JP3222241B2 - Diguanamines, their production methods, derivatives and uses - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymerizable monomer, a resin for paint, a resin for adhesive, a resin for paper processing, a resin for fiber processing, a resin for powder coating, a resin material for building materials, a guanamine compound derivative. Diguanamines useful as raw materials, curing agents such as epoxy resins and urethane resins, and polymer modifiers such as rubber materials, and their production methods, curing agents for various resins, useful as resin raw material intermediates, etc. The present invention relates to derivatives of the above diguanamines and uses of the above diguanamines and derivatives thereof.

[0002]

2. Description of the Related Art Conventionally, resin raw materials such as paint resins, adhesive resins, paper processing resins, fiber processing resins, leather processing agents, curing agents for various resins, modifiers for rubber materials, As a modifier for organic materials, high hardness and good gloss, colorless and transparent, high chemical and water resistance, excellent abrasion resistance and electrical properties, resin pot life as a curing agent Guanamines having an aminotriazine group, such as melamine and benzoguanamine, have been widely used.

Further, various research and development have been conducted on melamines and guanamines having such an aminotriazine group, and the resin has excellent properties in terms of flexibility, toughness, high hardness, water resistance, curability and the like. Polyfunctional guanamines having four or more functional groups that are expressed are also provided in the world.

[0004] The polyfunctional guanamines have completely different structures from the novel diguanamines according to the present invention and are very difficult to compare and contrast.

[0005]

Embedded image Phthaloganamin represented by

[0006]

Embedded image And spiroganamin represented by

However, the former compound is extremely poor in UV resistance and weather resistance of a resin obtained from such a compound, so that resins such as exterior paints, weather resistant paints, automotive paints, and resins for building materials are used. It cannot be used as a raw material at all or has significant restrictions, and the water dilutability of a phthalocyanine-based amino resin which is a derivative of such a compound is somewhat improved as compared with a conventional melamine-based amino resin. However, they are still insufficient for practical use, and have drawbacks such as being remarkably restricted when used as a resin raw material such as a resin for water-based paint. Further, the latter compound is inferior in heat resistance of a resin obtained using such a compound as a raw material,
Because the weather resistance, ultraviolet resistance, and water resistance of the resin are poor,
It has drawbacks such as difficulty in maintaining the desired function for a long period of time outdoors or the like as exterior paint, weather resistant paint, automotive paint, resin for building materials, and the like. In addition, the methylolation reaction of the latter compound, such as melamine, the reaction rate is slower than benzoguanamine, etc., because the reactivity of the amino group in such a compound is poor, useful guanamine provided by reacting the amino group of the useful guanamine Various derivatives, resins, various resin curing agents, such compounds and melamine,
It has defects such as the production of formaldehyde copolycondensate with a compound such as benzoguanamine is significantly restricted. Further, the reaction mixture obtained by the methylolation reaction of such a compound is difficult to obtain a transparent solution, the aqueous resin,
For example, water-based paint resin, adhesive resin, paper processing resin,
When used as a resin raw material such as a resin for fiber processing, it is difficult to obtain sufficient performance in the smoothness, curability, physical properties, etc. of the coating film, and it cannot be used for these applications at all, or it is significantly restricted. It also has defects. In the production of the latter compound, the production of spironitrile, which is a raw material for producing such a compound, requires a long and complicated process and requires complicated purification steps. Has defects such as being damaged.

As mentioned above, these compounds have been severely technically and economically restricted in their use and manufacture.

[0009]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies in view of the above-mentioned defects in guanamines, and as a result, have found that a compound having an active amino group exhibiting extremely excellent reactivity with compounds having various functional groups. , And has eight active hydrogens, so that the degree of methylolation can be selected widely,
It is extremely excellent in weather resistance, ultraviolet resistance, etc., and can maintain its intended function for a long time outdoors or the like. Furthermore, the methylol compound has excellent properties such as water dilutability, curability, water resistance, stain resistance, flexibility, hardness, and toughness. The polyfunctional guanamines described above for reference have found diguanamines having completely different structures and properties.Furthermore, in the production of such diguanamines, the desired target compound is obtained with significantly less by-products and high purity, The present invention has been accomplished by finding an excellent production method in which a desired compound can be obtained in a high yield by using dicarbonitrile which is easy to produce in a purification / separation step and is available at a low cost.

[0010] As a derivative obtained by using such a useful diguanamine, an N-methylolated diguanamine obtained by reacting with an aldehyde, and a derivative thereof,
-Etherified diguanamine obtained by etherification reaction between a methylolated product and an alcohol, producing an initial condensate thereof, containing a curing agent for various resins, a derivative thereof useful as a resin raw material such as a resin for coating, etc. Thermosetting composition, a resin for coatings, a resin for powder coatings, a thermosetting resin composition containing the above diguanamines and an epoxy group-containing resin useful as an adhesive resin and the like. And found the present invention.

The above-mentioned diguanamines are a rubber modifier,
Optical materials, resist materials, electrical insulation materials, automotive paints, home appliance paints, antifouling paints, weather-resistant paints, fluorescent paints,
Resin for building materials, powder paint, water-based paint, oil-based paint, resin for paper processing, resin for fiber processing, resin for adhesives, resin for IC encapsulant, corrosion resistant resin, polymer modifier, leather treatment agent It is a very useful compound that can provide excellent polymers, compounds and compositions as plastic magnets, antioxidants for latex, electrophotographic photoreceptors, surfactants, agricultural chemicals, pharmaceuticals and the like.

That is, the present invention provides: ( a ) a general formula (2)

[0013]

[0014]

Embedded image [Wherein, the bonding position of the (4,6-diamino-1,3,5-triazin-2-yl) group indicates the 1,2-, 1,3- or 1,4-position]. Diguanamines, ( b ) General formula (4)

[0015]

[0016]

Embedded image 2 (wherein the bonding position of the cyano group is 1,2-, 1,3-
Or a dicarbonitrile represented by 1,4-position) and dicyandiamide in the presence of a basic catalyst, (c) a method for producing a diguanamine, wherein the basic catalyst is an alkali metal At least one selected from the group consisting of alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal alcoholates, dicyandiamide alkali metal salts, dicyandiamide alkaline earth metal salts, amines and ammonia. The method for producing diguanamines according to the above (b), wherein (d) the reaction is performed using at least one selected from the group consisting of a nonaqueous protonic solvent and an aprotic polar solvent as a reaction solvent. The method for producing diguanamines according to (b) above, wherein (e) the reaction is carried out at a temperature of 60 to 200 ° C. Diguanamine such method for producing the above-mentioned (b) claim, wherein the door, (f) the general formula (1)

Embedded image [Wherein (4,6-diamino-1,3,5-triazine
-2-yl) group is bonded at the 2,5- or 2,6-position
Or the general formula (2)

Embedded image [Wherein (4,6-diamino-1,3,5-triazine
The bonding position of the (-2-yl) group is 1,2-, 1,3- or
N-methylolated diguanamine obtained by an addition reaction of a diguanamine represented by 1,4-position] with an aldehyde, (g) N-methylolated diguanamine according to the above (f) and 1 carbon atom At least one R ¹ OCH ² group obtained by an etherification reaction with at least one selected from alcohols having from 20 to 20 (R ¹ is a residue obtained by removing a hydroxyl group from the alcohols described above; Etherified diguanamine having the general formula (1)

Embedded image [Wherein (4,6-diamino-1,3,5-triazine
-2-yl) group is bonded at the 2,5- or 2,6-position
Or the general formula (2)

Embedded image [Wherein (4,6-diamino-1,3,5-triazine
The bonding position of the (-2-yl) group is 1,2-, 1,3- or
The diguanamine represented by 1,4-position], together with a compound that can be co-condensed, if necessary, with an aldehyde, the average degree of addition condensation of which is greater than 1 and at least one methylol N-methylolated diguanamine precondensate having a group, (i) general formula (1)

Embedded image [Wherein (4,6-diamino-1,3,5-triazine
-2-yl) group is bonded at the 2,5- or 2,6-position
Or the general formula (2)

Embedded image [Wherein (4,6-diamino-1,3,5-triazine
The bonding position of the (-2-yl) group is 1,2-, 1,3- or
1,4-position] and an aldehyde together with a compound capable of co-condensation, if necessary, with an aldehyde,
An etherification reaction is carried out with at least one selected from alcohols having from 20 to 20 alcohols, and a condensation reaction is optionally carried out at the same time.
An etherified diguanamine precondensate having a larger and at least one R ¹ OCH ² group (R ¹ has the same meaning as described above); (nu) an N-methylolated diguanamine according to the above (f);
Item (G): etherified diguanamine according to item (G), N-methylolated diguanamine precondensate according to item (H), and at least one selected from the group consisting of etherified diguanamine precondensate according to item (I). The thermosetting composition, characterized in that it contains as an essential component, (l) The above (nu), which comprises a curable resin that reacts with the component described in (nu) above. A thermosetting composition, (ヲ) a coating resin composition containing the thermosetting composition according to the above (l), (wa) a general formula (1)

Embedded image [Wherein (4,6-diamino-1,3,5-triazine
-2-yl) group is bonded at the 2,5- or 2,6-position
Or the general formula (2)

Embedded image [Wherein (4,6-diamino-1,3,5-triazine
The bonding position of the (-2-yl) group is 1,2-, 1,3- or
(Indicating 1,4-position), and a thermosetting resin composition characterized by comprising a diguanamine represented by the formula (1) and an epoxy group-containing resin: A coating resin composition comprising: (i) a coating resin composition according to the above (f), which is a powder coating resin composition; and (t) a thermosetting resin composition according to the above (a). An adhesive resin composition containing:

In the diguanamines (1) according to the present invention, (4,6-diamino-1,3,5-triazine-
The bonding position of the 2-yl) group is at the 2,5- or 2,6-position, and the configuration of such a group is an end-end form, an end-exo form, or an exo-exo form. It is a useful compound.

Further, the diguanamines (1) include:
Although the compound is a compound selected from the group consisting of the above-mentioned bonding positions and stereoisomers, the aggregate of different compounds selected from such a group is extremely industrially useful as in the case of a single compound. .

Specific examples of such diguanamines (1) include 2,5-bis (4,6-diamino-1,3,5-
Triazin-2-yl) -bicyclo [2.2.1] heptane (endo-exo form), 2,5-bis (4,6-diamino-1,3,5-triazin-2-yl) -bicyclo [ 2.2.1] heptane (exo-exo form), 2,
6-bis (4,6-diamino-1,3,5-triazin-2-yl) -bicyclo [2.2.1] heptane (end-end form), 2,6-bis (4,6-diamino −
1,3,5-triazin-2-yl) -bicyclo [2.
2.1] heptane (exo-exo form) and the like, but are not limited to these compounds.

The diguanamines (2) according to the present invention
In the above, the bonding position of the (4,6-diamino-1,3,5-triazin-2-yl) group is the 1,2-, 1,3- or 1,4-position, The configuration is trans or cis, both of which are useful compounds.

Further, the diguanamines (2) are
Although the compound is a compound selected from the group consisting of the above-mentioned bonding positions and stereoisomers, the aggregate of different compounds selected from such a group is extremely industrially useful as in the case of a single compound. .

