JPH06345897A - Modification of resin and its use - Google Patents

Abstract

PURPOSE:To make resin flame-retardant so that it shows better heat resistance than that of conventional products and extremely good char formation, thermally stabilized so that the deterioration-starting time is delayed, and compatible so that the dispersibility is improved. CONSTITUTION:The flame retardancy, thermally stabilization and improved compatibility of resin is attained by utilizing diguanamines including 2,5/2,6-bis(4,6,-diamino-1,3,5-triazin-2-yl)-bicyclo[2.2.1]heptane and 1,3/1,4-(4,6-diamino-1,3,5- triazin-2-yl)-cyclohexane and their derivatives. Fine granules of polymer containing the diguanamines and their derivatives are produced.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a polymerizable monomer, polyurethane resin, polyester resin, amino resin, paint resin, adhesive resin, paper processing resin, fiber processing resin,
Diguanamines and their derivatives that are useful as resins for foams, molding materials, resin raw materials such as laminated materials, resins, rubbers, etc. And polymer particles and their uses.

[0002]

2. Description of the Related Art Generally,
Resin has strength, chemical resistance, abrasion resistance, weather resistance, durability,
It has excellent properties such as dyeability and is used in a wide range of industrial fields such as building materials, electrical materials, vehicle materials such as automobiles, textile materials and household products as resin processed products.

However, these resins have the drawback that they are extremely flammable, and their use as a major source or fuel source in a fire has been remarkably increasing with widespread use. Therefore, high standards are set for the safety of these industrial materials, and it is strongly desired to improve the performance of resins such as flame retardancy, heat resistance, and compatibility between resins.

Further, these resins are apt to be deteriorated by heat, light, etc., and are required to have improved thermal stability with respect to the resins and further improved performance and impartment without impairing the characteristics of these resins. Rarely, such modification of resins and development of new materials are extremely important issues in industry.

A. Conventionally, various methods have been proposed to improve the flame retardancy of such resins, for example, a method of adding a flame retardant, a method of mixing with a flame retardant resin, and a flame retardancy-imparting raw material (monomer) during resin production. A method of incorporating into a resin skeleton using
A method of post-treating a resin to impart flame retardancy is known. Of these methods, a method of adding a flame retardant to a resin is generally used, and as such a flame retardant, halogen-containing compounds, phosphorus-containing compounds, inorganic compounds, nitrogen-containing compounds, etc. Are known.

In these publicly known flame retardants, when a halogen-containing compound is used, heat resistance is generally poor, sublimation, bleeding and the like are likely to occur, and it is difficult to obtain the effect unless it is used in common with antimony trioxide. There are many drawbacks, such as the discharge of a large amount of extremely harmful halogen-containing gas in case of fire. When the phosphorus-containing compound is used, the effect is small by itself, it is difficult to obtain the effect depending on the kind of the resin, and it is often used in combination with the halogen-containing compound, which has the above-mentioned drawbacks. Also, when an inorganic compound is used, it is a scarce resource such as antimony trioxide, so the raw materials are available.
There are problems such as price problems, small effects such as aluminum hydroxide, etc., which require large amounts of addition, and increase in specific gravity, deterioration of physical properties and moldability, and deterioration of heat resistance due to water content. Further, when a nitrogen-containing compound is used, typified by a melamine-based compound, defects such as sublimation during molding, bleeding, etc. easily occur, flame retardant effect due to sublimation during heat is small, manufacturing is difficult, and raw material cost is high. Have. The flame-retarding method for resins containing these known flame-retardant agents is still insufficient in practical use, and has been severely restricted technically and economically.

The inventors of the present invention have conducted extensive studies to overcome the above-mentioned deficiencies in the method of making a resin flame-retardant. As a result, a new specific diguanamine compound having a completely different structure and characteristics from the conventional known compounds has been obtained. By containing in, it is possible to significantly improve the flame retardancy of this resin, heat resistance is better than that of melamine and the like, sublimation, bleeding, etc. are not seen, char formation, etc. are extremely It was found that it is possible to provide an excellent method for flame retarding a resin such as oil droplets, dripping of a melt, and remarkably little dropping, and further, the above-mentioned diguanamines and phosphorus, isocyanuric acids, and cyanuric. By using a combination of acids, amino group-containing compounds and the like, it is found that it is possible to provide a flame retardant method for a resin that further improved flame retardancy is obtained,
The present invention has been reached.

B. Further, such a resin is liable to be brittle and colored due to the supply of heat, light, and other energy from the outside, and further the presence of oxygen and heavy metals, and thus the resin can be used in a wide range in spite of excellent characteristics of the resin. Was sometimes constrained. For this reason, various proposals have been made in the past to improve these, but they are still insufficient for overcoming the above-mentioned drawbacks, and in extreme cases, their excellent properties are lost and they are not put to practical use at all. There are also things.

Specific examples of such conventional heat stabilization methods include heat stabilization of a resin containing a heat stabilizer such as benzoates, amines, arylphosphonic diamides and organic phosphites. Although a method and the like have been disclosed, a method that is sufficiently satisfactory for practical use has not yet been obtained.

Further, a method for heat-stabilizing a resin containing melamine, acetoguanamine, benzoguanamine and the like is also known, but it does not show a specific effect of improving stability against heat, light and the like, and is practically used. There is a defect that the sufficient effect cannot be obtained.

Further, a method for heat-stabilizing a resin containing phthaloguanamine, spiroguanamine and the like is also known. However, these methods are inferior in ultraviolet resistance, weather resistance, etc., and have significant discoloration, etc., when molding at high temperature, coloring, discoloration, etc. are remarkable, and thermal stability is not sufficient. The heat stabilizer itself has a defect that it is susceptible to thermal decomposition during processing, etc., and the heat stabilization method for these resins is still insufficient in practical use, and is severely restricted technically and economically. Was there.

The inventors of the present invention have made earnest studies in view of the above-mentioned deficiencies in the heat stabilization method for the resin. By containing it, UV resistance, weather resistance, and thermal stability are significantly improved, and there is little coloration or discoloration even when molding is performed at high temperature, and deterioration is suppressed during long-term use at relatively high temperature. Further, they have found that such a heat stabilizer itself does not easily decompose even at a high temperature, and can provide a heat stabilization method for a resin which is excellent in handling and performance maintenance, and arrived at the present invention.

C. Further, such a resin has excellent properties and is used in a wide range of industrial fields, but without impairing such properties of the resin, improvement of various performances, as a method of modifying the resin to impart new performance, Various polymer alloying methods have been proposed.

Conventionally, as a method of polymer alloying such a resin, a method of modifying the resin itself, a method of adding a third component such as a compatibilizer, and the like have been proposed. In the method of modifying the resin, the modification reaction of the resin is difficult, the process required for the modification is complicated, the characteristics are deteriorated due to the decrease of the molecular weight of the resin during the modification, etc. There is. In addition, in the method of adding a compatibilizing agent or the like to the resin, the heat resistance, weather resistance, water resistance, properties, etc. of the resin are deteriorated by the inclusion of the third component, and the manufacturing process of the compatibilizing agent is complicated. There are defects such as high cost.

As a result of intensive studies to overcome the above-mentioned deficiencies in the resin compatibilization method, the present inventors have found that a new specific diguanamine compound having a completely different structure and characteristics from the conventional known compounds is used. By including in more than one kind of resin, compatibilization between different kinds of resins, excellent meltability of the resin, also excellent in heat resistance, weather resistance, water resistance, further, the production of such compatibilizing agent is simple, the production cost is low. The present invention has been accomplished by finding that an inexpensive resin compatibilizing method can be provided.

D. Further, the present invention provides a diguanamine derivative which is an N-substituted derivative of the above-mentioned diguanamine, a method for producing the same, and a use thereof.

Conventionally, N-substituted melamines and the like obtained by using melamine, benzoguanamine and the like, and methods for producing them are known. In such N-substituted melamine, melamine derivatives containing various hydroxyl groups are provided from the usefulness, and for example, N-polyoxaalkyl-substituted melamine obtained by addition reaction of melamine and epoxides, melamine and aminoalkanols N-hydroxyalkyl-substituted melamine and the like obtained by the reaction are known.

However, these N-substituted melamines are flame-retardant when used as resin raw materials, resin modifiers, etc.
Mechanical properties such as heat resistance, flexibility, toughness, etc. are not practically sufficient, and since the number of functional groups is not large, it is sufficient as a resin modifier, chain extender, curing agent, crosslinking agent, etc. It has a defect that it is difficult to exhibit various effects.

In the former method for obtaining N-polyoxaalkyl-substituted melamine, when the reaction is carried out in the absence of a solvent, the yield is extremely low, and the melamine solubility is higher than that of other solvents. Even when a good solvent such as dimethyl sulfoxide is used, the solubility of melamine is not sufficient even at high temperature, etc., so that the reaction does not proceed smoothly and it is difficult to obtain a good product, and only a high molecular weight product is desired. It is difficult to obtain a product having a molecular weight and a narrow molecular weight range, and there are significant restrictions on applications and performance. Furthermore, in the latter method for obtaining N-hydroxyalkyl-substituted melamine, the solubility of melamine is not sufficient even when the reaction is carried out in the presence of an excess amount of aminoalkanol or the like, a solvent or the like, and the reaction needs to be carried out at a high temperature. It is difficult to proceed the reaction uniformly because of the presence of such substances, it takes a long time for production, it is difficult to obtain a desired product due to a narrow molecular weight range.
There are defects such as marked coloring of the product, generation of by-products, and complicated purification and separation.

As mentioned above, known N-substituted melamines are
It was technically and economically restricted in use and production.

As a result of intensive studies to overcome the above-mentioned deficiencies in the N-substituted melamine, the present inventors have excellent properties such as heat resistance, flame retardancy, weather resistance, flexibility and toughness. Diguanamine derivatives having completely different structures and characteristics from known compounds, and further having active hydroxyl groups, imino groups, etc., which show extremely excellent reactivity with compounds having various functional groups, and have 8 active hydrogens. The present invention has been accomplished by discovering novel hydroxyl group-containing diguanamine derivatives, oxaalkyl group-containing diguanamine derivatives, and the like, which have a wide variety of functional groups to be possessed.

Further, in producing such a diguanamine derivative, a novel diguanamine having a completely different structure and characteristics from a known compound and HO-R ₉ -NH ₂ (R ₉ has two or more carbon atoms). (E.g., a valent group), an excellent production method such as the desired product can be easily obtained in a high yield by the reaction of the above-mentioned diguanamines, hydroxyl group-containing diguanamine derivatives and epoxides. The present invention has been reached by finding out.

By incorporating the above-mentioned diguanamine derivative into the resin, the flame retardancy of the resin can be remarkably improved, the heat resistance is better than that of melamine, and sublimation and bleeding occur. Is not seen, the generation of char is extremely good, and oil drops, melt dripping,
It is found that it is possible to provide an excellent resin flame retardant method such as that the drop is extremely small and the meltability with the resin is good, and further, phosphorus, isocyanuric acid,
The present invention has been found out that further improved flame retardancy can be obtained by using in combination with cyanuric acids, amino group-containing compounds and the like.

Further, by containing the above-mentioned diguanamine derivative and an organic polyisocyanate component, a polyurethane resin composition which can obtain a material excellent in properties such as flame retardancy, heat resistance, water resistance, abrasion resistance, elasticity, etc. The inventors arrived at the present invention by finding that they can provide things.

E. Further, conventionally, organic cured fine particles obtained by curing using an amino resin obtained by reacting an amino compound such as urea, melamine, benzoguanamine, and cyclohexanecarboguanamine with formaldehyde have been known.

However, among such organic cured fine particles, those obtained by using urea have defects such as weather resistance, particularly poor fastness to sunlight, unclear color, and low impact resistance. Further, those obtained by using melamine have poor impact resistance, and those obtained by using benzoguanamine have excellent water resistance, but have poor weather resistance and have defects such as significant discoloration during outdoor use. Further, the product obtained by using cyclohexanecarboguanamine has excellent weather resistance, but has defects such as insufficient heat resistance, impact resistance, abrasion resistance and solvent resistance.

As a method for obtaining colored organic cured fine particles, there is known a method in which a polymer is colored with a coloring agent such as a dye or pigment and then finely pulverized. This method has drawbacks such as difficulty in controlling the particle size during fine pulverization and high pulverization cost. Furthermore, when a resin is produced to facilitate fine pulverization, it is necessary to reduce the degree of crosslinking and the molecular weight of the resin, which causes defects such as insufficient impact resistance, solvent resistance, and heat resistance.

As a result of intensive studies to overcome the above-mentioned deficiencies in the organic cured fine particles, the present inventors have found that a novel amino compound containing a specific diguanamine compound having a structure and characteristics different from those of the above-mentioned compounds and the like. By emulsifying the amino resin obtained by reacting aldehydes with aldehydes and adding a curing agent to polymerize the polymer to obtain polymer fine particles with outstanding heat resistance, solvent resistance, weather resistance, impact resistance, abrasion resistance, etc. It has been found that it is possible to provide polymer fine particles useful as a resinous colorant excellent in weather resistance, color, solvent resistance, impact resistance, etc. The invention was reached.

Further, as described above, the improvement of the flame retardancy of the resin is an important industrial issue, but the present inventors have incorporated the novel polymer fine particles of the present invention into such a resin. The flame retardancy can be remarkably improved, sublimation, bleeding, etc. are not observed, char formation is very good, and oil drops, melt dripping, and falling are extremely small, harmful gas The inventors have found that it is possible to provide an excellent method for flame retarding a resin, such as that the occurrence of the above is extremely small, and arrived at the present invention.

[0030]

Means for Solving the Problems That is, according to the present invention, (a) Formula (1)

[0031]

[Chemical 10] [In the formula, the bonding position of the (4,6-diamino-1,3,5-triazin-2-yl) group represents the 2,5- or 2,6-position], and the formula (2)

[0032]

[Chemical 11] [In the formula, the bonding position of the (4,6-diamino-1,3,5-triazin-2-yl) group is 1,2-, 1,3- or 1,4-position] There is provided a method for flame retarding a resin, characterized in that at least one selected from diguanamines is contained in an amount of 3 to 50% by weight based on the resin.

According to the present invention, at least one selected from the diguanamines represented by the above formulas (1) and (2) is contained in an amount of 0.01 to 5% by weight based on the resin. A method for thermally stabilizing a resin is provided.

According to the present invention, at least one selected from the diguanamines represented by the formulas (1) and (2) is selected from polyamide resins, polyphenylene ether resins, polyimide resins and polyamide resins. Provided is a method of compatibilizing a resin, which is characterized in that it is contained in two or more different resins containing at least one kind.

In the present invention, a diguanamine derivative which will be described later, a method for producing the same, a method for flame retarding a resin using the same, a method for stabilizing heat and a method for compatibilizing the polymer, and polymer fine particles using the diguanamine and the method for producing the same. It is intended to provide a flame retarding method for a resin used.

In the diguanamines [formula (1)] according to the present invention, (4,6-diamino-1,3,5-
The bonding position of the triazin-2-yl) group is the 2,5- or 2,6-position, but the steric configuration of such a group is endo-
Endo type, endo-exo type or exo-exo type are all useful compounds.

Further, the diguanamines [formula (1)] is a compound selected from the group consisting of isomers having the above-mentioned bonding position and configuration, and even in an aggregate of different compounds selected from such group. , As in the case of a single compound, is extremely useful industrially.

Specific examples of such diguanamines [formula (1)] include 2,5-bis (4,6-diamino-1,
3,5-triazin-2-yl) -bicyclo [2.2.
1] Heptane (endo-exo form), 2,5-bis (4,6-diamino-1,3,5-triazin-2-yl) -bicyclo [2.2.1] heptane (exo-exo form) , 2,6-bis (4,6-diamino-1,3,5
-Triazin-2-yl) -bicyclo [2.2.1] heptane (endo-endo form), 2,6-bis (4,6-
Examples thereof include diamino-1,3,5-triazin-2-yl) -bicyclo [2.2.1] heptane (exo-exo form), but are not limited to these compounds.

The diguanamines according to the present invention [formula (1)] are represented by formula (3)

[0040]

[Chemical 12] (In the formula, the bonding position of the cyano group is 2,5- or 2,6-
Of a dicarboxylic acid corresponding to dicarbonitriles (3) and biguanides, if necessary, by reacting dicarbonitriles (3) represented by the formula (3) with dicyandiamide in the presence of a basic catalyst. It can be obtained by a method such as reacting in the presence of a basic compound. In the former method, the raw materials are easily available and easy to handle, the desired target compound is obtained with a high degree of purity with very few by-products, and the purification and separation steps are easy to manufacture,
It is technically and economically excellent and extremely practical from the viewpoints that the raw material loss is extremely small and the desired compound can be obtained in a high yield. The method for producing the diguanamines [Formula (1)] is not limited to these methods.

Dicarbonitriles (3) in the method for producing diguanamines [formula (1)] according to the present invention
The bonding position of the cyano group is the 2,5- or 2,6-position, and the steric configuration of such a group is endo-endo, endo-exo or exo-exo, and both are useful. Further, the dicarbonitriles (3) are compounds selected from the group consisting of isomers having the above-mentioned bonding position and configuration, but even in the aggregate of different compounds selected from such groups, a single compound As useful as it is.

The above-mentioned dicarbonitriles (3) are, for example, as disclosed in US Pat. No. 2,666,748 and the like, bicyclo [2.2.1] hept-5-ene-2-.
Carbonitrile and hydrogen cyanide are combined into Co ₂ (CO) ₈ ,
A method of reacting in the presence of a specific catalyst such as Fe (CO) ₅ , Ni [P (OC ₆ H ₅ ) ₃ ] ₄ , US Pat.
5- (and / or 6 disclosed in No. 43570 and the like.
-) Method of reacting cyano-bicyclo [2.2.1] hept-2-carbaldehyde with hydroxylamines, 2,5- (and / or 2,6-) dichloro-bicyclo [2.2.1] It can be obtained by a method of reacting heptane with a cyanating agent such as an alkali metal cyanide salt or an alkaline earth metal cyanide salt, but is not limited to these methods.

Specific examples of such dicarbonitriles (3) include bicyclo [2.2.1] heptane-2,5-
Dicarbonitrile (endo-exo type), bicyclo [2.2.1] heptane-2,5-dicarbonitrile (endo-end type), bicyclo [2.2.1] heptane-2,6-dicarbo Nitrile (End-exo type),
Examples thereof include bicyclo [2.2.1] heptane-2,6-dicarbonitrile (exo-exo form), but not limited to these compounds.

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

Further, the diguanamines [formula (2)] is a compound selected from the group consisting of isomers having the above-mentioned bonding position and configuration, but also in an aggregate of different compounds selected from such group. , As in the case of a single compound, is extremely useful industrially.

Specific examples of such diguanamines [formula (2)] include 1,2-bis (4,6-diamino-1,
3,5-triazin-2-yl) -cyclohexane (cis form), 1,3-bis (4,6-diamino-1,3,5
-Triazin-2-yl) -cyclohexane (trans form), 1,3-bis (4,6-diamino-1,3,5-
Triazin-2-yl) -cyclohexane (cis form),
1,4-bis (4,6-diamino-1,3,5-triazin-2-yl) -cyclohexane (trans form),
Examples thereof include 1,4-bis (4,6-diamino-1,3,5-triazin-2-yl) -cyclohexane (cis type), but are not limited to these compounds.

The diguanamines [formula (2)] according to the present invention are represented by the formula (4)

[0048]

[Chemical 13] (In the formula, the bonding position of the cyano group represents 1,2-, 1,3- or 1,4-position) and dicarbonitriles (4) and dicyandiamide in the presence of a basic catalyst. It can be obtained by a method of reacting, a method of reacting an ester of a dicarboxylic acid corresponding to dicarbonitrile (4) and a biguanide in the presence of a basic compound, if necessary. In the former method, the raw materials are easy to obtain and easy to handle, the desired target compound is obtained with a high degree of purity with very few by-products, the purification and separation steps are simple to manufacture, and the raw material loss is extremely small. In addition, it is technically and economically excellent and extremely practical in that the desired compound can be obtained in high yield.
The method for producing the diguanamines [formula (2)] is not limited to these methods.

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

The above-mentioned dicarbonitriles (4) are prepared by converting 4-cyano-cyclohexene and hydrogen cyanide into Ni [P (OC ₆ H ₅ ) ₃ ] ₄ as disclosed, for example, in US Pat. No. 3,496,217. Etc. in the presence of a catalyst, a method of reacting 3- (and / or 4-) cyano-cyclohexanecarbaldehyde with hydroxylamines, the above-mentioned dicarbonitriles (4)
A method of reacting a dihalogenated cyclohexane corresponding to the above with a cyanating agent such as an alkali metal cyanide or an alkaline earth metal cyanide, a dicarboxylic acid corresponding to the above dicarbonitrile (4) or a diammonium thereof. Obtained by a method of reacting a salt, a diamide, a diester derivative and ammonia with an alumina catalyst or a dehydrating agent such as thionyl chloride, a method of reacting 1-cyano-cyclohexene and hydrogen cyanide in the presence of an alkali such as caustic soda, etc. However, the method is not limited to these methods.

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

The amount of the above-mentioned diguanamines used in the flame retardant method of the resin according to the present invention is 3 to 50% by weight, preferably 4 to 40% by weight based on the resin. If the amount used is less than 3% by weight, it is difficult to obtain a sufficient flame retardancy-improving effect. If the amount used exceeds 50% by weight, the moldability of the composition becomes poor and the resin deteriorates. This is not preferable because it causes deterioration of physical properties.

In the above-described method for flame retarding a resin, when a phosphorus selected from the group consisting of phosphorus alone and a compound containing a phosphorus atom is used together with the diguanamines according to the present invention in the resin, flame retardancy is used. A synergistic effect of further improving the sexual effect can be imparted, which is particularly preferable. This not only makes it easier to form a flame-retardant coating with a relatively low volatility on the surface of the combustion resin, but also promotes char formation further and increases the char layer, thereby promoting diffusion of oxygen to the combustion surface. It is considered that such an excellent synergistic effect is produced by the functions of preventing, suppressing the generation of combustible gas from the resin part, and reducing the heat conduction to the resin part.

Examples of such phosphorus include simple phosphorus such as red phosphorus, phosphorous such as phosphoric acid, polyphosphoric acid, phosphorous acid, phosphonic acid, phosphate, polyphosphate, phosphite and phosphonate. Phosphoric acid esters such as acids, phosphoric acid triesters, polyphosphoric acid esters, acidic phosphoric acid esters and salts thereof, phosphorous acid triesters, phosphorous acid diesters and other phosphorous acid esters, phosphonic acid esters, acidic phosphones Acid esters and phosphonates such as salts thereof, phosphines, phosphine oxides, phosphines such as phosphonium salts, and sulfur-containing phosphorus compounds such as dialkylthiophosphoric acid and salts thereof are useful, but are not limited to these. It is not something that will be done.

Examples of the phosphorus-based acids include acids such as phosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, polyphosphoric acid, phosphorous acid, phosphonic acid and the like, and further bases such as ammonia, amine, alkali metal, alkaline earth metal and the like. So obtained by neutralizing a part or all, ammonium phosphate, ethylenediamine phosphate, sodium phosphate, calcium phosphate, melamine pyrophosphate, sodium pyrophosphate, ammonium tripolyphosphate, sodium tripolyphosphate, ammonium polyphosphate, Examples thereof include sodium polyphosphate, ammonium phosphite, calcium phosphite, ammonium phosphonate, and the like. General formula (NH ₄ ) _{n + 2} P _n O
Ammonium polyphosphate represented by _{3n + 1} (wherein n is an integer greater than 5) is preferable, but not limited thereto.

The above-mentioned general formula (NH ₄ ) _{n + 2} P _n O
_In ammonium polyphosphate represented by _{3n + 1} (in the formula, n is an integer greater than 5), n is sufficiently large in order to reduce the water solubility in view of the flame retardant effect and the physical properties of the composition. Particularly preferred is a salt in which n is an integer greater than 50, and in practice metaphosphate (N
H ₄ PO ₃ ) _n .

As an example of such ammonium polyphosphate, the trade name "Exolit 263",
"Exolit 422" (manufactured by Hoechst), trade name "Phoscheck P"
/ 30 ”(manufactured by Monsanto Chemical Company) and the like.

