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WO1994017047A1 - Diguanamine, sa production, et derive et utilisation de cette diguanamine - Google Patents

Diguanamine, sa production, et derive et utilisation de cette diguanamine Download PDF

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Publication number
WO1994017047A1
WO1994017047A1 PCT/JP1993/000094 JP9300094W WO9417047A1 WO 1994017047 A1 WO1994017047 A1 WO 1994017047A1 JP 9300094 W JP9300094 W JP 9300094W WO 9417047 A1 WO9417047 A1 WO 9417047A1
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WO
WIPO (PCT)
Prior art keywords
resin
reaction
group
diguanamines
diguanamine
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP1993/000094
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English (en)
Japanese (ja)
Inventor
Tetsuya Oishi
Hiroshi Ozawa
Minato Karasawa
Masamitu Inomata
Izumi Mega
Atsuyoshi Yamauchi
Kazunori Kamada
Shigeru Nakahata
Katsumi Sakamoto
Tatsunobu Nakashima
Akito Watanabe
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsui Toatsu Chemicals Inc
Original Assignee
Mitsui Toatsu Chemicals Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to JP20884292A priority Critical patent/JP3184617B2/ja
Priority claimed from JP20884292A external-priority patent/JP3184617B2/ja
Application filed by Mitsui Toatsu Chemicals Inc filed Critical Mitsui Toatsu Chemicals Inc
Priority to PCT/JP1993/000094 priority patent/WO1994017047A1/fr
Priority to DE69328554T priority patent/DE69328554T2/de
Priority to EP93902534A priority patent/EP0634406B1/fr
Priority to US08/201,391 priority patent/US5596039A/en
Publication of WO1994017047A1 publication Critical patent/WO1994017047A1/fr
Priority to US08/414,006 priority patent/US5536795A/en
Priority to US08/414,008 priority patent/US5569726A/en
Anticipated expiration legal-status Critical
Priority to US08/538,600 priority patent/US5545702A/en
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
    • C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
    • C08G12/30—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with substituted triazines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
    • C07D251/16—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to only one ring carbon atom
    • C07D251/18—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to only one ring carbon atom with nitrogen atoms directly attached to the two other ring carbon atoms, e.g. guanamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/5046—Amines heterocyclic
    • C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
    • C08G59/508—Amines heterocyclic containing only nitrogen as a heteroatom having three nitrogen atoms in the ring
    • C08G59/5086—Triazines; Melamines; Guanamines

Definitions

  • 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.
  • 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.
  • 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.
  • a melamine having such an aminotriazine group is used.
  • 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.
  • polyfunctional guanamines have very different structures from the novel diguanamines according to the present invention and are extremely difficult to compare and compare.
  • novel diguanamines according to the present invention are extremely difficult to compare and compare.
  • 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.
  • 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.
  • the methylolation reaction of the latter compound is related to the fact that the reaction rate is slower than that of melamin, benzoguanamine, etc.
  • 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.
  • Jiganamins whose structure and properties are completely different from those of the polyfunctional guanamines described above have been found.
  • Manufacture of minerals la 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.
  • 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.
  • 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.
  • 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
  • the bonding position of the cyano group indicates the 1,2—, 1,3— or 1,4— position.
  • 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.
  • 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.
  • (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).
  • a thermosetting composition characterized in that it contains at least one selected component as an essential component;
  • thermosetting composition according to the above (nu) characterized by containing a curable resin which reacts with the component described in the above (nu).
  • thermosetting resin composition characterized by containing the diguanamines described in (a) above and an epoxy group-containing resin;
  • thermosetting resin composition An adhesive resin composition containing the thermosetting resin composition described in the above (1).
  • 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.
  • 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.
  • 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.
  • 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 ⁇
  • 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),
  • the jiganamins according to the present invention have the general formula (3)
  • 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.
  • 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.
  • dicarboxylic bottles (3) are, for example, as disclosed in U.S. Pat. No. 2,666,748 and the like.
  • 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 ⁇ [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 .
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the reaction is carried out at a rate of 2.0 to 5.0 mol.
  • 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.
  • 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.
  • solvents that are useful but cause the formation of compounds other than the intended compounds, and can cause reaction inhibition.
  • solvents such as fatty acids, the acid anhydrides, trifluoroacetic acid, liquid sulfur dioxide, sulfuryl chloride, mineral acids, and water are not preferred.
  • 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
  • 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.
  • the level is as low as possible, particularly preferably less than 1.0% by weight.
  • 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.
  • 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 .
  • 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.
  • the above reaction temperature is not preferable.
  • 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.
  • 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.
  • 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.
  • the reaction solvent described above for example, alcohols, cellosolves, amino carboxylate.
  • 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.
  • ⁇ -force As the diguanamine derivative, ⁇ -force and the above-mentioned derivative may be used.
  • 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» ⁇ 4, ⁇ 5 »R 6, R 7 and R 8 represent one selected from ⁇ atoms and ⁇ 0 C ⁇ 2 groups, and R 2, ⁇ 3, R 4, 5 » ⁇ 6, ⁇ 7 and R 8 can be the same or different species]
  • 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]
  • 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
  • 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
  • R10, R11, R12, R13, R! 4 and R! 5 can be the same or different species]
  • 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.
  • compounds which can be co-condensed can be used as described above, but such co-condensable compounds can be used.
  • co-condensable compounds 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.
  • 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.
  • the reaction is
  • a reaction temperature of 30 ° C or higher preferably at 40 to 8 (when run under TC conditions, the reaction is
  • 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.
  • 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.
  • 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
  • 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.
  • an auxiliary agent such as ammonia
  • 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.
  • N-methylolated diguanamine initial condensate described above has a pH of 8.0 or less together with, for example, the above-mentioned arylide.
  • 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 .
  • 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
  • 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.
  • 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.
  • any resin having a functional group capable of reacting and curing with the above-described derivative is useful.
  • 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.
  • 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. .
  • 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.
  • 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.
  • 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.
  • thermosetting resin in 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.
  • a hardening accelerator such as a novolac type phenolic resin, a metal salt of an organic acid, or an imidazole.
  • a conductive resin composition examples 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.
  • phenols such as mouth phenols and aldehydes such as formaldehyde and noraformaldehyde in the usual manner.
  • the mixing ratio of the novolac type phenolic resin is usually from ⁇ . ⁇ to ⁇ 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.
  • 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.
  • 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.
  • the diguanamines according to the present invention include carboxylic acids, for example, phthalic acid, adipic acid, maleic acid, trimeric, and the like.
  • carboxylic acids for example, phthalic acid, adipic acid, maleic acid, trimeric, and the like.
  • 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 ⁇ ⁇ ⁇ ⁇ 1 1 1 1 1 1 1 1 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 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.
  • FIG. 1 shows the result of infrared absorption spectrum analysis of the target substance
  • FIG. 2 shows the result of mass spectrum analysis.
  • 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 powder
  • 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.
  • 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 3 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.
  • 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)).
  • the jigguanmins according to the present invention can be provided, and in addition, specific jigbonamines can be provided.
  • 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
  • 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.
  • 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.
  • 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
  • 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.
  • 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.
  • 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 ⁇ [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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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). .
  • 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.
  • 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
  • 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.
  • 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.
  • 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.
  • 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%.
  • 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.
  • 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.
  • 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
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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).
  • 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).
  • the ether product of the diguanamine and the etherified precondensate of the diguanamine according to the present invention are excellent in polymerizability.
  • 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 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.
  • 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.
  • thermosetting resin composition according to the present invention had extremely excellent storage stability.
  • Table 1 Epoxy group-containing resins Diguanamines Classification at 40 ° C Classification type Classification amount Storage stability
  • Example 29-2 100 .0 18.9 3 months or more
  • thermosetting resin composition obtained from thermosetting resin composition:
  • Example 30 100.0 g 19.6 ⁇ 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.
  • thermosetting resin composition 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.
  • 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.
  • 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.
  • 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
  • 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.
  • thermosetting resin composition Adhesion test of thermosetting resin composition:
  • thermosetting resin composition according to the present invention has excellent adhesiveness and is extremely useful as an adhesive resin or the like.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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

