JP3073201B2 - Semicarbazide derivative and composition containing the semicarbazide derivative - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a semicarbazide derivative and a coating composition containing the semicarbazide derivative and a polycarbonyl compound. More specifically, the present invention provides an isocyanate group having 3 to 20 isocyanates in one molecule.
The present invention relates to a semicarbazide derivative obtained by reacting hydrazine or a derivative thereof, or a mixture of an unblocked terminal and a terminal-blocked product thereof, with a polyisocyanate having the same, and a terminal-blocked product thereof. The present invention also relates to a coating composition using at least one selected from the above-mentioned semicarbazide derivatives and the terminal blockers thereof in combination with a polycarbonyl compound as a curing agent. Further, the present invention provides a composition comprising at least one selected from the above-mentioned semicarbazide derivatives as a curing agent and its terminal blocker, and at least one selected from a hydrophilic group-containing compound and its terminal blocker ( Hereinafter, the composition is often referred to as a “semicarbazide composition”), and also relates to a coating composition containing the semicarbazide composition and a polycarbonyl compound.

The coating composition of the present invention not only has excellent room temperature curability and storage stability, but also has water resistance, stain resistance, hardness, toughness, weather resistance, pigment dispersibility, gloss retention, adhesion, Excellent in properties such as rust prevention, water resistance, water resistance, heat resistance, chemical resistance, etc., especially in order to form a coating with extremely excellent water resistance, stain resistance and hardness, paints, underlaying or finishing materials for building materials, It is useful as an adhesive, a pressure-sensitive adhesive, a paper processing agent, and a finishing agent for a woven fabric.

[0003]

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. Has not yet shown sufficient 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 coating film composed of a crosslinked polymer (hereinafter, often referred to as a “crosslinked coating film”). .

[0004] The aqueous emulsion for forming the crosslinked coating film has a form in which a curing agent and a polymer are mixed from the viewpoint of workability, workability, and the like. Cold-curing, one-pack type, which can form a cured film with evaporation
), And hydrazone crosslinked aqueous emulsions utilizing a dehydration condensation reaction between a carbonyl group and a hydrazide group have recently been receiving attention.

For example, Japanese Patent Publication No. 46-20053, Japanese Patent Application Laid-Open No. 57-3850, Japanese Patent Application No. 57-3857, Japanese Patent Application No. 58-9664.
No. 3, JP-A-4-249587, and the like, cold-curing ability and storage by adding dicarboxylic acid dihydrazide as a curing agent to an aqueous dispersion of a carbonyl group-containing copolymer are disclosed. It has been proposed to provide a coating composition having both stability and excellent hardness, stain resistance and the like. However, in this method, the dicarboxylic acid dihydrazide used as a curing agent is hydrolyzed during storage of the coating composition, and the crosslinking ability (that is, curing property) is reduced, so that excellent hardness, stain resistance, Not only the ability to form a crosslinked coating film having solvent resistance and the like decreases with time, but also in the above-mentioned publication, such as adipic dihydrazide as a dicarboxylic acid dihydrazide, the compatibility with a carbonyl group-containing copolymer is low and Since a compound having high hydrophilicity is used, the resulting crosslinked film has a drawback that the water resistance is extremely poor.

[0006] As described above, the conventional aqueous coating composition containing a conventional curing agent and a polycarbonyl compound deteriorates in curing properties over time. Therefore, when this coating composition is applied to a substrate surface, Could not exhibit sufficient curing performance.
Further, since dicarboxylic acid dihydrazide having poor compatibility with the polycarbonyl compound is used as a curing agent, there is a problem that the water resistance of a crosslinked film obtained by coating becomes extremely poor. Therefore, there is a demand for the development of an aqueous coating composition that is excellent in room-temperature curability and storage stability, and that can provide a crosslinked film excellent in water resistance, stain resistance, hardness and the like.

[0007]

SUMMARY OF THE INVENTION The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result,
(Α) obtained by reacting a polyisocyanate having 3 to 20 isocyanate groups (hereinafter often referred to as “NCO group”) with hydrazine or a derivative thereof, or a mixture of an unblocked terminal blocker and a terminal blocker thereof. And (δ) at least one selected from the group consisting of the semicarbazide derivative and its terminal blocker, and a hydrophilic group-containing compound and its terminal blocker. It has been surprisingly found that a semicarbazide composition containing at least one selected from the group consisting of:

The present inventors further provide at least one member selected from the group consisting of the above-mentioned (α) semicarbazide derivative and its terminal blocker, or (δ) selected from the group consisting of the semicarbazide derivative and its terminal blocker. An aqueous coating composition prepared by combining a semicarbazide composition containing at least one compound and at least one selected from a hydrophilic group-containing compound and a terminal blocker thereof with a polycarbonyl compound as a curing agent is surprising. What should not only be excellent in room temperature curability and storage stability,
Compared to coatings that have a very high degree of cross-linking and various properties including hardness, toughness, water resistance, and stain resistance. It was found that it can be formed at a very low temperature (ambient temperature). The present invention has been completed based on the above findings.

Accordingly, an object of the present invention is to provide a novel compound which exhibits high compatibility with a polycarbonyl compound and is extremely useful as a curing agent for the polycarbonyl compound. Another object of the present invention is a coating composition comprising the above novel compound and a polycarbonyl compound, which is excellent not only in room temperature curability and storage stability but also in water resistance and stain resistance. Excellent properties such as hardness, toughness, weather resistance, pigment dispersibility, gloss retention, adhesion, rust resistance, water permeability, heat resistance, chemical resistance (eg, solvent resistance), and especially water resistance An object of the present invention is to provide a coating composition capable of forming a film having extremely excellent stain resistance, hardness and toughness at a relatively low temperature.

[0010]

According to one aspect of the present invention, there is provided a semicarbazide derivative represented by the formula (1) or an end-blocked derivative thereof.

Embedded image [In the formula, R ¹ is a diisocyanate trimer to oligomer which is formed by at least one diisocyanate forming at least one bond selected from an isocyanurate bond, a uretdione bond, an allohanate bond and a biuret bond. A polyisocyanate residue, or R ¹ , in which all terminal isocyanate groups have been removed from a polyisocyanate which is an oligomer, has 1 carbon atom.
Represents a triisocyanate residue obtained by removing all terminal isocyanate groups from triisocyanate which is an alkylene diisocyanate having 2 to 20 carbon atoms and substituted with one to 8 isocyanatoalkyl groups. Here, in the case of the polyisocyanate residue, the diisocyanate constituting the polyisocyanate residue is a linear or branched alkylene diisocyanate having 2 to 20 carbon atoms, which is not substituted or has 1 carbon atom.
C18-C18 alkyl group, C1-C8 alkoxy group, or C1-C6 alkylene group substituted with C5-C20 cycloalkylene diisocyanate, unsubstituted or C1-C18 Having 6 to 6 carbon atoms substituted with an alkyl group or an alkoxy group having 1 to 8 carbon atoms
20 arylene diisocyanate and an unsubstituted or C1-C18 alkyl group or C1
And at least one diisocyanate selected from the group consisting of aralkylenediisocyanates having 8 to 20 carbon atoms and substituted with an alkoxy group having 8 to 8 carbon atoms. R ² is a linear or branched alkylene group having 2 to 20 carbon atoms, a cycloalkylene group having 5 to 20 carbon atoms, or an unsubstituted or alkyl group having 1 to 18 carbon atoms or 1 to 2 carbon atoms. 6 to 10 carbon atoms substituted with an alkoxy group of 8
Wherein each R ³ is independently a hydrogen atom or a carbon number 1 to
Represents 20 alkyl groups; n is 0 or 1; and l and m are each 0 or a positive integer, provided that 3 ≦ (l + m) ≦ 20. ]

The terminal blocker of the semicarbazide derivative represented by the above formula (1) is a terminal group H ₂ NR in the formula (1).
³ at least Exemplary ethynylphenylbiadamantane derivatives R ⁹ R ⁸ C = NR ³ in which is converted to blocked terminal group represented by N- (wherein the N-, R ^8, R
⁹ is each independently hydrogen atom, linear or branched carbon number 1
To 20 alkyl groups, cycloalkyl groups having 5 to 20 carbon atoms, or unsubstituted or 1 to 18 carbon atoms
It represents an alkyl group or an aryl group having 6 to 10 carbon atoms which is substituted with an alkoxy group having 1 to 8 carbon atoms, R ⁸ and R
⁹ may optionally form a ring structure together. ). According to another aspect of the present invention, at least one (α) selected from the group consisting of the above-mentioned semicarbazide derivatives and terminal blockers thereof, and a hydrophilic group-containing compound represented by the formula (7) And at least one (β) selected from the group consisting of end-blockers thereof.

[0012]

Embedded image

Wherein R ⁴ is a linear or branched alkylene diisocyanate having 2 to 20 carbon atoms, an unsubstituted or alkyl group having 1 to 18 carbon atoms,
A cycloalkylene diisocyanate having 5 to 20 carbon atoms substituted with an alkoxy group having 8 to 8 carbon atoms or an alkylene group having 1 to 6 carbon atoms, which is not substituted or has 1 to 1 carbon atoms
C6-20 arylene diisocyanate substituted with an alkyl group having 8 or an alkoxy group having 1 to 8 carbon atoms, and an unsubstituted or an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 8 carbon atoms At least one diisocyanate selected from the group consisting of aralkylenediisocyanates having 8 to 20 carbon atoms substituted with a group, and excluding all terminal isocyanate groups, a diisocyanate residue or R ⁴ is at least one selected from the above diisocyanates Is an isocyanurate bond, a uretdione bond, a urethane bond, an allohanate bond, a urea bond, a diisocyanate trimer to 20-mer oligomer oligomerized by forming at least one bond selected from a biuret bond, poly R is a polyisocyanate residue obtained by removing all terminal isocyanate groups from a cyanate, or R is a terminal isocyanate from a triisocyanate which is an alkylene diisocyanate having 2 to 20 carbon atoms and substituted by one isocyanatoalkyl group having 1 to 8 carbon atoms. R ⁵ represents a linear or branched alkylene group having 2 to 20 carbon atoms, a cycloalkylene group having 5 to 20 carbon atoms, or an unsubstituted or substituted Represents an arylene group having 6 to 10 carbon atoms and substituted by an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 8 carbon atoms; each R ⁶ is independently a hydrogen atom or 1 carbon atom; ~
Y represents an organic group having at least one selected from the group consisting of a nonionic hydrophilic group, an ionic hydrophilic group, and a group convertible to an ionic hydrophilic group; n Is 0 or 1; and p and q are each 0 or a positive integer, r is a positive integer, and 0 ≦ (p + q)
And 2 ≦ (p + q + r) ≦ 20. ]

In the terminal-blocked form of the compound represented by the formula (7), at least one of the terminal groups H ₂ NR ⁶ N— in the formula (7) is represented by the formula R ⁹ R ⁸ C ＣNR ⁶ N—. Wherein R ⁸ and R ⁹ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclo group having 5 to 20 carbon atoms. Represents an alkyl group or an aryl group having 6 to 10 carbon atoms which is unsubstituted or substituted with an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, wherein R ⁸ and R ⁹ are May form a cyclic structure together), and in the composition, the weight ratio of the component (α) to the component (β) is 99/1 to 10/90.

According to still another aspect of the present invention, at least one (α) selected from the above-mentioned semicarbazide derivatives and the terminal blockers thereof, a carbonyl group-containing polyurethane, acetoacetylated polyvinyl alcohol, Acetylated hydroxyalkyl cellulose,
And (a) a carbonyl group-containing ethylenically unsaturated monomer, and (b) a carbonyl group-containing copolymer of an ethylenically unsaturated monomer copolymerizable with the monomer (a). A polycarbonyl compound (γ), which is one selected from the group consisting of:

According to still another aspect of the present invention, the above-mentioned composition (δ), a carbonyl group-containing polyurethane, acetoacetylated polyvinyl alcohol, acetoacetylated hydroxyalkyl cellulose, and (a) ) A carbonyl group-containing ethylenically unsaturated monomer;
(B) a polycarbonyl compound (γ), which is one kind selected from the group consisting of a carbonyl group-containing copolymer of the monomer (a) and a copolymerizable ethylenically unsaturated monomer. A coating composition is provided.

In the present invention, the above-mentioned and later-described semicarbazide derivatives and terminal-blocked bodies thereof, compounds containing a hydrophilic group, bisemicarbazide, monoketone, monoaldehyde, hydrazine and the terminal groups in the derivatives thereof and polyethylene glycol monoalkyl ethers R ¹ in the formula
To R ¹¹ , A ^{1 to} A ³ , an alkyl group substituting the groups represented by X ^{1 to} X ³ , and an alkyl part of the alkoxy group are
It may be linear or branched. The semicarbazide derivative of the present invention can be obtained by reacting a polyisocyanate having 3 to 20 NCO groups in one molecule with hydrazine or a derivative thereof. In contrast, NC
When a compound obtained by reacting a diisocyanate having two O groups with hydrazine or a derivative thereof has a low crosslinking ability when used as a curing agent for a coating composition, a compound having a tough and excellent water resistance is obtained. I can't get it.

As the polyisocyanate having 3 to 20 NCO groups in one molecule, for example, diisocyanate is formed by forming biuret bond, urea bond, isocyanurate bond, urethane bond, allophanate bond, uretdione bond and the like. Re-oligomerize and trimer ~
A 20-mer is exemplified. Regarding the production method of these polyisocyanates and the bond in the polyisocyanate, for example, G. Oertel, edited by Polyurethane
You can refer to Handbook (published by Hanser Publishers, Germany, 1985).

The diisocyanate of the present invention which can be used for producing the semicarbazide derivative represented by the formula (1) is a straight-chain or branched alkylene diisocyanate having 2 to 20 carbon atoms, unsubstituted or substituted carbon diisocyanate. Number 1
C18 substituted with an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or an alkylene group having 1 to 6 carbon atoms.
Cycloalkylene diisocyanate having a carbon number of 6 to 2 which is unsubstituted or substituted by an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 8 carbon atoms
0 arylene diisocyanate and an unsubstituted or C1-C18 alkyl group or C1-C1
And at least one diisocyanate selected from the group consisting of aralkylene diisocyanates having 8 to 20 carbon atoms and substituted with an alkoxy group of 8.