Examples of such phosphoric acid esters include trimethyl phosphate, triethyl phosphate, tri-n-butyl phosphate, trioctyl phosphate, trilauryl phosphate, tricetyl phosphate, tristearyl phosphate, trioleyl phosphate, tris (butoxyethyl) phosphate. , Triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xylene diphenyl phosphate, tris (isopropylphenyl) phosphate, ethyl diphenyl phosphate, isopropyl diphenyl phosphate,
n-butyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate, isodecyl diphenyl phosphate, cetyl diphenyl phosphate, stearyl diphenyl phosphate, oleyl diphenyl phosphate, butyl dicresyl phosphate, octyl dicresyl phosphate, lauryl dicresyl phosphate,
Diphenyl-2-methacryloyloxyethyl phosphate, tris (2-chloroethyl) phosphate, tris (2-chloropropyl) phosphate, tris (2,3
-Dichloropropyl) phosphate, tris (2,3-
Phosphate triesters such as dibromopropyl) phosphate, tris (bromochloropropyl) phosphate, tris (tribromophenyl) phosphate, (mono,
Di) Methyl acid phosphate (mixture), (mono,
Di) ethyl acid phosphate, diisopropyl acid phosphate, monobutyl acid phosphate,
Dibutyl acid phosphate, di-2-ethylhexyl phosphate, monoisodecyl acid phosphate, (mono, di) ularyl acid phosphate (mixture), (mono, di) tridecyl acid phosphate (mixture), (mono, di) Stearyl acid phosphate (mixture), (mono, di) oleyl acid phosphate (mixture), (mono, di) 2-chloroethyl acid phosphate (mixture), (mono, di) butoxyethyl acid phosphate (mixture) , Ethylene glycol acid phosphate, dibutyl pyrophosphate, monophenyl acid phosphate, diphenyl acid phosphate, monocresyl acid phosphate, dicresyl acid phosphate, monoxylenyl acid phosphate, Carboxymethyl Les alkenyl acid phosphate acid phosphate of sulfate such as dimethyl phosphate,
Ammonium salt, diethyl phosphate / ammonium salt, ethyl phosphate / ammonium salt, di-n-butyl phosphate / ammonium salt, dibutoxyethyl phosphate / triethanolamine salt, dioctyl phosphate / morpholine salt, mono-n-butyl phosphate / soda salt, diphenyl Phosphate ammonium salt, diphenyl phosphate melamine salt, diphenyl phosphate piperazine salt, phenyl phosphate
Ammonium salt, dicresyl phosphate / ethylenediamine salt, cresyl phosphate / soda salt, dixylenyl phosphate / melamine salt and other acidic phosphoric acid ester ammonia, amine, melamine, alkali metal, alkaline earth metal salt and the like. However, the present invention is not limited to these.

Examples of such phosphorous acid esters include trimethyl phosphite, triethyl phosphite,
Tributyl phosphite, tris (2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, trioleyl phosphite, tristearyl phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2,2 Four
-Di-t-butylphenyl) phosphite, tris (dinonylphenyl) phosphite, bis (nonylphenyl) dinonylphenylphosphite, diphenylmono (2-ethylhexyl) phosphite, diphenylmonodecylphosphite, diphenylmono ( Tridecyl) phosphite, phenyl diisooctyl phosphite, tetraphenyl dipropylene glycol diphosphite,
Poly (dipropylene glycol) phenyl phosphite, diisodecyl pentaerythritol diphosphite, bis (tridecyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2,2 4-di-t-butylphenyl) pentaerythritol diphosphite, phenyl
4,4'-isopropylidene diphenyl pentaerythritol diphosphite, tetraphenyl tetra (tridecyl) pentaerythritol tetraphosphite, tetra (tridecyl) -4,4'-isopropylidene diphenyl phosphite, hydrogenated bisphenol A / phosphite polymer , Pentaerythritol-hydrogenated bisphenol A-triphenylphosphite polycondensate, tetra (tridecyl) -4,4'-n-butylidene bis (2-t-
Butyl-5-methylphenol) diphosphite, bis (neopentyl glycol) 1,4-cyclohexanedimethylene phosphite, bis (octylphenyl) .bis [4,4'-n-butylidene bis (2-t-butyl-
5-Methylphenol)] 1,6-hexanediol phosphite, tetra (tridecyl) -1,1,3-tris (2'-methyl-5'-t-butyl-4'-oxyphenyl) butanediphosphite Phosphite triesters such as dimethyl hydrogen phosphite, dibutyl hydrogen phosphite, di (2-ethylhexyl)
Examples include, but are not limited to, phosphite diesters such as hydrogen phosphite, dibutyl hydrogen phosphite, dilauryl hydrogen phosphite, dioleyl hydrogen phosphite, and diphenyl hydrogen phosphite. .

Examples of such phosphonic acids include dimethyl methylphosphonate, ethyl diethylphosphonoacetate, bis (2-chloroethyl) vinylphosphonate,
Diethyl N, N-bis (2-hydroxyethyl) aminomethylphosphonate, dibutyl butylphosphonate, di-2-ethylhexyl hydroxymethylphosphonate, di-2-ethylhexyl 2-ethylhexylphosphonate, dimethyl phenylphosphonate, diethyl phenylphosphonate , Phosphonic acid diesters such as diallyl phenylphosphonate, dioctyl phenylphosphonate, dinaphthyl phenylphosphonate, 2-ethylhexylphosphonic acid mono 2
-Acid phosphonates such as ethylhexyl and monooctyl phenylphosphonate, 2-ethylhexylphosphonate mono-2-ethylhexyl ammonium salt, phenylphosphonate monooctyl-triethanolamine salt, 2
-Ethylhexylphosphonic acid mono-2-ethylhexyl-
Examples thereof include phosphonic acid ester salts such as melamine salt and monooctyl phenylphosphonic acid soda salt, but are not limited thereto.

Examples of such phosphines include triethylphosphine, tri-n-propylphosphine, tri-n-butylphosphine, tri-n-hexylphosphine,
Tri-n-octylphosphine, tris (2-cyanoethyl) phosphine, tris (3-hydroxypropyl) phosphine, tricyclohexylphosphine, dicyclohexylphosphine, triphenylphosphine, tri-p-
Tolylphosphine, tri (2,6-dimethoxyphenyl) phosphine, 9-phosphabicyclo [3.3.
1], [4.2.1] nonane (mixture), bis (1,2)
Phosphines such as -diphenylphosphino) ethane, bis (1,4-diphenylphosphino) butane, diphenyl-p-styrylphosphine, diphenylphosphinas chloride, bis (diphenylphosphino) ferrocene,
Triethylphosphine oxide, tri-n-propylphosphine oxide, tri-n-butylphosphine oxide, tri-n-hexylphosphine oxide, tri-n
-Octylphosphine oxide, tris (2-cyanoethyl) phosphine oxide, tris (3-carboxyethyl) phosphine oxide, tris (3-hydroxypropyl) phosphine oxide, phosphine oxide such as triphenylphosphine oxide, tetra-n-butylphosphonium bromide, Tri-n-butylallylphosphonium bromide, ethylenebistris (2
-Cyanoethyl) -phosphonium bromide, ethyltriphenylphosphonium bromide, tetraphenylphosphonium bromide, tri-n-octylethylphosphonium bromide, tetra-n-butylphosphonium O,
O-diethyl phosphorodithioate, tetrakis (hydroxymethyl) phosphonium sulfate, tetra n-
Butylphosphonium iodide, ethyltriphenylphosphonium iodide, triethylbenzylphosphonium chloride, tetra-n-butylphosphonium chloride, tri-n-butyltetradecylphosphonium chloride, tri-n-butylhexadecylphosphounime chloride, tris (2-cyanoethyl) Examples thereof include phosphonium salts such as allylphosphonium chloride, benzyltriphenylphosphonium chloride, and bis (triphenylphosphine) iminium chloride, but are not limited thereto.

Examples of such sulfur-containing phosphorus compounds include dimethylphosphorodithioate, diethylphosphorodithioate, di-n-propylphosphorodithioate, diethylphosphorodithioate / ammonium salt and di-n-propylphosphorodithioate. -Melamine salt, dimethylphosphorodithioate-soda salt, trilauryl trithiophosphite, tris (lauryl-2
-Thioethyl) phosphite, diphenyl bis (4,
4′-n-butylidene bis (2-t-butyl-5-methylphenyl)] thiodiethanol diphosphite, toluphenylphosphine sulfide, tris (2-cyanoethyl) phosphine sulfide, tri-n-butylphosphine sulfide and the like can be mentioned. However, the present invention is not limited to these.

The amount of phosphorus used in the present invention is 5 to 40% by weight, preferably 10 to 3 based on the resin.
It is 0% by weight. When the amount used is less than 5% by weight, the synergistic effect of improving the flame retardancy is not sufficient, while when it exceeds 40% by weight, it may have an effect such as causing deterioration of physical properties and is therefore preferable in practice. Absent.

The phosphorus may be present in the resin separately from the components such as diguanamines, or some or all of them may form a salt with the diguanamines according to the present invention. You may have. Salts such as phosphoric acid, polyphosphoric acid, phosphorous acid, phosphonic acid, ammonium acid polyphosphate, acidic phosphoric acid ester, when containing in the form of a salt formed with diguanamines such as acidic phosphonic acid ester, etc., The synergistic effect of improving flame retardancy is more excellent and preferable.

The diguanamines according to the present invention are
When used in combination with a specific isocyanuric acid and / or cyanuric acid in a resin and used as a flame retardant method for the resin, the flame retardancy of the resin can be further improved,
preferable.

That is, the specific isocyanuric acids and cyanuric acids are represented by the formula (5)

[0067]

[Chemical 14] (In the formula, R ₂ , R ₃ and R ₄ are a hydrogen atom and a carbon number 1
An alkyl group having 3 to 3, an oxyalkyl group having 1 to 3 carbon atoms, a phenyl group or a glycidyl group,
R ₂ , R ₃ and R ₄ may be the same or different, and isocyanuric acids represented by the formula (6)

[0068]

[Chemical 15] Cyanuric acids represented by the formula [wherein R ₂ , R ₃ and R ₄ have the same meanings as those in the formula (5)].

The isocyanuric acids according to the present invention have the formula
R is a compound represented by (5) ₂, R₃And R
_FourIs a hydrogen atom, an alkyl group having 1 to 3 carbon atoms,
Oxyalkyl group having 1 to 3 carbon atoms, phenyl group
And one selected from the group consisting of
R₂, R₃And R_FourCan be the same or different species
As specific examples of such isocyanuric acids, for example,
Isocyanuric acid, methyl isocyanurate, trimethyl
Isocyanurate, triethyl isocyanurate, tri
Sus (2-hydroxyethyl) isocyanurate, phenyl
Luisocyanurate, diphenyl isocyanurate, g
Liphenyl isocyanurate, dimethyl phenyl isocyanurate
Examples include anurate and triglycidyl isocyanate.
However, the present invention is not limited to these.

The cyanuric acids according to the present invention are compounds represented by the formula (6), and are R ₂ , R ₃ and R
₄ has the same meaning as in formula (5), and specific examples of such cyanuric acids include, for example, cyanuric acid, methylcyanurate, trimethylcyanurate, triethylcyanurate, tris (2-hydroxyethyl) cyanurate, phenylcyanurate, Diphenyl cyanurate, triphenyl cyanurate, dimethylphenyl cyanurate,
Examples thereof include triglycidyl cyanurate, but are not limited thereto.

The usage ratio (molar ratio) of the total amount of isocyanurate acids and cyanuric acids according to the present invention is 0.02 to 10, preferably 0.1 to 5 with respect to the above-mentioned diguanamines, and the usage ratio is 0. When it is less than 0.02, the combined effect is not sufficient, while when it exceeds 10, it is not practically preferable because it may cause the deterioration of physical properties.

Further, such isocyanuric acids and cyanuric acids may be present and contained in the resin separately from the components such as diguanamines, or a part or all of these isocyanurates and the like according to the present invention. It may be contained by forming and reacting with salts. In the case of forming and containing salts, for example, a product salt of isocyanuric acid and diguanamines, a reaction product such as a reaction product of triglycidyl cyanurate and diguanamines, the flame retardant effect, heat resistance, etc. Excellent and preferable.

As such salts, for example, isocyanuric acid, a salt obtained by dissolving or dispersing diguanamines in a solvent in advance and reacting by heating, and the like are useful. Examples thereof include salts obtained by a double molar reaction, mixtures of these reaction salts, and the like, but are not limited thereto.

The diguanamines according to the present invention are
When used in combination with an amino group-containing compound in a resin and used as a flame retardant method for the resin, the flame retardancy of the resin can be further improved, which is preferable.

The amino group-containing compound has an aliphatic group having 2 or more carbon atoms, an alicyclic group, an aromatic group or a heterocyclic group, and preferably an aliphatic group having 2 or more carbon atoms. A group, an alicyclic group, or a heterocyclic group, and more preferably,

[0076]

[Chemical 16] And a reaction product of dicyandiamide, guanidine, and an aldehyde such as formaldehyde or an epoxy compound.

Specific examples of such amino group-containing compounds include 1,2-ethylenediamine, 1,3-diaminopropane, 1,2-diaminopropane, 1,4-butylenediamine, 1,6-hexamethylenediamine, Polyalkylene polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, cyclohexylamine, cyclohexyldiamine, 1,3-bis (aminomethyl) cyclohexane, aniline, benzylamine, furfurylamine, N- (3- Aminopropyl) morpholine, N-
(2-Aminoethyl) morpholine, N- (2-aminoethyl) piperazine, N- (3-aminopropyl) piperazine, N- (2-aminoethyl) piperidine, N, N '.
-Bis (2-aminoethyl) piperazine, dicyandiamide, guanidine, urea, polyamide resins, reaction products of these with aldehydes such as formaldehyde, for example, ethylenediamine-formaldehyde (1/1) reaction product,
Examples include piperazine-formaldehyde (1/1) reaction product, pentamethylenehexamine, and salts thereof.
It is not limited to these.

The amount of the amino group-containing compound used in the present invention is 0.01 to 10% by weight based on the resin,
It is preferably 0.05 to 5% by weight. Usage is 0.0
If it is less than 1% by weight, the synergistic effect of improving the flame retardancy is not sufficient, whereas if it exceeds 10% by weight, the physical properties may be deteriorated, which is not preferable in practice.

Examples of the resin according to the present invention include thermoplastic resins, thermosetting resins, rubbers, blended products thereof, modified resins such as block copolymers, graft copolymers and rubber modified polymers. Synthetic resins and oils are useful.

Specific examples of such a resin include, for example, polystyrene, styrene and other monomers (for example, maleic anhydride, α-methylstyrene, butadiene, acrylonitrile, (meth) acrylic acid ester, etc.) binary and ternary. Original copolymer, rubber modified polystyrene, rubber modified styrene-
Acrylonitrile copolymer, styrene resin such as rubber-modified styrene-maleic anhydride copolymer, polyethylene,
Polypropylene, polybutyne, poly-3-methylbutene, ethylene-vinyl acetate copolymer, ethylene-propylene copolymer, polyolefin resin such as EPDM, (meth) acrylic resin such as polymethyl acrylate and polymethyl methacrylate, nylon 4, nylon 4, nylon 6, nylon 11, nylon 12, nylon 46, nylon 6
6, polyamide resin such as nylon 610, nylon 612 and copolymer nylon, saturated polyester resin such as polyethylene terephthalate and polybutylene terephthalate,
Poly (2,6-dimethyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, Poly (2,6-di-n-propyl-
1,4-phenylene) ether, poly (2-methyl-6)
-N-butyl-1,4-phenylene) ether, poly (2-methyl-6-chloro-1,4-phenylene) ether, poly (2-methyl-6-hydroxyethyl-1,
4-phenylene) ether, poly (2-methyl-6-chloroethylene-1,4-phenylene) ether, 2,6
-Copolymer of dimethylphenol and 2,3,6-trimethylphenol, polyphenylene ether resin capped at their ends, polyphenylene ether resin such as a resin obtained by modifying these with styrene resin, polyamide resin, etc., polyoxymethylene , Oxymethylene units and other units (eg succinic anhydride, n-dodecenyl succinic anhydride, methyl succinic anhydride, tetrapropyl succinic anhydride, maleic anhydride, phthalic anhydride, hexahydrophthalic anhydride, itaconic anhydride, β -Oxypropylene group, oxyalkylene group, etc.) and other polymers such as polyacetal resin, polyvinyl chloride, polyvinylidene chloride,
Chlorinated polyethylene, chlorinated polypropylene, chlorinated rubber, vinyl chloride and other monomers (for example vinyl acetate, ethylene, propylene, styrene, isobutylene, vinylidene chloride, maleic anhydride, acrylonitrile, butadiene, isoprene, chlorinated propylene, ( (Meth) acrylic acid ester, etc.], terpolymer, polyvinyl bromide, brominated polyethylene, polyvinyl fluoride, polyvinylidene fluoride, fluororesin, vinyl acetate resin, polyamideimide, polyimide resin, polyether Imide, polyphenylene sulfide resin, polyether sulfone,
Polysulfone resin, polyamine sulfone, polycarbonate, liquid crystal (polyester) polymer, cyclic polyolefin, polyether ether ketone, polyarylate,
Phenoxy resin, silicone resin and blends of these resins, thermoplastic resins such as block copolymers, graft copolymers, rubber modified polymers, diallyl phthalate, diallyl terephthalate, diallyl-2,6-naphthalene dicarboxylate, etc. Of unsaturated polyester resin such as diallyl phthalate resin, maleic acid (fumaric acid) -containing polyester-styrene resin, urethane resin, epoxy resin, silicone resin, phenol resin, furan resin,
Amino resins and blended products of these resins, thermosetting resins such as resins modified with rubbers, rubbers such as synthetic rubber and vulcanized rubber, and blended products of these resins,
Examples thereof include synthetic resins such as modified resins, lubricating oils, silicone oils, metalworking oils, and oils such as polypropylene wax, but are not limited to these.

The amount of these resins used is 50 with respect to the resin composition obtained by the resin flame retarding method according to the present invention.
˜98 wt%, preferably 65-96 wt%. When the amount of the resin exceeds 98% by weight, the flame retardant effect becomes small, and when the amount of the resin is less than 50% by weight, the moldability of the composition becomes poor and the physical properties are deteriorated due to deterioration of the resin. It is not desirable because it causes

Further, in the resin flame-retardant method according to the present invention, by using additives such as a phenol-based antioxidant, an amine-based antioxidant, a sulfur-based antioxidant, and a light stabilizer in combination, such a resin can be obtained. The thermal stability and the like can be improved and can be appropriately selected according to the purpose of use.

As such a phenolic antioxidant,
For example, 3-methyl-4-isopropylphenol, 2,
6-di-t-butylphenol, 2,4-dimethyl-6
-T-butylphenol, 2,6-di-t-butyl-4
-Methylphenol, 2,4-dimethyl-6- (2-methylcyclohexyl) phenol, 2,5-di-t-butylhydroquinone, 3-t-butyl-4-hydroxy-anisole, styrenated phenol, hydroquinonemonobenzyl Ether, 2,5-diamylhydroquinone, 2,6-di-t-butyl-4-methoxyphenol, 4-hydroxymethyl-2,6-di-t-butylphenol, 2,6-di-t-butyl- α-dimethylamino-p-cresol, 4- (N-stearoylamino)
Phenol, 4,4'-dihydroxydiphenyl, 4,
4'-bis- (2,6-di-t-butylphenol),
2,2'-methylene-bis- (4-methyl-6-t-butylphenol), 2,2'-methylene-bis- (4-
Ethyl-6-t-butylphenol), 4,4'-methylene-bis- (2-methyl-6-t-butylphenol), 4,4'-methylene-bis- (2,6-di-t-).
Butylphenol), 2,2'-dihydroxy-3,
3'-bis- (2-methylcyclohexyl) -5,5 '
-Dimethyl-diphenylmethane, 1,1-bis- (4-
Hydroxyphenyl) -cyclohexane, 4,4'-cyclohexylidene-bis- (2-cyclohexylphenol), 4,4'-butylidene-bis- (3-methyl-
6-t-butylphenol), octadecyl-3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate, triethylene glycol-bis- [3
-(3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-
Bis- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], pentaerystyryl-
Tetrakis- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], ethyl-3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate, 2,6-bis (2-hydroxy-3-
t-Butyl-5-methylbenzyl) -4-methylphenol, 1,1,3-tris- (2-methyl-4-hydroxy-5-t-butylphenyl) -butane, 1,3,5
-Tris- (3,5-di-t-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 2-
(3-Methyl-4-hydroxy-5-t-butylbenzyl) -dioctadecyl malonate, 4,4'-thiobis-
(2-Methyl-6-t-butylphenyl) didodecyl malonate, bis- (2-hydroxy-3,5-di-t-butylphenyl) sulfide, 4,4'-thio-bis-
(3-methyl-6-t-butylphenol), 1,1-
Bis- (2-methyl-4-hydroxy-5-t-butylphenyl) -3-dodecylmercapto-butane, S-
(3,5-Dimethyl-4-hydroxyphenyl) -octadecyl thioglycolate, 2,2'-thio-bis-
(4-methyl-6-t-butylphenol), dimethyl 4-hydroxy-3,5-di-t-butylbenzylphosphonate, diethyl 4-hydroxy-3,5-di-t-butylbenzylphosphonate, 4- Dioctadecyl hydroxy-3,5-di-t-butylbenzylphosphonate, tris- (3,5-di-t-butyl-4-hydroxyphenyl) phosphate, 4-hydroxymethyl-1-phospha-2,6. 7-trioxabicyclo- [2.2.2]
-Octane-3- (3,5-di-t-butyl-4-hydroxyphenyl) -propionate, 2,4-bis-
(Octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -s-triazine, 2,4-bis- (3,5-di-t-butyl-4-hydroxyphenoxy) -6 -Octyl-s-triazine, 1,3,5-
Tris- (3,5-di-t-butyl-4-hydroxy-
Hydrocinnamoyl) hexahydro-s-triazine, tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, tris [3- (3,5-
Di-t-butyl-4-hydroxyphenyl) propionyloxyethyl] -isocyanurate, N, N'-hexamethylenebis- (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), 2 -T-butyl-6-
(3'-t-butyl-5'-methyl-2'-hydroxybenzyl) -4-methylphenyl acrylate, 2,
2'-oxamide-bis [ethyl-3- (3,5-di-
t-butyl-4-hydroxyphenyl) propionate], 3,9-bis {1,1-dimethyl-2- [3-
(3-t-Butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl} -2,4,8,10-
Tetraoxapyro [5.5] undecane and the like can be mentioned. The amount of these used is 0.001 with respect to such resin.
Is about 2.0% by weight, preferably 0.05 to 1.0% by weight.

Examples of such amine antioxidants include phenyl-1-naphthylamine, phenyl-2-naphthylamine, N, N'-diphenyl-p-phenylenediamine, N, N'-di-2-naphthyl-p-. Phenylenediamine, N, N'-di-sec-butyl-p-phenylenediamine, 6-ethoxy-2,2,4-trimethyl-1,2-dihydroxyquinoline, 6-dodecyl-2,
2,4-trimethyl-1,2-dihydroxyquinoline,
Dioctyliminodibenzyl, diethanolamine, diisopropanolamine, dibutanolamine, triethanolamine, triisopropanolamine, tributanolamine, dodecylethanolamine, octadecyldiethanolamine, N, N'-diphenylethylenediamine, triethyltetramine, dodecylamine ethylene oxide 7 mol adduct, 4 mol ethylene oxide adduct of tridecyl amine, 10 mol ethylene oxide adduct of octadecyl amine, and 20 mol ethylene oxide adduct of hexadecyl amine. The amount used is 0.02 to 5.0% by weight based on the resin.

Examples of such sulfur-based antioxidants include diethyl-3,3'-thio-di-propionate, dilauryl-3,3'-thio-di-propionate and ditridecyl-3,3'-thio-di-. Propionate, dimyristyl-3,3'-thio-di-propionate, distearyl-3,3'-thio-di-propionate, 2-methylmercaptobenzimidazole, stearyl-
(3,5-dimethyl-4-oxybenzyl) thioglycolic acid ester, diphenylthiourea, thiodipropionic acid, phenothiazine, pentaerythritol-tetrakis- (β-lauryl-thiopropionate) and the like can be mentioned. The amount used is 0.01 to
It is 4.0% by weight, preferably 0.05 to 2.0% by weight.

Examples of such light stabilizers include benzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2 -Hydroxy-4-n-octyloxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-benzoyloxybenzophenone, 2,6-dihydroxy-5-benzoylbenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2,2 ', 4
4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone,
2-hydroxy-4-methoxy-4'-chlorobenzophenone, 2-hydroxy-5-chlorobenzophenone,
Benzophenone compounds such as 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, acetophenone compounds such as 2-hydroxy-5-methoxyacetophenone, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-
3 ', 5'-diisoamylphenyl) benzotriazole, 2- [2'-hydroxy-3', 5'bis (α, α)
-Dimethylbenzyl) phenyl] benzotriazole,
2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole, 2- (2'-hydroxy -3'-t-butyl-5 '
-Methylphenyl) -5-chloro-benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chloro-benzotriazole,
Benzotriazole compounds such as 2,2′-methylene-bis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol], phenylsalicylate , 4-t-butylphenyl salicylate, 4-t-octylphenyl salicylate, dibenzoylresorcinol, tribenzoylresorcinol, bis (4-t-butylbenzoyl) resorcinol, ethylene glycol monosalicylate, 2,4 −
Di-t-butylphenyl-3,5'-di-t-butyl-
Benzoate compounds such as 4'-hydroxybenzoate, 2-ethoxy-2'-ethyl oxalic acid bisanilide, 2-ethoxy-5-t-butyl-2'-
Oxalic acid anilide compounds such as ethyl oxalic acid bisanilide, 2-ethylhexyl-2-cyano-3,
3-diphenyl acrylate, ethyl-2-cyano-
Cyanoacrylate compounds such as 3,3-diphenylacrylate-n-butyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate, nickel-
Bis (octylphenyl) sulfide, [2,2'-thiobis (4-t-octylphenolate)]-n-butylamine-nickel, [2,2'-thiobis (4-t-)
Octylphenolate)]-2-ethylhexylamine-nickel, nickel-dibutyl-dithiocarbamate, [2,2′-thiobis (4-t-octylphenolate)]-triethanolamine-nickel and other organic nickel compounds, Tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6)
6-pentamethyl-4-piperidyl) -1,2,3,4
-Butane tetracarboxylate, bis (2,2,6
6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (N-methyl-2,2,6,6-)
Tetramethyl-4-piperidyl) sebacate, 2-
(3,5-di-t-butyl-4-hydroxybenzyl)
-2-n-butylmalonate bis (1,2,2,6,6-
Pentamethyl-4-piperidyl), dimethylsuccinic acid-
2- (4-hydroxy-2,2,6,6-tetramethyl-1-piperidyl) ethanol condensate, phenyl-4-
Examples thereof include hindered piperazine compounds such as piperidyl carboxylate and 1,1 ′-(1,2-ethanediyl) bis (3,3,5,5-tetramethylpiperazinone), but are not limited thereto. Not a thing.