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  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

L'invention concerne: une diguanamine représentée par la formule générale (1); un procédé de production de cette diguanamine par réaction d'un dicarbonitrile représenté par la formule générale: NC-R-CN avec un dicyandiamide, en présence d'un catalyseur basique; une composition thermodurcissable comprenant, par exemple, une résine de revêtement contenant de la diguanamine méthylolée, de la diguanamine éthérifiée, des précondensats et des dérivés de diguanamine, et une composition de résine thermodurcissable comprenant, par exemple, une résine de revêtement ou une résine adhésive contenant la diguanamine et une résine epoxy. Dans lesdites formules, R représente bicyclo[2.2.1]-2,5-heptylène, bicyclo[2.2.1]-2,6-heptylène ou cyclohexylène.
PCT/JP1993/000094 1991-08-07 1993-01-27 Diguanamine, sa production, et derive et utilisation de cette diguanamine Ceased WO1994017047A1 (fr)

Priority Applications (8)

Application Number Priority Date Filing Date Title
JP20884292A JP3184617B2 (ja) 1991-08-07 1992-08-05 新規ジグアナミン及びその製造方法
PCT/JP1993/000094 WO1994017047A1 (fr) 1992-08-05 1993-01-27 Diguanamine, sa production, et derive et utilisation de cette diguanamine
DE69328554T DE69328554T2 (de) 1993-01-27 1993-01-27 Diguanamine, herstellung, derivate und anwendung
EP93902534A EP0634406B1 (fr) 1992-08-05 1993-01-27 Diguanamine, sa production, et derive et utilisation de cette diguanamine
US08/201,391 US5596039A (en) 1993-01-27 1994-02-24 Diguanamines and preparation process, derivatives and use thereof
US08/414,008 US5569726A (en) 1993-01-27 1995-03-30 Diguanamines and preparation process, derivatives and use thereof
US08/414,006 US5536795A (en) 1993-01-27 1995-03-30 Diguanamines and preparation process, derivatives and use thereof
US08/538,600 US5545702A (en) 1993-01-27 1995-10-03 Diguanamines and preparation process, derivatives and use thereof

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP20884292A JP3184617B2 (ja) 1991-08-07 1992-08-05 新規ジグアナミン及びその製造方法
PCT/JP1993/000094 WO1994017047A1 (fr) 1992-08-05 1993-01-27 Diguanamine, sa production, et derive et utilisation de cette diguanamine

Publications (1)

Publication Number Publication Date
WO1994017047A1 true WO1994017047A1 (fr) 1994-08-04

Family

ID=26434370

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP1993/000094 Ceased WO1994017047A1 (fr) 1991-08-07 1993-01-27 Diguanamine, sa production, et derive et utilisation de cette diguanamine

Country Status (1)

Country Link
WO (1) WO1994017047A1 (fr)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4826786A (fr) * 1971-08-07 1973-04-09

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4826786A (fr) * 1971-08-07 1973-04-09

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0634406A4 *

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