JPH09323969A - Semicarbazide-based composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a semicarbazide-based composition capable of forming films excellent in water resistance, contamination resistance, hardness, etc., by reaction of a hydrazine derivative with a polyisocyanate reaction product made from each specific component. SOLUTION: This semicarbazide-based composition is obtained by reaction of (A) a polyisocyanate reaction product with (B) a hydrazine derivative. The component A is prepared by reaction of (i) a polyisocyanate compound bearing at least 3 NCO groups in one molecule with (ii) a carboxylic acid group-bearing glycol and (iii) a polyethylene glycol monoalkyl ether of the formula (R<1> is 1-25C monovalent hydrocarbon; (n) is an integer of 5-80). It is preferable that the component (i) has isocyanurate or biuret structure as the basic skeleton. Using this composition, a coating composition usable as a clear coating agent, topcoating agent, coating material, impregnant for paper, cloth, etc., can be obtained.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a composition useful as a coating agent for paper or cloth, an adhesive agent, and the like. Specifically, a semicarbazide composition and a clear coating agent, a top coating agent using the same, Paint, undercoat agent,
The present invention relates to an excellent coating composition that can be used for various purposes as an impregnating agent for cloths and papers, an adhesive agent, and the like.

[0002]

2. Description of the Related Art In recent years, an aqueous emulsion has been attracting attention in the coating field as a conversion material from an organic solvent type to an aqueous type, but it is still sufficient in terms of water resistance, stain resistance, hardness, etc. as compared with an organic solvent type coating agent. It does not show good physical properties. For the purpose of improving these physical 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-liquid room temperature curing type from the viewpoint of workability, workability, etc., and in response to this requirement, hydrazone crosslinking utilizing a dehydration condensation reaction of a carbonyl group and a hydrazide group has recently been made. System aqueous emulsions are receiving attention. For example,
In 20053, JP-A-57-3850, JP-A-57-3857, JP-A-58-96643, JP-A-4-249587, etc., a carbonyl group-containing copolymer aqueous dispersion is described. By adding a polyfunctional carboxylic acid hydrazide compound as a curing agent, a coating composition having both low-temperature curability and storage stability and excellent hardness, stain resistance, etc. has been proposed.

However, a polyfunctional carboxylic acid hydrazide compound which is a curing agent is not preferable because hydrazine is liberated by hydrolysis during storage and the curing ability changes with time. In addition, polyfunctional carboxylic hydrazide compounds have 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. On the contrary, a compound having low hydrophilicity such as sebacic acid dihydrazide is difficult to use as a curing agent for an aqueous emulsion.

As a curing agent for an aqueous emulsion which overcomes the disadvantages of the above-mentioned polyfunctional carboxylic acid hydrazide compounds,
WO96 / 01252 pamphlet proposes a semicarbazide derivative having a specific structure. The point of the technique of using the semicarbazide derivative having excellent hydrolysis resistance as a curing agent for an aqueous emulsion is to control the hydrophilicity of the semicarbazide derivative.
The technology to obtain sufficient performance has not been developed yet.

[0006]

An object of the present invention is to provide a semicarbazide composition capable of forming a film having both low-temperature curability and storage stability and having excellent water resistance, stain resistance, hardness and the like. It is to provide 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, the first aspect of the present invention is to react a polyisocyanate compound having three or more NCO groups in one molecule with a carboxylic acid group-containing glycol and a polyethylene glycol monoalkyl ether represented by the following formula (3). It is a semicarbazide composition obtained by reacting the polyisocyanate reaction product obtained as described above with a hydrazine derivative.

[0008]

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(In the formula, R ¹ represents a monovalent hydrocarbon group having 1 to 25 carbon atoms, and n represents an integer of 5 to 80.) A second aspect of the invention is a polyisocyanate compound. The semicarbazide composition according to the first aspect of the present invention has an isocyanurate structure or a buret structure as a basic skeleton.

A third aspect of the invention is a semicarbazone derivative obtained by reacting the semicarbazide composition according to the first aspect of the invention with a monoketone represented by the following formula (4). R ² R ³ C═O (4) (wherein R ² and R ³ are each a hydrogen atom, a linear or branched aliphatic residue having 2 to 20 carbon atoms, 5
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. Further, R ² and R ³ may form a cyclic structure. A fourth aspect of the invention is a hydrazine derivative reacted with a monoketone represented by the above formula (4), a polyisocyanate compound having three or more NCO groups in one molecule, and a carboxylic acid group-containing glycol and the above formula. It is a semicarbazone derivative obtained by reacting with a polyisocyanate reaction product obtained by reacting polyethylene glycol monoalkyl ethers represented by (3).

