JPH06157482A - Diguanamines, their production, derivative and use - Google Patents

Abstract

PURPOSE:To obtain new compounds, useful as a polymerizable monomer, a coating resin, a resin for adhesives, etc., and excellent in weather and ultraviolet ray resistance, reactivity of amino groups, etc. CONSTITUTION:The compounds of formula I (the binding positions of 4,6- diamino-1,3,5-triazin-2-yl group indicate the 3,5- or 2,6-positions) or formula II (the binding positions of the 4,6-diamino-1,3,5-triazin-2-yl group indicate the 1,2-, 1,3-or 1,4-positions), e.g. 2,5-bis(4,6-diamino-1,3,5-triazin-2-yl)- bicyclo[2.2.1]heptane. These compounds of formula I are obtained by reacting, e.g. a compound of formula III with dicyandiamide in the presence of a basic catalyst (e.g. an alkali metal or an alkali metallic hydroxide) in a nonaqueous protonic solvent or an aprotic polar solvent at 60-200 deg.C.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a polymerizable monomer, a coating resin, an adhesive resin, a paper processing resin, a fiber processing resin, a powder coating resin, a resin raw material for building materials, a guanamine compound derivative. , A novel diguanamine compound useful as a curing agent for epoxy resins, urethane resins, etc., a polymer modifier for rubber materials, etc., and a method for producing the same, a curing agent for various resins, a resin raw material intermediate, etc. The present invention relates to the above-mentioned diguanamine derivatives and uses of the above-mentioned diguanamines and their derivatives.

[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, and modifiers for rubber materials, As a modifier of organic materials, it has high hardness and good gloss, is colorless and transparent, has high chemical resistance and water resistance, has excellent abrasion resistance and electrical properties, and has a resin pot life as a curing agent. Therefore, guanamines such as melamine and benzoguanamine having an aminotriazine group have been widely used because they have excellent properties such as excellent.

Further, various researches and developments have been carried out on such melamine and guanamines having an aminotriazine group, and excellent properties such as flexibility, toughness, high hardness, water resistance and curability of the resin are exhibited. Polyfunctional guanamines having four or more functional functional groups have been provided to the world.

The polyfunctional guanamines have completely different structures from the novel diguanamines according to the present invention and it is extremely difficult to compare and contrast them.

[0005]

[Chemical 5] Phthaloguanamine represented by

[0006]

[Chemical 6] There is spiroguanamine represented by.

However, since the former compound is extremely inferior in ultraviolet resistance and weather resistance of the resin obtained from such compound as a raw material, the resin such as exterior coating, weather resistant coating, automobile coating, resin for building materials, etc. It cannot be used as a raw material at all, or has significant restrictions, and the water dilutability of phthaloguanamine-based amino resins, which are derivatives of such compounds, is somewhat improved compared to conventional melamine-based amino resins. However, it is still insufficient in practical use, and has drawbacks such as significant restrictions when used as a resin raw material such as a resin for water-based paints. Further, the latter compound is inferior in heat resistance of a resin obtained from such a compound as a raw material,
Since the weather resistance, ultraviolet resistance, and water resistance of the resin are poor,
It has a defect that it is difficult to maintain a desired function outdoors for a long time as an exterior paint, weather resistant paint, automobile paint, resin for building materials, etc. Further, the methylolation reaction of the latter compound is slower than melamine, benzoguanamine, etc., because the reactivity of the amino group in such a compound is poor. Therefore, useful guanamine of the guanamine provided by reacting the amino group Various derivatives, resins, various resin curing agents, such compounds and melamine,
It has a defect that the production of a formaldehyde copolycondensation product with a compound such as benzoguanamine is significantly limited. Furthermore, the reaction mixture obtained by the methylolation reaction of such a compound is difficult to obtain a transparent solution, and therefore an aqueous resin,
For example, water-based paint resin, adhesive resin, paper processing resin,
When it is used as a resin raw material such as a resin for fiber processing, it is difficult to obtain sufficient performance such as smoothness, curability and physical properties 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 the purification process is complicated. It has defects such as being damaged.

As mentioned above, these compounds have been technically and economically restricted in use and production.

[0009]

Means for Solving the Problems The inventors of the present invention have made extensive studies in view of the above-mentioned deficiencies in guanamines, and as a result, have compounds having various functional groups and active amino groups exhibiting extremely excellent reactivity. And since it has 8 active hydrogens, the degree of methylolation etc. can be widely selected,
It is remarkably excellent in weather resistance and ultraviolet resistance, and can maintain its intended function for a long time outdoors. Furthermore, the methylol compound is excellent in performance such as water dilutability, curability, water resistance, stain resistance, flexibility, hardness and toughness. For reference, the above-mentioned polyfunctional guanamines have a structure, a diguanamine having a completely different characteristic is found, and further, in the production of such a diguanamine, a desired product is obtained in a highly pure product having very few by-products, The present invention has been accomplished by finding an excellent production method by which a desired target compound can be obtained in high yield by using dicarbonitriles which can be easily produced at a low cost such as purification and separation steps.

As a derivative obtained by using such useful diguanamines, N-methylol diguanamine obtained by reacting with aldehydes, and its N
-Etherified diguanamine obtained by etherifying a methylol compound and alcohol, an initial condensate thereof is produced, and a derivative thereof which is useful as a resin raw material such as a curing agent for various resins and a resin for paints is contained. A thermosetting resin composition containing the above-mentioned diguanamines and an epoxy group-containing resin, which are useful as a resin for coating, a resin for powder coating, a resin for adhesives, etc. The inventors have also found out that they have reached the present invention.

The above-mentioned diguanamines are rubber modifiers,
Optical materials, resist materials, electrical insulation materials, automotive paints, home appliance paints, antifouling paints, weather resistant paints, fluorescent paints,
Resins for building materials, powder coatings, water-based coatings, oil-based coatings, paper processing resins, fiber processing resins, adhesive resins, IC sealant resins, corrosion resistant resins, polymer modifiers, leather treatment agents 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) the general formula (1)

[0013]

[Chemical 7] [In the formula, the bonding position of the (4,6-diamino-1,3,5-triazin-2-yl) group represents the 2,5- or 2,6-position], or the general formula (2)

[0014]

[Chemical 8] [In the formula, the bonding position of the (4,6-diamino-1,3,5-triazin-2-yl) group is 1,2-, 1,3- or 1,4-position] Diguanamines, (b)
General formula (3)

[0015]

[Chemical 9] (In the formula, the bonding position of the cyano group is 2,5- or 2,6-
Position) or general formula (4)

[0016]

[Chemical 10] (In the formula, the bonding position of the cyano group represents the 1,2-, 1,3- or 1,4-position), and the dicarbonitriles are reacted with dicyandiamide in the presence of a basic catalyst. A method for producing a diguanamine compound characterized by:
Basic catalyst is alkali metal, alkali metal hydroxide,
At least one selected from the group consisting of alkaline earth metal hydroxides, alkali metal alcoholates, alkali metal salts of dicyandiamide, alkaline earth metal salts of dicyandiamide, amines, and ammonia (b) above A method for producing a diguanamine according to the item,
(D) The method for producing a diguanamine according to (B) above, wherein the reaction is carried out using at least one selected from the group consisting of a non-aqueous protic solvent and an aprotic polar solvent as a reaction solvent. E) The reaction is carried out at a temperature of 60 to 200.
The method for producing a diguanamine according to the above (b), which is carried out in the range of ° C, (f) N-methylol obtained by the addition reaction of the diguanamines according to the above (a) with an aldehyde Diguanamine, (g) N-methylol diguanamine according to the above (f) and 1 to 20 carbon atoms
At least one selected from alcohols having individual
An etherified diguanamine having at least one R ₁ OCH ₂ group (R ₁ represents a residue obtained by removing a hydroxyl group from the above alcohols) obtained by an etherification reaction with a seed; ] The average degree of addition condensation obtained by subjecting the diguanamines described in the item 1) and a compound capable of co-condensation, together with an aldehyde, to an addition condensation reaction is 1
A larger N-methylol diguanamine precondensate having at least one methylol group, (i) above
(I) At least one selected from the alcohols having 1 to 20 carbon atoms by subjecting the diguanamines according to the item (1) and optionally a compound capable of cocondensation to an aldehyde with an addition reaction or an addition condensation reaction. Have an average degree of addition condensation of more than 1 and have at least one R ₁ OCH ₂ group (R ₁ has the same meaning as described above) Etherified diguanamine initial condensate, (nu) above
(F) N-methylol diguanamine according to the above item,
Item 6. Etherified diguanamine described in the above item, N described in the above item (H)
-Methylolated diguanamine initial condensate and (i) above
A thermosetting composition characterized by containing at least one selected from the group consisting of etherified diguanamine initial condensates as an essential component, (l) curing by reacting with the component described in (u) above. A thermosetting composition according to the above item (u), characterized by containing a possible resin, (wo) above
(L) A coating resin composition containing the thermosetting composition according to the item (W), a thermosetting method comprising the diguanamines according to the item (A) above and an epoxy group-containing resin Resin composition, (f) a coating resin composition containing the thermosetting resin composition according to (v) above, (yo) a coating according to (f) above which is a powder coating resin composition Resin composition, (ta) Above (wa)
An adhesive resin composition comprising the thermosetting resin composition as described in the item.

