JP3521991B2 - Semicarbazide composition and coating composition using the same - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous semicarbazide composition.
Object, clear coat agent and top coat using the same
Agent, paint, undercoat agent, cloth and paper impregnating agent, adhesive
Excellent coating group that can be used for various applications as
About adult. In recent years, aqueous coatings have been used in the coating field.
Marjon is used as a conversion material from organic solvent to water.
Although it is noted, it is more water resistant than organic solvent based coating agents
Still showing sufficient physical properties in terms of properties, stain resistance, hardness, etc.
Not in. To improve these physical properties, aqueous emulsions
It is possible to form a crosslinked coating film by introducing a functional group into John
Generally done. An aqueous emulsion for forming a crosslinked coating film
Requirements for workability, workability, etc. for one-part, room temperature curing type
In recent years, the reaction of dehydration condensation between carbonyl and hydrazide
Hydrazone cross-linking aqueous emulsions utilizing hydration
Have been. For example, JP-B-46-20053,
JP-A-57-3850, JP-A-57-3857
JP, JP-A-58-96643, JP-A-4-24
No. 9587 discloses an aqueous dispersion of a carbonyl group-containing copolymer.
Multifunctional carboxylic acid hydrazide compound as hardener in liquid
By adding a substance, it has both low-temperature curability and storage stability.
A coating composition with excellent preparation, hardness, and stain resistance has been proposed.
Have been. [0004] However, a polyfunctional carboxylic acid as a curing agent is used.
Acid hydrazide compounds are hydrolyzed during storage by hydrolysis.
Gins are liberated and the curing ability changes with time, which is not preferable.
Also, a representative of polyfunctional carboxylic hydrazide compounds
Harden some hydrophilic compounds like adipic dihydrazide
When used as an agent, the crosslinked coating film has poor water resistance. SUMMARY OF THE INVENTION The present invention relates to a low-temperature curable
And storage stability, water resistance, stain resistance, hardness, etc.
To provide a coating composition capable of obtaining an excellent film.
And That is, the present invention provides the following:
Semicarbazide compound represented by (1) and the following formula (2)
Consisting of a hydrophilic group-containing compound represented by
The quantity ratio is (1) / (2) = 99/1 to 10/90.
And a semicarbazide composition. [0007] (Where R ¹ Is a polyisocyanate compound
Represents a residue obtained by removing the NCO group from. l and m are each 0
Alternatively, it represents a positive integer, and (l + m) ≧ 3. R
^Two Is a divalent linear or branched 2-20 carbon atoms
An aliphatic residue having atoms or 5 to 20 carbon atoms
With or without alicyclic residues or substituents
Represents a good aromatic residue. n represents 0 or 1. [0009] (Wherein R ^Three Is a polyisocyanate compound
Represents a residue obtained by removing the NCO group from. p and q are each 0
Or r represents a positive integer, and r represents a positive integer. Also, (r
+ P + q) ≧ 2. A is a nonionic hydrophilic group and
And / or ionic systems (including those that can later be converted to ionic systems)
F) represents an organic group having a hydrophilic group. R ^Four Is divalent
Chain or branched fats having 2 to 20 carbon atoms
Aliphatic residue or alicyclic residue having 5 to 20 carbon atoms
Aromatic residue which may or may not have a group or substituent
Represents n represents 0 or 1. Further, the above semicarbazide composition (A) and polycarbonate
(B) having a solid content weight ratio of (A)
/(B)=0.1/99.9 to 90/10
Characteristic coating composition. Hereinafter, the present invention will be described in detail. In the present invention
The semicarbazide composition has NCO groups in one molecule.
And a polyisocyanate compound (a) having three or more
Ionic hydrophilic groups and / or ionic (later ionic
Hydrogenation with hydrophilic groups (including those that can be converted to
After reacting the compound (b) with NCO group in excess,
Reacting the derivative (c), represented by the formula (1)
Semicarbazide Compound and Hydrophilicity Represented by Formula (2)
By separately synthesizing and mixing the group-containing compound
Obtainable. First, a method for obtaining the above semicarbazide composition
As a method, a polymer having three or more NCO groups in one molecule
An isocyanate compound (a) and a nonionic hydrophilic group;
And / or ionic systems (including those that can later be converted to ionic systems)
V) An active hydrogen compound (b) having a hydrophilic group is
After reacting with excess groups, the hydrazine derivative (c) is reacted.