A fifth aspect of the invention comprises a semicarbazide composition (A) according to the first aspect of the invention and / or a semicarbazone derivative (B) according to the third or fourth aspect of the invention, and a polycarbonyl compound (C), The solid content weight ratio is (C) /
((A) + (B)) = 99.9 / 0.1 to 90/10. Hereinafter, the present invention will be described in detail.

In the present invention, examples of the polyisocyanate compound having three or more NCO groups in one molecule used for synthesizing the polyisocyanate reaction product include a diisocyanate compound having a buret bond, a urea bond, an isocyanurate bond, and a urethane. Bond, allophanate bond, uretdione bond, etc. oligomerized polyisocyanate compound, and further 1,8-diisocyanato-
4-isocyanatomethyl octane and a combination thereof are included.

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

Of these diisocyanate compounds, aliphatic diisocyanates and alicyclic diisocyanates are more desirable from the viewpoints of heat-resistant yellowing, weather resistance and the like of the film using the semicarbazide composition produced. The polyisocyanate reactant in the present invention is synthesized by reacting the above polyisocyanate compound with carboxylic acid group-containing glycols and polyethylene glycol monoalkyl ethers represented by the above formula (3).

The carboxylic acid group-containing glycols include α, α'-dimethylolpropionic acid and α, α'-
Dimethylol acetic acid, α, α′-dimethylol butyric acid, α,
Examples include α, α′-dimethylolalkanoic acids such as α′-dimethylolvaleric acid. The carboxylic acid group of the carboxylic acid group-containing glycol can be neutralized with a base during or after the reaction with the polyisocyanate compound. Examples of the base used for neutralization include amine compounds such as triethylamine, ammonia, diethanolamine, dimethylaminoethanol, methyldiethanolamine and dibutylamine, hydroxides of alkali metals such as KOH, NaOH and LiOH, and combinations thereof. To be

Examples of polyethylene glycol monoalkyl ethers include polyethylene glycol monomethyl ether having a molecular weight of 250 to 3,500, polyethylene glycol monoethyl ether, polyethylene glycol monobutyl ether, polyethylene glycol monostearyl ether and the like. The polyisocyanate reaction product is obtained by subjecting a polyisocyanate compound, a carboxylic acid group-containing glycol and a polyethylene glycol monoalkyl ether to a urethanization reaction under a substantially anhydrous condition at a temperature of about 20 ° C to about 130 ° C. can get. The equivalent ratio of the NCO group of the polyisocyanate compound used for producing the urethane prepolymer to the OH group of the carboxylic acid group-containing glycols and the polyethylene glycol monoalkyl ethers is usually 1.1 to 500:
1 and preferably 2 to 100: 1. 1.1:
If it is less than 1, the amount converted later into a semicarbazide group becomes very small and it does not work as a crosslinking agent. Also, 5
When it is more than 00: 1, the product is not dispersed or dissolved in water, which is not preferable.

In producing the polyisocyanate reactant, a catalyst can be used if necessary. Specific examples of the catalyst include salts of metals and organic and inorganic acids such as dibutyltin dilaurate, stannous octoate, lead octylate, and organic metal derivatives, organic tertiary amines such as triethylamine and triethylenediamine, and diamines. Examples thereof include zabicycloundecene catalyst.

The production of the polyisocyanate reactant is
It can be solvent-free or in a solvent. This solvent is NC
Those which are inert to the O group or less active than the reaction components can be used. Specifically, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and other ketone solvents, dioxane, tetrahydrofuran, diethylene glycol dimethyl ether and other ether solvents, dimethylformamide, dimethylacetamide and other amide solvents, N-methyl-2-pyrrolidone Such as lactam solvents, sulphoxide solvents such as dimethyl sulfoxide, ester solvents such as ethyl acetate and cellosolve acetate, t-butanol, isopropanol, 2-
Examples thereof include alcohols such as butoxyethanol, aromatic hydrocarbon solvents such as toluene and xylene, aliphatic hydrocarbon solvents such as n-hexane, and their combinations.

The semicarbazide composition in the present invention is
Obtained by reacting a polyisocyanate reactant with a hydrazine derivative. Examples of the hydrazine derivative include hydrazine and its hydrate, monoalkylhydrazines such as methylhydrazine and ethylhydrazine, ethylene-1,2-dihydrazine, propylene-1,3-.
Dihydrazine, dihydrazine compounds such as butylene-1,4-dihydrazine, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, maleic acid dihydrazide, fumaric acid dihydrazide,
Itaconic dihydrazide, isophthalic dihydrazide,
Dicarboxylic acid dihydrazides such as phthalic acid dihydrazide, tricarboxylic acid trihydrazides such as trimellitic acid trihydrazide, carbonic acid dihydrazides represented by the following general formula (5), or bissemicarbazides represented by the following general formula (6) Etc., and combinations thereof.