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 the 2,5- or 2,6-position, but the steric configuration of such a group is endo-endo, endo-exo or exo-exo, and both are It is a useful compound.

Further, such diguanamines (1) are
Although the compound is selected from the group consisting of isomers having the above-mentioned bonding positions and configurations, it is an industrially extremely useful compound in the aggregate of different compounds selected from the group, 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 (endo-endo 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 according to the present invention (2)
In, the bonding position of the (4,6-diamino-1,3,5-triazin-2-yl) group is 1,2-, 1,3- or 1,4-position, but the steric structure of such group is The configurations are trans or cis, both of which are useful compounds.

Further, such diguanamines (2) are
Although the compound is selected from the group consisting of isomers having the above-mentioned bonding positions and configurations, it is an industrially extremely useful compound in the aggregate of different compounds selected from the group, 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]

[Chemical 11] (In the formula, the bonding position of the cyano group is 2,5- or 2,6-
Position) or general formula (4)

[0025]

[Chemical 12] (In the formula, the binding position of the shimino group represents 1,2-, 1,3-, or 1,4-position) A method of reacting dicarbonitriles with dicyandiamide in the presence of a basic catalyst. , A dicarboxylic acid ester corresponding to dicarbonitrile and a biguanide may be reacted in the presence of a basic compound, if necessary. In the former method, the raw materials are easily available and easy to handle, the desired target compound is obtained with a high degree of purity with very few by-products, and the purification and separation steps are easy to manufacture,
It is technically and economically excellent and extremely practicable from the viewpoints that the raw material loss is extremely small and the desired compound can be obtained in a high yield. The method for producing such diguanamines is not limited to these methods.

In the dicarbonitriles (3) in the method for producing diguanamines according to the present invention, the bonding position of the cyano group is the 2,5- or 2,6-position, but the steric configuration of such groups is endo-. End type, endo-exo type or exo-exo type are all useful. Further, such dicarbonitriles (3) are compounds selected from the group consisting of isomers having the above-mentioned bonding positions and configurations, but even in the aggregate of different compounds selected from such groups,
It is as useful as a single compound.

The above-mentioned dicarbonitriles (3) are, for example, as disclosed in US Pat. No. 2666748,
Bicyclo [2.2.1] hept-5-ene-2-carbonitrile and cyanogen hydrogen are converted into CO ₂ (CO) ₈ , Fe (CO) ₅ , Ni [P
(OC ₆ H _{5) 3]} a method reacting at a specific presence of a catalyst such as _4, are disclosed in U.S. Pat. No. 3,143,570, etc. 5- (and / or 6) cyano - bicyclo [2.2. 1] Method for reacting hepta-2-carbaldehyde with hydroxylamines, 2,5- (and / or 2,6) dichloro-bicyclo [2.2.1] heptane with cyanated alkali metal 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 such dicarbonitriles (3) include bicyclo [2.2.1] heptane-2,5-dicarbonitrile (endo-exo form), bicyclo [2.2.1] heptane-2, 5-dicarbonitrile (end-to-end type),
Bicyclo [2.2.1] heptane-2,6-dicarbonitrile (endo-exo form), bicyclo [2.2.1]
Examples thereof include heptane-2,6-dicarbonitrile (exo-exo form), but are not limited to these compounds.

In the dicarbonitriles (4) in the method for producing diguanamines according to the present invention, the bonding position of the cyano group is 1,2-, 1,3- or 1,4-position. The configuration is trans or cis, and both are useful compounds. Further, the dicarbonitriles (4) are compounds selected from the group consisting of isomers having the above-mentioned bonding positions and configurations, but even in the aggregate of different compounds selected from such groups, a single compound As useful as it is.

The above-mentioned dicarbonitriles (4) can be used as 4 carbon atoms as disclosed in, for example, US Pat.
-Cyano-cyclohexene and hydrogen cyanide were mixed with 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) A method of reacting a dihalogenated cyclohexane corresponding to the above with a cyanating agent such as an alkali metal cyanide or an alkaline earth metal cyanide, a dicarboxylic acid corresponding to the above dicarbonitrile (4) or a diammonium thereof. Obtained by a method of reacting a salt, a diamide, a diester derivative and ammonia with an alumina catalyst or a dehydrating agent such as thionyl chloride, a method of reacting 1-cyano-cyclohexene and hydrogen cyanide in the presence of an alkali such as caustic soda, etc. However, the method is not limited to these methods.

Specific examples of such dicarbonitriles (4) include 1,2-cyclohexanedicarbonitrile (trans type), 1,3-cyclohexanedicarbonitrile (trans type) and 1,3-cyclohexanedicarbonitrile. Examples thereof include nitrile (cis type), 1,4-cyclohexanedicarbonitrile (trans type), and 1,4-cyclohexanedicarbonitrile (cis type), but are not limited to these compounds.

Further, in the method for producing diguanamines according to the present invention, the reaction molar ratio of such dicarbonitriles and dicyandiamide can be appropriately selected if necessary. The reaction molar ratio between such dicarbonitriles and dicyandiamide is stoichiometrically 1: 2. If the molar ratio of dicyandiamide to dicarbonitriles is used in an excessively small amount, the diguanamines according to the present invention will be used. Of not only low yield but also monoguanamine [1: 1 (molar ratio) reaction product of dicarbonitriles and dicyandiamide)
And the purification and separation steps are complicated, which is not preferable, and when a large excess amount is used, removal and separation of unreacted dicyandiamide and the like are complicated, which is not preferable from a technical and economical viewpoint. In order to improve the yield of the diguanamines according to the present invention and to simplify the production such as the purification and separation step, the molar ratio of dicyandiamide to dicarbonitriles is usually dicyandiamide to 1 mol of dicarbonitriles.
It is preferable to carry out the reaction at a ratio of 1.5 to 10.0 mol, preferably 2.0 to 5.0 mol.

Examples of the basic catalyst in the method 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 metal, alkaline earth metal hydroxide, potassium carbonate, sodium carbonate, barium carbonate and other alkali metal, alkaline earth metal carbonate, potassium ethylate, sodium methylate, sodium ethylate and other alkali metal alcoholate, Alkali metal or alkaline earth metal salts of dicyandiamide, 1,8-diazabicyclo [5.4.0] undecene-7, triethylenediamine, piperidine, ethylenediamine, diethylenetriamine, pyrrolidone, amines such as tetrahydroquinoline, ammonia, etc. And the like. Especially alkali metals,
Alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal alcoholates, dicyandiamide alkali metal salts, dicyandiamide alkaline earth metal salts, amines and ammonia are preferred, and these are used alone or in combination with 2
More than one species may be used. Further, the addition amount of such a catalyst is not particularly limited, but from the viewpoint of production conditions and economical efficiency, it is preferably 500 to 0.001 mol%, and more preferably 0.001 mol% with respect to the dicarbonitrile.
The amount is 300 to 0.1 mol%, and can be appropriately selected if necessary.

Further, in the method for producing such diguanamines, a method of using various solvents as a reaction solvent in order to carry out the reaction more smoothly is extremely useful. A solvent that causes inhibition,
For example, solvents such as fatty acid, the acid anhydride, trifluoroacetic acid, liquid sulfur dioxide, sulfuryl chloride, mineral acid and water are not preferable.

Examples of the 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-tri 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, N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, carboxylic acid amides such as 1,3-dimethyl-2-imidazolidinone, sulfolane , Sulfolanes such as methylsulfolane and 1,3-propanesultone, sulfoxides such as dimethylsulfoxide, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, isopropylamine, butylamine, 2-ethylhexylamine, allylamine, aniline, Cyclohexylamine, pyridine, piperidine, monoethanolamine, 2- (dimethylamino) ethanol, diethanolamine, triethanolamine, isopropanolamine, triisoprene 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. Incidentally, 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, dimethylsulfoxide and cellosolve, etc., and can be appropriately selected if necessary. The water content is preferably as low as possible, particularly preferably 1.0% by weight or less.

