JPH07268127A - Flame-retardant thermosetting resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition having heat resistance, mechanical strength and flame retardant and free from elution and bleed out of a flame- retarded agent by blending a thermosetting resin with specific insoluble polyphosphoric acid ammonium particles as a flame-retarded agent. CONSTITUTION:This composition is obtained by blending (A) a thermosetting resin (preferably an epoxy resin or melamine resin) with (B) insoluble polyphosphoric acid ammonium particles obtained by crosslinking (i) the surface of a melamine-coated polyphosphoric acid ammonium particles with (ii) a compound having active hydrogen attributing to amino in melamine and a reactive functional group (e.g. a NCO-containing compound such as hexamethylene diisocyanate) at a ratio of 4-50wt.% based on the composition. Furthermore, the component B is obtained by mixing the component (i) with the component (ii) in a reactor equipped with a heating and kneading mechanism and then, reacting the component (i) with the component (ii) at 100-150 deg.C for 0.5-2hr. As the component (i), particles obtained by coating powdery polyphosphoric acid ammonium salt with 2-10wt.% of melamine are preferably used.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a flame-retardant thermosetting resin composition containing a non-halogen flame retardant. More specifically, melamine present in the coating layer of melamine-coated ammonium polyphosphate particles as a non-halogen flame retardant contains insoluble ammonium polyphosphate particles having a crosslinked structure, and has excellent water resistance and mechanical properties. Resin composition.

[0002]

2. Description of the Related Art Conventionally, thermosetting resins represented by epoxy resin, urethane resin, phenol resin, etc. have excellent heat resistance and mechanical strength. It is widely used in building materials, automobile parts materials, paints, adhesives, and synthetic resin impregnated paper. In order to make the thermosetting resin flame-retardant, the object has been generally achieved by blending a halogen-based organic compound or by halogenating a part of the polymer chain. However, the halogen-containing thermosetting resin composition has been regarded as a problem because corrosive halogen gas is generated during combustion. On the other hand, it has been proposed to add ammonium polyphosphate, which is a phosphorus compound, in order to make it flame-retardant without containing halogen. However, the ammonium polyphosphate is a compound which is very susceptible to hydrolysis due to its chemical structure, and there is a problem that the ammonium polyphosphate is eluted or bleed out from the resin composition under a high temperature and high humidity environment. Further, deterioration of mechanical properties due to the addition of an inorganic compound such as ammonium polyphosphate is also regarded as a problem. Therefore, a halogen-free thermosetting resin composition that does not generate halogen gas at the time of combustion, has no leaching of blending components from the resin composition, does not bleed out, and suppresses deterioration of mechanical properties of the resin has begun to be demanded. There is.

In order to meet these demands, a metal hydrate has recently been used as an inorganic flame retardant which can suppress the combustion of the resin by decomposing and dehydrating by an endothermic reaction at the combustion temperature of the resin. A thermosetting resin composition has been proposed (JP-A-3-190965). However, since the effect of imparting flame retardancy is extremely weak in the metal hydrate, the target flame retardancy cannot be achieved unless a large amount of the metal hydrate is blended. Therefore, there is a problem that various properties such as deterioration of molding processability and mechanical strength of the obtained molded product are deteriorated. Moreover, JP-A-1-10
Japanese Patent No. 8261 discloses a flame-retardant polymer composition containing ammonium polyphosphate coated with a synthetic resin, aluminum hydroxide and an organic nitrogen compound.
By using ammonium polyphosphate coated with a synthetic resin, it becomes difficult to dissolve ammonium polyphosphate in water, but the compatibility with the thermosetting resin decreases as in the case of adding a metal hydrate, When the composition is used for molding, there is a problem that the mechanical strength of the obtained molded article is lowered.