[0020]

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(In the formula, x means an integer of 0 to 5)

[0022]

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(Wherein R ⁴ is a divalent linear or branched aliphatic residue having 2 to 9 carbon atoms, an alicyclic residue having 5 to 8 carbon atoms or a substituent) Represents an aromatic residue which may or may not be present.) In the production of the semicarbazide composition of the present invention, the NCO group of the polyisocyanate reactant and the -NHNH ₂ group or -NHNH ₂ in the hydrazine derivative are represented. The equivalent ratio with the group convertible into a group is 1: 1.2 to 100, preferably 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: 100
If it becomes larger, a large amount of unreacted hydrazine derivative exists, which is not preferable.

After producing the semicarbazide composition, the excess hydrazine derivative can be removed by distillation, extraction or the like, if necessary. In producing the semicarbazide composition of the present invention, a catalyst that can be used in the synthesis of the polyisocyanate reactant can be used if necessary.
The semicarbazide composition can be produced without a solvent or in a solvent. The solvent is inert to NCO groups,
Alternatively, one having lower activity than the reaction component can be used. Specifically, the solvents exemplified as the solvent that can be used for synthesizing the polyisocyanate reactant, water, and a combination thereof are included.

The solvent may remain in the semicarbazide composition, but it can also be removed by distillation by heating under normal pressure or reduced pressure. Among the semicarbazide compositions and semicarbazone derivatives obtained by the present invention, those having good compatibility with the above-mentioned polycarbonyl compound and having hardness, chemical resistance, heat resistance and the like of the film produced from the coating composition are preferable. Examples of the polyisocyanate compound having 3 or more NCO groups in one molecule used for obtaining the polyisocyanate reaction product of the present invention have an isocyanurate structure or a buret structure as a basic skeleton.

The polyisocyanurate compound having an isocyanurate structure as a basic skeleton is described, for example, in JP-A-55-38380, and isocyanurate-type polyisocyanate of hexamethylene diisocyanate, and JP-A-57-. As disclosed in JP-A-78460, copolymerization of isophorone diisocyanate and hexamethylene diisocyanate, such as isocyanurate type polyisocyanate, JP-A-57-47321.
As described in JP-A-6-33115, isocyanurate type polyisocyanates modified with polyfunctional alcohols, and low-viscosity isocyanurate-type polyisocyanates described in JP-A-64-33115, JP-A-6- After carrying out a cyclic trimerization reaction with a catalyst of a diisocyanate typified by a highly branched isocyanurate type polyisocyanate as described in 312969 gazette and stopping the addition rate at about 10 to 60% by weight, Examples thereof include polyisocyanate compounds having an isocyanurate structure obtained by removing and purifying excess diisocyanate.

Examples of the polyisocyanurate compound having a burette structure as a basic skeleton include, for example, JP-A-53.
No. 106797, Japanese Patent Application Laid-Open No. 55-11452, and the like, hexamethylene diisocyanate-based buret type polyisocyanate, Japanese Patent Application Laid-Open No. 59-59.
As described in JP-A-95259, a burette containing a so-called buret-forming agent such as water, t-butanol, urea and the like, represented by a copolymerized burette type polyisocyanate of isophorone diisocyanate and hexamethylene diisocyanate, and a diisocyanate. A polyisocyanate compound having a buret structure obtained by reacting the agent / diisocyanate at an equivalent ratio of about 1/3 to 1/50 and then removing and purifying excess diisocyanate can be mentioned.

In the present invention, a semicarbazone derivative having the same basic skeleton as that of the above semicarbazide composition is obtained by the following two methods using the monoketones represented by the above formula (4). That is, a method of reacting at least a part of the semicarbazide group in the semicarbazide composition with the monoketone represented by the formula (4) at −20 ° C. to 80 ° C. A method in which at least a part of the hydrazide group or hydrazine group of the hydrazine derivative is previously reacted with the monoketone represented by the formula (4) at −20 ° C. to 80 ° C. to form a hydrazone group and then reacted with a polyisocyanate reactant. .

As the monoketones represented by the above formula (4), those having a relatively low boiling point of 30 to 200 ° C. (for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.) are preferable because of easy handling. The semicarbazide composition and semicarbazone derivative obtained by the present invention have very good dispersibility or solubility in water.

When the semicarbazide composition or the semicarbazone derivative is dispersed or dissolved in water, a surfactant may be added if necessary. 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.

The semicarbazide composition and semicarbazone derivative of the present invention have good dispersibility or solubility in water, are polyfunctional, and have excellent compatibility with polycarbonyl compounds, and thus cannot be achieved by conventional methods. Water resistance and various curing properties can be expressed. Therefore, the semicarbazide composition and semicarbazone derivative of the present invention are useful as a curing agent for polycarbonyl compounds.

