WO1994017047A1 - Diguanamine, and production, derivative and use thereof - Google Patents

Abstract

A diguanamine represented by general formula (1); a process for producing the same by the reaction of a dicarbonitrile represented by the general formula: NC-R-CN with dicyandiamide in the presence of a basic catalyst; and a thermosetting composition comprising, for example, a coating resin containing methylolated diguanamine, etherified diguanamine, precondensates thereof and derivatives thereof, and a thermosetting resin composition comprising, for example, a coating resin or an adhesive resin containing the diguanamine and an epoxy resin. In said formulae, R represents bicyclo[2.2.1]-2,5-heptylene, bicyclo[2.2.1]-2,6-heptylene or cyclohexylene.

Description

 Description Jiaguanamines, their production methods, derivatives and application technologies

 The present invention relates to resin raw materials for polymerizable monomers, coating resins, adhesive resins, paper processing resins, textile processing resins, powder coating resins, building materials, etc. Jiganamins useful as raw materials for carbohydrate compound derivatives, curing agents such as epoxy resins and urethane resins, and polymer modifiers such as rubber materials And a method for producing the same, a derivative of the above-mentioned diguanamine which is useful as a curing agent for various resins, an intermediate for a resin raw material, etc., and the above-mentioned diguanamine and the like. It relates to the use of derivatives.

 Background technology

 Conventionally, resin materials for paints, resins for adhesives, resins for paper processing, resins for textile processing, leather processing agents, etc., curing agents for various resins, rubber material modifiers, organic material modifiers, etc. It has high hardness and good gloss, is colorless and transparent, has high chemical and water resistance, and has excellent abrasion resistance and electrical properties. The resin pot life as an agent has advantages such as its superiority, and therefore, the resin having an aminotriazine group has advantages. Guanamines such as min, benzoguanamine, etc. have been widely used.

In addition, a melamine having such an aminotriazine group is used. And guanamines have been researched and developed, and have excellent properties in terms of resin flexibility, toughness, high hardness, water resistance, and curability. Multifunctional guanamines having four or more functional groups that express guanine have also been provided to the world.

 The polyfunctional guanamines have very different structures from the novel diguanamines according to the present invention and are extremely difficult to compare and compare. However, for reference only,

H H, which is represented by

H

There is a spiro guanine etc. represented by However, the former compound is not suitable for exterior paints and weather-resistant paints because the resin obtained by using such a compound as a raw material has remarkably inferior ultraviolet light resistance and weather resistance. Whether it can be used as a resin raw material such as a conductive paint, a paint for an automobile, a resin for a building material, etc., and whether there are some serious restrictions. The water dilutability of the phthaloguanamine-based amino resin, which is an inducer of the Ruichin compound, is somewhat improved as compared with the conventional melamin-based amino resin. Although it is used, it is still inadequate for practical use and has defects such as the fact that there are severe restrictions when used as resin raw materials such as resins for water-based paints. You In addition, the latter compound is inferior in heat resistance of a resin obtained by using such a compound as a raw material, and inferior in weather resistance, ultraviolet resistance, and water resistance of the resin. Lack of difficulty in maintaining the desired functions over a long period of time outdoors, such as exterior paints, weather-resistant paints, automotive paints, resin for building materials, etc. There is a fall. In addition, the methylolation reaction of the latter compound is related to the fact that the reaction rate is slower than that of melamin, benzoguanamine, etc. Various reactive guanamine derivatives provided by reacting the amino group due to the poor reactivity of the amino group in the compound. , Resin, various resin hardeners, formaldehyde copolycondensation of such aldehyde compounds with compounds such as melamin, benzoguanamine, etc. There is a defect such as that the production of goods is severely restricted. In addition, the reaction obtained by the methylolation reaction of such a lig compound. The mixture is used as a resin raw material for water-based resins, for example, resins for water-based paints, resins for adhesives, resins for paper processing, and resins for textile processing, since a transparent solution is difficult to obtain. In some cases, it is difficult to obtain sufficient performance in terms of smoothness, curability, physical properties, etc. of the coating film, and it cannot be used in these applications completely. There are also deficiencies such as being subject to severe restrictions. 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. Not only are there any technical obstacles such as complications, but also there are deficiencies such as a significant loss of economics. As noted above, these compounds were severely and technically and economically restricted in their use and manufacture.

 Disclosure of the invention

The inventors of the present invention have conducted intensive studies in view of the above-mentioned defects in guanamines, and as a result, they have found that the compounds having various functional groups have excellent reactions. Since it has an active amino group showing its properties and has eight active hydrogens, it is possible to select a wide range of degrees of methylolation, etc. It is remarkably excellent in ultraviolet rays, etc., and can maintain its intended function for a long period of time outdoors. Furthermore, the Michigo-Iruichi product is excellent in properties such as water dilutability, curability, water resistance, stain resistance, flexibility, hardness, and toughness. For reference, Jiganamins whose structure and properties are completely different from those of the polyfunctional guanamines described above have been found. Manufacture of minerals la The by-products are remarkable, the amount of by-products is low, the desired compound can be obtained in high purity, the purification and separation steps are easy to manufacture, and it is available at low cost. The present invention has been achieved by finding an excellent production method by which a desired compound can be obtained in a high yield by using phenol.

 Further, as a derivative obtained by using such a useful diguanamine, a derivative obtained by reacting with an aldehyde is obtained. Methylolated diguaminine, an ethereal jig obtained by the etherification reaction of N-methylolide and alcohol-relate. It contains animin and their precondensates, and contains these derivatives which are useful as curing agents for various resins, resin raw materials for paint resins, etc. Contains the above-mentioned diguanamines and epoxy-containing resins, which are useful as thermosetting compositions, coating resins, powder coating resins, adhesive resins, and the like. The present inventors have also found a thermosetting resin composition which has been obtained, and have reached the present invention.

The above-mentioned jiganamins are rubber modifying agents, optical materials, registry materials, electrical insulating materials, automotive paints, home electrical paints, antifouling paints, weatherproof paints. Paint, fluorescent paint, resin for building materials, powder paint, water-based paint, oil-based paint, resin for paper processing, resin for fiber coating, adhesive resin, resin for IC sealant, corrosion-resistant resin, polymer Excellent as a modifier, leather treatment agent, plastic magnet, antioxidant for latex, electrophotographic photoreceptor, surfactant, pesticide, pharmaceutical, etc. It is an extremely useful compound that can provide a polymer, a compound, and a composition.

 In other words, the present invention

 (A) General formula (1)

[In the formula, the bonding position of the (4,6—diamino1,3,5—triazine-2—yl) group is the first position of 2,5—or 2,6. You] or

 General formula (2)

H

Η

[In the formula, the bonding position of the (4.6—diamino 1,3,5-triazine-2—yl) group is 1.2—, 1,3—or 1, 4 show first place]

Jigguanamines represented by

 (D) General formula (3)

( 式 中 、 シ ァ ノ 基 の 結 合位 置 は 、 2 5 — 又 は 2 ， 6 — 位 を 示 す ） 、 又 は N (3)

(In the formula, the bonding position of the cyano group indicates the 25- or 2,6-position), or

General formula (4)

(In the formula, the bonding position of the cyano group indicates the 1,2—, 1,3— or 1,4— position.)

Characterized in that it reacts the dicarbinolinoles represented by the formula (I) with dicyanediamid in the presence of a basic catalyst. Manufacturing methods for minerals,

 (A) The basic catalyst is selected from the group consisting of alkaline metals, alkaline metal hydroxides, alkaline earth metal hydroxides, alkaline metal hydroxides, and alkaline metals. A group consisting of alkali metal salts of ammonium, alkaline earth metal salts of disiamdiamid, amines and ammonia. The method for producing jigguanmines described in (i) above, which is characterized in that at least one kind is selected.

 (D) The reaction is carried out by using at least one selected from the group consisting of a non-aqueous proton solvent and a non-proton polar solvent as a reaction solvent. The method for producing jigguanmines described in the above (ϋ), which is characterized in that:

(E) The production of jignamines as described in (portion) above, wherein the reaction is carried out at a temperature in the range of 60 to 200 ° C. Method ,

 (F) N-methylo-reign jig ana obtained by subjecting the jig guanamines and aldehydes described in the above (a) to an addition reaction. Min,

(G) It is selected from N-methylolated diguanamine described in (f) above and alcohols having 1 to 20 carbon atoms. least Na rather as one of R, 0 CH ₂ groups may be one and the the er Te Ri by the and this to Ru by Le reaction resulting et been that low Do rather (R, is a Le co before Symbol A residue obtained by removing a hydroxyl group from a group of alcohols).

 (H) The addition reaction of the diguanamines described in the above (a) with the aldehydes together with a compound that can be co-condensed in some cases. N—methyoxylated diguanamine having an average degree of addition condensation obtained of greater than 1 and having at least one methylol group Precondensate,

(I) Addition reaction or addition condensation reaction between the diguanamines described in (a) above and a compound that can be cocondensed, if necessary, with an aldehyde. Then, at least one alcohol selected from alcohols having 1 to 20 carbon atoms is subjected to an etherification reaction. The condensation reaction is carried out at the same time, so that the average degree of addition condensation obtained by this is greater than 1 and at least 1 R! An etherified diguanamine precondensate having a CH ₂ group (R, has the same meaning as above), (Nu) N-methylolated jigguanmin described in (f) above, etherified jigguanin described in (g) above, (h) described above A group consisting of the N-methylolated jiganamin initial condensate described above and the etherified diguaminin early condensate described in (i) above. A thermosetting composition characterized in that it contains at least one selected component as an essential component;

 (L) The thermosetting composition according to the above (nu), characterized by containing a curable resin which reacts with the component described in the above (nu).

 (Ii) a paint resin composition containing the thermosetting composition described in (l) above;

 (Ii) a thermosetting resin composition characterized by containing the diguanamines described in (a) above and an epoxy group-containing resin;

 (Force) a paint resin composition containing the thermosetting resin composition described in (i) above;

 (G) The coating resin composition according to (1) above, which is a powder coating resin composition,

 (Evening) An adhesive resin composition containing the thermosetting resin composition described in the above (1).

 Brief explanation of drawings

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

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

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

 Best mode for carrying out the invention

 In the jiaguanamines (1) related to the present invention, the (4,6—diamino 1,3,5—triazine-12-yl) group is used. Is bonded at the 2,5—or 2,6—position, but the configuration of such a group is end-to-end, end-exo, or end-exo. It is a exo-exo form, and both are useful compounds.

 Further, the diguanamines (1) are compounds selected from the group consisting of the isomers having the above-mentioned bonding positions and configurations, and the diguanamines (1) are the above-mentioned groups. The aggregate of different compounds selected from them is as industrially useful as the case of a single compound.

Specific examples of such jiaguanamines (1) include 2,5-vis (4, 6-diamine 1, 3.5-triazine). 2 (yl) -bicyclo [2.2.1.1] heptane (end-exo type), 2, 5-bis (4, 6-diamino 1, 3, 5 — Triazine 1 2 — yl) [2.2.2. 1] heptane (exo-exo-type), 2, 6-bis (4, 6-diamino 1, 3, 3-5-triazine 1-dino)-bicyclo [2.2.1. End-end type), 2, 6-vis (4, 6-diamin 1, 1, 3, 5-triazine-1 2 _ yl) -bicycle [2 . 2.1] heptane (exo-exo form) and the like, but are not limited to these compounds ο

 In addition, in the jiaguanamines (2) according to the present invention, (4, 6—diamino 1, 3, 3, 5—triazine 12 1 yl) ) The bonding positions of the groups are at the 1,2—, 1,3—or 1,4—position, but the configuration of such groups is trans or cis. All of them are useful compounds.

 Furthermore, the diguanamines (2) are compounds selected from the group consisting of the isomers having the above-mentioned bonding position and steric configuration. The aggregate of different compounds selected from such a group is as industrially useful as the case of a single compound.