Specific examples of such diguanamines (2) include 1,2-bis (4,6-diamino-1,3,5-
Triazin-2-yl) -cyclohexane (cis form),
1,2-bis (4,6-diamino-1,3,5-triazin-2-yl) -cyclohexane (trans form),
1,3-bis (4,6-diamino-1,3,5-triazin-2-yl) -cyclohexane (trans form),
1,3-bis (4,6-diamino-1,3,5-triazin-2-yl) -cyclohexane (cis form), 1,4
-Bis (4,6-diamino-1,3,5-triazine-
2-yl) -cyclohexane (trans form), 1,4-
Bis (4,6-diamino-1,3,5-triazine-2
-Yl) -cyclohexane (cis form) and the like, but are not limited to these compounds.

The diguanamines according to the present invention have the general formula
(3)

[0024]

Embedded image (Wherein the bonding position of the cyano group is 2,5- or 2,6-
) Or general formula (4)

[0025]

Embedded image (Wherein the bond position of the sino group indicates the 1,2-, 1,3- or 1,4-position) wherein dicyandiamide is reacted with dicyandiamide in the presence of a basic catalyst. And a method in which an ester of a dicarboxylic acid corresponding to a dicarbonitrile is reacted with a biguanide in the presence of a basic compound, if necessary. In the former method, the raw material is easily available and the handling is simple, the expected target compound is obtained with a high purity with few by-products, and the production such as the purification / separation step is simple,
From the viewpoint that the raw material loss is remarkably small and the intended compound can be obtained in a high yield, it is technically and economically excellent and extremely practical. The method for producing such diguanamines is not limited to these methods.

The dicarbonitrile (3) in the method for producing diguanamines according to the present invention has a cyano group bonded at the 2,5- or 2,6-position. Both endo-, endo-exo and exo-exo forms are useful. The dicarbonitrile (3) is a compound selected from the group consisting of the isomers having the above-mentioned bonding position and steric configuration. However, in the aggregate of different compounds selected from such a group,
It is as useful as a single compound.

The dicarbonitrile (3) described above can be used, for example, as disclosed in US Pat. No. 2,666,748.
Bicyclo [2.2.1] hept-5-ene-2-carbonitrile and cyanogenous hydrogen are converted into CO ₂ (CO) ₈ , Fe (CO) ₅ , Ni [P
(OC ₆ H ₅ ) ₃ ] _{4 and the} like, and a reaction method in the presence of a specific catalyst, such as 5- (and / or 6) cyano-bicyclo [2.2. 1] A method of reacting hepta-2-carbaldehyde with hydroxylamines, 2,5- (and / or 2,6) dichloro-bicyclo [2.2.1] heptane and an alkali metal cyanide salt, cyanation Although it can be obtained by a method of reacting with a cyanating agent such as an alkaline earth metal salt,
It is not limited to these methods. Specific examples of the dicarbonitrile (3) include bicyclo [2.2.1] heptane-2,5-dicarbonitrile (endo-exo form), bicyclo [2.2.1] heptane-2, 5-dicarbonitrile (end-end type),
Bicyclo [2.2.1] heptane-2,6-dicarbonitrile (endo-exo form), bicyclo [2.2.1]
Heptane-2,6-dicarbonitrile (exo-exo form) and the like, but are not limited to these compounds.

The dicarbonitrile (4) in the process for producing diguanamines according to the present invention has a cyano group bonded at the 1,2-, 1,3- or 1,4-position. The configuration is trans or cis, and both are useful compounds. The dicarbonitrile (4) is a compound selected from the group consisting of the above-mentioned isomers having the bonding position and steric configuration. It is just as useful.

The dicarbonitrile (4) described above can be used, for example, as disclosed in US Pat. No. 3,496,217.
-Cyano-cyclohexene and hydrogen cyanide are converted to Ni [P (OC ₆
H _{5) 3]} a method reacting at presence of a catalyst such as _4, 3 (and / or 4) cyano - cyclohexane carbaldehyde and dicarbonitrile compounds methods, described above reacting a hydroxylamine compound (4) Reacting a dihalogenated cyclohexane corresponding to the above with a cyanating agent such as an alkali metal cyanide salt or an alkaline earth metal cyanide salt; a dicarboxylic acid corresponding to the above-mentioned dicarbonitrile (4) or a diammonium thereof A method in which a salt, a diamide, a diester derivative is reacted with ammonia using an alumina catalyst or a dehydrating agent such as thionyl chloride, a method in which 1-cyano-cyclohexene and hydrogen cyanide are reacted in the presence of an alkali such as sodium hydroxide, or the like. However, the present invention is not limited to these methods.

Specific examples of the dicarbonitrile (4) include 1,2-cyclohexanedicarbonitrile (trans form), 1,3-cyclohexanedicarbonitrile (trans form), and 1,3-cyclohexanedicarbonate. Examples thereof include, but are not limited to, nitrile (cis form), 1,4-cyclohexanedicarbonitrile (trans form), 1,4-cyclohexanedicarbonitrile (cis form) and the like.

In the method for producing diguanamines according to the present invention, the reaction molar ratio between the dicarbonitrile and dicyandiamide can be appropriately selected as necessary. The reaction molar ratio of such dicarbonitrile to dicyandiamide is stoichiometrically 1: 2. When the molar ratio of dicyandiamide to dicarbonitrile is used in an excessively small amount, the diguanamine according to the present invention can be used. Not only low yield, but also monoguanamine [1: 1 (molar ratio) reaction product of dicarbonitrile and dicyandiamide)
If the excess amount is used, removal and separation of unreacted dicyandiamide and the like become complicated, which is technically and economically undesirable. In order to improve the yield of diguanamines according to the present invention and to facilitate production such as purification and separation steps, the molar ratio of dicyandiamide to dicarbonitrile is usually set to 1 mole of dicyandiamide to 1 mole of dicarbonitrile.
It is preferable to carry out the reaction at a ratio of 1.5 to 10.0 mol, preferably at a ratio of 2.0 to 5.0 mol.

Examples of the basic catalyst in the process for producing diguanamines according to the present invention include alkali metals such as potassium and sodium, lithium hydroxide, potassium hydroxide, sodium hydroxide, calcium hydroxide, barium hydroxide and the like. Alkali metals, hydroxides of alkaline earth metals, alkali metals such as potassium carbonate, sodium carbonate, barium carbonate, carbonates of alkaline earth metals, alkali metal alcoholates such as potassium ethylate, sodium methylate, sodium ethylate, Alkali metals, alkaline earth metal salts of dicyandiamide, 1,8-diazabicyclo [5.4.0] undecene-7, amines such as triethylenediamine, piperidine, ethylenediamine, diethylenetriamine, pyrrolidone, tetrahydroquinoline, ammonia, etc. And the like. Especially alkali metals,
Alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal alcoholates, alkali metal salts of dicyandiamide, alkaline earth metal salts of dicyandiamide, amines, and ammonia are preferred.
More than one species may be used. The amount of the catalyst to be added is not particularly limited.
The amount is 300 to 0.1 mol%, and can be appropriately selected as needed.

In such a method for producing diguanamines, a method in which various solvents are used as reaction solvents is very useful for performing the reaction more smoothly. Solvents that cause inhibition,
For example, solvents such as fatty acids, the acid anhydrides, trifluoroacetic acid, liquid sulfur dioxide, sulfuryl chloride, mineral acids, and water are not preferred.

Examples of such a reaction solvent include methanol, ethanol, n-propanol, isopropanol, n-butanol, iso-butanol, tert-butanol, 2-ethylhexanol, dodecyl alcohol,
Allyl alcohol, propargyl alcohol, benzyl alcohol, cyclohexanol, ethylene glycol, butanediol, glycerin, 1,2,6-hexanetriol, 2-methoxyethanol, 2-ethoxyethanol, 2-isopropoxyethanol, 2-butoxyethanol, Furfuryl alcohol, tetrahydrofurfuryl alcohol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, diacetone alcohol, 2,2,2-triol Alcohols such as fluoroethanol and 1,3-dichloro-2-propanol, acetone, methyl ethyl ketone, methyl isobutyl Tons, ketones acetophenone, ethyl acetate, butyl acetate, esters such as benzyl acetate, diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether,
Tetrahydrofuran, dioxane, crown ether,
Ethers such as anisole, carboxylic acid amides such as N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, and sulfolane , Methyl sulfolane, sulfolane such as 1,3-propane sultone, sulfoxides such as dimethyl sulfoxide, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, isopropylamine, butylamine, 2-ethylhexylamine, allylamine, aniline, Cyclohexylamine, pyridine, piperidine, monoethanolamine, 2- (dimethylamino) ethanol, diethanolamine, triethanolamine, isopropanolamine, triisoprop Amines such as Panoruamin, Ammonia, and the like, in particular alcohols, amines, non-aqueous protic solvents, carboxylic acid amides such as ammonia, sulfolane, aprotic polar solvents such as sulfoxides are preferred. These solvents may be used alone or in a mixed system of two or more kinds, such as a mixed solvent of ammonia and alcohol, dimethyl sulfoxide and cellosolves, and may be appropriately selected as necessary. Is preferably as low as possible, particularly preferably 1.0% by weight or less.

Further, such a reaction is not preferable because the reaction is extremely slow at a reaction temperature of 60 ° C. or lower, and not only takes a long time for the production but also the yield is extremely low. Normal 6
When the reaction is carried out at a temperature of 0 ° C. or higher, preferably 80 ° C. or higher, the reaction proceeds rapidly and smoothly, and the desired compound can be obtained in high yield. However, if the reaction temperature exceeds about 200 ° C., the reaction temperature of 200 ° C. or more is not preferable because the generation of by-products increases rapidly to a non-negligible degree and the product purity is significantly reduced. Therefore, in the method for producing diguanamines according to the present invention, a method in which the production is carried out at a reaction temperature in the range of 60 to 200 ° C., more preferably 80 to 180 ° C. is more preferred, and the method is highly pure with little by-products. The desired compound can be obtained, the production such as the purification / separation step can be performed more easily, and the desired compound can be obtained in higher yield.

The reaction system is not particularly limited, but may be under normal pressure or under a naturally occurring pressure in a closed vessel.
Furthermore, it can be performed under pressure, and can be appropriately selected as needed.

In order to obtain the desired target compound of the present invention from the reaction mixture of the above-mentioned reaction, it is best to cool the reaction solution and filter off the crystallized diguanamine. However, the reaction mixture may be poured directly into hot water and separated by crystallization filtration. Unreacted dicyandiamide and / or dicarbonitrile accompanying the crude diguanamine can be easily separated and removed by washing the crude diguanamine with hot water or methanol.
Depending on the purpose of use, when further purification is required, the above-mentioned reaction solvents, for example, alcohols, cellosolves, carboxylic acid amides, sulfolanes, sulfoxides, etc., a mixed solvent of these solvents and water, water and the like A method of performing recrystallization, a method of dissolving in the above-mentioned reaction solvent and pouring it into hot water for reprecipitation, dissolving crude diguanamines in an aqueous hydrochloric acid solution, and mixing this with an alkali to reprecipitate diguanamines It can be performed by a method or the like. However, the yield of the method for producing diguanamines according to the present invention is extremely good, and the diguanamines have a sufficiently high purity for practical use simply by washing with various solvents such as methanol, water, or a mixed solvent thereof. Thus, the above purification method is practically unnecessary.