The coating composition of the present invention preferably comprises a semicarbazide composition and / or a semicarbazone derivative and a polycarbonyl compound. Examples of the polycarbonyl compound include a carbonyl group-containing copolymer and a carbonyl group-containing polyurethane prepared from a mono- or polyalcohol having a carbonyl group such as hydroxyacetone as described in JP-A-2-238015. , Acetoacetylated polyvinyl alcohol, acetoacetylated hydroxyalkyl cellulose and the like, and combinations thereof.

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.

As the carbonyl group-containing ethylenically unsaturated monomer monomer (a), diacetone acrylamide,
Examples include diacetone methacrylamide, acrolein, vinyl methyl ketone, acetoacetoxyethyl methacrylate, acetoacetoxyethyl acrylate, formylstyrene, and the like, and combinations thereof. As the ethylenically unsaturated monomer (b) copolymerizable with the monomer (a),
Acrylic acid esters, methacrylic acid esters, ethylenically unsaturated monomers having a carboxyl group, acrylamide monomers, methacrylamide monomers, vinyl cyanides, etc. Examples include (meth) acrylic acid alkyl esters having 1 to 18 carbon atoms in the alkyl part, and 1 to 1 carbon atoms in the alkyl part.
8, hydroxyalkyl (meth) acrylates,
(Poly) oxyethylene (meth) acrylate having 1 to 100 ethylene oxide groups, (poly) oxypropylene (meth) acrylate having 1 to 100 propylene oxide groups, and 1 ethylene oxide group
To 100 (poly) oxyethylene di (meth) acrylates.

Specific examples of the (meth) acrylic acid ester include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid n-butyl ester, (meth) acrylic acid 2-ethylhexyl ester, and (meth) acrylic acid ester. Examples thereof include methyl cyclohexyl acrylate and dodecyl acrylate (meth). 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.

Specific examples of the (poly) oxyethylene (meth) acrylate include (meth) acrylic acid ethylene glycol, methoxy (meth) acrylic acid ethylene glycol, (meth) acrylic acid diethylene glycol, methoxy (meth) acrylic acid diethylene glycol, Examples include (meth) acrylic acid tetraethylene glycol and methoxy (meth) acrylic acid tetraethylene glycol.

Specific examples of the (poly) oxypropylene (meth) acrylate include propylene glycol (meth) acrylate, propylene glycol methoxy (meth) acrylate, dipropylene glycol (meth) acrylate, and methoxy (meth) acrylic acid. Dipropylene glycol, (meth) acrylic acid tetrapropylene glycol,
Methoxy (meth) acrylic acid tetrapropylene glycol and the like can be mentioned.

Specific examples of the (poly) oxyethylene di (meth) acrylate include di (meth) acrylic acid ethylene glycol, di (meth) acrylic acid diethylene glycol, methoxy (meth) acrylic acid diethylene glycol, di (meth) acrylic acid. Examples thereof include tetraethylene glycol. Specific examples of ethylenically unsaturated monomers having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid, maleic acid half-esters, crotonic acid, and the like (meth) acrylamide Examples of the monomers include (meth) acrylamide, N-methylol (meth) acrylamide, N-
Examples include butoxymethyl (meth) acrylamide, and examples of vinyl cyanides include (meth) acrylonitrile.

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, vinyl n-butyrate, vinyl benzoate, vinyl pt-butyl benzoate, vinyl pivalate, 2-ethylhexane. Carboxylic acid vinyl esters such as vinyl acetate, vinyl versatate, vinyl laurate, isopropenyl acetate, carboxylic acid isopropenyl esters such as isopropenyl propionate, vinyl ethers such as ethyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether, styrene, Aromatic vinyl compounds such as vinyltoluene, allyl acetates such as allyl acetate and allyl benzoate, allyl ethers such as allyl ethyl ether, allyl glycidyl ether and allyl phenyl ether, and γ- ( Data) acryloxy propyl trimethoxy silane, 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, glycidyl (meth) acrylate, (meth)
Examples thereof include 2,3-cyclohexene oxide acrylate, allyl (meth) acrylate, and the like, and combinations thereof.

The polycarbonyl compound is preferably obtained by suspension polymerization, emulsion polymerization or solution polymerization, and 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 radical-polymerizable double bond and is partly modified by a group which is an ammonium salt, sodium salt or potassium salt of the 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 ester group has a radical-polymerizable double bond and is partially substituted with a group which is an ammonium salt, sodium salt or potassium salt of a sulfate ester group. Also, carbon number 1-2
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.

Specific examples of the compound having a succinic acid group partially substituted with a group which is an ammonium salt, a sodium salt or a potassium salt of a sulfonic acid group include allylsulfosuccinic acid salts such as those represented by the formulas (7) and (8 ), (9),
The compound represented by (10) may be mentioned.