 Examples of the specific examples of the jigguanamines (2) are 1, 2-bis (4, 6-polyamide 1, 3, 5-triazine). 2 — yl)-cyclohexane (cis type),

1, 2 — bis (4, 6 — dia 1, 3, 5 — triazine 1 2 — isole) 1 cyclohexane (transform type), 1 , 3—Visions (4, 6—Jaminors 1, 3, 5 1-triazine 1-cyclohexane (translation type), 1, 3-vis (4.6-diamin 1, 3, 5) Triazines 1-2-yl)-cyclohexane (cis type), 1, 4-1-bis (4.6-diamin 1, 3, 5-1-tria) Gin 1 2 — yl) 1 cyclohexane (translation type), 1, 4 — vis (4, 6 — dia 1, 3, 5 — tri ag 1-cyclohexane (cis-form) and the like, but are not limited to these compounds.

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

 (In the formula, the bonding position of the cyano group indicates the 25-or 2.6-position), or

 General formula (4)

 (In the formula, the bonding position of the cyano group is 1, 2-, 1, 3- or 1.4-position.)

A method for reacting dicarboxylic diisoles represented by the formula (I) with dicyanediamid in the presence of a basic catalyst, and dicarbonitriles A method for reacting esters of dicarboxylic acid and biguanides, which are equivalent to the above, in the presence of a basic compound, if necessary. be able to . The former new paper In the method, the raw materials are easily available and the handling is simple, the by-products are remarkable, the purity is low, the desired compound is obtained with high purity, and the production of the purification and separation steps is carried out. It is technically and economically superior in that it is simple, the raw material loss is remarkable, the amount of raw material loss is small, and the desired compound can be obtained in high yield. Therefore, it is extremely practical. It should be noted that the method for producing such jiganamins is not limited to these methods.

 The dicarbotriols (3) in the method for producing diguanamines according to the present invention have a cyano group bonding position of 2.5 — or 2. 6 — position, but the configuration of such groups is not end-end, end-exo, or exo-exo. They are also useful. Further, the dicanole nitriles (3) are compounds selected from the group consisting of the above-described heterogeneous compounds having the bonding position and steric configuration. However, an aggregate of different compounds selected from such a group is also useful as in the case of a single compound.

 The above-mentioned dicarboxylic bottles (3) are, for example, as disclosed in U.S. Pat. No. 2,666,748 and the like.

[. 2 2 - 1] F-flop te 5 - E down one 2 - a mosquito Le volume two preparative Li Le and Shi A down-based hydrogen _{C0 2 (C0) e, Fe} (CO) 5, N i [P (0C ₆ H ₅ ) ₃ ] A method for reacting in the presence of a specific catalyst such as ₄ , and the method disclosed in US Pat. No. 3,143,570, which discloses 5-(and Z or 6 — ) Cyanobicyclo [2.2.1.1] Hep

New paper Method for reacting hydroxydeamine with hydroxylamine, 2, 5-(and 2.6 or 2.6) dichloro Reaction of bicyclo [2.2.1.1] heptane with cyanogenating agents such as metal cyanide halides and earth metal salts of cyanide halides Although it can be obtained by methods such as shrinking, it is not limited to these methods.

 Examples of the concrete examples of such dicanole polytriles (3) include bicyclo α [2.2.1. 1] heptane 1, 2, 5-dicarnitol. Lil (end-exo type), bicyclo [2.2.1] heptane 1-2,5 — dicarnbolyl (end-end type) ), Bicyclo [2.2.1] heptane 12, 6-dicanole bonito resole (end-exo type), bicyclo [2.2.2. 1] Heptane-12,6—dicalbotolyl (exo-exo-form) and the like, but are not limited to these compounds is not .

In the method for producing diguanamines according to the present invention, the dihydryl nitriles (4) are characterized in that the bonding position of the cyano group is 1, 2-, 1,, 3 — or 1,4th position, but the configuration of such a group is not a trans- or a cis-configuration, but both are useful compounds. Further, the dicarboxylic dilinoles (4) are compounds selected from the group consisting of the isomers having the above-mentioned bonding position and steric configuration. An aggregate of different compounds selected from a group is as useful as a single compound. The above-mentioned dicarboxylic bottles (4) are, for example, as disclosed in US Pat. No. 3,496,217 or the like, as described in US Pat. No. 3,496,217. A method for reacting sen and cyanide hydrogen in the presence of a catalyst such as Ni [P (0 C ₆ H ₅ ) ₃ ] ₄ , a method of reacting 3-(and no or 41) A method for reacting hydroxycyclohexamines with hydroxycyclohexylamines, the method of reacting dicarboxyls described above (4). ) And the cyanogenation of cyanogen and other metal salts, cyanogenized alkaline earth metal salts, etc. The method for reacting the dicarboxylic acid with a dicarboxylic acid, and the dicarboxylic acid corresponding to the dicarboxylic acid (4) described above are those diammonium salts. Salt A method of reacting ammonia, diamide, a diester derivative and ammonia with a dehydrating agent such as an alumina catalyst or titanium chloride; 1 -The reaction can be obtained by reacting cyanocyclohexene and cyanide hydrogen in the presence of Al force such as caustic soda. However, the method is not limited to these methods.

Examples of such concrete barrels (4) include 1,2—cyclohexancanole and polytrisole (transform type). , 1, 3 — Cyclohexanol canole (tri-transform), 1, 3 — Cyclohexanol ), 1,4-cyclohexyl carbonyl (transformation type), 1,4-cyclohexyl phenol Paper type), but these new papers However, the present invention is not limited to these compounds.

 In addition, in the method for producing jiganamins according to the present invention, the reaction model between the dicasoleporinitols and dicyanidiamid is described. The ratio can be appropriately selected as needed. The reaction molar ratio between the dicarboxylic diaryls and dicyanediamid is 1: 2 stoichiometrically. If the molar ratio of dicyanediamid to lily is used in an excessively small amount, the yield of diguanamines according to the present invention may be low. In addition, the amount of monoguanamine (a reaction product of dicarbonitrile and dicyandiamide in a ratio of 1: 1 (mole ratio)) increases, resulting in an increase in purification. If the separation step becomes complicated and unfavorable, and if a large excess is used, the removal and separation of unreacted dicyandiamide and the like become complicated, resulting in a technical problem. However, it is not economically favorable. In order to improve the yield of diguanamines according to the present invention and to simplify the production such as the purification and separation process, dicarpineols were added to dicarpineols. The molar ratio of an amide is generally defined as a ratio of 1.5 to 10.0 moles of dithiamide with respect to 1 mole of zinc phenol. Preferably, the reaction is carried out at a rate of 2.0 to 5.0 mol.

As the basic catalyst in the process for producing jigguanines according to the present invention, for example, an alkali metal such as potassium or sodium is used. Genus, lithium hydroxide, hydroxyadium, sodium hydroxide, calcium hydroxide, hydroxide hydroxide Alkali metal such as lime, alkaline earth metal hydroxide, potassium carbonate, sodium carbonate, barium carbonate, etc. Alkali metal alcohols such as carbonates of alkaline earth metals, potassium limestone, sodium limestone, sodium limestone, etc. Alkali metal, Alkaline earth metal salt of lactate, dicyandiamidide, 1,8-diazabicyclo [5.4.0] 1-7, triethylamine, perylene, ethylamine, diethyltriamine, pyrrolido, tetra Amines such as quinoline and ammonia, etc. are mentioned. In particular, Alkali metal, Alkali metal hydroxide, Alkaline earth metal hydroxide, Alkali metal alcohol, and Disiadiamide Preference is given to alkaline metal salts, alkaline earth metal salts of dicyandiamidides, amines and ammonia, either alone or in combination. More than one species may be used. The amount of the catalyst to be added is not particularly limited. However, from the viewpoints of production conditions and economical efficiency, the amount of the catalyst is 500 to 0.0 with respect to dicarbotriles. The amount is 0.1 mol%, preferably 300 to 1 mol%, and can be appropriately selected as required.

In addition, in the production method of such jig guanamines, in order to carry out the reaction more smoothly, a method using various solvents as a reaction solvent is extremely necessary. Solvents that are useful but cause the formation of compounds other than the intended compounds, and can cause reaction inhibition. For example, solvents such as fatty acids, the acid anhydrides, trifluoroacetic acid, liquid sulfur dioxide, sulfuryl chloride, mineral acids, and water are not preferred.

Such reaction solvents include, for example, methanol, ethanol, n-prono-nor, isoprono-no-reile, n-bu-no-no , Is 0 — butanol, tert — butanol, 2 — ethylhexanol, dodecyl alcohol, aryl alcohol , Pro-Girl Razor Call, Benzilla Call, Cyclohexanol, Ethylene glycol, Butanediol , Glycerin, 1.2, 6—hexantol, 2—methoxyethanol, 2—ethoxyquinone, 2— Isopropoxy ethanol, 2—butoxy ethanol, furfur alcohol, tetrahydrofurfur alcohol , Jewel Chile coil, polyethylene glycol, metal foil, polyethylene glycol, rubber butter, 1- METROXY 1-PRONO-NOL, 11-EXOXY 2-PRONO-NOL, J-PROPELLING COLOR, JIASETON ALUCO 1、2,2,2―Trifluoroethanol 、 1、3―Dichloro 2―Alcohols such as propylene Ketones such as ethylene, methyl ethynoleketone, methyl isobutyl ketone, and acetate pentane, ethyl acetate, butylacetate, and acetic acid Esters such as benzyl, etc., ethyl alcohol, ethyl alcohol, alcohol, alcohol, etc. Long-call Ethyl alcohol, methyl ether, tetrahydrofuran, dioxan, crown ether, anisol etc. Teres, N, N — dimethyl holamide, N, N-methyl holamide, N, N — dimethyl acetate, N — Methylpyrrolidon, 1 and 3 — Dimethylol 21-imidazolidinone and other olenoic acid amides, sulfolane, methyls Lehoran, 1, 3 —Snorreholanes such as prononnce norretone, sulfolides such as dimethyl sulfoloxide, methizole Amin, dimethyl oleamine, trimethylamine, ethylamine, dimethylamine, triethylamine, isoprone Pilami , Butyramine, 2 — ethylamine, arylamine, aniline, sissy mouth, pyramid, pigment Resin, monoethanolamine, 2 — (dimethylamino) ethanol, jetanol realm, triethanolamine Amins such as MIN, ISOPRONONOLUMIN, TRIISOPRONONOLUMIN, and ammonia, etc., are mentioned. Non-aqueous protonic solvents such as alcohols, amines, ammonia, etc., carboxylic acid amides, sulfolane, and Nonproton polar solvents such as xids are preferred. These solvents may be used alone or in a mixture of ammonia and alcohol, or a mixture of dimethyl sulfoxide and cellosolves. It can be used in a mixture of two or more, and can be selected as needed, and furthermore, the water content of such a solvent. Preferably, the level is as low as possible, particularly preferably less than 1.0% by weight.

 Furthermore, the reaction is very slow and slow at a reaction temperature of 60 ° C or lower, and requires a long time for the production, and the yield is remarkable. It is not good because it is too low. When the reaction is usually carried out at a temperature of 60 ° C. or more, preferably 80 ° C. or more, the reaction proceeds rapidly and smoothly, and the desired compound can be obtained in a high yield. Wear . However, if the reaction temperature exceeds about 200 ° C., the production of by-products is rapidly added to such an extent that it cannot be neglected, and the purity of the product is remarkably reduced. However, the above reaction temperature is not preferable. Therefore, in the method for producing jig guanines according to the present invention, the production is preferably 6 Q to 200, more preferably 8D. It is more preferable to carry out the reaction at a reaction temperature in the range of ~ 18 D, and the desired compound can be obtained in a high purity with few by-products. The production can be carried out more easily, and the desired compound can be obtained in a higher yield.

 Although the reaction system is not particularly limited, it can be carried out under normal pressure or in a hermetically closed container under a naturally occurring pressure, and further under a pressurized condition. You can make a selection as needed.

