invention provides an excellent coating composition that can be used for various applications as a clear coat agent, a top coat agent, a paint, an undercoat agent, a cloth or paper impregnating agent, various adhesives, and the like.

[Brief description of the drawings]

FIG. 1 is an infrared absorption spectrum of one example of the composition of the present invention.

FIG. 2 is an infrared absorption spectrum of one example of the composition of the present invention.

FIG. 3 is an infrared absorption spectrum of one example of the composition of the present invention.

Claims (6)

[Claims] 1. An aqueous hydrazine derivative composition containing a mixture of a polyhydrazine compound having two or more hydrazine residues in one molecule and a ketone acid and / or a salt thereof. 2. The aqueous hydrazine derivative composition according to claim 1, wherein the polyhydrazine compound is a semicarbazide derivative composition represented by the formula (1). Embedded image (Wherein R ¹ is a linear or branched C 2-20
Alkylene diisocyanate, cycloalkylene diisocyanate having 5 to 25 carbon atoms which may or may not have a substituent, arylene diisocyanate having 6 to 20 carbon atoms which may or may not have a substituent, and A terminal isocyanate group derived from a trimer to 20-mer oligomer of at least one diisocyanate selected from the group consisting of aralkylenediisocyanates having 8 to 20 carbon atoms which may or may not have a substituent; polyisocyanate residues without triisocyanate residue or R ¹ is derived from alkylene diisocyanates having 2 to 20 carbon atoms which is substituted with isocyanatoalkyl group having 1 to 8 carbon atoms, without the terminal isocyanate groups, Represents R ²
Represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
R ³ is a linear or branched alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 5 to 20 carbon atoms, or a 6 to 10 carbon atoms which may or may not have a substituent. Represents an arylene group. n represents 0 or 1. l and m
Represents 0 or a positive integer, respectively. However, 20 ≧ (l +
m) ≧ 3. ) 3. The aqueous hydrazine derivative composition according to claim 1, wherein the ketone acid or a salt thereof is represented by the formula (2) or (4). Embedded image ｛R ⁴ is a hydrogen atom, a phenyl group, or a straight-chain or branched C 1 -C 1 unsubstituted or substituted with a hydroxyl group or an alkoxy group having 1 to 8 carbon atoms.
Represents 30 alkyl groups. R ⁵ is a straight-chain or branched C 1-30 unsubstituted or substituted by a hydroxyl group or a C 1-8 alkoxy group.
Represents an alkylene group. p represents 0 or 1. X is
Represents a hydrogen atom, an alkali metal, ammonium or a substituted ammonium represented by the formula (3). HNR ⁶ R ⁷ R ⁸ (3) (R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom,
Or a linear or branched C1-C20 alkyl group which is not substituted or substituted with a hydroxyl group. R ⁶ and R ⁷ , R ⁷ and R ⁸ , R ⁶ and R
⁷ and R ⁸ may form a cyclic structure together. )｝ Embedded image ｛R ⁹ and R ¹⁰ are each independently a straight-chain or branched alkylene group having 1 to 30 carbon atoms which is unsubstituted or substituted with a hydroxyl group or an alkoxy group having 1 to 8 carbon atoms. Represents q and r each represent 0 or 1.
Y and Z each independently represent a hydrogen atom, an alkali metal, ammonium or a substituted ammonium represented by the formula (3). HNR ⁶ R ⁷ R ⁸ (3) (R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom,
Or a linear or branched C1-C20 alkyl group which is not substituted or substituted with a hydroxyl group. R ⁶ and R ⁷ , R ⁷ and R ⁸ , R ⁶ and R
⁷ and R ⁸ may form a cyclic structure together. )｝ 4. The aqueous hydrazine derivative composition according to claim 1, which comprises alkenyl succinic acid and / or a salt thereof. 5. A coating composition comprising the aqueous hydrazine derivative composition according to claim 1 and a polycarbonyl compound and / or a polyepoxy compound. 6. The coating composition according to claim 5, comprising a monoketone represented by the formula (5). R ¹¹ R ¹² C ＝ O (5) (wherein R ¹¹ and R ¹² are each a hydrogen atom, a linear or branched aliphatic residue having 2 to 20 carbon atoms,
It represents at least one selected from an alicyclic residue having 20 carbon atoms and an aromatic residue which may or may not have a substituent. R ¹¹ and R ¹² may form a cyclic structure. )