Further, such a reaction is not preferable at a reaction temperature of 60 ° C. or less because the reaction is extremely slow, it takes a long time for production and the yield is extremely low. Usually 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 to obtain the desired target compound in high yield. However, when the reaction temperature exceeds about 200 ° C, the production temperature of by-products rapidly increases to a non-negligible level and the product purity is significantly lowered, so that the reaction temperature of 200 ° C or higher is not preferable. Therefore, in the method for producing diguanamines according to the present invention, it is more preferable to carry out such production at a reaction temperature in the range of 60 to 200 ° C., more preferably 80 to 180 ° C. The desired compound can be obtained, the production such as the purification and separation step can be more easily performed, and the desired compound can be obtained in a higher yield.

The system of such reaction is not particularly limited, but may be under normal pressure or under a natural pressure in a closed container.
Further, it can be carried out under pressure, and can be appropriately selected if necessary.

Further, in order to obtain the intended diguanamines according to the present invention from the reaction mixture of the above reaction, it is best to cool the reaction solution and filter out the crystallized diguanamines. However, the reaction mixture may be poured as it is into hot water for crystallization filtration. Unreacted dicyandiamide and / or dicarbonitriles associated with the crude diguanamines can be easily separated and removed by washing the crude diguanamines with hot water or methanol.
Depending on the purpose of use, when further purification is required, the reaction solvent described above, for example, alcohols, cellosolves, carboxylic acid amides, sulfolanes, sulfoxides, etc., a mixed solvent of these solvents and water, water, etc. Recrystallization method, dissolving in the above-mentioned reaction solvent, pouring it into hot water for reprecipitation, dissolving crude diguanamines in hydrochloric acid acidic aqueous solution, and mixing this with alkali to reprecipitate diguanamines It can be performed by a method or the like. However, the production method of the diguanamines according to the present invention has an extremely good yield, and the diguanamines are those having a sufficiently high purity for practical use simply by washing with various solvents such as methanol, water, and a mixed solvent thereof. Therefore, the above-mentioned purification method is practically unnecessary.

The diguanamines according to the present invention are excellent in polymerizability with various compounds such as aldhydrides, epoxies, carboxylic acids, and isocyanates, and also excellent in various reactivities, and are extremely useful as resin raw materials and derivative raw materials. However, a diguanamine derivative such as a reaction product with an aldehyde, a reaction product obtained by etherifying this reaction product with an alcohol, a reaction product obtained by subjecting these reaction products to a condensation reaction, etc. It is particularly useful as a curing agent, a resin raw material and the like.

Examples of such diguanamine derivatives include those represented by the following general formula (5) and general formula (6) obtained by addition reaction of the above-mentioned derivative (f) diguanamines described in the above (a) with aldehydes. N-methylol diguanamine represented by the general formula (5)

[0040]

[Chemical 13] [In the formula, 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 kind selected from H atom and HOCH ₂ group, and R
₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ may be the same or different species] General formula (6)

[0041]

[Chemical 14][Wherein (N-substituted-4,6-diamino-1,3,5-to
The bonding position of the riazin-2-yl) group is 1,2-, 1,3
-Or 1,4-position, R₂ , R₃ , R_Four , R_Five , R ₆ , R
₇ And R₈ Represents the above meaning, R₂ , R₃ , R_Four ，
R_Five , R₆ , R₇And R₈ Can be the same species or different species
May be used] (g) The N-methylol diol described in (f) above.
Of guanamine and alcohols having 1 to 20 carbon atoms
Etherification reaction with at least one selected from
At least 1 R obtained by₁OCH₂Group (R₁Is
(Indicates the residue obtained by removing the hydroxyl group from the above alcohols)
Having the following general formulas (7) and (8)
Diguanamine telluride, general formula (7)

[0042]

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

[0043]

[Chemical 16] [In the formula, the bonding positions of the (N-substituted-4,6-diamino-1,3,5-triazin-2-yl) group are 1,2-, 1,3
-Or 1,4-position, R ₁ is a residue obtained by removing a hydroxyl group from the above alcohols, R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄
And R ₁₅ have the above-mentioned meanings, and R ₉ , R ₁₀ , R ₁₁ and R
₁₂ , R ₁₃ , R ₁₄ and R ₁₅ may be the same or different species.] (H) Addition condensation reaction of the diguanamines described in the above (A) with an optional aldehyde together with a compound capable of co-condensation The N-methylol diguanamine initial condensate having an average addition condensation degree of more than 1 and having at least one methylol group obtained by the above, (i) optionally co-condensable with the diguanamines according to the above (a) With another compound, an aldehyde is subjected to an addition reaction or an addition condensation reaction, and then at least one selected from alcohols having 1 to 20 carbon atoms is subjected to an etherification reaction, and optionally a condensation reaction is performed at the same time. The average addition condensation degree thus obtained is greater than 1 and at least one R ₁ OCH ₂ group (R ₁ has the same meaning as described above)
And an etherified diguanamine initial condensation product having

Examples of the above-mentioned aldehydes used for the production of these derivatives include formaldehyde, paraform, hexamethylenetetramine, methyl hemiformal, butyl hemiformal, formaldehyde sodium bisulfite adduct, glyoxal, etc., preferably formaldehyde. , Formalin, paraform, hexamethylenetetramine, methylhemiformal, and butylhemiformal, but 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. Alcohol, alcohol having an aromatic group, 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,
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 can be mentioned, but not limited thereto.

In the production of these derivatives, a compound which can be co-condensed can be optionally used as described above. Examples of such a co-condensable compound include melamine, urea, alkylurea, thiourea, alkylthiourea, and the like. Examples thereof include guanamines such as aniline, benzoguanamine, and cyclohexylcarboguanamine, but are not limited thereto.

The above-mentioned N-methylol diguanamine can be used, for example, in a solvent, if necessary in the presence of a basic compound, at pH 8.0 to 13.0, preferably pH 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 at least one HO
Although a derivative having a CH ₂ group can be obtained, in the case of obtaining a highly methylolated N-methylol diguanamine, a high purity and a high yield can be obtained by reducing the amounts of water and alcohols. Although it can be obtained well, if excessively reduced, it is not preferable because it causes deterioration of stirring effect, nonuniformity of reaction temperature, etc., and hinders smooth reaction. Are insoluble and do not inhibit the reaction, for example, toluene, xylene, ethylbenzene, cumene, aromatic hydrocarbons such as benzene, hexane, heptane, octane, aliphatic hydrocarbons such as cyclohexane, halogenated hydrocarbons such as dichloromethane, Method carried out in the presence of aliphatic ether such as diisopropyl ether, amines such as hexamethylenetetramine, piperazine, piper Add 0.01 to 10 mol% of aliphatic amines such as lysine, aliphatic amines such as triethylamine, diethylamine, dibutylamine, hexylamine, aromatic amines such as pyridine and aniline, and auxiliary agents such as ammonia to aldehydes. How to do it is useful,
It can be appropriately selected depending on the case, and is not limited to these methods.

The above-mentioned etherified diguanamine is obtained by, for example, adding the N-methylol diguanamine obtained above to pH.
1 to 8 in the presence of the above-mentioned alcohols for carrying out the etherification reaction under the acidic conditions of 2 to 4 at a temperature of 40 to 80 ° C.
It can be obtained by reacting for a time, but in particular, the amount of water in the reaction system is reduced as much as possible, and the molar ratio of the charged reaction is 20 mol or more of the above alcohols per mol of N-methylol diguanamine. Is preferred.

The above-mentioned N-methylol diguanamine initial condensate 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 conditions of pH 8.0 or lower or pH 13.0 or higher.

Further, the above-mentioned etherified diguanamine initial condensate is, for example, the N-methylol diguanamine or N-methylol diguanamine initial condensate obtained above at 50 to 100 ° C. under acidic conditions of pH 1.0 to 5.0. The etherification reaction is carried out at a temperature, which can be obtained by carrying out the etherification reaction or the etherification reaction and the condensation reaction simultaneously in the presence of the above-mentioned alcohols.
It is not limited to these methods.