A method for causing the error will be described. In the present method (method), NCO is contained in one molecule.
A polyisocyanate compound (a) having three or more groups,
To form a biuret bond of the diisocyanate compound, urea
Bond, isocyanurate bond, urethane bond, allopha
Oligomerization by nate bond, uretdione bond, etc.
Polyisocyanate compound, furthermore, 1,8-diisocyanate
Anato-4-isocyanatomethyloctane and their derivatives
Combination is mentioned. As a diisocyanate compound, hexame
Aliphatic diisocyanates such as tylene diisocyanate (HDI)
Anate; 4,4'-methylenebiscyclohexyldii
Socyanate (hydrogenated MDI), isophorone diisocyanate
Nitrate (IPDI), dimethylcyclohexanediisocyanate
Alicyclic diisocyanate such as anate (hydrogenated XDI);
2,4-tolylene diisocyanate, 2,6-tolylene
Diisocyanates and their mixtures (TDI), dife
Nylmethane-4,4'-diisocyanate (MDI),
Naphthalene-1,5-diisocyanate (NDI),
3,3-dimethyl-4,4-biphenylene diisocyanate
(TODI), crude TDI, polymethylene polyfe
Aromatic diisocyanates such as nyl diisocyanate and crude MDI
Anate, xylylene diisocyanate (XDI),
Aromatic and alicyclic diisocyanes such as enylene diisocyanate
And the like, and combinations thereof. In addition, the nonionic system used in the present method (method)
Hydrophilic groups and / or ionic systems (converted later to ionic systems)
Active hydrogen compound having a hydrophilic group
Among the nonionic hydrophilic groups in (b), for example, poly
Ethylene glycol, polyoxyethylene-oxypro
Pyrene (random and / or block) glycos
, Polyoxyethylene-oxytetramethylene (run
Dames and / or blocks) Polyers such as glycols
Terpolyols and polyethers represented by the following general formula (3)
Tylene glycol monoalkyl ethers, and further,
As described in U.S. Pat. No. 3,905,929.
Diols with pendant polyoxyethylene chains
No. Embedded image (Where R ^Four Has 1 to 25 carbon atoms
Represents a monovalent hydrocarbon group. N is an integer of 5 to 80
Represents The ionic hydrophilic groups include tertiary amines of carboxylic acids.
Groups such as quaternary ammonium salts
Groups. Anionic group (or later to anionic group
Examples of active hydrogen compounds having a group which can be converted
For example, lactic acid, glycolic acid, 4-hydroxybutyric acid, p-f
Monohydroxycarboxylic acids such as enolcarboxylic acids;
Glycine, alanine, aspartic acid, β-alanine, etc.
Amino acids; α, α′-dimethylolpropionic acid;
α, α'-dimethylol such as α, α'-dimethylolacetic acid
Monoalkanes such as p-phenolsulfonic acid
Droxysulfonic acids; aminosulfonic acids such as taurine
And combinations thereof. These active hydrogens
Synthesis of hydrophilic polyisocyanate reactant by acid group of compound
At the time of emulsification or emulsification (or solubilization) with a base
Can be converted to an anionic group. Used for neutralization
As the base, for example, triethylamine, ammonia,
Diethanolamine, dimethylaminoethanol, methyl
Amine compounds such as rudiethanolamine and dibutylamine
Substance; water of alkali metal such as KOH, NaOH, LiOH
Oxides and the like, and a combination thereof can be used. A cationic group (or later converted to a cationic group)
Examples of the active hydrogen compound having a group which can be
N, N-dimethylethanolamine, N, N-diethyl
N, N-dialkylmonoalkano such as ethanolamine
N-methyldiethanolamine, N-butyl
N-alkyl dialkanos such as tildiethanolamine
Luamines and the like, and alkylene alkyls having 2 to 4 carbon atoms.
With oxide (ethylene oxide, propylene oxide, etc.)
Additives and the like, and further, a combination of these. these
The tertiary amino group of the active hydrogen compound is a hydrophilic polyisocyanate
During the synthesis of the salt compound or emulsification (or water-solubilization)
Sometimes neutralized with an acid or quaternized with an alkylating agent
To a cationic group. As acid used for neutralization
Are, for example, acetic acid, lactic acid, hydrochloric acid, phosphoric acid, sulfuric acid, etc.