Examples of the above diisocyanates include:
Alkylene diisocyanates such as hexamethylene diisocyanate (HDI); cycloalkylene diisocyanates such as 4,4'-methylenebiscyclohexyl diisocyanate (hydrogenated MDI), isophorone diisocyanate (IPDI) and dimethylcyclohexane diisocyanate (hydrogenated XDI); , 4-Tolylene diisocyanate, 2,6-tolylene diisocyanate and mixtures thereof (TDIs), diphenylmethane-4,4'-diisocyanate (MDI), naphthalene-1,5-diisocyanate (NDI), 3,3-dimethyl- 4,4-diphenylene diisocyanate (TODI), crude TDI
s, 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 diisocyanates, alkylene diisocyanate is used as a curing agent with a semicarbazide derivative obtained from these diisocyanates as a curing agent in view of improving heat yellowing resistance and weather resistance of a coating obtained from a coating composition containing the polycarbonyl compound. Cycloalkylenediisocyanates are preferred. As mentioned above, at least one trimer of these diisocyanates
The polyisocyanate which is a 20-mer oligomer is reacted with hydrazine or a derivative thereof to obtain the semicarbazide derivative of the present invention. In this case, R ¹ in equation (1) is
The above-mentioned polyisocyanate residue having no terminal isocyanate group.

Further, the semicarbazide derivative of the present invention comprises
In addition to the above polyisocyanates, such as 1,8-diisocyanato-4-isocyanatomethyloctane,
An alkylene diisocyanate having 2 to 20 carbon atoms substituted with an isocyanate alkyl group having 1 to 8 carbon atoms,
It can also be obtained by reacting with hydrazine or a derivative thereof. In this case, R ¹ in the formula (1) is a triisocyanate residue having no terminal isocyanate group, which is derived from the above-mentioned alkylene diisocyanate. In the present invention, from the viewpoint of compatibility with the polycarbonyl compound, 1 is obtained by oligomerizing diisocyanate.
It is preferable to use a polyisocyanate having 3 to 20 NCO groups in the molecule.

In the present invention, the semicarbazide derivative obtained by reacting the above-mentioned polyisocyanate with hydrazine or a derivative thereof is polyfunctional. Therefore, a coating composition using the semicarbazide derivative as a curing agent is:
It has high crosslinking ability and can provide a tough film. The number of NCO groups in one molecule of polyisocyanate is 20
Is exceeded, the resulting semicarbazide group [here, for convenience, the formula H ₂ NRN—C (＝ O) —NH— (wherein R
Is a linear or branched alkylene group having 2 to 20 carbon atoms, a cycloalkylene group having 5 to 20 carbon atoms, or an unsubstituted or alkyl group having 1 to 18 carbon atoms or 1 to 8 carbon atoms. (Representing an arylene group having 6 to 10 carbon atoms substituted with an alkoxy group) is referred to as a "semicarbazide group"], and the semicarbazide derivative has an increased viscosity, which makes handling difficult. . Therefore, the number of NCO groups in one molecule of the polyisocyanate used in the present invention is 3 to 20, preferably 3
10 to 10.

Among these polyisocyanates, preferred are, for example, those obtained by subjecting a diisocyanate to a cyclic trimerization reaction in the presence of a catalyst and having a conversion of about 5%.
To about 80% by weight, preferably about 10 to about 60% by weight, after stopping the reaction, removing excess diisocyanate and purifying the resulting polyisocyanate having an isocyanurate bond (isocyanurate-type polyisocyanate). ). Specific examples of these isocyanurate-type polyisocyanates are described in
Polyisocyanates derived from hexamethylene diisocyanate as described in JP-A-5-38380 and copolymerization of isophorone diisocyanate and hexamethylene diisocyanate as described in JP-A-57-78460. Polyisocyanates obtained, polyisocyanates modified with polyfunctional alcohols as described in JP-A-57-47321, low-viscosity polyisocyanates as described in JP-A-64-33115 And highly branched polyisocyanates as described in Japanese Patent Application No. 6-16688.

In the present invention, a semicarbazide derivative obtained by reacting these isocyanurate-type polyisocyanates with hydrazine or a derivative thereof, or a mixture of a non-terminal-blocked and a terminal-blocked product thereof, or a terminal-blocked product thereof is obtained. Is a compound in which the polyisocyanate residue represented by R ¹ in the compound of the formula (1) is at least a compound represented by the following formula (2 ′) in the skeleton of the trimer to 20-mer oligomer of at least one diisocyanate described above. Those having a structure containing a represented trimer skeleton are preferable (the respective terminal blockers of hydrazine or a derivative thereof and a semicarbazide derivative will be described later).

[0026]

Embedded image

[In the formula, A ¹ , A ² and A ³ each independently represent a linear or branched alkylene group having 2 to 20 carbon atoms, unsubstituted or 1 to 18 carbon atoms. Alkyl group, alkoxy group having 1 to 8 carbon atoms or 1 to 6 carbon atoms
A cycloalkylene group having 5 to 20 carbon atoms, which is substituted with an alkylene group,
An arylene group having 6 to 20 carbon atoms substituted with an alkyl group having 18 or an alkoxy group having 1 to 8 carbon atoms, or an unsubstituted or an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 8 carbon atoms Represents an aralkylene group having 8 to 20 carbon atoms substituted with a group. For example, a diisocyanate having a trimer skeleton represented by the above formula (2 ′), which is formed by isocyanurate bond of 3
A semicarbazide derivative or a terminal-blocked product thereof obtained by reacting a monomer with hydrazine or a derivative thereof, or a mixture of a terminal-unblocked product and a terminal-blocked product thereof is represented by the following formula (2).

[0028]

Embedded image Wherein A ¹ , A ² , A ³ are as defined in formula (2 ′); and X ¹ , X ² , X ³ each independently represent formula (3) or formula ( Represents a group represented by 4).

[0029]

Embedded image (Wherein, R ² is a linear or branched alkylene group having 2 to 20 carbon atoms, a cycloalkylene group having 5 to 20 carbon atoms,
Or represents unsubstituted or arylene group having 6 to 10 carbon atoms which is substituted with an alkyl group or an alkoxy group having 1 to 8 carbon atoms having 1 to 18 carbon atoms; each R ³ is
Each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms; n is 0 or 1; )

Embedded image Wherein R ³ is as defined above.

The terminal blocker of the semicarbazide derivative represented by the above formula (2) is a compound represented by the formula R ⁹ R ⁸ C = NR ³ derived from the terminal group H ₂ NR ³ N- in the formula (3) or (4). N
Wherein R ⁸ and R ⁹ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, Number 5-2
0 represents a cycloalkyl group, or a substituted of not not or C1-18 alkyl group or an aryl group having 6 to 10 carbon atoms which is substituted with an alkoxy group having 1 to 8 carbon atoms, R ⁸ and R ⁹ may optionally form a ring structure together. ).

As another preferred example of the polyisocyanate, a biuretating agent such as water, t-butanol, urea or the like and a diisocyanate may be used in a molar ratio of biuretizing agent / diisocyanate of about 1/2 to about 1 / 10
0, preferably from about 1/3 to about 1/50,
A polyisocyanate having a biuret bond (biuret-type polyisocyanate) obtained by removing and purifying an excess diisocyanate is exemplified. Specific examples of these biuret-type polyisocyanates include JP-A-53-106797 and JP-A-55-114.
No. 52, etc., a polyisocyanate derived from hexamethylene diisocyanate, obtained by copolymerizing isophorone diisocyanate and hexamethylene diisocyanate as described in JP-A-59-95259. Polyisocyanate and the like can be mentioned.

In the present invention, the semicarbazide derivative obtained by reacting the biuret-type polyisocyanate with hydrazine or a derivative thereof, or a mixture of the terminal non-blocked product and the terminal-blocked product, or the terminal-blocked product thereof is In the compound of the formula (1), the polyisocyanate residue represented by R ¹ is at least represented by the following formula (5 ′) in the skeleton of at least one kind of the trimer to 20-mer oligomer of diisocyanate. Those having a structure containing a trimer skeleton are also preferable.

[0033]

Embedded image [Wherein, A ¹ , A ² , and A ³ each independently represent a linear or branched alkylene group having 2 to 20 carbon atoms, an unsubstituted or an alkyl group having 1 to 18 carbon atoms, A cycloalkylene group having 5 to 20 carbon atoms substituted with an alkoxy group having 1 to 8 carbon atoms or an alkylene group having 1 to 6 carbon atoms, an unsubstituted or an alkyl group having 1 to 18 carbon atoms or 1 carbon atom An arylene group having 6 to 20 carbon atoms substituted with an alkoxy group having 8 to 8 carbon atoms, or an unsubstituted or an alkyl group having 1 to 18 carbon atoms or 1 carbon atom
Represents an aralkylene group having 8 to 20 carbon atoms, which is substituted with an alkoxy group having 8 to 8 carbon atoms. ]

For example, a mixture of a trimer formed by a biuret bond of diisocyanate having a trimer skeleton represented by the above formula (5 ′) and hydrazine or a derivative thereof, or a terminal unblocked and terminal-blocked product thereof And the terminal-blocked body thereof obtained by reacting with the following formula (5).

Embedded image Wherein A ¹ , A ² , A ³ are as defined in formula (5 ′); and X ¹ , X ² , X ³ are each independently of formula (3) or formula (4) ) Represents a group represented by ]

[0035]

Embedded image (Wherein, R ² is a linear or branched alkylene group having 2 to 20 carbon atoms, a cycloalkylene group having 5 to 20 carbon atoms,
Or represents unsubstituted or arylene group having 6 to 10 carbon atoms which is substituted with an alkyl group or an alkoxy group having 1 to 8 carbon atoms having 1 to 18 carbon atoms; each R ³ is
Each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms; n is 0 or 1; )

Embedded image Wherein R ³ is as defined above.

The terminal-blocked compound of the semicarbazide derivative represented by the above formula (5) has a formula R ⁹ R ⁸ C = NR derived from the terminal group H ₂ NR ³ N- in the formula (3) or (4). ^Three
Having at least one blocked terminal group represented by N- (wherein R ⁸ and R ⁹ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, 5 carbon atoms
Represents 20 cycloalkyl group or unsubstituted or substituted with or aryl group having 6 to 10 carbon atoms which is substituted with an alkyl group or an alkoxy group having 1 to 8 carbon atoms having 1 to 18 carbon atoms,, R ₈ and R ₉ may optionally form a ring structure together. ).

The semicarbazide derivative obtained by using the above-mentioned isocyanurate-type polyisocyanate and biuret-type polyisocyanate and the terminal-blocked body thereof have good compatibility with the polycarbonyl compound. Therefore,
When a coating composition comprising a polycarbonyl compound and at least one selected from the group consisting of the semicarbazide derivative and its terminal blocker as a curing agent is applied to the surface of the substrate, hardness, water resistance, Chemical resistance, weather resistance,
A film having excellent heat resistance and appearance can be obtained.
Further, as still another preferred example of the polyisocyanate used in the present invention, polycaprolactone polyol and polycaprolactone polyol described in Japanese Patent Application Laid-Open No. 61-28518 and Japanese Patent Application Laid-Open No. H50-50277, etc. The diisocyanate and the -NCO / -OH molar ratio of about 3 to about 5
After reacting at 0, preferably about 5 to about 40, a polyisocyanate having a urethane bond (urethane-type polyisocyanate) obtained by removing and purifying excess diisocyanate is exemplified.

The semicarbazide derivative and its terminal blocking agent obtained by using the urethane-type polyisocyanate have good compatibility with the polycarbonyl compound. Therefore, when a coating composition comprising at least one selected from the group consisting of the polycarboxy compound and the semicarbazide derivative and its terminal blocker as a curing agent is applied to the surface of the substrate, the coating composition has excellent flexibility. Film can be obtained. In this case, particularly when the weight average molecular weight of the semicarbazide derivative is less than 2,000 and the weight average molecular weight of the terminal blocker of the semicarbazide derivative is less than 3,000, hardness, flexibility, water resistance, heat resistance, etc. An excellent film can be obtained.

In the present invention, the semicarbazide derivative or the terminal-blocked product obtained by reacting the urethane-type polyisocyanate with hydrazine or a derivative thereof, or a mixture of the non-terminal-blocked and terminal-blocked products thereof is used. In the compound of the formula (1), the polyisocyanate residue represented by R ¹ is at least a compound represented by the following formula (6 ′) in the skeleton of at least one kind of trimer to 20-mer oligomer of diisocyanate. Those having a structure containing a trimer skeleton are also preferable.

[0040]

Embedded image [Wherein, A ¹ , A ² , and A ³ each independently represent a linear or branched alkylene group having 2 to 20 carbon atoms, an unsubstituted or an alkyl group having 1 to 18 carbon atoms, A cycloalkylene group having 5 to 20 carbon atoms substituted with an alkoxy group having 1 to 8 carbon atoms or an alkylene group having 1 to 6 carbon atoms, an unsubstituted or an alkyl group having 1 to 18 carbon atoms or 1 carbon atom An arylene group having 6 to 20 carbon atoms substituted with an alkoxy group having 8 to 8 carbon atoms, or an unsubstituted or an alkyl group having 1 to 18 carbon atoms or 1 carbon atom
Represents an aralkylene group having 8 to 20 carbon atoms substituted with an alkoxy group having 8 to 8 carbon atoms; B represents an aliphatic triol having 1 to 20 carbon atoms, an alicyclic triol having 5 to 20 carbon atoms, or a C6 to 20 Represents a hydroxyl-free triol residue derived from an aromatic triol; and i, j and k are each an integer from 0 to 50, where i, j and k are (i
+ J + k) ≧ 1. ]

For example, a mixture of a trimer formed by a urethane bond of diisocyanate having a trimer skeleton represented by the above formula (6 ′) and hydrazine or a derivative thereof, or a terminal unblocked and terminal-blocked product thereof And the terminal-blocked body thereof obtained by reacting with the above is represented by the following formula (6).