N-methylol diguanamine as described above,
The etherified diguanamine, N-methylol diguanamine initial condensation product, and etherified diguanamine initial condensation product are
It has extremely high 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, (f), (to), (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 (b) as an essential component, and even in the case of having only these derivatives as a curing component. , Glue, fiber,
For example, polyester fibers, synthetic fibers such as acrylic fibers,
Cotton, natural wrinkles and other wrinkle-proofing agents, excellent surface modifiers such as stain-proofing agents, paper processing agents, useful as a thermosetting composition such as leather treatment agent, but further, 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 cross-linking agent, a curing agent, a modifier, a modifier, etc. together with various polymers such as resin, aminoalkyd resin, phenol resin, fluororesin and vinyl resin. It is useful for a wide range of applications such as adhesive resins, paint resins, and building material resins.
In particular, it contains at least one selected from the group consisting of the above-mentioned N-methylol diguanamine, etherified diguanamine, N-methylol diguanamine initial condensate and etherified diguanamine initial condensate, and a resin curable by reaction therewith. The thermosetting composition characterized in that it is useful as a resin for paints such as a resin for water-based paints and a resin for oil-based paints.

The above-mentioned curable resin that reacts with these is useful as long as it is a resin having a functional group that reacts with and cures with the above-mentioned derivative. For example, hydroxyl group, carboxyl group, epoxy group, methylolamide group, At least one of alkoxymethylolamide group and isocyanate group
Resins containing seeds are useful and include, but are not limited to, acrylic resins, epoxy resins, polyester resins, phenol resins, phenol / alkyd resins, urethane resins, fluororesins, silicone resins, and modified resins thereof. Not something.

The diguanamines according to the present invention provide 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 in which an amine is used as a curing agent in an epoxy group-containing resin cures at a relatively low temperature, but the amines used as a curing agent are chemically active. It has a drawback that it reacts when stored, the pot life is shortened and it is difficult to handle, and the composition containing dicyandiamide as a curing agent is
It has relatively good storage stability, but this resin cured product is flexible,
There is a drawback that properties such as light resistance are not good, and these were remarkably limited in use.However, as a result of diligent studies in view of these drawbacks, the present inventors have found that the composition has excellent storage stability and is acceptable. The above-mentioned thermosetting resin composition has been found that can provide a resin cured 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.

The epoxy group-containing resin according to the present invention can be widely used as long as it is a resin having one or more epoxy groups, but is usually a polyepoxide having two or more epoxy groups per molecule. Well, 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 resorcin, 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 Xytetraphenylethane, polyglycidyl ether of novolac type phenol formaldehyde resin, triglycidyl ether of trimethylolpropane, triglycidyl ether of glycerin, diglycidyl ether type epoxy resin of halogenated bisphenol A, ha Polyglycidyl ether of rogenated novolak type phenol formaldehyde resin, vinyl cyclohexene dioxide, cycloaliphatic epoxy resin such as 3,4-epoxycyclohexylmethyl 3,4 epoxycyclohexanecarboxylate, hydantoin epoxy resin, triglycidyl isocinaurate, etc. Heterocyclic epoxy resins, epoxy group-containing vinyl monomers such as glycidyl acrylate and glycidyl methacrylate, and acrylic acid esters, methacrylic acid esters, fumaric acid esters, maleic acid esters, acrylamides, methacrylamides, acrylonitrile, methacryloyl Examples thereof include polymers with copolymerizable vinyl monomers such as nitriles, styrenes, butadienes and vinyl esters, and modified polymers thereof. Not intended to be constant.

In the present invention, when the polymer type bisphenol A diglycidyl ether type epoxy resin cannot be used due to its high viscosity, bisphenol A, bisphenol S, brominated bisphenol A, brominated bisphenol S, etc. can be used as the modifier. Alternatively, a low molecular weight bisphenol A glycidyl ether type epoxy resin or the like may be used for modification.

The compounding ratio of the diguanamines and the epoxy group-containing resin according to the present invention can be appropriately selected depending on the case, but usually, the ratio of the diguanamines is 0.2 to 3.0 equivalents relative to the epoxy group-containing resin / epoxy equivalent. Yes,
The ratio is preferably 0.4 to 1.5 equivalents.

Further, in the thermosetting resin according to the present invention, a curing accelerator such as a novolac type phenol resin, an organic acid metal salt or an imidazole may be appropriately selected and blended, but a novolac type phenol resin is particularly preferable. The use of is preferable because a thermosetting resin composition having excellent storage stability and curability can be obtained. Examples of the novolac 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 those obtained by using a conventional method, but the invention is not limited thereto. The compounding ratio of this novolac 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 the above-mentioned diguanamines, epoxy group-containing resin, and optionally other ingredients in a predetermined compounding ratio as raw material ingredients in a Z-Blade mixer, extruder, dry It can also be obtained by a method of sufficiently mixing mechanically by a ball mill or the like, and further, by a method of performing melt mixing by a hot roll or the like, however, since the diguanamines according to the present invention have a high melting point, the flow may be non-uniform. In some cases, inhomogeneity of the cured product may occur, and when it is not preferable, the above-mentioned diguanamines and a low-viscosity diluent, a compatibilizer, a novolac type phenol resin, etc. are heated and melt-mixed in advance, and then an epoxy group-containing resin is blended. Heating and mixing, 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, the thermosetting resin composition according to the present invention contains, in addition to the above-mentioned diguanamines and epoxy group-containing resins, inorganic fillers such as silica powder, alumina, antimony trioxide and talc, if necessary. , Calcium carbonate, titanium white, clay, mica, red iron oxide, glass fiber, carbon fiber, natural waxes, synthetic waxes, metal salts of fatty acids, acid amides, esters, paraffins and other release agents, chlorinated paraffins , Bromtoluene,
Hexabromobenzene, flame retardants such as antimony trioxide,
A coloring agent such as carbon black or red iron oxide, a silane coupling agent, a flexibility-imparting agent, a viscosity reducing diluent, and various curing accelerators may be appropriately added and blended.

Further, the diguanamines according to the present invention are
Carboxylic acids such as phthalic acid, adipic acid, maleic acid, trimellitic acid, ethyletetracarboxylic acid, cyclopentanetetracarboxylic acid, pyromellitic acid, 3,3 ', 4,
4'-benzophenone tetracarboxylic acid, 2,2 ', 3,3'-
Benzophenonetetracarboxylic 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-anthracene tetracarboxylic acid, 1,2,7,8-
Phenanthrenetetracarboxylic acid, or a precursor thereof, a partial ester, an acid anhydride, by reacting with a halogen acylate and the like, a compound having excellent performance, a polyamic acid, a polyimide, it is possible to provide a resin such as polyamide. It is also possible to use 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-naphthalene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, etc., or by reaction of these with polyols, amines, water, etc. Compounds having excellent performance by reacting with a polyvalent isocyanate or the like, resins such as polyurea, compounds having an N-substituted unsaturated imide group such as monophenyl maleimide, monophenyl citraconimide, monophenyl itacone imide, 2 −
Chlorphenylmaleimide, 2,6-dichlorophenylmaleimide, 2-methylphenylmaleimide, 2,6-dimethylphenylmaleimide, 4-hydroxyphenylmaleimide, N, N'-ethylenebismaleimide, N, N'-hexamethylenebis Maleimide, N, N'-dodecane methylene bismaleimide, N, N'-m-phenylene bismaleimide, N,
N'-p-phenylene bismaleimide, N, N'-p-phenylene biscitraconimide, N, N'-p-phenylene bisitaconimide, N, N'-p-phenylene-endomethylene tetrahydrophthalimide, N, N '-4,4'-Diphenylmethane bismaleimide, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, N, N'-4,4'-dicyclohexylmethane bismaleimide, N, N'-m -Xylene bismaleimide, N, N'-diphenylcyclohexane bismaleimide, -4,4'-bismaleimide cinnamanilide, -4,4'-methylene-bis (2-isopropyl-6-
Methyl-phenylmaleimide), 2,2-bis [4- (4-maleimidophenoxy) phenyl] hexafluoropropane and the like to react to provide a resin or the like having excellent performance, and further various polymers, For example, it can be used as a metal extender having excellent characteristics such as urethane resin and epoxy resin, a cross-linking agent, a curing agent, a polymer modifier, etc., but is not limited thereto.

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

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

In the method for producing diguanamines according to the present invention, by using the above-mentioned specific compound and appropriately selecting the reaction catalyst, solvent, reaction temperature, raw material molar ratio, etc. The desired product can be obtained with a high purity, the purification and separation steps can be easily manufactured, the raw material loss is extremely small, and the desired product can be obtained at a high yield using raw materials that are available at low cost. And economically superior,
It is extremely practical.