In combination. As the alkylating agent, for example, di
Methyl sulfate, diethyl sulfate, methyl chloride, methyl
Iodide, benzyl chloride and the like. [0019] A polymer having three or more NCO groups in one molecule
An isocyanate compound (a) and a nonionic hydrophilic group;
And / or ionic systems (including those that can later be converted to ionic systems)
V) Reaction with an active hydrogen compound (b) having a hydrophilic group
At a temperature of 20 ° C to 130 ° C under substantially anhydrous conditions
Of NCO group and active hydrogen group capable of reacting with NCO group
Operating at a ratio of 1.1 to 500: 1, preferably 2 to 100: 1
U. These reactions are carried out without solvent or in a solvent.
Can be carried out using a catalyst if necessary
You. The solvent may be inert to the NCO group, or
Alternatively, those having lower activity than the reaction components can be used. Concrete
Typically, acetone, methyl ethyl ketone, methyl isobut
Ketone solvents such as tyl ketone and cyclohexanone; Geo
Xane, tetrahydrofuran, diethylene glycol di
Ether solvents such as methyl ether; dimethylforma
Amide solvents such as amide and dimethylacetamide;
Lactam solvents such as tyl-2-pyrrolidone; dimethyls
Sulfoxide solvents such as rufoxide; ethyl acetate, cello
Ester solvents such as Solve acetate; t-butanol
And alcohols such as diacetone alcohol; toluene
Aromatic hydrocarbon solvents such as xylene; n-hexane and the like
Examples thereof include aliphatic hydrocarbon solvents and the like, and combinations thereof. As a specific example of the above-mentioned catalyst, for example,
Butyltin dilaurate, stannous octoate, octylic acid
Salts of organic and inorganic acids with metals such as lead, and organic metal derivatives
Body: organic such as triethylamine and triethylenediamine
Tertiary amines; diazabicycloundecene catalysts, etc.
I can do it. The semicarbazide composition in the present invention is
The above-mentioned polyisocyanate having three or more NCO groups in one molecule.
Anate compound (a) and a nonionic hydrophilic group and / or
Is the ionic parent (including those that can later be converted to ionic)
NCO group excess with active hydrogen compound (b) having aqueous group
And then reacting the hydrazine derivative (c)
Gained by things. Examples of the above hydrazine derivative (c) include:
For example, hydrazine and its hydrate; ethylene-1,2-di
Hydrazine, propylene-1,3-dihydrazine, butyric
Dihydrazine compounds such as len-1,4-dihydrazine;
Oxalic dihydrazide, malonic dihydrazide, succinic di
Hydrazide, glutaric dihydrazide, adipic dihydric
Drazide, sebacic acid dihydrazide, maleic acid dihydride
Razide, fumaric dihydrazide, itaconic dihydrazide
, Isophthalic dihydrazide, phthalic dihydrazide
Dicarboxylic acid dihydrazides; trimellitic acid
Tricarboxylic acid trihydrazides such as drazide, general formula
Carbonic dihydrazides represented by (4), represented by the general formula (5)
Bisemicarbazides represented and the like and combinations thereof
It is. Embedded image (Wherein x represents an integer of 0 to 5) (Where R ^Five Is divalent linear or branched
An aliphatic residue having 2 to 9 carbon atoms or 5 to 8
With an alicyclic residue or substituent having
Represents an aromatic residue which may or may not have. The hydrazine derivative may be a hydrazide group or
At least a part of the hydrazine group is converted into the following formula (6)
Reacts with monoaldehyde or monoketone represented by
Hydrazone group. Embedded image (Where R ⁶ , R ⁷ Is a hydrogen atom and / or
Has 2 to 20 carbon atoms, linear or branched
Aliphatic residues and / or having from 5 to 20 carbon atoms
With or without alicyclic residues and / or substituents
Also represents a good aromatic residue. Also, R ^Four , R ^Five Is a chemical bond
Therefore, an annular structure may be formed. In this case, the resulting semicarbazide-based composition is converted to a blocking agent.
Of monoaldehyde or monoketone used as
Considering that the blocking agent is 30 to 200 ° C.