Embedded image Wherein A ¹ , A ² , A ³ , B and i, j, k are as defined in formula (6 ′); and X ¹ , X ² , X
³ independently represents a group represented by the formula (3) or the formula (4). ]

[0042]

Embedded image (Wherein, R ² is a linear or branched alkylene group having 2 to 20 carbon atoms, a cycloalkylene group having 5 to 20 carbon atoms,
Or represents unsubstituted or arylene group having 6 to 10 carbon atoms which is substituted with an alkyl group or an alkoxy group having 1 to 8 carbon atoms having 1 to 18 carbon atoms; each R ³ is
Each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms; n is 0 or 1; )

[0043]

Embedded image (In the formula, R ³ is as defined above.) The terminal blocker of the semicarbazide derivative represented by the above formula (6) is a terminal group H ₂ NR ³ in the formula (3) or (4).
Having at least one blocked end group represented by the formula R ⁸ R ⁹ c = NR ³ N- derived from N-
R ⁸ and R ⁹ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or unsubstituted or 1 to 3 carbon atoms; Represents an aryl group having 6 to 10 carbon atoms substituted by an alkyl group having 18 or an alkoxy group having 1 to 8 carbon atoms, and R ⁸ and R ⁹ may optionally form a cyclic structure together . ).

The hydrazine or a derivative thereof used in the present invention includes, for example, hydrazine and hydrates thereof; monoalkyl-substituted hydrazine compounds such as monomethylhydrazine, monoethylhydrazine and monobutylhydrazine; ethylene-1,2-dihydrazine, propylene Dihydrazine compounds such as -1,3-dihydrazine and butylene-1,4-dihydrazine; oxalic dihydrazide, malonic dihydrazide, succinic dihydrazide, glutaric dihydrazide;
Adipic acid dihydrazide, sebacic acid dihydrazide, maleic acid dihydrazide, fumaric acid dihydrazide, itaconic acid dihydrazide, isofucuric acid dihydrazide, etc .; dicarboxylic acid dihydrazide; tricarboxylic acid trihydrazide such as trimellitic acid trihydrazide; Carbonic dihydrazide represented;

[0045]

Embedded image (In the formula, x represents an integer of 0 or 1.) Bisemicarbazides represented by the following formula (9);

Embedded image (Wherein, R ⁷ is a linear or branched alkylene group having 2 to 20 carbon atoms, a cycloalkylene group having 5 to 20 carbon atoms, or an unsubstituted or alkyl group having 1 to 18 carbon atoms or carbon Represents an arylene group having 6 to 10 carbon atoms, which is substituted with an alkoxy group having 1 to 8), and a mixture thereof.

In the present invention, human azine or a derivative thereof is converted to a monoketone (for example, acetone, By reacting with methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.) or monoaldehyde (eg, acetaldehyde), etc., to block one terminal group of a part of the molecule of hydrazine or its derivative, and use it as hydrazone or its derivative. Can also.

R ⁸ R ⁹ C ＝ O (10) (wherein R ⁸ and R ⁹ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, 5 carbon atoms)
To 20 cycloalkyl groups, or unsubstituted or C1 to C18 alkyl groups or C1 to C8
Represents an aryl group having 6 to 10 carbon atoms, which is substituted with an alkoxy group, and R ⁸ and R ⁹ may form a cyclic structure in some cases. )

When the above-mentioned terminal-blocked hydrazine or derivative thereof is used, at least one terminal semicarbazide group is blocked to form a semicarbazide group. A mixture with the blocker is obtained.
That is, the terminal blocker of the semicarbazide derivative of the present invention is:
At least one of the terminal groups H ₂ NR ³ N— in the formula (1)
Exemplary ethynylphenylbiadamantane derivatives ^{R 8 R 9 C = NR 3} N- (R 3, R 8 and R ⁹ are as defined above) has a blocked terminal group represented by the.

In the present invention, when a coating composition containing a polycarbonyl compound and a semicarbazide derivative as a curing agent thereof is applied to the surface of a base material, the semicarbazide group of the semicarbazide derivative and the carbonyl group of the polycarbonyl compound are mixed. It is necessary that the cross-linking between them proceeds. Therefore, in order to form a coating film having a high degree of crosslinking, the terminal blocking group (R ⁸ R ⁹ C =) derived from the monoaldehyde or monoketone used as the blocking agent is obtained by hydrolysis of the terminal portion of the semicarbazide derivative. Elimination as an aldehyde or monoketone is required.

Terminal blocking of the above semicarbazide derivative
And a semicarbazide derivative and its terminal-blocked body
End-blocking groups from the mixture of
(R⁸R ⁹C =) monoketone or monoaldehyde
Elimination prior to mixing with the polycarbonyl compound.
It may be carried out by water splitting and distillation, or
To prepare a coating composition using as it is as a curing agent
May be naturally released during the curing process after application.
No. Therefore, the blocking agent has a boiling point of 30 to 200 ° C.
Are preferred.

The semicarbazide derivative and its terminal-blocked product of the present invention can be obtained by combining a polyisocyanate with hydrazine or a derivative thereof, or a mixture of the terminal-blocked and non-terminal-blocked product with the NCO group of polyisocyanate, hydrazine or its hydrazine. The molar ratio of the terminal group represented by the following formula (11) in the derivative to the total of blocked terminal groups derived therefrom is 1:
0 to 100 ° C., preferably 10 to 100 ° C., in a quantitative ratio of 1.5 to 1: 100, preferably 2: 5 to 2:50.
It is produced by reacting at a temperature of 60 ° C. The reaction is completed instantly when the terminal group of hydrazine or a derivative thereof is not blocked, but when the blocked hydrazine or a derivative thereof is used, the reaction is performed for 30 minutes to 10 hours.

Embedded image -NR ¹⁰ NH ₂ (11) (wherein, R ¹⁰ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.) After completion of the reaction, the excess hydrazine or derivative thereof, or those terminal The blocker can be appropriately removed by distillation, extraction, or the like.

The reaction for producing the semicarbazide derivative of the present invention and the terminal blocker thereof can be carried out in the absence or presence of a solvent. Solvents which are inert to the NCO groups or less active than the reaction components can be used. Specifically, acetone,
Ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; 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 and dimethyl Sulfoxide solvents such as sulfoxide; ester solvents such as ethyl acetate and cellosolve acetate; alcohols such as t-butanol and diacetone alcohol; aromatic hydrocarbon solvents such as toluene and xylene; aliphatics such as n-hexane Examples thereof include hydrocarbon solvents and the like, and combinations thereof.

These solvents can be used in a polyisocyanate / solvent weight ratio of 0.1 / 99.9 to 99/1, preferably 0.1 / 99.9 to 50/50. The semicarbazide derivative obtained according to the present invention preferably has a weight average molecular weight of less than 2,000, and the terminal blocker of the semicarbazide derivative preferably has a weight average molecular weight of less than 3,000.
If the semicarbazide derivative or its terminal blocker has a molecular weight larger than the above range, the degree of crosslinking of the coating composition containing at least one selected from the semicarbazide derivative and its terminal blocker and a polycarbonyl compound during film formation , And a tough film having excellent water resistance cannot be obtained.

As described below, the polycarbonyl compound is preferably dissolved and / or dispersed in an aqueous medium. Therefore, from the viewpoint of preventing aggregation when mixed with the polycarbonyl compound and improving diffusion, the semicarbazide derivative or the terminal-blocked body thereof of the present invention is more preferably dispersed in an aqueous medium and dissolved in an aqueous medium. It is preferable to use in at least one state selected from the group consisting of: As the aqueous medium, water or a mixture of water and a polar solvent such as acetone and / or ether can be used. The semicarbazide derivative and / or its terminal blocker of the present invention can be added to an aqueous medium by a method of adding an aqueous medium under stirring or a method of adding the semicarbazide derivative and / or its terminal blocker to the aqueous medium under stirring. It can be dispersed and / or dissolved. At this time, the concentration of the semicarbazide derivative and / or its terminal blocker in the aqueous medium is as follows:
It can range from 0.1 to 90% by weight. In addition, for the purpose of assisting the dispersibility, dispersion stability and solubility of the semicarbazide derivative represented by the formula (1) and / or the terminal-blocked body thereof in an aqueous medium, the hydrophilic represented by the following formula (7) is used. At least one selected from the group consisting of a compound having an acidic group and a terminal blocker thereof, as a surfactant, at least one member selected from the group consisting of the semicarbazide derivative and the terminal blocker thereof;
Can be used in combination.

[0054]

Embedded image

[In the formula, R ⁴ is a linear or branched alkylene diisocyanate having 2 to 20 carbon atoms, an unsubstituted or an alkyl group having 1 to 18 carbon atoms,
A cycloalkylene diisocyanate having 5 to 20 carbon atoms substituted with an alkoxy group having 8 to 8 carbon atoms or an alkylene group having 1 to 6 carbon atoms, which is not substituted or has 1 to 1 carbon atoms
C6-20 arylene diisocyanate substituted with an alkyl group having 8 or an alkoxy group having 1 to 8 carbon atoms, and an unsubstituted or an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 8 carbon atoms At least one diisocyanate selected from the group consisting of aralkylenediisocyanates having 8 to 20 carbon atoms substituted with a group, and excluding all terminal isocyanate groups, a diisocyanate residue or R ⁴ is at least one selected from the above diisocyanates Is an isocyanurate bond, a uretdione bond, a urethane bond, an allohanate bond, a urea bond, a diisocyanate trimer to 20-mer oligomer oligomerized by forming at least one bond selected from a biuret bond, poly R is a polyisocyanate residue obtained by removing all terminal isocyanate groups from the isocyanate, or R is a terminal isocyanate from triisocyanate which is an alkylene diisocyanate having 2 to 20 carbon atoms substituted by one isocyanatoalkyl group having 1 to 8 carbon atoms. R ⁵ represents a linear or branched alkylene group having 2 to 20 carbon atoms, a cycloalkylene group having 5 to 20 carbon atoms, or an unsubstituted or substituted Represents an arylene group having 6 to 10 carbon atoms, which is substituted by an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 8 carbon atoms; each R ⁶ is independently a hydrogen atom or 1 to carbon atoms;
Y represents an organic group having at least one selected from the group consisting of a nonionic hydrophilic group, an ionic hydrophilic group, and a group convertible to an ionic hydrophilic group; n Is 0 or 1; and P and q are each 0 or a positive integer, r is a positive integer, and 0 ≦ (p + q)
And 2 ≦ (p + q + r) ≦ 20. ].

In the terminal-blocked compound of the compound represented by the formula (7), at least one of the terminal groups H ₂ NR ⁶ N— in the formula (7) is represented by the formula R ⁸ R ⁹ C = NR ⁶ N—. Wherein R ⁸ and R ⁹ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl having 5 to 20 carbon atoms. A group having 6 carbon atoms which is unsubstituted or substituted with an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 8 carbon atoms
It represents 10 aryl group, R ⁸ and R ⁹ may form a cyclic structure jointly in some cases. ).

That is, at least one (α) selected from the group consisting of a semicarbazide derivative represented by the formula (1) and a terminal blocker thereof, a hydrophilic group-containing compound represented by the formula (7) and a terminal thereof A so-called semicarbazide composition containing at least one (β) selected from the group consisting of blockers can be advantageously used as a curing agent for polycarbonyl. This semicarbazide composition of the present invention,
As described above, at least one state selected from the group consisting of dispersion in an aqueous medium and dissolution in an aqueous medium is preferable so as to be easily mixed with the polycarbonyl compound.

The semicarbazide derivative of the present invention and the terminal-blocked product thereof may optionally include a hydrophilic group-containing compound represented by the above formula (7) and the terminal-blocked product thereof.
Other surfactants may be added. Examples of such surfactants include anionic surfactants such as fatty acid soaps, alkyl sulfonic acids, alkyl succinic acids, polyoxyethylene alkyl sulfates, polyoxyethylene alkyl aryl sulfates, and polyoxyethylene alkyl aryl ethers. Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters, oxyethylene oxypropylene block copolymers, known reaction products of ethylene oxide and phosphoric acids, and cationic surfactants containing quaternary ammonium salts and the like; (Partial saponification) Polymer dispersion stabilizers such as polyvinyl alcohol and the like, and mixtures thereof.

However, as the surfactant, a hydrophilic group-containing compound represented by the formula (7) and a terminal blocker thereof are particularly preferable because of their high affinity with the semicarbazide derivative and the terminal blocker. In particular, at least one (α) selected from the group consisting of a semicarbazide derivative represented by the formula (1) and a terminal blocker thereof, and a hydrophilic group-containing compound represented by the formula (7) and a terminal blocker thereof A semicarbazide composition containing at least one member selected from the group consisting of a body, wherein the weight ratio of component (α) to component (β) is in the range of 10/90 to 99/1. Is used as a curing agent for the polycarbonyl compound,
In particular, a coating composition that is stable and has excellent curing performance can be obtained.
The hydrophilic group-containing compound represented by the formula (7) and the terminal blocker thereof according to the present invention are classified into a hydrophilic group-containing compound having no semicarbazide group and a semicarbazide group and a hydrophilic group-containing compound. Can be.