[0004]

DISCLOSURE OF THE INVENTION The inventors of the present invention did not generate halogen gas, did not elute or bleed out a flame retardant compounded therein, and did not reduce the mechanical properties of the resin. Earnestly conducted to obtain a thermosetting thermosetting resin composition. As a result, the melamine-coated ammonium polyphosphate particles surface obtained by adding and / or adhering melamine to the powdery ammonium polyphosphate particles surface by sublimation instead of the conventional ammonium polyphosphate particles are treated with melamine molecules existing in the particle surface coating layer. It was found that the above-mentioned problems can be solved by using insoluble ammonium polyphosphate particles obtained by crosslinking reaction with a compound having a functional group capable of reacting with active hydrogen belonging to the amino group, and based on this finding, the present invention was completed. did. As is clear from the above description, the object of the present invention can be suitably used in the fields of electric / electronic component materials, civil engineering building materials, automobile component materials, etc. as coating materials, adhesives, synthetic resin-impregnated paper, etc. It has heat resistance, mechanical strength and flame retardant properties, and elution / blurring of flame retardant
It is intended to provide a thermosetting resin composition having no deadout.

[0005]

The present invention has the following constitution. 1) Composition of insoluble ammonium polyphosphate particles obtained by crosslinking a thermosetting resin with a compound having a functional group capable of reacting with active hydrogens belonging to amino groups in melamine molecules on the surface of melamine-coated ammonium polyphosphate particles A flame-retardant thermosetting resin composition containing 4 to 50% by weight of the composition. 2) The thermosetting resin is a glycidyl group, an isocyanate group,
The flame-retardant thermosetting resin composition according to item 1, which is a thermosetting resin having a methylol group or an aldehyde group. 3) The above-mentioned item 1 wherein the compound having a functional group capable of reacting with active hydrogen belonging to the amino group in the melamine molecule is a compound having an isocyanate group, a glycidyl group, a carboxyl group, a methylol group or an aldehyde group. The flame-retardant thermosetting resin composition described. 4) The flame-retardant thermosetting resin composition according to the above 1, wherein the compound having a functional group capable of reacting with active hydrogen attributed to an amino group in a melamine molecule is a compound having two or more functional groups. 5) The flame-retardant thermosetting property according to claim 1, wherein the melamine-coated ammonium polyphosphate is a melamine-coated ammonium polyphosphate obtained by coating 0.5 to 20% by weight of melamine with respect to powdery ammonium polyphosphate. Resin composition 6) Thermosetting resin is epoxy resin, hard urethane resin,
The flame-retardant thermosetting resin composition according to item 1, which is a soft urethane resin, a phenol resin, a melamine resin, a guanamine resin, a xylene resin or a urea resin.

The insoluble ammonium polyphosphate particles used in the present invention are an isocyanate group capable of reacting the melamine molecule present in the melamine coating layer of the melamine-coated ammonium polyphosphate with the active hydrogen attributed to the amino group in the melamine molecule, Ammonium polyphosphate having a structure cross-linked with a compound having a functional group such as a glycidyl group or an aldehyde group. Such insoluble ammonium polyphosphate particles can be produced, for example, by coating a reactor equipped with a heating stirring or heating kneading mechanism with melamine. A compound having a functional group capable of reacting with the ammonium polyphosphate particles and the active hydrogen belonging to the amino group in the melamine molecule, for example, an aqueous formaldehyde solution is charged and mixed. Temperature at which a crosslinked structure between active hydrogen is easily formed 80 to 200 ° C., preferably 100
It is possible to obtain insoluble ammonium polyphosphate particles having a crosslinked structure formed in the coating layer of the melamine-coated ammonium polyphosphate particles by heating up to 150 ° C. and reacting for 0.5 to 2 hours. This cross-linking reaction may be either a non-solvent system or a solvent system, and the solvent system may be water, an organic solvent, or a mixed solvent composed of two or more of these solvents. The functional group of the compound used for the crosslinking reaction is 0.5 to 6 times equivalent, preferably 1 to 2 times equivalent to the amino group in the melamine molecule of the melamine-coated ammonium polyphosphate. If the amount is less than 0.5 times the equivalent, crosslinking between melamine is not sufficiently performed, and the obtained ammonium polyphosphate particles are easily hydrolyzed. On the other hand, if the amount is more than 6 times equivalent, unreacted compound remains, which is not preferable. The functional group that reacts with the active hydrogen attributed to the amino group in the melamine molecule is an isocyanate group, a glycidyl group, a carboxyl group, a methylol group or an aldehyde group, and the number of the functional groups is 1 or 2 or more. is there. Examples of the compound having the functional group include compounds having an isocyanate group such as hexamethylene diisocyanate and toluylene diisocyanate, various epoxy resins represented by bisphenol A and phenol novolac, and oxalic acid. Compounds having a carboxyl group such as malonic acid and phthalic acid, compounds having a methyl group such as trimethylolpropane and trimethylolethane, formaldehyde, glyoxal,
Examples thereof include compounds having an aldehyde group such as malonic aldehyde.