Monoketones having boiling points of
Tyl ketone, methyl isobutyl ketone, cyclohexano
Are preferred. In preparing the semicarbazide composition of the present invention,
And the NCO group and hydra of the reaction product of (a) and (b) above.
-NHNH in gin derivative _Two Group or -NHNH _Two Turn to base
The equivalent ratio with the group capable of forming is 1: 1.5 to 100, preferably
Is 1: 2 to 50. The semicarbazide group of the present invention
After manufacturing the product, excess hydrazine derivative is steamed if necessary.
It can be removed by distillation or extraction. Reaction of NCO group with hydrazine derivative (c)
Is carried out without a solvent or with a catalyst if necessary in a solvent.
I can do it. The solvents and catalysts that can be used are described above.
(A) and (b)
The above-mentioned examples are mentioned. Solvent is semicarbazide group
May remain in the product, but heated under normal pressure or reduced pressure
It can also be removed by distillation. The semicarbazide composition of the present invention has the formula
A semicarbazide compound represented by (1) and a compound represented by formula (2):
Separately synthesize and mix with the hydrophilic group-containing compound represented
It can also be obtained by a method. In this method (law)
The semicarbazide compound represented by the formula (1)
The above-mentioned polyisocyanate having three or more NCO groups in one molecule.
An anate compound (a) and a hydrazine derivative (c)
It is obtained by responding. The reaction conditions are
Reaction product of (a) and (b) and hydrazine derivative
According to the reaction with (c). The compound having a hydrophilic group represented by the formula (2)
The product is a polyisocyanate having two or more NCO groups in one molecule.
Nonionic hydrophilic groups and / or ion
(Including those that can later be converted to ionic) hydrophilic groups
An active hydrogen compound (b) having
It is obtained by reacting a drazine derivative (c). 1 minute above
Polyisocyanate having two or more NCO groups in the polymer
As a compound, a compound having three or more NCO groups in one molecule is used.
Examples of the lysocyanate compound (a) and its raw material
The diisocyanate compounds described above can be used. The hydrophilic group-containing compound represented by the formula (2)
In the synthesis, a polymer having two or more NCO groups in one molecule
Lithocyanate compound and nonionic hydrophilic group and / or
Or ionic system (including those that can be later converted to ionic system)
The reaction with the active hydrogen compound (b) having a hydrophilic group is carried out by N
Equivalent ratio of CO groups to active hydrogen groups capable of reacting with NCO groups: 1
Perform at 〜１０10: 1. Other reaction conditions are
According to the reaction between (a) and (b). In the present invention, the compound represented by the formula (2)
Are preferably two or more NCO groups in one molecule.
Polyisocyanate Compound and Nonionic Hydrophilic Group
And / or ionic systems (which can be later converted to ionic systems)
An active hydrogen compound (b) having a hydrophilic group
Equivalent ratio of O groups to active hydrogen groups capable of reacting with NCO groups
Polyester reacted with 1-10: 1 under NCO group excess condition
Hydrazine is added to the cyanate reactant by the method described above.
A compound obtained by reacting the derivative (c)
You. The compound obtained in this manner is used as a polycarbonate as described later.
The reaction with the rubonyl compound becomes possible,
Strength and water resistance are improved. In the present method (method),
Semicarbazide compound represented by the formula (1)
The weight ratio of the hydrophilic group-containing compound represented by (2) to the solid content
(1) / (2) = mixing at 99/1 to 10/90
Can obtain the semicarbazide composition of the present invention.
You. Semicarbazide composition obtained by the present invention,
Method of adding sewage with moderate stirring or moderate stirring
Under the method of adding the semicarbazide composition to water, etc.
Therefore, it can be dispersed or dissolved in water. this
When necessary, dispersibility and dispersion of the aqueous semicarbazide composition
Surfactants may be used to aid dispersion stability
No. Surfactants used include, for example, higher fats
Acid, resin acid, acid fatty alcohol, sulfate, sulf
Higher alkyl fonates, alkyl allyl sulfonates,
For sulfonated castor oil, sulfosuccinate, etc.
Representative anionic surfactants or ethylene oxide
Oxides and long-chain fatty alcohols or phenols,
Nonionic field typified by known reaction products with acid
Cationic containing surfactant, quaternary ammonium salt, etc.