Further, in order to obtain the desired target compound, diguanamines according to the present invention, from the reaction mixture of the above reaction, the reaction solution is cooled and crystallized. Filters out the jigguanin It is best to pour the reaction mixture as it is into hot water and filter by crystallization. Unreacted dicyamide diamide and z or dicarboditriol accompanying the crude diguanamine heat the crude diguanamine. It can be easily separated and removed by washing with water or methanol. Depending on the purpose of use, if further purification is required, use the reaction solvent described above, for example, alcohols, cellosolves, amino carboxylate. , Sulfolans, sulfoxides, etc., a mixed solvent of these solvents and water, a method of performing recrystallization with water, etc. A method of dissolving and pouring the mixture into hot water for reprecipitation; dissolving the crude jiganamin in an aqueous hydrochloric acid solution, mixing the mixture with the alkaline solution, and dissolving the mixture. It can be carried out by a method of reprecipitating minerals. However, the production method of the jiganamins according to the present invention has an extremely good yield, and the jiganamins are simply used as the methanol. Washing with various solvents such as water, water, and a mixed solvent of these, etc., can provide a product of sufficiently high purity for practical use.Therefore, the above purification method is practically necessary. There is no such thing.

The diguanamines related to the present invention are polymerized with various compounds such as aldehydes, epoxies, carboxylic acids, isocyanates and the like. It is excellent in properties and excellent in various reactivity and is extremely useful as a resin raw material and a derivative raw material. However, it is possible to use a reaction product with an aldehyde or an alcohol. Rules New paper The diguanamine derivatives such as reactants obtained by the etherification reaction with, and the reaction products obtained by the condensation reaction of these reactants are used for various resins. It is particularly useful as a hardener, a resin raw material, and the like.

 As the diguanamine derivative, τ-force and the above-mentioned derivative may be used.

 (F) The following general formulas (5) and (5) obtained by performing an addition reaction between the diguanamines described in the above (a) and the aldehydes. N — methylolated jiggan, represented by (6),

 General formula 5)

[In the formula, the bonding position of the (N-substituted 1,4,6—diamino1.3,5-triazine-2—yl) group is 2, 5— or 2,6-1 AR 2 »3» Γλ 4, Κ 5 »R 6, R ₇ and R ₈ represent one selected from Η atoms and Η 0 C Η 2 groups, and R 2, Κ 3, R 4, 5 »Κ 6, Κ 7 and R ₈ can be the same or different species]

General formula (6)

 [Wherein, the bonding position of the (N-substituted 1,4,6—diamino1,3.5-triazine-2—yl) group is 1,2—,

1, 3-or 1, 4th place, R ₂ , R ₃ , R ₄ , R ₅ , R 6, R 7 and R 8 have the meanings given above, R ₂ , R 3, R 4, R 5, R 6, R 7 and R 8 can be the same or different species]

(G) N-methylolated diguanamine described in (v) above and alcohols having 1 to 20 carbon atoms. R, 1 pieces of both one and the pictures over Te Ruihi by Ri obtained, et al. is that small Do rather than in a child Ru reacted small Do rather than with that 0 CH ₂ groups (R! is before Symbol a Le of (Indicating a residue obtained by removing a hydroxyl group from a call)) An etherified jigana represented by the following general formulas (7) and (8) having the following formula: Min,

 General formula (7)

[ 式 中 、 （ N 置換 — 4 , 6 — ジ ァ ミ ノ ー 1 , 3 , 5 — 卜 リ ア ジ ン — 2 — ィ ル ） 基 の 結合位置 は 2 , 5 — 又 は 2 , 6 — 位 、 R は 前記 の ア ル コ ー ル類 よ り 水酸基 を 除 い た 残基 、 R 9 , l O , R 1 1 , R 1 2 , R ！ 3 , R ！ 4お よ び R _{1 5}は H 原 子 、 H 0 CH ₂ 基 お よ び R i O CF 基 の 中 か ら 選 ば れ る 1 種 を 示 し 、 R ₉ , R ! 。， R H . R i ₂ ,

[In the formula, the bonding position of the (N-substituted—4, 6—diamino 1, 3, 5—triazine—2—yl) group is 2, 5, — or 2, 6—position. , R is a residue obtained by removing a hydroxyl group from the above-mentioned alcohols, and R 9, 10 O, R 11, R 12, R! 3, R! 4 and R ₁₅ represent _one selected from the group consisting of an H atom, a H 0 CH ₂ group and a RIOCF group, and R ₉ , R! , RH. R i ₂ ,

R 13, R i 4 and R i 5 can be the same or different species]

 General formula (8)

[Wherein, the bonding position of the (N-substituted 1,4,6—diammino—1,3,5—triazine-12-yl) group is 1,2—, 1,3— Or 1st, 4th place, R! Residue was divided hydroxyl Ri by A Le copolymers Lumpur such above, R _9, R i. , R,,, R i 2 , R i 3, R 1 4 your good beauty R _{1 S} is shows the meaning of the previous SL, R _9,

R10, R11, R12, R13, R! 4 and R! 5 can be the same or different species]

(H) The addition and condensation reaction between the diguanamines described in the above (a) and the aldehydes together with a compound that can be co-condensed as the case may be. The average degree of addition condensation obtained by An N-methylol-luigijiguanamine precondensate having more than 1 and at least one methylol group,

(I) Addition reaction or addition of the diguanamines described in the above (a) with the aldehydes together with a compound that can be co-condensed as the case may be. The condensation reaction is followed by an etherification reaction of at least one selected from alcohols having 1 to 20 carbon atoms. And, if appropriate, the condensation reaction is carried out at the same time, whereby the average degree of addition condensation obtained is greater than 1 and at least one Ri 0 CH Etherified diguanamine initial condensate having _two groups (R i has the same meaning as described above)

And so on.

 Examples of the above-mentioned aldehydes used in the production of these derivatives include, for example, formaldehyde, norahonolem, and hexamethylentene. Tramin, methyl to methyl, butyral to methyl, formaldehyde, sodium bisulfite Additive, glyoxal And so on, preferably to home aldehyde, holmarin, noraholm, hexamethylene teramine, methinele Mihonomar and Butyl to Mihomar, but are not limited to these.

The alcohols used for the etherification reaction in the production of these derivatives include carbon numbers of 1 to 20. Saturated or unsaturated aliphatic alcohols having Useful are alcohols, alicyclic alcohols, alcohols having an ether group, alcohols having an aromatic group, and the like. Chile alcohol call, ethyl alcohol call, n—buco pinole alcohol, is 0—propyl alcohol call, n—butinole alcohol , Is 0-butyral alcohol, tert-vinyl, n-hexyl alcohol, sec. Chiral alcohol, 2-ethyl alcohol, n-nonyl alcohol, n-hexadecyl alcohol, n- Octal desiral call, n—Ecosyl alcohol call, cyclohexanol disc, and x 、, ー ー 4 へ 4 4 、 、 4 4 、 、 4 、 、 4 、 4 4 4. -Ethernet, ethyl glycol-monobutyl ether, propylene glycol, monopoly propylene, ethylene glycol Examples include, but are not limited to, konoremonomethyl ether, benzyl alcohol, etc.

In the production of these derivatives, compounds which can be co-condensed can be used as described above, but such co-condensable compounds can be used. Examples include melamin, urea, alkyl urea, thiourea, phenolic urine, aniline, benzoguanamine, cyclone. Guanamines such as hexagonamine, etc., are mentioned, but are not limited to these. -21-The above-mentioned N-methyl-i-luigiguanamine is, for example, in a solvent, optionally in the presence of a basic compound, and has a pH of 8.0 to 13.0. , Preferably at pH 8.5 to 11.5, at a reaction temperature of 30 ° C or higher, preferably at 40 to 8 (when run under TC conditions, the reaction is Although it is possible to obtain a derivative having at least one H 0 CH ₂ group as described above, it is possible to obtain a derivative having at least one H 0 CH ₂ group. In order to obtain the N-methylolated jignanamin, it is necessary to reduce the amount of water and alcohols to obtain high purity. It is possible to obtain a good yield.However, an excessive reduction may cause a decrease in the stirring effect, an uneven reaction temperature, etc., and may hinder a smooth reaction. Not good In order to smoothly carry out such a reaction, a solvent which is substantially insoluble in water and does not inhibit the reaction, for example, toluene, xylene, ethylbenzene, etc. Aromatic hydrocarbons such as benzene, cumene, benzene and the like; aliphatic hydrocarbons such as hexane, heptane, octane, and hexane hexane; Method in the presence of octalogenic hydrocarbons such as dichloromethane, aliphatic ethers such as diisopropyl ether, amines For example, aliphatic amides such as hexamethylene pentamine, pyrazine, and piberidine, trimethylamine, dimethyl, and the like. Aliphatic amines such as pyridine, dibutylamine, hexylamine, and aromatic amides such as pyridine and aniline It is effective to add 0.01 to 10 mol% of an auxiliary agent such as ammonia to the aldehydes to the aldehydes. New paper as needed It is possible to make a choice and not be limited to these methods.

 The above-described etherified jigguanamine can be obtained, for example, by subjecting the N-methyl-obtained diguanamine obtained above to an acidic condition of pH 2 to 4 with the N-methylamine. 4 Q to 8 (at the temperature of TC, the reaction can be carried out for 1 to 8 hours in the presence of the above-mentioned alcohols for carrying out the etherification reaction) It is possible to reduce the amount of water in the reaction system as much as possible, and to reduce the reaction charge mole ratio to N— It is preferred that the above alcohols be used at a minimum of 20 moles.

 In addition, the N-methylolated diguanamine initial condensate described above has a pH of 8.0 or less together with, for example, the above-mentioned arylide. Can be obtained by carrying out the reaction at a temperature of 40 to 100 ° C. under the condition of pH 13.0 or more.

 Further, the above-mentioned etherified diguanamine precondensate is, for example, obtained from the N-methylolated diguanamine, N-methyl obtained above. Rolled jig aluminin Initial condensate pH! ) To 5.0 (acidic reaction at TC temperature in the presence of the alcohols described above. The reaction or etherification reaction and the condensation reaction can be obtained at the same time, but are not limited to these methods. is not .

N as described above-Mouth mouth

The heat-generating heat-shrinking agent of the leather-producing tree, Jiganamin, N-Met Diguanamine precondensates are remarkable for their reactivity with compounds having various functional groups, resins, etc., and are used as curing agents for various resins, intermediates of resin materials, etc. It is extremely useful, for example, at least one selected from the group consisting of the derivatives described in (v), (v), (v) and (v) above as an essential component As a result, it is possible to provide a curable composition characterized in that the curable composition is contained, and even when only these derivatives are used as the cured component. Adhesion, fiber, synthetic fiber such as polyester fiber, acrylic fiber, etc., and natural fiber such as cotton, wool, etc. It is useful as a thermosetting composition such as an excellent surface modifier such as an anti-wrinkle treatment and an anti-stain treatment agent, a paper additive, a skin treatment agent, etc. Excellent performance by reacting the diguanamine derivative of the above with a compound having a hydroxyl group, a calcium group, an isocyanate group, an epoxy group, etc. Resin, etc., can be provided, and acrylic resin, epoxy resin, reester resin, urethane resin, and amino resin liquid resin can be provided. It is extremely useful as a chain extender, cross-linking agent, curing agent, modifier, modifier, etc. with various polymers such as phenolic resin, fluororesin, vinyl resin, etc. Can be used for a wide range of applications such as resin for adhesives, resin for paints, resin for building materials, etc. Useful for applications. In particular, the above-mentioned N—Methyl-Louis-Jig-Anamin and Ether-Jig Selected from the group consisting of anamin, N-methylolated diguanamine precondensate and tert-diguanide precondensate A thermosetting composition characterized by containing at least one kind and a resin which can be cured by reacting with the thermosetting composition is a resin such as a resin for water-based paint or a resin for oil-based paint. It is useful as a paint resin.

 As the resin capable of reacting and curing with the above-mentioned resins, any resin having a functional group capable of reacting and curing with the above-described derivative is useful. For example, hydroxyl group, hydroxyl group, epoxy group, methyl amide group, alkoxymethyl amide group, iso-analyte group Resins containing at least one of the following are useful: acrylic resins, epoxy resins, polyester resins, phenolic resins, phenolic resins. Phenolic resin, urea resin, fluorine resin, silicone resin, and modified resins of these. However, it is not limited to this.