The hydrophilic group-containing compound having no semicarbazide group or its terminal-blocked compound has three NCO groups per molecule.
~ 20 dimer diisocyanates
A polyisocyanate which is a 20-mer oligomer, an alkylene diisocyanate (triisocyanate) having 2 to 20 carbon atoms and having 3 NCO groups in a molecule and substituted by an isocyanate alkyl group having 1 to 8 carbon atoms, The same diisocyanate itself used for the oligomerization of isocyanate is used as a nonionic hydrophilic group,
An active hydrogen-containing compound having at least one group selected from the group consisting of an ionic hydrophilic group and a group convertible to an ionic hydrophilic group (hereinafter, often referred to simply as “hydrophilic group”) is reacted. Manufacturing. [When the above-mentioned diisocyanate is reacted with an active hydrogen-containing compound, R ^{4 of the} resulting hydrophilic group-containing compound having no semicarbazide group is used.
Is divalent. In the present invention, a hydrophilic group-containing compound having no semicarbazide group or a terminal-blocked body thereof can be used. However, from the viewpoint of obtaining a film having high water resistance, a hydrophilic group-containing compound having no semicarbazide group or a terminal-blocked body thereof, and further hydrazine or a derivative thereof, or a mixture of the terminal unblocked body and the terminal-blocked body. It is preferable to use a compound containing a semicarbazide group and a hydrophilic group obtained by reacting

As these diisocyanates, the same diisocyanates as used in the production of the semicarbazide derivative represented by the formula (1) and the terminal-blocked body thereof can be used. That is, a linear or branched alkylene diisocyanate having 2 to 20 carbon atoms, an unsubstituted or an alkyl group having 1 to 18 carbon atoms,
A cycloalkylene diisocyanate having 5 to 20 carbon atoms substituted by an alkoxy group having 8 or an alkylene group having 1 to 6 carbon atoms, which is not substituted or has 1 to 18 carbon atoms
C6-20 arylene diisocyanate substituted with an alkyl group or a C1-8 alkoxy group, and an unsubstituted or C1-18 alkyl group or a C1-8 alkoxy group And at least one diisocyanate selected from the group consisting of aralkylenediisocyanates having 8 to 20 carbon atoms and substituted with.

According to the present invention, at least one (α) selected from the group consisting of a semicarbazide derivative represented by the formula (1) and a terminal blocker thereof, a hydrophilic group-containing compound represented by the formula (7) and Specific methods for obtaining a semicarbazide composition containing at least one (β) selected from the group consisting of the terminal blockers include, for example, the following two methods. However, it is not limited to these methods. Method [I]: A method of obtaining a mixture of component (α) and component (β) in a single reaction system, and Method [II]: Firstly obtaining only component (β) and separately preparing component (α) How to mix with. Each of the above methods may be implemented in combination.

First, the method [I] will be specifically described below. In the method [I], the polyisocyanate or the diisocyanate (triisocyanate) substituted with an isocyanate alkyl group and the active hydrogen-containing compound having a hydrophilic group described above are mixed with a molar ratio of NCO group to hydrophilic group. In an amount of from 1.1 / 1 to 500/1, preferably from 2/1 to 100/1, under substantially anhydrous conditions, from about 0 ° C to about 130 ° C, preferably from about 20 ° C to about 1 ° C.
The reaction is carried out at a temperature of 00 ° C. for about 30 minutes to about 10 hours (reaction 1), and the obtained reaction product is mixed with hydrazine or a derivative thereof, or a mixture of an unblocked terminal blocker and a terminal blocker thereof, By reacting polyisocyanate with hydrazine or its derivative under substantially the same conditions as in the reaction of producing the semicarbazide derivative represented by the above formula (1) (reaction 2), The semicarbazide composition containing the component (β) can be obtained in a single reaction system.

These reactions can be carried out in the absence or presence of a solvent. Solvents which are inert to the NCO groups or less active than the reaction components can be used. Specific examples of the solvent include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ether solvents such as dioxane, tetrahydrofuran and diethylene glycol dimethyl ether; amide solvents such as dimethylformamide and dimethylacetamide; Lactam solvents such as methyl-2-pyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; ester solvents such as ethyl acetate and cellosolve acetate; alcohols such as t-butanol and diacetone alcohol; aromatic hydrocarbons such as toluene xylene System solvents: aliphatic hydrocarbon solvents such as n-hexane and the like, and combinations thereof.

These solvents are based on the weight ratio of the polyisocyanate or triisocyanate (in reaction 1) / solvent and the weight ratio of the reaction product of the polyisocyanate or triisocyanate with the active hydrogen-containing compound (in reaction 2) / solvent. Can be used in the range of 0.1 / 99.9 to 99/1, preferably 0.1 / 99.9 to 50/50. The above reaction can be carried out using a catalyst as appropriate. Specific examples of the catalyst include:
Salts of metals such as dibutyltin dilaurate, stannous octylate, lead octylate and organic and inorganic acids, and organic metal derivatives; organic tertiary amines such as triethylamine and triethylenediamine; diazabicycloundecene-based catalysts and the like Can be

An active hydrogen-containing compound having at least one hydrophilic group used in the method [I], that is, a nonionic hydrophilic group, an ionic hydrophilic group and a group convertible to an ionic group. Among them, examples of the compound having a nonionic hydrophilic group include polyethylene glycol monoalkyl ether represented by the following formula (12), polyethylene glycol, and polyoxyethylene-oxypropylene (random and / or block). And polyether polyols such as glycol and polyoxyethylene-oxytetramethylene (random and / or block) glycol.

[0067]

Embedded image (Wherein, R ¹¹ represents an alkyl group having 1 to 25 carbon atoms;
Represents an integer of 5 to 80. )

Of these, polyethylene glycol monoalkyl ether is preferably used because polyether or polyol tends to cause a chain extension reaction with polyisocyanate to increase the molecular weight. As the active hydrogen-containing compound having an ionic hydrophilic group,
Preferred examples include a carboxylic acid or a sulfonic acid which is an active hydrogen-containing compound having an anionic group, or a salt thereof with an amine compound or an alkali metal salt thereof, and an active hydrogen-containing compound having a cationic group. Onium salts and the like are preferred examples.

As the active hydrogen-containing compound having an anion group, for example, an active hydrogen-containing compound having an acid group which can be converted into an anion group may be used at the time of synthesizing the above semicarbazide composition, or When dispersing and / or dissolving in an aqueous medium, the base is neutralized with a base to convert the acid group into an anionic group, thereby preparing the base. The neutralization is preferably performed when dispersing and / or dissolving the semicarbazide composition in an aqueous medium.

Examples of the active hydrogen-containing compound having an acid group which can be converted into an anionic group include monohydroxycarboxylic acids such as lactic acid, glycolic acid, 4-hydroxybutyric acid, p-phenolcarboxylic acid; glycine, alanine; Amino acids such as aspartic acid and β-alanine;
Monohydroxysulfonic acid such as phenolsulfonic acid;
Aminosulfonic acids such as taurine and the like, combinations thereof, and α, α′-dimethylolpropionic acid, α, α′-
Α, α′-Dimethylolalkanoic acid such as dimethylolacetic acid. Of these, α, α'-dimethylolalkanoic acid tends to cause a chain extension reaction with polyisocyanate to increase the molecular weight, so that the above-mentioned monohydroxycarboxylic acid, amino acid, monohydroxysulfonic acid, aminosulfonic acid Or a combination thereof is preferred. Examples of the base that can be used to neutralize the acid group of the active hydrogen-containing compound having an acid group capable of being converted to an anion group include, for example, triethylamine, ammonia, diethanolamine, dimethylaminoethanol,
Amine compounds such as methyldiethanolamine and dibutylamine; hydroxides of alkali metals such as KOH, NaOH and LiOH; and combinations thereof.

As the active hydrogen-containing compound having a cationic group, for example, an active hydrogen-containing compound having a base which can be converted into a cationic group may be used at the time of synthesizing the above-mentioned semicarbazide composition, or by adding the semicarbazide composition to an aqueous solution. When dispersing and / or dissolving in a medium, the base is converted into a cationic group by neutralization with an acid group to prepare the base. In the case of an active hydrogen-containing compound having a tertiary amino group, the tertiary amino group is alkylated when the above-mentioned semicarbazide composition is synthesized or when the semicarbazide composition is dispersed and / or dissolved in an aqueous medium. By quaternizing with an agent to convert to a cationic group,
An active hydrogen-containing compound having a cationic group can be obtained. The neutralization is preferably performed when dispersing and / or dissolving the semicarbazide composition in an aqueous medium.

Examples of the active hydrogen-containing compound having a base which can be converted into a cationic group include N-alkyl dialkanolamines such as N-methyldiethanolamine and N-butyldiethanolamine, and those having 2 to 4 carbon atoms. N. alkylene oxide (ethylene oxide, propylene oxide, etc.) adducts, N, N-dimethylethanolamine, N.N. N-dialkylmonoalkanolamines and the like, and combinations thereof. Of these, especially N, N-
N, N-dialkylmonoalkanolamines such as dimethylethanolamine and N, N-diethylethanolamine are preferred. Acids that can be used to neutralize the base of these active hydrogen-containing compounds include, for example, acetic acid, lactic acid,
Hydrochloric acid, phosphoric acid, sulfuric acid and a combination thereof can be mentioned. Examples of the alkylating agent include dimethyl sulfate, diethyl sulfate, methyl chloride, methyl iodide, benzyl chloride and the like.

Next, the method [II] will be described specifically. As described above, in the method [II], at least one (β) selected from the group consisting of the hydrophilic group-containing compound represented by the formula (7) and the terminal blocker thereof is first obtained, and then separately obtained. It is mixed with at least one (α) selected from the group consisting of the prepared semicarbazide derivative represented by the formula (1) and a terminal blocker thereof. First, as a specific method for obtaining the component (β), for example, a diisocyanate having two NCO groups in one molecule, a nonionic hydrophilic group, an ionic hydrophilic group, and an ionic hydrophilic group can be converted. An active hydrogen-containing compound having at least one group (hydrophilic group) selected from the group consisting of groups is reacted in a quantitative ratio such that the molar ratio of the NCO group to the hydrophilic group is 1/1 to 10/1. And then reacting with hydrazine or a derivative thereof, and a polyisocyanate having 3 to 20 NCO groups in one molecule or 3 NCO groups in one molecule.
Triisocyanate and a nonionic hydrophilic group,
An active hydrogen-containing compound having at least one group (hydrophilic group) selected from the group consisting of an ionic hydrophilic group and a group that can be converted to an ionic system is mixed with a compound having a molar ratio of NCO group to hydrophilic group of 0.1. / 1 to 1.1 / 1, and then reacting with hydrazine or a derivative thereof.

In the method [II], NCO is contained in one molecule.
As a polyisocyanate having 3 to 20 groups and a triisocyanate having 3 NCO groups in one molecule,
The same polyisocyanate and triisocyanate as used in the production of the semicarbazide derivative represented by the formula (1) and the terminal blocker thereof can be used. As the diisocyanate having two NCO groups in one molecule,
The diisocyanate used for the synthesis of the polyisocyanate can be used. The two different components (β) obtained by the above two methods may be mixed alone with the component (α), or both may be mixed with the component (α).

Active hydrogen-containing compound having at least one group (hydrophilic group) selected from the group consisting of a nonionic hydrophilic group, an ionic hydrophilic group, and a group convertible into an ionic group used in the method [II] The same as those used in the above method [I] can be used. In the method [II], first, a diisocyanate having two NCO groups in one molecule, a polyisocyanate having 3 to 20 NCO groups in one molecule, or a triisocyanate having three NCO groups in one molecule, The reaction with an active hydrogen-containing compound having at least one group (hydrophilic group) selected from the group consisting of an ionic hydrophilic group, an ionic hydrophilic group, and a group that can be converted to an ionic system is carried out by the method [I]. The reaction is performed under the same reaction conditions. The above reaction can be carried out in the absence or presence of a solvent, if desired, using a catalyst. The same solvent and catalyst as those used in the method [I] can be used.

Then, the obtained reaction product and a mixture of hydrazine or a derivative thereof, or a terminal-blocked product and a terminal-unblocked product thereof are combined with the terminal NCO group in the reaction product in hydrazine or a derivative thereof. The molar ratio to the group and the terminal blocking group derived therefrom is represented by the above formula (1) in a quantitative ratio of 1: 1.5 to 1: 100, preferably 2: 5 to 2:50. When producing a semicarbazide derivative or a terminal blocker thereof, the reaction is carried out under substantially the same conditions as those used for the reaction of the polyisocyanate with hydrazine or a derivative thereof or a mixture of the terminal blocker and the terminal non-blocker. By doing so, the component (β) is obtained.

The component (β) thus obtained and the component (α) separately prepared were mixed with each other at a weight ratio of (α) / (β) of 10 /
The semicarbazide composition of the present invention can be obtained by mixing so as to be 90 to 99/1. The semicarbazide composition of the present invention obtained by the above-mentioned method [I] or method [II] can be prepared by adding an aqueous medium under stirring or by adding the semicarbazide composition to the aqueous medium under stirring. It can be dispersed and / or dissolved in a medium. At that time, the concentration of the semicarbazide composition in the aqueous medium can be in the range of 0.1 to 90% by weight. If desired, the above-mentioned surfactant may be used for the purpose of assisting the dispersibility and dispersion stability of the semicarbazide composition.

At least one (α) selected from the group consisting of the semicarbazide derivative of the present invention and its terminal blocker
In addition, the semicarbazide composition (δ) has excellent compatibility with the polycarbonyl compound (γ), and therefore is selected from the group consisting of the polycarboxy compound (γ) and the semicarbazide derivative and its terminal-blocked body as a curing agent thereof. The coating composition containing at least one (α) or the so-called semicarbazide composition (δ) not only has excellent room-temperature curability and storage stability, but also has hardness, water resistance, A film excellent in various properties such as stain resistance can be formed.

In the present invention, at least one (α) selected from the group consisting of the above-mentioned semicarbazide derivatives and the terminal blockers thereof or the above-mentioned semicarbazide composition (δ), carbonyl group-containing polyurethane, acetoacetylated polyvinyl alcohol Acetoacetylated hydroxyalkyl cellulose, and (a) 0.1 to 30% by weight of a carbonyl group-containing ethylenically unsaturated monomer;
A polycarbonyl compound containing at least one member selected from the group consisting of a carbonyl group-containing copolymer of 70 to 99.9% by weight of an ethylenically unsaturated monomer copolymerizable with the monomer (a) ( By mixing γ), a coating composition is obtained which not only has excellent room-temperature curability and storage stability, but also can form a film having various properties such as hardness, water resistance and stain resistance. be able to.