The diguanamines according to the present invention are excellent in polymerizability with various compounds such as aldehydes, epoxies, carboxylic acids, isocyanates, etc., and also excellent in various reactivities, and are extremely useful as resin raw materials and derivative raw materials. However, diguanamine derivatives such as reactants with aldehydes, reactants obtained by etherifying this reactant with alcohols, and reactants obtained by condensing these reactants are various resins Particularly useful as a curing agent, a resin raw material, and the like.

Such diguanamine derivatives include the above
(F) according to claim, diguanamine compound with the following general formula obtained by addition reaction of an aldehyde (5) and represented by N- methylol diguanamine by the general formula (6), the general formula (5)

[0040]

Embedded image [Wherein, the bonding position of the (N-substituted-4,6-diamino-1,3,5-triazin-2-yl) group is 2,5- or 2,
6-position, R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R
₈ represents one selected from the group consisting of an H atom and a HOCH ₂ group;
₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ may be the same or different.] General formula (6)

[0041]

Embedded imageWherein, (N-substituted-4,6-diamino-1,3,5-to
Riadin-2-yl) groups are attached at 1,2-, 1,3
-Or 1,4-position, R_Two , R_Three , R_Four , R_Five , R ₆ , R
₇ And R₈ Represents the above-mentioned meaning, and R_Two , R_Three , R_Four ,
R_Five , R₆ , R₇And R₈ Are different species of the same species
(G) N-methylolated diene according to the above (f))
Of guanamine and alcohols having 1 to 20 carbon atoms
Etherifying with at least one selected from the group
At least one R obtained by₁OCH_TwoGroup (R₁Is
Which represents the residue obtained by removing the hydroxyl group from the alcohols)
Having the following general formulas (7) and (8)
-Diguanamine telluride, general formula (7)

[0042]

Embedded image [Wherein, the bonding position of the (N-substituted-4,6-diamino-1,3,5-triazin-2-yl) group is 2,5- or 2,
In the 6-position, R ₁ is a residue obtained by removing a hydroxyl group from the above-mentioned alcohols, R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ and R ₁₅
Is 1 selected from the group consisting of H atom, HOCH ₂ group and R ₁ OCH ₂ group
A species, and R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ and R ₁₅ may be the same or different species] general formula (8)

[0043]

Embedded image [Wherein, the bonding position of the (N-substituted-4,6-diamino-1,3,5-triazin-2-yl) group is 1,2-, 1,3
-Or 1,4-position, R ¹ is a residue obtained by removing a hydroxyl group from the above-mentioned alcohols, R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴
And R ¹⁵ have the same meaning as described above, and R ⁹ , R ¹⁰ , R ¹¹ , R
^12, R ^13, R ¹⁴ and R ¹⁵ may be a different species in the same species (h) wherein (h) according to claim, addition condensation and diguanamine compound, an aldehyde together with co-condensable compounds, optionally The average degree of addition condensation obtained by the reaction is greater than 1 and has at least one methylol group.
Methylol diguanamine precondensate, (i) said (i) above, wherein the diguanamine compound, together with co-condensable compound optionally by addition reaction or addition condensation reaction with aldehydes and then to 20 carbon atoms Etherification reaction with at least one selected from alcohols having, and optionally simultaneous condensation reaction, the resulting average addition condensation degree is greater than 1 and at least one R ¹ OCH ² group ( R ¹ has the same meaning as described above), and etherified diguanamine precondensates.

Examples of the aldehydes used in the production of these derivatives include formaldehyde, paraform, hexamethylenetetramine, methylhemiformal, butylhemiformal, formaldehyde sodium bisulfite adduct, and glyoxal, and preferably formaldehyde. , Formalin, paraform, hexamethylenetetramine, methylhemiformal, and butylhemiformal, but are not limited thereto.

The alcohols used for the etherification reaction in the production of these derivatives include saturated or unsaturated aliphatic alcohols having 1 to 20 carbon atoms, alicyclic alcohols and ether groups. Alcohols, alcohols having aromatic groups, etc. are useful,
For example, methyl alcohol, ethyl alcohol, n-propyl alcohol, iso-propyl alcohol, n-butyl alcohol, iso-butyl alcohol, tert-butyl alcohol, n-hexyl alcohol, sec-heptyl alcohol, 2-ethylhexyl alcohol, n-nonyl Alcohol, n-hexadecyl alcohol, n-octadecyl alcohol, n-eicosyl alcohol, cyclohexyl alcohol, cyclohexenyl alcohol,
Examples include, but are not limited to, 4-methylhexyl alcohol, 4-hexylcyclohexyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol monoisopropyl ether, diethylene glycol monomethyl ether, benzyl alcohol, and the like.

In the production of these derivatives, compounds capable of co-condensation may be used as described above. Examples of such co-condensable compounds include melamine, urea, alkyl urea, thiourea, alkyl thiourea, Examples include guanamines such as aniline, benzoguanamine, cyclohexylcarboguanamine and the like, but are not limited thereto.

The above-mentioned N-methylolated diguanamine can be used, for example, in a solvent, if necessary in the presence of a basic compound, at a pH of 8.0 to 13.0, preferably at a pH of 8.5 to 11.5, at a reaction temperature.
When the reaction is carried out at a temperature of 30 ° C. or higher, preferably 40 to 80 ° C., the reaction proceeds rapidly and smoothly, and the at least one HO
Although it is possible to obtain a derivative having a CH ₂ group, further, when obtaining a highly methylolated N-methylolated diguanamine, high purity and yield can be obtained by reducing the amount of water and alcohols. Although it can be obtained well, if the reduction is performed excessively, the stirring effect is reduced, the reaction temperature becomes nonuniform, etc., which is not preferable because a smooth reaction is inhibited. Solvents that are insoluble and do not hinder the reaction, for example, aromatic hydrocarbons such as toluene, xylene, ethylbenzene, cumene, and benzene; hexane, heptane, octane, aliphatic hydrocarbons such as cyclohexane, and halogenated hydrocarbons such as dichloromethane; A method performed in the presence of an aliphatic ether such as diisopropyl ether, amines such as hexamethylenetetramine, piperazine, Aids such as aliphatic amines such as lysine, aliphatic amines such as triethylamine, diethylamine, dibutylamine and hexylamine, aromatic amines such as pyridine and aniline and ammonia are added in an amount of 0.01 to 10 mol% based on aldehydes. Although the method of performing is useful,
The method can be appropriately selected in some cases, and is not limited to these methods.

The above-mentioned etherified diguanamine can be prepared, for example, by subjecting the N-methylolated diguanamine obtained above to pH.
The etherification reaction is carried out at a temperature of 40 to 80 ° C. under acidic conditions of 2 to 4 in the presence of the alcohols described above.
The reaction can be carried out for a period of time. In particular, the amount of water in the reaction system is reduced as much as possible, and the molar ratio of the reaction is carried out at 20 mol or more of the alcohols per mol of N-methylolated diguanamine. Is preferred.

The above-mentioned N-methylolated diguanamine precondensate can be used together with, for example, the above-mentioned aldehydes.
It can be obtained by carrying out the reaction at a temperature of 40 to 100 ° C. under the condition of pH 8.0 or less or pH 13.0 or more.

Furthermore, the above-mentioned etherified diguanamine precondensate can be obtained, for example, by subjecting the above-obtained N-methylolated diguanamine or the N-methylolated diguanamine precondensate to acidic conditions of pH 1.0 to 5.0 at 50 to 100 ° C. It can be obtained by simultaneously performing the etherification reaction or the etherification reaction and the condensation reaction in the presence of the above-described alcohols that perform the etherification reaction at a temperature,
It is not limited to these methods.

N-methylolated diguanamine as described above,
Etherified diguanamine, N-methylolated diguanamine precondensate, etherified diguanamine precondensate are
It is extremely excellent in reactivity with compounds having various functional groups, resins, etc., and is extremely useful as a curing agent for various resins, a resin raw material intermediate, and the like, for example, the above (f), (g), (h),
It is possible to provide a thermosetting composition characterized by containing at least one selected from the group consisting of the derivatives described in (i) as an essential component, and even when only these derivatives are used as a curing component. , Adhesives, fibers,
For example, synthetic fibers such as polyester fiber and acrylic fiber,
Cotton, wrinkle-proofing agents such as natural fibers such as wool, excellent surface modifiers such as anti-fouling agents, paper processing agents, useful as a thermosetting composition such as a leather treatment agent, These diguanamine derivatives can be reacted with those having a hydroxyl group, a carboxyl group, an isocyanate group, an epoxy group or the like to provide a resin or the like having excellent performance, such as an acrylic resin, an epoxy resin, a polyester resin, or a urethane. To provide a thermosetting composition which is extremely useful as a chain extender, a crosslinking agent, a curing agent, a modifying agent, a modifying agent, etc. together with various polymers such as resins, amino alkyd resins, phenolic resins, fluororesins, and vinyl resins. It is useful for a wide range of applications such as resin for adhesives, resin for paints, and resin for building materials.
In particular, it contains at least one selected from the group consisting of the above-mentioned N-methylolated diguanamine, etherified diguanamine, N-methylolated diguanamine precondensate and etherified diguanamine precondensate, and a resin capable of reacting therewith and curing. The thermosetting composition is useful as a coating resin such as a water-based coating resin and an oil-based coating resin.

As the above-mentioned resin which can be reacted and cured, any resin having a functional group which reacts and cures with the above-mentioned derivative is useful. For example, a hydroxyl group, a carboxyl group, an epoxy group, a methylolamide group, At least one of an alkoxymethylolamide group and an isocyanate group
Resins containing seeds are useful, including, but not limited to, acrylic resins, epoxy resins, polyester resins, phenolic resins, phenolic alkyd resins, urethane resins, fluororesins, silicone resins, and modified resins thereof. Not something.

The diguanamine according to the present invention provides a thermosetting resin composition characterized by containing at least one selected from the above-mentioned diguanamines and an epoxy group-containing resin as essential components. it can. Conventionally, a composition comprising an epoxy group-containing resin and an amine as a curing agent cures at a relatively low temperature, but since the amines used as the curing agent are chemically active, they are compounded together with the epoxy group-containing resin. It reacts when stored, has a disadvantage that pot life is short and handling is difficult, and a composition containing dicyandiamide as a curing agent is:
Relatively good storage stability, but this cured resin is flexible,
There are drawbacks in which properties such as light fastness are not good, and their uses have been severely restricted. The present inventors have found the above-mentioned thermosetting resin composition capable of providing a cured resin product having cured product characteristics such as excellent flexibility and light resistance. This thermosetting resin composition is an IC
It is useful for a wide range of applications such as sealants, adhesives, powder coatings, oil-based coatings, and electrical insulating materials.