High surfactant, (partially saponified) polyvinyl alcohol, etc.
Examples include a molecular dispersion stabilizer and the like, and combinations thereof. In the present invention, the thus obtained semi-
Carbazide composition (A) is converted to polycarbonyl compound (B)
The solid content ratio is (A) / (B) = 0.1 / 9
Low temperature by adding in the range of 9.9 to 90/10
It has both curability and storage stability, water resistance, stain resistance, and hardness.
A film excellent in degree and the like can be obtained. Polycarbonyl
The compound (B) contains, for example, a carbonyl group
Copolymer described in JP-A-2-238015
Carbonyl groups such as hydroxyacetone
Carbo made from mono and / or poly alcohol
Nyl group-containing polyurethanes, acetoacetylated polyvinyl
Alcohol, acetoacetylated hydroxyalkyl
Lurose and the like, and combinations thereof. The carbonyl group-containing copolymer is as follows:
(A) 0.1% of a carbonyl group-containing ethylenically unsaturated monomer.
1 to 30% by weight, (b) d) copolymerizable with the monomer (b)
Contains 70 to 99.9% by weight of a thylene unsaturated monomer
A monomer mixture is prepared by a suspension polymerization method, an emulsion polymerization method, a solution polymerization method.
It can be produced by copolymerizing the above. Single amount
The body (a) is diacetone acrylamide, die
Acetone methacrylamide, acrolein, vinyl meth
Ketone, acetoacetoxyethyl methacrylate, e
Lumil styrene and the like, and combinations thereof. As the monomer (b), for example, ethylene,
Olefins such as propylene and isobutylene; butadie
Dienes; halo such as vinyl chloride and vinylidene chloride
Olefins: vinyl acetate, n-vinyl butyrate, benzoic acid
Vinyl, p-t-butyl benzoate, pivalate
Nyl, vinyl 2-ethylhexanoate, versatic acid
Carboxylic acid esters such as vinyl and laurate
And isopropenyl acetate, isopropenyl propionate
Carboxylic acid isopropenyl esters and the like; ethyl vinyl acetate
Ether, isobutyl vinyl ether, cyclohexyl
Vinyl ethers such as vinyl ether; styrene, vinyl
Aromatic vinyl compounds such as toluene; allyl acetate, benzoate
Allyl esters such as allyl fragrance; allyl ethyl acetate
Ter, allyl glycidyl ether, allyl phenyl ether
Allyl ethers such as ter; butyl (meth) acrylate
Methyl, (meth) acrylate, cyclohexyl (meth
TA) acrylate, isobornyl (meth) acrylate
G, 2-ethylhexyl (meth) acrylate, 2-h
Droxyethyl (meth) acrylate, glycidyl (meth
T) acrylate, γ- (meth) acryloyloxyp
Ropirtrimethoxysilane, 4- (meth) acryloyl
Oxy-2,2,6,6-tetramethylpiperidine,
4- (meth) acryloyloxy-1,2,2,6
6, -pentamethylpiperidine, perfluoromethyl
(Meth) acrylate, perfluoropropyl (meth)
Acrylate, perfluoropropyromethyl (meth) a
Esters of acrylic acid and methacrylic acid such as acrylate
, Acrylic acid, methacrylic acid, maleic acid, fumaric
Acid, itaconic acid, crotonic acid, acrylamide, N-meth
Tyrol (meth) acrylamide, acrylonitrile, etc.
And combinations thereof. The semicarbazide composition of the present invention
Set consisting of the product (A) and the polycarbonyl compound (B)
The product may be a polyepoxy compound (C), if necessary.
When the solid content weight ratio is within the range of (B) / (C) ≧ 10/90
Can be used together. Combined use of polyepoxy compounds
Therefore, the water resistance of the obtained film is further improved. Polyeppo
As the oxy compound (C), for example, an epoxy group-containing
Other unsaturated monomer containing lenic unsaturated monomer as an essential component
And bulk polymerization, suspension polymerization, emulsion polymerization, and solution polymerization.