The jigguanmins according to the present invention are at least one selected from the above-mentioned jigganmins and containing an epoxy group. A thermosetting resin composition characterized by containing a resin as an essential component can be provided. Conventionally, a composition in which an amine is used as a curing agent in an epoxy group-containing resin is cured at a relatively low temperature, but the amine used as a curing agent is used as a curing agent. Is chemically active, it reacts when stored in combination with epoxy-containing resin, There are drawbacks in that the trifle is short and difficult to handle, and compositions containing dicyandiamide as hard U are: Although it has comparatively good storage stability, this resin cured product has the drawback that its properties, such as flexibility and light resistance, are not good, and these applications have been severely restricted. However, the inventors of the present invention have conducted intensive studies in view of these disadvantages, and as a result, have found that the composition has excellent storage stability and has excellent curing properties such as flexibility and light resistance. The present inventors have found the above-mentioned thermosetting resin composition capable of providing a cured resin having physical properties. This thermosetting resin composition is useful for a wide range of applications such as Ic sealants, adhesives, powder coatings, oil-based coatings, and electrical insulating materials. .

As the epoxy group-containing resin according to the present invention, a resin having at least one epoxy group can be widely used. However, it is sufficient if the molecule is a polyepoxyside having two or more epoxy groups per molecule. In particular, there is no limit to the level of the epoxy resin, for example, bisphenol. Knoll A dizzy sizzle resin-terepoxy resin, butadiene epoxide, 4, 4-ge (1, 2-epoxie) (Ethyl) diphenyl-ter, 4.4 '(epoxy) bi-factor, resorcin's jiggle , Fluoroglycin's jigrigidyl ether, p-Aminofenol's triglycidyl ether, m-Aminofyen No My rig Li Shi di Le et over Te le, te door lag Li Shi di le one-bi scan one (Family phenol) methane, 1,3,5-tri (1.

2-Epoxy) Benzene, 2, 2, 4, 4-Tetraglucidone Benzofenon, Tetraglucidone Raf-enzore-no-yen, nopolak-type phenolic-formal aldehyde resin poly-polyethylene resin, trimethylo-one Triprosynthesis level of Lepronon, Triglycilysis level of glycerin, Norogene Bisphenol A of the resin of the resin type A resin, the polyphenol resin of the mouth-opening type, and the polyphenol resin of the resin Residual ether, vinyl chloride, xenodixide, 3, 4-epoxy cyclohexyl methyl, 3, 4-epoxy To Kishi Shikuro Cyclic aliphatic epoxy resins, such as xanthate reoxylate, etc., hydantoin epoxy resin, triglyceride resin, triglyceride, etc. Epoxy group-containing vinyl units, such as heterocyclic epoxy resins such as monoliths, glycidyl acrylates, and glycidyl methacrylates Monomer, acrylic acid ester, methyl acrylate ester, fumaric acid ester, maleic acid ester, acrylic acid Mids, methacrylamides, acrylonitriles, methacrylonitriles, styrenes, butylenes, vinylenes Examples include polymers with vinyl monomers that can be copolymerized, such as steles, and modified polymers of these, but are not limited to these. Also the in is not the name is Ru.

Also, in the present invention, a polymer-type bisphenol When the viscosity of epoxy resin is too high to be used due to its high viscosity, use bisphenol A or bisphenol as a modifier. Low molecular weight bisphenol A, such as Knoll S, Bromwich Bisphenol A, Bromich Bisphenol A, etc. -It can be denatured by using epoxy resin.

 The mixing ratio between the jigguanamines and the epoxy group-containing resin according to the present invention can be appropriately selected depending on the case. The ratio of diguanamines to 0.2 to 3.0 equivalents relative to the epoxy group-containing resin epoxy equivalents, preferably 0.4 to 1.5. It is the equivalent ratio.

In addition, in the thermosetting resin according to the present invention, a hardening accelerator such as a novolac type phenolic resin, a metal salt of an organic acid, or an imidazole is used. It is possible to select and mix as appropriate depending on the case, but especially when using a novolac-type phenolic resin, it has excellent storage stability and curability, etc. It is preferable to obtain a conductive resin composition. Examples of the novolac type phenolic resin include phenol, cresol, xylene phenol, ethyl phenol, and ethyl phenol. Butyl phenol, p — phenyl phenol, nonyl phenol, bisphenol phenol A, phenol phenol, black Use phenols such as mouth phenols and aldehydes such as formaldehyde and noraformaldehyde in the usual manner. There are some things that can be manufactured more and more. It is not limited. The mixing ratio of the novolac type phenolic resin is usually from ο.ι to ΐ parts by weight with respect to the loos by weight of the epoxy group-containing resin. Although it is a ratio, it can be selected as appropriate depending on the case.

 The thermosetting resin composition according to the present invention has a predetermined distribution together with the above-mentioned diguanamines, an epoxy group-containing resin and, in some cases, other components. The raw material components selected for the ratio

Z-Blade Mixer, extruder, dry ball mill, etc., mix mechanically well, and in some cases, heat roll Although it can be obtained by a method of performing melt-mixing according to the method described above, it is more difficult when the jiganamins according to the present invention show a high melting point. This may cause uneven flow and uneven hardened material, which is not preferable. Sometimes, the above-mentioned diguanamines and low-viscosity diluents are used. A method in which a compatibilizing agent, a nopol-type phenolic resin, etc. are mixed by heating and melting in advance, and then an epoxy group-containing resin is blended and heated and mixed, using a solvent. And mixing by dissolving and dissolving with this mixed solution. Although it is possible to obtain a thermosetting resin composition in a state, it can be appropriately selected depending on the case, and the method is limited to these methods. Let's go.

Further, the thermosetting resin composition according to the present invention may further comprise, if necessary, an inorganic filler in addition to the above-mentioned diguanamines and epoxy group-containing resins. Agents, such as silica powder, Lumina, triacid thimon, talc, calcium carbonate, titanium white, creed, my strength, vengar, glass Release of fiber, carbon fiber, etc., natural waxes, synthetic waxes, metal salts of fatty acids, acid amides, esters, krafts, etc. , Flame retardants such as chlorinated rafaffin, bromtoluene, hexabrombenzen, triacid thiamine, carbon dioxide Coloring agents such as lacquer and red iron, silane coupling agents, flexible additives, low-viscosity diluents, various curing accelerators, etc. are appropriately added and blended. You can also do it.

Furthermore, the diguanamines according to the present invention include carboxylic acids, for example, phthalic acid, adipic acid, maleic acid, trimeric, and the like. Tonic acid, ethyl tetracarboxylic acid, cyclopentene, tetracarboxylic acid, pyromellitic acid, 3, 3 ', 4.4' 2,2 ', 3.3'-Benzofenententracasolevonic acid, 3,3', 4, -Benzofenententracasolevonic acid, 3,3 ', 4, 4 '-Biphenyltetracarboxylic acid, 2, 2', 3, 3 '-Biphenyltetracarboxylic acid, 1, 1 bis (3, 4-dicarboxifenyl) Pronon, bis (2, 3-dicarboxifenyl) metatan, 2, 3, 6, 7-na Phthalentetracarbonic acid, 1, 4, 5, 8 — naphthalenetracarbohydrate Acid, 1,2,5,6 — naphthalene tetracarboxylic acid olevonic acid, 1,2,3,4 —benzenteturacasolevonic acid, 2,3 6, 7 — entragon tetracarboxylic acid, 1, 2, 7, 8 — phenanthrene tetracarboxylic acid, a Or reacts with these precursors, such as partial esterified compounds, acid anhydrides, phenols, and rosin acylated compounds. It is possible to provide resins such as thiamine compounds, polyamidic acid, polyimid, polyamido, etc. Natos, for example, 1,6—hexamethyl range isocyanate, 2,2,4—trimethyl toxamethyl range isotope Cyano, diisocyanate from bisphenol, bis (2-isocyanate ethyl) fumarate, methyl 2,3,4,-,-,-,-,-,-,-,-,-,-,-. The IS Isopropylidenvise (4—cyclohexylene isocyanate), silicone range isocyanate, m—phenylene Diisocyanate, trizine diisocyanate, janizyzin diisocyanate, 3,3'-dimethyl-1,4ー フ ニ フ 1 1 1 1 1 1 フ フ フ フ フ フ フ フ フ フ フ フ フ フ フ フ フ フ フ フ フ フ フ フ フ フ フ フ フ フ フ フ フ フ フ フ フ フ フ フ フ フ フ フ フ フ フ フ フ フ フ フ フ フ フ フ フ フ フ フ フ フ フ フ フ フ フ フ フ フ フ フ. Nato, 2,6—Tri-Region Isoanato, etc. Certain levels can be obtained by reacting these with polio, amide, water, etc. By reacting with such multivalent isocyanates and the like, compounds having excellent performance, resins such as polyurea, N-substituted Saturated imido groups Compounds, for example, monophenolic maleimide, monophenolic imide, monophenolic imidate , 2—Crolfenyl maleimide, 2, 6 ― Dimethyl phenyl maleimide, 2 — methylphenyl maleimide, 2, 6 — Dimethylphenyl maleimide, 41 Hydroxy-family memory, N.N'-ethylene-male-mix, 'Ν, Ν''',Ν,-'-Dodecane Methylen vice Male Midi, N, N'-m ― Noe "^ ~ Levi's Male Midi, Ν, Ν '— Ρ — Phenylenevisimide, Ν, Ν' — ρ — Phenomenvistraconimid, Ν, Ν '-Ρ — Feniビ Ρ Ρ Ρ Ρ レ レ レ レ レ タ タ レ レ レ レ レ レ レ レ レ タ レ レ タ-4, 4 '-Diphenyl en vim. (4—Male Mid-Fenoxy) Vinyl] Pronon, Ν, Ν '-4, 4' — Dicyclone Mid, Ν, Ν '— m — X-ray マ マ m m m, ,, Ν ジ4,4 "-vis-m-ray-medium-simple-animal ', -4,4'-methylene-vis (2—isopropyl-61-methylフ [2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. By reacting with pans and the like, it is possible to provide resins and the like having excellent performance. In addition, various polymers such as urethane resins and epoxy resins can be provided. Metal extender with excellent properties such as resin Cross-linking agents, curing agents, the polymer is a modifier, such as the city and this Ru physicians use to is that Ki de, such than even Ru limited to this is found Rere. As described above, the jigguanmins according to the present invention are superior in reactivity with various compounds and polymerizability, but such Ji. The polymerization may be in any of the polymerization and reaction forms, such as solution polymerization, emulsification polymerization, suspension polymerization, bulk filling, interfacial polymerization, solution reaction, and aqueous reaction. Can be selected as appropriate.

 The jigguanmins according to the present invention are remarkably excellent in weather resistance, ultraviolet ray resistance, etc., and can maintain the initial performance for a long period of time outdoors, etc. This means that the methylol chloride of the compound is extremely excellent in water dilutability, and the restriction as a water-based resin raw material is hardly restricted, and excellent characteristics can be obtained. Has an excellent active amino group which is remarkably excellent in reactivity with aldehydes, epoxy acids, carboxylic acids, isocyanates and the like. It has unique properties such as a wide selection of the degree of methylation due to the presence of individual active hydrogens, and it is more flexible and tough. Various properties that have excellent properties such as high hardness, high water resistance, and high curability, and excellent performance. Derivative conductor, Ru Oh resin Te pole Me that Ki de and this you provide at usefulness compound.

In addition, the method for producing diguanamines according to the present invention uses the above-mentioned specific compound and appropriately selects a reaction catalyst, a solvent, a reaction temperature, a raw material mole ratio, and the like. In particular, the amount of by-products is remarkably small, the desired product can be obtained with high purity, the production of the purification and separation steps is simple, and the raw material loss is remarkable. In addition, the desired product can be obtained at a high yield by using raw materials that can be obtained at low cost, and are technically and economically excellent and extremely practical. It is something.

 Such diguanamines are excellent in polymerizability with various compounds such as aldehydes, epoxies, carboxylic acids, and iso- annathates. It is also excellent in various reactivities and is extremely useful as a resin raw material or a derivative raw material. For example, it can be obtained by reacting with aldehydes. N-methylolated diguanamine, which is obtained by an etherification reaction of the N-methylolated compound with alcohol — Hardening agents for various resins such as diguanamine telluride, their precondensates, etc., derivatives extremely useful as intermediates for resin raw materials, and containing no such derivatives. It is useful as a thermosetting composition, resin for IC sealant, resin for paint, resin for adhesive, etc. A thermosetting resin composition containing the diguanamines of the present invention and an epoxy group-containing resin can be provided.