Further, nucleating agents such as 4-t-butylbenzoic acid, adipic acid and diphenylacetic acid, metal deactivators such as oxanilide, dicarboxylic acid dihydrazide,
Dicarboxylic acid-bis-phenylhydrazide, salicylic acid hydrazide, N-salicyloyl-N'-salicylidene hydrazine, bis-salicyloyl-dicarboxylic acid dihydrazide, bis-acylated dicarboxylic acid dihydrazide, salicyloyl-hydrazinotriazine, bis-salicyloyl-hydrazine , Oxalic acid bis (benzylidene hydrazide)
Free radical promoters such as 2,3-dimethyl-2,3-
Diphenyl butane [Brand name Interlocks CC DFB
(Peroxide Chemie GmbH production)], 3,
4-Dimethyl-3,4-diphenylhexane [Brand name Interlocks CC DFH (Peroxide Chemie G.
m. b. H production)], 2,3-dimethyl-2,3-diphenylhexane, cyclohexenecarboguanamine, norbornenecarboguanamine and the like can be appropriately selected and used.

In the method for flame retarding a resin according to the present invention, the method for producing such a resin composition is not particularly limited, and the production method usually used when a powdery additive is mixed with such a resin is applicable. is there. For example, in the case of a thermoplastic resin or the like, a resin pellet or powder and additives are premixed at room temperature and then melt-mixed using an extruder, a heating roll, a kneader, etc. A manufacturing method in which a resin is manufactured in advance, and this and an ordinary resin are melt-kneaded and then molded, and in the case of a thermosetting resin or the like, a monomer before curing, a prepolymer, or a dope prepared by adding a reinforcing material to these. Examples thereof include, but are not limited to, a production method in which an essential component according to the present invention is added to a compound, and the mixture is kneaded and then molded.

In the method for flame retarding a resin according to the present invention, other additives such as a plasticizer, a dye / pigment, a dispersant, an organic chelating agent, a stabilizer and a foaming agent are used as long as the effects of the present invention are not impaired. Agent, anti-fog agent, matting agent, surface treatment agent,
Fluorescent agent, antifungal agent, bactericidal agent, antioxidant, ultraviolet absorber,
Conventional flame retardants such as antimony trioxide, barium metaborate, zirconium dioxide, lead oxide and zinc borate, flame retardant aids, higher fatty acids, higher fatty acid esters, higher fatty acid metal salts, lubricants such as bisamides, sulfonic acids, Tetraammonium salt, polyhydric alcohol ester, alkylamide, alkylamine, antistatic agent such as conductive carbon black, reinforcing material such as glass fiber and carbon fiber, talc, clay, calcined clay, mica, calcium silicate, calcium sulfate , Calcium carbonate, glass beads, molybdenum disulfide, fillers such as graphite, processing aids, mold release agents, other polymers and the like can be included as required.

In the method for flame retarding a resin of the present invention, it is preferable to contain at least one selected from phosphorus consisting of phosphorus alone and a compound containing a phosphorus atom as a component. , Phosphoric acid, polyphosphoric acid, phosphorous acid, phosphonic acid, phosphate, polyphosphate, phosphite, phosphonate, phosphates, phosphites, phosphonates, phosphines and More preferably, it is a sulfur-containing phosphorus compound, and the polyphosphate is represented by the general formula (NH ₄ ) _{n + 2} P _n O _{3n + 1} (wherein
It is more preferable that ammonium polyphosphate is represented by the formula (n is an integer greater than 5). Further, it is preferable to contain at least one selected from isocyanuric acids and cyanuric acids represented by the formulas (5) and (6) as a component.

Further, it is preferable that at least one selected from the amino group-containing compounds is contained as a component, and the amino group-containing compound is

[0092]

[Chemical 17] More preferably, it is a compound having cis, dicyandiamide, guanidine and a reaction product thereof with an aldehyde or an epoxy compound.

Further, it is particularly preferable that the above-mentioned phosphorus-containing compound and amino group-containing compound are contained as components.

Further, the resin is preferably a thermoplastic resin, and the thermoplastic resin is a polyolefin resin, a polyamide resin, a styrene resin, a polyphenylene ether resin, a saturated polyester resin, a polycarbonate resin,
More preferably, it is at least one selected from the group consisting of polyacetal resins and acrylic resins.

Further, the resin is preferably a thermosetting resin, and the thermosetting resin is at least one selected from the group consisting of unsaturated polyester resin, diallyl phthalate resin, epoxy resin and urethane resin. More preferable.

Further, in the method for heat-stabilizing a resin according to the present invention, by incorporating the diguanamines represented by the formulas (1) and (2) into the resin, the heat stability and ultraviolet resistance of the resin are remarkably improved. Not only is it improved, but there is little coloration and discoloration of the resin during high temperature processing. It can be remarkably suppressed, and an excellent method for modifying a resin can be provided.

The amount of diguanamines used in the method for heat stabilizing a resin of the present invention is 0.01 to 5% by weight, preferably 0.02 to 1% by weight, based on the resin. 0.
When the amount is less than 01% by weight, it is difficult to obtain a sufficient effect of improving stability against heat, light, etc., and when the amount is more than 5% by weight, the effect of improving stability is not particularly improved, and the economy is improved. Is not preferable.

As the resins which can be the object of the heat stabilization method for the resin of the present invention, the resins which are the objects of the flame retardant method can be mentioned in almost the same manner. In addition, the heat stabilization method of the resin according to the present invention includes additives such as the above-mentioned phenolic antioxidants, amine antioxidants, sulfur antioxidants, light stabilizers, nucleating agents, and other additives. It is also possible to further improve the effect of improving the stability according to the present invention by using the phosphite-based antioxidant shown below in combination with the above-mentioned amount in the same amount, and depending on the purpose of use. It can be appropriately selected.

Examples of phosphite antioxidants include triphenyl phosphite, tris (nonylphenyl) phosphite, tris (dinonylphenyl).
Phosphite, tris (2,4-di-t-butylphenyl) phosphite, tris (2,5-di-t-butylphenyl) phosphite, tris (2,6-di-t-butylphenyl) phosphite , Tris (mono, di mixed nonylphenyl) phosphite, diphenyl decyl phosphite, 2-ethylhexyl diphenyl phosphite, phenyl diisodecyl phosphite, diphenyl acid phosphite, trilauryl phosphite, tridecyl phosphite, tris (2-ethylhexyl) ) Phosphite, tributyl phosphite, dibutyl acid phosphite, dilauryl acid phosphite, ditridecyl pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, bis (2,4-di-
t-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite,
Diisodecyl pentaerythritol diphosphite, phenyl 4,4'-isopropylidene diphenol pentaerythritol diphosphite, trilauryl trithiophosphite, tris (lauryl-2-thioethyl) phosphite, diphenyl bis [4,4 ' -N-
Butylidene bis (2-t-butyl-5-methylphenol)] thiodiethanol diphosphite, bis (neopentyl glycol) 1,4-cyclohexanedimethylene phosphite, hydrogenated-4,4'-isopropylidene diphenol polyphos Fight, bis (octylphenyl) .bis [4,4'-n-butylidene bis (2-t-
Butyl-5-methylphenol)] 1,6-hexanediol diphosphite, tetratridecyl-4,4'-
n-butylidene bis (2-t-butyl-5-methylphenol) diphosphite, tetratridecyl-1,1,
3-tris (2'-methyl-5'-t-butyl-4'-
Oxyphenyl) butanediphosphite, tetra (C
_12-15 mixed alkyl) 4,4'-isopropylidene diphenyldiphosphite and the like. The amount of these used is 0.01-10. Weight percent is preferred.

In the heat stabilization method for a resin according to the present invention, the method for producing such a resin composition and the use of other additives can be carried out in the same manner as in the above-mentioned method for flame retarding a resin. However, the present invention is not limited to these.

In the heat stabilization method for a resin according to the present invention, the resin is preferably a thermoplastic resin, and at least one selected from the group consisting of polyphenylene ether resin, polyacetal resin, polyamide resin and polyolefin resin. Is more preferable, and a polyethylene resin as the polyolefin resin,
More preferably, it is at least one selected from the group consisting of polypropylene resin and ethylene-propylene copolymer.

Furthermore, the resin compatibilizing method according to the present invention comprises at least one of the diguanamines represented by the formulas (1) and (2) selected from polyamide resin, polyphenylene ether resin, polyimide resin and polyaramid resin. By including it in two or more different types of resins containing, not only the compatibility of two or more different types of resins is significantly improved, but also the physical properties are improved and new materials can be provided. Coloring and discoloration of resins during high temperature processing. Less, the diguanamines high temperature stability, excellent non-volatility, sublimation, handling with less occurrence of bleeding, easy manufacturing, the polyamide resin, good melt dispersibility in polyphenylene ether resin, etc. In addition, the heat stability of the resin is improved, and an excellent method for modifying the resin can be provided.

The amount of diguanamines used in the resin compatibilizing method of the present invention is usually 0.
It is 5 to 20% by weight, and can be appropriately selected depending on the case. When it is less than 0.5% by weight, it is difficult to obtain a sufficient effect of improving the compatibility, and when it is more than 20% by weight, not only the improving effect is not particularly improved, but also the resin characteristics are deteriorated, which is economical. Is also not preferable.

As the resins applicable to the resin compatibilizing method of the present invention, the above-mentioned resins subject to the flame retarding method are almost the same. Specific examples of the two or more different resins are selected from polyamide resin, polyphenylene ether resin, polyimide resin and polyaramid resin.
Seed and other resins such as polyamide resin and ABS resin, polyamide resin and polyphenylene ether resin, polyimide resin and polyphenylene ether resin, etc. 2
Examples include heterogeneous multi-component resins such as original resins, polyamide resins, polyphenylene ether resins and other resins,
It is not limited to these.

Further, in the resin compatibilizing method according to the present invention, the above-mentioned phenol-based antioxidant, amine-based antioxidant, sulfur-based antioxidant, phosphite-based antioxidant,
Additives such as a light stabilizer, a nucleating agent, and other additives can be used in the same amount as the above amount, and can be appropriately selected according to the purpose of use.

Further, in the resin compatibilizing method according to the present invention, the method for producing such a resin composition can be carried out in the same manner as in the above-mentioned resin flame retarding method.
It is not limited to these.

The present invention provides not only the use of the diguanamines represented by the above formulas (1) and (2), but also the derivatives of these diguanamines, the production method thereof and the use thereof.

As such a diguanamine derivative, a compound represented by the formula (7)

[0109]

[Chemical 18] [In the formula, the bonding position of the (1,3,5-triazin-2-yl) group represents 2,5- or 2,6-position, R ₁ ,
R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are species selected from the group consisting of hydrogen atoms and groups having 2 or more carbon atoms, and R ₁ , R ₂ , R ₃ , R ₄ , R ₅ ,
R ₆ , R ₇ and R ₈ may be the same or different and at least one of the group consisting of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ has a carbon number. And a formula (8).

[0110]

[Chemical 19] [In the formula, the bonding position of the (1,3,5-triazin-2-yl) group represents the 1,2-, 1,3- or 1,4-position,
R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈
Has the same meaning as in formula (7)].

In the diguanamine derivative according to the present invention [formula (7)], the bonding position of the (1,3,5-triazin-2-yl) group is 2,5- or 2,6-position. The configuration of such a group is endo-endo, endo-exo or exo-exo, and all of them are useful derivatives. In the diguanamine derivative [Formula (8)], the bonding position of the (1,3,5-triazin-2-yl) group is 1,2-, 1,3- or 1,4-
However, the configuration of such a group is trans or cis, and both are useful derivatives. Further, such a diguanamine derivative is a derivative selected from the group including isomers having the above-mentioned bonding positions and configurations, but different derivatives selected from such a group and an aggregate of isomers also have a single derivative. It is extremely useful industrially as in the case of.

R ₁ , R ₂ in the formulas (7) and (8),
At least one of the group consisting of R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ is a group having 2 or more carbon atoms, and the number and position of the group having 2 or more carbon atoms, The configuration and the like are not particularly limited, but R ₂ , R ₄ , R ₆
And R ₈ are both hydrogen atoms, and R ₁ , R ₃ , R
Diguanamine derivatives in which ₅ and R ₇ are a hydrogen atom or a group having 2 or more carbon atoms, for example, N-monosubstituted diguanamine derivatives, N, N'-disubstituted diguanamine derivatives, N, N ', N "- Tri-substituted diguanamine derivatives, N, N ′, N ″, N ′ ″-tetra-substituted diguanamine derivatives and the like are readily available as raw materials, reaction is easy, purification and separation steps are simple, and amino group 1 is used. It is preferable from the viewpoints of production and use such as easy production using amines having a single group, especially N, N ', N "-tri-substituted diguanamine derivatives, N, N', N", N "'. -Tetra-substituted diguanamine derivatives are preferred.

R ₁ , R ₂ in the equations (7) and (8),
R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are species selected from the group consisting of a hydrogen atom and a group having 2 or more carbon atoms. As a group having 2 or more carbon atoms, Has 2 or more carbon atoms and is a hydroxyl group, an ester group, an ether group, a carboxyl group, a carbonyl group, an amide group, an imide group, a nitro group, a sulfonic acid group, a sulfonic acid amide group, an amino group, an imino group, Functional groups such as saturated groups, aliphatic groups that may have branched chains, alicyclic groups, aromatic groups,
Heterocyclic groups are useful, for example, aliphatic groups, alicyclic groups, aromatic groups, heterocyclic groups, HO having 2 to 30 carbon atoms.
A group represented by —R ₉ — (R ₉ is a divalent group having 2 or more carbon atoms), a formula (9)

[0114]

[Chemical 20] [In the formula, R ₁₀ is at least one selected from the group consisting of ethylene, trimethylene and tetramethylene which may have a substituent containing 2 to 22 carbon atoms, and n is 1 to 1
An integer selected from 00, R ₉ has the same meaning as above], a group of the formula (10)

[0115]

[Chemical 21] [Wherein R ₁₀ and n have the same meanings as in formula (9)], and the like, but are not limited thereto.

Aliphatic groups having 2 to 30 carbon atoms,
Specific examples of the alicyclic group and the heterocyclic group include ethyl, isopropyl, isobutyl, n-butyl and 1,2-
Dimethylpropyl, n-hexyl, n-octyl, 2-
Ethylhexyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, allyl, oleyl, 4-aminobutyl, 3-ethoxypropyl, butoxypropyl, myristyloxypropyl, methoxyethyl, ethoxyethyl, cyclohexyl, 4-methylcyclohexyl, phenyl, o- Trilyl, α-naphthyl, benzyl,
β-phenethyl, o-methoxycarbonylphenyl, p
-Ethoxycarbonylphenyl, 4-methoxyphenyl, tetrahydrofurfuryl, 2- (1-piperazinyl) ethyl, 2- (piperidino) ethyl, 2- (morpholino) ethyl, 3- (morpholino) propyl, 2- (1
-Pyrrolidinyl) ethyl, 2-pyridinyl, and the like, but not limited thereto.

The group represented by HO—R ₉ — is a divalent group in which R ₉ has 2 or more carbon atoms, and is an aliphatic group, alicyclic group, aromatic group, heterocyclic group or the like. There is no particular limitation, but those having 2 to 20 carbon atoms are preferable from the viewpoints of production and use such as availability of raw materials, easiness of reaction, simplicity of steps such as purification and separation. Since such a group contains a hydroxyl group, it is a resin raw material as a diguanamine derivative,
It is extremely useful for a wide range of applications such as modifiers and crosslinking agents.

Specific examples of the group represented by HO-R ₉ -include, for example, 2-hydroxyethyl, 2-hydroxypropyl, 4-hydroxybutyl, 1-hydroxymethylpropyl, 3-hydroxypropyl and 2-hydroxy-.
2-methylpropyl, 5-hydroxypentyl, 1-
(2-hydroxyethyl) propyl, 3-hydroxypentyl, 3-hydroxy-2,2-dimethylpropyl,
1-hydroxyhexyl, 1-ethyl-3-hydroxybutyl, 8-hydroxyoctyl, 10-hydroxydecyl, 12-hydroxydodecyl, 1- (2-hydroxyethyl) -2-propenyl, 1- (3-hydroxypropyl) -1-propenyl, 1- (2-hydroxypropyl) -2-propenyl, 1- (1-hydroxypropyl) -3-pentenyl, 5-hydroxy-3-oxapentyl, 1-hydroxymethyl-3-oxabutyl, 1
-(2-hydroxyethyl) -4-oxahexyl, 1
-(2-hydroxypropyl) -5-oxahexyl,
4-hydroxycyclohexyl, 4-hydroxyphenyl, 2-methyl-4-hydroxyphenyl, 7-hydroxynaphthyl, 4- (hydroxymethyl) phenyl, 2
-(4-hydroxyphenyl) ethyl, 4- (2-hydroxyethyl) phenyl, 3-hydroxypyridine-2
-Yl, 8-hydroxyquinolin-4-yl and the like, but not limited thereto.

In the group represented by the above formula (9),
R ₉ is a divalent group having 2 or more carbon atoms and having an aliphatic group, an alicyclic group, an aromatic group, a heterocyclic group or the like as described above and is not particularly limited, but has 2 carbon atoms. Those having up to 20 are preferred. Specific examples of R ₉ is, for example above HO-R ₉ - residues such as by eliminating a hydroxyl group from the groups listed as specific examples of the group represented by including without being limited thereto.

R ₁₀ of the groups represented by the above formulas (9) and (10) is selected from the group consisting of ethylene, trimethylene and tetramethylene groups which may have a substituent containing 2 to 22 carbon atoms. And various functional groups, an aliphatic group which may have a branched chain, an alicyclic group, an aromatic group,
It is a group having a heterocyclic group and is not particularly limited. Specific examples of R ₁₀ include, for example, ethylene, propylene, ethyl ethylene, n-butyl ethylene, n-dodecyl ethylene, phenyl ethylene, butoxy ethylene, phenoxy ethylene, 3-acryloxy propylene, 1,2-cyclohexylene, tricyclo. [4.3.1.0] -dec-7-ene-2,3-diyl, trimethylene, tetramethylene and the like are mentioned, and ethylene and propylene are preferable, but not limited thereto. It should be noted that one kind or two or more kinds of R ₁₀ may be contained in one kind of the groups represented by the formulas (9) and (10) as a random arrangement, a block arrangement, etc., and may be appropriately selected as necessary. it can.

Further, n is an integer selected from 1 to 100 and can be appropriately selected if necessary, but it is usually an integer in the range of 1 to 50, preferably an integer in the range of 1 to 30. is there.

The above-mentioned oxaalkyl group-containing diguanamine derivative is a derivative containing 1 to 8 species selected from the group consisting of groups represented by the formulas (9) and (10). The same derivative may contain two or more species. As the oxaalkyl group-containing diguanamine derivative represented by the formula (9), an N-monosubstituted oxaalkylated diguanamine derivative of such a group, N, N ′, is used because of easy reaction, availability of raw materials, and the like. −
Disubstituted oxaalkylated diguanamine derivatives, N,
N ', N "-trisubstituted oxaalkylated diguanamine derivatives and N, N', N", N "'-tetrasubstituted oxaalkylated diguanamine derivatives are particularly useful and are represented by formula (8). As the oxaalkyl group-containing diguanamine derivative, an oxaalkyl group-containing diguanamine derivative having 3 to 8 such groups is particularly useful in view of availability of raw materials, but is not limited thereto. Absent.

Specific examples of the diguanamine derivative according to the present invention include 2- (4,6-diamino-1,
3,5-triazin-2-yl) -5- (4-amino-
6-n-octylamino-1,3,5-triazine-2
-Yl) -bicyclo [2.2.1] heptane, 2-
(4,6-Diamino-1,3,5-triazin-2-yl) -6- (4-amino-6-anilino-1,3,5-
Triazin-2-yl) -bicyclo [2.2.1] heptane, 2- (4,6-diamino-1,3,5-triazin-2-yl) -5- [4-amino-6- (2 -Morpholinoethylamino) -1,3,5-triazin-2-yl] -bicyclo [2.2.1] heptane, 1- (4,6
-Diamino-1,3,5-triazin-2-yl) -2
-(4-amino-6-cyclohexylamino-1,3,3
5-triazin-2-yl) -cyclohexane, 1-
(4,6-Diamino-1,3,5-triazin-2-yl) -4- [4-amino-6- (2-morpholinoethylamino) -1,3,5-triazin-2-yl]- Cyclohexane,

2- (4,6-diamino-1,3,5-triazin-2-yl) -5- [4-amino-6- (2-
Hydroxyethylamino) -1,3,5-triazine-
2-yl] -bicyclo [2.2.1] heptane, 2-
(4,6-Diamino-1,3,5-triazin-2-yl) -6- [4-amino-6- (2-hydroxypropylamino) -1,3,5-triazin-2-yl]- Bicyclo [2.2.1] heptane, 2- (4,6-diamino-1,3,5-triazin-2-yl) -6- [4-
Amino-6- (5-hydroxy-3-oxapentylamino) -1,3,5-triazin-2-yl] -bicyclo [2.2.1] heptane, 2- (4,6-diamino-
1,3,5-triazin-2-yl) -5- [4-amino-6- (4-hydroxyphenylamino) -1,3,3
5-triazin-2-yl] -bicyclo [2.2.1]
Heptane, 1- (4,6-diamino-1,3,5-triazin-2-yl) -3- [4-amino-6- (2-hydroxyethylamino) -1,3,5-triazine-2
-Yl] -cyclohexane, 1- (4,6-diamino-
1,3,5-triazin-2-yl) -4- [4-amino-6- (3-hydroxypropylamino) -1,3
5-triazin-2-yl] -cyclohexane, 1-
(4,6-Diamino-1,3,5-triazin-2-yl) -3- [4-amino-6- (5-hydroxy-3-
Oxapentylamino) -1,3,5-triazine-2
-Yl] -cyclohexane, 1- (4,6-diamino-
1,3,5-triazin-2-yl) -4- [4-amino-6- (4-hydroxyphenylamino) -1,3,3
5-triazin-2-yl] -cyclohexane, 2,5
-Bis (4-amino-6-cyclohexylamino-1,
3,5-triazin-2-yl) -bicyclo [2.2.
1] heptane, 2,6-bis (4-amino-6-benzylamino-1,3,5-triazin-2-yl) -bicyclo [2.2.1] heptane,

2,5-bis [4-amino-6- (2-morpholinoethylamino) -1,3,5-triazine-2
-Yl] -bicyclo [2.2.1] heptane, 2-
(4,6-Diamino-1,3,5-triazin-2-yl) -6- [4,6-bis (4-methoxycarbonylphenylamino) -1,3,5-triazin-2-yl]
-Bicyclo [2.2.1] heptane, 1,4-bis (4
-Amino-6-n-decylamino-1,3,5-triazin-2-yl) -cyclohexane, 1,3-bis [4
-Amino-6- (2-morpholinoethylamino) -1,
3,5-triazin-2-yl] -cyclohexane, 1
-(4,6-Diamino-1,3,5-triazine-2-
Yl) -2- (4,6-dianilino-1,3,5-triazin-2-yl) -cyclohexane, 2,5-bis [4-amino-6- (2-hydroxyethylamino)-
1,3,5-triazin-2-yl] -bicyclo [2.
2.1] Heptane, 2,6-bis [4-amino-6-
(2-Hydroxypropylamino) -1,3,5-triazin-2-yl] -bicyclo [2.2.1] heptane, 2,5-bis [4-amino-6- (5-hydroxy-3-) Oxapentylamino) -1,3,5-triazin-2-yl] -bicyclo [2.2.1] heptane,
2,5-bis [4-amino-6- (4-hydroxyphenylamino) -1,3,5-triazin-2-yl]-
Bicyclo [2.2.1] heptane, 2- (4,6-diamino-1,3,5-triazin-2-yl) -6-
[4,6-bis (2-hydroxyethylamino) -1,
3,5-triazin-2-yl] -bicyclo [2.2.
1] heptane,

1,4-bis [4-amino-6- (2-hydroxyethylamino) -1,3,5-triazine-2
-Yl] -cyclohexane, 1,3-bis [4-amino-6- (3-hydroxypropylamino) -1,3,5
-Triazin-2-yl] -cyclohexane, 1-
(4,6-Diamino-1,3,5-triazin-2-yl) -4- [4,6-bis (5-hydroxy-3-oxapentylamino) -1,3,5-triazine-2- Yl] -cyclohexane, 2- (4-amino-6-cyclohexylamino-1,3,5-triazin-2-yl)
-5- [4,6-bis (cyclohexylamino) -1,
3,5-triazin-2-yl] -bicyclo [2.2.
1] Heptane, 2- [4-amino-6- (2-morpholinoethylamino) -1,3,5-triazin-2-yl] -6- [4,6-bis (2-morpholinoethylamino)- 1,3,5-triazin-2-yl] -bicyclo [2.2.1] heptane,