Containing epoxy group obtained by copolymerization
Copolymer, bisphenol A type epoxy resin, bisphenol
Nord F type epoxy resin, cycloaliphatic epoxy resin,
Glycidyl ester epoxy resin, glycidylamine
Epoxy resin, hydantoin type epoxy resin, trig
Ricidyl isocyanurate or the like dispersed in water, and
And combinations thereof. Semicarbazide group obtained by the present invention
Of the product (A), the polycarbonyl compound (B) and
Hardness, chemical resistance and heat resistance of the film formed by mixing
For example, N is preferably included in one molecule.
Polyisocyanate compound having three or more CO groups
As (a), for example, JP-A-55-38380
Hexamethylene diisocyanate as described in
Isocyanurate type polyisocyanate
No. 57-78460.
Holon diisocyanate and hexamethylene diisocyanate
Isocyanurate-type polyisocyanate
And JP-A-57-47321.
Isocyanurate modified with polyfunctional alcohol
G-type polyisocyanate, JP-A-64-33115
Low viscosity isocyanurate type as described in the report
Polyisocyanate, described in Japanese Patent Application No. 6-16688
Highly branched isocyanurate type poly
Represented by the following general formula (7) represented by isocyanate, etc.
Using the isocyanurate compound
Semicarbazide composition prepared by the above method, and NC in one molecule
Polyisocyanate compound having three or more O groups (a)
For example, JP-A-53-106797,
As described in JP-A-55-11452, etc.
Hexamethylene diisocyanate buret type poly
Socyanate, described in JP-A-59-95259.
Isophorone diisocyanate and hexa
Bullet-type polystyrene copolymerized with methylene diisocyanate
Represented by the following general formula (8) represented by isocyanate, etc.
Using the burette compound
The prepared semicarbazide composition is preferably used. Embedded image (Where R ¹ , R ^Two , R ^Three Is a divalent linear
Or branched aliphatic residue having 2 to 20 carbon atoms
Or an alicyclic residue having 5 to 20 carbon atoms or
Represents an aromatic residue which may or may not have a substituent.
Also R ¹ , R ^Two , R ^Three May be the same or different
It may be. ) (Where R ¹ , R ^Two , R ^Three Is a divalent linear
Or branched aliphatic residue having 2 to 20 carbon atoms
Or an alicyclic residue having 5 to 20 carbon atoms or
Represents an aromatic residue which may or may not have a substituent.
Also R ¹ , R ^Two , R ^Three May be the same or different
It may be. ) The semicarbazide composition of the present invention comprises a polycarbonyl compound.
If necessary, the coating composition can be
Agents, dispersants, light stabilizers, wetting agents, thickeners, rheology
Control agents, defoamers, plasticizers, film-forming aids, rust inhibitors, etc.
Selected and combined for each purpose
, Clear coat agent, top coat agent, paint, under
-Various coating agents, impregnating agents for cloth and paper, various adhesives, etc.
Can be used for applications. EXAMPLES Parts in the examples mean parts by weight. In the example
The measurement methods for various measurements used for
You. The infrared absorption spectrum is JASCO FT / IR-
Measured at 5300. The film strength was measured using a Tensilon tensile tester (Ori Co., Ltd.)
Entec RTA-100) Measurement length: 300 mm, pull
Elongation speed: Measured under the condition of 50 mm / min. Solvent resistance of the film, the film is 200 mesh
After immersion in acetone at room temperature for 24 hours,
The retention rate of the film weight
Weight) ÷ (film weight before immersion in acetone) × 100
I asked. Water resistance of the film is measured by immersing the film in water at room temperature for 6 days.
After immersion, visually observe the state of the film and absorb the film.
Rate ((film weight after water immersion)-(film before water immersion)
Film weight)) ÷ (film weight before water immersion) × 100
Asked. The film's wet strength retention is measured by placing the film in water at room temperature.
Measure the breaking strength after immersion for 24 hours and measure the breaking strength before immersion.
The retention rate with respect to (rupture strength after water immersion) ÷ (before water immersion)
Was determined as the breaking strength × 100. Production Example of Polycarbonyl Compound Anti-refrigerator having reflux condenser, dropping tank, thermometer and stirrer
220 parts of ion exchange water, Perex OTP (flower)
Sodium dioctyl sulfosuccinate manufactured by Oo Corporation
(0% aqueous solution), 2.3 parts, and the temperature in the reaction vessel was set at 8 parts.