The jiganamins according to the present invention include rubber modifiers, optical materials, registry materials, electrical insulating materials, paints for home appliances, paints for automobiles, and antifouling properties. Paints, corrosion-resistant paints, weather-resistant paints, fluorescent paints, powder paints, water-based paints, oil-based paints, building materials, Ic sealants, paper processing agents, Rikiten, softeners Anti-fouling treatment of interior products such as wall, wall cloth and force-pulp, prevention of moisture permeation of textiles, sweat absorption, sP force, anti-wrinkle treatment, new paper Textile finishing agents such as water- and oil-repellent finishing, resins for adhesives, leather treatment agents, plastic magnet nets, acid inhibitors for latex, corrosion inhibitors, An excellent ability to provide guanamine derivatives, resins, and compositions useful as electrophotographic photoreceptors, surfactants, agricultural chemicals, pharmaceuticals, and the like, which are extremely widely useful in industry. It is a compound.

 Next, reference examples and implementation examples of the present invention will be described in more detail. However, these reference examples and working examples are not intended to limit the scope of the present invention to only these examples.

Reference example 1

 Manufacture of zizobononitriles (3)

 A 500-meter flask equipped with a stirrer, thermometer, liquid inlet pipe, and cooler is connected to a bicyclo [2.2.1]. Tar 5 — 一 1 2 — Power report 297.92 g (2.50 mol), Ni [P (0

C 6 Π 5; 3] 4 8. 77 g (6. 75 millimeter _{molar), ZnC 1 2 4. 80 g} (

35.22 millimeter molar), viewed charged to _{P (0 C 6 H 5)} 3 32. 27 g (0. 104 molar), after replacing the inside thoroughly system with nitrogen gas, although such stirring The reaction mixture was kept at 65 ° C. Next, 94.59 g (3.50 mozole) of ice-cooled liquid hydrocyanic acid was supplied to the reactor at a flow rate of 45 to 55 m £ hr for 3 hours, and then further. One hour reaction.

Next, after replacing the inside of the system with nitrogen gas, deionized water was added, and the aqueous layer was separated and removed to obtain a semi-solid oily substance. The oily substance was filtered and distilled under reduced pressure to give 362.20 g (yield [2.2.1] heptanes with a rate of 9901%) 1,2,5-dicapitol and bicyclo [2.2.1] heptane A mixture of —2, 6—divinyl alcohol (boiling point: 129 to 137 ° C., 1 mmHg) was obtained. The results of elemental analysis of the target are shown below.

 Elemental analysis C H N

 Measured value 73.9% 6.9% 19.2% Calculated value 73.94% 6.90% 19.16% Reference example 2

 Bicyclo 2.2.1]. Manufacture of tan-1,2 dicasole polycarbonate:

 A 21-Flasco equipped with a stirrer, a thermometer and a reflux condenser is equipped with a 5-cyano-bicyclo [2.2.1] heptad 1-2-power valve 179.0 g (1.2 mol), N, 0—Vis (Trifluoroethyl) Hydroxylamin 292.6 g (1.3 mol) , 197.8 g (2.5 mono) of pyridine, and 600 m £ of Benzen. This mixture was stirred and heated for 3 hours while gradually heating and refluxing. Next, 500 m of deionized water was applied to the reaction mixture, and the aqueous layer was separated and removed to obtain an oily substance. The oily substance was distilled under reduced pressure to obtain 128.0 g (yield 73%) of bicyclo [2.2.1] heptane-2,5-d-carbylylbottle (boiling point). A point of 131-136 ° CZ 1 mmHg) was obtained. The results of elemental analysis of the target are shown below.

 Elemental analysis C H N

Measured value 74.0% 6.9% 19.1% Calculated value: 73.94% 6.90% 19.16% Reference example 3

 Manufacture of dicarbonates (4):

In a 500 m £ flask equipped with a stirrer, thermometer, liquid inlet tube and cooler, 48.6 g of xenocyclohexene, 188.6 g of Ni, N i [P (0 C _{6 H 5) 3] 4 6. 0} g, see charged the ZnC 12 3. 0 g, P ( 0 C 6 H 5) 3 23. 9 g, after replacing the inside thoroughly system with nitrogen gas, stirring The reaction mixture was kept at 75 ° C. Next, nitrogen-diluted 42 mol% concentration cyanogen acid gas was fed to the reactor at a rate of 177.0 millimoles Z hours for 7 hours. Next, after the inside of the system was replaced with nitrogen gas, the reaction solution was cooled and analyzed. As a result, a dicarbotriles (4) with a yield of 64.9% was obtained.

 To this reaction solution, add water and ethyl acetate to 5 Q 5g each, and let it stand for 5 hours under stirring, then separate the organic layer, and vaporize the ethyl acetate. Departed. Next, reduced-pressure distillation was performed, and as a fraction with a pressure of 0.5 to 1.0 mmHg and a temperature of 120 to 130 ° C, 132.0 g of 1,3—cyclohexan A mixture of dicarboxyl and 1,4-cyclohexanol was obtained. As a result of analyzing this fraction, it was found that 1,3—cyclohexylcarboxylic bottle 64.4% and 1,4—cyclohexanical The composition of the bottle was 35.6%. The results of elemental analysis of the target are shown below.

Elemental analysis CHN Measured value: 7 1.5% 7.6% 20.9% Calculated value: 7 1.61% 7.51% 20.88% Example 1

 Manufacture of jiaguanamines (1):

 In a 31 flask equipped with a stirrer, thermometer and reflux condenser, 146.2 g of the dicarboxylic bottles (3) obtained by the method of Reference Example 1 (1. 0 mol), 21.2 g (2.5 mol) of dicyanediamid, 16.8 g of caustic cal, 1 1 メ 0 m of methyl chloride solution Heated separately. As the temperature rose, the reaction solution became transparent, and when the temperature approached 105 ° C, the reaction rapidly progressed, and the solvent refluxed due to significant heat generation. Shortly after the start of the return flow, the reaction solution became cloudy. The reaction was carried out for 10 hours while stirring the solution at a temperature of 120 to 125 ° C.

Next, after removing the solvent from the reaction mixture, the deionized water of 31 was poured, the precipitated white precipitate was separated by filtration, and the solid fraction was deionized. After washing with water, it was washed with methanol and dried under reduced pressure. Further, this solid was dissolved in an ethyl acetate-soluble solvent, deionized water was added to this solution, reprecipitation was performed, followed by filtration, and the obtained solid was obtained. Was washed with water. The solid is dried under reduced pressure to give 2,5-bis (4,6-diamino 1, 3, 5-triazine-1-yl)-bicyclo [2 [2.1.1] Heptane and 2,5—vis (4,6—damino—1,3.5—triazine 2—yl) —bicyclo [ 2. 2. 1] Mixing of heptane The compound [white powdery crystal, melting point: 317 to 324 ° C (DSC measurement) was obtained. The reaction mixture (before the treatment) was analyzed by liquid chromatography. As a result, the yield (mol%) of the above-mentioned diguanamines (1) was 98%. 2% (based on the amount of divinyl alcohol (3)), and 0.08% by weight (based on the amount of compound other than raw materials and intended compound). (The amount of preparation of nitriles (3)). The results of elemental analysis of the target substance and ¹ H magnetic resonance absorption spectrum analysis are shown below. FIG. 1 shows the result of infrared absorption spectrum analysis of the target substance, and FIG. 2 shows the result of mass spectrum analysis.

 Elemental analysis C H N

 Measured value = 49.7% 5.8% 44.5% Calculated value: 49.67% 5.77% 44.56%

¹ H nuclear magnetic resonance absorption spectrum analysis (internal standard: TMS, solvent: d 6-DMS 0)

Absorption S value based on _two NH groups 6.50 ppm

 (Single let) 6.72 ppm

 (Single-lett) Example 2

2, 5 — bis (4, 6 — diamino 1, 3, 5 — triazine 1 2 — yl) 1 bicyclo [2.2.1] Heptane Manufacture: In place of 146.2 g (1.0 mol) of diphenyl bonito lilles (3) obtained by the method of Reference Example 1 in Example 1 To bicyclo [2.2.1] obtained by the method of Reference Example 2 Puttan-2,5-dicarboxylic sodium 160.8 g (1.1 monole) The reaction was carried out in the same manner as in Example 1 except that the reaction mixture was used, and the reaction mixture was processed. The obtained solid is dried under reduced pressure and dried under reduced pressure to give 2,5-bis (4,6-diamino 1, 3, 5-triazine-1 2-isole)-bi. Cyclo [2.2.1] heptane [white powder crystal, melting point 318-321. C (DSC measurement) was obtained. The reaction mixture (before treatment) was analyzed by liquid chromatography, and as a result, the yield of the above-mentioned diguanamines (1) (mol) was analyzed. %) Was 96.4% (based on the amount of dicarboxylic nitriles (3) charged). In the infrared absorption spectrum of the target substance, the absorption (2235 cm " ¹ ) of nitrile having a raw material compound disappeared, and a new triazine was found. The absorption

(821 cm " ¹ ) appeared, and the measured values of the elemental analysis agreed well with the calculated values as shown below.

 Elemental analysis C H N

 Measured value: 49.7% 5.7% 44.6% Calculated value: 49.67% 5.77% 44.56% Example 3

 Production of jigguanamines (2):

In a 31 flask equipped with a stirrer, thermometer and reflux condenser, the dicarbotriles obtained by the method of Reference Example 3 (4) 134.2 g (1. 0 mozorejiangjito '210.2 g (2.5 mol), caustic force 16.8 g, methizole cellosol A batch of 1ϋ0ϋm was charged and gradually heated. As the temperature increased, the reaction solution became transparent, and when the temperature reached about 105 ° C, the reaction proceeded rapidly, generating a large amount of heat and refluxing the solvent. . Shortly after the start of the reflux, the reaction solution became turbid. The reaction was carried out for 10 hours while stirring this solution at a temperature of 120 to 125 ° C.

 Next, after the solvent is removed from the reaction mixture, the deionized water of 31 is poured in, the precipitated white precipitate is separated by filtration, and the solid component is removed. After washing with ion water, it was washed with methanol and dried under reduced pressure. Further, this solid was dissolved in an ethyl acetate-soluble solvent, deionized water was added to this solution, reprecipitation was performed, followed by filtration, and the obtained solid was obtained. The part was washed with water. The solid content is dried under reduced pressure to obtain 1.3-bis (4,6-diamino 1, 3, 5-triazine 2-yl)-cyclohexa. And 1.4-vis (4,6—diamino 1,3,5—triazine-12-yl) -a mixture of cyclohexane [white Color powder powder

Said point 3 17 ~ 32 1 ° C (DSC measurement)] was obtained. The reaction mixture (before treatment) was analyzed by liquid chromatography, and as a result, the yield (mol%) of the diguanamines (2) described above was determined. 97.3% (based on the amount of divinyl nitrols (4) charged), and 0.12% by weight (based on the amount of compound other than the raw materials and the intended compound) (The amount of bottles (4)). The results of elemental analysis and ¹ H nuclear magnetic resonance absorption spectrum analysis of the target substance are shown below. In addition, the infrared ray of the object Fig. 3 shows the results of a line absorption spectrum analysis, and Fig. 4 shows the results of a quality spectrum analysis.

 Vat analysis C H N

 Measured value 47.6% 6.1% 46.3% Calculated value 47.67% 6.00% 46.33% Nuclear magnetic resonance absorption spectrum analysis (internal standard:

TMS solvent: d 6-DMS 0)

 Absorption δ value based on NH 2 V 6.49 ppm

 (Single-lett) Example 4

 1.4 One-vis (4,6-dia 1, 3,5 -triazine 1 -yl)-Production of cyclohexan:

 In place of 134.2 g (1.0 mol) of divinyl bonitols (4) obtained by the method of Reference Example 3 in Example 3, 1,4-one cycle was used. The reaction was carried out in the same manner as in Example 3, except that 147.6 g (1.1 mol) of the mouth hexagonal sodium nitrile was used. Was performed. The obtained solid matter was dried under reduced pressure, and dried under reduced pressure to obtain 1.4-vis (4,6-diamino-1,3-, 5-triazine-12-yl) Black Hexane

A melting point of 319 to 322 ° C (measured by DSC) was obtained. The reaction mixture (before treatment) was analyzed by liquid chromatography, and as a result, the above-mentioned diguanamines were analyzed.