1- [4-amino-6- (4-ethoxycarbonylphenylamino) -1,3,5-triazine-
2-yl] -4- [4,6-bis (4-ethoxycarbonylphenylamino) -1,3,5-triazine-2-
-Yl] -cyclohexane, 2- [4-amino-6- (2
-Hydroxyethylamino) -1,3,5-triazin-2-yl] -6- [4,6-bis (2-hydroxyethylamino) -1,3,5-triazin-2-yl]-
Bicyclo [2.2.1] heptane, 2- [4-amino-
6- (2-hydroxypropylamino) -1,3,5-
Triazin-2-yl] -5- [4,6-bis (2-hydroxypropylamino) -1,3,5-triazine-
2-yl] -bicyclo [2.2.1] heptane, 2-
[4-amino-6- (2-hydroxyethylamino)-
1,3,5-triazin-2-yl] -5- [4,6-
Bis (5-hydroxy-3-oxapentylamino)-
1,3,5-triazin-2-yl] -bicyclo [2.
2.1] Heptane, 2- [4-amino-6- (5-hydroxy-3-oxapentylamino) -1,3,5-triazin-2-yl] -6- [4,6-bis (5 -Hydroxy-3-oxapentylamino) -1,3,5-triazin-2-yl] -bicyclo [2.2.1] heptane, 2- [4-amino-6- (4-hydroxyphenylamino)- 1,3,5-triazin-2-yl] -5-
[4,6-bis (4-hydroxyphenylamino)-
1,3,5-triazin-2-yl] -bicyclo [2.
2.1] Heptane, 2- [4-amino-6-anilino-
1,3,5-triazin-2-yl] -6- [4,6-
Bis (3-hydroxypropylamino) -1,3,5-
Triazin-2-yl] -bicyclo [2.2.1] heptane, 1- [4-amino-6- (2-hydroxyethylamino) -1,3,5-triazin-2-yl] -4-
[4,6-bis (2-hydroxyethylamino) -1,
3,5-triazin-2-yl] -cyclohexane, 1
-[4-Amino-6- (1-hydroxymethylpropylamino) -1,3,5-triazin-2-yl] -3-
[4,6-bis (1-hydroxymethylpropylamino) -1,3,5-triazin-2-yl] -cyclohexane, 1- [4-amino-6- (5-hydroxy-3
-Oxapentylamino) -1,3,5-triazine-
2-yl] -4- [4,6-bis (5-hydroxy-3)
-Oxapentylamino) -1,3,5-triazine-
2-yl] -cyclohexane, 1- [4-amino-6-
(4-amino-6- (4-hydroxyphenylamino)
-1,3,5-triazin-2-yl] -2- [4,6
-Bis (4-hydroxyphenylamino) -1,3,5
-Triazin-2-yl] -cyclohexane,

2,5-bis [4,6-bis (n-octylamino) -1,3,5-triazin-2-yl] -bicyclo [2.2.1] heptane, 2,6-bis [ 4,6
-Bis (cyclohexylamino) -1,3,5-triazin-2-yl] -bicyclo [2.2.1] heptane,
2,5-bis [4,6-dianilino-1,3,5-triazin-2-yl] -bicyclo [2.2.1] heptane, 2,5-bis [4,6-bis (2-morpholino Ethylamino) -1,3,5-triazin-2-yl] -bicyclo [2.2.1] heptane, 2,6-bis [4,6
-Yl] -bicyclo [2.2.1] heptane, 2,6-
Bis [4,6-bis (5-hydroxy-3-oxapentylamino) -1,3,5-triazin-2-yl]-
Bicyclo [2.2.1] heptane, 2,6-bis [4,
6-bis (4-hydroxyphenylamino) -1,3,
5-triazin-2-yl] -bicyclo [2.2.1]
Heptane, 2,5-bis [4,6-bis (N, N-di n
-Butylamino) -1,3,5-triazin-2-yl] -bicyclo [2.2.1] heptane, 1,3-bis [4,6-bis (2-hydroxyethylamino) -1,
3,5-triazin-2-yl] -cyclohexane,
1,4-bis [4,6-bis (2-hydroxypropylamino) -1,3,5-triazin-2-yl] -cyclohexane, 1,2-bis [4,6-bis (1-hydroxymethyl) Propylamino) -1,3,5-triazin-2-yl] -cyclohexane, 1,4-bis [4,6
-Bis (3-hydroxypropylamino) -1,3,5
-Triazin-2-yl] -cyclohexane, 1,3-
Bis [4,6-bis (5-hydroxy-3-oxapentylamino) -1,3,5-triazin-2-yl]-
Cyclohexane, 1,4-bis [4,6-bis (4-hydroxyphenylamino) -1,3,5-triazine-
2-yl] -cyclohexane,

Polyoxyethylenated 2,5-bis [4,
6-Diamino-1,3,5-triazin-2-yl]-
Bicyclo [2.2.1] heptane, polyoxypropyleneated 2,6-bis [4,6-diamino-1,3,5-triazin-2-yl] -bicyclo [2.2.1] heptane, poly Oxyethylenated 2- [4,6-diamino-
1,3,5-Triazin-2-yl] -6- [4-amino-6-anilino-1,3,5-triazin-2-yl] -bicyclo [2.2.1] heptane, polyoxyethylene 2,6-bis [4-amino-6- (2-hydroxypropylamino) -1,3,5-triazine-2-
Yl] -bicyclo [2.2.1] heptane, polyoxypropyleneized 2- [4-amino-6- (2-hydroxyethylamino) -1,3,5-triazin-2-yl]
-5- [4,6-bis (2-hydroxyethylamino)
-1,3,5-Triazin-2-yl] -bicyclo [2.2.1] heptane, polyoxyethylenated 2,6
-Bis [4,6-bis (5-hydroxy-3-oxapentylamino) -1,3,5-triazin-2-yl]
-Bicyclo [2.2.1] heptane, polyoxyethylenated 2,5-bis [4,6-bis (2-hydroxypropylamino) -1,3,5-triazin-2-yl]-
Bicyclo [2.2.1] heptane, polyoxypropyleneized 2,6-bis [4,6-bis (4-hydroxyphenylamino) -1,3,5-triazin-2-yl]-
Bicyclo [2.2.1] heptane, polyoxyethylenated 2,5-bis [4,6-bis (N, N-dimethylolamino) -1,3,5-triazin-2-yl] -bicyclo [ 2.2.1] Heptane, polyoxypropyleneized 2,6-bis [4,6-bis (N-methylolamino)]
-1,3,5-Triazin-2-yl] -bicyclo [2.2.1] heptane, polyoxyethylenated 1,4
-Bis (4,6-diamino-1,3,5-triazine-
2-yl) -cyclohexane, polyoxypropyleneated 1,3-bis (4,6-diamino-1,3,5-triazin-2-yl) -cyclohexane, polyoxystyrenated 1- (4,6-diamino -1,3,5-Triazin-2-yl) -2- [4-amino-6-benzylamino-1,3,5-triazin-2-yl) -cyclohexane, polyoxypropyleneized 1,4-bis [4,6-bis (2-hydroxypropylamino) -1,3,5-triazin-2-yl] -cyclohexane, polyoxyethylenated 1,3-bis [4,6-bis (4-hydroxyphenylamino) ) -1,3,5-Triazin-2-yl] -cyclohexane,

Polyoxyethylenated 1,4-bis [4,
6-bis (N, N-dimethylolamino) -1,3,5
-Triazin-2-yl] -cyclohexane, polyoxypropyleneized 1,3-bis [4,6-bis (N-methylolamino) -1,3,5-triazin-2-yl]
-Cyclohexane, 2- (4,6-diamino-1,3,3
5-triazin-2-yl) -5- [4-amino-6-
(2-piperazinoethylamino) -1,3,5-triazin-2-yl] -bicyclo [2.2.1] heptane,
2,6-bis [4,6-bis (2-aminoethylamino) -1,3,5-triazin-2-yl] -bicyclo [2.2.1] heptane, 2,5-bis [4,4] 6-bis (2-piperidinoethylamino) -1,3,5-triazin-2-yl] -bicyclo [2.2.1] heptane,
2,6-bis [4,6-bis (3-piperazinopropylamino) -1,3,5-triazin-2-yl] -bicyclo [2.2.1] heptane, 2,5-bis [ 4,6-
Bis (N-aminoethylpiperazinoethylamino)-
1,3,5-triazin-2-yl] -bicyclo [2.
2.1] Heptane, 1,3-bis [4,6-bis (2-
Piperazinoethylamino) -1,3,5-triazine-
2-yl] -cyclohexane, 1,4-bis [4,6-
Bis (3-piperidinopropylamino) -1,3,5-
Examples thereof include, but are not limited to, triazin-2-yl] -cyclohexane.

In the diguanamine derivatives according to the present invention, R ₁ , R ₂ in the formulas (7) and (8),
R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are selected from the group consisting of a hydrogen atom and a HO—R ₉ — group (R ₉ is a divalent group having 2 or more carbon atoms). It is preferably a hydroxyl group-containing diguanamine derivative, and the HO-R ₉ -group is a 2-hydroxyethyl group or a 2-hydroxyethyl group.
Hydroxypropyl group, 1-hydroxymethylpropyl group, 3-hydroxypropyl group, 5-hydroxy-3-
A hydroxyl group-containing diguanamine derivative which is a species selected from the group consisting of an oxapentyl group and a 4-hydroxyphenyl group is preferable.

Further, R ₁ , R ₂ in the formulas (7) and (8),
At least one of the group consisting of R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ is an oxaalkyl group which is a species selected from the group consisting of groups represented by formula (9) and formula (10). It is preferably a diguanamine derivative containing,
R ₁₀ in the above formulas (9) and (10) is preferably an oxaalkyl group-containing diguanamine derivative which is at least one selected from ethylene and propylene.

The diguanamine derivatives represented by the above formulas (7) and (8) contain at least one member selected from the diguanamines represented by the formulas (1) and (2) and an amino group, and have a carbon number of It can be produced by a method of reacting with at least one selected from amines having two or more.

As the amines involved in the production of the above-mentioned diguanamine derivatives, any amine containing an amino group and having 2 or more carbon atoms is useful, and the number of amino groups is not particularly limited. Also, amines have 2 carbon atoms.
It has one or more aliphatic groups, alicyclic groups, aromatic groups, heterocyclic groups and the like, and is not particularly limited, but availability of raw materials, ease of reaction, purification, separation, etc. Those having 2 to 20 carbon atoms are preferable in terms of simplicity and the like. Further, amines are groups other than amino groups, such as hydroxyl group, ester group, ether group, carboxyl group, carbonyl group, amide group, imide group, sulfonic acid group, carboxylic acid amide group,
It may contain an imino group, an unsaturated group and the like, and those containing a hydroxyl group, an ester group, an ether group, an imino group and the like are particularly useful.

Specific examples of such amines include 2-aminoethanol, 3-amino-1-propanol and 2-aminoethanol.
Amino-1-propanol, 1-amino-2-propanol, 4-amino-1-butanol, 2-amino-1-
Butanol, 1-amino-2-methyl-2-propanol, 5-amino-1-pentanol, 3-amino-1-
Pentanol, 1-amino-3-pentanol, 2,2
-Dimethyl-3-amino-1-propanol, 6-amino-1-hexanol, 4-amino-2-hexanol, 8-amino-1-octanol, 10-amino-1
-Decanol, 12-amino-1-dodecanol, 3-
Amino-1-penten-5-ol, 4-amino-2-
Hexen-6-ol, 3-amino-1-hexene-5
-Ol, 5-amino-2-octen-6-ol, 5
-Amino-3-oxapentan-1-ol, 2-amino-3-methoxy-1-propanol, 3-amino-5
-Ethoxy-1-pentanol, 4-amino-7-methoxy-2-heptanol, 4-amino-1-cyclohexanol, p-anomiphenol, 4-amino-m-cresol, p-aminophenylethanol, 8- Amino-2-naphthol, p-aminobenzyl alcohol, 4
- hydroxy phenethylamine, 2-amino-3-hydroxypyridine, 5-amino -8- HO-R ₉ -NH _2, such as hydroxyquinoline (R ₉ is a divalent radical having 2 or more carbon atoms) The compound represented by , Ethylamine, isopropylamine, butylamine, 1,2-dimethylpropylamine, hexylamine, 2-ethylhexylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, allylamine, oleylamine, 3-ethoxypropylamine, propoxypropyl Aliphatic monoamines such as amine, butoxypropylamine, 2-ethylhexyloxypropylamine, myristyloxypropylamine, aniline, o-toluidine, α-naphthylamine, β-phenethylamine,
Aromatic monoamines such as benzylamine, cyclohexylamine, alicyclic monoamines such as 4-methylcyclohexylamine, furfurylamine, N- (2-aminoethyl) morpholine, N- (2-aminoethyl) piperidine, N- Heterocyclic monoamines such as (3-aminopropyl) piperazine and 2-aminopyridine, 1,2-ethylenediamine, 1,3-diaminopropane, 1,2-diaminopropane, 1,4-butylenediamine, 1,6 -Hexamethylenediamine, 1,4-diaminocyclohexane, 1,3-bis (aminomethyl) cyclohexane, N
-(2-aminoethyl) piperazine, N, N'-bis (2-aminoethyl) piperazine, m-phenylenediamine, benzidine, 4,4'-diaminodiphenylmethane, xylylenediamine, 1,2-bis (3- Aminopropoxy) ethane and other polyamines, p-aminobenzoic acid ethyl, methyl anthranilate, butyl m-aminobenzoate and other aminobenzoic acid alkyl esters, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and other polyamines. alkylene polyamines, and the like, especially HO-R ₉ -NH ₂
The compound represented by is preferable because it can obtain a hydroxyl group-containing diguanamine derivative which is useful in a wide range of applications, but is not limited thereto. The use ratio of amines can be appropriately selected as necessary, but is usually 0.5 to 20 mol of amines, preferably 1 to 16 mol per 1 mol of diguanamine. When using amines such as 1-aminoethanol, which easily produces by-products such as cyclized compounds, the reaction may be carried out by using amines in a proportion of 8 mol or more in order to suppress by-products. preferable. It should be noted that when the proportion of amines used is excessively large, the reaction rate is likely to decrease, but in such a case, the reaction may be carried out by continuously or discontinuously adding amines to the reaction system. It is preferable to appropriately select and use a method such as performing.

The above reaction is usually carried out in the presence of an acidic catalyst at a temperature of 120 to 250 ° C, preferably 150 to 200 ° C.

As the acidic catalyst, compounds that release or form a proton under the production conditions are useful, and examples thereof include mineral acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, and amide sulfone. Acids, thiocyanic acid, p-toluenesulfonic acid, sulfonic acids such as metasulfonic acid, carboxylic acids such as trifluoroacetic acid and trichloroacetic acid, salts thereof with diguanamines, amines, ammonia and the like,
Examples thereof include Lewis acids such as boron trifluoride, aluminum chloride, tin (IV) chloride, antimony fluoride (V), and iron (III) bromide, but are not limited thereto. The use ratio of the acidic catalyst can be appropriately selected as necessary, but usually the acidic catalyst is 0.0 per mol of the diguanamine.
The ratio is 5 to 5.0 mol, preferably 0.1 to 2.0 mol.

The above-mentioned reaction can be carried out in the presence or absence of a solvent, and it is preferable to carry out in the absence of a solvent.
-Pentanol, 2-methyl-1-butanol, 1-hexanol, 3-heptanol, 1-octanol, 2
-Ethyl-1-hexanol, 1-decanol, ethylene glycol, 1,2-propylene glycol, diethylene glycol, triethylene glycol, 2-methyl-2,4-pentanediol, ethylene glycol diethyl ether, ethylene glycol dibutyl ether,
It is possible to appropriately select and use ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol dimethyl ether, triethylene glycol monoethyl ether, or the like.

Furthermore, the reaction system described above is not particularly limited, but it is preferable because it has the effect of reducing the coloring of the product when carried out in the presence of a reaction inert gas such as nitrogen or argon, and under normal pressure. Alternatively, it can be carried out in a closed container under autogenous pressure, and further under pressure, and can be appropriately selected if necessary.

The hydroxyl group-containing diguanamine derivatives and oxaalkyl group-containing diguanamine derivatives according to the present invention include active hydrogen-containing diguanamine derivatives represented by the formulas (7) and (8), and the formula (1), It can be produced by a method in which at least one selected from the group consisting of diguanamines and N-methylol diguanamine derivatives represented by (2) and at least one selected from epoxides are subjected to an addition reaction.

Such a method yields a diguanamine derivative having a hydroxyl group and an oxaalkyl group-containing diguanamine derivative having at least one selected from the group consisting of the groups represented by the above formulas (9) and (10). It is an excellent product that can be obtained easily.

As the diguanamine derivative, any diguanamine derivative containing active hydrogen such as imino group, amino group and hydroxyl group is useful, and the diguanamine derivative represented by the above formulas (1) and (2) can be used. s and aliphatic monoamines, alicyclic monoamines, aromatic monoamines, _{polyamines, HO-R 9 -NH 2 (} R 9 is a divalent radical having 2 or more carbon atoms) amino, such as compounds represented by Examples thereof include diguanamine derivatives which are obtained by reacting a group-containing compound having 2 or more carbon atoms, hydroxyl group-containing diguanamine derivatives, and the like, preferably hydroxyl group-containing diguanamine derivatives, but not limited thereto. Not something. Such a diguanamine derivative is
The reaction can be carried out substantially in the absence of a solvent, a good product having a narrow molecular weight distribution can be obtained, the yield is good, the purity is high, the production steps such as purification and separation are simple, etc. It is particularly preferable because it has the excellent characteristics of

As the diguanamines, the compounds represented by the above formulas (1) and (2) are all useful, and the solubility in the solvent is remarkably better than that of melamine and the like. Can be carried out under mild conditions, desired molecular weight compared to melamine, etc., having excellent characteristics that are completely unpredictable from known techniques such as being able to obtain a good product with a narrow molecular weight distribution, It is extremely useful as a raw material for producing the above-mentioned derivative.

As the N-methylol diguanamine derivative, any of those containing an N-methylol group and derived from the above-mentioned diguanamines is useful, and for example, the above-mentioned diguanamines and aldehydes such as formaldehyde are included. N-methylol diguanamines obtained by addition reaction, etherified diguanamines obtained by etherifying the N-methylol diguanamines and alcohols having 1 to 20 carbon atoms,
Examples thereof include N-methylol diguanamine initial condensation products and etherified diguanamine initial condensation products obtained by subjecting these to a condensation reaction, preferably N-methylol diguanamine initial condensation products, and N-methylol diguanamine initial condensation products. , And particularly preferably N-methylol diguanamines, but not limited thereto. Such N-methylol diguanamine derivatives can be reacted substantially in the absence of a solvent, a good product having a narrow molecular weight distribution can be obtained, and the production steps such as purification and separation are simple. It is preferable since it is possible to easily obtain a polyol having a hydroxyl group, etc., and it is excellent in yield, etc.

As the epoxides relating to the production of the above-mentioned diguanamine derivatives, alkylene oxides having an aliphatic group, an alicyclic group, an aromatic group or the like having 2 to 22 carbon atoms are useful. Ethylene oxide, propylene oxide, butylene oxide, isoprene oxide, n-hexene oxide, cyclohexene oxide,
Styrene oxide, cyclopentadiene monoxide,
Examples thereof include allyl glycidyl ether, n-butyl glycidyl ether, phenyl glycidyl ether, glycidyl methacrylate, butadiene dioxide, and the like, with ethylene oxide and propylene oxide being preferred, but not limited thereto. The epoxides may be used alone or as a mixture of two or more,
It is also possible to use it by a method of reacting one species and then reacting another species, etc. There is no particular limitation on the reaction mode such as selection of these species and order of charging method, and they can be appropriately selected as necessary. . The use ratio of the epoxides can be appropriately selected as necessary, but is usually 1 to 200 moles, preferably 2 to 2 moles of the epoxides per 1 mole of the total amount of the diguanamine derivative, the diguanamine and the N-methylol diguanamine derivative. The amount is 100 mol, more preferably 4 to 20 mol.

The above reaction is usually carried out in the presence of a basic catalyst at a temperature of 80 to 200 ° C, preferably 100 to 150 ° C.

Examples of the basic catalyst include alkali metal such as lithium hydroxide, potassium hydroxide, sodium hydroxide and calcium hydroxide, alkaline earth metal hydroxide, sodium methylate, sodium ethylate, potassium ethylate and the like. Alkali metal alcoholates and the like, but are not limited to these. The use ratio of the basic catalyst can be appropriately selected if necessary,
Usually diguanamine derivatives, diguanamines and N-
The basic catalyst is 0.01 to 1.0 mol, preferably 0.0 to 1 mol of the total amount of the methylolated diguanamine derivative.
It is a ratio of 5 to 0.5 mol.

Further, the above-mentioned reaction can be carried out in the presence or absence of a solvent, and it is preferable to carry out in the absence of a solvent, but the solvent is appropriately selected and used depending on the starting materials, production conditions and the like. be able to. As the solvent, any compound that is inert to the reaction is useful, and examples thereof include ethers, dialkyl sulfoxides, alkyl-substituted acid amides, aprotic polar solvents such as sulfolanes, esters, and ketones. However, ethers and aprotic polar solvents are preferable, but not limited thereto.

Further, the reaction system described above can be carried out under normal pressure or in a closed vessel under a naturally occurring pressure and further under pressure, and can be appropriately selected if necessary.

Further, the hydroxyl group-containing diguanamine derivatives and the oxaalkyl group-containing diguanamine derivatives according to the present invention include diguanamines represented by the formulas (1) and (2) and ethylene carbonate, propylene carbonate, carbonic acid 1,2. It can also be obtained by a method of reacting alkylene carbonate such as butylene with a basic catalyst such as potassium carbonate, sodium carbonate, caustic potash, caustic soda and pyridine at a temperature of 75 to 250 ° C. in the presence or absence of a solvent. it can.

The diguanamine derivative according to the present invention can be obtained by the above-mentioned production method, etc., but is not limited to these methods.

In the above-mentioned method for producing a diguanamine derivative of the present invention, the amines are HO-R ₉ -NH ₂ (R
₉ has the same meaning as above), and is preferably a method for producing a hydroxyl group-containing diguanamine derivative. Further, the compound represented by HO-R ₉ -NH ₂ is 2-aminoethanol, 1-amino-propan-2-ol, 2-amino-butan-1-ol, 3-amino-propan-1-. All, 5-amino-
More preferably, it is a method for producing a hydroxyl group-containing diguanamine derivative, which is a species selected from the group consisting of 3-oxapentan-1-ol and 4-aminophenol.

Further, a method for producing an oxaalkyl group-containing diguanamine derivative which is capable of undergoing an addition reaction of at least one selected from the group consisting of the above-mentioned diguanamine derivatives and at least one selected from epoxides is preferable. .

Further, at least one selected from the group consisting of diguanamines represented by the above formulas (1) and (2).
It is preferable to use a method for producing an oxaalkyl group-containing diguanamine derivative which is capable of undergoing an addition reaction between a seed and at least one selected from epoxides, and the epoxide is a species selected from ethylene oxide and propylene oxide. More preferably.

The diguanamine derivatives according to the present invention are
Resin flame retardants, heat resistance improvers, abrasion resistance improvers, heat stabilizers, modifiers such as compatibilizers, and further isocyanates,
It has excellent polymerizability and reactivity with various compounds such as aldehydes, epoxides and carboxylic acids. It is useful in a wide range of applications as resin raw materials, derivative raw materials, curing agents, chain extenders, cross-linking agents, etc. that can be provided.
For example, it is possible to provide a flame-retardant resin composition, a polyurethane resin composition, an amino resin composition, a polyester resin composition and the like having excellent properties.

The diguanamine derivatives according to the present invention are
It is possible to provide a flame retardant method for a resin, characterized in that the resin contains at least one selected from the above-mentioned diguanamine derivatives in an amount of 3 to 50% by weight based on the resin. Further, by using the above-mentioned diguanamine derivative and at least one selected from phosphorus, isocyanuric acid and cyanuric acid, and an amino group-containing compound in combination, a resin having further improved flame retardancy due to a synergistic effect is obtained. It has been found that a flame retardant method can be provided. The resin composition obtained by such a flame retarding method is also useful in a wide range of industrial fields such as building materials, electrical materials, vehicle materials such as automobiles, textile materials, and household products.

The above-mentioned diguanamine derivatives are useful in the flame retarding method for resins, like the above-mentioned diguanamines. The conditions for combined use with, the compounding composition with respect to the resin, the target resin, and the like are the same as above, but some of them will be summarized and described below.

The amount of the above-mentioned diguanamine derivative to be used can be appropriately selected according to need, but it is usually 3 to 50% by weight, preferably 4 to 40% by weight based on the resin.

As phosphorus, both simple phosphorus and compounds containing a phosphorus atom are useful, for example, red phosphorus,
Phosphoric acid, polyphosphoric acid, phosphorous acid, phosphoric acid such as phosphonic acid, further ammonia, amine, alkali metal,
Salts obtained by neutralizing a part or all with a base such as alkaline earth metals, and may also contain halogen (mono-, di-, tri-) phosphoric acid esters, acidic phosphoric acid ester ammonia, amine, melamine, alkali Metals, salts with alkaline earth metals, phosphite triesters, phosphites such as phosphite diesters, phosphonates, acidic phosphonates and phosphonates such as salts thereof, phosphines, phosphine oxide, phosphines such as phosphonium salts, sulfur-containing phosphorus compounds such as dialkyl thiophosphoric acids and their salts, and the like, the general formula _{(NH 4) n + 2 P} n O 3n + 1 (n is 5 integer greater than Ammonium polyphosphate represented by the formula [trade name "Exolit (Exolit 263)", "Exolit (Ex
Olit) 422 "(manufactured by Hoechst) and the like], phosphoric acid esters and the like are preferable, but not limited thereto. The amount of phosphorus used is 5 to 40% by weight, preferably 10 to 30% by weight, based on the resin.