[0044]

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[0045]

[Chemical 6]

[0046]

[Chemical 7]

[0047]

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[0048] (In the formula 7 to 10, R ^{1 'is} hydrogen or a methyl group, R ^2' is a cycloalkyl group having 5 to 12 carbon atoms,
A hydrocarbon group such as an aryl group having 5 to 10 carbon atoms, an aralkyl group having 6 to 19 carbon atoms, or a part of which is substituted with a hydroxyl group, a carboxylic acid group, or the like, or a polyoxyalkylene alkyl ether group (alkyl portion Has 0 carbons
20, the number of carbon atoms of the alkylene portion is 2 to 4), the polyoxyalkylene alkylphenyl ether group (the number of carbon atoms of the alkyl portion is 0 to 20, the number of carbon atoms of the alkylene portion is 2 to
An organic group containing an alkylene oxide compound such as 4). 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. ) As one containing the above formulas (7) and (8), for example, there is Eleminol JS-2 (trade name) (manufactured by Sanyo Kasei Co., Ltd.), and one containing the above formulas (9) and (10), For example, Latemur S-120, S-180A or S-1
80 (trade name) (manufactured by Kao Corporation) and the like.

Further, an alkyl ether group having 2 to 4 carbon atoms or 2 to 4 carbon atoms, which is partially substituted with a group which is an ammonium salt, sodium salt or potassium salt of a sulfonic acid group.
Examples of the compound having a polyalkyl ether group of 4 include compounds represented by the formula (11) or (12).

[0050]

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Each of [0051] (wherein R ^{3 ',} R ^4' are each independently an alkyl group having 6 to 18 carbon atoms, alkenyl or aralkyl group, R 5 ^'is hydrogen or a propenyl group .A 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. )

[0052]

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[0053] (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 .A is an alkylene group having 2 to 4 carbon atoms .n Is an integer of 0 to 20, and m is an integer of 0 to 50. M
Is ammonium, sodium or potassium. ) As an alkylphenol ether compound represented by the above formula (11), there is, for example, Aqualon HS-10 (trade name) (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), and the above formula (12)
As a compound represented by, for example, Adecaria Soap SE
-1025N (trade name) (manufactured by Asahi Denka Kogyo KK).

Other specific examples of the compound having an aryl group partially substituted with 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.

As the compound having an alkyl ether group having 2 to 4 carbon atoms or a polyalkyl ether group having 2 to 4 carbon atoms, a part of which is substituted with an ammonium salt, sodium salt or potassium salt of a sulfuric acid ester group, For example, there are compounds represented by the above formulas (11) and (12) having an alkyl ether group partially substituted with a sulfonate group.

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

By increasing the ratio of the above state, 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 usual surfactant may be used in combination with the anionic ethylenically unsaturated monomer (c). For example, fatty acid soap, alkyl sulfonate,
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 obtaining 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 water-soluble or oil-soluble. 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 within the range of 5 to 10. If necessary, an amine such as ammonia, sodium hydroxide, potassium hydroxide or dimethylaminoethanol can be used. It is also possible to add acids, such as acids, hydrochloric acid, sulfuric acid, acetic acid, lactic acid. The coating composition of the present invention comprises a semicarbazide composition (A) and / or a semicarbazone derivative (B) and a polycarbonyl compound (C),
And the solid content weight ratio is (C) / ((A) + (B)) =
It is necessary to exist within the range of 0.1 / 99.9 to 90/10. As a result, a film having both low-temperature curability and storage stability and having excellent water resistance, stain resistance, hardness and the like can be provided. When this ratio is less than 99.9 / 0.1, the crosslinking density is low and the effect of crosslinking does not appear, which is not preferable. If it exceeds 90/10, the obtained film becomes very brittle, which is not preferable.

Further, the coating composition comprising the semicarbazide composition (A) and / or the semicarbazone derivative (B) and the polycarbonyl compound (C) in the present invention may optionally contain the polyepoxy compound (D) in the solid state. They can be used together in a weight-to-weight ratio of (C) / (D) ≧ 10/90. The combined use of the polyepoxy compound further improves the water resistance of the resulting film.

As the polyepoxy compound, for example, an epoxy group-containing ethylenically unsaturated monomer such as glycidyl (meth) acrylate is used as an essential component together with other unsaturated monomers in a bulk polymerization method, a suspension polymerization method, an emulsion weight method and the like. A copolymer containing an epoxy group obtained by copolymerization by a legal method or a solution polymerization method, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a cycloaliphatic epoxy resin, a glycidyl ester epoxy resin, Examples thereof include glycidyl amine epoxy resins, hydantoin type epoxy resins, epoxy compounds such as triglycidyl isocyanurate dispersed in water, and combinations thereof.

The coating composition of the present invention contains, if necessary, components that are usually added to paints and the like, such as pigments, fillers, dispersants, light stabilizers, wetting agents, thickeners, rheology control agents and defoaming agents. Agents, plasticizers, film-forming aids, rust preventives, dyes, preservatives and the like can be selected and combined according to the purpose. This is useful as a paint, a base material or a finishing material for building materials, an adhesive, a pressure-sensitive adhesive, a paper processing agent, or a finishing agent for a woven fabric.