The yield (mol%) of (2) was 95.8% (vs. the amount of dicarboxylic nitrile (4) charged). Infrared absorption of the object The absorption spectrum showed that the absorption of nitrile (2237 cm " ¹ ) of the raw material compound disappeared, and the absorption of triazines (821 cm" ¹ ) was lost. Appeared, and the measured values of the elemental analysis were in good agreement with the calculated values as shown below.

 Elemental analysis C H N

 Measured value: 47.7% 6.1% 46.2% Calculated value: 47.67% 6.00% 46.33%

1 H nuclear magnetic resonance absorption spectrum analysis (internal standard: TMS, solvent: d ₆ -DMS 0)

Absorption δ value based on NH ₂ group 6.50 ppm

 (Single-lett) Example 5

 1. Production of 2-vis (4,6-diamino-1,3,5-triazine-12-yl) per cyclohexane:

The divinyl bonitols (4) 134.2 g (1.0 mol) obtained by the method of Reference Example 3 in Example 3 were replaced by 1,2—six The reaction was carried out in the same manner as in Example 3, except that 134.2 g (1.0 mol) of hexylcarboxylic nitrile was used, and the reaction mixture was treated. went . The obtained solid was dried under reduced pressure to obtain 1.2-bis (4,6-diamino 1, 3, 5-triazine 1-2) of white powdery crystals. 1) I got a cyclohexane. In the infrared absorption spectrum of the target substance, the absorption of nitrile contained in the raw material compound disappears, and the absorption of the triazine ring newly appears, and the elemental element appears. analysis The measured value of-was in agreement with the calculated value as shown below.

 Elemental analysis C H N

 Measured value: 47.7% 6.0% 46.3% Calculated value: 47.67% 6.00% 46.33% Example 6

 Manufacture of jiaguanamines (1):

 The reaction and treatment were carried out in the same manner as in Example 1 except that the charge amount (mol) of disocyanide amide and the type of the reaction solvent in Example 1 were changed. Was performed. The yield of the target compound, diguanamines (1), is shown in Table 1.

 Table 1

(Note 1) Indicates the value calculated from the result of liquid chromatographic analysis of the obtained reaction mixture (before treatment). New paper Example 7

 Manufacture of jiaguanamines (1):

 In a 31 flask equipped with a stirrer, thermometer and reflux condenser, 146.2 g of the dicarboxylic bottles (3) obtained by the method of Reference Example 1 (1. 0 mol), dicyane diamide 210.2 g (2.5 mol), sodium methyl chloride 54.0 g, dimethyl sulfoxide Charge 1000 m £, gradually power! ] It was heated. When the temperature was close to 1.5 ° C, the reaction progressed rapidly and the heat generation became remarkable. Thereafter, the temperature was gradually increased to 14 (TC. The reaction was carried out for 2 hours while stirring the solution at a temperature of 140 to 145 ° C.

 Next, the reaction mixture was treated in the same manner as in Example 1, and the 2,5—vis (4,6—damino 1, 3.5.5—triazine 1 2 — [2.2.1] Heptane and 2,6 1-vis (4.6-diamino 1,3,5—triagin 1 2 1) A mixture of bicyclo [2.2.1] heptane was obtained. The reaction mixture (before treatment) was analyzed by liquid chromatography to find that the yield of the above-mentioned diguanamines (1) %) Was 99.7% (based on the amount of dicarboxylic bottle (3)).

Example 8

 Production of jigguanamines (2):

In the same manner as in Example 3 except that the charge amount (mol) of disocyanamide and the type of the reaction solvent in Example 3 were changed. The reaction and processing were performed according to the procedure described above. The yield of the target compound, diguanamines (2), is shown in Table 1.

Two

(Note 1) Shows the value calculated from the result of liquid chromatographic analysis of the obtained reaction mixture (before treatment). Example 9

 1.4 One-vis (4,6-diamine 1, 3, 5-triazine-1 2-yl)-Production of cyclohexan:

 In a 31 flask equipped with a stirrer, thermometer, and reflux condenser, 1,4-cyclohexylcarboxylic nitrile 134.2 g (1.0 mole), Prepared with 21.2 g (2.5 mol) of dicyane diamide, 54.0 g of sodium methylate, and 1000 m £ of dimethinolesulfoxide , Gradually heated. When the temperature approached 105 ° C, the reaction rapidly progressed and exotherm became remarkable. Thereafter, the temperature was gradually increased to 140 ° C. The solution was reacted for 2 hours with stirring at a temperature of 140 to 145 ° C.

 Next, the reaction mixture was treated in the same manner as in Example 3, and the white powdery crystal 1,4,1-vis (4,6-diamino-1,3,5-to-1) was treated. Reargin 1 2-yl)-I got a cyclohexane. The reaction mixture (before the treatment) was analyzed by liquid chromatography, and as a result, the yield (monoole%) of the above diguanamines (2) was 99%. It was 1% (total amount of zinc chloride (4)).

As shown in Examples 1 to 9, the jigguanmins according to the present invention can be provided, and in addition, specific jigbonamines can be provided. According to the production method in which the reaction is carried out by appropriately selecting a reaction catalyst, a solvent, a reaction temperature, a raw material mole ratio, and the like using the compound and dicyanediamide, by-products are significantly reduced. High purity In addition, the production of the desired compound was simple and easy in the purification / separation step, etc., and the desired compound could be obtained at a high yield, which was remarkably excellent. Example 10

 Manufacture of N-methyl mono-Luich products of diguanamines (1) and water dilutability test of the derivatives:

 The diguanamines (1) obtained by the method of Example 1 (1) (15.7 g, 0.05 mol) was added with 10% aqueous sodium hydroxide solution to pH 10.5. Adjusted to 37% of holmarein 42.2 g (honolemu aldehyde 0.52 monole). The mixture was heated at a temperature of 60-65 ° C with stirring for 30 minutes. The reaction mixture was a uniform and transparent liquid, and as a result of analyzing the same, it was found that 1 mol of the diguanamines (1) and 1 mol of formanolamide 7. Two moles were methylol-bonded.

 Further, 50 g of deionized water was gradually added to the obtained N-methylolide solution at room temperature, but this solution was a homogeneous and transparent liquid. there were .

Example 1 1

 Production of N-methyl mono-monohydrate of diguanamines (2) and water dilutability test of the compound:

The diguanamines (2) obtained by the method of Example 3 (2) (15.1 g, 0.05 mol) were added with 10% aqueous sodium hydroxide solution to adjust the pH to 10.5 g. The adjusted 37% formalin 42.2 g (0.52 moles of formalaldehyde) was added. The temperature of this mixture is 60-65. C. The mixture was heated with stirring for 30 minutes. This reaction mixture was a homogeneous and transparent liquid, and as a result of analysis of the liquid, it was found that 1 mol of the diguanamines (2) and 7 mol of honolemaldehyde were added to 1 mol of the diguanamines (2). 3 moles were methylol-bonded

 Further, 50 g of deionized water was gradually added to the obtained N-methylolide solution at room temperature, but this solution was a homogeneous and transparent liquid. there were .

 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. It was remarkably superior as a water-based resin raw material such as a base paint resin, and was found to be extremely useful for a wide range of uses.

Comparative Example 1

 Preparation of N-methylolated phthalguanamine and water dilutability test of the compound:

 In place of 15.7 g (0.05 mol) of jigganmins (1) obtained by the method of Example 1 in Example 10 instead of o- The reaction was carried out in the same procedure as in Example 10 except that 14.8 g (0.05 mol) of loganamin was used.

This reaction mixture is a liquid containing a large amount of insoluble solids, which is subjected to solid-liquid separation by hot filtration, and the solids are dried under reduced pressure to obtain 13.7 g of crystals (elemental analysis). From the results, o-phthaloguanine (13.6 g, 0.046 mol) was obtained. Furthermore, 1.0 g of deionized water was added to this solution at room temperature, and this was remarkably effected. It became cloudy.

Comparative Example 2

 Production of N-methylollich of spiroguanamine and water dilutability test of the compound:

 Example 10 In place of 15.7 g (0.05 mol) of diguanamines (1) obtained by the method of Example 1 in place of 3,9,1-vis [2- (3,5——Diamin 2, 4,6—Tri-A-Z-Final) Ethyl] 1 2. 4, 8.10—Tetra Oxa Spi Π [5.5] Pendin [(trade name) CTU Guanamin, manufactured by Ajinomoto Co., Inc.] Except for using 21.7 g (0.05 ml), The reaction was carried out in the same procedure as in Example 10.

The reaction mixture This Ri Ah in the liquid that exists a large amount of insoluble solids, the Re this solid-liquid separation performance similar hot filtration, the solid was vacuum Drying forming _Η ¾ 18. 3 g _[Elemental analysis As a result, 18.2 g (0.042 mol) of CTU guanamine were obtained]. Furthermore, when 1.0 g of deionized water was added to this solution at room temperature, the solution became very cloudy.

As shown in Comparative Examples 1 and 2, the above-mentioned phthaloguanamine and spiroguanamine showed a significant methylolation reaction with phenolic aldehydes. The reactivity of the amino group in such a compound is poor, and the copolycondensate with melamin, guanamines, ureas, etc. It must be difficult to produce resin intermediates and various derivatives, and the N-methyl chloride of such a compound is extremely poor in water dilutability. , Water-based paint It was not only difficult to use it as a raw material for water-based resins, but also had significant restrictions on its use. Example 1 2

 Production of N-methylolated product of jiaguanamines (1) 15.7 g (0.0 g) of diguanamines (1) obtained by the method of Example 1 5 mol), 17.9 g of 37% formalin adjusted to pH 9.0 with 5% aqueous sodium carbonate solution (0.2 mol of honolaldehyde aldehyde) 2 moriles). The mixture was heated at a temperature of 70-75 ° C with stirring for 30 minutes. This reaction mixture was a clear liquid, and as a result of analyzing this, it was found that 4.0 moles of the diazonamines (1) per mole of the diguanamines (1). It was the result of a methyl-bonded mole.

Example 13

Production of N-methylolated diguanamines (1) 15.7 g of diguanamines (1) obtained by the method of Example 1 (0.0 g) 5 moles), add 19.9 g (0.32 moles) of methyl alcohol and 40.0 g of methanol, and add 20% caustic The pH was adjusted to 9.5 with an aqueous solution. The mixture was heated at a temperature of 60 with stirring for 1 hour. This reaction mixture is a clear liquid, and as a result of analysis of this liquid, 6.1 moles of formaldehyde was used per mole of the diguanamines (1). Was a methyl roll bond. Example 14

 Production of N-methylol compound of diguanamines (1) 2,5-bis (4,6-diamino-1,3 obtained by the method of Example 2) , 5-Triazine-2-cisole) [2.2.1] Heptane 15.7 g (0.05 mol) with 5% caustic soda 81.2 g of 37% formalin (formaldehyde 0 mol) adjusted to pH 10.5 with an aqueous solution was added. The mixture was heated with stirring at a temperature of 6 (TC for 1 hour. The reaction mixture was a clear liquid, which was analyzed to show that the 2,5 4, 6-diamino 1, 3.5-triagin 1 2-dinocyclo) [2.2.1] Heptane 1 7.8 mol of methylaldehyde was methylol-bonded.

Example 15

 Manufacture of N-methoxy-Luich products of jiaguanamines (1):

Diguanamines (1) obtained by the method of Example 10 (1) 5.0 g of N-methyl-Luichi product (equivalent to 1 mol of the diguanamine) The reaction mixture of aldehyde (7.2 mol bond) was dehydrated under reduced pressure, and 50 ml of methanol was added thereto. This mixture was adjusted to pH 2.0 with 2Q% nitric acid, and then heated at a temperature of 4Q to 45 ° C for 2 hours. After adjusting the reaction mixture to pH 8.Q with 10% aqueous sodium hydroxide solution, Then, methanol and water were removed under reduced pressure, and the solid matter was further filtered to obtain a viscous liquid. As a result of the analysis, it was found that 5.3 mol of N-methoxymethyl group was bound to 1 mol of the diguanamines (1). .