As the epoxy group-containing resin according to the present invention, any resin having at least one epoxy group can be widely used. Although not particularly limited, for example, diglycidyl ether type epoxy resin of bisphenol A, butadiene epoxide, 4,
4-di (1,2-epoxyethyl) diphenyl ether, 4,4′-di (epoxyethyl) biphenyl, diglycidyl ether of resorcinol, diglycidyl ether of phloroglysin, triglycidyl ether of p-aminophenol, m-amino Triglycidyl ether of phenol, tetraglycidyl-bis- (aminophenol) methane, 1,3,5-tri (1,2-epoxyethyl) benzene, 2,2,4,4-tetraglycidoxybenzophenone, tetraglycid Xyltetraphenylethane, polyglycidyl ether of novolak type phenol formaldehyde resin, triglycidyl ether of trimethylolpropane, triglycidyl ether of glycerin, diglycidyl ether type epoxy resin of halogenated bisphenol A, epoxy resin Cycloaliphatic epoxy resins such as polyglycidyl ether of a novolak type phenol formaldehyde resin, vinylcyclohexene dioxide, 3,4-epoxycyclohexylmethyl 3,4 epoxycyclohexanecarboxylate, hydantoin epoxy resin, triglycidyl isocyanurate, etc. Epoxy group-containing vinyl monomers such as heterocyclic epoxy resins, glycidyl acrylate, and glycidyl methacrylate, and acrylates, methacrylates, fumarates, maleates, acrylamides, methacrylamides, acrylonitrile, and methacryloyl. Nitriles, styrenes, butadienes, polymers with copolymerizable vinyl monomers such as vinyl esters, modified polymers thereof, and the like. Not intended to be constant.

In the present invention, when high-viscosity bisphenol A diglycidyl ether type epoxy resin cannot be used because of its high viscosity, bisphenol A, bisphenol S, brominated bisphenol A, brominated bisphenol S, etc. may be used as a modifier. It can also be modified using a low molecular weight bisphenol A glycidyl ether type epoxy resin or the like.

The mixing ratio of the diguanamine and the epoxy group-containing resin according to the present invention can be appropriately selected depending on the case. Yes,
Preferably, the ratio is 0.4 to 1.5 equivalents.

In the thermosetting resin according to the present invention, a curing accelerator such as a novolak type phenol resin, a metal salt of an organic acid, or an imidazole may be appropriately selected and blended as appropriate. The use of is preferred because a thermosetting resin composition having excellent storage stability, curability and the like can be obtained. Examples of the novolak type phenol resin include phenols such as phenol, cresol, xylenol, ethylphenol, butylphenol, p-phenylphenol, nonylphenol, bisphenol A, resorcinol, and chlorophenol, and aldehydes such as formaldehyde and paraformaldehyde. Examples thereof include, but are not limited to, those obtained by using a conventional method. Incidentally, the compounding ratio of the novolak type phenol resin is usually 0.1 to 100 parts by weight of the epoxy group-containing resin.
The ratio is 10 parts by weight, but can be appropriately selected depending on the case.

The thermosetting resin composition according to the present invention comprises a Z-Blade mixer, an extruder, a dry mix, and a raw material component selected in a predetermined mixing ratio together with the above-mentioned diguanamine, an epoxy group-containing resin, and optionally other components. It can be obtained by a method of mechanically sufficiently mixing with a ball mill or the like, and optionally, a method of performing melt mixing with a hot roll or the like.However, since the diguanamines according to the present invention show a high melting point, the flow may be unevenly formed in some cases. In some cases, the cured product may be inhomogeneous. When it is not preferable, the above-mentioned diguanamine and a low-viscosity diluent, a compatibilizer, a novolak-type phenol resin, etc. are preliminarily heated and melt-mixed, and then an epoxy group-containing resin is compounded. And mixing by heating, dissolving and mixing with a solvent, and further removing the solvent with this mixed solution. Although it is possible to obtain a more sufficient compatible state is a thermosetting resin composition, optionally can be suitably selected, but is not limited to these methods.

Further, in addition to the above-mentioned diguanamines and epoxy group-containing resins, an inorganic filler such as silica powder, alumina, antimony trioxide, talc, etc. , Calcium carbonate, titanium white, clay, mica, red iron oxide, glass fiber, carbon fiber, etc., natural waxes, synthetic waxes, metal salts of fatty acids, release agents such as acid amides, esters, paraffins, chlorinated paraffins , Bromtoluene,
Flame retardants such as hexabromobenzene and antimony trioxide,
Coloring agents such as carbon black and red iron oxide, silane coupling agents, flexibility-imparting agents, viscosity reducing diluents, various curing accelerators, and the like can be appropriately added and blended.

Further, the diguanamines according to the present invention include:
Carboxylic acids such as phthalic acid, adipic acid, maleic acid, trimellitic acid, ethyltetracarboxylic acid, cyclopentanetetracarboxylic acid, pyromellitic acid, 3,3 ', 4,
4'-benzophenonetetracarboxylic acid, 2,2 ', 3,3'-
Benzophenone tetracarboxylic acid, 3,3 ', 4,4'-biphenyltetracarboxylic acid, 2,2', 3,3'-biphenyltetracarboxylic acid, 2,2-bis (3,4-dicarboxyphenyl)
Propane, bis (2,3-dicarboxyphenyl) methane,
2,3,6,7-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,2,3,4-benzenetetracarboxylic acid acid,
2,3,6,7 -anthracenetetracarboxylic acid, 1,2,7,8-
By reacting with phenanthrene tetracarboxylic acid or a precursor thereof, such as partial esterification, acid anhydride, halogen acylation, etc., it is possible to provide a compound having excellent performance, polyamic acid, polyimide, resin such as polyamide. And isocyanates such as 1,6-hexamethylene diisocyanate, 2,2,4-
Trimethylhexamethylene diisocyanate, diisocyanate from dimer acid, bis (2-isocyanatoethyl) fumarate, methylcyclohexane-2,4-diisocyanate, isophorone diisocyanate, 4,4'-
Dicyclohexylmethane diisocyanate, isopropylidene bis (4-cyclohexyl isocyanate), xylylene diisocyanate, m-phenylene diisocyanate, tolidine diisocyanate, dianisidine diisocyanate, 3,3′-dimethyl-4,4 '-Diphenylmethane diisocyanate, 1,5-naphthalenediisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, or the like, or obtained by reacting these with polyols, amines, water, etc. Compounds having excellent performance by reacting with polyvalent isocyanate and the like, resins such as polyurea, compounds having an N-substituted unsaturated imide group, for example, monophenylmaleimide, monophenylcitraconimide, monophenylitaconimide, −
Chlorophenylmaleimide, 2,6-dichlorophenylmaleimide, 2-methylphenylmaleimide, 2,6-dimethylphenylmaleimide, 4-hydroxyphenylmaleimide, N, N'-ethylenebismaleimide, N, N'-hexamethylenebis Maleimide, N, N'-dodecanemethylene bismaleimide, N, N'-m-phenylenebismaleimide, N,
N'-p-phenylenebismaleimide, N, N'-p-phenylenebiscitraconimide, N, N'-p-phenylenebisitaconimide, N, N'-p-phenylene-endomethylenetetrahydrophthalimide, N, N '-4,4'-diphenylmethanebismaleimide, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, N, N'-4,4'-dicyclohexylmethanebismaleimide, N, N'-m -Xylenebismaleimide, N, N'-diphenylcyclohexanebismaleimide, -4,4'-bismaleimidocinnamanilide, -4,4'-methylene-bis (2-isopropyl-6-
Methyl-phenylmaleimide), 2,2-bis [4- (4-maleimidophenoxy) phenyl] hexafluoropropane, and the like, to provide a resin having excellent performance. For example, it can be used as a metal extender, a cross-linking agent, a curing agent, a polymer modifier or the like having excellent properties such as urethane resin and epoxy resin, but is not limited thereto.

As described above, the diguanamines according to the present invention are excellent in reactivity with various compounds and polymerizability. Any polymerization form and reaction form such as a tool, an interfacial polymerization, a solution reaction, and an aqueous reaction may be used, and can be appropriately selected as needed.

The diguanamines according to the present invention are remarkably excellent in weather resistance, ultraviolet light resistance, etc., can maintain initial performance for a long period of time outdoors, etc., and have excellent water dilutability of a methylol compound of the compound. There are almost no restrictions as raw materials and excellent characteristics can be obtained,
It has an active amino group with extremely excellent reactivity with aldehydes, epoxies, carboxylic acids, isocyanates, etc., and has eight active hydrogens. Has the property of
Further, it is an extremely useful compound having excellent properties such as flexibility, toughness, high hardness, water resistance, and curability, and capable of providing various guanamine derivatives and resins having excellent performance.

In the process for producing diguanamines according to the present invention, by using the above-mentioned specific compound and appropriately selecting a reaction catalyst, a solvent, a reaction temperature, a raw material molar ratio, etc., by-products are extremely reduced, The desired product can be obtained at a high purity, the production of the purification / separation step and the like is simple, the raw material loss is extremely small, and the desired product can be obtained at a high yield using raw materials that can be obtained at low cost. Economic and economical,
It is extremely practical.

Such diguanamines include aldehydes,
It is excellent in polymerizability with various compounds such as epoxies, carboxylic acids, and isocyanates, and is also excellent in various reactivities, and is extremely useful as a resin raw material and a derivative raw material. -Methylolated guanamine, etherified diguanamine obtained by etherifying N-methylolation with alcohol and etherification reaction thereof, curing agents for various resins such as their initial condensates, very useful derivatives as resin raw material intermediates, Thermosetting composition containing the above diguanamines and epoxy group-containing resin useful as thermosetting composition containing derivative, resin for IC encapsulant, resin for coating, resin for adhesive, etc. A resin composition or the like can be provided.

The diguanamines according to the present invention include a rubber modifier, an optical material, a resist material, an electrical insulating material, a paint for home appliances, a paint for automobiles, an antifouling paint, a corrosion-resistant paint, a weather-resistant paint, a fluorescent paint, and a powder. Body paints, water-based paints, oil-based paints, building materials, IC sealants, paper processing agents, stainproofing of interior products such as curtains, sofas, wall cloths, carpets, etc. Textile processing agents such as processing, anti-wrinkle processing, water / oil repellent processing, adhesive resin, leather treatment agent, plastic magnet, antioxidant for latex, corrosion inhibitor, electrophotographic photoreceptor, surfactant, pesticide, It is an excellent compound that can provide a guanamine derivative, resin, and composition that is industrially very widely useful as a medicine and the like.

[0066]

Next, reference examples and embodiments of the present invention will be described in more detail. However, these Reference Examples and Examples are not intended to limit the scope of the present invention. The book
In Examples, Examples 1, 2, 6, and
Example 7 corresponds to Reference Example 4, Reference Example 5, and Reference Example 6, respectively.
And Reference Example 7. Reference Example 1 Production of dicarbonitrile (3): 500 ml equipped with a stirrer, thermometer, liquid inlet tube, and cooler
Add bicyclo [2.2.1] hepta-5-ene-2-
297.92 g (2.50 mol) of carbonitrile, Ni [P (OC ⁶ H ⁵ ) ³ ] ⁴
8.77 g (6.75 mmol), ZnCl ² 4.80 g (35.22 mmol), P (OC ⁶ H ⁵ ) ³ 32.27 g (0.104 mol) were charged,
After sufficiently replacing the inside of the system with nitrogen gas, the reaction mixture was kept at 65 ° C. while stirring. Next, ice-cooled liquid hydrocyanic acid 94.59
g (3.50 mol) was supplied to the reactor over a period of 3 hours at a flow rate of 45 to 55 ml / hr, and the reaction was further performed for 1 hour.