In the coating composition of the present invention, the weight ratio of component (α) or component (δ) to component (γ) is 0.1%.
/99.9 to 90/10, preferably 0.5
/99.5 to 30/70. As the polycarbonyl compound (γ), for example, a carbonyl group-containing polyurethane that can be produced from a mono- and / or polyalcohol having a carbonyl group, such as hydroxyacetone, described in JP-A-2-238015 is used. it can. Regarding the production of acetoacetylated polyvinyl alcohol and acetoacetylated hydroxyalkylcellulose, for example, reference can be made to “Shin Jikken Kagaku Koza” Vol. 14, published by Maruzen Co., Ltd. in 1977. Further, as a specific example of acetoacetylated polyvinyl alcohol, Gohsefimer
-2 (Nippon Gogaku Chemical Industry Co., Ltd. of Japan).

In the coating composition of the present invention, the component (γ) comprises (a) 0.1 to 30% by weight of a carbonyl group-containing ethylenically unsaturated monomer, and (b) the monomer (a) ) Is preferably a carbonyl group-containing copolymer of 70 to 99.9% by weight of an ethylenically unsaturated monomer copolymerizable with the above. 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.
And combinations thereof.

In the present invention, examples of the ethylenically unsaturated monomer (b) copolymerizable with the monomer (a) include acrylic acid esters, methacrylic acid esters, and ethylenically unsaturated monomers having a carboxyl group. And acrylamide monomers, methacrylamide monomers, and vinyl cyanide. Examples of the above (meth) acrylic acid esters include (meth) acrylic acid alkyl esters having 1 to 18 carbon atoms in the alkyl portion and 1 to 18 carbon atoms in the alkyl portion.
(Meth) acrylic acid hydroxyalkyl ester, (poly) oxyethylene mono (meth) acrylate having 1 to 100 ethylene oxide groups, and 1 to 100 (poly) oxypropylene mono (propylene oxide group) (Meth) acrylate, (poly) oxyethylene di (meth) having 1 to 100 ethylene oxide groups
Acrylate and the like.

Specific examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and (meth) acrylate. ) Methylcyclohexyl acrylate, dodecyl (meth) acrylate and the like. Specific examples of the hydroxyalkyl (meth) acrylate include (meth) acrylic acid 2-
Examples include hydroxyethyl, 2-hydroxypropyl (meth) acrylate, 2-hydroxycyclohexyl (meth) acrylate, and hydroxydodecyl (meth) acrylate.

Specific examples of (poly) oxyethylene mono (meth) acrylate include ethylene glycol (meth) acrylate, ethylene glycol methoxy (meth) acrylate, diethylene glycol (meth) acrylate,
Diethylene glycol methoxy (meth) acrylate,
Examples thereof include tetraethylene glycol (meth) acrylate and tetraethylene glycol methoxy (meth) acrylate. Specific examples of (poly) oxypropylene mono (meth) acrylate include propylene glycol (meth) acrylate, propylene glycol methoxy (meth) acrylate, dipropylene glycol (meth) acrylate, and dipropylene methoxy (meth) acrylate. Glycol, tetrapropylene glycol (meth) acrylate, tetrapropylene glycol methoxy (meth) acrylate, 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) acrylic acid. Tetraethylene glycol and the like. Specific examples of the ethylenically unsaturated monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid and its half ester, crotonic acid, and the like. Are, for example, (meth) acrylamide, N-methylol (meth) acrylamide, N-butoxymethyl (meth) acrylamide, etc. Specific examples of vinyl cyanide include, for example, (meth) acrylamide
Acrylonitrile and the like.

Other specific examples of the ethylenically unsaturated monomer (b) copolymerizable with the monomer (a) include olefins such as ethylene, propylene and isobutylene; dienes such as butadiene; vinyl chloride; Haloolefins such as vinylidene chloride; vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl benzoate, vinyl pt-butyl benzoate, vinyl pivalate, vinyl 2-ethylhexanoate, vinyl versatate, lauric acid Carboxylic acid vinyl esters such as vinyl; carboxylic acid isopropenyl esters such as isopropenyl acetate and isopropenyl propionate; vinyl ethers such as ethyl vinyl ether, isobutyl vinyl ether and cyclohexyl vinyl ether; aromatic vinyl compounds such as styrene and vinyl toluene; acetic acid Allyl, benzoic Allyl ester of an allyl and the like;
Allyl ethers such as allyl ethyl ether, allyl glycidyl ether and allyl phenyl ether; γ- (meth) acryloxypropyltrimethoxysilane;
(Meth) acryloyloxy-2,2,6,6-tetramethylpiperidine; 4- (meth) acryloyloxy-1,2,2,6,6-pentamethylpiperidine; perfluoromethyl (meth) acrylate; Perfluoropropyl (meth) acrylate; perfluoropropylmethyl (meth) acrylate; vinylpyrrolidone; trimethylolpropane tri (meth) acrylate; glycidyl (meth) acrylate; 2,3 (meth) acrylate
-Cyclohexene oxide; and allyl (meth) acrylate and the like, and combinations thereof.

The coating composition of the present invention is preferably in at least one state selected from the group consisting of dispersion in an aqueous medium and dissolution in an aqueous medium. The coating composition of the present invention comprises at least one component selected from the group consisting of dispersion and dissolution of component (α) and component (γ) in an aqueous medium.
When provided in two states, the coating composition comprises component (α) and component (α), each in at least one state selected from the group consisting of dispersion in an aqueous medium and dissolution in an aqueous medium. (Γ) and the sum of component (α) and component (γ) is 0 with respect to the weight of the coating composition dispersion and / or the solution thereof. It is preferably in the range of 0.1 to 70% by weight. In the dispersion and / or solution of the component (α) to be mixed,
Component (α) is preferably in the range of 0.1 to 90% by weight based on the weight of the dispersion and / or the solution. In the dispersion and / or solution of the component (γ) to be mixed, the component (γ) may be in the range of 0.1 to 70% by weight based on the weight of the dispersion and / or the solution. preferable.

Similarly, the coating composition of the present invention is provided in at least one state selected from the group consisting of dispersion and / or dissolution of component (δ) and component (γ) in an aqueous medium. In this case, the coating composition mixes the component (δ) and the component (γ), each of which is in at least one state selected from the group consisting of dispersion in an aqueous medium and dissolution in an aqueous medium. That was obtained by
And the sum of the component (δ) and the component (γ) is 0.1 to 7 with respect to the weight of the coating composition dispersion and / or the solution thereof.
It is preferably in the range of 0% by weight. In the dispersion and / or solution of the component (δ) to be mixed, the component (δ)
, Based on the weight of the dispersion and / or the solution.
Preferably it is in the range of 1 to 70% by weight. In the dispersion and / or solution of the component (γ) to be mixed, the component (γ) may be in the range of 0.1 to 70% by weight based on the weight of the dispersion and / or the solution. preferable.

In both the dispersion and / or the solution of the component (α) and the component (γ) and the dispersion and / or the solution of the component (δ) and the component (γ), the component (γ)
Are (a) 0.1-30% by weight of a carbonyl group-containing ethylenically unsaturated monomer, and (b) 70-99. The carbonyl group-containing copolymer is preferably 9% by weight. In the present invention, the carbonyl group-containing copolymer as the component (γ) in the dispersion and / or the solution includes (a) a carbonyl group-containing ethylenically unsaturated monomer, and (b) the monomeric monomer. It is preferably obtained by at least one method selected from the group consisting of suspension polymerization, emulsion polymerization, and solution polymerization of the monomer (a) and a copolymerizable ethylenically unsaturated monomer. However, a latex obtained by emulsion polymerization is particularly preferred.

Further, in the present invention, a copolymer of (a) an ethylenically unsaturated monomer containing a carbonyl group and (b) an ethylenically unsaturated monomer copolymerizable with the monomer (a) is used. Is particularly preferably performed in the presence of at least one (c) emulsifier selected from the group consisting of an ethylenically unsaturated monomer having a sulfonic acid group and an ethylenically unsaturated monomer having a sulfonate group. In the present invention,
At least one emulsifier (c) selected from the group consisting of an ethylenically unsaturated monomer having a sulfonic acid group and an ethylenically unsaturated monomer having a sulfonate group has a radical polymerizable double bond, And a group that is a sulfonic acid group or its ammonium salt or alkali metal salt (ammonium sulfonate group or alkali metal sulfonate group)
Is preferable.

Among these, an alkyl group having 1 to 20 carbon atoms, which has a radical polymerizable double bond and is substituted by a group which is an ammonium salt, a sodium salt or a potassium salt of a sulfonic acid group, Or a compound having a substituent selected from the group consisting of an alkyl ether group having 4 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, or ammonium having a sulfonic acid group. More preferably, it is a vinyl sulfonate compound having a vinyl group to which a salt, sodium salt or potassium salt group is bonded. As a specific example of a compound having a succinic acid group substituted by a group which is an ammonium salt, a sodium salt or a potassium salt of a sulfonic acid group, an allyl sulfosuccinate salt such as a compound represented by the formula (1)
6), (17), (18) and (19).

[0092]

Embedded image

[Wherein R ^{1 ′} is hydrogen or a methyl group, R ^{2 ′} is an alkyl group having 1 to 20 carbon atoms and 1 to 2 carbon atoms.
A hydrocarbon group such as an alkenyl group having 0, a cycloalkyl group having 5 to 12 carbon atoms, an aryl group having 5 to 10 carbon atoms, an aralkyl group having 6 to 19 carbon atoms, or a part of which is a hydroxyl group, a carboxylic acid group, or the like; A substituted or polyoxyalkylene alkyl ether group (the alkyl moiety has 0 to 20 carbon atoms and the alkylene moiety has 2 to 4 carbon atoms), a polyoxyalkylene alkyl phenyl ether group (the alkyl moiety has 0 carbon atoms; -20, and an organic group containing an alkylene oxide compound such as an alkylene moiety having 2 to 4 carbon atoms, A is an alkylene group having 2 to 4 carbon atoms or a substituted alkylene group, and n is 0 to 20 An integer of 200 and M is ammonium, sodium or potassium. As a compound containing the above compounds (16) and (17), for example, Eleminol (trademark) J manufactured by Sanyo Chemical Co., Ltd. of Japan
S-2, which includes the above compounds (18) and (19), includes, for example, Latemul (trademark) S-120, S-180A and S-180 manufactured by Kao Corporation of Japan.
Examples of compounds having an alkyl ether group having 2 to 4 carbon atoms or a polyalkyl ether group having 2 to 4 carbon atoms substituted by a group which is an ammonium salt, a sodium salt or a potassium salt of a sulfonic acid group include a compound represented by the formula ( 20) (2)
The compound represented by 1) is mentioned.

[0094]

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

[0095]

Embedded image (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, and n is 0 to 20 is an integer, m is an integer of 0 to 50, M is ammonium,
Sodium or potassium. )

The alkylphenol ether derivative represented by the above formula (20) includes, for example, Aqualon (trademark) HS-10 manufactured by Daiichi Kogyo Seiyaku Co., Ltd. For example, Adecaria Soap (trademark) SE-1025 manufactured by Asahi Denka Kogyo Co., Ltd. of Japan
There is N. In addition, specific examples of the compound having an aryl group substituted by a sulfonate group include an ammonium salt, a sodium salt, and a potassium salt of p-styrenesulfonic acid. Specific examples of the compound having an alkyl group substituted by a sulfonate group include ammonium salt, sodium salt and potassium salt of methylpropanesulfonic acid (meth) acrylamide. Specific examples of the compound having a sulfonate group other than the above include a 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.

These ethylenically unsaturated monomers as the emulsifier (c) are used in the emulsion to form [i] emulsion particles comprising a copolymer of the monomer (a) and the monomer (b). Exists as a copolymer obtained by radical polymerization, or (ii) adsorbs to the emulsion particles as an unreacted substance,
Or emulsion particles as a copolymer with a water-soluble or hydrophilic monomer present in the aqueous phase of the emulsion or as a by-product in the emulsion, or as a polymer of the ethylenically unsaturated monomer Or present in the emulsion aqueous phase.

In particular, by increasing the ratio present in the state of [i], the coating composition obtained by using the emulsion comprising the copolymer of the monomer (a) and the monomer (b) is satisfactory. A film having excellent water resistance can be obtained. The ethylenically unsaturated monomer as the emulsifier (c) is identified by pyrolysis gas chromatogram mass spectrometry (Py-GC-MS) or pyrolysis mass spectrometry (Py-MS) of a film obtained from the emulsion. be able to. Alternatively, after separating the aqueous phase component of the emulsion,
It is also possible to identify by fast atom bombardment mass spectrometry (FAB mass spectrum).

In the present invention, in addition to the emulsifier (c) selected from the group consisting of ethylenically unsaturated monomers having a sulfonic acid group or a sulfonate group and a mixture thereof, ordinary surfactants usable as emulsifiers are used. They can be used together. 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 and Adecaria Soap NE-2 manufactured by Asahi Denka Kogyo KK
Α- [1-[(allyloxy) methyl] -2- (nonylphenoxy) ethyl] such as 0, NE-30 and NE-40
-Ω-hydroxy polyoxyethylene, and Aqualon RN-10, RN-20 manufactured by Daiichi Pharmaceutical Industry Co., Ltd. of Japan
A reactive nonionic surfactant such as polyoxyethylene alkylpropenyl phenyl ether such as RN-30 and RN-50 may be used in combination with a nonionic surfactant copolymerizable with an ethylenically unsaturated monomer. it can.

The above surfactant is used in an amount of 0.5% by weight for the anionic surfactant as a percentage by weight based on the emulsion comprising the monomers (a) and (b).
Or less, preferably 0.25% or less, more preferably 0.1% or less.
1% or less, and about 2.0% or less for the non-reactive nonionic surfactant and the reactive nonionic surfactant.
Preferably it is 1.0% or less, more preferably 0.5% or less. When used beyond this range, a coating having satisfactory water resistance cannot be obtained from the coating composition obtained using the emulsion. In the coating composition comprising the component (α) or the component (δ) of the present invention and the component (γ), the total amount of the surfactant containing the emulsifier (c) is 0.1 to 20% by weight. Preferably, there is.