Example 16

 Manufacture of N-methoxy-Norreich products of diguanans (2):

 Jigguanamines obtained by the method of Example 11 (2)

A reaction mixture of 5.0 g of N-methyl chloride (7.3 mol bond of formanolamide to 1 mol of diguanamine) was added under reduced pressure. After dehydration, 50 mjg of methanol was added thereto. The mixture was adjusted to pH 2.0 with 20% nitric acid and then at a temperature of 40-45. Heated in C for 2 hours. The reaction mixture was adjusted to pH 8.8 G with a 10% aqueous solution of sodium hydroxide, and then methanol and water were removed under reduced pressure. The solid was further filtered off. A viscous liquid was obtained. As a result of analyzing this, the N-methoxymethyl group was added to the diguanamines (2) 1 monole.

4.9 equivalents were bound.

As shown in Examples 15 and 16, the N-methylol compound of the diguanamines according to the present invention was formed under mild conditions with alcohol. It is an alkyl ether compound that easily undergoes an alkyl ether reaction and has very excellent reactivity. Further, the N-A compound of this compound that is extremely useful as a resin intermediate is used. O Provided methyl chloride compound Example 17

 Production of N-methylollich precondensate of diguanamines (2):

 Jigguanamines (2) 15 obtained by the method of Example 4

Add 1 g (0.05 mol.) To para-horizon medium (80% o

 PP

 13.1 g (formaldehyde 0.35 mol) and 50 ml of methanol are squeezed, and the mixture is stirred and mixed with 2 Q% aqueous caustic solution. The pH was adjusted to pH 13.2. The mixture was heated at a temperature of 80 ° C. with stirring for 1 hour. After the completion of heating, the reaction mixture was adjusted to pH 8.3 with a 1 D% aqueous hydrochloric acid solution, and the precipitate was filtered to obtain a uniform transparent solution. As a result of analysis of the resinous material obtained by desolvating the solution from this solution, it was found that the dimethylguanine (2) structural unit was not used for one of the diguanamines (2) structural units. 0.0 mol was a methylol bond and had an average degree of addition condensation of 1.3. Example 18

 Etherification of jiaguanamines (1) Production of the initial compact:

The diguanamines (1) obtained by the method of Example 1 (1) (15.7 g, 0.05 mol) were combined with norphorformazole (80%). % Product) 18.8 g (0.55 mol of formaldehyde) and 50 ml of n-butanol are mixed with 10% while mixing and stirring. The pH was adjusted to 1.0 with caustic soda aqueous solution. The mixture is brought to a temperature of 60 ° C. After heating for 30 minutes while stirring for 30 minutes, the pH was adjusted to 3.0 by adding a 20% aqueous nitric acid solution. Further, the reaction mixture was heated under reflux conditions with stirring for 2 hours while performing reflux dehydration. After completion of the heating, the reaction mixture was adjusted to pH 8.0 with a 10% aqueous solution of sodium hydroxide, and the precipitate was filtered to obtain a uniform and transparent solution. Analysis of the resinous material obtained by desolvation from this solution showed that one unit of the diguanamines (1) was not contained in one of the structural units. This was an etherified diguanamine precondensate having an average degree of addition of 1.6 and containing a butyral ether group with a methylol-bonded methylol.

Example 19

 Polymerization of N-methylolated diguanamine and UV resistance test of the resin:

 N-methylol compound of diguanamines (1) obtained by the method of Example 10 (equivalent to 1 mol of the diguanamines (1) 5.0 g of zolemaldehyde (7.2 mol bond) was dissolved in n-butyl alcohol 1 Qm, and P-toluenesul was used as a curing catalyst. 0.025 g of phosphoric acid was applied, applied to a zinc plated steel sheet, and then cured by heating at 14 Q ° C-20 minutes.

Using this coated steel sheet, irradiating the test steel sheet with a vertical distance of 25 cm from the service water for 200 hours using a germicidal lamp (manufactured by Toshiba 19 W) as an ultraviolet light source. Was Surface light of the test steel sheet As a result of measuring the stream in accordance with JISK540 (600 ° specular reflectance), the light spot retention rate was 97%.

Example 20

 Polymerization of N-methyl sulfide and the UV resistance test of the resin:

 Example 11 N-methylolated compound of diguanamines (2) obtained by the method of Example 11 (equivalent to 1 mol of the diguanamines (2) 5.0 g was dissolved in 10 ml of n-butyl alcohol, and p-toluene was used as a curing catalyst. 0.025 g of sulfonic acid was added, applied to a zinc plated steel sheet, and then heat-cured at 140 ° C-20 minutes.

 The test steel sheet was irradiated from a height of a vertical distance of 25 to the test steel sheet for 200 hours using a germicidal lamp (19 W made by Toshiba) as an ultraviolet light source using the coated steel sheet of . The surface gloss of the test steel sheet was measured in accordance with JIS K540 (600 ° specular reflectance). As a result, the gloss retention was 98%.

 As shown in Examples 19 and 20, the diguanamine N-methylolates according to the present invention are excellent in polymerizability, and furthermore, the compounds are resistant to ultraviolet rays. The gloss deterioration was extremely small and had very excellent properties.

Example 2 1

Anti-wrinkle test of fiber treatment agent using N-methylolated diguanamine: New paper N-methylollic product of diguanamines (1) obtained by the method of Example 10 (the amount of diol per 1 mole of the diguanamines (1)) A 10% by weight aqueous solution was prepared in deionized water by using aldehyde (7.2 mozole bond). To this, as a catalyst, ammonium diphosphoric acid 3% by weight (based on the solid content of the derivative) was added with an aiding force α. Using this solution, immerse it in cotton cloth (cotton cloth: 60), perform the notching treatment, and then dry this cotton cloth for 8 (TC-5 minutes). Then, it was further heated under the condition of 140 ° C. for 5 minutes.

 As a result of performing a wrinkle resistance test in accordance with JISL1059 (Monsant method) using a cotton cloth treated as described above, the wrinkle resistance was 86%, which was extremely excellent. It exhibited anti-wrinkle properties.

 As described above, when the fiber is treated with the N-methylolated diguanamine according to the present invention, a very excellent protection against the fiber is obtained. The thermosetting composition containing the diguanamine derivative can impart properties such as wrinkle properties, and is extremely useful as a fiber treatment agent. It was something.

Example 22

 Curing test of water-based paint resin using N-methylol

N-methyl-Luich product of the jiaguanamines (1) obtained by the method of Example 10 (for 1 mol per mol of the jiganamins (1)) Mualdehyde (7.2 mol bond) 6.0 g of 50 % Aqueous solution WA 911 [Mitsui Toatsu Kagaku Co., Ltd., V 60%] While stirring to 40.0 g, dimethylene ethanol was stirred. 1.84 g of the solution was gradually added, and then mixed with a solution adjusted to have a nonvolatile content of 2% by deionized water. The obtained resin solution was applied to a zinc plating steel sheet, and then 160. C Heated for 20 minutes

 No coating, blistering, discoloration, etc. were observed on the coating film of the coated steel sheet treated with the above method. As a result, the gloss was 98%, and it had extremely excellent smoothness and gloss. Furthermore, even when the coating film surface was rubbed 50 times with a cloth impregnated with acetone, no separation of the coating film was observed, and the coating film was sufficiently cured. It was a coating film.

Example 23

 Curing test of water-based paint resin using N-methylol

Example 11 N-methylolated compound of diguanamines (2) obtained by the method of Example 11 (equivalent to 1 mol of the diguanamines (2) 5.9 g of a 50% by weight aqueous solution was added to Almatex WA 911 [Mitsui Toatsu Chemicals, NV 60%] 40 While stirring to 0 g, slowly add 1.84 g of dimethylethano-soleamine and then add the solution adjusted to a nonvolatile content of 2 G% with deionized water. Eh mixed. After applying the obtained resin solution to a zinc plating steel sheet, Heat treatment was performed at 60 ° C for 20 minutes.

 No coating, blistering, discoloration, or the like was observed on the coating film of the coated steel sheet subjected to this treatment, and the surface gloss of the coating film was measured according to JISK 5400 (60 ° specular reflectance). As a result, the gloss was 94%, and the material had extremely excellent smoothness and gloss. Furthermore, even when the coating film surface was rubbed 50 times with an acetate-impregnated cloth, no peeling of the coating film was observed and the coating film was sufficiently cured. It was a coating.

 As shown in Examples 21 to 23, the diguanamine derivative according to the present invention is extremely excellent in water dilutability, and has a thermosetting property containing the diguanamine derivative. The composition is not only excellent as an aqueous resin such as an aqueous paint resin, an adhesive resin, and a fiber treatment agent, but also has a curability of a paint resin and a bridging property. And it was found to be extremely useful in a wide range of applications.

Example 2 4

 Curing test of water-based coating resin using N-method

N-methoxymethylated compound of diguanamines (1) obtained by the method of Example 15 [to 1 mol of the diguanamines (1) N—Methoxymethyl group 5.3 equivalents] 6.8 g of a 50% by weight solution in a solvent mixture of solvent and water (weight ratio 5QZ50) And 0.15 g of P-toluenesulphonic acid was added to Almatex WA 911 [Mitsui Toatsu Chemicals, Inc. NV 60%], while gradually adding 1.84 g of dimethylamine-lamine while stirring to 40.0 g, and then adding to deionized water. The solution was adjusted to a non-volatile content of 20% and mixed with calorie. The obtained resin solution was applied to a zinc-containing steel sheet and a steel sheet, and then heat-treated under a condition of 160 ° C. for 20 minutes.

 No coating, blistering, discoloration, or the like was observed in the coating film of the coated steel sheet after this treatment, and the surface light of the coating film was measured by JISK5400

As a result of measuring according to (60 ° specular reflectance), the gloss was 96%, and it had extremely excellent smoothness and gloss. Furthermore, even if the coating film surface was rubbed 50 times with a cloth impregnated with acetone, no separation of the coating film was observed, and the coating film was sufficiently cured. It was a coating.

 As shown above, the etherified diguanamine according to the present invention is excellent in polymerizability, and furthermore, reacts with this ethereous diguanide. It has been found that a thermosetting resin composition containing a curable resin is extremely useful as a resin for water-based paints and the like.

Example 2 5

 (I) Polymerization of methoxymethylated diguanamine and weathering test of the resin:

N-methoxymethylated compound of diguanamines (2) obtained by the method of Example 16 [to 1 mole of the diguanamines (2) N — methoxymethyl group 4.9 equivalents] 4.9 g was dissolved in 10 g of methyl butyl ketone, and then dissolved. 47.2 g of Almatex P6464 [manufactured by Mitsui Toatsu Chemicals, Inc., NV 60%] was mixed with power CI and mixed. This resin solution was applied to a zinc plated steel sheet, and then heat-cured under a condition of 18 (TC-50 minutes).

 Using this coated steel sheet, an exposure test of 500 hours was performed using Weather 0-meter. No blisters, discoloration, etc. were observed on the surface of the coating film of the test steel sheet, and the surface gloss of the coating film was measured in accordance with JIS 5400 (60 ° specular reflectance). As a result, the gloss retention was 95%.

Example 26

 Polymerization of etherified diguanamine initial condensate and weathering test of the condensate:

 Example 18 Etherified initial condensate of diguanamines (1) obtained by the method of Example 18 [for one structural unit of diguanamines (1) Average degree of addition condensation 1.6] 5. After dissolving Q g in 10 g of methyl isobutyl ketone, this was added to Almatex P 6 4 6 [Mitsui Manufactured by Toatsu Chemical Co., Ltd., NV 60%] was added and mixed. After this resin solution was applied to a zinc plating steel plate, it was heated and hardened under the conditions of 16 (TC-30 minutes).