Further, the melamine-coated ammonium polyphosphate particles are those in which melamine is added and / or attached to the surface of ammonium polyphosphate particles, and such melamine-coated ammonium polyphosphate particles can be obtained by the following method. That is, the ammonium polyphosphate particles are put into a heating and kneading device such as a heated kneader,
The temperature at which the ammonium polyphosphate particles do not melt and the ammonia in the ammonium polyphosphate easily desorbs, that is, 300 ° C. or less, preferably 200
Part of the ammonia that is originally present in stoichiometric amount in ammonium polyphosphate by heating at a temperature of ~ 300 ° C for 0.5 to 5 hours (5 to 10% by weight based on stoichiometric amount of ammonia) In the known production process of ammonium polyphosphate or ammonium polyphosphate in the state of depleted ammonia, the amount of bound ammonium is less than the stoichiometric amount of ammonium polyphosphate. Ammonium polyphosphate) and then in the same equipment at a temperature at which ammonia-deficient ammonium polyphosphate particles do not melt and at which melamine can sublime 250-30
Melamine is added by heating to a temperature of 0 ° C., and the melamine is added and / or attached to the hydroxyl group which has become an acid by removing ammonia on the surface of the ammonium-deficient ammonium polyphosphate particles. Here, the addition means a state in which melamine is chemically bonded to a proton of an oxygen-proton bond derived from ammonium polyphosphate, and the added melamine is stable even when heated and does not desorb again.
Further, the adhesion means a state in which melamine is adsorbed on the surface of the ammonium polyphosphate particles, and the melamine adsorbed on the surface of the ammonium polyphosphate particles by continued heating repeats sublimation and adsorption and is chemically combined with oxygen-proton-bonded protons. Join together. The proportion of melamine added at this time is 0.5 to 20% by weight, preferably 2 to 10% by weight, based on the ammonium polyphosphate, and the total amount of added melamine is added and / or attached to the ammonium polyphosphate particles. , Melamine-coated ammonium polyphosphate particles are obtained.

As the ammonium polyphosphate which is a raw material of the above-mentioned melamine-coated ammonium polyphosphate, a commercially available product may be used, and as the commercially available product, Sumisafe-P (trademark, manufactured by Sumitomo Chemical Co., Ltd.) and Exolite- 422
(Trademark, manufactured by Hoechst), Exorit-700 (trademark, manufactured by Hoechst), Foscheck P / 40 (trademark,
(Manufactured by Monsanto Co., Ltd.) and the like, and II type ammonium polyphosphate fine particles can also be used. The type II ammonium polyphosphate fine particles can be obtained, for example, by the following method. That is, equimolar amounts of diammonium phosphate and phosphorus pentoxide were mixed, heated and stirred at a temperature of 290 to 300 ° C., and then 0.5 times mol of urea was dissolved in diammonium phosphate to give a concentration of 77% by weight. It is obtained by a method in which a urea solution is added while spraying, and subsequently, the mixture is baked at a temperature of 250 to 270 ° C. for several hours in an ammonia atmosphere.
The melamine used may be a commercially available melamine monomer.

The proportion of the insoluble ammonium polyphosphate particles used in the present invention is 4 to 50% by weight, preferably 10 to 45% by weight based on the weight of the composition. If the blending ratio is 3% by weight or less, sufficient flame retardancy cannot be obtained, and if the blending ratio exceeds 60% by weight, the mechanical properties are more deteriorated than the flame retardancy obtained and the product cannot be used.