Next, after the inside of the system was replaced with nitrogen gas, deionized water was added, and the aqueous layer was separated and removed to obtain a semi-solid oil. This oil was filtered and distilled under reduced pressure to give 362.20 g.
(Yield 9901%) of bicyclo [2.2.1] heptane-2,5-dicarbonitrile and bicyclo [2.2.1] heptane-2,6-
Mixture of dicarbonitrile (boiling point 129-137 ° C / 1mmH
g) was obtained. The results of elemental analysis of the target product are shown below.

[0068] Reference Example 2 Production of bicyclo [2.2.1] heptane-2,5-dicarbonitrile: 5-cyano-bicyclo [2.2.1] hepta-2- was placed in a 21 flask equipped with a stirrer, thermometer and reflux condenser. 179.0 g (1.2 mol) of carbaldehyde, 292.6 g of N, O-bis (trifluoroacetyl) hydroxylamine (1.3 mol)
Mol), pyridine 197.8 g (2.5 mol), benzene 600
ml. The mixture was gradually heated and stirred and heated under reflux for 3 hours. Next, 500 ml of deionized water was added to the reaction mixture, and the aqueous layer was separated and removed to obtain an oily substance. This oily substance was distilled under reduced pressure to obtain 128.0 g (yield 73%).
Of bicyclo [2.2.1] heptane-2,5-dicarbonitrile (boiling point: 131-136 ° C./1 mmHg) was obtained. The results of elemental analysis of the target product are shown below.

[0069]Reference Example 3 Production of dicarbonitrile (4): stirrer, thermometer, liquid
In a 500 ml flask equipped with an inlet tube and a condenser,
188.6 g of ano-cyclohexene, Ni [P (OC₆H_Five)_Three]_Four 6.0
g, ZnCl_Two 3.0 g, P (OC₆H _Five)_Three Charge 23.9 g, nitrogen
After sufficiently replacing the inside of the system with gas, the reaction mixture is
Was kept at 75 ° C. Next, a 42 mol% concentration diluted with nitrogen
Of hydrocyanic acid gas into the reactor at a rate of 177.0 mmol / hr
It was supplied for 7 hours. Next, the inside of the system was replaced with nitrogen gas.
After that, the reaction solution was cooled and analyzed.
Bononitriles (4) were obtained.

To this reaction solution were added water and ethyl acetate for 5 times each.
After adding 00 g and leaving the mixture for 5 hours with stirring, the organic layer was separated and ethyl acetate was evaporated off. Next, vacuum distillation was carried out to obtain 132.0 g of a mixture of 1,3-cyclohexanedicarbonitrile and 1,4-cyclohexanedicarbonitrile as a fraction having a pressure of 0.5 to 1.0 mmHg and a temperature of 120 to 130 ° C. As a result of analyzing this fraction, it was found that the composition was 64.4% of 1,3-cyclohexanedicarbonitrile and 35.6% of 1,4-cyclohexanedicarbonitrile. The results of elemental analysis of the target product are shown below.

[0071] Example 1 Production of diguanamines (1): 146.2 g (1.0 mol) of dicarbonitrile (3) obtained by the method of Reference Example 1 was placed in a 31 flask equipped with a stirrer, a thermometer and a reflux condenser.
210.2 g (2.5 mol) of dicyandiamide, 16.8 g of potassium hydroxide
g and 1000 ml of methyl cellosolve were charged and gradually heated. As the temperature rises, the reaction solution becomes transparent,
When the temperature reached around 105 ° C., the reaction rapidly progressed, generating a large amount of heat and refluxing the solvent. Some time after the start of reflux, the reaction solution became cloudy. The solution was reacted for 10 hours while stirring at a temperature of 120 to 125 ° C.

Next, after the solvent was removed from the reaction mixture, 31 deionized water was poured, and the precipitated white precipitate was separated by filtration. This solid was washed with deionized water, washed with methanol, and decompressed. Dried. Further, this solid was dissolved in ethyl cellosolve, and deionized water was added to this solution, followed by reprecipitation and filtration, and the obtained solid was washed with water. The solid content was dried under reduced pressure to give 2,5-bis (4,6-diamino-1,3,5-
Triazin-2-yl) -bicyclo [2.2.1] heptane and 2,5-bis (4,6-diamino-1,3,5-triazine-
A mixture of 2-yl) -bicyclo [2.2.1] heptane [white powdery crystals, melting point 317 to 324 ° C (DSC measurement) was obtained. still,
As a result of analyzing the reaction mixture (before treatment) by liquid chromatography, the yield (mol%) of the above diguanamines (1) was 98.2% (based on the charged amount of dicarbonitrile (3)). And compounds other than the intended compound
It was 0.08% by weight (based on the charged amount of dicarbonitrile (3)). The results of elemental analysis and ¹ H magnetic resonance absorption spectrum analysis of the target product are shown below. FIG. 1 shows the results of infrared absorption spectrum analysis of the target substance, and FIG. 2 shows the results of mass spectrum analysis.

[0073] ¹ H nuclear magnetic resonance absorption spectrum analysis (internal standard: TMS
, Solvent: d ₆ -DMSO) Absorption based on NH ₂ group δ value 6.50 ppm (singlet) 6.72 ppm (singlet) Example 2 2,5-bis (4,6-diamino-1,3,5-triazine) -2
Preparation of -yl) -bicyclo [2.2.1] heptane: Example 1
In place of 146.2 g (1.0 mol) of the dicarbonitrile (3) obtained by the method of Reference Example 1 in Example 2, the bicyclo [2.2.1] heptane-2,5-dicarbonitrile obtained by the method of Reference Example 2 The reaction was carried out in the same manner as in Example 1 except that 160.8 g (1.1 mol) was used, and the reaction mixture was treated. The obtained solid is dried under reduced pressure to give 2,5-bis (4,6-diamino-1,3,5-triazin-2-yl)-
Bicyclo [2.2.1] heptane [white powder, melting point 318
~ 321 ° C (DSC measurement) was obtained. Incidentally, as a result of analyzing the reaction mixture (before treatment) by liquid chromatography, the yield (mol%) of the diguanamines (1) was 96.4% (based on the charged amount of dicarbonitrile (3)). Was. In the infrared absorption spectrum of the target product, the absorption of nitrile having the starting compound (2235 cm ^-1 ) disappeared, and the absorption of triazines newly appeared (821 cm ^-1 ), and the measured value of elemental analysis was calculated as follows. Good agreement with values.

[0074] Example 3 Production of diguanamines (2): 134.2 g (1.0 mol) of dicarbonitrile (4) obtained by the method of Reference Example 3 was placed in a 31 flask equipped with a stirrer, a thermometer and a reflux condenser.
210.2 g (2.5 mol) of dicyandiamide, 16.8 g of potassium hydroxide
g and 1000 ml of methyl cellosolve were charged and gradually heated. As the temperature increased, the reaction solution became transparent, and when the temperature reached about 105 ° C., the reaction proceeded rapidly, generating a large amount of heat and refluxing the solvent. Some time after the start of reflux, the reaction solution became cloudy. The solution was reacted for 10 hours while stirring at a temperature of 120 to 125 ° C.

Next, after removing the solvent from the reaction mixture, 31 deionized water was poured, and the precipitated white precipitate was separated by filtration. The solid was washed with deionized water, washed with methanol, and decompressed. Dried. Further, this solid was dissolved in ethyl cellosolve, and deionized water was added to this solution, followed by reprecipitation and filtration, and the obtained solid was washed with water. The solid was dried under reduced pressure to give 1.3-bis (4,6-diamino-1,3,5-
Triazin-2-yl) -cyclohexane and 1.4-bis (4,6-diamino-1,3,5-triazin-2-yl)
A mixture of cyclohexane [white powdery crystals, mp 317
321 ° C. (DSC measurement)]. In addition, as a result of analyzing the reaction mixture (before treatment) by liquid chromatography, the yield (mol%) of the diguanamines (2) was 97.3%.
(Based on the charged amount of dicarbonitrile (4)), and 0.12% by weight (based on the charged amount of carbonitrile (4)) of the compound other than the raw material and the intended target compound. The results of elemental analysis and ¹ H nuclear magnetic resonance absorption spectrum analysis of the target product are shown below. FIG. 3 shows the result of infrared absorption spectrum analysis of the target product, and FIG. 4 shows the result of mass spectrum analysis.

[0076] ¹ H nuclear magnetic resonance absorption spectrum analysis (internal standard: TMS
, Solvent: d ₆ -DMSO) Absorption based on NH ₂ group δ value 6.49 ppm (singlet) Example 4 1.4-Bis (4,6-diamino-1,3,5-triazine-2)
Preparation of -yl) -cyclohexane: dicarbonitrile (4) obtained by the method of Reference Example 3 in Example 3 134.
The reaction was carried out in the same manner as in Example 3 except that 147.6 g (1.1 mol) of 1,4-cyclohexanedicarbonitrile was used instead of 2 g (1.0 mol), and the reaction mixture was treated. The obtained solid was dried under reduced pressure to give 1.4-bis (4,6-diamino-1,3,5-triazin-2-yl)-
Cyclohexane [white powdery crystals, melting point 319-322 ° C (D
SC measurement)]. Incidentally, as a result of analyzing the reaction mixture (before treatment) by liquid chromatography, the yield (mol%) of the above diguanamines (2) was 95.8% (based on the charged amount of dicarbonitrile (4)). Was. In the infrared absorption spectrum of the target product, the absorption of nitrile (2237 cm ^-1 ) contained in the starting compound disappears, and the absorption of triazines (821 cm ^-1 ) newly appears, and the measured value of elemental analysis is calculated as follows. Good agreement with values.

[0077] ¹ H nuclear magnetic resonance absorption spectrum analysis (internal standard: TMS
, Solvent: d ₆ -DMSO) Absorption based on NH ₂ group δ value 6.50 ppm (singlet) Example 5 1.2-Bis (4,6-diamino-1,3,5-triazine-2)
Preparation of -yl) -cyclohexane: dicarbonitrile (4) obtained by the method of Reference Example 3 in Example 3 134.
The reaction was carried out in the same manner as in Example 3 except that 134.2 g (1.0 mol) of 1,2-cyclohexanedicarbonitrile was used instead of 2 g (1.0 mol), and the reaction mixture was treated. The obtained solid was dried under reduced pressure to obtain 1.2-bis (4,6-diamino-1,3,5-triazin-2-yl) -cyclohexane as white powdery crystals. In the infrared absorption spectrum of the target product, the absorption of the nitrile contained in the raw material compound disappeared, and the absorption of a triazine ring newly appeared.

[0078] Example 6 Production of diguanamines (1): The reaction and treatment were carried out in the same procedures as in Example 1 except that the charged amount (mol) of dicyandiamide and the type of the reaction solvent in Example 1 were changed.
The yield of the target compound, diguanamines (1), is shown in Table 1.
It is shown in FIG.