Such diguanamines include aldehydes,
It is excellent in polymerizability with various compounds such as epoxies, carboxylic acids, and isocyanates, and also excellent in various reactivities, and is very useful as a resin raw material and a derivative raw material. For example, N obtained by reacting with aldehydes -Methylolated guanamine, etherified diguanamine obtained by the etherification reaction of the N-methylolation thereof and alcohol, a curing agent for various resins such as their initial condensates, and a derivative extremely useful as a resin raw material intermediate, Thermosetting composition containing the above-mentioned diguanamines and epoxy group-containing resin useful as a thermosetting composition containing a derivative, a resin for IC sealant, a resin for paint, a resin for adhesive, etc. A resin composition etc. can be provided.

The diguanamines according to the present invention are rubber modifiers, optical materials, resist materials, electric insulating materials, paints for home appliances, paints for automobiles, antifouling paints, corrosion resistant paints, weather resistant paints, fluorescent paints, powders. Body paints, water-based paints, oil-based paints, building materials, IC sealants, paper processing agents, curtains, sofas, wall cloths, carpets, etc. Textile processing agents such as processing, anti-wrinkle processing, water and oil repellent processing, adhesive resins, leather processing agents, plastic magnets, antioxidants for latex, corrosion inhibitors, electrophotographic photoreceptors, surfactants, agricultural chemicals, It is an excellent compound that can provide a guanamine derivative, a resin, and a composition which are industrially extremely useful as medicines and the like.

[0066]

EXAMPLES Next, reference examples and examples of the present invention will be described in more detail.
Reveal However, these reference examples and the description of the examples are related to the present invention.
The range is not limited to these. Reference Example 1 Production of dicarbonitriles (3): stirrer, thermometer, liquid
In a 500 ml flask equipped with an introduction tube and a condenser,
[2.2.1] Hept-5-ene-2-carbonitrile 297.
92 g (2.50 mol), Ni [P (OC₆H_Five)₃]_Four 8.77g (6.75 mm
Mol), ZnCl₂ 4.80 g (35.22 mmol), P (OC₆H _Five)₃ 
 Charge 32.27 g (0.104 mol), nitrogen gas is enough in the system
After replacing, keep the reaction mixture at 65 ° C with stirring.
It was Next, 94.59 g (3.50 mol) of ice-cold liquid hydrocyanic acid was added,
Use the reactor at a flow rate of 45-55 ml / hr for 3 hours.
After feeding, the reaction was further performed for 1 hour.

Next, after replacing the inside of the system with nitrogen gas, deionized water was added and the aqueous layer portion was separated and removed to obtain a semi-solid oily substance. This oily substance was filtered and distilled under reduced pressure to obtain 362.20 g.
(Yield 9901%) bicyclo [2.2.1] heptane-2,5-dicarbonitrile and bicyclo [2.2.1] heptane-2,6-
Mixture of dicarbonitrile (boiling point 129-137 ℃ / 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: In a 21 flask equipped with a stirrer, a thermometer, and a reflux condenser, 5-cyano-bicyclo [2.2.1] hept-2- Carbaldehyde 179.0 g (1.2 mol), N, O-bis (trifluoroacetyl) hydroxylamine 292.6 g (1.3
Mol), pyridine 197.8 g (2.5 mol), benzene 600
I charged ml. The mixture was stirred and heated for 3 hours while gradually heating and refluxing. Next, 500 ml of deionized water was added to this reaction mixture, and the aqueous layer portion was separated and removed to obtain an oily substance. This oily substance was distilled under reduced pressure to obtain 128.0 g (yield 73%).
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 dicarbonitriles (4): stirrer, thermometer, liquid
In a 500 ml flask equipped with an introduction tube and a cooler,
Ano-cyclohexene 188.6g, Ni [P (OC₆H_Five)₃]_Four 6.0
g, ZnCl₂ 3.0 g, P (OC₆H _Five)₃ Charge 23.9 g, nitrogen
After the system is sufficiently replaced with gas, the reaction mixture is stirred.
Was maintained at 75 ° C. Next, 42 mol% concentrated diluted with nitrogen
Degree of hydrogen cyanide gas into the reactor at a rate of 177.0 mmol / hr
It was supplied for 7 hours. Next, the system was replaced with nitrogen gas.
After that, the reaction solution was cooled and analyzed.
Vonitriles (4) were obtained.

Water and ethyl acetate were added to the reaction solution 5 times each.
00 g was added, and the mixture was left under stirring for 5 hours, then the organic layer was separated, and ethyl acetate was evaporated. 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 analysis of this fraction, the composition was 1,4-cyclohexanedicarbonitrile 64.4% and 1,4-cyclohexanedicarbonitrile 35.6%. The results of elemental analysis of the target product are shown below.

[0071] Example 1 Production of diguanamines (1): In a 31 flask equipped with a stirrer, a thermometer, and a reflux condenser, 146.2 g (1.0 mol) of dicarbonitriles (3) obtained by the method of Reference Example 1,
Dicyandiamide 210.2 g (2.5 mol), caustic potash 16.8
g and 1000 ml of methyl cellosolve were charged and gradually heated. As the temperature rises, the reaction solution becomes transparent and the temperature
When the temperature reached around 105 ° C, the reaction rapidly proceeded and the heat was generated remarkably and the solvent was refluxed. After a while after the reflux was started, the reaction solution became cloudy. This solution was reacted at a temperature of 120 to 125 ° C. for 10 hours while stirring.

Next, the reaction mixture was desolvated, deionized water (31) was poured, the white precipitate was filtered off, and the solids were washed with deionized water and then with methanol and depressurized. Dried. Further, this solid content was dissolved in ethyl cellosolve, deionized water was added to this solution, reprecipitation was performed, and then filtration was performed, and the obtained solid content 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 317-324 ° C (DSC measurement) was obtained. still,
As a result of analyzing this reaction mixture (before treatment) by liquid chromatography, the yield (mol%) of the above-mentioned diguanamines (1) was 98.2% (the charged amount of dicarbonitriles (3)), And compounds other than the target compound
It was 0.08% by weight (amount of dicarbonitrile (3) charged). The results of elemental analysis and ¹ H magnetic resonance absorption spectrum analysis of the target product are shown below. The infrared absorption spectrum analysis result of the target product is shown in FIG. 1, and the mass spectrum analysis result is shown in FIG.

[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 dicarbonitriles (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 was used. The reaction was carried out in the same procedure as in Example 1 except that 160.8 g (1.1 mol) was used to treat the reaction mixture. The solid thus obtained was dried under reduced pressure to give 2,5-bis (4,6-diamino-1,3,5-triazin-2-yl)-
Bicyclo [2.2.1] heptane [white powdery crystal, melting point 318
~ 321 ° C (DSC measurement) was obtained. As a result of analyzing this reaction mixture (before treatment) by liquid chromatography, the yield (mol%) of the above-mentioned diguanamines (1) was 96.4% (the charged amount of dicarbonitriles (3)). It was In the infrared absorption spectrum of the target product, the absorption of the nitrile containing the starting compound (2235 cm ^-1 ) disappeared, and the absorption of triazines (821 cm ^-1 ) newly appeared, and the measured values of elemental analysis were calculated as follows. Good agreement with the value.

[0074] Example 3 Production of diguanamines (2): In a 31 flask equipped with a stirrer, a thermometer, and a reflux condenser, 134.2 g (1.0 mol) of dicarbonitriles (4) obtained by the method of Reference Example 3,
Dicyandiamide 210.2 g (2.5 mol), caustic potash 16.8
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 approached 105 ° C, the reaction proceeded rapidly and the solvent was refluxed with significant heat generation. After a while after the reflux was started, the reaction solution became cloudy. This solution was reacted at a temperature of 120 to 125 ° C. for 10 hours while stirring.

Then, the reaction mixture was desolvated, deionized water (31) was poured, the white precipitate was filtered off, and the solids were washed with deionized water and then with methanol and depressurized. Dried. Further, this solid content was dissolved in ethyl cellosolve, deionized water was added to this solution, reprecipitation was performed, and then filtration was performed, and the obtained solid content was washed with water. The solid content 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, melting point 317
~ 321 ° C (DSC measurement)] was obtained. As a result of analyzing this reaction mixture (before treatment) by liquid chromatography, the yield (mol%) of the above-mentioned diguanamines (2) was 97.3%.
(The amount of the dicarbonitrile (4) charged) was 0.12% by weight for the compounds other than the raw material and the intended target compound (the amount of the carbonitrile (4) charged). The results of elemental analysis and ¹ H nuclear magnetic resonance absorption spectrum analysis of the target product are shown below. The infrared absorption spectrum analysis result of the target product is shown in FIG. 3, and the mass spectrum analysis result is shown in FIG.