The thermosetting resin suitable for use in the present invention is a thermosetting resin having a glycidyl group, an isocyanate group, a methylol group or an aldehyde group, specifically, an epoxy resin or a hard urethane resin. , Soft urethane resin, phenol resin, melamine resin, guanamine resin, xylene resin and urea resin. Further, as the thermosetting resin other than the above, unsaturated polyester resin and diallyl phthalate resin can also be preferably used as the thermosetting resin used in the present invention.

The insoluble ammonium polyphosphate particles used in the present invention are melamine molecules present in the melamine coating layer of melamine-coated ammonium polyphosphate, and an isocyanate group capable of reacting with active hydrogen belonging to an amino group in the melamine molecule. , Ammonium polyphosphate particles in which a crosslinked structure is formed between melamine molecules on the same particle by reacting with a compound having a functional group such as a glycidyl group or an aldehyde group. Therefore, active hydrogen in the melamine molecules remains by controlling the degree of crosslinking between melamine molecules, such active hydrogen is a glycidyl group derived from the thermosetting resin at the stage where the thermosetting resin is cured,
By reacting with an isocyanate group, a methylol group or an aldehyde group, a chemical bond is formed between the insoluble ammonium polyphosphate particles and the thermosetting resin. Therefore, the compatibility between the insoluble ammonium polyphosphate particles and the thermosetting resin is improved, and deterioration of mechanical properties due to the incorporation of the insoluble ammonium polyphosphate particles can be suppressed.

The thermosetting resin composition of the present invention contains other additives which are usually added to the thermosetting resin as required, for example, curing agents, curing accelerators, other flame retardants, flame retarding aids, and colorings. Agents, surfactants, heat stabilizers, plasticizers, light stabilizers, solvents and the like can be added.

【Example】

In order to specifically explain the present invention, examples and comparative examples are shown below, but the present invention is not limited thereto. The evaluations carried out in Examples and Comparative Examples were based on the following methods.

1) Flame Retardancy Evaluation UL Subject 94
(Underwriter Laboratories, Inc., Inc.) "Combustion test of plastic materials for equipment parts"
Complies with the vertical combustion test specified in. Thickness of test piece 1.6
mm (1/16 inch) 2) Oxygen Index (O.I.) Japanese Industrial Standard JIS K7
201 (combustion test method for polymer materials by oxygen index method)
Complies with. 3) Hot water immersion test evaluation Test piece (length 100 mm x width 1
(00 mm × thickness 2 mm) was molded by hot pressing, and the surface electric resistance value of the test piece was measured by a vibration capacitance type micro-current / electrometer (Takeda Riken Industry Co., Ltd.). Then, the test piece is heated to 95 ° C.
The sample was soaked in hot water for 2 hours and then taken out, and water droplets adhering to the test piece were wiped off with a wiper paper, and the surface electric resistance value of the test piece was measured. If the surface electric resistance value was significantly reduced after hot water immersion, the bleeding resistance was poor. 4) Tensile strength and tensile elongation Japanese Industrial Standard JIS K71
13 (plastic tensile test method). However, the shape of the test piece is 100 mm in length, 20 mm in width, and 2 in thickness.
mm. 5) Bending strength It conformed to Japanese Industrial Standard JIS K7203 (bending test method for hard plastics). However, the shape of the test piece was 100 mm in length, 25 mm in width, and 2 mm in thickness.

Preparation of Melamine-Coated Ammonium Polyphosphate Particles A kneader preheated to 280 ° C. had an average particle size of 6.4 μm.
2000 g of II type ammonium polyphosphate fine particles of m of m was introduced, and the mixture was heated and mixed in a nitrogen gas atmosphere or an inert gas atmosphere for 3 hours to desorb ammonia. 200 g of melamine is added to powdery ammonium polyphosphate in a state where the amount of ammonia is less than the stoichiometric amount. At this point, the upper lid of the kneader is closed, and heating and mixing is performed at 280 ° C. for 4 hours in this state. The hot mixing was done without changing the morphology of the ammonium polyphosphate. In this way, the melamine-coated ammonium polyphosphate particles are
g was obtained. As a result of observation with an electron microscope, it was confirmed that the particle surfaces of the type II ammonium polyphosphate microparticles were uniformly coated with melamine.