Examples of the isocyanuric acids and cyanuric acids include isocyanuric acid, trimethylisocyanurate, tris (2-hydroxyethyl) isocyanurate, triphenylisocyanurate, cyanuric acid, trimethylcyanurate, tris (2-hydroxyethyl).
Examples thereof include cyanurate, diphenyl cyanurate, triphenyl cyanurate, dimethylphenyl cyanurate, triglycidyl cyanurate, and the like, but are not limited thereto. The use ratio of isocyanuric acids and cyanuric acids can be appropriately selected as necessary, but is usually 0.02 to 10 mol per 1 mol of the above-mentioned diguanamine derivative.

When at least one selected from the above-mentioned amino group-containing compounds is used as a component in combination with the resin, the flame retardancy of the resin can be further improved, which is preferable. The amount of such a compound to be used can be appropriately selected if necessary, but is usually 0.01 to 10% by weight with respect to the resin.

Further, it is particularly preferable that the above-mentioned phosphorus-containing and amino group-containing compound is contained in the resin as a component.

The above-mentioned diguanamine derivatives can be produced by a method of reacting at least one selected from the formulas (1) and (2) with amines. With one or more, a diguanamine polymer can be obtained depending on the reaction conditions and the like.

The method for flame retarding a resin characterized in that the diguanamine-based polymer is contained in an amount of 3 to 50% by weight based on the resin is also used in the flame-retardant method of the resin as in the above-mentioned diguanamine-based derivative. It can be remarkably improved and is extremely useful.

When the above-mentioned diguanamine derivative is contained in an amount of 0.01 to 5% by weight with respect to the resin, the thermal stability and UV resistance of the resin are remarkably improved, and the resin during high temperature processing is improved. There is little coloring and discoloration, and such a derivative is excellent in high-temperature stability and non-volatility and easy to handle, and it is possible to provide an excellent method for thermally stabilizing a resin.

The amount of the diguanamine derivative used in the heat stabilization method of the resin is 0.01 to 5 with respect to the resin.
% By weight, preferably 0.02-1% by weight.

In the heat stabilization method of the resin of the present invention, the target resins of the above-mentioned flame retardant method are almost the same as the applicable resins.

Such a resin is preferably a thermoplastic resin, more preferably at least one selected from the group consisting of polyphenylene ether resins, polyacetal resins, polyamide resins and polyolefin resins, and a polyethylene resin as a polyolefin resin,
More preferably, it is at least one selected from the group consisting of polypropylene resin and ethylene-propylene copolymer.

Further, in the heat stabilization method of such a resin, a method for producing such a resin composition, a phenolic antioxidant, an amine antioxidant, a sulfur antioxidant, a light stabilizer, a nucleating agent, a phosphite The use of the system antioxidant and other additives can be carried out in the same manner as in the above-mentioned method for flame retarding a resin, but is not limited thereto.

Furthermore, the present invention is characterized in that the above-mentioned diguanamine derivative is contained in two or more different resins including at least one selected from polyamide resins, polyphenylene ether resins, polyimide resins and polyaramid resins. It is also possible to provide a method for compatibilizing the resin.

Such a method not only remarkably improves the compatibility of two or more different resins, but also causes little coloration and discoloration of the resin during high temperature processing, and the above derivative is excellent in high temperature stability, sublimation, bleeding, etc. It is excellent in that it is less likely to occur and is easy to handle, and that it has good melt dispersibility in the above-mentioned polyamide resin, polyphenylene ether resin and the like.

The amount of the diguanamine derivative used in the method of compatibilizing the resin of the present invention is usually 0.5 to 20% by weight based on the total amount of the resin, and can be appropriately selected depending on the case.

As the resins applicable to the resin compatibilizing method of the present invention, almost the same resins as the above flame retardant methods can be mentioned. Specific examples of the two or more different resins include one selected from a polyamide resin, a polyphenylene ether resin, a polyimide resin and a polyaramid resin, and another resin such as a polyamide resin and an ABS.
Resin, polyamide resin and polyphenylene ether resin,
Examples thereof include, but are not limited to, a polyimide resin, a polyphenylene ether resin, a polyamide resin, a polyphenylene ether resin, and other resins.

In addition, in the method of compatibilizing such a resin,
The method for producing such a resin composition, a phenolic antioxidant, an amine antioxidant, a sulfur antioxidant, a light stabilizer, a nucleating agent, a phosphite antioxidant, and the use of other additives are as described above. However, the method is not limited to these.

The diguanamine derivatives according to the present invention include a polyol component containing at least one selected from the group consisting of the hydroxyl group-containing diguanamine derivatives and the oxaalkyl group-containing diguanamine derivatives described above, and an organic polyamine. A polyurethane resin composition containing an isocyanate component can be provided. Such a resin composition can provide a material having excellent properties such as flame retardancy, heat resistance, water resistance, abrasion resistance, flexibility, toughness, and mechanical properties such as elasticity. , Rigid polyurethane foam, paints, adhesives, plasticizers, sealants, caulks, waterproof coatings, flooring,
Polyurethane resin concrete, fiber treatment agent, sheet, film, roll, tire, anti-vibration material, belt, tube, diaphragm, air brake, shoe sole, artificial leather,
It is useful for a wide range of applications such as elastic fibers, and is particularly useful for soft and rigid polyurethane foams, but is not limited thereto.

As an example of a specific mode of such use,
Examples include, but are not limited to, producing a polyurethane resin composition for a foam, which is characterized by containing the above-mentioned polyol component, organic polyisocyanate component, blowing agent and catalyst, and producing a polyurethane foam. It is not something that will be done.

As the essential component of the polyol component, any one derived from the above-mentioned diguanamines and containing a hydroxyl group is useful. For example, the above-mentioned hydroxyl group-containing diguanamine derivatives and the above-mentioned oxaalkyl group-containing Examples thereof include diguanamine derivatives, and if necessary, the number of hydroxyl groups, the molecular weight, the type of epoxides, the mode of addition and the like can be appropriately selected and used. Incidentally, the polyol component may include a polyol other than the above-mentioned essential components within a range that does not impair the effects of the present invention, for example, water, ethylene glycol, trimethylolpropane, glycerin, pentaerythritol, sorbitol, sugar and the like. Alkylene oxide adduct, polyester polyol, acrylic polyol, butadiene polyol, phenolic polyol, halogen-containing polyol, phosphorus-containing polyol, tris (2-hydroxyethyl) isocyanurate, tris (2-hydroxyethyl) melamine, etc. However, the present invention is not limited to these.

Examples of the organic polyisocyanate component include 2,4- (2,6-) tolylene diisocyanate,
Diphenylmethane-4,4'-diisocyanate, 2,
2'-dimethylphenylmethane-4,4'-diisocyanate, biphenyl-4,4'-diisocyanate,
1,5-naphthalene diisocyanate, tolidine diisocyanate, isophorone diisocyanate, p-phenylene diisocyanate, cyclohexane-1,4-diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane-4,4'-diisocyanate , Lysine diisocyanate, triphenylmethane triisocyanate, tris (isocyanatophenyl)
Thiophosphate, tetramethylxylene diisocyanate, lysine ester triisocyanate, 1,6,1
1-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyl octane, 1,
3,6-hexamethylene triisocyanate, trimethylhexamethylene diisocyanate, azobenzene-
4,4'-diisocyanate, 2-nitrobiphenyl-
4,4'-diisocyanate, diphenyl sulfone-
Examples thereof include, but are not limited to, 4,4′-diisocyanate and blocked isocyanates thereof, isocyanate prepolymers, urethane adducts, modified compounds such as isocyanurate, and derivatives. The use ratio of the organic polyisocyanate can be appropriately selected according to need, but it is usually an amount corresponding to the OH value of the polyol component, or an excess amount of a small amount or a small amount.

Furthermore, in the above-mentioned polyurethane resin composition for foams, any known foaming agent for urethane foams can be used as the foaming agent, for example, water, nitroethane, acetaldoxime, formamidoboric acid,
Reactive foaming agents such as diazoaminobenzene and azodiisobutyronitrile, non-reactive foaming agents such as trichlorofluoromethane, dichlorodifluoromethane, and trichlorotrifluoroethane, and the like, and known amine-based catalysts and organic tin Examples thereof include, but are not limited to, catalysts, alkali metal salts, alkali metal salt alcoholates, and the like.

Further, the diguanamine derivative according to the present invention is obtained by reacting an amino compound containing at least one selected from the above-mentioned diguanamine derivatives with at least one selected from aldehydes. To provide an amino resin composition comprising at least one selected from the group consisting of an amino resin and a product obtained by subjecting a product and an alcohol to an etherification reaction of the product. it can. Such a resin composition can provide a material having excellent properties such as flame resistance, heat resistance, flexibility, toughness, and mechanical properties such as elasticity. For example, a partition wall of a building or a house. , Thermal insulation materials for transportation equipment, soundproofing materials, heat insulating materials, elastic foam moldings for impact resistant packaging materials, general molding materials for housing equipment, automobile parts, various machines, electrical parts, etc., laminated molding materials, SMC, BMC It is useful for a wide range of applications such as molding materials, paints and adhesives, but is not limited to these.

Further, in the present invention, an amino compound containing at least one selected from the diguanamines represented by the formulas (1) and (2) is reacted with at least one selected from the aldehydes. There is provided polymer fine particles obtained by emulsifying the amino resin thus obtained with a protective colloid and polymerizing the mixture with a curing agent. At the same time, there is also provided the above-mentioned polymer fine particles which are colored with a coloring agent, and a method for flame retarding a resin, characterized in that the above-mentioned polymer fine particles are contained in an amount of 3 to 50% by weight based on the resin.

The use ratio of the diguanamines in the polymer fine particles of the present invention can be appropriately selected depending on the desired performance, but it provides an amino resin having good solubility and dispersibility in a solvent such as water and is excellent. In order to provide polymer fine particles having heat resistance, solvent resistance, weather resistance, impact resistance, abrasion resistance, etc., the amount is preferably 40% by weight or more, more preferably 60% by weight or more in the amino compound. More preferably. Further, the amino compounds include compounds other than the above-mentioned diguanamines, such as melamine, N-methylmelamine, benzoguanamine, acetoguanamine, cyclohexanecarboguanamine, cyclohexenecarboguanamine, norbornanecarboguanamine, norbornenecarboguanamine, dicyandiamide, urea, thiourea. , Guanidine, urethane, phenol, p-methylphenol, nonylphenol, resole, aniline, tetramethylenediamine, furfural, furfuryl alcohol, p-toluenesulfonic acid amide, o-toluenesulfonic acid amide, benzenesulfonic acid amide, tetralinsulfonic acid An amide, a carboxylic acid amide, a sulfuryl amide, a diamide phosphorus nitride low polymer, etc. may be included, but the amino compound according to the present invention As long as it does not impair the significance of using, it is preferably in an amount less than the amino compound 60 wt%.

Examples of aldehydes related to the polymer fine particles of the present invention include formaldehyde, paraformaldehyde, hexamethylenetetramine, methylhemiformal, butylhemiformal, formaldehydes such as adduct of formaldehyde sodium bisulfite, glyoxal, acetaldehyde, trimethylol. Examples thereof include acetaldehyde, acrolein, benzaldehyde, furfural, phthalaldehyde, terephthalaldehyde and the like, but formaldehydes and glyoxal are preferable, and formaldehyde aqueous solution and paraformaldehyde are more preferable. It is preferable that the amount of such formaldehyde in the aldehyde is 50% by weight or more. The amount of the aldehyde used is usually 1.5 to 16 mol, preferably 2.0 to 1 mol, based on 1 mol of the amino compound.
It is 10 moles, and more preferably 2.5 to 6.0 moles.

The method for obtaining the amino resin relating to the polymer fine particles of the present invention is not particularly limited, but the above-mentioned amino compound and aldehydes are mixed with hydroalcohol,
A mixed solution obtained by stirring and mixing one or more solvents such as aromatic compounds is stirred at a temperature of 30 at a pH of 8 to 13.
Method for obtaining N-methylol diguanamines by addition reaction at -80 ° C., such mixture is subjected to addition condensation reaction under strong alkaline conditions of pH 13 or higher or under pH 8 or lower to give N-methylol diguanamines initial A method for obtaining a condensate, etc., and further the N-methylolated diguanamines, N-methylol diguanamines initial condensate and the like obtained above are subjected to a condensation reaction at a temperature of 30 to 80 ° C. under a condition of pH 1 to 6 And a method of obtaining a condensate having a high degree of condensation. Furthermore, the N-methylol diguanamines, N-methylol guanamines initial condensate and the like obtained above are treated under conditions of pH 1 to 6 and temperature of 30 to 90 ° C. using an alcohol having 1 to 20 carbon atoms. The partially etherified product obtained by the etherification reaction can also be used as the amino resin according to the present invention in some cases.
When such a partially etherified product is used, emulsification during production of polymer particles, poor curing, impact resistance of the resulting polymer particles, deterioration of solvent resistance and the like are likely to occur, which is usually not preferable, but It is possible to provide useful polymer fine particles depending on the field and the like. The method for obtaining the amino resin relating to the polymer particles of the present invention is not limited to these methods.

Examples of the protective colloid related to the polymer fine particles of the present invention include alkali metal salts of polyacrylic acid, alkali metal salts of styrene-maleic acid copolymer,
An isobutylene-maleic acid copolymer alkali metal salt,
Examples include alkali metal salts of p-sulfonic acid styrene polymers, alkali metal salts of sulfonic acid-modified amino resins, saponified products of vinyl acetate polymers such as polyvinyl alcohol, and polyvinylpyrrolidone. Saponified products of vinyl acetate polymers. Are preferred, but are not limited to these. The amount of protective colloid used can be appropriately selected depending on the desired performance, particle size, etc., but is usually 0.2 to 25% by weight, preferably 1.0 to
It is 15% by weight. Also, the method of emulsification is not particularly limited, and a method used when emulsifying a resin of a known technique is applicable, for example, an anchor type, a propeller type,
A method of stirring and emulsifying using a turbine-type stirring blade,
Examples thereof include a method of emulsifying using a stirrer such as a colloid mill, a disper mill and a homomixer, but the method is not limited to these.

As the curing agent for the polymer fine particles of the present invention, compounds that release or form a proton under the production conditions are useful, such as hydrochloric acid, sulfuric acid, phosphoric acid,
Mineral acids such as nitric acid, formic acid, benzoic acid, phthalic acid, acetic acid, α
-Chloroacetic acid, trifluoroacetic acid, propionic acid, oxalic acid,
Lactic acid, amino acids, carboxylic acids such as salicylic acid, benzenesulfonic acid, p-toluenesulfonic acid, o-toluenesulfonic acid, dodecylbenzenesulfonic acid and other sulfonic acids, ammonium chloride, ammonium sulfate, ammonium phosphate, ammonium dihydrogen phosphate, Diammonium hydrogen phosphate, ammonium nitrate, ammonium formate,
Ammonium salts such as ammonium acetate, ammonium p-toluenesulfonate, ammonium sulfamate, and diammonium imidosulfonate, chloroacetic acid amide,
Examples thereof include water-soluble metal salts of metals such as zinc, magnesium, calcium and aluminum and acids such as nitric acid, sulfuric acid and phosphoric acid, and sulfonic acids are preferable, but not limited to these. The amount of the curing agent used is 0.01 to 5% by weight, preferably 0.05 to 3% by weight based on the amino resin.
% By weight. If the amount used is less than 0.01% by weight, curing will be insufficient and the resulting polymer fine particles will have a reduced impact resistance, solvent resistance, etc., while if it exceeds 5% by weight, It is not preferable because it becomes difficult to obtain a good emulsified state.

The present invention also provides fine polymer particles colored with a coloring agent, and the coloring agent can be appropriately selected depending on the application of the fine polymer particles. As the colorant, dyes such as water-soluble dyes and oil-soluble dyes, pigments, etc. are useful. For example, Rhodamine B, Rhodamine 6GCF, Methyl Violet B, Eisen Astrafloxin FF, Malachite Green A, Victoria Pure Blue RB, Methylene Turquoise J. Basic dyes such as Acilanth Scarlet A, Acid Red XB,
Acid dyes such as eosin, lisamiflavin FF, alizarin fast violet 2RC, sulforhodamine G,
Cationic dyes such as Astrazone Pink FG, Astrazone Red 6B, Aizen Catylon Brilliant Yellow 5GLH, and Aizen Catylon Orange RH, Rhodamine B Base, Azosol Brilliant Yellow 8GF, Azosol Brilliant Yellow 6GF, Azosol Brilliant Blue B, etc. Solvent-soluble dye, Ubitex ER
Examples thereof include fluorescent brightening dyes such as N and Tibanol PCR, and pigments such as Heliogen Green 6G and Heliogen Blue LBGM, but are not limited to these methods.
The method of coloring using such a colorant is not particularly limited, and a method used when coloring a resin or the like of a known technique can be applied, but the method is used from the start of hydrophobization of the product in the production of polymer particles. It is preferable to add the colorant at the stage until the end of. Examples of the coloring method include a method of adding a coloring agent during or after the production of the above-mentioned amino resin, a method of adding a coloring agent after emulsifying the amino resin with a protective colloid, and the like. It is not limited.

Further, the polymer fine particles according to the present invention may contain other additives such as a flame retardant, an antistatic agent, an antifogging agent, a lubricant, a fluorescent agent, a plasticizer, an antireflective agent as long as the effects of the present invention are not impaired. A fungicide, a bactericidal agent, an antioxidant, an ultraviolet absorber, a filler, a metal deactivator and the like can be included as necessary.

In the method for producing polymer fine particles according to the present invention, a desired amount of 0.1 to 20 is usually obtained by the above-mentioned method.
Those having a micron particle size, performance, etc. can be obtained, and further, the obtained polymer fine particles are separated by a method such as filtration and centrifugation, washed with water, dried, etc. 0.5 to 5 at 250 ° C.
Post-treatment such as a method of performing heat treatment for 0 hours is also useful, and can be appropriately selected depending on the application.

The polymer fine particles according to the present invention are excellent in heat resistance, solvent resistance, weather resistance, abrasion resistance, flame retardancy, etc.
Thermoplastic resin, thermosetting resin, resin modifier such as rubber, resin compatibilizer, filler, plastic film, cellophane, anti-blocking agent such as ink, epoxy resin, abrasion resistance improving agent such as phenol resin, Stress relaxation agent, fluidity improver for plastic, rubber, etc., heat resistance improvement for plastic, film, sheet, etc., thermal stability improver, elasticity control agent for impact resistance, slipperiness improver, surface modification of paint Agents, paints, inks, viscosity control agents such as adhesives, paper modifiers, powder dispersibility improvers, anti-caking agents, adhesive tapes, release adhesiveness imparting agents such as adhesive tapes, dispersants such as pigments , Dispersion stability, matting agent, powder lubricant, car wax, shaping aid for sintering material, unevenness imparting agent, release agent, release modifier, plastic transparency, gloss improver , Cosmetic additives, cosmetic pigments, scrubs, feeling Paints, inks modifiers, pressure-sensitive paper modifying agent, the liquid crystal panel spacer, recording materials for special ink such as toner, aqueous, oily coating resins colorants, fluorescent paint,
It is useful in a wide range of applications as a resin colorant for printing inks such as traffic paints, gravure inks, offset inks and silk screen inks, resin colorants such as plastics and fibers, and pigment printing agents.

Further, the above-mentioned polymer fine particles are useful in the flame retarding method for resins like the above-mentioned diguanamines, and the conditions adopted when utilizing the above-mentioned diguanamines in these methods, such as other additives. The conditions for combined use with, the compounding composition with respect to the resin, the target resin and the like are the same as described above, but some of them will be given as an example.

In the method for flame retarding a resin characterized by containing the above-mentioned polymer fine particles, at least one selected from phosphorus, which is a simple substance of phosphorus and a compound containing a phosphorus atom, is contained as a component. Preferably, such phosphorus is red phosphorus, phosphoric acid, polyphosphoric acid, phosphorous acid, phosphonic acid, phosphoric acid salt, polyphosphoric acid salt, phosphorous acid salt, phosphonic acid salt, phosphoric acid ester, phosphorous acid ester. , Phosphonates, phosphines, and sulfur-containing phosphorus compounds are more preferable, and the polyphosphate has a general formula (NH ₄ ) _{n + 2} P _n P _{3n + 1} (wherein n is 5 An ammonium polyphosphate represented by (indicating a larger integer) is more preferable. The amount of phosphorus used is 5 to 40% by weight, preferably 10 to 30% by weight, based on the resin.

Further, it is preferable to contain at least one selected from the isocyanuric acids and cyanuric acids represented by the formulas (5) and (6) as a component, and the use ratio of the isocyanuric acids and the cyanuric acids is appropriately selected as necessary. However, it is usually 0.02 to 10 with respect to 1 equivalent of the diguanamine skeleton in the polymer fine particles described above.
It is a molar ratio.

Further, in such a method, when the amino group-containing compound of the above-mentioned diguanamines used in these methods is used as a component, the flame retardancy of the resin can be further improved, which is preferable. The amount of such a compound to be used can be appropriately selected if necessary, but is usually 0.01 to 10% by weight with respect to the resin.

Further, it is particularly preferable to incorporate the above-mentioned phosphorus and amino group-containing compound as a component into the resin.

Further, such a resin is preferably a thermoplastic resin or a thermosetting resin, and as the thermoplastic resin, a polyolefin resin, a polyamide resin, a styrene resin and a polyphenylene ether resin, a saturated polyester resin, a polycarbonate resin, a polyacetal resin are used. And at least one selected from the group consisting of polyacrylic resins and unsaturated polyester resins as thermosetting resins, diallyl phthalate resins, epoxy resins and urethane resins.

Furthermore, at least one selected from the diguanamines represented by the formulas (1) and (2) and the diguanamine derivatives represented by the formulas (7) and (8) and the above-mentioned aldehydes are selected. A product obtained by reacting at least one of the above, and a product obtained by subjecting this product to an etherification reaction with an alcohol, and further, a condensate or a polymer thereof in an amount of 3 to 50 relative to the resin. A flame retarding method for a resin, which is characterized by containing an amount of wt% is also a very useful method because the flame retardancy of the resin can be remarkably improved as in the above case.

In such a method, the conditions of the above-mentioned diguanamines used in these methods, such as phosphorus, isocyanuric acid, cyanuric acid, combined use condition with amino group-containing compound, etc., compounding composition with respect to resin, target resin, etc. Can be used as described above.

The following effects of the invention are brought about in the use of the diguanamines according to the present invention described above, the diguanamine derivative and the method for producing the same, the use thereof, and the polymer fine particles and use thereof.

The method of making the resin flame-retardant according to the present invention is a method in which the flame retardancy of the resin can be remarkably improved by incorporating a novel diguanamine compound having a specific structure into the resin. Heat resistance is better than melamine etc., sublimation, bleeding, etc. are not seen, char formation etc. are extremely good, oil drops, melt dripping, dropping is extremely small, and further during combustion It is excellent in the effect of improving the flame retardancy of the resin such as the emission of extremely harmful gas is not seen, and further, the above-mentioned diguanamines and phosphorus, isocyanuric acids, cyanuric acids, amino group-containing compounds By using and together, it is possible to provide a method for making a resin flame-retardant that further improves the flame-retardant property by a synergistic effect, and it is possible to expand the resin to a wider range of applications, which is extremely excellent in industry. It is an invention.

Further, in the method for heat-stabilizing a resin according to the present invention, by incorporating a novel diguanamine compound having a specific structure into the resin, the UV resistance, heat stability, etc. are remarkably improved, and Coloring when performing molding,
Has little discoloration, improved thermal stability, suppressed deterioration when used for a long time at relatively high temperature, and significantly improved retention of physical properties. , It does not induce any adverse effects, and further, it is remarkably excellent in the effect of improving the thermal stability of the resin, such that it significantly suppresses the drawback that decomposition and deterioration of the resin is promoted by heavy metal ions such as copper. However, the invention can be applied to a wider range of applications and is an extremely excellent invention in industry.

Further, in the resin compatibilizing method according to the present invention, by incorporating a novel diguanamine compound having a specific structure into two or more different resins, the compatibility of the two or more different resins is remarkably improved. Not only let
Coloring of resin during high temperature processing, little discoloration, high temperature stability and excellent nonvolatility of the above-mentioned diguanamines, sublimation, handling with less occurrence of bleeding, etc., easy manufacturing, polyamide resin, polyphenylene ether resin, etc. Melt dispersibility is good, further excellent in the effect of compatibilization improvement of different resins such as further improved thermal stability of the resin, it is possible to develop a wider range of uses of the resin, This is an extremely excellent invention in industry.

The diguanamine derivatives according to the present invention are
Remarkably excellent in heat resistance, flame resistance, weather resistance, flexibility and toughness, and shows excellent reactivity with compounds having various functional groups such as isocyanate group, carboxyl group, epoxy group, aldehyde group. It has characteristics such as having a wide range of functional groups such as those having active hydroxyl groups, imino groups, and having 8 active hydrogens, and also has excellent characteristics such as curability and high strength. It is possible to provide a compound, a resin, a composition, etc. having excellent properties, and it is useful for an extremely wide range of applications. Furthermore, the method for producing a diguanamine derivative according to the present invention comprises reacting a novel diguanamine having a specific structure with an amine, or reacting the above-mentioned diguanamine and / or diguanamine derivative with an epoxide under specific conditions. By providing an excellent method, it is possible to easily obtain the desired product in a high yield.