[0079]

[Table 1] (Note 1) Indicates the value calculated from the result of liquid chromatography analysis of the obtained reaction mixture (before treatment). Example 7 Production of diguanamines (1): 146.2 g (1.0 mol) of dicarbonitrile (3) obtained by the method of Reference Example 1 and dicyandiamide were placed in a 31 flask equipped with a stirrer, a thermometer and a reflux condenser. 210.2
g (2.5 mol), 54.0 g of sodium methylate, and 1000 ml of dimethyl sulfoxide, and gradually heated. When the temperature approached 105 ° C, the reaction rapidly progressed, and the heat generation became remarkable. Thereafter, the temperature was gradually raised to 140 ° C.
The solution was reacted for 2 hours while stirring at a temperature of 140 to 145 ° C.

Next, the reaction mixture was treated in the same manner as in Example 1 to give 2,5-bis (4,6-diamino-1,3,5-
Triazin-2-yl) -bicyclo [2.2.1] heptane and 2,6-bis (4,6-diamino-1,3,5-triazine-
A mixture of 2-yl) -bicyclo [2.2.1] heptane was obtained. The reaction mixture (before treatment) was analyzed by liquid chromatography, and as a result, the above-mentioned diguanamines (1) were analyzed.
Was 99.7% (based on the charged amount of dicarbonitrile (3)). Example 8 Production of diguanamines (2): The reaction and treatment were carried out in the same procedure as in Example 3 except that the charged amount (mol) of dicyandiamide and the type of the reaction solvent in Example 3 were changed.
The yield of the target compound, diguanamines (2), is shown in Table 1.
It is shown in FIG.

[0081]

[Table 2] (Note 1) Indicates the value calculated from the result of liquid chromatography analysis of the obtained reaction mixture (before treatment). Example 9 1.4-Bis (4,6-diamino-1,3,5-triazine-2
Preparation of -yl) -cyclohexane: 134.2 g (1.0 mol) of 1,4-cyclohexanedicarbonitrile, 210.2 g (2.5 mol) of dicyandiamide, sodium methylate 5 were placed in a 31 flask equipped with a stirrer, thermometer and reflux condenser.
4.0 g and 1000 ml of dimethyl sulfoxide were charged and gradually heated. When the temperature approached 105 ° C, the reaction rapidly progressed, and the heat generation became remarkable. Then gradually increase the temperature to 140
° C. The solution was reacted for 2 hours while stirring at a temperature of 140 to 145 ° C.

Next, the reaction mixture was treated in the same manner as in Example 3 to give 1,4-bis (4,6-diamino-1,3,5-triazin-2-yl) as white powdery crystals. -Cyclohexane was obtained. As a result of analyzing the reaction mixture (before treatment) by liquid chromatography, the yield (mol%) of the above diguanamines (2) was 99.1% (based on the charged amount of dicarbonitrile (4)). Was.

As shown in Examples 1 to 9, the diguanamines according to the present invention can be provided. Furthermore, a specific dicarbonitrile and dicyandiamide can be used to prepare a reaction catalyst, a solvent, a reaction temperature, and a raw material molar ratio. According to the production method of appropriately selecting and reacting, etc., the by-products are remarkably excellent because the expected target compound can be obtained with a very small amount of by-products, high purity, simple production and purification steps, and a high yield. . Example 10 Production of N-methylolated diguanamines (1) and water dilutability test of the derivatives: 15.7 g (0.05 mol) of diguanamines (1) obtained by the method of Example 1 were added to a 10% aqueous solution of caustic soda. 42.2g of 37% formalin adjusted to pH 10.5 with
(Formaldehyde 0.52 mol) was added. The mixture was heated with stirring at a temperature of 60-65 ° C for 30 minutes. This reaction mixture was a homogeneous and transparent liquid. As a result of analysis, it was found that 7.2 mol of formaldehyde was methylol-bonded to 1 mol of the diguanamine (1).

Further, 50 g of deionized water was gradually added to the obtained N-methylolated solution at room temperature, and the solution was uniform and transparent. Example 11 Production of N-methylolated product of diguanamines (2) and water dilutability test of the compound: 15.1 g (0.05 mol) of diguanamines (2) obtained by the method of Example 3 were added to a 10% aqueous solution of caustic soda. 42.2g of 37% formalin adjusted to pH10.5 with
(Formaldehyde 0.52 mol) was added. The mixture was heated with stirring at a temperature of 60-65 ° C for 30 minutes.

This reaction mixture is a homogeneous and transparent liquid,
As a result of analysis, it was found that 7.3 mol of formaldehyde was methylol-bonded to 1 mol of the diguanamine (2).

Further, 50 g of deionized water was gradually added to the obtained N-methylolated solution at room temperature, and the solution was uniform and transparent.

As shown in Examples 10 and 11, the N-methylol compounds of diguanamines according to the present invention are extremely excellent in water dilutability, and are extremely excellent as a water-based resin raw material such as a water-based paint resin. It was found to be extremely useful for various applications. Comparative Example 1 Production of N-methylolated phthaloguanamine and water dilutability test of the compound: 15.7 g (0.05 mol) of diguanamines (1) obtained by the method of Example 1 in Example 10
Instead of o-phthaloganamin 14.8 g (0.05 mol)
The reaction was carried out in the same manner as in Example 10, except for using.

This reaction mixture is a liquid in which a large amount of insoluble solids are present. The liquid is subjected to solid-liquid separation by hot filtration, and the solid content is dried under reduced pressure to obtain 13.7 g of crystals. 13.6 g (0.046 mol)]. Further, when 1.0 g of deionized water was added to this solution at room temperature, the solution became extremely cloudy. Comparative Example 2 Production of N-methylolated spiroguanamine and water dilutability test of the compound: 15.7 g (0.05 mol) of diguanamines (1) obtained by the method of Example 1 in Example 10
In place of 3,9-bis [2- (3,5-diamino-2,
4,6-triazaphenyl) ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane [(trade name) CTU guanamine, manufactured by Ajinomoto Co.] 21.7 g (0.05 mol) The reaction was carried out in the same procedure as in Example 10.

This reaction mixture is a liquid containing a large amount of insoluble solids, which is subjected to solid-liquid separation by hot filtration, and the solids are dried under reduced pressure to obtain 18.3 g of crystals [18. (0.042 mol). Further, when 1.0 g of deionized water was added to this solution at room temperature, it became extremely cloudy.

As shown in Comparative Examples 1 and 2, the above-mentioned phthaloguanamine and spiroguanamine have a very slow methylolation reaction with aldehydes, the amino group reactivity in such compounds is poor, and melamine, guanamines and ureas Not only is it difficult to produce resin intermediates such as copolycondensation products with various compounds, and various derivatives, but also N-methylol compounds of such compounds have extremely poor water dilutability and are used as aqueous resin raw materials such as aqueous paints. Not only is it difficult to do this, but it also has significant restrictions on applications. Example 12 Production of N-methylolated product of diguanamines (1): 15.7 g of diguanamines (1) obtained by the method of Example 1
(0.05 mol) and 17.9 g of 37% formalin (formaldehyde 0.22
Mol) was added. The mixture was heated with stirring at a temperature of 70-75 ° C for 30 minutes. The reaction mixture was a clear liquid, and as a result of analyzing this, the diguanamines (1) 1
4.0 moles of formaldehyde were bonded to the moles with respect to moles. Example 13 Production of N-methylolated product of diguanamines (1): 15.7 g of diguanamines (1) obtained by the method of Example 1
(0.05 mol), 19.9 g (0.32 mol) of methyl hemiformal and 40.0 g of methanol were added, and the pH was adjusted to 9.5 with a 20% aqueous potassium hydroxide solution. The mixture was heated with stirring at a temperature of 60 ° C. for 1 hour. The reaction mixture was a clear liquid, and as a result of analysis, it was found that 6.1 mol of formaldehyde was methylol-bonded to 1 mol of the diguanamine (1). Example 14 Production of N-methylol compound of diguanamines (1): 2,5-bis (4,6-diamino- obtained by the method of Example 2
1,3,5-Triazin-2-yl) -bicyclo [2.2.1] To 15.7 g (0.05 mol) of heptane with 5% aqueous sodium hydroxide solution
81.2 g of 37% formalin (1.0 mol of formaldehyde) adjusted to pH 10.5 was added. This mixture is heated at 60 ° C for 1
Heat with stirring for hours. The reaction mixture was a clear liquid, and as a result of analysis, 2,5-bis (4,6-diamino-1,3,5-triazin-2-yl) -bicyclo [2.
2.1] One mole of heptane was 7.8 moles of formaldehyde bonded to methylol. Example 15 Production of N-methoxymethylated diguanamines (1): diguanamines (1) obtained by the method of Example 10
A reaction mixture of 5.0 g of N-methylol compound (7.2 mol bond of formaldehyde to 1 mol of the diguanamine) was dehydrated under reduced pressure, and 50 ml of methanol was added thereto. The mixture was adjusted to pH 2.0 with 20% nitric acid and then heated at a temperature of 40-45 ° C for 2 hours. The reaction mixture was adjusted to pH 8.0 with a 10% aqueous sodium hydroxide solution, methanol and water were removed under reduced pressure, and the solid was filtered to obtain a viscous liquid. As a result of analysis, it was found that 5.3 equivalents of N-methoxymethyl group was bonded to 1 mol of the diguanamine (1). Example 16 Production of N-methoxymethylated diguanamines (2): diguanamines (2) obtained by the method of Example 11
A reaction mixture of 5.0 g of N-methylolated product (7.3 moles of formaldehyde per mole of the diguanamine) was added to
Dehydration was performed under reduced pressure, and 50 ml of methanol was added thereto. The mixture was adjusted to pH 2.0 with 20% nitric acid and then heated at a temperature of 40-45 ° C for 2 hours. 10% of the reaction mixture
After adjusting the pH to 8.0 with an aqueous sodium hydroxide solution, methanol and water were removed under reduced pressure, and the solid was filtered to obtain a viscous liquid. As a result of analyzing this, the diguanamines (2)
4.9 equivalents of N-methoxymethyl group was bonded to 1 mole.

As shown in Examples 15 and 16, the N-methylolated diguanamines of the present invention easily undergo an alkyl etherification reaction under mild conditions with alcohol, and have extremely excellent reactivity. And an N-alkoxymethylated product of the compound which is extremely useful as a resin intermediate. Example 17 Production of N-methylolated initial condensate of diguanamines (2): diguanamines (2) obtained by the method of Example 4
To 15.1 g (0.05 mol), paraformaldehyde (80%
13.1 g (formaldehyde 0.35 mol) and 50 ml of methanol were added, and the mixture was adjusted to pH 13.2 with a 20% aqueous potassium hydroxide solution while stirring. The mixture was heated with stirring at a temperature of 80 ° C. for 1 hour. After heating is complete, the reaction mixture is
The pH was adjusted to 8.0 with a 10% aqueous hydrochloric acid solution, and the precipitate was filtered to obtain a uniform transparent solution. As a result of analyzing the resinous substance obtained by removing the solvent from this solution, the diguanamines (2)
6.0 mol of formaldehyde was methylol-bonded to one structural unit, and it was an N-methylolated diguanamine precondensate having an average degree of addition condensation of 1.3. Example 18 Preparation of initial etherified condensate of diguanamine (1): 15.7 g of diguanamine (1) obtained by the method of Example 1
(0.05 mol), paraformaldehyde (80% product) 18.8
g (0.50 mol of formaldehyde) and n-butanol 50
Add 10 ml of caustic soda solution while mixing and stirring.
The pH was adjusted to 11.0. The mixture was heated with stirring at a temperature of 60 ° C. for 30 minutes, and a 20% aqueous nitric acid solution was added thereto to adjust the pH.
Adjusted to 3.0. Further, the reaction mixture was heated with stirring for 2 hours while performing reflux dehydration under reflux temperature conditions. After the heating, the reaction mixture was adjusted to pH 8.0 with a 10% aqueous sodium hydroxide solution, and the precipitate was filtered to obtain a uniform and transparent solution. As a result of analyzing the resinous substance obtained by removing the solvent from this solution, 1.9 mol of formaldehyde was methylol-bonded to one diguanamine (1) structural unit, and the average degree of addition condensation containing a butyl ether group was 1.6.
Was an etherified diguanamine precondensate. Example 19 Polymerization of N-methylolated diguanamine and UV resistance test of the resin: N-methylolated product of diguanamine (1) obtained by the method of Example 10 (based on 1 mol of diguanamine (1)) Formaldehyde 7.2 mol bond)
5.0 g was dissolved in 10 ml of n-butyl alcohol, and 0.025 g of p-toluenesulfonic acid was added as a curing catalyst, applied to a galvanized steel sheet, and then cured by heating at 140 ° C. for 20 minutes.