Further, the above-mentioned type II ammonium polyphosphate was obtained by the following method. That is, a mixture of 660 g (5 moles) of diammonium phosphate and 710 g (5 moles) of phosphorus pentoxide was added to 5 liters heated to 290 to 300 ° C. in a table kneader while maintaining a nitrogen gas atmosphere, and heated and stirred. After the lapse of minutes, 195 g of 76.9% urea solution at 80 ° C. was added by spraying. Subsequently, the product was baked in an ammonia atmosphere at 250 to 270 ° C. for 2.5 hours to obtain 1460 g of powdery ammonium polyphosphate. This ammonium polyphosphate had a mixture of single particles and a part of agglomerates, and was coarsely crushed in an ammonia atmosphere with a crusher (AP-B type manufactured by Hosokawa Micron) to separate the single particles. The crystal form by X-ray diffraction was type II, and the average particle size of the particles was 6.4 μm.

Reference Example 1 (Production of Insoluble Ammonium Polyphosphate) Melamine-coated ammonium polyphosphate particles 1 in a 5 liter internal volume kneader equipped with a heat kneading mechanism and a degassing mechanism.
000 g and 120 g of 37% formalin were added and mixed at room temperature for 30 minutes, then heated to 100 ° C. and mixed for 1 hour. In this way, about 50% of the active hydrogens attributed to the amino groups of melamine present on the surface of the melamine-coated ammonium polyphosphate particles are crosslinked with aldehyde groups to form insoluble ammonium polyphosphate particles (hereinafter referred to as insoluble ammonium polyphosphate (A)). Is said to be 1
005 g was obtained.

Reference Example 2 (Production of Insoluble Ammonium Polyphosphate) Melamine-coated ammonium polyphosphate 100 was added to a flask having an internal volume of 5 liters equipped with a heating and stirring mechanism and a reflux mechanism.
Add 0 g and 900 g of toluene. Next, 132 g of hexamethylene diisocyanate and 2.6 g of Nikka octic tin catalyst are added and mixed at room temperature. Next, the temperature was raised to the reflux temperature, the mixture was heated and mixed for 2 hours, cooled, filtered, and dried in a dryer at 100 ° C. for 1 hour. In this way, about 50% of the active hydrogens attributed to the amino groups of melamine present on the surface of the melamine-coated ammonium polyphosphate particles are crosslinked by insoluble ammonium polyphosphate particles (hereinafter referred to as insoluble ammonium polyphosphate (B)). Was obtained in an amount of 1080 g.

Example 1 20 parts by weight of the insoluble ammonium polyphosphate (A) obtained in Reference Example 1 and a bisphenol A type epoxy resin Epicoat 828 (trademark, manufactured by Yuka Shell Epoxy Co., Ltd.) 71.2 as an epoxy resin were used. 7. Part by weight was well dispersed and mixed in advance, and then diethylenetriamine was used as a curing agent.
Add 8 parts by weight and mix further. After deaeration, the mixture was heated at 30 ° C. for 60 minutes and then hot press molded at 100 ° C. for 15 minutes to prepare a flat plate. The obtained flat plate was cut out to prepare a test piece having a predetermined shape (hereinafter referred to as a molded product A). Using the obtained test piece, flame retardancy evaluation, oxygen index measurement, hot water immersion test evaluation, tensile strength, and bending strength measurement were performed. The evaluation results are shown in Table 1.

Example 2 20 parts by weight of the insoluble ammonium polyphosphate (B) obtained in Reference Example 2 and 71. bisphenol A type epoxy resin Epicoat 828 (trademark, manufactured by Yuka Shell Epoxy Co., Ltd.) as an epoxy resin were used. Predetermined test pieces were produced in accordance with Example 1 except that 2 parts by weight and 8.8 parts by weight of diethylenetriamine as a curing agent were used (hereinafter referred to as molded article B), and the obtained test pieces Flame retardancy evaluation, oxygen index measurement, hot water immersion test evaluation, tensile strength, and bending strength measurement. The evaluation results are shown in Table 1.
It was shown to.