[0064]

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: Determined from a polystyrene standard calibration curve using gel permeation chromatography.

(Device used) -Device: Tosoh Corp. HLC-8020-Column: Tosoh Corp. TSKgel G-5000 HXL TSKgel G-4000 HXL TSKgel G-2000 HXL-Data processing: Tosoh Corp. SC8010 ・ Carrier: Tetrahydrofuran Infrared absorption spectrum: 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 Δ: Transparent but rough on the film surface ×: Opaque and rough on the film surface The film strength is Tensilon tensile tester (RTA manufactured by Orientec Co., Ltd.). -100) measurement length: 300m
m, tensile speed: measured under the conditions of 50 mm / min. The solvent resistance of the film is determined by placing the film in a 200-mesh wire mesh bag and immersing it in tetrahydrofuran at room temperature for 24 hours, and then measuring the retention rate of the film weight (the film weight after dipping in tetrahydrofuran. ) ÷ (film weight before immersion in tetrahydrofuran) × 100. The water resistance of the film was evaluated by the following method.

After immersing the film in water at room temperature for 6 days,
The water absorption rate (%) of the film was determined as ((film weight after water immersion)-(film weight before water immersion)) / (film weight before water immersion) * 100. Further, after immersing the film in water at room temperature for 24 hours, the breaking strength and the strength at the elongation rate of 100% were measured, and the respective retention ratios to the breaking strength before the immersion and the strength at the elongation rate of 100% were calculated as ( Strength after immersion in water) / (strength before immersion in water) x 100
Asked.

[0068]

Reference Example 1 Synthesis of polyisocyanate compound. 222 parts of isophorone diisocyanate, 168 parts of hexamethylene diisocyanate, and 2.4 parts of water as a buretizing agent were dissolved in 130 parts of a mixed solvent of ethylene glycol methyl ether acetate and trimethyl phosphate at a ratio of 1: 1 (weight ratio), and reacted. The reaction was carried out at a temperature of 160 ° C. for 1.5 hours. The obtained reaction solution was first used under a condition of 1.0 mmHg / 160 ° C. using a thin-film distillation can, and the second reaction was performed under 0.1 mmHg / 160 ° C.
Excess isophorone diisocyanate and hexamethylene diisocyanate and the solvent were distilled off and recovered by two-stage treatment under the conditions of 1 mmHg / 200 ° C.

The obtained polyisocyanate compound is a co-burette type polyisocyanate of isophorone diisocyanate and hexamethylene diisocyanate,
0.7% by weight of residual isophorone diisocyanate, 0.1% by weight of residual hexamethylene diisocyanate, -NC
O content is 19.6% by weight, viscosity is 20000 (± 30
00) mPa · s / 40 ° C, number average molecular weight is about 800
(± 100), and the average number of -NCO functional groups is about 3.7.
Met. Polyisocyanate compound is ethyl acetate 7
A 9.6% solution was obtained.

[0070]

[Reference Example 2] Preparation of polycarbonyl compound. In a reactor having a reflux condenser, a dropping tank, a thermometer and a stirring device, 218 parts of ion-exchanged water, a surfactant (trade name:
ADEKA RIASOAP SE-1025N, Asahi Denka Kogyo Co., Ltd.
3.7 parts of a 25% aqueous solution of methacrylic acid) was added and the temperature in the reaction vessel was raised to 80 ° C., then 9 parts of methacrylic acid, 4.5 parts of styrene, 234 parts of butyl acrylate, 13 parts of diacetone acrylamide. .5 parts, methyl methacrylate 18
9 parts, 225 parts of ion-exchanged water, ADEKA REASOAP SE-
A mixture of 14.4 parts of 1025N, 10 parts of a 25% aqueous solution of polyoxyethylene nonylphenyl ether (trade name: Emulgen 950, manufactured by Kao Co., Ltd.), and 1 part of ammonium persulfate was dropped into a reaction vessel from a dropping tank for 3 hours. It was made to flow in. The temperature in the reaction vessel was maintained at 80 ° C during the inflow. After completion of the inflow, the temperature in the reaction vessel was kept at 80 ° C. and kept for 2 hours. After cooling to room temperature, the pH is adjusted to 8 by adding a 25% aqueous ammonia solution, and then filtered through a 100-mesh wire net to obtain a solid content of 46.8% and an average particle size of 1060.
A carbonyl group-containing copolymer aqueous emulsion of Å was obtained.