The diguanamine derivatives according to the present invention are
When used as a flame-retardant method for resin by including it in resin,
The flame retardancy of the resin can be remarkably improved, char formation is extremely good, oil drops, melt dripping and dropping are extremely small, and self-extinguishing property is excellent. Is. Furthermore, in the above method,
By using phosphorus, isocyanuric acid, cyanuric acid, and an amino group-containing compound in combination, it is possible to provide a flame-retardant method for a resin that further improves flame retardancy due to a synergistic effect. It is an invention.

When the above-mentioned diguanamine derivative is contained in a resin and used as a method for heat stabilization of the resin,
Thermal stability of resin, UV resistance is remarkably improved, coloring and discoloration of resin during high temperature processing are small, and such derivative is excellent in high temperature stability and is easy to handle with less occurrence of sublimation and bleeding. It has excellent effects such as good melt dispersibility in a resin. Furthermore, when the above-mentioned diguanamine derivative is used as a method of compatibilizing resins by incorporating it in two or more different resins, the compatibility of the different resins is not only significantly improved, but also the coloring of the resin during high temperature processing, It has excellent effects such as little discoloration, little occurrence of sublimation and bleeding, easy handling, and extremely good melt dispersibility in a resin. The method for modifying these resins using the above-mentioned diguanamine derivatives of the present invention is an industrially extremely excellent invention because it enables development of the resin to a wider range of applications.

Further, the above-mentioned diguanamine derivative can be provided as a polyurethane resin composition in which it is contained together with an organic isocyanate component. Such a resin composition can provide a material having excellent properties such as flame retardancy, heat resistance, water resistance, abrasion resistance, flexibility, toughness, and mechanical properties such as elasticity, and is industrially available. It is an extremely excellent invention.

The polymer fine particles according to the present invention are prepared by emulsifying an amino resin obtained by reacting an amino compound containing a novel diguanamine having a specific structure with an aldehyde using a protective colloid and adding a curing agent. By polymerizing, it is possible to provide fine polymer particles having excellent heat resistance, solvent resistance, weather resistance, impact resistance, abrasion resistance, etc., and further useful as a resinous colorant by coloring with a colorant. It is possible to provide fine polymer particles. Such polymer fine particles include thermoplastic resins, thermosetting resins, fillers such as rubber, heat resistance improvement, flame retardancy improvement, thermal stability improvement, abrasion resistance improver, elasticity control agent, surface modifier, etc. Resin modifier, plastic film, cellophane, anti-blocking agent for ink, paint, ink, adhesive,
It is extremely useful in a wide range of applications such as viscosity control agents for cosmetics and surface modifiers, and is an extremely excellent invention in industry.

When the polymer fine particles according to the present invention are contained in a resin and used as a flame retardant method for the resin, the flame retardancy of the resin can be remarkably improved. Generation is not seen, heat resistance is good, char formation is very good, oil drops,
It has excellent effects such that the melt droops and drops very little, and the generation of extremely harmful gas and the like during combustion is small. Furthermore, in the above-mentioned method, by using phosphorus, isocyanuric acid, cyanuric acid, and an amino group-containing compound in combination, there is also provided a flame-retarding method for a resin, in which a further improved flame retardancy is obtained by a synergistic effect. Can
This is an extremely excellent invention in the industry as it enables the application of resins to a wider range of applications.

[0209]

EXAMPLES Next, the present invention will be explained in detail by reference examples and examples. However, the description of these reference examples and examples does not limit the scope of the present invention thereto. Reference Example 1 Production of dicarbonitriles (3): Bicyclo [2.2.1] hept-5-ene-2-carbonitrile 297 was placed in a 500 ml flask equipped with a stirrer, a thermometer, a liquid introduction tube, and a cooler. 0.92 g (2.50 mol), Ni [P (OC
₆ H ₅ ) ₃ ] ₄ 8.77 g (6.75 mmol), Zn
Cl ₂ 4.80 g (35.22 mmol), P (OC ₆
After 32.27 g (0.104 mol) of H ₅ ) ₃ was charged and the system was sufficiently replaced with nitrogen gas, the reaction mixture was kept at 65 ° C. with stirring. Next, 94.5 of ice-cold liquid hydrocyanic acid
9 g (3.50 mol) was supplied to the reactor at a flow rate of 45 to 55 ml / hr for 3 hours, and then the reaction was further performed for 1 hour.

Next, after replacing the inside of the system with nitrogen gas, deionized water was added and the aqueous layer was separated and removed to obtain a semi-solid oily substance. The oil was filtered and distilled under reduced pressure to give 362.
20 g (99.1% yield) of bicyclo [2.2.1] heptane-2,5-dicarbonitrile and bicyclo [2.
2.1] A mixture of heptane-2,6-dicarbonitrile (boiling point 129 to 137 ° C / 1 mmHg) was obtained. The results of elemental analysis of the target product 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 Production of dicarbonitriles (4) : In a 500 ml flask equipped with a stirrer, a thermometer, a liquid introduction tube, and a condenser, 4-
188.6 g of cyano-cyclohexene, Ni [P (OC
₆ H ₅ ) ₃ ] ₄ 6.0 g, ZnCl ₂ 3.0 g, P (O
After charging 23.9 g of C ₆ H ₅ ) ₃ and sufficiently replacing the inside of the system with nitrogen gas, the reaction mixture was kept at 75 ° C. with stirring. Next, 1 mol of 42 molar hydrogen cyanide gas diluted with nitrogen is used.
The reactor was fed for 7 hours at a rate of 77.0 mmol / hour. Next, after purging the system with nitrogen gas, the reaction solution was cooled and analyzed to obtain dicarbonitriles (4) with a yield of 64.9%.

Water and ethyl acetate were added to the reaction solution in an amount of 5 times each.
00 g was added, and the mixture was left under stirring for 5 hours, the organic layer was separated, and ethyl acetate was evaporated. Next, vacuum distillation is performed and the pressure is 0.5 to 1.0 mmHg and the temperature is 120 to 130.
As a distillate at ° C, 132.0 g of a mixture of 1,3-cyclohexanedigalvonitrile and 1,4-cyclohexanedicarbonitrile was obtained. As a result of analyzing this fraction, 1,3-cyclohexanedicarbonitrile 64.
4%, 1,4-cyclohexanedicarbonitrile 35.
The composition was 6%. The results of elemental analysis of the target product are shown below.

Elemental analysis C H N Measured value: 71.5% 7.6% 20.9% Calculated value: 71.61% 7.51% 20.88% Reference Example 3 Production of diguanamines (1): Stirrer In a 3 L flask equipped with a thermometer and a reflux condenser, 146.2 g (1.0 mol) of the dicarbonitriles (3) obtained by the method of Reference Example 1 and 210.2 g (2.5 mol) of dicyandiamide. ,
Caustic potash 16.8 g and methyl cellosolve 1000 ml were charged and gradually heated. When the temperature increased, the reaction solution became transparent, and when the temperature became close to 105 ° C., the reaction rapidly proceeded and the solvent was refluxed due to significant heat generation. After a while after the reflux was started, the reaction solution became cloudy. This solution was reacted at a temperature of 120 to 125 ° C. for 10 hours while stirring.

Next, the reaction mixture was desolvated, 3 L of deionized water was poured, the white precipitate was filtered off, and the solid content was washed with deionized water and then with methanol and depressurized. Dried. Further, this solid content was dissolved in ethyl cellosolve, deionized water was added to this solution, reprecipitation was performed, and then filtration was performed, and the obtained solid content was washed with water. The solid content is dried under reduced pressure to give 2,5-bis (4,6-diamino-1,
3,5-triazin-2-yl) -bicyclo [2.2.
1] Heptane and 2,6-bis (4,6-diamino-
1,3,5-triazin-2-yl) -bicyclo [2.
2.1] Heptane mixture [white powdery crystals, melting point 31
7 to 324 ° C. (DSC measurement)] was obtained. As a result of analyzing this reaction mixture (before treatment) by liquid chromatography, the yield (mol%) of the above-mentioned diguanamines (1) was 98.2% [vs. the amount of dicarbonitriles (3) charged]. Yes, 0.08 for compounds other than raw materials and intended target compounds
The content was% by weight [amount of dicarbonitrile (3) charged]. The results of elemental analysis and ¹ H nuclear magnetic resonance absorption spectrum analysis of the target compound are shown below.

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 substance) : TMS, solvent: d ₆ -DMSO) Absorption based on NH ₂ group δ value 6.50 ppm (singlet) 6.72 ppm (singlet) Reference Example 4 Production of diguanamines (2): stirrer, thermometer, reflux cooling In a 3 L flask equipped with a vessel, 134.2 g (1.0 mol) of dicarbonitriles (4) obtained by the method of Reference Example 2, 210.2 g (2.5 mol) of dicyandiamide,
Caustic potash 16.8 g and methyl cellosolve 1000 ml were charged and gradually heated. When the temperature increased, the reaction solution became transparent, and when the temperature became close to 105 ° C., the reaction rapidly proceeded and the solvent was refluxed due to significant heat generation. After a while after the reflux was started, the reaction solution became cloudy. This solution was reacted at a temperature of 120 to 125 ° C. for 10 hours while stirring.

Next, the reaction mixture was desolvated, 3 L of deionized water was poured, the white precipitate was filtered off, and the solids were washed with deionized water and then with methanol and depressurized. Dried. Further, this solid content was dissolved in ethyl cellosolve, deionized water was added to this solution, reprecipitation was performed, and then filtration was performed, and the obtained solid content was washed with water. The solid content is dried under reduced pressure to give 1,3-bis (4,6-diamino-1,
3,5-triazin-2-yl) -cyclohexane and 1,4-bis (4,6-diamino-1,3,5-triazin-2-yl) -cyclohexane mixture [white powdery crystal, melting point 317- 321 ° C. (DSC measurement)] was obtained. As a result of analyzing this reaction mixture (before treatment) by liquid chromatography, the above-mentioned diguanamines (2)
The yield (mol%) was 97.3% (vs. the amount of dicarbonitrile (4) charged), and the compounds other than the raw material and the intended target compound were 0.12% by weight [vs. dicarbonitrile (4). The charged amount]. Elemental analysis of the target, ¹ H
The results of nuclear magnetic resonance absorption spectrum analysis are shown below.

Elemental analysis C H N measured value: 47.6% 6.1% 46.3% calculated value: 47.67% 6.00% 46.33% ¹ H nuclear magnetic resonance absorption spectrum analysis (internal standard substance) : TMS, solvent: d ₆ -DMSO) Absorption based on NH ₂ group δ value 6.49 ppm (singlet) Reference Example 5 1,4-bis (4,6-diamino-1,3,5-triazine-2) Production of -yl) -cyclohexane: In place of 134.2 g (1.0 mol) of the dicarbonitriles (4) obtained by the method of Reference Example 2 in Reference Example 4, 1,4-
Cyclohexanedicarbonitrile 147.6 g (1.1
The reaction mixture was treated according to the same procedure as in Reference Example 4, except that the reaction mixture was used. The solid thus obtained was dried under reduced pressure to give 1,4-bis (4,6-diamino-
1,3,5-triazin-2-yl) -cyclohexane [white powdery crystal, melting point 319 to 322 ° C. (DSC measurement)] was obtained. As a result of analyzing this reaction mixture (before treatment) by liquid chromatography, the yield (mol%) of the above-mentioned diguanamines (2) was 95.8% [vs. the amount of dicarbonitriles (4) charged]. there were. In the infrared absorption spectrum of the target product, the absorption of nitrile (2237 cm ^-1 ) contained in the raw material compound disappeared, and the absorption of triazine ring (821 cm ^-1 ) newly appeared, and the measured values of elemental analysis were calculated as follows. Good agreement with the value.

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 substance) : TMS, solvent: d ₆ -DMSO) Absorption based on NH ₂ group δ value 6.50 ppm (singlet) Example 1 Polypropylene resin Mitsui Noblene BJH [manufactured by Mitsui Toatsu Chemicals, Inc.] 84 parts by weight, reference example A polypropylene resin composition consisting of 15 parts by weight of diguanamines (1) obtained by the method of 3 and 1 part by weight of dilauryl thiodipropionate was kneaded by a mixing roll under the conditions of 190 ° C.-6 minutes, and then extruded. It was kneaded and pelletized. This was molded by an injection molding machine to prepare a flammability measuring test piece having a thickness of 1/16 inch.

Using this test piece, Under Wr, USA
iters Laboratories Inc. Of S
As a result of performing the test based on the vertical combustion test method shown in the object 94, it is level V-1, there is no molten fallen matter at the time of combustion, and the shape retention state of the combustion matter is good, and the polypropylene resin composition described above is It had excellent flame retardancy. Example 2 Polypropylene resin Mitsui Noblene BJH [manufactured by Mitsui Toatsu Chemicals, Inc.] 75 parts by weight, 6 parts by weight of diguanamines (1) obtained by the method of Reference Example 3, ammonium polyphosphate "Exorit 422" (Hoechst Co.) A polypropylene resin composition consisting of 18 parts by weight and 1 part by weight of dilauryl thiodipropionate was prepared into a test piece in the same manner as in Example 1. Using this test piece, a flammability test was carried out in the same manner as in Example 1. As a result, the level was V-0, the shape retention state of the burned material was good, and the diguanamines and phosphorus according to the present invention were added. It was found that when used in combination, the flame retardancy was further improved due to the synergistic effect, and the polypropylene resin composition described above had excellent flame retardancy. Examples 3 to 6 75 parts by weight of polyethylene resin HiZex 5100E (manufactured by Mitsui Petrochemical Co., Ltd.), 15 parts by weight of diguanamines (2) obtained by the method of Reference Example 5, phosphorus 1 shown in Table-1
A polyethylene resin composition consisting of 0 parts by weight was kneaded by a mixing roll under the conditions of 160 ° C. for 6 minutes, and then kneaded by an extruder to form pellets. A test piece for combustion measurement was prepared and tested in the same manner as in Example 1. The results are shown in Table-1.

As shown in Table 1, the polyethylene resin composition according to the present invention is excellent in flame retardancy and improved in flame retardancy when the diguanamines and phosphorus of the present invention are used in combination. It was

[0221]

[Table 1] Table-1 ┌───┬────────────────┬────────────┐ │ │ │ Flame retardant │ │ │ Kind of phosphorus ├─────┬──────┤ │ │ │ UL standard 94 │ Melt falling │ │ │ │ level │ Presence │ ├─┬─┼────── ──────────┼─────┼──────┤ │ │3│2-ethylhexyldiphenyl │ V-0 │ None │ │ │ │ Phosphate │ │ │ │ Actual ├─ ┼────────────────┼─────┼──────┤ │ │ 4│ Tris (tridecyl) phosphite │ V-1 │ None │ │ ├─┼────────────────┼─────┼──────┤ │ │ 5│N, N-bis (2-hydroxyethyl) │ V -1 │ None │ │ Example │ │ Diethyl aminomethylphosphonate │ │ │ │ ├─┼────────────────┼─────┼──────┤ │ │ 6│ ethylenebistris (2-cyano │ V- 1 │ None │ │ │ │ Ethyl) phosphine oxide │ │ │ └─┴─┴────────────────┴─────┴──────┘ Implemented Example 7 To 50 parts by weight of butyl cellosolve, 8 parts by weight of the diguanamines (1) obtained by the method of Reference Example 3 and 12 parts by weight of diphenyl acid phosphate were added and dissolved by heating, followed by solvent removal to obtain a solid content. It was 15 parts by weight of this solid content was added to 85 parts by weight of diallyl phthalate resin Dapol D-600 (manufactured by Fudochemical Co., Ltd.), and the mixture was heated and mixed at 60 to 80 ° C., and after cooling, 3 parts by weight of dicumyl peroxide. Parts were added and mixed to obtain a diallyl phthalate resin composition. This is poured into a glass casting plate and cured to give a thickness of 1/1
A 6-inch test piece for measuring flammability was prepared.

Using this test piece, a test was conducted in the same manner as in Example 1. As a result, it was level V-0 and the shape retention state of the combusted material was good. It had a nature. Example 8 To 90 parts by weight of nylon 66 pellets, 10 parts by weight of the diguanamines (1) obtained by the method of Reference Example 3 was added, and the obtained nylon resin composition was mixed with a Henschel mixer, and then the cylinder temperature was 280. The mixture was kneaded and pelletized by an extruder set at ° C. This was molded by an injection molding machine to prepare a flammability measuring test piece having a thickness of 1/16 inch.

Using this test piece, a test was carried out in the same manner as in Example 1. As a result, the combustion product having a level V-1 and an excellent char-forming property and having a good shape-retaining state was obtained, and the above nylon resin composition was used. The product had excellent flame retardancy. Example 9 To 90 parts by weight of diallyl phthalate resin Dapol D-600 (manufactured by Fudochemical Co., Ltd.), 7 parts by weight of diguanamines (2) obtained by the method of Reference Example 4 and 3 parts of isocyanuric acid were added.
After adding 1 part by weight and heating and mixing at 60 to 80 ° C., after cooling, 3 parts by weight of dicumyl peroxide was added and mixed to obtain a diallyl phthalate resin composition. This was poured into a glass casting plate and cured to prepare a flammability measuring test piece having a thickness of 1/16 inch.

Using this test piece, a test was conducted in the same manner as in Example 1. As a result, the level was V-0, and the shape retention of the combustion product was good, and the above diallylphthalate resin had excellent flame retardancy. It was something that had. Examples 10 to 13 The resin composition in Example 8 was changed to the resin compositions shown in Table 2, and flammability measuring test pieces were prepared and tested in the same manner as in Example 8. The results are shown in Table-2. Example 14 Epoxy resin Epicoat # 828 [Shell Chemical Co., Ltd.
Manufacture] To 44 parts by weight, 11 parts by weight of diguanamines (2) obtained by the method of Reference Example 5, 9 parts by weight of isocyanuric acid and 36 parts by weight of methylhexahydrophthalic anhydride are added and mixed with a hot roll to prepare an epoxy resin. A resin composition was obtained. This was poured into a casting plate and cured to prepare a flammability measuring test piece having a thickness of 1/16 inch.

Using this test piece, a test was conducted in the same manner as in Example 1. The results are shown in Table-2. Example 15 To 80 parts by weight of unsaturated polyester resin Ester CR211 [manufactured by Mitsui Toatsu Chemicals, Inc.], 9 parts by weight of the diguanamines (1) obtained by the method of Reference Example 3, 11 parts by weight of cyanuric acid, and methyl ethyl ketone par. 0.7 parts by weight of oxide and 0.3 parts by weight of cobalt naphthenate were added and mixed in a mixer to obtain an unsaturated polyester resin composition. This was poured into a glass casting plate and cured to prepare a 1/16 inch-thick flammability measuring test piece.

Using this test piece, a test was conducted in the same manner as in Example 1. The results are shown in Table-2.

[0227]

[Table 2] As shown in Examples 10 to 15, the flame-retardant resin composition according to the present invention exhibits excellent flame retardancy in a wide range of resins such as thermoplastic resins and thermosetting resins, and further, the diguanamine according to the present invention. It has been found that the flame retardancy is further improved by the synergistic effect when the compounds are used in combination with isocyanuric acid and cyanuric acid. Example 16 Polyphenylene ether resin poly (2,6-dimethyl-
48 parts by weight of 1,4-phenylene) ether, 32 parts by weight of polystyrene, 11 parts by weight of diguanamines (1) obtained by the method of Reference Example 3, 4 parts by weight of isocyanuric acid and ammonium polyphosphate "Exorit 422" (Hoechst Company) 5 parts by weight of a polyphenylene ether resin composition were mixed by a Henschel mixer, and then kneaded into pellets by an extruder. This is molded with an injection molding machine,
A test piece for measuring flammability having a thickness of 1/16 inch was prepared.

Using this test piece, in the same manner as in Example 1.
As a result of the test, it is level V-1 and the combustion products
Good shape retention, polyphenylene ether described above
The resin composition had excellent flame retardancy. Example 17 Polypropylene glycol (average molecular weight 2000) 10
0.4 parts by weight of water (total water content in the system) was added to 0 parts by weight,
The mixture was heated and mixed at 40 ° C. for 60 minutes. Then add 2,4-
NCO / OH equivalent ratio of tolylene diisocyanate is 1.2
5, NCO / H ₂ If added so that the O equivalent ratio becomes 1.0
I got a fever, but once it's gone, it's 120
Raise the temperature to ℃ and keep the mixture at 120 ℃ for 75 minutes.
The reaction was allowed to stir. Then cool it to 80 ° C. for 2,4
-Add 30 parts by weight of tolylene diisocyanate and mix well.
After combining, it cooled to room temperature and created the prepolymer.

Next, 85 parts by weight of this prepolymer, 15 parts by weight of the diguanamines (1) obtained by the method of Reference Example 3,
0.5 parts by weight of Silicone DC-199 (manufactured by Dow Chemical Co.), 1.0 parts by weight of N-ethylmorpholine, 0.2 parts by weight of triethylamine and 2.3 parts by weight of water are mixed and immediately poured into a mold, A polyurethane foam was prepared by foaming inside. As a result of carrying out a combustion test using this polyurethane foam, it was found to be self-extinguishing and the state of shape retention of the combustion product was good, and the above-mentioned urethane resin composition had excellent flame retardancy. Example 18 Polypropylene resin 78 parts by weight of Mitsui Noblene BJH [manufactured by Mitsui Toatsu Chemicals, Inc.], 5 parts by weight of diguanamines (1) obtained by the method of Reference Example 3, ammonium polyphosphate “Exorit 422” (Hoechst company) 15 parts by weight,
A polypropylene resin composition containing 1 part by weight of pentaethylenehexamine and 1 part by weight of dilaurylthiopropionate was prepared in the same manner as in Example 1 to prepare a test piece. Using this test piece, a flammability test was carried out in the same manner as in Example 1. As a result, the level was V-0, the self-extinguishing property was remarkably excellent, and the shape-retaining state of the combustion product was good. , When phosphorus and an amino group-containing compound are used together,
It was found that the synergistic effect improves the flame retardancy more significantly. Example 19 A treatment and a test were carried out in the same procedure as in Example 18 except that an ethylene-propylene copolymer (containing 45% by weight of propylene) was used instead of the polypropylene resin in Example 18. As a result, the level was V-0, the self-extinguishing property was remarkably excellent, and the shape retention state of the combustion product was good.

The method of making the resin flame-retardant according to the present invention was excellent when the use of the diguanamines, phosphorus and the amino group-containing compound of the present invention together improved the flame retardancy. Examples 20 to 27 Polypropylene resin 76 parts by weight of Mitsui Noblene BJH [manufactured by Mitsui Toatsu Chemicals, Inc.], 5.5 parts by weight of diguanamines (2) obtained by the method of Reference Example 4, ammonium polyphosphate "exolite 422" A polypropylene resin composition consisting of 17 parts by weight (manufactured by Hoechst), 0.5% by weight of the amino group-containing compound shown in Table 3 and 1 part by weight of dilaurylthiopropionate was treated in the same manner as in Example 1. And a test was conducted. The results are shown in Table-3.

As shown in Table 3, in the method for flame-retarding the resin according to the present invention, the combined use of the phosphoric acid and the amino group-containing compound together with the diguanamines according to the present invention further improves the flame retardancy and is excellent. It was a thing.

[0232]

[Table 3] Example 28 Thermal stability test of polyphenylene ether resin: poly2,6-dimethyl-1,4 having an intrinsic viscosity [η] of 0.52
-To a polyphenylene ether resin consisting of 45 parts by weight of a phenylene ether component, 50 parts by weight of a polystyrene component, and 5 parts by weight of a hydrogenated SBS rubber component, 0.1% by weight of diguanamines (1) obtained by the method of Reference Example 3 was added. The polyphenylene ether resin composition thus obtained was mixed by a Henschel mixer, and then melt-kneaded by a twin-screw extruder set at a cylinder temperature of 300 ° C. to form pellets. Using an injection molding machine with the cylinder temperature set at 290 ° C, thickness 1
A test piece for measuring Izod impact strength of / 8 inch was prepared. This test piece was left for 200 hours in a hot air circulating constant temperature bath set at 130 ° C. to perform an aging test. Determine the Izod impact strength before and after the aging test by ASTM D25
It measured based on 6, and the result is shown in Table-4. Examples 29, 30 Thermal stability test of polyphenylene ether resin: Example 2
Treatment and testing were carried out in the same procedure as in Example 28, except that the type of diguanamines according to the present invention in Example 8 was changed. The results are shown in Table-4. Comparative Example 1 Treatment and testing were carried out in the same procedure as in Example 28, except that the diguanamines (1) obtained by the method of Reference Example 3 in Example 28 was not added. The results are shown in Table-4.

[0233]

[Table 4] (Note 1) The number in parentheses indicates the retention rate of Izod impact strength before and after aging in%. Examples 31 to 33 Thermal Stability Test of Polyphenylene Ether Resin: Example 2
The polyphenylene ether resin composition in Example 8 was treated and tested in the same procedure as in Example 28 except that the following additives were added. The results are shown in Table-5.

[0234]

[Table 5] (Note 1) Weight% based on polyphenylene ether resin
Indicates. (Note 2) Pentaerythrityl-tetrakis [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate] Example 34 Thermal stability test of polyacetal resin: Diguanamine obtained by the method of Reference Example 4 was added to 100 parts by weight of a trioxane-dioxolane copolymer having 4% by weight of a constitutional unit composed of dioxolane having an intrinsic viscosity of 1.6. Class (2) 1.0% by weight
The polyacetal resin composition obtained by adding
It was heated and pulverized under the condition of 0 ° C.-40 minutes.