Example 3 51 parts by weight of DN-980S (trade name, manufactured by Dainippon Ink and Chemicals, Inc.) as polyisocyanate and D-220 (trade name, Dainippon Ink and Chemicals (trade name) of polyester polyol) (Manufactured by K.K.) and 13 parts by weight of the insoluble ammonium polyphosphate (A) obtained in Reference Example 1 were well dispersed and mixed, and further deaerated, and then the mixture was mixed with 15
Hot press molding was performed at 0 ° C. for 30 minutes to obtain a flat plate. The obtained flat plate is cut out to prepare a test piece having a predetermined shape (hereinafter referred to as a molded product C), and the obtained test piece is used for flame retardancy evaluation, oxygen index measurement, hot water immersion test evaluation, and tensile strength. The strength and tensile elongation were measured. The evaluation results are shown in Table 2.
It was shown to.

Example 4 A flat plate was obtained in the same manner as in Example 3 except that the insoluble ammonium polyphosphate (A) was changed to 20 parts by weight, and then each predetermined test piece was prepared using the flat plate (hereinafter, referred to as "test piece"). Molded product D) and the obtained test piece were used for flame retardancy evaluation, oxygen index measurement, hot water immersion test evaluation, tensile strength, and tensile elongation measurement. The evaluation results are shown in Table 2.

Example 5 13 parts by weight of the insoluble ammonium polyphosphate (A) obtained in Reference Example 1 was mixed with 87 parts by weight of a melamine resin for molding material (containing cellulose powder) (manufactured by Fuji Kasei Co., Ltd.). 16
Hot press molding was performed at 5 ° C. for 4 minutes to obtain a flat plate. The obtained flat plate is cut out to prepare a test piece having a predetermined shape (hereinafter referred to as a molded product E), and the obtained test piece is used for flame retardancy evaluation, oxygen index measurement, hot water immersion test evaluation, Tensile strength,
And the bending strength was measured. The evaluation results are shown in Table 3.

Example 6 90 parts by weight of a phenol resin for molding material (containing cellulose powder) (manufactured by Fudo Co., Ltd.) and 10 parts by weight of the insoluble ammonium polyphosphate (A) obtained in Reference Example 1 Mixed 17
A flat plate was obtained by hot press molding at 0 ° C. for 4 minutes. The obtained flat plate is cut out to prepare a test piece having a predetermined shape (hereinafter referred to as a molded product F), and the obtained test piece is used for flame retardancy evaluation, oxygen index measurement, hot water immersion test evaluation, and tensile strength. The strength and bending strength were measured. The evaluation results are shown in Table 3.

Example 7 94 parts by weight of a phenol resin (containing cellulose powder) for molding material (manufactured by Fudo Co.) and 6 parts by weight of the insoluble ammonium polyphosphate (B) obtained in Reference Example 2 Mix 1
Hot pressing was performed at 70 ° C. for 4 minutes to obtain a flat plate. Various test pieces having a predetermined shape were prepared using the obtained flat plate (hereinafter referred to as a molded product G). Using the obtained test piece, flame retardancy evaluation, oxygen index measurement, hot water immersion test evaluation, tensile strength, and bending strength measurement were performed. The evaluation results are shown in Table 3.

Comparative Example 1 Bisphenol A type epoxy resin Epicoat 828 (trademark, manufactured by Yuka Shell Epoxy Co., Ltd.) as an epoxy resin
89 parts by weight and 11 parts by weight of diethylenetriamine as a curing agent are mixed. After degassing, the mixture was stirred at 30 ° C for 6
After heating for 0 minutes, hot press molding was performed at 100 ° C. for 15 minutes to obtain a flat plate. The obtained flat plate is cut out to prepare a test piece having a predetermined shape (hereinafter referred to as a molded article H), and the obtained test piece is used for flame retardancy evaluation, oxygen index measurement, hot water immersion test evaluation, and tensile strength. The strength and bending strength were measured. The evaluation results are shown in Table 1.

Comparative Example 2 A flat plate was obtained in the same manner as in Example 1 except that the insoluble ammonium polyphosphate (A) was replaced with 20 parts by weight of II type ammonium polyphosphate fine particles. A test piece was prepared (hereinafter referred to as a molded article I), and the obtained test piece was used for flame retardancy evaluation, oxygen index measurement, hot water immersion test evaluation, tensile strength, and bending strength measurement. . The evaluation results are shown in Table 1.