After raising the temperature to 0 ° C, 9 parts of methacrylic acid and styrene
4.5 parts, 234 parts of butyl acrylate, diacetone
Acrylamide 13.5 parts, methyl methacrylate 189
Parts, 230 parts of ion exchange water, 9 parts of Perex OTP,
Emulgen 950 (manufactured by Kao Corporation, polyoxyethylene
10 parts of a 25% aqueous solution of nonylphenyl ether)
Drop a mixture of 1 part of ammonium sulfate into the reaction vessel
For 3 hours. Temperature in the reaction vessel during inflow
Was kept at 80 ° C. After the inflow is completed, the temperature in the reaction vessel is reduced to 8
It was kept at 0 ° C. for 2 hours. Then cool to room temperature, 25
% Ammonia solution to adjust the pH to 8, then
Filtered through a 100 mesh wire mesh, 46.8% solids, granules
Aqueous emulsion containing carbonyl group-containing copolymer having a diameter of 1050A
I got it. Example 1 A reflux condenser, a thermometer and a stirrer were provided.
23 parts of acetone in a reactor
0 ”(Hexamethylene diisocyanate, manufactured by Asahi Kasei Corporation)
Cobulette type of nitrate and isophorone diisocyanate
Oligomer (NCO group content 15.6wt%, 75.4%
Ethyl acetate solution)) 23 parts, "Uniox M100
0 "(Polyoxy having a hydroxyl value of 56.9, manufactured by NOF Corporation)
10 parts of diethylene methyl ether)
Add 0.001 part of rutin dilaurate at 60 ° C for 4 hours
Reacted. Next, a reflux condenser, thermometer and stirrer are installed.
Hydrazine 1 water was added to 421 parts of acetone
74 parts of the hydrate were added at room temperature over 30 minutes with stirring
Thereafter, the mixture was further stirred for 1 hour. The reaction obtained earlier in this reaction solution
The product is added over 1 hour with stirring at 40 ° C. and then
The mixture was further stirred at 40 ° C. for 4 hours. Then 1183 parts of water
At 40 ° C. over 30 minutes and continue stirring for another 30 minutes.
Was. Acetone, ethyl acetate, hydra in the obtained reaction solution
Gin, the reaction product of acetone and hydrazine, water, etc.
Semicarbazide with 25% solids
An aqueous solution of the composition was obtained. FIG. 1 shows the infrared absorption spectrum of this product.
Show. 50 parts of an aqueous solution of the obtained semicarbazide composition
(10 parts of solid content) and 100 parts of cyclohexanone
After shaking at 150 rpm for 5 hours, 10,000 rpm
and centrifugation at 10 m for 10 minutes. Hydrophilic in lower aqueous phase
Polyoxyethylene methyl ether group
Hydrophilic group having "Duranate V3000" skeleton
6.7 parts of the compound contained, and cyclohexanone in the upper layer
In the phase, Semika having "Duranate V3000" skeleton
3.3 parts of the rubazide compound was present. Example 2 Having a reflux condenser, a thermometer and a stirrer
259 parts of acetone and isophorone diisocyanate
86 parts (IPDI), "Uniox M1000"
(Polyoxye with a hydroxyl value of 56.9, manufactured by NOF Corporation)
310 parts, dibutyl as a catalyst
Add 0.04 parts of tin dilaurate and react at 60 ° C for 7 hours
did. Next has a reflux condenser, thermometer and stirrer
Hydrazine monohydrate in 2600 parts of acetone placed in a reactor
459 parts were added at room temperature over 30 minutes with stirring
Thereafter, the mixture was further stirred for 1 hour. The reaction obtained earlier in this reaction solution
The product is added over 1 hour with stirring at 40 ° C. and then
The mixture was further stirred at 40 ° C. for 4 hours. Then 4100 parts of water
At 40 ° C. over 30 minutes and continue stirring for another 30 minutes.
Was. Acetone, hydrazine, aceto
The reaction product of hydrazine and hydrazine, water, etc. are distilled off under heating and reduced pressure.
Hydrophilicity having an IPDI skeleton with a solid content of 40%
An aqueous solution of the group-containing compound was obtained. FIG. 2 shows the infrared absorption spectrum of this product.
Show. Reaction with reflux condenser, thermometer and stirrer
Hydrazine monohydrate 5 in 3390 parts of acetone
After adding 97 parts at room temperature over 30 minutes with stirring,
For 1 hour. The reaction mixture was added to “Duranate V30
00 ”(made by Asahi Kasei Kogyo Co., Ltd.