Using this coated steel sheet, a 500-hour exposure test was performed with a laser meter. No blisters, discoloration, etc. were found on the surface of the coating film of the test steel sheet, and the surface gloss of the coating film was measured in accordance with JISK540 (60 ° specular reflectance). As a result, the gloss retention was 97%.

 As shown in Examples 25 and 26, the ether product of the diguanamine and the etherified precondensate of the diguanamine according to the present invention are excellent in polymerizability. In addition, a cured product obtained from these derivatives and a thermosetting resin composition containing a curable resin that reacts with these derivatives also has excellent weather resistance, It was found to be extremely useful as a resin for paints.

Example 2 7

 Curing test of epoxy group-containing resin by diguanamines (1):

Dissolve 100 g of epoxy resin containing epoxy resin ^# 8228 (manufactured by Shell) in 1000.0 g of butyrose-solvent. Was added to 19.6 g of the diguanamines (1) obtained by the method of Example 1 and dissolved to prepare a resin solution. This resin solution was applied to a zinc plated steel sheet, and then heated at 11 Q ° C for 30 minutes, and further heated to 20 (TC for 40 minutes). The coating film of the coated steel sheet was sufficiently hardened even if the coating film surface was rubbed 50 times with a cloth impregnated with toluene, and no peeling of the coating film was observed. It was a transparent coating.

Example 2 8

 Curing test of epoxy group-containing resin with diguanamines (2):

Example 27 In place of 19.6 g of diguanamines (1) obtained by the method of Example 1 in Example 7, the method of Example 3 was used. The resin solution was prepared in the same manner as in Example 27 except that 18.9 g of the jiganamins (2) obtained in the above was used, and a coating film hardening test was conducted.

 The coating film of the coated steel sheet that has been heat treated is sufficiently separated even if the coating film surface is rubbed 50 times with a cloth impregnated with toluene, and the coating film is not separated. It was an excellent transparent coating that had hardened.

 Example 2 9

 Storage stability test of thermosetting resin composition:

 The epoxy group-containing resin and the diguanamine are blended in the types and amounts shown in Table 3 and 90 to 11 in advance until each component is sufficiently uniform. The mixture was kneaded with two rolls heated to 0 ° C for 15 to 30 minutes, taken out in a sheet form, and pulverized. Using this sample, it was left standing in a dryer kept at 40 ° C to determine the storage stability. The results are shown in Table 1-3.

 As shown in Table 3, it was found that the thermosetting resin composition according to the present invention had extremely excellent storage stability. Table 1 3 Epoxy group-containing resins Diguanamines Classification at 40 ° C Classification type Classification amount Storage stability

 (Parts by weight) (parts by weight)

 Shrimp coat * 828

Example 29-1 1000.0 Example 1 19.6 3 months or more

 (Manufactured by Shell) Diguanamines (1) Ebicoat * 828 Example 4

Example 29-2 100 .0 18.9 3 months or more

(Manufactured by Shell) Diguanamines (2) Example 30

 Flexibility test of cured resin obtained from thermosetting resin composition:

Et Po key sheet group-containing organic resin We pin co one Bok ^# 828 (Shi et le Co.

) Combine 100 g with 19.6 g of diguanamines (1) obtained by the method of Example 1, and in advance 90-11 until each component is sufficiently uniform. The mixture was kneaded with two rolls heated to o ° c for 30 minutes, taken out in a sheet form and pulverized. A resin cured product was prepared using this sample under the curing conditions of 190 ° C-3B. Using this resin cured product, a Charby impact value was measured as a measure of flexibility. The results are shown in Table 1-4.

 In addition, as a comparative example, in place of the above-mentioned jiganamins, dicyanediamid was used, and the optimum compounding amount and curing conditions were the same as above. Table 1 4 Epoxy group-containing resin Diguanamines or Charby impact value Dicyan diamide Curing conditions

Example 30 100.0 g 19.6 ε 190 ° (No. 3 hours 8.0 Comparative Example 3 100.0 g 5.5 g 170 ° C No. 1 hour 3.0 EP * 828 Compounding amount Compounding amount (Kg «cm / cin ² ) As shown in FIG. 4, the cured resin obtained from the thermosetting resin composition according to the present invention was found to be excellent in flexibility.

Example 3 1

 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 Dissolved in 200 g of rosenoleb and dissolved in a solution of jiganamin (1) obtained by the method of Example 1.

11.1 g was added and dissolved to prepare a resin solution. This resin solution was applied to a zinc plated steel sheet and then heat-cured under the conditions of 2 G (TC-40 minutes).

 Using this painted steel plate, the

Exposure to 3,000 temples was performed and a weather resistance test was performed. The glossiness of the surface of the coating film on the test steel sheet was measured in accordance with JIS K 5400 (60. Mirror reflectivity). As a result, the gloss retention was 94%.

 As shown above, the cured resin obtained from the thermosetting resin composition according to the present invention has excellent weather resistance and is extremely useful as a resin for paints and the like. It turned out that it was.

Example 3 2

Coating test of resin for powder coatings obtained from thermosetting resin composition: Using a resin solution of the thermosetting resin composition obtained by the method of Example 31, this was heated and depressurized to remove the solvent, thereby obtaining a solid resin. Further, the solid resin was coarsely pulverized by a coarse pulverizer, and then finely pulverized by an atomizer. This was sieved through a 150 mesh sieve, and the pass product was used as a resin for powder coating in a test. Using the resin for powder coating, a zinc phosphate converted chemical steel sheet is electrostatically coated to a film thickness of about 5 D micron, and then subjected to a temperature of 200 ° C — 40 ° C. Heat treatment was carried out under the conditions described above.

 The coating film of the heat-treated coated steel sheet has good coating smoothness (visual judgment), and the coating surface is rubbed 50 times with a cloth impregnated with toluene. No separation of the coating film was observed even after this, and the coating film was an excellent transparent coating film which was sufficiently cured.

 Furthermore, using this coated steel sheet, a sterilizing lamp (19 W made by Toshiba) was used as an ultraviolet light source, and a vertical distance of 25 cm from the test steel sheet to 20 Q As a result of the irradiation during the irradiation, no blisters or discoloration were observed on the surface of the paint, and the surface gloss of the paint film was changed to << SK540 (60 ° specular reflectance). As a result, the gloss retention was 96%, and the coating film had excellent ultraviolet resistance.

Example 3 3

 Adhesion test of thermosetting resin composition:

100 g of epoxy resin containing epoxy resin containing epoxy resin ^# 828 (manufactured by Ziel) and a jig ganami obtained by the method of Example 1. (1) 15.7 g, 30 minutes with two rolls heated to 90 to 110 ° C before each component becomes sufficiently homogeneous Kneaded. A steel plate was bonded using the kneaded resin and hardened under a condition of 20 (TC-1 hour). Tensile bond strength of the cured resin (At 25) was 176 kg / cm ² .

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

 The invention's effect

The jig anamins according to the present invention are remarkably excellent in weather resistance, ultraviolet ray resistance, etc., and can maintain their intended functions over a long period of time outdoors. As a result, the methylol compound of the compound is extremely excellent in water dilutability, has almost no restriction as a water-based resin raw material such as a water-based paint, and has excellent performance. It has an active amino group with excellent reactivity with formaldehyde, epoxy compound, etc., and has eight active hydrogens. Therefore, it has properties such as a wide selection of the degree of methylolation, etc., and further has flexibility, toughness, high hardness, water resistance, and curability. It is also possible to provide compounds, resins, compositions, etc. that also have excellent properties and have excellent properties. It is very useful for a wide variety of applications. Further, the method for producing jiaguanamines according to the present invention is a method for identifying specific dicarbotriles and dicyanidiamid. Under the above conditions, it is possible to obtain easily and inexpensively a high-purity, low-cost, highly purified, and highly purified by-product process. It provides an excellent method for obtaining the desired compound in high yield using nitriles.

 In addition, such jiganamins can be polymerized with various compounds such as asoaldehydes, epoxies, carboxylic acids, isocyanates, and the like. It is excellent in properties and excellent in various reactivities, and is extremely useful as a raw material for a resin or a derivative. For example, it is obtained by reaction with aldehydes and the like. It is used as a curing agent for various resins such as N-methylated jigganmin, esterified diguanamine, and their initial condensate, and as a resin raw material. And useful derivatives, thermosetting compositions containing these derivatives, resins for paints, resins for adhesives, and the like, which are useful as the above-mentioned jigganamines It is possible to provide a thermosetting resin composition or the like containing the epoxy resin and the epoxy group-containing resin. It is an excellent invention in the industry

Claims

Request box General Formula mi α ΐ (I)

[In the formula, the bonding position of the (4, 6-diamino I, 3.5-triazine-2-yl) group is 2.5-or 2, 6-position. ] Or the general formula (2) NH ₂ H ₂ N. N- C, ^C , z C = N ', <(2) NH H ₂ N [Wherein, the bonding position of the (4,6—diaminol, 3,5triazine-2-yl) group is represented by I.2—1,3— or I, 4 1 [Indicating the position]].  2. General formula (3) N

(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 indicates the 1, 2, 1-, 3- or 1-, 4-position.) Characterized by reacting the dicarbotriles represented by the formula (1) with dicyanediamid in the presence of a basic catalyst. Manufacturing method of minerals.  3. Alkaline metal, alkaline metal hydroxide, alkaline earth metal hydroxide, alkaline metal hydroxide, disilane Select from the group consisting of azorecal metal salts of amide, earth metal salts of disocyanide, earth metals, amides and ammonia. Claims characterized in that at least one kind is a method for producing a jiganamin according to claim 1.  4. The reaction is carried out using at least one selected from the group consisting of a non-aqueous proton solvent and a non-proton polar solvent. The method for producing jigguanmines according to claim 2, wherein the method is characterized in that: 5. The scope of the claim that the reaction is carried out at a temperature in the range of 60 to 200 ° C The method for producing jigguanamines described in Paragraph 2 6. An N-methyl-one-opening jig obtained by subjecting an addition reaction between a diguanamine and an aldehyde described in paragraph 1 of the claim. Anamin. 7. Scope of the Claim Select from N-methylolated diguanamine and alcohols having 1 to 20 carbon atoms described in Paragraph 6 of the claim. that low Do rather as one of R, 0 CH ₂ groups may be one and the the error over Te Ri by the and this to Ru by Le reaction resulting et been that low Do rather (R t is said a Le (Representing a residue obtained by removing the hydroxyl group from a call)).  8. Addition condensation reaction of the diguanamines described in claim 1 with the aldehydes together with the aldehyde compound which can be co-condensed in some cases. N-methylolated jigs with an average degree of addition of at least 1 and at least one methyl group Anamin Initial condensate.  9. Addition reaction or addition condensation of the diguanamines described in claim 1 with an aldehyde together with a compound that can be co-condensed in some cases. Reacting with at least one alcohol selected from alcohols having 1 to 20 carbon atoms, and then reacting with at least one alcohol selected from alcohols having 1 to 20 carbon atoms. , The resulting average degree of addition condensation is greater than 1 and at least one R! OC group. (R represents the same meaning as described above), which is an etherified diguanamine precondensate having the following formula: 10. Scope of Claims N-Mechi of Claim 6 Scope of Claims Etherified Jiganamin of Claims, Scope of Claims 8 N — Methyl ichirui diguanamin First-to-first primary condensate Consists of the etherified diguanamin condensate according to claim 9 within the scope of the claim A thermosetting composition characterized by containing at least one selected from the group as an ingredient 11. Scope of Claim Remarks Reacted with the 7 essential components described in the first paragraph of the tenth paragraph of the tenth set, and hardened. 11. The thermosetting material according to claim 10, wherein the thermosetting material does not contain a possible resin.  12.5 The scope of the claim 13. A paint resin composition containing the thermosetting composition of the article 11. 13 · The scope of the claim 13. The jigannamins and the epoxy according to the paragraph 1. A thermosetting resin composition characterized by containing a resin containing a xyl group.  14. Claims A paint resin composition comprising the thermosetting resin composition according to claim 13.  15. The paint resin composition according to claim 13, which is a powder paint resin composition. 16. Scope of the Claim An agent resin composition comprising the thermosetting resin composition according to claim 13.