Comparative Example 3 A flat plate was obtained in the same manner as in Example 1 except that the insoluble ammonium polyphosphate (A) was replaced with 20 parts by weight of Exolite-462 (trade name of Hoechst), and the obtained flat plate was used. Each predetermined test piece was prepared (hereinafter referred to as "molded product J"), and the obtained test piece was used for flame retardancy evaluation, oxygen index measurement, hot water immersion test evaluation, tensile strength, and bending strength measurement. I went. The evaluation results are shown in Table 1.

Comparative Example 4 A flat plate according to Example 1 except that the insoluble ammonium polyphosphate (A) was replaced with 80 parts by weight of magnesium hydroxide ((Kisuma 5A) (trademark, manufactured by Kyowa Chemical Industry Co., Ltd.)). And using the obtained flat plate to produce each predetermined test piece (hereinafter referred to as a molded product K), using the obtained test piece, flame retardancy evaluation, oxygen index measurement, hot water immersion test Evaluation, tensile strength, and bending strength were measured. The evaluation results are shown in Table 1.

Comparative Example 5 51 parts by weight of DN-980S (trade name, manufactured by Dainippon Ink and Chemicals, Inc.) as polyisocyanate and D-220 (trade name, manufactured by Dainippon Ink and Chemicals, Inc.) as polyester polyol ) Was mixed and deaerated, and then the mixture was hot-press molded at 150 ° C. for 30 minutes to obtain a flat plate. The obtained flat plate is cut out to prepare a test piece having a predetermined shape (hereinafter referred to as a molded product L), and the obtained test piece is used for flame retardancy evaluation, oxygen index measurement, hot water immersion test evaluation, and tensile strength. The strength and tensile elongation were measured. The evaluation results are shown in Table 2.

Comparative Example 6 A flat plate was obtained in the same manner as in Example 3 except that the insoluble ammonium polyphosphate (A) was replaced with 20 parts by weight of II type ammonium polyphosphate fine particles. A test piece is prepared (hereinafter referred to as a molded product M), and the obtained test piece is used for flame retardancy evaluation, oxygen index measurement, hot water immersion test evaluation, tensile strength, and tensile elongation measurement. It was The evaluation results are shown in Table 2.

Comparative Example 7 Instead of insoluble ammonium polyphosphate, magnesium hydroxide ((Kisuma 5A) (trademark of Kyowa Chemical Industry Co., Ltd.) was used.
Manufactured)) A flat plate was obtained according to Example 3 except that the amount was 100 parts by weight, and each predetermined test piece was produced using the obtained flat plate (hereinafter referred to as "molded product N"). Using the piece, flame retardancy evaluation, oxygen index measurement, hot water immersion test evaluation, tensile strength, and tensile elongation were measured. The evaluation results are shown in Table 2.

Comparative Example 8 A melamine resin for molding material (containing cellulose powder) (manufactured by Fuji Kasei Co., Ltd.) was hot press molded at 165 ° C. for 4 minutes to obtain a flat plate. The obtained flat plate is cut out to prepare a test piece having a predetermined shape (hereinafter referred to as a molded product P), and the obtained test piece is used to evaluate flame retardancy, measure oxygen index, evaluate hot water immersion test, and pull. The strength and bending strength were measured. The evaluation results are shown in Table 3.

Comparative Example 9 A flat plate was obtained in the same manner as in Example 5 except that 13 parts by weight of Sumicef P (trade name, manufactured by Sumitomo Chemical Co., Ltd.) was used instead of the melamine-coated ammonium polyphosphate particles, and the obtained flat plate was obtained. Each test piece was prepared in a predetermined manner (hereinafter referred to as a molded product Q), and the obtained test piece was used for flame retardancy evaluation, oxygen index measurement, hot water immersion test evaluation, tensile strength, and bending. The strength was measured. The evaluation results are shown in Table 3.

Comparative Example 10 A phenol resin for molding material (containing cellulose powder) (Food Co., Ltd.) was hot press molded at 170 ° C. for 4 minutes to obtain a flat plate. The obtained flat plate is cut out to prepare a test piece having a predetermined shape (hereinafter referred to as a molded product R), and the obtained test piece is used for flame retardancy evaluation, oxygen index measurement, hot water immersion test evaluation, and tensile strength. The strength and bending strength were measured. The evaluation results are shown in Table 3.