[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
-Yl) -Cyclohexane production: dicarbonitriles (4) 134. obtained by the method of Reference Example 3 in Example 3.
The reaction mixture was treated by the same procedure 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). The obtained solid content was dried under reduced pressure to give 1.4-bis (4,6-diamino-1,3,5-triazin-2-yl)-
Cyclohexane [white powdery crystal, melting point 319-322 ° C (D
SC measurement)] was obtained. As a result of analyzing this reaction mixture (before treatment) by liquid chromatography, the yield (mol%) of the above-mentioned diguanamines (2) was 95.8% (the charged amount of dicarbonitriles (4)). It was In the infrared absorption spectrum of the target substance, the absorption of nitrile (2237 cm ^-1 ) contained in the raw material compound disappeared, and the absorption of triazines (821 cm ^-1 ) newly appeared, and the measured values of elemental analysis were calculated as follows. Good agreement with the value.

[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)
-Yl) -Cyclohexane production: dicarbonitriles (4) 134. obtained by the method of Reference Example 3 in Example 3.
The reaction was carried out by treating the reaction mixture in the same procedure 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). The obtained solid content 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 substance, the absorption of nitrile contained in the raw material compound disappeared, and the absorption of triazine ring newly appeared, and the measured values of elemental analysis were in good agreement with the calculated values as follows.

[0078] Example 6 Production of diguanamines (1): Reaction and treatment were carried out in the same procedure as in Example 1 by changing the charged amount (mol) of dicyandiamide and the type of reaction solvent in Example 1.
The yield of the target compound, diguanamines (1), is shown in Table-
Shown in 1.

[0079]

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

Then, 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. As a result of analyzing this reaction mixture (before treatment) by liquid chromatography, the above-mentioned diguanamines (1)
The yield (mol%) was 99.7% (the amount of dicarbonitrile (3) charged). Example 8 Production of Diguanamines (2): The reaction and treatment were carried out in the same procedure as in Example 3 while changing the charged amount (mol) of dicyandiamide and the type of reaction solvent in Example 3.
The yield of the target compound, diguanamines (2), is shown in Table-
2 shows.

[0081]

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

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

As shown in Examples 1 to 9, the diguanamines according to the present invention can be provided. Furthermore, a reaction catalyst, a solvent, a reaction temperature, and a molar ratio of raw materials can be obtained by using a specific dicarbonitrile and dicyandiamide. According to the production method of appropriately selecting and reacting, etc., the byproduct was remarkably excellent in that the amount of by-products was extremely low, the purity was high, the purification separation step was easy to produce, and the desired target compound could be obtained in high yield. . Example 10 Production of N-methylol compound of diguanamines (1) and water dilutability test of the derivative: 15.7 g (0.05 mol) of diguanamines (1) obtained by the method of Example 1 was added to 10% aqueous caustic soda solution. 37% formalin 42.2g adjusted to pH 10.5 with
(Formaldehyde 0.52 mol) was added. The mixture was heated at a temperature of 60-65 ° C for 30 minutes with stirring. The reaction mixture was a uniform and transparent liquid, and as a result of analysis, it was found that 7.2 mol of formaldehyde was bound to methylol with respect to 1 mol of the diguanamine (1).

Further, 50 g of deionized water was gradually added to the obtained solution of the N-methylol compound at room temperature, and the solution was a uniform and transparent liquid. Example 11 Production of N-methylol compound 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 was added to 10% aqueous caustic soda solution. 37% formalin 42.2g adjusted to pH 10.5 with
(Formaldehyde 0.52 mol) was added. The mixture was heated at a temperature of 60-65 ° C for 30 minutes with stirring.

The reaction mixture is a homogeneous and transparent liquid,
As a result of analysis, it was found that 7.3 mol of formaldehyde was bound to methylol with respect to 1 mol of the diguanamines (2).

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

As shown in Examples 10 and 11, the N-methylol compound of the diguanamines according to the present invention is extremely excellent in water dilutability and is extremely excellent as a raw material for water-based resins such as water-based paint resins. It has been found to be extremely useful for various applications. Comparative Example 1 Production of N-methylol compound of 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-phthaloguanamine 14.8 g (0.05 mol)
The reaction was carried out in the same procedure as in Example 10 except that was used.

This reaction mixture was a liquid in which a large amount of insoluble solid matter was present. This was subjected to solid-liquid separation by hot filtration, and the solid matter was dried under reduced pressure to give crystals 13.7 g [from the elemental analysis results, o-phthaloguanamine Containing 13.6 g (0.046 mol). Furthermore, when 1.0 g of deionized water was added to this solution at room temperature, it became extremely cloudy. Comparative Example 2 Production of N-methylol compound of 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
Instead 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., Inc.] except that 21.7 g (0.05 mol) is used The reaction was carried out in the same procedure as in Example 10.

This reaction mixture was a liquid in which a large amount of insoluble solid matter was present, and this was subjected to solid-liquid separation by hot filtration. (Containing 0.042 mol)] was obtained. Furthermore, 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 markedly slow methylolation reaction with aldehydes, and the reactivity of the amino group in such compounds is poor, resulting in melamine, guanamines and ureas. Not only is it difficult to produce a resin intermediate such as a copolycondensate with the above, various derivatives, but the N-methylol compound of such a compound has extremely poor water dilutability and is used as a water-based resin raw material for water-based paints and the like. Not only was it difficult to use, but it also had significant restrictions on the application. Example 12 Production of N-methylol compound of diguanamines (1): 15.7 g of diguanamines (1) obtained by the method of Example 1
(0.05 mol), 37% formalin 17.9 g (formaldehyde 0.22) adjusted to pH 9.0 with 5% sodium carbonate aqueous solution.
Mol) was added. The mixture was heated at a temperature of 70-75 ° C for 30 minutes with stirring. The reaction mixture was a transparent liquid, and as a result of analysis, it was confirmed that the diguanamines (1) 1
Methylol was bonded to 4.0 mol of formaldehyde per mol. Example 13 Production of N-methylol compound of diguanamines (1): 15.7 g of diguanamines (1) obtained by the method of Example 1
To (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 at a temperature of 60 ° C. for 1 hour with stirring. The reaction mixture was a transparent liquid, and as a result of analysis, it was found that 6.1 mol of formaldehyde was bound to methylol with respect 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] heptane 15.7 g (0.05 mol) in 5% caustic soda solution
81.2 g (formaldehyde 1.0 mol) of 37% formalin adjusted to pH 10.5 was added. This mixture at a temperature of 60 ° C.
Heated with stirring for hours. The reaction mixture was a clear liquid which was analyzed to show 2,5-bis (4,6-diamino-1,3,5-triazin-2-yl) -bicyclo [2.
2.1] 7.8 mol of formaldehyde was methylol-bonded to 1 mol of heptane. Example 15 Production of N-methoxymethylated product of 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 of formaldehyde bonded 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 to 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 substance was filtered to give a viscous liquid. As a result of analysis of this, 5.3 equivalents of N-methoxymethyl group was bonded to 1 mol of the diguanamines (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-methylol compound (7.3 mol of formaldehyde bound to 1 mol 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 to 45 ° C for 2 hours. 10% of this reaction mixture
After adjusting the pH to 8.0 with a caustic soda aqueous solution, methanol and water were removed under reduced pressure, and the solid matter was filtered to obtain a viscous liquid. As a result of analyzing this, the diguanamines (2)
It was one in which 4.9 equivalents of N-methoxymethyl group were bonded to 1 mol.

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

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

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

As shown in Examples 19 and 20, the N-methylol derivative of the diguanamines according to the present invention has excellent polymerizability, and the compound has very little deterioration in gloss due to ultraviolet rays and has very excellent properties. It was a thing. Example 21 Wrinkle resistance test of fiber treatment agent using N-methylol diguanamine: N-methylol compound of diguanamines (1) obtained by the method of Example 10 (the diguanamines (1)
Formaldehyde 7.2 moles bond to 1 mole),
A 10 wt% aqueous solution was prepared with deionized water. to this,
As a catalyst, 3% by weight of dibasic ammonium phosphate (based on the solid content of the derivative) was added. Using this solution, after dipping it in cotton cloth (cotton 60 broad) and padding it,
Pre-dry the cotton cloth at 80 ℃ for 5 minutes,
It heat-processed on condition of (degree C) -5 minutes.