The treated resin composition was placed in an open container and kept in a circulating air dryer at 220 ° C. to measure the weight reduction. As a result, the thermal depolymerization rate was 0.68% by weight / min. The thermal depolymerization rate of the resin without the addition of diguanamines was 2.9% by weight / minute. Example 35 Thermal stability test of polyacetal resin: Diguanamines (2) obtained by the method of Reference Example 4 in Example 34 1.
Instead of adding 0% by weight, 1.0 part by weight of diguanamines (1) obtained by the method of Reference Example 3 and 2,2′-methylenebis (4-methyl-6-t-butylphenol)
Processing and testing were carried out in the same procedure as in Example 34, except that 1.0% by weight was added. As a result, the thermal depolymerization rate of this resin composition was 0.08% by weight / minute.

As shown in Examples 34 and 35, the polyacetal resin composition according to the present invention had remarkably improved thermal stability. Example 36 Thermal stability test of polyethylene resin: Polyethylene resin HiZex 5100E [manufactured by Mitsui Petrochemical Co., Ltd.] 100
160 parts by weight of a polyethylene resin composition comprising 1.0 part by weight of copper fine powder and 0.5 part by weight of diguanamines (1) obtained by the method of Reference Example 3 with a mixing roll.
Knead under the condition of -6 minutes, then 150 ℃, 200kg
A sheet film was obtained by compression molding for 5 minutes under the condition of / cm ² .

[0237] Using this sheet film, the temperature is 150 ° C.
A heat deterioration acceleration test was performed in an air atmosphere in the hot pack oven set to. The time when this test piece changed its color was regarded as the start of deterioration, and the thermal stability of the resin composition was determined by the time until this time. The results are shown in Table-6.

In the above polyethylene resin composition, the diguanamines (1) obtained by the method of Reference Example 3 were used.
Treatment and testing were carried out in the same procedure as above except that 0.5 part by weight was not added, and the results are shown in Table 6 as "Comparative Example-2".

[0239]

[Table 6] Example 37 Thermal stability test of polypropylene resin: polypropylene resin Mitsui Noblen BJH [manufactured by Mitsui Toatsu Chemicals, Inc.] 10
A polypropylene resin composition consisting of 0 part by weight, 1.0 part by weight of fine copper powder and 0.3 part by weight of the diguanamines (2) obtained by the method of Reference Example 4 was mixed with a mixing roll to prepare 1
Kneading at 90 ° C for 6 minutes, then 180 ° C, 200
A sheet film was obtained by compression molding for 5 minutes under the condition of kg / cm ² .

Using this sheet film, treatment and testing were carried out in the same procedure as in Example 36, and the results are shown in Table 7.

In the above polypropylene resin composition, the diguanamines (2) obtained by the method of Reference Example 4 were used.
Treatment and testing were carried out in the same procedure as above except that 0.3 part by weight was not added, and the results are shown in Table 7 as "Comparative Example-3".

[0242]

[Table 7] Example 38 Polyamide resin-polyphenylene ether resin-polystyrene resin ternary resin compatibilization test: polyphenylene ether resin composed of poly2,6-dimethyl-1,4-phenylene ether having an intrinsic viscosity [η] of 0.52 45 parts by weight of component, 50 parts by weight of polystyrene resin component, hydrogenated S
A resin composition consisting of 5 parts by weight of a BS rubber component was added to Reference Example 3
8 parts by weight of the diguanamines (1) obtained by the above method was added and mixed with a Henschel mixer, and then melt-kneaded and pelletized with a twin-screw extruder set to a cylinder temperature of 300 ° C. After 54 parts by weight of the pellets were finely pulverized, 50 parts by weight of polyamide resin Toyobo Nylon T-802 [manufactured by Toyobo Co., Ltd.] was added. This resin composition was mixed with a Henschel mixer, then the cylinder temperature was adjusted to 28
It was melt-kneaded and pelletized by a twin-screw extruder set at 0 ° C.

As a result of observing this ternary resin composition with an electron microscope, it was found that the resin-melted structure had a sea-island structure and the spherical particles controlled to have a diameter of approximately 2.4 μ were uniformly dispersed. It was excellent in compatibilizing the resin. Example 39 Polyphenylene ether resin-polyamideimide resin Binary resin compatibilization test: 70 parts by weight of a polyphenylene ether resin composed of poly2,6-dimethyl-1,4-phenylene ether having an intrinsic viscosity [η] of 0.52 , Polyamideimide resin Torlon 4203T [manufactured by Amoco Co.] 30 parts by weight and 5 parts by weight of the diguanamines (2) obtained by the method of Reference Example 4 were mixed in a Henschel mixer, and then the twin screw whose cylinder temperature was set to 330 ° C. It was melt-kneaded and pelletized by an extruder.

As a result of observing this binary resin composition with an electron microscope, it was found that the resin-melted structure had a sea-island structure and the spherical particles controlled to have a diameter of 3.6 μ were uniformly dispersed. Was excellent in compatibilization of the resin. Comparative Example 4 A pelletized resin composition was obtained by the same procedure as in Example 39 except that the diguanamines (2) obtained by the method of Reference Example 4 in Example 39 was not added.

As a result of observing this resin composition with an electron microscope, the resin-melted structure has a sea-island structure, but there is no control over a wide range of spherical particles having a diameter of 0.5 to 40 μm.
It was a dispersion of oblong spheres, and the compatibility of the resin was extremely poor. Example 40 Preparation of N, N ', N ", N'"-tetrakis (5-hydroxy-3-oxapentyl) diguanamine: stirrer,
3l equipped with a thermometer, N ₂ inlet pipe, liquid inlet, and cooler
In a flask, 314.4 g (1.0 mol) of diguanamine (1) obtained by the method of Reference Example 3 and 5-amino-3 were added.
-Oxapentan-1-ol 1471.9 g (14.
(0 mol) was charged, the system was sufficiently replaced with nitrogen gas, and then 30.0 g (0.3 mol) of concentrated sulfuric acid was gradually added with stirring. The reaction mixture was gradually heated with stirring and reacted at a temperature of 210 ° C. for 20 hours. The reaction mixture was cooled and then neutralized with a 50% aqueous sodium hydroxide solution. Next, the precipitate was removed from this reaction mixture by filtration while hot, and then excess 5-amino-3-oxapentan-1-ol was distilled off under reduced pressure to obtain a pale yellow oily product 6
74.1 g was obtained. As a result of analyzing the crude product by liquid chromatography, 2,5-bis [4,6-bis (5-
Hydroxy-3-oxapentylamino) -1,3,5
-Triazin-2-yl] -bicyclo [2.2.1] heptane and 2.6-bis [4,6-bis (5-hydroxy-3-oxapentylamino) -1,3,5-triazine-2 -Yl] -bicyclo [2.2.1] heptane mixture containing hydroxyl group-containing diguanamine derivative 93
% Was included. As a result of separating and analyzing and identifying the derivative, the infrared absorption spectrum has a hydroxyl group absorption (3500 cm ⁻¹ wide absorption) and a triazine ring absorption (820 cm ⁻¹ ), and the ¹ H nuclear magnetic resonance absorption spectrum shows Absorption (6.5, 6.7 ppm) based on the NH ₂ groups of the raw material compounds disappears, and absorption (3.6 ppm) based on CH ₂ groups newly appears, and the measured values of elemental analysis are calculated as follows. Good agreement with the value.

Elemental analysis CHN Measured value: 52.1% 7.5% 20.8% Calculated value: 52.24% 7.56% 21.01% Example 41 N, N ', N ", N '''- tetrakis (2-hydroxypropyl) diguanamine of manufacturing: stirrer, thermometer, N ₂
In a 3 l flask equipped with an introduction tube and a condenser, 302.3 g (1.
0 mol), 1-amino-2-propanol 751.1 g
(10.0 mol), ammonium chloride 42.8 g (0.
8 mol) and 274 g of ethylene glycol were charged, and the system was sufficiently replaced with nitrogen gas. The reaction mixture was gradually heated with stirring and reacted for 20 hours under reflux. The reaction mixture was cooled and then neutralized with a 50% aqueous sodium hydroxide solution. Next, the precipitate was removed from this reaction mixture by filtration while hot, and then excess 1-amino-2-propanol and ethylene glycol were distilled off under reduced pressure to obtain 541.4 g of a pale yellow crude product. It was As a result of analyzing the crude product by liquid chromatography, 1,3-bis [4,6-bis (2-hydroxypropylamino)-
1,3,5-Triazin-2-yl] -cyclohexane and 1,4-bis [4,6-bis (2-hydroxypropylamino) -1,3,5-triazin-2-yl]-
It contained 83% of a hydroxyl group-containing diguanamine derivative consisting of a mixture of cyclohexane. As a result of separating and analyzing and identifying the derivative, the infrared absorption spectrum has absorption of a hydroxyl group and a triazine ring, and the ¹ H nuclear magnetic resonance absorption spectrum has disappeared absorption based on the NH ₂ group of the starting compound, Absorption based on CH ₂ groups newly appeared, and the measured values of elemental analysis were in good agreement with the calculated values as follows.

Elemental analysis C H N Measured value: 53.7% 7.8% 26.1% Calculated value: 53.91% 7.92% 26.20% Example 42 N, N ′, N ″, N Production of '''-tetrakis (2-hydroxyethyl) diguanamine: 314.4 g of diguanamine (1) obtained by the method of Reference Example 3 was placed in a 3 l flask equipped with a stirrer, thermometer, N ₂ inlet tube, and condenser. (1.0
), 2-aminoethanol 1221.7 g (20.
0 mol) and 64.2 g (1.2 mol) of ammonium chloride were charged, and the system was sufficiently replaced with nitrogen gas. The reaction mixture was gradually heated with stirring and reacted for 30 hours under reflux. The reaction mixture was cooled and then neutralized with a 50% aqueous sodium hydroxide solution. Next, the precipitate was removed from this reaction mixture by filtration while hot, and then excess 1-aminoethanol was distilled off under reduced pressure to obtain 500.4 g of a pale yellow crude product. As a result of analyzing the crude product by liquid chromatography, 2.5-bis [4,6-bis (2-hydroxyethylamino) -1,3,5-triazin-2-yl] -bicyclo [2.2] .1] heptane and a mixture of 2.6-bis [4,6-bis (2-hydroxyethylamino) -1,3,5-triazin-2-yl] -bicyclo [2.2.1] heptane. It contained 79% of a hydroxyl group-containing diguanamine derivative. Results of analysis identified separate the derivative, in the infrared absorption spectrum has a hydroxyl group, the absorption of a triazine ring, ¹
In the H nuclear magnetic resonance absorption spectrum, the absorption based on the NH ₂ group of the raw material compound disappeared, and the absorption based on CH ₂ group newly appeared, and the measured values of elemental analysis were in good agreement with the calculated values as follows. .

Elemental analysis C H N Measured value: 51.3% 7.0% 28.4% Calculated value: 51.42% 6.99% 28.55% Example 43 N, N ′, N ″, N '''- tetrakis (2-hydroxyphenyl) diguanamine of manufacturing: stirrer, thermometer, N ₂
302.3 g of diguanamine (2) obtained by the method of Reference Example 5 (1.
0 mol), 873.0 g of p-aminophenol (8.0
Mol), 32.1 g (0.6 mol) of ammonium chloride and 1400 g of ethylene glycol were charged, and the system was sufficiently replaced with nitrogen gas. The reaction mixture was gradually heated with stirring and reacted at a temperature of 200 ° C. for 30 hours. The reaction mixture was cooled and then neutralized with a 50% aqueous sodium hydroxide solution. Next, the precipitate was removed from this reaction mixture by filtration while hot, and further washed with deionized water,
It was dried under reduced pressure to obtain 643.9 g of a pale yellow crude product. As a result of analyzing the crude product by liquid chromatography, 1,
It contained 94% of 4-bis [4,6-bis (4-hydroxyphenylamino) -1,3,5-triazin-2-yl] -cyclohexane. As a result of separating and analyzing the target, the infrared absorption spectrum had absorptions of hydroxyl group, benzene ring and triazine ring, and the ¹ H nuclear magnetic resonance absorption spectrum had NH ₂ of the starting compound.
The absorption based on the group disappeared, a new absorption based on the phenyl group appeared, and the measured values of elemental analysis were in good agreement with the calculated values as follows.

Elemental analysis C H N Measured value: 64.2% 5.0% 20.8% Calculated value: 64.47% 5.11% 20.88% Example 44 N, N ′, N ″, N Preparation of '''-Tetrakis (2-hydroxypropyl) diguanamine: 2 in Example 42
-Aminoethanol 1221.7 g (20.0 mol) instead of 3-aminopropanol 1502.2 g (2
The reaction and treatment were carried out by the same procedure as in Example 42 except that (0.0 mol) was used to obtain 554.9 g of a crude product.
As a result of analyzing this crude product by liquid chromatography, 2.5-bis [4,6-bis (3-hydroxypropylamino) -1,3,5-triazin-2-yl]-
Bicyclo [2.2.1] heptane and 2,6-bis [4,6-bis (3-hydroxypropylamino)-
1,3,5-Triazin-2-yl] -bicyclo [2.
2.1] It contained 84% of a hydroxyl group-containing diguanamine derivative consisting of a mixture of heptane. The derivative was separated and analyzed and identified by the same method as in Example 42. As a result, it was in good agreement with the target product, and the measurement results of elemental analysis are shown below.

Elemental analysis C H N Measured value: 54.8% 7.6% 25.4% Calculated value: 54.93% 7.74% 25.62% Example 45 N, N ′, N ″, N Preparation of '''-Tetraphenyldiguanamine: 2-aminoethanol 12 in Example 42
Aniline 93 instead of 21.7 g (20.0 mol)
The reaction and the treatment were carried out in the same procedure as in Example 42 except that 1.3 (10.0 mol) was used to obtain the crude product 629.9.
g was obtained. As a result of analyzing this crude product by liquid chromatography, 2,5-bis [4,6-dianilino-1,
3,5-triazin-2-yl] -bicyclo [2.2.
1] Heptane and 2,6-bis [4,6-dianilino-
1,3,5-Triazin-2-yl] -bicyclo [2.
2.1] It contained 89% of a diguanamine derivative consisting of a mixture of heptane. Separating the derivative,
As a result of analysis and identification by the same method as in Example 42, it was in good agreement with the target product, and the measurement results of elemental analysis are shown below.

Elemental analysis C H N Measured value: 71.6% 5.5% 22.6% Calculated value: 71.82% 5.54% 22.64% Example 46 N-mono (4-methoxycarbonylphenyl) ) Preparation of diguanamine: Same as in Example 43 except that 151.2 g (1.0 mol) of methyl p-aminobenzoate was used instead of 873.0 g (8.0 mol) of p-aminophenol in Example 43. The reaction was performed according to the procedure. The reaction mixture was cooled and then neutralized with a 50% aqueous sodium hydroxide solution. Next, the precipitate was removed from the reaction mixture by filtration while hot, further washed with deionized water and dried under reduced pressure to obtain a pale yellow crude product. The crude product was extracted with ethanol, the solvent was removed therefrom, and the product was dried under reduced pressure to obtain the extracted product 37.
4.5 g was obtained. As a result of analyzing this extract by liquid chromatography, 1- (4,6-diamino-1,3,5
-Triazin-2-yl) -4- [4-amino-6-
(4-Methoxycarbonylphenylamino) -1,3
It contained 79% of 5-triazin-2-yl] -cyclohexane. As a result of separating and analyzing and identifying the target substance, the infrared absorption spectrum had absorptions of an ester group and a triazine ring, and the measured values of elemental analysis were in good agreement with the calculated values as follows.

Elemental analysis C H N measured value: 54.9% 5.5% 32.0% calculated value: 55.04% 5.54% 32.09% Example 47 of oxaalkyl group-containing diguanamine derivative Manufacturing:
In a 3 l flask equipped with a stirrer, a thermometer, a N ₂ introduction tube, a liquid inlet, and a condenser, 157.2 g (0.5 mol) of diguanamine (1) obtained by the method of Reference Example 3, potassium hydroxide 15 0.0 g and N, N-dimethylformamide 50
0 g was charged, and the inside of the system was sufficiently replaced with nitrogen gas. The reaction mixture is gradually heated to 130 ° C. and propylene oxide 1277.8 g (2
(2.0 mol) was gradually added dropwise, and the reaction was carried out by adding it for about 5 hours. After the addition of propylene oxide was completed, the reaction was continued at the same temperature for about 2 hours. Next, the reaction mixture was cooled and then neutralized with a 30% aqueous solution of sulfuric acid.
Furthermore, N, N-dimethylformamide was distilled off from this reaction mixture under reduced pressure, and the precipitate was filtered to obtain a pale yellow, highly viscous product. As a result of measuring the weight increase of this product, the reaction addition amount of propylene oxide was 106.
It was 2.9 g. As a result of analyzing the obtained oxaalkyl group-containing diguanamine derivative, an OH value of 162 was obtained.
The measured values of elemental analysis were as follows.

Elemental analysis C H N measurement: 60.2% 9.8% 5.6% Example 48 Preparation of oxaalkyl group-containing diguanamine derivative:
A 3 l flask equipped with a stirrer, a thermometer, a N ₂ introduction tube, a liquid inlet, and a condenser was charged with N, obtained by the method of Example 41,
331.5 g of N ′, N ″, N ′ ″-tetrakis (2-hydroxypropyl) diguanamine and 6.6 g of potassium hydroxide were charged, and the system was sufficiently replaced with nitrogen gas.
The reaction mixture was gradually heated to 130 ° C., and while stirring at this temperature, 2079.3 g of propylene oxide was gradually added dropwise, and the reaction was carried out by adding for about 5 hours. After the addition of propylene oxide was completed, the reaction was continued at the same temperature for about 2 hours. The obtained reaction product was a pale yellow highly viscous substance, and as a result of measuring the weight increase of this reaction product, the reaction addition amount of propylene oxide was 184.
It was 7.0 g.

The obtained oxaalkyl group-containing diguanamine derivative was analyzed. As a result, the OH value was 93, and the measured values by elemental analysis were as follows.

Elemental analysis C H N measured value: 60.8% 10.0% 3.9% Example 49 Preparation of oxaalkyl group-containing diguanamine derivative:
1 liter equipped with a stirrer, thermometer, N ₂ inlet pipe, liquid inlet pipe
The N, obtained by the method of Example 43, was placed in an autoclave.
N ′, N ″, N ′ ″-Tetrakis (2-hydroxyphenyl) diguanamine 134.1 g Diethylene glycol dimethyl ether 100 g and potassium hydroxide 2.0 g
Was charged, and the system was sufficiently replaced with nitrogen gas. The reaction mixture is gradually heated to 120 ° C., and 440.5 g of ethylene oxide is dividedly fed while stirring at this temperature.
It took about 5 hours to supply and react. Even after the supply of ethylene oxide was completed, the reaction was continued at the same temperature for about 2 hours. Next, after cooling this reaction mixture, the system was sufficiently replaced with nitrogen gas to take out the reaction mixture. Further, this was neutralized with a 30% aqueous solution of sulfuric acid, diethylene glycol dimethyl ether was distilled off under reduced pressure, and the precipitate was filtered to obtain a pale yellow, highly viscous product. As a result of measuring the weight increase of this reaction product, the reaction addition amount of ethylene oxide was 381.5 g.

As a result of analyzing the thus obtained oxaalkyl group-containing diguanamine derivative, the OH value was 139, and the measured values by elemental analysis were as follows.

Elemental analysis C H N measurement: 57.0% 8.1% 5.3% Example 50 Preparation of diguanamine derivative containing oxaalkyl group:
In a 3 l flask equipped with a stirrer, a thermometer, a N ₂ introduction tube, a liquid inlet, and a condenser, the N-methylol compound of the diguanamines (2) obtained by the method of Reference Example 4 [diguanamines (2) 1 mol To 7.3 equivalents of methylol group]
08.6 g, diethylene glycol dimethyl ether 2
00.0 g and 5.0 g of potassium hydroxide or potassium were charged, and the system was sufficiently replaced with nitrogen gas. The reaction mixture was added to 130
The mixture was gradually heated to 0 ° C., and 2032.8 g of propylene oxide was gradually added dropwise with stirring at this temperature, and the reaction was carried out by adding for about 8 hours. After the addition of propylene oxide was completed, the reaction was continued at the same temperature for about 2 hours.
Next, the reaction mixture was cooled and then neutralized with a 30% aqueous solution of sulfuric acid. Furthermore, diethylene glycol dimethyl ether was distilled off from this reaction mixture under reduced pressure, and the precipitate was filtered to obtain a pale yellow, highly viscous product. As a result of measuring the weight increase of this product, the reaction addition amount of propylene oxide was 1783.1 g.

As a result of analyzing the obtained oxaalkyl group-containing diguanamine derivative, the OH value was 86,
The measured values of elemental analysis were as follows.

Elemental analysis CHN measured: 60.1% 10.0% 2.7% Example 51 Preparation of N, N ', N ", N"'-tetrakis (2-morpholinoethyl) diguanamine: P− in Example 43
Instead of 873.0 g (8.0 mol) of aminophenol, 1041.5 g of N-aminoethylmorpholine (8.
The reaction and treatment were carried out in the same procedure as in Example 43 except that 0 mol) was used. As a result of analyzing the crude product by liquid chromatography, 1.4-bis [4,6-bis (2
-Morpholinoethylamino) -1,3,5-triazin-2-yl] -cyclohexane 92%. As a result of separating and analyzing and identifying the target substance, the infrared absorption spectrum had absorption of a triazine ring, and the measured values of elemental analysis were in good agreement with the calculated values as follows.

Elemental analysis CHN Measured value: 57.4% 8.2% 26.1% Calculated value: 57.27% 8.28% 25.97% Example 52 Polypropylene resin Mitsui Noblene BGH [Mitsui Toatsu] Manufactured by Kagaku KK] 84 parts by weight, 15 parts by weight of N-mono (4-methoxycarbonylphenyl) diguanamine obtained by the method of Example 46 and dilaurylthiodipropionate 1
A polypropylene resin composition consisting of parts by weight was kneaded with a mixing roll at 190 ° C. for 6 minutes, and then kneaded with an extruder to form pellets. This was molded by an injection molding machine to prepare a flammability measuring test piece having a thickness of 1/16 inch.

Using this test piece, a flammability test was conducted in the same manner as in Example 1. As a result, the result was level V-1, there was no molten fallen object during combustion, and the shape retention state of the combusted material was good.
The polypropylene resin composition described above had excellent flame retardancy. Example 53 Polypropylene resin Mitsui Noblene BJH [manufactured by Mitsui Toatsu Chemicals, Inc.] 75 parts by weight, N-mono (4-methoxycarbonylphenyl) diguanamine 6 parts by weight obtained by the method of Example 46, ammonium polyphosphate " A polypropylene resin composition comprising 18 parts by weight of "Exorit 422" (manufactured by Hoechst) and 1 part by weight of dilaurylthiopropionate was prepared in the same manner as in Example 1 to prepare a test piece.

Using this test piece, a flammability test was conducted in the same manner as in Example 1. As a result, the level was V-0, the shape retention of the burned material was good, and the resin according to the present invention was made flame-retardant. In the method, when the diguanamine derivative according to the present invention was used in combination with phosphorus, the flame retardancy was further improved and it was excellent. Examples 54 and 55 Examples 53 and 55 except that the diguanamine derivatives shown in Table 8 were used instead of the N-mono (4-methoxycarbonylphenyl) diguanamine obtained by the method of Example 46 in Example 53. Test pieces were prepared and tested in the same manner. The results are shown in Table-8.

As shown in Table-8, in the flame retarding method of the resin according to the present invention, the diguanamines according to the present invention are excellent in improving the flame retardancy, and when phosphorus is used in combination, the flame retardancy is further improved. I found out.

[0264]

[Table 8] Example 56 75 parts by weight of polyethylene resin Hi-Zex 5100E (manufactured by Mitsui Petrochemical Co., Ltd.), N, N ′, N ″, N ″ ′-tetrakis (2-hydroxypropyl) diguanamine obtained by the method of Example 41 A polyethylene resin composition consisting of 15 parts by weight and 10 parts by weight of 2-ethylhexyldiphenyl phosphate was mixed at 160 ° C. with a mixing roll.
The mixture was kneaded under the condition of 6 minutes and then kneaded with an extruder to form pellets. A test piece for measuring flammability was prepared in the same manner as in Example 1.

Using this test piece, a flammability test was conducted in the same manner as in Example 1. As a result, the level was V-0, there was no molten fallen object during combustion, and the shape retention state of the combusted material was good.
The resin flame-retardant method according to the present invention was excellent in improving flame retardancy. Example 57 Ethylene-propylene copolymer (45% by weight of propylene
75 parts by weight, N obtained by the method of Example 40,
N ', N ", N'"-tetrakis (5-hydroxy-3
-Oxapentyl) diguanamine 14 parts by weight, ammonium polyphosphate "Exolit 422" (manufactured by Hoechst) 10 parts by weight, and a resin composition comprising 1 part by weight of dilauryl thiopropionate, and test pieces were prepared in the same manner as in Example 1. It was made.