Comparative Example 11 A flat plate was obtained in the same manner as in Example 6 except that 10 parts by weight of Sumicef P (trade name, manufactured by Sumitomo Chemical Co., Ltd.) was used in place of the melamine-coated ammonium polyphosphate particles, and a flat plate was obtained. Each test piece was prepared in a predetermined manner using a flat plate.
That is, the obtained test pieces were used to evaluate flame retardancy, measure oxygen index, evaluate hot water immersion test, and measure tensile strength and bending strength. The evaluation results are shown in Table 3.

Since the epoxy resin composition of Comparative Example 1 does not contain ammonium polyphosphate, flame retardancy cannot be obtained, and the epoxy resin composition of Comparative Example 2 contains II in place of insoluble ammonium polyphosphate. Type ammonium polyphosphate fine particles are used, so the surface resistance value after the test is greatly reduced in the hot water immersion test, and ammonium polyphosphate, which is a flame retardant, elutes and bleeds out, resulting in poor bleed resistance. Is. The epoxy resin composition of Comparative Example 3 is flame-retardant, shows no decrease in surface electric resistance value in a hot water immersion test, and has good bleed resistance, but has a large decrease in mechanical properties. Since the epoxy resin composition of Comparative Example 4 uses magnesium hydroxide (Kisuma 5A) as a flame retardant, it cannot obtain flame retardancy even if it is blended at 50% by weight.
The epoxy resin compositions of Examples 1 and 2 of the present invention using insoluble ammonium polyphosphate have high flame retardancy, good bleed resistance, and a thermal property that suppresses deterioration of mechanical properties. It can be seen that it is a cured resin composition. The same applies to the thermosetting resin compositions of Comparative Examples 5 to 11 and Examples 3 to 7.

[0038]

The flame-retardant thermosetting resin composition of the present invention comprises
By blending the insoluble ammonium polyphosphate particles, a halogen gas is not generated, and the blended insoluble ammonium polyphosphate does not elute or bleed out, and the resin composition can suppress deterioration of mechanical properties. Therefore, as molding materials, such as electrical and electronic parts materials, civil engineering building materials, automotive parts materials, paints, adhesives,
It can be suitably used for a wide range of applications such as synthetic resin impregnated paper.

[0039]

[Table 1]

[0040]

[Table 2]

[0041]

[Table 3]

Claims (6)

[Claims] 1. Insoluble polyphosphoric acid ammonium particles obtained by crosslinking a surface of a melamine-coated ammonium polyphosphate particle with a thermosetting resin with a compound having a functional group capable of reacting with active hydrogen belonging to an amino group in a melamine molecule. A flame-retardant thermosetting resin composition containing 4 to 50% by weight of the composition. 2. The flame-retardant thermosetting resin composition according to claim 1, wherein the thermosetting resin is a thermosetting resin having a glycidyl group, an isocyanate group, a methylol group or an aldehyde group. 3. A compound having a functional group capable of reacting with active hydrogen belonging to an amino group in a melamine molecule is an isocyanate.
The flame-retardant thermosetting resin composition according to claim 1, which is a compound having a tol group, a glycidyl group, a carboxyl group, a methylol group or an aldehyde group. 4. The flame-retardant thermosetting resin composition according to claim 1, wherein the compound having a functional group capable of reacting with active hydrogen belonging to an amino group in a melamine molecule is a compound having two or more functional groups. object. 5. The melamine-coated ammonium polyphosphate particles are contained in an amount of 0.5 to 20 with respect to the powdery ammonium polyphosphate particles.
The flame-retardant thermosetting resin composition according to claim 1, which is a melamine-coated ammonium polyphosphate particle coated with wt% of melamine. 6. The flame-retardant thermosetting resin composition according to claim 1, wherein the thermosetting resin is an epoxy resin, a hard urethane resin, a soft urethane resin, a phenol resin, a melamine resin, a guanamine resin, a xylene resin or a urea resin. object.