Using this treated cotton cloth, a wrinkle prevention test is performed according to JIS.
As a result of carrying out in accordance with L 1059 (Monsanto method), the wrinkle-proof rate was 86%, and extremely excellent wrinkle-proof property was exhibited.

As described above, when the fibers are treated with the N-methylol diguanamine according to the present invention, it is possible to impart extremely excellent performances such as wrinkle resistance to the fibers, and the diguanamine derivative. The thermosetting composition containing the was extremely useful as a treating agent for fibers. Example 22 Curing test of water-based coating resin using N-methylol diguanamine: N-methylol compound of diguanamines (1) obtained by the method of Example 10 (the diguanamines (1)
Formaldehyde 7.2 mol bond to 1 mol) 6.0 g
While stirring 50% by weight aqueous solution of Almatex WA 911 [Mitsui Toatsu Chemical Co., Ltd., NV 60%] 40.0 g, gradually add 1.84 g of dimethyl ethanolamine and adjust to a nonvolatile content of 20% with deionized water. The above solution was added and mixed. The resin solution thus obtained was applied to a galvanized steel sheet and then heat-treated at 160 ° C. for 20 minutes.

The coating film of the coated steel sheet thus treated had cissing,
No blister, discoloration, etc. are observed, and the surface gloss of the coating film is JIS K
Measured in accordance with 5400 (60 ° specular reflectance), glossiness
It was 98% and had extremely excellent smoothness and gloss.
Further, the coating film was an excellent coating film in which no peeling of the coating film was observed even when the surface of the coating film was rubbed 50 times with a cloth impregnated with acetone, and which was sufficiently cured. Example 23 Curing test of aqueous coating resin using N-methylol diguanamine: N-methylol compound of diguanamines (2) obtained by the method of Example 11 (the diguanamines (2)
Formaldehyde 7.3 mole bond to 1 mole) 5.9g
50% by weight aqueous solution of Almatex WA 911 [Mitsui Toatsu Kagaku KK, NV 60%] while stirring 40.0 g of dimethylethanolamine 1.84 g of dimethylethanolamine was gradually added, and then deionized water to a nonvolatile content of 20%. The prepared solution was added and mixed. After applying this resin solution to galvanized steel sheet,
Heat treatment was performed under the condition of minutes.

The coating film of the coated steel sheet thus treated had cissing,
No blister, discoloration, etc. are observed, and the surface gloss of the coating film is JIS K
Measured in accordance with 5400 (60 ° specular reflectance), glossiness
It was 94% and had extremely excellent smoothness and gloss.
Further, the coating film was an excellent coating film in which no peeling of the coating film was observed even when the surface of the coating film was rubbed 50 times with a cloth impregnated with acetone, and which was sufficiently cured.

As shown in Examples 21 to 23, the diguanamine derivative according to the present invention is extremely excellent in water dilutability.
The thermosetting composition containing this is not only excellent as a water-based resin such as a water-based coating resin, an adhesive resin, a fiber treating agent, etc. It has also been found to be extremely useful in a wide range of applications. Example 24 Curing test of water-based coating resin using N-methoxymethylated diguanamine: N-methoxymethylated diguanamine (1) obtained by the method of Example 15 [based on 1 mol of the diguanamine (1)] N-methoxymethyl group 5.3 equivalents]
A 50 wt% solution of 6.8 g dissolved in a butyl cellosolve-water (weight ratio 50/50) mixed solvent and 0.15 g of p-toluenesulfonic acid were used as Almatex WA 911 [Mitsui Toatsu Chemicals, Inc., NV60 %] Dimethylethanolamine (1.84 g) was gradually added to 40.0 g with stirring, and the mixture was added to a solution adjusted to a nonvolatile content of 20% with deionized water and mixed. The resin solution thus obtained was applied to a galvanized steel sheet and then heat-treated at 160 ° C. for 20 minutes.

The coating film of the coated steel sheet thus treated had cissing,
No blister, discoloration, etc. are observed, and the surface gloss of the coating film is JIS K
Measured in accordance with 5400 (60 ° specular reflectance), glossiness
It was 96% and had extremely excellent smoothness and gloss.
Further, the coating film was an excellent coating film in which no peeling of the coating film was observed even when the surface of the coating film was rubbed 50 times with a cloth impregnated with acetone, and which was sufficiently cured.

As shown above, the etherified diguanamine according to the present invention has excellent polymerizability, and further, a thermosetting resin composition containing the etherified product and a resin curable by reacting with the etherified product is It has been 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 diguanamine (2) obtained by the method of Example 16 [based on 1 mol of the diguanamine (2)] N-methoxymethyl group 4.9 equivalents]
After dissolving 4.9 g in 10 g of methyl isobutyl ketone,
Almatex P 646 [Mitsui Toatsu Chemical Co., Ltd.,
NV 60%] 47.2 g was added and mixed. This resin solution was applied to a galvanized steel sheet and then cured by heating at 180 ° C. for 50 minutes.

Using this coated steel sheet, an exposure test was conducted for 500 hours with a weather O-meter. No blister, discoloration, etc. were observed on the coating surface of the test steel sheet, and the surface gloss of the coating film was measured according to JIS K 5400 (60 ° specular reflectance). As a result, the gloss retention was 95%. . Example 26 Polymerization of etherified diguanamine initial condensate and weather resistance test of the condensate: Etherified precondensate of diguanamine (1) obtained by the method of Example 18 [the diguanamine (1) constitutional unit 1 Average addition condensation degree 1.6] 5.0 g
Was dissolved in 10 g of methyl isobutyl ketone, and then Almatex P 646 [manufactured by Mitsui Toatsu Chemicals, Inc., NV60
%] 47.2 g was added and mixed. This resin solution was applied to a galvanized steel sheet and then heat-cured at 160 ° C. for 30 minutes.

Using this coated steel sheet, an exposure test was conducted for 500 hours with a weather O-meter. No blister, discoloration or the like was found on the coating surface of the test steel sheet, and the surface gloss of the coating film was measured according to JIS K 5400 (60 ° specular reflectance). As a result, the gloss retention rate was 97%. ..

As shown in Examples 25 and 26, the diguanamine etherification product and etherification precondensation product according to the present invention are excellent in polymerizability and further contain these derivatives and a resin curable by reacting with them. It has been found that the cured product obtained from the thermosetting resin composition also has excellent weather resistance and is extremely useful as a resin for paints and the like. Example 27 Curing test of epoxy group-containing resin with diguanamines (1): Epoxy group-containing resin Epicoat ^# 828 (product of Shell Co.) 100 g was dissolved in butyl cellosolve 100.0 g,
Diguanamines (1) obtained by the method of Example 1
19.6 g was added and dissolved to prepare a resin solution. After applying this resin solution to a galvanized steel sheet,
It was further heated at 200 ° C for 40 minutes. The coating film of this heat-treated coated steel sheet is a cloth impregnated with toluene.
No peeling of the coating film was observed even after rubbing 0 times, and the film was a sufficiently cured and excellent transparent coating film. Example 28 Curing test of epoxy group-containing resin with diguanamines (2): Obtained by the method of Example 3 instead of 19.6 g of the diguanamines (1) obtained by the method of Example 1 in Example 27 A resin solution was prepared in the same procedure as in Example 27 except that 18.9 g of diguanamines (2) was used, and a coating film curing test was performed.

The coating film of this heat-treated coated steel sheet was an excellent transparent coating film which was sufficiently cured without peeling of the coating film even after rubbing the coating film surface 50 times with a cloth impregnated with toluene. Met. Example 29 Storage stability test of thermosetting resin composition: Epoxy group-containing resin and diguanamines were blended in the types and blending amounts shown in Table 3, and each component was preliminarily 90- 110
The mixture was kneaded for 15 to 30 minutes with a two-roll heated to ℃, taken out into a sheet and pulverized. Using this sample, the storage stability was evaluated by leaving it in a dryer kept at 40 ° C. The results are shown in Table-3.

As shown in Table 3, the thermosetting resin composition according to the present invention was found to have 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 Co.) 100 g and diguanamines (1) 19.6 obtained by the method of Example 1 g and kneaded with each other for 30 minutes with a two-roll mill previously heated to 90 to 110 ° C. until the respective components are sufficiently uniform, and then taken out into a sheet and pulverized. Using this sample 190
A resin cured product was prepared under the curing conditions of ℃ for 3 hours. Using this resin cured product, the Charpy impact value was measured as a measure of flexibility. The results are shown in Table-4.