Using this test piece, a flammability test was conducted in the same manner as in Example 1. As a result, the level was V-0 and the shape retention state of the burned material was also good. Example 58 N, N ′, N ″, N ″ ′-tetrakis (2-) obtained by the method of Example 41 was added to 90 parts by weight of nylon 66 pellets.
The nylon resin composition obtained by adding 10 parts by weight of (hydroxypropyl) diguanamine was mixed with a Henschel mixer, and then kneaded with an extruder set at a cylinder temperature of 280 ° C. to form a pellet. This was molded by an injection molding machine to prepare a flammability measuring test piece having a thickness of 1/16 inch.

Using this test piece, a test was conducted in the same manner as in Example 1, and as a result, it was level V-1, and the char-forming property was excellent, and the shape retention state of the combustion product was good. Example 59 N-N, N ', N ", N"'-tetrakis (2-) obtained by the method of Example 41 was added to 90 parts by weight of nylon 66 pellets.
A nylon resin composition containing 7 parts by weight of (hydroxypropyl) diguanamine and 3 parts by weight of isocyanuric acid was used to prepare a test piece in the same manner as in Example 58.

Using this test piece, a flammability test was conducted in the same manner as in Example 1. As a result, the level was V-0, the shape retention of the burned material was good, and excellent flame retardancy was exhibited. Furthermore, it was found that in the resin flame-retardant method according to the present invention, the combined use of the isocyanuric acids with the diguanamine derivative according to the present invention further improves the flame retardancy by a synergistic effect. Example 60 Instead of the diguanamines (2) obtained by the method of Reference Example 4 in Example 9, N, N ′, N ″, N ″ ′-tetrakis (3 obtained by the method of Example 44 was used. A test piece for measuring flammability was prepared in the same manner as in Example 9 except that -hydroxypropyl) diguanamine was used.

Using this test piece, a flame-retardant test was conducted in the same manner as in Example 1. As a result, the result was level V-0, the shape retention state of the combustion product was good, and excellent flame retardancy was exhibited. It was Example 61 Epoxy resin Epicoat ^# 828 [Shell Chemical Co., Ltd.
Manufacture] 44 parts by weight of N obtained by the method of Example 42,
N ′, N ″, N ′ ″-tetrakis (2-hydroxyethyl) diguanamine 11 parts by weight, tris (2-hydroxyethyl) isocyanurate 9 parts by weight and methylhexahydrophthalic anhydride 36 parts by weight were added to a hot roll. The mixture was mixed to obtain an epoxy resin composition, which was poured into a casting plate and cured to prepare a 1 / 16-inch thick test piece for measuring flammability.

Using this test piece, a test was conducted in the same manner as in Example 1. As a result, the level was V-0, the shape retention state of the combustion product was good, and excellent flame retardancy was exhibited. Example 62 In place of the diguanamines (1) obtained by the method of Reference Example 4 in Example 15, N, N ′, N ″, N ″ ′-tetrakis (2 obtained by the method of Example 41 was used. A test piece for measuring flammability was prepared in the same manner as in Example 15 except that -hydroxypropyl) diguanamine was used.

Using this test piece, a flame retardant test was conducted in the same manner as in Example 1. As a result, the result was Level V-1, and the shape retention of the combustible was good. Examples 63 to 66 Instead of the diguanamines (2) obtained by the method of Reference Example 4 in Example 20, N, N ′, N ″, N ″ ′-tetrakis obtained by the method of Example 42 was used. (2-Hydroxyethyl) diguanamine and also the table in Example 20
A test piece was prepared and a flammability test was conducted in the same manner as in Example 20 except that the amino group-containing compound shown in Table 9 was used in place of the amino group-containing compound shown in Table 3. The results are shown in Table-9.

As shown in Table 9, in the flame retarding method for the resin according to the present invention, the combined use of the phosphorus-containing and amino group-containing compound with the diguanamine derivative according to the present invention further improves the flame retardancy, It was excellent.

[0273]

[Table 9] Example 67 Thermal stability test of polyphenylene ether resin: Example 2
8 instead of the diguanamines (1) obtained by the method of Reference Example 3 in Example 8, N obtained by the method of Example 41,
A procedure similar to that of Example 28 is performed except that 0.1% by weight of N ′, N ″, N ′ ″-tetrakis (2-hydroxypropyl) diguanamine and 0.3% by weight of tris (nonylphenyl) phosphite are used. Treated and tested.

As a result, the Izod impact strength was 12.6 before aging, 8.1 after aging, and the same strength retention rate was 6.
It was remarkably good at 4%. Example 68 Thermal stability test of polyacetal resin: Instead of the diguanamines (2) obtained by the method of Reference Example 4 in Example 34, N, N ′, N ″ obtained by the method of Example 42,
The treatment and the test were performed in the same procedure as in Example 34 except that N ″ ′-tetrakis (2-hydroxyethyl) diguanamine was used. As a result, this resin composition had a thermal depolymerization rate of 0.83% by weight / minute.

As described above, the resin thermal stabilization method according to the present invention markedly improves the thermal stability of the polyacetal resin. Example 69 Thermal stability test of polypropylene resin: N, N ′, N ″ obtained by the method of Example 44, instead of the diguanamines (2) obtained by the method of Reference Example 4 in Example 37,
A sheet film was prepared by the same procedure as in Example 37 except that N ″ ′-tetrakis (3-hydroxypropyl) diguanamine was used.

Using this sheet film, a test was conducted in the same procedure as in Example 36. As a result, it was found that the period until deterioration started was 2
The heat stability was remarkably good after 0 days, and the heat stabilization method for the resin according to the present invention was excellent. Example 70 Polyphenylene resin-polyetherimide resin Binary resin compatibilization test: poly2,6 with an intrinsic viscosity [η] of 0.52
-60 parts by weight of polyphenylene ether resin consisting of dimethyl-1,4-phenylene ether, 40 parts by weight of polyetherimide resin Ultem 1000 [manufactured by Engineering Plastics Co., Ltd.] and N, N 'obtained by the method of Example 45 , N ", N"'-tetraphenyldiguanamine (5 parts by weight) was mixed by a Henschel mixer, and then melt-kneaded and pelletized by a twin-screw extruder set to a cylinder temperature of 300 ° C.

As a result of observing this resin composition with an electron microscope, it was found that the molten structure of the resin had a sea-island structure and the spherical particles controlled to have a diameter of approximately 2.8 μ were uniformly dispersed. It was excellent in compatibilizing the resin. Example 71 Polyamide resin-polyphenylene ether resin-polystyrene resin Ternary resin compatibilization test: Obtained by the method of Example 42 instead of the diguanamines (1) obtained by the method of Reference Example 3 in Example 38. Given N, N ', N ",
A treatment and a test were performed in the same procedure as in Example 38 except that N ″ ′-tetrakis (2-hydroxyethyl) diguanamine was used.

This ternary resin composition is a composition in which the resin-melted structure has a sea-island structure and the spherical particles whose diameter is controlled to 2.8 μ are uniformly dispersed. Such a method is excellent in compatibilization of the resin. Met. Example 72 300.3 g of paraformaldehyde (80% product, formaldehyde content 8.0 mol) and 300.3 g of deionized water were placed in a 3 l flask equipped with a stirrer, a thermometer and a condenser, and a 10% caustic soda aqueous solution was used. After adjusting the pH to 8.5, 628.7 g (2.0 mol) of the diguanamines (1) obtained by the method of Reference Example 3 was added and mixed. While maintaining the mixed solution at pH 8.5 to 9.0, the reaction was carried out at 80 ° C for 2 hours, and then the pH was adjusted to 20% with a sulfuric acid aqueous solution.
It was adjusted to 7.0 to obtain an amino resin.

Next, 2300 g of a 1.5 wt% aqueous solution of polyvinyl alcohol [trade name "Kuraray Poval 205", manufactured by Kuraray Co., Ltd.] was stirred at a high speed in a disper mill while maintaining the temperature at 90 ° C. The amino resin obtained in (1) was added under stirring to obtain an emulsion. 4 this emulsion
After cooling to 0 ° C, 8.0 g of dodecylbenzenesulfonic acid
After adding, while stirring at low speed with an anchor type stirring blade, about 1
The temperature was gradually raised at a rate of 0 ° C./hour. After reaching 90 ℃,
The reaction was carried out at that temperature for 2 hours to obtain a suspension of polymer particles.

The solid content was separated from this suspension by using a centrifuge, and the obtained solid content was heated and dried at 150 ° C. for 4 hours to obtain white powdery polymer fine particles. . The polymer fine particles swell even when immersed in a solvent such as isopropanol, methyl ethyl ketone, or xylene.
It does not show any dissolution, has excellent solvent resistance, and has a set temperature of 250.
Even when heated in a dryer at 0 ° C, no fusion or the like was observed and the heat resistance was excellent. Example 73 To a 3 l flask equipped with a stirrer, a thermometer, and a condenser, 450.4 g of paraformaldehyde (80%, formaldehyde content 12.0 mol) and 523.4 g of deionized water were placed, and pH was adjusted to 9 using a 10% caustic soda aqueous solution. After adjusting to 0.0, 604.7 g (2.0 mol) of diguanamines (2) obtained by the method of Reference Example 5 was added and mixed. While maintaining the mixed solution at pH 9.0 to 9.5, the reaction was carried out at 80 ° C. for 1 hour. Furthermore, p with 20% sulfuric acid aqueous solution
After adjusting to H6.0 and reacting at 60 ° C. for 1 hour,
The pH was adjusted to 7.0 with a 10% aqueous sodium hydroxide solution to obtain an amino resin.

Next, 3300 g of a 1.0 wt% aqueous solution of polyvinyl alcohol [trade name "Kuraray Poval 205", manufactured by Kuraray Co., Ltd.] was stirred at a high speed with a disper mill while maintaining the temperature at 90 ° C. The amino resin obtained above was added under stirring to obtain an emulsion.

Using this emulsion, a reaction and a treatment were carried out in the same manner as in Example 72 to obtain white powdery polymer fine particles.

This polymer fine particle has a preset temperature of 250 ° C.
Even when heated in the dried kiln, no fusion was observed and the heat resistance was excellent. Example 74 A 3-liter flask equipped with a stirrer, thermometer and condenser was charged with 3
81% 7% formalin (formaldehyde content 1
0.0 mol) and use a 10% sodium carbonate aqueous solution to
After adjusting to H8.0, 604.7 g (2.0 mol) of diguanamines (2) obtained by the method of Reference Example 4 was added and mixed. After keeping the mixed solution at pH 8.0 to 8.5 for 2 hours at 90 ° C., oil orange S40.0 g was added thereto and stirred for 1 hour to obtain a colored amino resin. It was

Next, 600 g of a 5.0% by weight aqueous solution of polyvinyl alcohol [trade name "Kuraray Poval 205", manufactured by Kuraray Co., Ltd.] was stirred at a high speed for 2 times in a disper mill while maintaining the temperature at 90 ° C. The above colored amino resin was added under stirring to obtain an emulsion.

Using this emulsion, a reaction and a treatment were carried out in the same manner as in Example 72 to obtain orange-colored powdery polymer fine particles having a vivid chroma. Example 75 With respect to the polymer fine particles obtained by the method of Examples 72 to 74, the polymer fine particles were changed to 30% PWC by using a constantly dry acrylic resin Armatex L-1042 (NV 40.0%, manufactured by Mitsui Toatsu Chemicals, Inc.). Each of them was added as described above and kneaded with a paint shaker to prepare a resin solution containing each polymer fine particle.The resin solution was applied to a galvanized steel sheet and heat-treated at 140 ° C. for 20 minutes.

Using these coated steel sheets, irradiation with a fade odometer was performed for 50 hours, and a weather resistance test was conducted on the coating films. As a result, no discoloration or blister change was observed in any of the test coating films. It showed extremely good weather resistance.

As shown in Examples 72 to 74, by using the specific novel diguanamines according to the present invention, polymer fine particles excellent in heat resistance, solvent resistance, weather resistance and the like can be obtained and colored. It was found that polymer fine particles useful as a resinous colorant excellent in weather resistance and color can be obtained by coloring with an agent. Example 76 Combustibility was the same as in Example 1 except that the polymer fine particles obtained in the method of Example 73 were used in place of the diguanamines (1) obtained in the method of Reference Example 3 in Example 1. A test piece for measurement was prepared.

Using this test piece, a flammability test was conducted in the same manner as in Example 1. The result was level V-1, and the shape retention of the burned material was good, and the polypropylene resin composition was excellent. It had flame retardancy. Example 77 Combustibility was the same as in Example 2 except that the polymer fine particles obtained in the method of Example 72 were used in place of the diguanamines (1) obtained in the method of Reference Example 3 in Example 2. A test piece for measurement was prepared.

Using this test piece, a flammability test was conducted in the same manner as in Example 1. As a result, the result was level V-0, the shape retention of the burned material was good, and the resin of the present invention was difficult to handle. When the polymer particles according to the present invention and phosphorus were used together in the combusting method, the flame retardancy was further improved and it was excellent. Example 78 90 parts by weight of nylon 66 pellets, 7 parts by weight of polymer fine particles obtained by the method of Example 72 and 3 of isocyanuric acid
A test piece for measuring flammability was prepared in the same manner as in Example 58 except that the nylon resin composition consisting of parts by weight was used.

Using this test piece, a combustion test was conducted in the same manner as in Example 1. As a result, it was level V-0, the shape retention state of the combustion product was good, and excellent flame retardancy was exhibited. Further, in the resin flame-retardant method according to the present invention, it was found that when the polymer fine particles according to the present invention and isocyanuric acid are used in combination, the flame retardancy is further improved by a synergistic effect. Example 79 N obtained by the method of Example 42 in Example 61,
For flammability measurement in the same manner as in Example 61, except that the polymer fine particles obtained by the method of Example 72 are used instead of N ′, N ″, N ′ ″-tetrakis (2-hydroxyethyl) diguanamine. A test piece was prepared.

Using this test piece, a flammability test was conducted in the same manner as in Example 1. As a result, the level was V-0, the shape retention state of the burned material was good, and excellent flame retardancy was exhibited. It was Example 80 Polypropylene resin Mitsui Noblene BJH [manufactured by Mitsui Toatsu Chemicals, Inc.] 76 parts by weight, polymer fine particles 5.5 parts by weight obtained by the method of Example 72, ammonium polyphosphate "Exorit 422" (manufactured by Hoechst) ) 17 parts by weight,
A polypropylene resin composition containing 0.5 part by weight of pentaethylenehexamine and 1 part by weight of dilaurylthiopropionate was prepared in the same manner as in Example 1 to prepare a test piece for measuring flammability.

Using this test piece, in the same manner as in Example 1.
As a result of a flammability test, it was level V-0, and self-extinguishing
Is excellent and the shape retention of the combustion products is good
Flame retardant. Further, the flame retardancy of the resin according to the present invention
In the method for conversion into a polymer, the polymer fine particles according to the present invention, phosphorus
Synergistic effect can be obtained by using a compound and an amino group-containing compound in combination.
It was found that the flame retardancy was improved significantly. Example 81 Polyurethane resin composition containing diguanamine derivative and
Production of the foam: N obtained by the method of Example 40,
N ', N ", N'"-tetrakis (5-hydroxy-3
-Oxapentyl) diguanamine 30.0 parts by weight and fruit
Oxaalkyl group-containing jig obtained by the method of Example 47
To 70.0 parts by weight of the anamine derivative, water (the amount of water in the system)
0.1 parts by weight are added, and the mixture is heated and mixed at 40 ° C. for 60 minutes.
It was Next, 2,4-tolylene diisocyanate was added to NCO.
/ OH equivalent ratio 1.1, NCO / H ₂O equivalent ratio becomes 1.0
I got a fever when I added it like this, but it is 3
The mixture is heated to 120 ° C at a rate of 120 ° C.
The mixture was kept at 75 ° C. for 75 minutes, stirred and reacted. Then this is 8
Cooled to 0 ° C, 2,4-tolylene diisocyanate 3
Add 0 parts by weight and mix well, cool to room temperature, and press.
A repolymer was made.

Next, 100 parts by weight of this prepolymer, 0.5 parts by weight of silicone DC-199 (manufactured by Dow Chemical Co.), 1.2 parts by weight of N-ethylmorpholine, 0.2 parts by weight of triethylamine and 2.7 parts of water. The parts by weight were mixed, immediately poured into a mold, and foamed in the mold to prepare a polyurethane foam.

As a result of carrying out a combustion test using this polyurethane foam, it was found that it was self-extinguishing and that the shape retention of combustibles was good, and that the above-mentioned polyurethane resin composition containing a diguanamine derivative had excellent combustibility. there were.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C08G 18/50 NED 59/50 NJA C08K 3/02 KAB 5/5313 KCC C08L 23/00 KFB 31 / 08 LHN 61/26 LNL 63/00 NLB 67/06 MSD 71/12 LQN 75/04 NFY NGB 77/00 KKZ 79/08 LRB 101/00 C09D 5/18 PQR (31) Japanese Patent Application No. 5 −87499 (32) Priority Sun 5 (1993) April 14 (33) Priority claiming country Japan (JP) (72) Inventor Satoshi Furusawa 1900 Togo, Mobara-shi, Chiba Mitsui Toatsu Chemical Co., Ltd. (72 ) Hiroshi Ono, 1-6-6 Takasago, Takaishi-shi, Osaka Prefecture Mitsui Toatsu Chemical Co., Ltd. (72) Inventor, Kazuo Sugazaki 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd.

Claims (35)

[Claims] 1. Formula (1): [In the formula, the bonding position of the (4,6-diamino-1,3,5-triazin-2-yl) group represents the 2,5- or 2,6-position] and the formula (2) ] [In the formula, the bonding position of the (4,6-diamino-1,3,5-triazin-2-yl) group is 1,2-, 1,3- or 1,4-position] A flame-retardant method for a resin, comprising at least one selected from diguanamines in an amount of 3 to 50% by weight based on the resin. 2. Thermal stability of the resin, characterized in that at least one selected from the diguanamines represented by the formulas (1) and (2) is contained in an amount of 0.01 to 5% by weight based on the resin. Method. 3. At least one selected from the diguanamines represented by the formulas (1) and (2) contains at least one selected from a polyamide resin, a polyphenylene ether resin, a polyimide resin and a polyaramid resin. A method of compatibilizing a resin, characterized in that it is contained in two or more different resins. 4. Formula (7): [In the formula, the bonding position of the (1,3,5-triazin-2-yl) group represents 2,5- or 2,6-position, R ₁ ,
R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are species selected from the group consisting of hydrogen atoms and groups having 2 or more carbon atoms, and R ₁ , R ₂ , R ₃ , R ₄ , R ₅ ,
R ₆ , R ₇ and R ₈ may be the same or different and at least one of the group consisting of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ has a carbon number. A group having two or more groups] or the formula (8): [In the formula, the bonding position of the (1,3,5-triazin-2-yl) group represents the 1,2-, 1,3- or 1,4-position,
R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈
Has the same meaning as in formula (7)]. 5. R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ ,
R ₇ and R ₈ are a hydrogen atom and a HO—R ₉ — group (R
₉ diguanamine derivatives, according to claim 4 wherein a species selected from the group consisting of divalent radicals) having more than 2 carbon atoms. 6. The HO—R ₉ — group is a —hydroxyethyl group, a 2-hydroxypropyl group, a 1-hydroxymethylpropyl group, a 3-hydroxypropyl group, a 5-hydroxy-3-oxapentyl group and a 4-hydroxy group. The diguanamine derivative according to claim 5, which is a species selected from the group consisting of phenyl groups. 7. R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ ,
At least one of the group consisting of R ₇ and R ₈ has the formula (9) [In the formula, R ₁₀ is at least one selected from the group consisting of ethylene, trimethylene and tetramethylene which may have a substituent containing 2 to 22 carbon atoms, and n is 1 to 1
, An integer selected from 00, R ₉ has the same meaning as above] and the formula (10): A compound selected from the group consisting of groups represented by the formula: wherein R ₁₀ and n have the same meaning as in formula (9).
The described diguanamine derivative. 8. The diguanamine derivative according to claim 7, wherein R ₁₀ is at least one selected from ethylene and propylene. 9. At least one selected from the diguanamines represented by the formulas (1) and (2) and at least one selected from amines containing an amino group and having 2 or more carbon atoms. A process for producing a diguanamine derivative, which comprises reacting. 10. The amine is HO—R ₉ —NH ₂ (R
_{9. The} method for producing a diguanamine derivative according to claim 9, wherein 9 is a compound represented by the same meaning as above). 11. A compound represented by HO—R ₉ —NH ₂ is 2-aminoethanol, 1-amino-propane-
A species selected from the group consisting of 2-ol, 2-aminobutan-1-ol, 3-amino-propan-1-ol, 5-amino-3-oxapentan-1-ol and 4-aminophenol. 10. The method for producing a diguanamine derivative according to item 10. 12. The diguanamines according to claim 7, wherein at least one selected from the group consisting of diguanamine derivatives according to claim 4 and at least one selected from epoxides are subjected to an addition reaction. Method for producing derivative. 13. At least one selected from the group consisting of diguanamines represented by the formulas (1) and (2).
The method for producing a diguanamine derivative according to claim 7, wherein the species and at least one selected from epoxides are subjected to an addition reaction. 14. The method for producing a diguanamine derivative according to claim 13, wherein the epoxide is a species selected from ethylene oxide and propylene oxide. 15. A flame-retardant method for a resin, comprising at least 3 kinds by weight of the diguanamine derivatives represented by the formulas (7) and (8) selected from the resin, in an amount of 3 to 50% by weight. 16. A resin containing at least one diguanamine derivative represented by the formula (7) or (8) in an amount of 0.01 to 5% by weight based on the weight of the resin. Method. 17. At least one selected from the diguanamine derivatives represented by the formulas (7) and (8) is at least one selected from a polyamide resin, a polyphenylene ether resin, a polyimide resin and a polyaramid resin. A method of compatibilizing a resin, characterized in that the resin is incorporated into two or more different types of resins. 18. Obtained by reacting an amino compound containing at least one selected from diguanamines represented by the formulas (1) and (2) with at least one selected from aldehydes. Polymer fine particles obtained by emulsifying an amino resin with a protective colloid, adding a curing agent and polymerizing. 19. The method according to claim 1, which is colored with a coloring agent.
8. The polymer fine particles according to 8. 20. Obtained by reacting an amino compound containing at least one selected from diguanamines represented by the formulas (1) and (2) with at least one selected from aldehydes. Amino resin is emulsified using a protective colloid, and at least one kind selected from polymer fine particles characterized by being obtained by polymerizing by adding a curing agent is contained in an amount of 3 to 50% by weight based on the resin. Resin flame retardant method. 21. At least one selected from the group consisting of the diguanamine derivatives according to claim 5, 6, 7 and 8.
A polyurethane resin composition comprising a polyol component containing a seed and an organic polyisocyanate component. 22. The flame retardant method according to claim 1, wherein at least one selected from the group consisting of phosphorus and a phosphorus-containing compound is contained as a component. 23. The phosphorus is red phosphorus, phosphoric acid, polyphosphoric acid, phosphorous acid, phosphonic acid, phosphate, polyphosphate,
The flame-retardant method according to claim 22, which is a phosphite, a phosphonate, a phosphoric acid ester, a phosphorous acid ester, a phosphonic acid ester, a phosphine, or a sulfur-containing phosphorus compound. 24. The polyphosphate has the general formula (NH ₄ ) _{n + 2}
P _n O _{3n + 1} (wherein, n represents 5 greater than an integer) flame-retarding method according to claim 23, wherein the ammonium polyphosphate represented by. 25. Formula (5): (In the formula, R ₂ , R ₃ and R ₄ are a hydrogen atom and a carbon number 1
An alkyl group having 3 to 3, an oxyalkyl group having 1 to 3 carbon atoms, a phenyl group or a glycidyl group,
R ₂ , R ₃ and R ₄ may be the same or different, and isocyanuric acid represented by the formula (6) [Claim 1] wherein at least one selected from cyanuric acids represented by the formula: wherein R ₂ , R ₃ and R ₄ have the same meanings as in formula (5).
The flame retardant method according to any one of 15 and 20. 26. The flame-retardant method according to claim 1, which further comprises an amino group-containing compound. 27. The amino group-containing compound is represented by: The flame retardant according to claim 26, which is at least one selected from the group consisting of a compound containing at least one selected from the group represented by: dicyandiamide, guanidine, and a reaction product of these compounds with an aldehyde. Method. 28. The flame-retardant method according to any one of claims 1, 15 and 20, wherein phosphorus and an amino group-containing compound are contained as components. 29. The flame retardant method according to claim 1, wherein the resin is a thermoplastic resin. 30. The thermoplastic resin is at least one selected from the group consisting of polyolefin resins, polyamide resins, styrene resins, polyphenylene ether resins, saturated polyester resins, polycarbonate resins, polyacetal resins and acrylic resins. The flame retardant method described. 31. The flame-retardant method according to claim 1, wherein the resin is a thermosetting resin. 32. The flame-retardant method according to claim 31, wherein the thermosetting resin is at least one selected from the group consisting of unsaturated polyester resin, diallyl phthalate resin, epoxy resin and urethane resin. 33. The heat stabilization method according to claim 2, wherein the resin is at least one selected from the group consisting of a thermoplastic resin and a thermosetting resin. 34. The thermoplastic resin is at least one selected from the group consisting of polyphenylene ether resins, polyacetal resins, polyamide resins and polyolefin resins.
34. The heat stabilization method according to claim 33, which is a seed. 35. The heat stabilization method according to claim 34, wherein the polyolefin resin is at least one selected from the group consisting of a polyethylene resin, a polypropylene resin and an ethylene-propylene copolymer.