Using this coated steel sheet, a test steel sheet was irradiated for 200 hours from a height of a vertical distance of 25 cm using a germicidal lamp (Toshiba 19W) as an ultraviolet light source. The surface gloss of the test steel sheet was measured in accordance with JIS K 5400 (60 ° specular reflectance). As a result, the gloss retention was 97%. Example 20 Polymerization of N-methylolated diguanamine and UV resistance test of the resin: N-methylolated product of diguanamine (2) obtained by the method of Example 11 (based on 1 mol of diguanamine (2) Formaldehyde 7.3 molar bond)
5.0 g was dissolved in 10 ml of n-butyl alcohol, and 0.025 g of p-toluenesulfonic acid was added as a curing catalyst, applied to a galvanized steel sheet, and then cured by heating at 140 ° C. for 20 minutes.

Using the coated steel sheet, a test steel sheet was irradiated for 200 hours from a height of a vertical distance of 25 cm using a germicidal lamp (19W manufactured by Toshiba) as an ultraviolet light source. The surface gloss of the test steel sheet was measured according to JIS K 5400 (60 ° specular reflectance), and as a result, the gloss retention was 98%.

As shown in Examples 19 and 20, the N-methylolated diguanamines according to the present invention are excellent in polymerizability, and the compounds have very little deterioration in gloss due to ultraviolet rays and have very excellent properties. Was something. Example 21 Wrinkle resistance test of fiber treating agent using N-methylolated diguanamine: N-methylolated product of diguanamines (1) obtained by the method of Example 10 (the diguanamines (1)
Using 7.2 moles of formaldehyde per mole)
A 10% by weight aqueous solution was prepared with deionized water. to this,
As a catalyst, 3% by weight of ammonium diphosphate (based on the solid content of the derivative) was added. Using this solution, dipped in cotton cloth (cotton 60 broad) and padded,
This cotton cloth is pre-dried at 80 ° C. for 5 minutes, and further dried for 140 minutes.
Heat treatment was performed at a temperature of -5 minutes.

Using this treated cotton cloth, a wrinkle resistance test was performed according to JIS.
As a result of performing in accordance with L1059 (Monsanto method), the wrinkle resistance was 86%, and extremely excellent wrinkle resistance was exhibited.

As described above, when a fiber is treated with the N-methylolated diguanamine according to the present invention, the fiber can be provided with very excellent properties such as anti-wrinkling property. Is extremely useful as a fiber treatment agent. Example 22 Curing test of water-based paint resin using N-methylolated diguanamine: N-methylolated product of diguanamine (1) obtained by the method of Example 10 (the diguanamine (1)
6.0 mol of formaldehyde (7.2 mol bond to 1 mol)
While stirring a 50% by weight aqueous solution to 40.0 g of Armatex WA 911 [manufactured by Mitsui Toatsu Chemical Co., Ltd., NV 60%], 1.84 g of dimethylethanolamine is gradually added, and then the non-volatile content is adjusted to 20% with deionized water. The resulting solution was mixed. The obtained resin solution was applied to a galvanized steel sheet and then heat-treated at 160 ° C. for 20 minutes.

[0097] The coating film of the treated coated steel sheet was
No blistering, discoloration, etc. were observed, and the surface gloss of the coating film was measured according to JIS K
As a result of measuring according to 5400 (60 ° specular reflectance), gloss
It was 98% and had extremely excellent smoothness and gloss.
Further, the coating film was a sufficiently cured excellent coating film without peeling off even after rubbing the coating surface 50 times with a cloth impregnated with acetone. Example 23 Curing test of water-based paint resin using N-methylolated diguanamine: N-methylolated product of diguanamines (2) obtained by the method of Example 11 (the diguanamines (2)
7.3 g formaldehyde to 1 mol) 5.9 g
Dimethylethanolamine (1.84 g) was gradually added with stirring to 40.0 g of Armatex WA 911 (manufactured by Mitsui Toatsu Chemicals, NV 60%) and then deionized water was used to reduce the nonvolatile content to 20%. The mixture was added to the prepared solution and mixed. After applying the obtained resin solution to the galvanized steel sheet,
Heat treatment was performed under the conditions of minutes.

[0098] The coating film of the treated coated steel sheet is
No blistering, discoloration, etc. were observed, and the surface gloss of the coating film was measured according to JIS K
As a result of measuring according to 5400 (60 ° specular reflectance), gloss
It was 94% and had extremely excellent smoothness and gloss.
Further, the coating film was a sufficiently cured excellent coating film without peeling off even after rubbing the coating surface 50 times with a cloth impregnated with acetone.

As shown in Examples 21 to 23, the diguanamine derivative according to the present invention has extremely excellent water dilutability,
The thermosetting composition containing this is not only excellent as a water-based resin such as a water-based paint resin, a resin for an adhesive, and a treatment agent for a fiber, but also has a curability and a cross-linking property of a paint resin. And it was found to be extremely useful for a wide range of applications. Example 24 Curing test of water-based paint resin using N-methoxymethylated diguanamine: N-methoxymethylated product of diguanamine (1) obtained by the method of Example 15 [based on 1 mol of diguanamine (1) N-methoxymethyl group 5.3 equivalents]
6.8 g of a 50% by weight solution obtained by dissolving 6.8 g of a butyl cellosolve-water (weight ratio: 50/50) mixed solvent and 0.15 g of p-toluenesulfonic acid were mixed with Armatex WA 911 (manufactured by Mitsui Toatsu Chemicals, NV60). %) While gradually adding 1.84 g of dimethylethanolamine with stirring to 40.0 g, and adding to a solution adjusted to have a nonvolatile content of 20% with deionized water and mixing. The obtained resin solution was applied to a galvanized steel sheet and then heat-treated at 160 ° C. for 20 minutes.

[0100] The coating film of the treated coated steel sheet was
No blistering, discoloration, etc. were observed, and the surface gloss of the coating film was measured according to JIS K
As a result of measuring according to 5400 (60 ° specular reflectance), gloss
It was 96% and had extremely excellent smoothness and gloss.
Further, the coating film was a sufficiently cured excellent coating film without peeling off even after rubbing the coating surface 50 times with a cloth impregnated with acetone.

As described above, the etherified diguanamine according to the present invention is excellent in polymerizability, and the thermosetting resin composition containing the etherified product and a resin capable of reacting with and curing the etherified product is as follows: It was found to be extremely useful as a resin for water-based paints. Example 25 Polymerization of N-methoxymethylated diguanamine and weather resistance test of the resin: N-methoxymethylated product of diguanamine (2) obtained by the method of Example 16 [based on 1 mol of diguanamine (2) N-methoxymethyl group 4.9 equivalents]
After dissolving 4.9 g in 10 g of methyl isobutyl ketone,
To this, Armatex P 646 [Mitsui Toatsu Chemical Co., Ltd.
NV60%] was added and mixed. After applying this resin solution to a galvanized steel sheet, it was cured by heating at 180 ° C. for 50 minutes.

Using this coated steel sheet, an exposure test was performed for 500 hours using a weather O-meter. No blister, discoloration, etc. were observed on the surface of the coating film of the test steel sheet, and the surface gloss of the coating film was measured in accordance with JIS K 5400 (60 ° specular reflectance). As a result, the gloss retention was 95%. . Example 26 Polymerization of Etherified Diguanamine Precondensate and Weathering Test of Condensate: Etherified Precondensate of Diguanamine (1) Obtained by Method of Example 18 [Structural Unit 1 of Diguanamine (1) Average addition condensation degree per individual 1.6] 5.0g
Was dissolved in 10 g of methyl isobutyl ketone, and then added to Armatex P 646 [NV60 manufactured by Mitsui Toatsu Chemicals, Inc.]
%] 47.2 g was added and mixed. After applying this resin solution to a galvanized steel sheet, it was heated and cured at 160 ° C. for 30 minutes.

Using this coated steel sheet, an exposure test was performed for 500 hours using a weather O-meter. No blisters, discoloration, etc. were found on the surface of the coating film of the test steel sheet, and the surface gloss of the coating film was measured in accordance with JIS K 5400 (60 ° specular reflectance). As a result, the gloss retention was 97%. .

As shown in Examples 25 and 26, the etherified diguanamine and the etherified precondensate according to the present invention are excellent in polymerizability, and further contain their derivatives and resins curable by reacting with these derivatives. The cured product obtained from the resulting thermosetting resin composition also has excellent weather resistance, and has been found to be extremely useful as a resin for paints and the like. Example 27 Curing test of epoxy group-containing resin with diguanamines (1): 100 g of epoxy group-containing resin Epicoat ^# 828 (product of Shell) was dissolved in 100.0 g of butyl cellosolve,
Diguanamines obtained by the method of Example 1 (1)
19.6 g was added and dissolved to prepare a resin solution. After applying this resin solution to galvanized steel sheet, at 110 ° C for 30 minutes,
Further heating was performed at 200 ° C. for 40 minutes. The coating film of the heat-treated coated steel sheet was coated with a cloth impregnated with toluene to form a coating film of 5%.
Even after rubbing 0 times, no peeling of the coating was observed, and the coating was a sufficiently cured and excellent transparent coating. Example 28 Curing test of epoxy group-containing resin with diguanamines (2): obtained by the method of Example 3 in place of 19.6 g of diguanamines (1) obtained by the method of Example 1 in Example 27 A resin solution was prepared in the same manner as in Example 27 except that 18.9 g of diguanamines (2) was used, and a coating film curing test was performed.

The coated film of the heat-treated coated steel sheet showed no peeling even after rubbing the coated surface 50 times with a cloth impregnated with toluene, and was a sufficiently cured excellent transparent coated film. Met. Example 29 Storage stability test of thermosetting resin composition: An epoxy group-containing resin and a diguanamine were blended in the kinds and amounts shown in Table 3, and 90 to 90% before each component became sufficiently uniform. 110
The mixture was kneaded for 15 to 30 minutes with two rolls heated to ℃, taken out into a sheet, and pulverized. Using this sample, it was left standing in a dryer kept at 40 ° C. to determine the storage stability. Table 3 shows the results.