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 above with the optimum compounding amount and curing conditions.
The Charpy impact value was measured.

[0109]

[Table 4] As shown in Table 4, it was found that the resin cured product obtained from the thermosetting resin composition according to the present invention was 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 Chemicals, Inc., epoxy equivalent 530 (solid content)] 100.
0 g was dissolved in 200 g of butyl cellosolve, and 11.1 g of the diguanamines (1) obtained by the method of Example 1 was added and dissolved to prepare a resin solution. This resin solution was applied to a galvanized steel sheet and then heat-cured at 200 ° C. for 40 minutes.

Using this coated steel sheet, a weather resistance test was conducted by exposing it to a weather O-meter for 300 hours. 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 rate was 94%.

As described above, it has been found that the cured resin product obtained from the thermosetting resin composition according to the present invention has excellent weather resistance and is extremely useful as a coating resin or the like. Example 32 Coating film test of resin for powder coating obtained from thermosetting resin composition: The resin solution of thermosetting resin composition obtained by the method of Example 31 was used, and this was depressurized by heating. Solvent was applied to obtain a solid resin. Further, this solid resin was roughly pulverized by a coarse pulverizer and then finely pulverized by an atomizer. This one
After screening with a 50 mesh screen, the pass product was used as a resin for powder coating in the test. Using this powder coating resin, a zinc phosphate chemical conversion treated dull steel sheet was electrostatically coated so as to have a film thickness of about 50 μm, and heat-treated at 200 ° C. for 40 minutes.

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

Further, using this coated steel sheet, a germicidal lamp (19W manufactured by Toshiba) was used as an ultraviolet light emitting source, and the test steel sheet was irradiated for 200 hours from a vertical distance of 25 cm. As a result, blisters and discoloration were observed on the coating surface. Etc. were not observed, and the surface gloss of this coating film was measured according to JIS K 5400 (60 ° specular reflectance). As a result, the gloss retention rate was 96%, and the coating film has excellent UV resistance. It was a thing. Example 33 Adhesion test of thermosetting resin composition: 100 g of epoxy group-containing resin Epicoat ^# 828 (manufactured by Shell Co.) and 15.7 g of diguanamines (1) obtained by the method of Example 1 were blended, and Kneading was carried out for 30 minutes with a two-roll machine preheated to 90 to 110 ° C. until the components were sufficiently uniform. Steel plates were bonded using this kneaded resin and cured under the conditions of 200 ° C. for 1 hour. Tensile shear adhesive strength of this cured resin (25 ℃)
Was 176 kg / cm ² .

As shown above, the thermosetting resin composition according to the present invention was found to be excellent in adhesiveness and extremely useful as an adhesive resin and the like.

[0115]

INDUSTRIAL APPLICABILITY The diguanamines according to the present invention are remarkably excellent in weather resistance, ultraviolet resistance and the like and can maintain a desired function for a long time outdoors and the like, and the water dilutability of the methylol compound of the compound is extremely high. Excellent water-based paints with almost no restrictions as raw materials for water-based resins and excellent performance, with active amino groups that have outstanding reactivity with formaldehyde and epoxy compounds, and 8 active hydrogens Therefore, it has characteristics such as a wide selection of methylolation degree, etc., and further has flexibility, toughness,
It also has excellent properties such as high hardness, water resistance, and curability, and can provide compounds, resins, compositions, etc. having excellent properties, which are useful for a wide range of applications. Furthermore, the method for producing diguanamines according to the present invention is a reaction in which specific dicarbonitriles and dicyandiamide are reacted under specific conditions, so that byproducts are remarkably low in high purity, purification and separation steps are easy to produce, Further, it is an object of the present invention to provide an excellent method for obtaining a desired target compound in a high yield by using dicarbonitriles which are available at low cost.

Further, such 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. A curing agent for various resins such as N-methylol diguanamine, etherified diguanamine and their initial condensates obtained by reaction with aldehydes, derivatives useful as resin raw materials, and these derivatives. A thermosetting resin composition comprising the above-mentioned diguanamines and an epoxy group-containing resin, which are useful as a thermosetting composition, a coating resin, an adhesive resin, etc. It is an extremely excellent invention.

[Brief description of drawings]

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

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

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

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

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Masami Inomata 1900 Togo, Mobara-shi, Chiba Prefecture Mitsui Toatsu Chemical Co., Ltd. (72) Inventor Izumi Iga 1900, Togo, Mobara-shi Chiba Prefecture Mitsui Toatsu Chem. (72) Inventor Atsura Yamauchi 1900, Togo, Mobara-shi, Chiba Mitsui Toatsu Chemical Co., Ltd. (72) Inventor Kazunori Kamata 1-6 Takasago, Takaishi-shi, Osaka Mitsui Toatsu Chemical Co., Ltd. Shigeru 1-6 Takasago, Takaishi-shi, Osaka Prefecture Mitsui Toatsu Kagaku Co., Ltd. (72) Inventor Katsumi Sakamoto 1-6 Takasago, Takaishi-shi Mitsui Toatsu Chemical Co., Ltd. (72) Inventor Tatsunobu Nakajima Osaka Prefecture 1-6 Takasago, Takaishi-shi Mitsui Toatsu Chemical Co., Ltd. (72) Inventor Akito Watanabe 1-6 Takasago, Takaishi-shi, Osaka Mitsui Toatsu Chemical Co., Ltd. Inside the company

Claims (16)

[Claims] 1. A general formula (1): [In the formula, the bonding position of the (4,6-diamino-1,3,5-triazin-2-yl) group represents the 2,5- or 2,6-position], or the general formula (2) Chemical 2] [In the formula, the bonding position of the (4,6-diamino-1,3,5-triazin-2-yl) group is 1,2-, 1,3- or 1,4-position] Diguanamines. 2. A general formula (3): (In the formula, the bonding position of the cyano group is 2,5- or 2,6-
Position) or general formula (4) (In the formula, the bonding position of the cyano group represents the 1,2-, 1,3- or 1,4-position) and reacting dicarbonitriles with dicyandiamide in the presence of a basic catalyst. A method for producing diguanamines, which comprises: 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,
The method for producing diguanamines according to claim 2, which is at least one selected from the group consisting of alkaline earth metal salts of dicyandiamide, amines and ammonia. 4. The method for producing a diguanamine according to claim 2, wherein the reaction is carried out by using at least one selected from the group consisting of a non-aqueous protic solvent and an aprotic polar solvent as a reaction solvent. 5. The method for producing diguanamines according to claim 2, wherein the reaction is carried out at a temperature of 60 to 200 ° C. 6. An N-methylol-diguanamine obtained by the addition reaction of the diguanamines according to claim 1 and an aldehyde. 7. At least one R ₁ obtained by etherifying the N-methylol diguanamine according to claim 6 and at least one selected from alcohols having 1 to 20 carbon atoms. An etherified diguanamine having an OCH ₂ group (R ₁ represents a residue obtained by removing a hydroxyl group from the above alcohols). 8. An average addition condensation degree obtained by subjecting the diguanamines according to claim 1 and a compound capable of co-condensation together with an aldehyde to an addition condensation reaction of more than 1 and at least one methylol group. N-methylol diguanamine precondensate having 9. The diguanamines according to claim 1, and optionally a co-condensable compound, and an aldehyde are subjected to an addition reaction or an addition condensation reaction, and then having 1 to 1 carbon atoms.
At least one R ₁ OCH ₂ group having an average degree of addition condensation of more than 1 and at least one R ₁ OCH ₂ group is obtained by subjecting at least one selected from alcohols having 20 to an etherification reaction and optionally a condensation reaction at the same time. (R ₁ has the same meaning as described above), and an etherified diguanamine precondensate having 10. An N-methylol diguanamine according to claim 6, an etherified diguanamine according to claim 7, an N-methylol diguanamine precondensate according to claim 8, and an etherified diguanamine precondensate according to claim 9. A thermosetting composition comprising at least one selected from the group consisting of as an essential component. 11. A resin containing a curable resin which reacts with the essential component according to claim 10 and is curable.
The thermosetting composition according to 0. 12. A coating resin composition containing the thermosetting composition according to claim 11. . 13. A thermosetting resin composition comprising the diguanamine according to claim 1 and an epoxy group-containing resin. 14. A coating resin composition comprising the thermosetting resin composition according to claim 13. 15. The powder coating resin composition according to claim 13.
The coating resin composition described. 16. An adhesive resin composition containing the thermosetting resin composition according to claim 13.