[0071]

Example 1 75 parts of tetrahydrofuran was placed in a reactor equipped with a reflux condenser, a thermometer and a stirrer, and a 79.6% ethyl acetate solution of the polyisocyanate compound obtained in Reference Example 1 (NCO group content 15.6 wt. %) 106 parts, dimethylolpropionic acid 5.3 parts, triethylamine 4.
0 parts, polyoxyethylene methyl ether (hydroxyl value 9
After adding 8.7 parts, trade name: UNIOX M550, manufactured by NOF CORPORATION, and reacting at 60 ° C. for 4 hours, 282 parts of tetrahydrofuran were added. Next, 27.8 parts of hydrazine monohydrate was added to the mixed solution of 80 parts of tetrahydrofuran and 240 parts of water placed in a reactor equipped with a reflux condenser, a thermometer and a stirrer at room temperature with stirring. The reaction product obtained above was added to this mixture with stirring at 10 ° C. over 2 hours, and then further stirred at 40 ° C. for 4 hours. Then, 350 parts of water was added over 30 minutes while stirring the reaction system at 40 ° C.
Minor stirring was continued. Tetrahydrofuran, ethyl acetate, hydrazine, water and the like in the obtained reaction solution were distilled off under heating and reduced pressure to obtain an aqueous dispersion of a semicarbazide composition having a solid content of 30%.

The infrared absorption spectrum of this product is shown in FIG.

[0073]

Example 2 75 parts of acetone in a reactor equipped with a reflux condenser, a thermometer and a stirrer, and a 79.6% ethyl acetate solution of the polyisocyanate compound obtained in Reference Example 1 (NC
O group content 15.6 wt%) 98 parts, dimethylolpropionic acid 4.9 parts, triethylamine 3.7 parts, polyoxyethylene methyl ether (having a hydroxyl value of 56.9,
Product name: UNIOX M1000, manufactured by NOF CORPORATION
17.8 parts was added and reacted at 60 ° C. for 4 hours. Next, 284 parts of hydrazine monohydrate was added to 1500 parts of acetone placed in a reactor equipped with a reflux condenser, a thermometer and a stirrer at room temperature over 30 minutes with stirring, followed by further stirring for 1 hour. The polyisocyanate reaction product obtained above was added to this reaction solution while stirring at 40 ° C. over 1 hour, and then further stirred at 40 ° C. for 4 hours. Then 2183
Some water was added at 40 ° C. over 30 minutes and stirring was continued for another 30 minutes. Acetone, ethyl acetate in the obtained reaction solution,
Hydrazine, a reaction product of acetone and hydrazine, water and the like were distilled off under heating and reduced pressure to obtain an aqueous dispersion of a semicarbazide composition having a solid content of 25%.

The infrared absorption spectrum of this product is shown in FIG.

[0075]

Example 3 Tetrahydrofuran 60 parts, isocyanurate type polyisocyanate of isophorone diisocyanate in a reactor equipped with a reflux condenser, a thermometer and a stirrer (number average molecular weight about 800, average NCO group number about 3.
2. NCO group content of 16.4 wt% (100% pellet product), trade name: VESTANAT T-189
0, manufactured by Huls Japan KK) 47 parts, dimethylolpropionic acid 2.5 parts, triethylamine 1.9.
Parts, polyoxyethylene methyl ether (hydroxyl value 5
After adding 8.8 parts of 6.9, trade name: UNIOX M1000, manufactured by NOF CORPORATION, and reacting at 60 ° C. for 4 hours, 169 parts of tetrahydrofuran was added. Then, 12.8 parts of hydrazine monohydrate was added at room temperature with stirring to a mixed solution of 37 parts of tetrahydrofuran and 110 parts of water placed in a reactor having a reflux condenser, a thermometer and a stirrer. The reaction product obtained above was added to this mixture with stirring at 10 ° C. over 2 hours, and then further stirred at 40 ° C. for 4 hours. Then, 250 parts of water was added over 30 minutes while stirring the reaction system at 40 ° C., and stirring was continued for another 30 minutes. Tetrahydrofuran, ethyl acetate, hydrazine, water and the like in the obtained reaction solution were distilled off under heating and reduced pressure to obtain an aqueous dispersion of a semicarbazide composition having a solid content of 30%.

The infrared absorption spectrum of this product is shown in FIG.

[0077]

Example 4 To 100 parts of the carbonyl group-containing copolymer aqueous emulsion synthesized in Reference Example 2 was added 9.6 parts of the aqueous dispersion of the semicarbazide composition obtained in Example 1, and the mixed coating composition was added to a glass. After forming a film on the plate at room temperature, it was further dried at room temperature for 1 month to obtain a transparent and smooth coating film.

The physical properties of this coating film were measured. The results are shown in Table 1.

[0079]

Example 5 To 100 parts of the carbonyl group-containing copolymer aqueous emulsion prepared in Reference Example 2, 10.6 parts of the aqueous dispersion of the semicarbazizone derivative obtained in Example 2 was added, and the mixed coating composition was added to a glass plate. After forming a film at room temperature on the above, it was further dried at room temperature for 1 month to obtain a transparent and smooth coating film.