As shown in Table 3, it was found that the thermosetting resin composition according to the present invention had extremely excellent storage stability.

[0107]

[Table 3] Example 30 Flexibility test of cured resin obtained from thermosetting resin composition: epoxy group-containing resin Epicoat ^# 828 (product of Shell) 100 g and diguanamines (1) 19.6 obtained by the method of Example 1 g were kneaded with two rolls preheated to 90 to 110 ° C. for 30 minutes until the respective components became sufficiently uniform, and were taken out into a sheet and pulverized. Using this sample 190
A cured resin product was prepared under a curing condition of 3 ° C. for 3 hours. Using this cured resin, a Charpy impact value was measured as a measure of flexibility. Table 4 shows the results.

As a comparative example, dicyandiamide was used in place of the above-mentioned diguanamines, and a resin cured product was prepared in the same manner as described above under the optimum blending amount and curing conditions.
The Charpy impact value was measured.

[0109]

[Table 4] As shown in Table 4, the cured resin obtained from the thermosetting resin composition according to the present invention was found to be excellent in flexibility. Example 31 Weather resistance test of cured coating film obtained from thermosetting resin composition: Epoxy group-containing resin Almatex PD ^# 7610 [Mitsui Toatsu Chemical Co., Ltd., epoxy equivalent 530 (solid content)] 100.
0 g was dissolved in 200 g of butyl cellosolve, and 11.1 g of diguanamines (1) obtained by the method of Example 1 was added and dissolved to prepare a resin solution. After applying this resin solution to a galvanized steel sheet, it was cured by heating at 200 ° C. for 40 minutes.

The coated steel sheet was exposed to a weather O-meter for 300 hours to conduct a weather resistance test. As a result of measuring the surface gloss of the coating film on the test steel sheet in accordance with JIS K 5400 (60 ° specular reflectance), the gloss retention was 94%.

As described above, it has been found that a cured resin obtained from the thermosetting resin composition according to the present invention has excellent weather resistance and is extremely useful as a resin for paints and the like. Example 32 Test of coating film of resin for powder coating obtained from thermosetting resin composition: A resin solution of thermosetting resin composition obtained by the method of Example 31 was used. The solvent was removed to obtain a solid resin. Further, the solid resin was coarsely pulverized by a coarse pulverizer and then finely pulverized by an atomizer. This one
The mixture was sieved with a 50-mesh sieve, and the pass product was used as a resin for powder coating in the test. Using this resin for powder coating, a zinc phosphate chemical conversion treated dull steel plate was electrostatically coated so as to have a film thickness of about 50 microns, and heated at 200 ° C. for 40 minutes.

The coating film of the heat-treated coated steel sheet had good coating film smoothness (visual judgment), and peeling of the coating film was not observed even if the coating film surface was rubbed 50 times with a cloth impregnated with toluene. It was an excellent transparent coating which was sufficiently cured.

Further, using this coated steel sheet, a test steel sheet was irradiated for 200 hours from a height of 25 cm vertically using a germicidal lamp (19W made by Toshiba) as an ultraviolet light source. No gloss was observed, and the surface gloss of this coating film was measured in accordance with JIS K 5400 (60 ° specular reflectance). As a result, the gloss retention was 96%, and the coating film had excellent ultraviolet resistance. Was something. Example 33 Adhesion test of thermosetting resin composition: 100 g of epoxy group-containing resin Epicoat ^# 828 (manufactured by Shell) and 15.7 g of diguanamines (1) obtained by the method of Example 1 were blended. The mixture was kneaded with two rolls preheated to 90 to 110 ° C. for 30 minutes until the components were sufficiently uniform. A steel sheet was adhered using the kneaded resin and cured at 200 ° C. for 1 hour. Tensile shear bond strength of this cured resin (25 ° C)
Was 176 kg / cm ² .

As described above, it was found that the thermosetting resin composition according to the present invention has excellent adhesiveness and is extremely useful as an adhesive resin or the like.

[0115]

The diguanamines according to the present invention have remarkably excellent weather resistance, ultraviolet resistance, etc., can maintain their intended functions for a long period of time outdoors and the like, and have extremely low water dilutability of a methylol compound of the compound. It has almost no restrictions as a water-based resin raw material such as water-based paints, and has excellent performance. It has an active amino group with extremely good reactivity with formaldehyde and epoxy compounds, and has eight active hydrogens. Therefore, it has properties such that the degree of methylolation can be selected widely, and further, flexibility, toughness,
It also has excellent properties such as high hardness, water resistance, and curability, and can provide compounds, resins, compositions, and the like having excellent properties, and is useful for an extremely wide range of applications. Furthermore, the method for producing diguanamines according to the present invention is characterized in that by reacting a specific dicarbonitrile with dicyandiamide under specific conditions, by-products are extremely low in purity, production by a purification / separation step and the like is simple, Another object of the present invention is to provide an excellent method for obtaining an intended compound in high yield by using inexpensively available dicarbonitrile.

The diguanamines are excellent in polymerizability with various compounds such as aldehydes, epoxies, carboxylic acids and isocyanates, and are also excellent in various reactivities, and are extremely useful as resin raw materials and derivative raw materials. For example, N-methylolated diguanamine, etherified diguanamine obtained by reaction with aldehydes and the like, curing agents for various resins such as initial condensates thereof, derivatives useful as resin raw materials, containing these derivatives A thermosetting resin composition containing the above-mentioned diguanamines and an epoxy group-containing resin useful as a thermosetting composition, a resin for coatings, a resin for adhesives, etc. This is an extremely superior invention.

[Brief description of the drawings]

FIG. 1 is an infrared absorption spectrum of one example of a compound according to Example 1.

FIG. 2 is a mass spectrum diagram of one example of a compound according to Example 1.

FIG. 3 is an infrared absorption spectrum of one example of the compound according to Example 3.

FIG. 4 is a mass spectrum diagram of an example of a compound according to Example 3.

──────────────────────────────────────────────────の Continued on the front page (72) Inventor Masami Inomata 1900 Togo, Mogo-shi, Chiba Prefecture Inside Mitsui Toatsu Chemicals Co., Ltd. In-house (72) Inventor Junyo Yamauchi 1900 Togo, Mobara-shi, Chiba Mitsui Toatsu Chemicals Co., Ltd. Inventor Shigeru Nakahata 1-6-6 Takasago, Takaishi City, Osaka Pref., Mitsui East Pressure Chemical Co., Ltd. (72) Inventor Katsumi Sakamoto 1-6-6 Takasago, Takaishi City, Osaka Pref. Shin No. 1-6-6 Takasago, Takaishi-shi, Osaka Mitsui East Pressure Chemical Co., Ltd. (72) Inventor Akito Watanabe 1-6 Takasago, Takaishi-shi, Osaka Mitsui East Pressure Chemical Within the company (56) Reference Patent flat 5-202007 (JP, A) (58 ) investigated the field (Int.Cl. ^7, DB name) C07D 251/18 CA (STN) REGISTRY (STN)

Claims (16)

(57) [Claims] [Claim 1] The general formula (2) [Wherein, the bonding position of the (4,6-diamino-1,3,5-triazin-2-yl) group indicates the 1,2-, 1,3- or 1,4-position]. Diguanamines. 2. A compound of the general formula (4) (Wherein the bonding position of the cyano group indicates the 1,2-, 1,3- or 1,4-position) wherein dicyandiamide is reacted with dicyandiamide in the presence of a basic catalyst. A method for producing diguanamines, characterized in that: 3. The basic catalyst is an alkali metal, an alkali metal hydroxide, an alkaline earth metal hydroxide, an alkali metal alcoholate, an alkali metal salt of dicyandiamide,
3. The method for producing diguanamines according to claim 2, wherein the method is at least one selected from the group consisting of alkaline earth metal salts of dicyandiamide, amines and ammonia. 4. The process for producing diguanamines according to claim 2, wherein the reaction is carried out using at least one selected from the group consisting of a non-aqueous protonic solvent and a non-protonic polar solvent as a reaction solvent. 5. The process for producing diguanamines according to claim 2, wherein the reaction is carried out at a temperature of 60 to 200 ° C. 6. A compound of the general formula (1) [Wherein (4,6-diamino-1,3,5-triazine
-2-yl) group is bonded at the 2,5- or 2,6-position
Or the general formula (2) : [Wherein (4,6-diamino-1,3,5-triazine
The bonding position of the (-2-yl) group is 1,2-, 1,3- or
N-methylolated diguanamine obtained by subjecting a diguanamine represented by 1,4-position] to an aldehyde. 7. At least one R ¹ obtained by subjecting the N-methylolated diguanamine according to claim 6 to an etherification reaction with at least one selected from alcohols having 1 to 20 carbon atoms. Etherified diguanamine having an OCH ² group (R ¹ represents a residue obtained by removing a hydroxyl group from the above alcohols). 8. A compound of the general formula (1) [Wherein (4,6-diamino-1,3,5-triazine
-2-yl) group is bonded at the 2,5- or 2,6-position
Or the general formula (2) : [Wherein (4,6-diamino-1,3,5-triazine
The bonding position of the (-2-yl) group is 1,2-, 1,3- or
Which represents an 1,4-position] and an aldehyde together with a compound capable of co-condensation, if necessary, having an average degree of addition condensation of at least 1 and at least one methylol. N-methylolated diguanamine precondensate having a group. 9. A compound of the general formula (1) [Wherein (4,6-diamino-1,3,5-triazine
-2-yl) group is bonded at the 2,5- or 2,6-position
Or the general formula (2) : [Wherein (4,6-diamino-1,3,5-triazine
The bonding position of the (-2-yl) group is 1,2-, 1,3- or
1,4-position] and an aldehyde together with a compound capable of co-condensation, if necessary, with an aldehyde,
An etherification reaction is performed with at least one selected from alcohols having from 20 to 20 alcohols, and a condensation reaction is optionally carried out at the same time.
An etherified diguanamine precondensate having a larger size and at least one R ¹ OCH ² group (R ¹ has the same meaning as described above). 10. An N-methylolated diguanamine according to claim 6, an etherified diguanamine according to claim 7, an N-methylolated diguanamine precondensate according to claim 8, and an etherified diguanamine precondensate according to claim 9. A thermosetting composition comprising as an essential component at least one member selected from the group consisting of: 11. A resin which is capable of reacting with the essential component according to claim 10 and being curable.
0 thermosetting composition. 12. A coating resin composition comprising the thermosetting composition according to claim 11. . 13. A compound of the general formula (1) [Wherein (4,6-diamino-1,3,5-triazine
-2-yl) group is bonded at the 2,5- or 2,6-position
Or the general formula (2) : [Wherein (4,6-diamino-1,3,5-triazine
The bonding position of the (-2-yl) group is 1,2-, 1,3- or
Which represents a 1,4-position] and a resin having an epoxy group. 14. A coating resin composition comprising the thermosetting resin composition according to claim 13. 15. The resin composition according to claim 13, which is a powder coating resin composition.
The coating resin composition according to the above. 16. An adhesive resin composition comprising the thermosetting resin composition according to claim 13.