In obtaining the polycarbonyl compound (γ) used in the present invention, the radical polymerization catalyst is decomposed by heat or a reducing substance to generate radicals, and the ethylenically unsaturated monomer (a) And compounds causing addition polymerization of (b). As these compounds, water-soluble or oil-soluble persulfates, peroxides, azobis compounds and the like can be advantageously used. Examples include potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, t-
Butyl hydroperoxide, t-butyl peroxybenzoate, 2,2-azobisisobutyronitrile,
Examples thereof include 2,2-azobis (2-diaminopropane) hydrochloride and 2,2-azobis (2,4-dimethylvaleronitrile). The amount of the radical polymerization catalyst is usually 0.1 to 1% by weight based on the ethylenically unsaturated monomers (a) and (b).

Usually, it is preferable to carry out the polymerization under normal pressure at a polymerization temperature of 65 to 90 ° C., but it is also possible to carry out the reaction under a high pressure in a closed system for the purpose of preventing volatilization of the monomer at the polymerization temperature of the monomer. The polymerization time includes an introduction time and a ripening (cooking) time after the introduction. The introduction time is usually several minutes when simultaneously introducing the various raw materials into the reaction system, and when sequentially introducing the various raw materials into the reaction system, since the exothermic heat generated by the polymerization is sequentially introduced into the reaction system within a range where heat can be removed, Although it depends on the polymer concentration in the finally obtained emulsion, it is usually 10 minutes or more. The aging time after introduction is preferably at least 10 minutes or more. If the polymerization time is shorter than this, each raw material may remain as it is. When acceleration of the polymerization rate and low-temperature polymerization at 70 ° C. or lower are desired, for example, sodium bisulfite,
It is advantageous to use a reducing agent such as ferrous chloride, ascorbate, Rongalite or the like in combination with a radical polymerization catalyst. In order to further control the molecular weight, a chain transfer agent such as dodecyl mercaptan can be optionally added.

In the present invention, amines such as ammonia, sodium hydroxide, potassium hydroxide, dimethylaminoethanol, hydrochloric acid, sulfuric acid, and acetic acid are used to keep the polycarbonyl compound (γ) in the coating composition stable for a long period of time. It is preferable to adjust the pH of the coating composition to a range of 4 to 10 using an acid such as lactic acid. Further, in the coating composition of the present invention, if desired, 90% by weight or less of the polycarbonyl compound can be used by replacing it with a polyepoxy compound. The combined use of the polyepoxy compound further improves the water resistance of the resulting film.

As the polyepoxy compound, for example, an ethylenically unsaturated monomer containing an epoxy group such as glycidyl (meth) acrylate is mixed with another unsaturated monomer in a bulk polymerization method, a suspension polymerization method, an emulsion polymerization method, a solution polymerization method, or the like. A copolymer containing an epoxy group obtained by copolymerization by a polymerization method, a bisphenol A epoxy resin, a bisphenol F epoxy resin, a cycloaliphatic epoxy resin, a glycidyl ester epoxy resin, a glycidylamine epoxy resin,
Hydantoin type epoxy resin, triglycidyl isocyanurate or the like dispersed in water, and a combination of these are used.

If desired, the composition of the present invention may contain additives, such as pigments, fillers, dispersants, light stabilizers, wetting agents, thickeners, which are conventionally added to water-based paints. Agents, rheology control agents, defoamers, plasticizers, film-forming aids,
Rust inhibitors, dyes, preservatives and the like may be used alone or in combination according to the purpose, and may be used in the amounts and amounts conventionally used. The coating composition of the present invention is not only excellent in room-temperature curability and storage stability as described above, but also has various properties such as hardness, toughness, water resistance and stain resistance. It is useful as an undercoating or finishing agent, an adhesive, a pressure-sensitive adhesive, a paper processing agent, and a finishing agent for a woven fabric.

[0106]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to Reference Examples, Examples and Comparative Examples, but the present invention is not limited to these Examples and the like. In addition,
Parts in Reference Examples, Examples and Comparative Examples mean parts by weight.
Various measurements in Reference Examples, Examples and Comparative Examples were performed according to the following methods. 1. Measurement of molecular weight distribution: It was determined from a calibration curve of a polystyrene standard using gel permeation chromatography.

2. The infrared absorption spectrum was measured with FT / IR-5300 manufactured by JASCO Corporation of Japan. 3. Measurement of the curing performance of the coating composition: The appearances of the films obtained in Examples 9 to 11 and Comparative Examples 1 to 4 were visually evaluated according to the following criteria. ：: Transparent and smooth film 誘: Lightening but rough surface is observed ×: Opaque and rough surface is observed

Further, the following measurements were carried out using the films obtained by peeling the films obtained in Examples 9 to 11 and Comparative Examples 1 to 4 from the glass surface. (1) Measure the film strength using a Tensilon tensile tester [
Orientec RTA-100] under the conditions of a sample length for measurement: 300 mm and a tensile speed: 50 mm / min. (2) The solvent resistance of the film was measured by placing the film in a 200-mesh wire mesh bag and then immersing it in tetrahydrofuran at room temperature for 24 hours.
(The weight of the film after immersion in tetrahydrofuran) ÷ (the weight of the film before immersion in tetrahydrofuran) × 100. (3) The water resistance of the film was determined by immersing the film in water at room temperature for 6 days, visually observing the state of the film, and further measuring the film water absorption (%) by [(film weight after water immersion) − (Weight of film before immersion in water)] ÷ (weight of film before immersion in water) × 100. (4) The strength retention rate (%) of the film was determined by immersing the film in water at room temperature for 24 hours, and then measuring the breaking strength and elongation rate of 10%.
The strength at 0% was measured, and the respective retention rates with respect to the breaking strength before immersion and the strength at an elongation of 100% were determined as (strength after immersion in water) 強度 (strength before immersion in water) × 100 and evaluated. did.

Reference Example 1 Preparation of Aqueous Emulsion of Polycarbonyl Compound (γ) [Emulsion (1)] In a reactor having a reflux condenser, a dripping tank, a thermometer and a stirring device, ion-exchanged water 220 was added.
2.3 parts of a 40% aqueous solution of sodium dioctyl sulfosuccinate (Pelex (trademark) OTP, manufactured by Kao Corporation of Japan) was added, and the temperature in the reaction vessel was raised to 80 ° C., and then methacrylic acid was added. 9 parts, 4.5 parts of styrene, 234 parts of butyl acrylate, diacetone acrylamide 1
3.5 parts, 189 parts of methyl methacrylate, 230 parts of ion-exchanged water, 9 parts of Perex OTP, polyoxyethylene nonylphenyl ether [Emulgen (trademark) 95
0, manufactured by Kao Corporation of Japan], a mixture of 10 parts of a 25% aqueous solution and 1 part of ammonium persulfate was allowed to flow into the reaction vessel from the dropping tank over 3 hours. 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 is raised to 80
The temperature was kept at 2 ° C. for 2 hours. Then cool to room temperature, 25%
After adjusting the pH to 8 by adding aqueous ammonia, 1
The mixture was filtered through a 00 mesh wire net to obtain an aqueous emulsion (1) of a carbonyl group-containing copolymer having a solid content of 46.8% and an average particle size of 1050 °.

[Emulsion (2)] In a reactor having a reflux condenser, a dropping tank, a thermometer and a stirrer, 218 parts of ion-exchanged water, Adecaria Soap (trademark) SE-102 were added.
2. 25% aqueous solution of 5N [manufactured by Asahi Denka Kogyo KK]
After charging 7 parts and raising the temperature in the reaction vessel to 80 ° C., 9 parts of methacrylic acid, 4,5 parts of styrene, 234 parts of butyl acrylate, and 1 part of diacetone acrylamide
13. 3.5 parts, 189 parts of methyl methacrylate, 225 parts of ion-exchanged water, and Adecaria Soap SE-1025N.
4 parts, 25 parts of polyoxyethylene nonylphenyl ether [Emulgen (trademark) 950, manufactured by Kao Corporation of Japan]
A mixture of 8 parts of a 1% aqueous solution and 1 part of ammonium persulfate was allowed to flow into the reaction vessel from the dropping tank over 3 hours. 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. 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. (2) was obtained.

Reference Example 2 Synthesis of Polyisocyanate [Polyisocyanate (1)] 222 parts of isophorone diisocyanate represented by the following formula (13), 168 parts of hexamethylene diisocyanate, and 2.4 parts of water as a biuretizing agent were used. Was dissolved in 130 parts of a 1: 1 (weight ratio) mixed solvent of ethylene glycol methyl ether acetate and trimethyl phosphate, and reacted at a reaction temperature of 160 ° C. for 1.5 hours.

[0112]

Embedded image (13)

[0113] The obtained reaction solution was applied to a thin film distillation can (wiped film).
evaporator) [Type 2-03 WFE: manufactured by Shinko Pantech Co., Ltd. in Japan], two-stage treatment (first time: 1.0 mmHg / 160 ° C., second time: 0.1 mHg)
Excess isophorone diisocyanate and hexamethylene diisocyanate, and the solvent were distilled off and collected by distillation under a condition of mHg / 200 ° C. to obtain a residue. The residue obtained is 99.2% by weight of polyisocyanate (1) (cobiuret-type polyisocyanate of isophorone diisocyanate and hexamethylene diisocyanate), 0.7% by weight of residual isophorone diisocyanate, and 0.1% by weight of residual hexane. It contained methylene diisocyanate. The obtained residue has an NCO group content of 15.6% by weight and a viscosity of 20,000 (± 3000) mP.
a. sec / 40 °, number average molecular weight is about 800 (± 10
0), the average number of NCO groups was about 3.7. Ethyl acetate was added to the residue, and polyisocyanate (1) was added to 79.
A 6% solution was obtained.

[Polyisocyanate (2)] 168 parts of hexamethylene diisocyanate and 1.5 parts of water as a biuretizing agent were mixed with a mixed solvent of ethylene glycol methyl ether acetate and trimethyl phosphate at a weight ratio of 1: 1 (weight ratio). And reacted at a reaction temperature of 160 ° C. for 1 hour. The obtained reaction solution is transferred to a thin film distillation can (wiped film e).
vaporizer) [Type 2-03 WFE: manufactured by Shinko Pantech Co., Ltd. in Japan], two-stage treatment (first time at 1.0 mmHg / 160 ° C, second time 0.1 m
Excess hexamethylene diisocyanate and the solvent were distilled off and collected under reduced pressure (mHg / 160 ° C.) to obtain a residue. The residue obtained contained 99.9% by weight of polyisocyanate (2) (biuret-type polyisocyanate of hexamethylene diisocyanate) and 0.1% by weight of residual hexamethylene diisocyanate. The viscosity of the obtained residue is 1900 (± 200) mP
a. sec / 25 °, number average molecular weight is about 600 (± 10
0), the average number of NCO groups was about 3.3, and the NCO group content was 23.3% by weight.

[Polyisocyanate (3)] Tetramethylammonium acetate as an isocyanuration catalyst was added to 1000 parts of hexamethylene diisocyanate.
01 parts were added and reacted at 60 ° C. for 4 hours. After adding 0.2 parts of phosphoric acid and terminating the reaction, the mixture was further heated at 90 ° C. for 1 hour and cooled to room temperature, whereby a catalyst deactivated substance was precipitated as a solid. After removing this precipitate by filtration, the obtained reaction solution was used as a thin film distillation can (wiped film evaporator).
[Type 2-03WFE: Shinko Pantech Co., Ltd. of Japan
The first process was performed under a condition of 1.0 mmHg / 160 ° C., the second process was performed under a condition of 0.1 mmHg / 160 ° C., and the excess hexamethylene diisocyanate and the solvent were removed by distillation in two steps. To give a residue. The residue obtained contained 99.9% by weight of polyisocyanate (3) (isocyanurate-type polyisocyanate of hexamethylene diisocyanate) and 0.1% by weight of residual hexamethylene diisocyanate. The viscosity of the obtained residue is 1400 (± 200) mPa. sec / 25 °, the number average molecular weight was about 580 (± 80), the average number of NCO groups was about 3.2, and the NCO group content was 23.4% by weight.

[0116]

Example 1 In a reactor having a reflux condenser, a thermometer and a stirrer, 23 parts of acetone, a 79.6% ethyl acetate solution of the polyisocyanate (1) obtained in Reference Example 2 (NCO group content: 15.6% by weight) %) 23 parts, "Uniox (trademark)
M1000 "[manufactured by Nippon Oil & Fats Co., Ltd., Japan, hydroxyl value 5
6.9 polyoxyethylene methyl ether], 10 parts,
0.001 part of dibutyltin dilaurate was added as a catalyst and reacted at 60 ° C. for 4 hours. Next, acetone 421 was placed in a reactor having a reflux condenser, a thermometer and a stirrer.
To the mixture, 74 parts of hydrazine monohydrate was added at room temperature over 30 minutes while stirring, and the mixture was further stirred for 1 hour. The reaction product obtained above was added to this reaction solution with stirring at 40 ° C. over 1 hour, and then further stirred at 40 ° C. for 4 hours. Thereafter, 1183 parts of water was added over 30 minutes while stirring the reaction system at 40 ° C., and stirring was continued for another 30 minutes. Acetone, ethyl acetate, hydrazine,
The 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%.

FIG. 1 shows the infrared absorption spectrum of this product. 100 parts of cyclohexanone was added to 50 parts of an aqueous dispersion of the obtained semicarbazide composition (solid content: 10 parts), and the mixture was shaken at 150 rpm for 5 hours, and then 10,000 rpm
and centrifugation at 10 m for 10 minutes. The lower aqueous phase contains 6.7 parts of a hydrophilic group-containing compound derived from polyisocyanate (1) having a polyoxyethylene methyl ether group introduced as a hydrophilic group and a terminal blocker thereof, and the upper cyclohexanone phase contains 3.3 parts of a semicarbazide derivative derived from polyisocyanate (1) were present.

[0118]

Example 2 In a reactor equipped with a reflux condenser, a thermometer and a stirrer, 22 parts of tetrahydrofuran, a 79.6% ethyl acetate solution of the polyisocyanate (1) obtained in Reference Example 2 (NCO group content: 15 23 parts, "UNIOX (trademark) Ml000" (Nippon Oil & Fats Co., Ltd., Japan)
Polyoxyethylene methyl ether having a hydroxyl value of 56.9], and 10 parts of dibutyltin dilaurate as a catalyst.
001 parts were added and reacted at 60 ° C. for 4 hours.