Koblet of anate and isophorone diisocyanate
Oligomer (NCO group content 15.6 wt%, 75.4
% Ethyl acetate solution)) while stirring 161 parts at 40 ° C.
Over 1 hour and then stirred at 40 ° C for 4 hours
did. Then add 180 parts of water at 40 ° C over 30 minutes
The stirring was continued for another 30 minutes. Ase in the resulting reaction solution
Tons, ethyl acetate, hydrazine, acetone and hydrazine
The reaction product, water, etc. is distilled off under heating and reduced pressure to give a white color.
A crystalline semicarbazide compound was obtained. FIG. 3 shows the infrared absorption spectrum of this product.
Show. 20 parts of the obtained semicarbazide compound is
After dissolving in 80 parts of tylpyrrolidone, the above IPDI skeleton
Aqueous solution of a hydrophilic group-containing compound having a solid content of 40%
50 parts are added with stirring at room temperature, followed by 50 parts of water.
Is added with stirring to obtain a semi-solid with a solid content of 20%.
An aqueous solution of the rubazide composition was obtained. Example 3 Copolymer containing carbonyl group synthesized in Production Example
Polysemi obtained in Example 1 was added to 100 parts of the aqueous body emulsion.
Add 13.2 parts of carbazide compound emulsion and mix
The coating composition was formed on a glass plate at room temperature for one day,
Further, vacuum drying at 50 ° C for 30 hours
Got Lum. The physical properties of this film were measured. Table of results
1 is shown. Comparative Example 1 Copolymer containing carbonyl group synthesized in Production Example
The aqueous emulsion alone was formed in the same manner as in Example 3.
The film was dried to obtain a film. Measure the physical properties of this film
did. Table 1 shows the results. Comparative Example 2 Polysemicarbazide compound obtained in Example 1
The emulsion was mixed with adipic dihydrazide (Nippon Hydrazi)
Except for 14.2 parts of a 5% aqueous solution of
Compounded in the same manner as in Example 3, dried and deposited into a film
Got. The physical properties of this film were measured. Table 1 shows the results
Show. [Table 1] The coating composition of the present invention has a high crosslinking density and a high
A film that is relatively tough and has excellent water resistance, chemical resistance, heat resistance, etc.
Can be obtained at low temperatures. Therefore, according to the present invention,
Archcoat, Topcoat, Paint, Undercoat
For use in various applications as an adhesive, impregnating agent for cloth and paper, various adhesives, etc.
An excellent coating composition that can be used is provided.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is an infrared absorption spectrum of the compound of Example 1. FIG. 2 is an infrared absorption spectrum diagram of a compound according to IPDI skeleton of Example 2. FIG. 3 is an infrared absorption spectrum of the semicarbazide compound of Example 2.

Claims (1)

(57) [Claim 1] It comprises a semicarbazide compound represented by the following formula (1) and a hydrophilic group-containing compound represented by the following formula (2), and the solid content ratio by weight thereof is (1) / (2) = 99/1 to 1
0/90 der is, selected from other keto groups and aldo group
Compounds having at least two groups in one molecule
The semicarbazide composition characterized by not containing. Embedded image (Wherein, R ¹ represents a residue obtained by removing an NCO group from a polyisocyanate compound. L and m each represent 0 or a positive integer, and (l + m) ≧ 3. R ² represents a divalent compound. A linear or branched aliphatic residue having 2 to 20 carbon atoms or an alicyclic residue having 5 to 20 carbon atoms or an aromatic group with or without a substituent Represents a group residue, and n represents 0 or 1.) (Wherein, R ³ represents a residue obtained by removing the NCO group from the polyisocyanate compound. P and q each represent 0 or a positive integer, r represents a positive integer, and (r + p + q) ≧
2. A represents an organic group having a nonionic hydrophilic group and / or an ionic (including a substance which can be later converted into an ionic) hydrophilic group. R ⁴ may have a divalent linear or branched aliphatic residue having 2 to 20 carbon atoms or an alicyclic residue having 5 to 20 carbon atoms or a substituent. Represents an aromatic residue which may not be present. n represents 0 or 1. )