The physical properties of this coating film were measured. The results are shown in Table 1.

[0081]

Example 6 12.6 parts of the aqueous dispersion of the semicarbazide composition obtained in Example 3 was added to 100 parts of the carbonyl group-containing copolymer aqueous emulsion prepared in Reference Example 2, and the mixed coating composition was mixed with glass. After forming a film on the plate at room temperature, it was further dried at room temperature for 1 month to obtain a transparent and smooth coating film.

The physical properties of this coating film were measured. The results are shown in Table 1.

[0083]

Comparative Example 1 A reaction product was obtained in the same manner as in Example 1 except that dimethylolpropionic acid was 6.6 parts, triethylamine was 5.0 parts, and polyoxyethylene methyl ether was not used. The deposited reaction product could not be dispersed or dissolved in water.

[0084]

Comparative Example 2 A reaction product was obtained in the same manner as in Example 3 except that dimethylolpropionic acid and triethylamine were not used. The deposited reaction product could not be dispersed or dissolved in water.

[0085]

[Comparative Example 3] A film was dried using the carbonyl group-containing copolymer aqueous emulsion 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 film were measured.
The results are shown in Table 1.

[0086]

Comparative Example 4 The same as Example 4 except that the aqueous dispersion of the semicarbazide composition obtained in Example 1 was replaced with 14.5 parts of a 5% aqueous solution of adipic dihydrazide (manufactured by Nippon Hydrazine Industry Co., Ltd.). It was compounded by the method, and the film was dried to obtain a coating film.
The physical properties of this coating film were measured. The results are shown in Table 1.

[0087]

[Table 1]

[0088]

The coating composition using the semicarbazide composition and the semicarbazone derivative of the present invention as a curing agent for a polycarbonyl compound has a high crosslink density, is tough, and has water resistance.
A film having excellent chemical resistance and heat resistance can be obtained at a relatively low temperature. Therefore, the present invention provides an excellent coating composition which can be used for various purposes as a clear coating agent, a top coating agent, a paint, an undercoating agent, an impregnating agent for cloth or paper, various adhesives and the like.

[Brief description of 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.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] August 1, 1996

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claim 5

[Correction method] Change

[Correction contents]

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0011

[Correction method] Change

[Correction contents]

A fifth aspect of the invention is a coating comprising the semicarbazide composition (A) according to the first aspect of the invention and / or the semicarbazone derivative (B) according to the third or fourth aspect of the invention and a polycarbonyl compound (C). It is a composition. Hereinafter, the present invention will be described in detail.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0060

[Correction method] Change

[Correction contents]

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 within the range of 5 to 10. If necessary, an amine such as ammonia, sodium hydroxide, potassium hydroxide or dimethylaminoethanol can be used. It is also possible to add acids, such as acids, hydrochloric acid, sulfuric acid, acetic acid, lactic acid. The coating composition of the present invention needs to comprise a semicarbazide composition (A) and / or a semicarbazone derivative (B) and a polycarbonyl compound (C). This makes it possible to provide a film having both low-temperature curability and storage stability, and excellent water resistance, stain resistance, hardness and the like.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display area C09D 175/08 PHS C09D 175/08 PHS

Claims (5)

[Claims] 1. A polyisocyanate compound having three or more NCO groups in one molecule is obtained by reacting a carboxylic acid group-containing glycol and a polyethylene glycol monoalkyl ether represented by the following formula (1). A semicarbazide composition obtained by reacting a polyisocyanate reaction product with a hydrazine derivative. Embedded image (In the formula, R ¹ represents a monovalent hydrocarbon group having 1 to 25 carbon atoms, and n represents an integer of 5 to 80.) 2. The semicarbazide composition according to claim 1, wherein the polyisocyanate compound has an isocyanurate structure or a buret structure as a basic skeleton. 3. A semicarbazone derivative obtained by reacting the semicarbazide composition according to claim 1 or 2 with a monoketone represented by the following formula (2). R ² R ³ C═O (2) (wherein R ² and R ³ are each a hydrogen atom, a linear or branched aliphatic residue having 2 to 20 carbon atoms, 5
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. Further, R ² and R ³ may form a cyclic structure. ) 4. A hydrazine derivative reacted with a monoketone represented by the above formula (2), a polyisocyanate compound having three or more NCO groups in one molecule, and a carboxylic acid group-containing glycol and the above formula (1). ) A semicarbazone derivative obtained by reacting a polyisocyanate reaction product obtained by reacting a polyethylene glycol monoalkyl ether represented by 5. The semicarbazide composition (A) according to claim 1 and / or the semicarbazone derivative (B) according to claim 3 or 4 and a polycarbonyl compound (C) are contained, and the solid content weight ratio thereof. (C) / ((A) +
(B)) = 99.9 / 0.1-90 / 10 coating composition.