Next, 7.3 parts of hydrazine monohydrate was added to 147 parts of tetrahydrofuran in a reactor having a reflux condenser, a thermometer and a stirrer at room temperature over 30 minutes while stirring, and further added. Stir for 1 hour. The reaction product obtained above was added to this mixture with stirring at 40 ° C. over 1 hour, and then further stirred at 40 ° C. for 4 hours. Thereafter, 182 parts of water was added to 3 parts while stirring the reaction system at 40 ° C.
It was added over 0 minutes 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 reduced pressure by heating to obtain an aqueous dispersion of a semicarbazide composition having a solid content of 30%. FIG. 2 shows the infrared absorption spectrum of this product.

[0120]

Example 3 In a reactor having a reflux condenser, a thermometer and a stirrer, 259 parts of acetone, 86 parts of isophorone diisocyanate (IPDI), "Uniox M1000"
310 parts (polyoxyethylene methyl ether having a hydroxyl value of 56.9, manufactured by Nippon Oil & Fats Co., Ltd., Japan) and 0.04 part of dibutyltin dilaurate as a catalyst were reacted at 60 ° C. for 7 hours. Next, 459 parts of hydrazine monohydrate was added to 2600 parts of acetone placed in a reactor having a reflux condenser, a thermometer and a stirrer with stirring over a period of 30 minutes at room temperature, and further stirred for 1 hour. The reaction product obtained above was added to this reaction solution with stirring at 40 ° C. over 1 hour, and further stirred at 40 ° C. for 4 hours. Thereafter, 4100 parts of water was added over 30 minutes while stirring the reaction system at 40 ° C., and stirring was further continued for 30 minutes. Acetone, hydrazine, a reaction product of acetone and hydrazine, water, and the like in the obtained reaction solution are distilled off under reduced pressure by heating to obtain a solid content of 40%.
% Of an aqueous dispersion of a hydrophilic group-containing compound having an IPDI skeleton and a terminal blocker. FIG. 3 shows the infrared absorption spectrum of this product.

To a reactor having a reflux condenser, a thermometer and a stirrer was added 597 parts of hydrazine monohydrate at room temperature over 30 minutes while stirring, and the mixture was further stirred for 1 hour. 161 parts of a 79.6% ethyl acetate solution (NCO group content: 15.6% by weight) of the polyisocyanate (1) obtained in Reference Example 2 was added to this reaction solution at 40 ° C.
With stirring over 1 hour, and then 4 more
Stirred at 0 ° C. for 4 hours. Thereafter, 180 parts of water was added over 30 minutes while stirring the reaction system at 40 ° C., and stirring was further continued for 30 minutes. Acetone in the obtained reaction solution,
Ethyl acetate, hydrazine, a reaction product of acetone and hydrazine, water and the like were distilled off under reduced pressure under heating to obtain a white crystalline semicarbazide derivative and a terminal-blocked body thereof. FIG. 4 shows the infrared absorption spectrum of this product. After dissolving 20 parts of the obtained semicarbazide derivative and its terminal blocker in 80 parts of N-methylpyrrolidone, the above hydrophilic group-containing compound having an IPDI skeleton and its terminal blocker in water dispersion (solid content 40%) 50 Then, 50 parts of water was added while stirring at room temperature to obtain a water dispersion of a semicarbazide composition having a solid content of 20%.

[0122]

Example 4 400 parts of hydrazine monohydrate was added to 3600 parts of methyl ethyl ketone in a reactor having a reflux condenser, a thermometer and a stirrer while stirring at room temperature over about 30 minutes, and then heated to 40 ° C. And stirred for 1 hour. The polyisocyanate (2) obtained in Reference Example 2 (NCO
A solution prepared by dissolving 144 parts of 144 parts of methyl ethyl ketone (group content: 23.3 wt%) was added at 40 ° C. over about 1 hour, and stirring was continued at 40 ° C. for 3 hours. Methyl ethyl ketone, hydrazine, a reaction product of methyl ethyl ketone and hydrazine, water and the like in the obtained reaction solution were distilled off under heating and reduced pressure to obtain 168 parts of a semicarbazide derivative having a biuret structure and a terminal-blocked body thereof. As a result of analysis by gel permeation chromatography, the obtained semicarbazide compound contained the following formula (14)
And its terminal blocker were present in an area of 47% by area.

[0123]

Embedded image FIG. 5 shows the infrared absorption spectrum of this product.

[0124]

Example 5 80 parts of hydrazine monohydrate was added at room temperature to 720 parts of tetrahydrofuran placed in a reactor having a reflux condenser, a thermometer and a stirrer. A solution prepared by dissolving 72 parts of the polyisocyanate (2) (NCO group content: 23.3 wt%) obtained in Reference Example 2 in 72 parts of tetrahydrofuran was added thereto at 40 ° C. over about 1 hour. Stirring was continued for 3 hours at ° C. Thereafter, 360 parts of water was added over 30 minutes while stirring the reaction system at 40 ° C., and the reaction was further continued for 30 minutes. By distilling off tetrahydrofuran, hydrazine, water and the like in the obtained reaction solution under heating and reduced pressure, an aqueous solution of a semicarbazide derivative having a biuret structure with a solid content of 23% was obtained. As a result of analysis by gel permeation chromatography, the compound of the following formula (14) was present in the obtained semicarbazide derivative in an area of 57% by area.

[0125]

Embedded image FIG. 6 shows the infrared absorption spectrum of this product.

[0126]

Example 6 400 parts of hydrazine monohydrate was added to 3600 parts of methyl ethyl ketone in a reactor having a reflux condenser, a thermometer and a stirrer while stirring at room temperature over about 30 minutes, and then heated to 40 ° C. And stirred for 1 hour. The polyisocyanate (3) obtained in Reference Example 2 (NCO
73 parts of methyl ethyl ketone 7
The solution dissolved in 3 parts was added at 40 ° C. over about 30 minutes, and stirring was further continued at 40 ° C. for 3 hours. By distilling off methyl ethyl ketone, hydrazine, a reaction product of methyl ethyl ketone and hydrazine, water and the like in the obtained reaction solution under heating and reduced pressure, 84 parts of a semicarbazide derivative having an isocyanurate structure and a terminal-blocked body thereof were obtained. As a result of analysis by gel permeation chromatography, the obtained semicarbazide derivative contained the following formula (15)
And its terminal blocker were present in an area of 58% by area.

[0127]

Embedded image FIG. 7 shows the infrared absorption spectrum of this product. After dissolving 50 parts of the obtained semicarbazide derivative and its terminal blocker in 40 parts of toluene, "GAFAC-RE61" was dissolved.
10 "(special phosphate ester type nonionic anionic surfactant, manufactured by Toho Chemical Industry Co., Ltd., Japan). The mixture was vigorously stirred at 5000 rpm with a homogenizer, and 100 parts of ion-exchanged water was added thereto over 20 minutes to obtain an aqueous dispersion of a lysemicarbazide derivative and a terminal-blocked body thereof.

[0128]

EXAMPLE 7 After dissolving 120 parts of adipic dihydrazide in 1180 parts of ion-exchanged water, methyl ethyl ketone 3 was dissolved.
Seven parts were added at room temperature over about 10 minutes with stirring. The polyisocyanate (3) 13 obtained in Reference Example 2
Was dissolved in 13 parts of toluene, and a mixture obtained by adding 2.5 parts of the same anionic surfactant (GAFAC-RE610) used in Example 6 to a homogenizer at 5000 rpm.
Was added over about 20 minutes with vigorous stirring to obtain an aqueous dispersion of the semicarbazide derivative and its terminal-blocked body. FIG. 8 shows the infrared absorption spectrum of this product.

[0129]

EXAMPLE 8 Hexamethylene diisocyanate was added to a triol having a number average molecular weight of 800 obtained by successively adding ε-caprolactone to trimethylolpropane with an NCO group / O
After reacting at a molar ratio such that the molar ratio of the H groups is 8, excess hexamethylene diisocyanate is removed by distillation to obtain a triol-modified urethane-type oligomer of hexamethylene diisocyanate (NCO group content of 8.0 wt.
%). 133 parts of hydrazine monohydrate was added to 1200 parts of methyl ethyl ketone in a reactor having a reflux condenser, a thermometer and a stirrer at room temperature over about 30 minutes while stirring, and then stirred at 40 ° C. for 1 hour. . While stirring a solution prepared by dissolving 140 parts of the above-mentioned hexamethylene diisocyanate triol-modified urethane-type oligomer in a mixture of 15 parts of toluene and 124 parts of methyl ethyl ketone, the mixture was added at 40 ° C. for about 1 hour. For 3 hours. Methyl ethyl ketone, hydrazine, toluene, a reaction product of methyl ethyl ketone and hydrazine, water, and the like in the obtained reaction solution were distilled off under reduced pressure by heating to obtain 147 parts of a semicarbazide derivative having a urethane structure and a terminal-blocked body thereof. FIG. 9 shows the infrared absorption spectrum of this product.

[0130]

Example 9 To 100 parts of the carbonyl group-containing copolymer aqueous emulsion (1) synthesized in Reference Example 1, 13.2 parts of the aqueous dispersion of the semicarbazide composition obtained in Example 1 was added.
The coating composition was obtained by stirring at room temperature for 30 minutes. After forming the obtained coating composition on a glass plate at room temperature, it was further dried at room temperature for one month to obtain a transparent and smooth coating film. The physical properties of this coating were measured. Table 1 shows the results.

[0131]

Example 10 To 100 parts of the aqueous carbonyl group-containing copolymer aqueous emulsion (2) synthesized in Reference Example 1 was added 13.2 parts of the aqueous dispersion of the semicarbazide composition obtained in Example 1, and the mixture was allowed to stand at room temperature for 30 minutes. The composition for coating was obtained by stirring. After forming the obtained coating composition on a glass plate at room temperature, it was further dried at room temperature for one month to obtain a transparent and smooth coating film.
The physical properties of this coating were measured. Table 1 shows the results.

[0132]

Example 11 To 100 parts of the aqueous carbonyl group-containing copolymer aqueous emulsion (2) synthesized in Reference Example 1 was added 10.5 parts of the aqueous dispersion of the semicarbazide composition obtained in Example 2, and the mixture was allowed to stand at room temperature for 30 minutes. The composition for coating was obtained by stirring. After forming the obtained coating composition on a glass plate at room temperature, it was further dried at room temperature for one month to obtain a transparent and smooth coating film.
The physical properties of this coating were measured. Table 1 shows the results.

[0133]

Example 12 To 100 parts of the carbonyl group-containing copolymer aqueous emulsion (1) synthesized in Reference Example 1 was added 18.8 parts of the aqueous dispersion of the semicarbazide composition obtained in Example 3, and the mixture was allowed to stand at room temperature for 30 minutes. The composition for coating was obtained by stirring. After forming the obtained coating composition on a glass plate at room temperature, it was further dried at room temperature for one month to obtain a transparent and smooth coating film.
The coating film was peeled from the glass plate to obtain a film, and the physical properties of the film were measured. The weight retention, which is an indicator of the solvent resistance of the film, was 92%. As a result of the water resistance test, the water absorption was 5% and the state of the coating film was unchanged, which was good.

[0134]

Example 13 To 100 parts of the aqueous carbonyl group-containing copolymer aqueous emulsion (2) synthesized in Reference Example 1 was added 18.8 parts of the aqueous dispersion of the semicarbazide composition obtained in Example 3, and the mixture was allowed to stand at room temperature for 30 minutes. The composition for coating was obtained by stirring. After forming the obtained coating composition on a glass plate at room temperature, it was further dried at room temperature for one month to obtain a transparent and smooth coating film.
Peeling the physical properties of this coating film from the glass plate to obtain a film,
The film was measured. The weight retention, which is an indicator of the solvent resistance of the film, was 95%. The results of the water resistance test show that the water absorption is 4% and the state of the film is unchanged.
It was good.

[0135]

Comparative Example 1 A film was dried by using the aqueous carbonyl group-containing copolymer aqueous emulsion (1) synthesized in Reference Example 1 alone in substantially the same manner as in Example 9 to obtain a coating film. The physical properties of this coating were measured. Table 1 shows the results.

Comparative Example 2 Example 9 was substantially the same as Example 9 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 Japan Hydrazine Industry Co., Ltd., Japan). It was blended in a similar manner, and the film was dried to obtain a coating film. The physical properties of this coating were measured. Table 1 shows the results.

[0136]

Comparative Example 3 In a reactor having a reflux condenser, a thermometer and a stirrer, 105.2 parts of isophorone diisocyanate (IPDI), 308.7 parts of polytetramethylene glycol (weight average molecular weight 2000), dimethylolpropionic acid 21.2 parts, 16.0 parts of triethylamine, 452.7 parts of methyl ethyl ketone and 0.013 part of dibutyltin dilaurate were added, and a urethanization reaction was carried out at 80 ° C. for 5 hours in a nitrogen stream to obtain an NCO-terminated prepolymer solution. Was. In 290 parts of the obtained prepolymer solution, under stirring,
At 40 ° C., 309 parts of water was added, and the mixture was further stirred at 40 ° C. for 4 hours. After methyl ethyl ketone in the obtained reaction solution was distilled off under heating and reduced pressure, the concentration was adjusted with ion-exchanged water to obtain an aqueous dispersion of a semicarbazide group-containing oligourethane having a solid content of 30%. As a result of analysis by gel permeation chromatography, the weight average molecular weight was 29,0.
00. Fig. 1 shows the infrared absorption spectrum of this product.
0 is shown. Further, 100 parts of the above-mentioned semicarbazide group-containing oligourethane aqueous dispersion was added to 100 parts of the carbonyl group-containing copolymer aqueous emulsion (2) synthesized in Reference Example 1, and the mixed coating composition was placed on a glass plate. After forming the film at room temperature, it was further dried at room temperature for one month to obtain a transparent and smooth coating film. The physical properties of this coating were measured. Table 1 shows the results.

[0137]

Comparative Example 4 In a reactor having a reflux condenser, a thermometer, and a stirrer, 40 parts of hydrazine monohydrate was added to 360 parts of tetrahydrofuran with stirring for 30 minutes at room temperature. Xamethylene diisocyanate 1
A mixture consisting of 6 parts and 16 parts of tetrahydrofuran was added over 1 hour at room temperature, and the mixture was further stirred for 24 hours.
Thereafter, 80 parts of water was added over 30 minutes while stirring the reaction system, and stirring was further continued for 30 minutes. Tetrahydrofuran, hydrazine, water and the like in the obtained reaction solution were distilled off under reduced pressure by heating to obtain an aqueous solution of a semicarbazide derivative having a solid content of 30%. To 100 parts of the carbonyl group-containing copolymer aqueous emulsion (1) synthesized in Reference Example 1, 3.2 parts of a 30% aqueous solution of this semicarbazide derivative was added and stirred at room temperature for 30 minutes to obtain a coating composition. The obtained coating composition was formed on a glass plate at room temperature, and then dried at room temperature for one month to obtain a coating film. Table 1 shows the results.

[0138]

[Table 1]

[0139]

According to the present invention, the semicarbazide derivative, its terminal-blocked body or a mixture thereof (α), or the above-mentioned (α) and a hydrophilic group-containing compound, its terminal-blocked body or a mixture thereof are contained. Semicarbazide composition (δ) shows high compatibility of the polycarbonyl compound,
In addition, it has excellent solubility in various solvents. The above (α)
Alternatively, the coating composition prepared by combining (δ) with a polycarbonyl compound as a curing agent is not only excellent in room-temperature curability and storage stability, but also has a very high degree of crosslinking, hardness, toughness, water resistance, A film excellent in various properties including stain resistance and the like, and particularly in terms of water resistance, substantially equivalent to a conventional organic solvent-based coating material can be formed at a relatively low temperature (ambient temperature). Therefore, the coating composition of the present invention is a paint, a base material or a finishing material for building materials,
It can be advantageously used as an adhesive, a pressure-sensitive adhesive, a paper processing agent, or a finishing agent for a woven fabric.

[Brief description of the drawings]

FIG. 1 is an infrared absorption spectrum of the semicarbazide composition obtained in Example 1.

FIG. 2 is an infrared absorption spectrum of the semicarbazide composition obtained in Example 2.

FIG. 3 is an infrared absorption spectrum of the hydrophilic group-containing compound obtained in Example 3.

FIG. 4 is an infrared absorption spectrum of the semicarbazide derivative obtained in Example 3.

FIG. 5 is an infrared absorption spectrum of the semicarbazide derivative obtained in Example 4.

FIG. 6 is an infrared absorption spectrum of the semicarbazide derivative obtained in Example 5.

FIG. 7 is an infrared absorption spectrum of the semicarbazide derivative obtained in Example 6.

FIG. 8 is an infrared absorption spectrum of the semicarbazide derivative obtained in Example 7.

FIG. 9 is an infrared absorption spectrum of the semicarbazide derivative obtained in Example 8.

FIG. 10 is an infrared absorption spectrum of a semicarbazide group-containing oligourethane obtained in Comparative Example 3.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-6-299116 (JP, A) JP-A-6-93077 (JP, A) JP-A-6-93078 (JP, A) 43196 (JP, B1) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07C 281/06 C07D 251/34 CA (STN) CAOLD (STN) REGISTRY (STN)

Claims (8)

(57) [Claims] 1. A semicarbazide derivative represented by the following formula (1) or a terminal-blocked body thereof. Embedded image Wherein R ¹ is at least one diisocyanate
Isocyanurate bond, uretdione bond, Aloha
At least one selected from a nate bond and a biuret bond.
Diisomers oligomerized by forming species bonds
Polyisocyanate, which is a cyanate trimer to 20-mer oligomer
Remove all terminal isocyanate groups from the cyanate
The polyisocyanate residue or R ¹ has ¹ carbon atom.
Which are alkylene diisocyanates having 2 to 20 carbon atoms and are substituted by one isocyanatoalkyl group
From cyanate, to display the <br/> triisocyanate residue obtained by removing all of the terminal isocyanate groups. Here, the above polyiso
In the case of a cyanate residue, the diisocyanate that constitutes it
DOO is a linear or branched alkylene diisocyanates having 2 to 20 carbon atoms, unsubstituted or substituted or 1 carbon atoms
C18-C18 alkyl group, C1-C8 alkoxy group, or C1-C6 alkylene group substituted with C5-C20 cycloalkylene diisocyanate, unsubstituted or C1-C18 Having 6 to 6 carbon atoms substituted with an alkyl group or an alkoxy group having 1 to 8 carbon atoms
20 arylene diisocyanate and an unsubstituted or C1-C18 alkyl group or C1
And at least one diisocyanate selected from the group consisting of aralkylenediisocyanates having 8 to 20 carbon atoms and substituted with an alkoxy group having 8 to 8 carbon atoms. R ² is a linear or branched alkylene group having 2 to 20 carbon atoms, a cycloalkylene group having 5 to 20 carbon atoms, or an unsubstituted or alkyl group having 1 to 18 carbon atoms or 1 to 2 carbon atoms. 6 to 10 carbon atoms substituted with an alkoxy group of 8
Wherein each R ³ is independently a hydrogen atom or a carbon number 1 to
Represents 20 alkyl groups; n is 0 or 1; and l and m are each 0 or a positive integer, provided that 3 ≦ (l + m) ≦ 20. ]
In the terminal-blocked semicarbazide derivative represented by the above formula (1), at least one of the terminal groups H ₂ NR ³ N- in the formula (1) is a blocked one represented by the formula R ⁹ R ⁸ C = NR ³ N-. Wherein R ⁸ and R ⁹ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, Or an aryl group having 6 to 10 carbon atoms which is unsubstituted or substituted with an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, wherein R ⁸ and R ⁹ may be To form a ring structure.) 2. A semicarbazide derivative represented by the following formula (1) or a terminal-blocked body thereof. Embedded image [Wherein, R ¹ is oligomerized by at least one diisocyanate forming at least two types of bonds selected from isocyanurate bonds, uretdione bonds, urethane bonds, allohanate bonds, urea bonds, and biuret bonds. Diisocyanate trimer to 20-mer oligomer, a polyisocyanate residue obtained by removing all terminal isocyanate groups from polyisocyanate, or a carbon in which R ¹ is substituted by one isocyanatoalkyl group having 1 to 8 carbon atoms It represents a triisocyanate residue in which all terminal isocyanate groups have been removed from triisocyanate which is an alkylene diisocyanate of Formulas 2 to 20. Here, in the case of the above polyisocyanate residue, the diisocyanate constituting the polyisocyanate is a linear or branched alkylene diisocyanate having 2 to 20 carbon atoms, an unsubstituted or an alkyl group having 1 to 18 carbon atoms, A cycloalkylene diisocyanate having 5 to 20 carbon atoms substituted with an alkoxy group having 1 to 8 carbon atoms or an alkylene group having 1 to 6 carbon atoms, an unsubstituted or an alkyl group having 1 to 18 carbon atoms or 1 carbon atom Arylene diisocyanate having 6 to 20 carbon atoms substituted with an alkoxy group having 8 to 8 carbon atoms, and unsubstituted or having 1 to 1 carbon atoms
It is at least one diisocyanate selected from the group consisting of aralkylenediisocyanates having 8 to 20 carbon atoms and substituted with an alkyl group having 8 or an alkoxy group having 1 to 8 carbon atoms. R ² is a linear or branched carbon number 2
Alkylene group having from 20 to 20 carbon atoms, a cycloalkylene group having from 5 to 20 carbon atoms, or unsubstituted or
Represents an arylene group having 6 to 10 carbon atoms and substituted by an alkyl group having 18 or an alkoxy group having 1 to 8 carbon atoms; each R ³ independently represents a hydrogen atom or a carbon atom having 1 to 8 carbon atoms;
Represents 20 alkyl groups; n is 0 or 1; and l and m are each 0 or a positive integer, provided that 3 ≦ (l + m) ≦ 20. ]
In the terminal-blocked semicarbazide derivative represented by the above formula (1), at least one of the terminal groups H ₂ NR ³ N- in the formula (1) is a blocked one represented by the formula R ⁹ R ⁸ C = NR ³ N-. Wherein R ⁸ and R ⁹ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, Or an aryl group having 6 to 10 carbon atoms which is unsubstituted or substituted with an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, wherein R ⁸ and R ⁹ may be To form a ring structure.) 3. The weight average molecular weight of the semicarbazide derivative is less than 2,000, and the weight average molecular weight of the terminal blocker is less than 3,000.
Or the semicarbazide derivative or the terminal-blocked body thereof according to 2 . 4. The semicarbazide derivative according to claim 1 or 2 , wherein the polyisocyanate residue represented by R ¹ has a skeleton represented by the following formula (2 ′): . Embedded image [Wherein, A ¹ , A ² , and A ³ each independently represent a linear or branched alkylene group having 2 to 20 carbon atoms, an unsubstituted or an alkyl group having 1 to 18 carbon atoms, A cycloalkylene group having 5 to 20 carbon atoms substituted with an alkoxy group having 1 to 8 carbon atoms or an alkylene group having 1 to 6 carbon atoms, an unsubstituted or an alkyl group having 1 to 18 carbon atoms or 1 carbon atom An arylene group having 6 to 20 carbon atoms substituted with an alkoxy group having 8 to 8 carbon atoms, or an unsubstituted or an alkyl group having 1 to 18 carbon atoms or 1 carbon atom
Represents an aralkylene group having 8 to 20 carbon atoms, which is substituted with an alkoxy group having 8 to 8 carbon atoms. ] 5. The semicarbazide derivative according to claim 1 or 2 , wherein the polyisocyanate residue represented by R ¹ has a skeleton represented by the following formula (5 ′): . Embedded image [Wherein, A ¹ , A ² , and A ³ each independently represent a linear or branched alkylene group having 2 to 20 carbon atoms, an unsubstituted or an alkyl group having 1 to 18 carbon atoms, A cycloalkylene group having 5 to 20 carbon atoms substituted with an alkoxy group having 1 to 8 carbon atoms or an alkylene group having 1 to 6 carbon atoms, an unsubstituted or an alkyl group having 1 to 18 carbon atoms or 1 carbon atom An arylene group having 6 to 20 carbon atoms substituted with an alkoxy group having 8 to 8 carbon atoms, or an unsubstituted or an alkyl group having 1 to 18 carbon atoms or 1 carbon atom
Represents an aralkylene group having 8 to 20 carbon atoms, which is substituted with an alkoxy group having 8 to 8 carbon atoms. ] 6. The dispersion and semicarbazide derivative or a terminal-blocked body according to claim 1 or 2, wherein the at least one condition selected from the group consisting of dissolution in an aqueous medium into the aqueous medium. 7. A hydrophilic group-containing compound represented by formula (7) and at least one (α) selected from the group consisting of the semicarbazide derivative according to claim 1 or 2 and a terminal blocker thereof, and a terminal blocker thereof. A composition comprising at least one selected from the group consisting of bodies. Embedded image [Wherein, R ⁴ is a linear or branched alkylene diisocyanate having 2 to 20 carbon atoms, an unsubstituted or an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or a carbon atom having 1 to 8 carbon atoms. A cycloalkylene diisocyanate having 5 to 20 carbon atoms substituted with an alkylene group having 1 to 6 carbon atoms not substituted or substituted with an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 8 carbon atoms; From the group consisting of arylene diisocyanates of numbers 6 to 20, and aralkylenediisocyanates of 8 to 20 carbon atoms which are unsubstituted or substituted by an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 8 carbon atoms. From at least one selected diisocyanate ,
Diisocyanate excluding all terminal isocyanate groups
The residue or R ⁴ is selected from the above diisocyanates
At least one diisocyanate is isocyanurate
Bond, uretdione bond, urethane bond, allohane
Or urea or biuret bonds.
Oligomerization by forming at least one kind of bond
Diisocyanate trimer to 20-mer oligomer
To remove terminal isocyanate groups from polyisocyanate.
All the polyisocyanate residues removed, or R ⁴ ,
Substituted with one isocyanatoalkyl group having 1 to 8 carbon atoms
Alkylene diisocyanate having 2 to 20 carbon atoms
From the triisocyanate, remove any terminal isocyanate groups.
It represents triisocyanate residue obtained by removing Te; R ⁵ is a linear or branched alkylene group having 2 to 20 carbon atoms, a cycloalkylene group or a unsubstituted or substituted, or 1 carbon atoms, 5 to 20 carbon atoms It represents an arylene group having 6 to 10 carbon atoms which is substituted with ~ 18 alkyl or alkoxy group having 1 to 8 carbon atoms; each R ⁶ is independently a hydrogen atom or a carbon number 1 to
Y represents an organic group having at least one selected from the group consisting of a nonionic hydrophilic group, an ionic hydrophilic group, and a group convertible to an ionic hydrophilic group; n Is 0 or 1; and p and q are each 0 or a positive integer, r is a positive integer, and 0 ≦ (p + q)
And 2 ≦ (p + q + r) ≦ 20. The above equation (7)
Is a compound having at least one terminal group H ₂ NR ⁶ N— in the formula (7) represented by the formula R ⁹ R ⁸ C =
It has a blocked terminal group represented by NR ⁶ N— (wherein,
R ⁸ and R ⁹ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or unsubstituted or 1 to 3 carbon atoms. Represents an aryl group having 6 to 10 carbon atoms substituted by an alkyl group having 18 or an alkoxy group having 1 to 8 carbon atoms, and R ⁸ and R ⁹ may optionally form a cyclic structure together ), And in the composition, the weight ratio of the component (α) to the component (β) is 10/90.
９９99/1. 8. The composition according to claim 7 , wherein the composition is in at least one state selected from the group consisting of dispersion in an aqueous medium and dissolution in an aqueous medium.