JPS5919586B2 - Flame retardant synthetic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a flame-retardant synthetic resin composition, and more specifically to a flame-retardant synthetic resin composition containing halogenated diphenyl sulfides.

Polyolefin resin, polystyrene resin, ABS resin,
Epoxy resin, polyester resin, acrylic resin, polycarbonate resin, polyamide resin, phenolic resin,
Polyurethane resins, polyacetal resins, etc. have various properties and are used in various fields.

For example, vinyl resins such as polyolefin resin, polyvinyl acetate, its saponified products, polyacrylic acid ester, polyacrylonitrile, polystyrene, etc. These synthetic resins are strong, lightweight, water resistant, chemical resistant, and electrically insulating. Because it has excellent properties and is easy to mold, it is widely used as building materials, materials for electrical equipment, household goods, and sub-materials thereof. but,
These resins all have the disadvantage of being easily combustible, although there are differences depending on the resin, which limits the expansion of their uses.

Many methods have been proposed to make these synthetic resins flame retardant, but none are perfect yet.

For example, in the case of polyolefin resins, the most widely used method is to add a halogen-containing compound and antimony oxide. However, in order to make polyolefin resin sufficiently flame retardant with these conventional general flame retardants, it is necessary to mix an extremely large amount of flame retardant with polyolefin resin, and as a result, the composition of polyolefin resin It has the disadvantage that physical properties such as strength, whiteness, gloss, and electrical insulation properties are reduced. Similarly, in the case of vinyl resins, it is necessary to mix extremely large amounts of flame retardants in order to make them sufficiently flame retardant, and as a result, the physical properties of the resin, such as strength, whiteness, gloss, etc. It has the disadvantage of decreasing electrical insulation properties. An object of the present invention is to provide a flame-retardant synthetic resin composition that has extremely excellent flame retardancy.

In particular, it is an object of the present invention to provide a flame-retardant synthetic resin composition that retains as much of the properties of a synthetic resin as possible by using a flame retardant that provides excellent flame retardancy even when added in a relatively small amount. The composition of the present invention preferably contains at least 0.1 parts by weight of combustible synthetic resin.
The composition contains at least one halogenated diphenyl sulfide in an amount by weight, preferably from 0.1 to 40 parts by weight, more preferably from 0.5 to 25 parts by weight. The halogenated di-2enyl sulfides used in the present invention have the following general formula [where X is a halogen atom, A is a hydrogen atom, or a hydrocarbon group having 1 to 6 carbon atoms or a halogenated hydrocarbon group, They may be the same or different.

In addition, m1 and M2 are each O or an integer from 1 to 5 as n1
, N2 each indicate 0 or 1. However, m1, M2
Both n1 and N2 are never 0, and the sum of m1 and n1 and M2 and N2 is never more than 5. ] This is a compound represented by Among these compounds, compounds having two or more halogen atoms, particularly bromine atoms, per phenyl group are particularly effective.

Examples of some of these compounds include not only those with symmetric structures but also those with asymmetric structures, such as dibromodiphenyl sulfide, dichlorodiphenyl sulfide, chloropromodiphenyl sulfide, and tetrapromodiphenyl sulfide. Phenyl sulfide, tetrachlorodiphenyl sulfide, dichlorodibromodiphenyl sulfide, monochlorotripromodiphenyl sulfide, hexapromodiphenyl sulfide, hexachlorodiphenyl sulfide, trichlorotripromodiphenyl sulfide , octapromodiphenyl sulfide, octachlorodiphenyl sulfide, tetrachlorotetrapromodiphenyl sulfide,
Various compounds in which at least one hydrogen atom of a phenyl group is substituted with an 0A group, such as nonapromodiphenyl sulfide, nonachlorodiphenyl sulfide, and tetrachlorotetrapromodiphenyl sulfide, Some of them are shown below for 3,5,3',5'-tetrahalogenodiphenyl sulfide derivatives.
These halogenated diphenyl sulfides are simply 1
Only one type of compound may be used, or two or more types may be used in combination.

These halogenated diphenyl sulfides have excellent compatibility with flammable synthetic resins, and can impart excellent flame retardancy even when added in small amounts. Various combustible synthetic resins can be used in the composition of the present invention.

First of all, the formula that can be used is the general formula [In the above formula, R1 represents a hydrogen atom or an organic group consisting only of carbon atoms with 6 or less carbon atoms and hydrogen atoms, and R2 represents a carbon atom with 6 or less carbon atoms and a hydrogen atom. An organic group consisting of hydrogen atoms, chlorine atoms,
Bromine atom, fluorine atom, -COOH group, -COOCH3 group, -CnnC. ．． TT one-Cnnc6H one-C
nOr. H. , group, -CN group, -COCH3 group, -NC
O group, -00CCH3 group, -0H group, -0CH3 group or -CHO group, R3 is hydrogen atom, chlorine atom, bromine atom, fluorine atom, -CH3 group, -COOCH3 group, -C
It represents an OOC6Hll group, -CN group or -C6H5 group.

], a copolymer obtained from two or more monomers, or a mixture thereof.

Some examples include polyethylene, polypropylene, polybutene-1, polybenzene-1, ethylene vinyl acetate copolymer, saponified ethylene vinyl acetate copolymer, polyacrylonitrile, polyvinyl chloride, polystyrene, polyvinyl acetate. , polyvinyl alcohol, polymethyl methacrylate, ABS resin, etc. Other flammable synthetic resins used in the present invention include unsaturated polyester resins mainly made from maleic anhydride and ethylene glycol, polyester resins such as polyethylene terephthalate, polybutylene terephthalate, 6-, 6-
・6-, 6・10-11-12-Polyamide resin such as nylon, polycarbonate resin, epoxy resin,
Examples include phenolic resin and polyurethane resin.

These synthetic resins may be used alone or in combination of two or more. Furthermore, it may contain stabilizers, colorants, weathering agents, ultraviolet absorbers, matting agents, antistatic agents, fillers, and other additives. In addition to the combustible synthetic resin and the halogenated diphenyl sulfide, the composition of the present invention may also contain other flame retardants and flame retardant aids, especially when antimony oxide is used in combination. In some cases, the amount of diphenyl sulfides used can be significantly reduced by about 5 parts by weight per 100 parts by weight of combustible synthetic resin.

The composition of the present invention contains at least 0.1 part by weight, preferably 0.1 to 40 parts by weight, more preferably 0.5 to 25 parts by weight of halogenated diphenyl per 100 parts by weight of the combustible synthetic resin. It contains ruphids.

When this content is less than 0.1 parts by weight, the resulting composition has insufficient flame retardancy, and even if this content is more than 40 parts by weight, no improvement in the flame retardant effect is observed. ,
Further, increasing the amount from 25 parts to 40 parts improves the flame retardant effect, but on the other hand, it may deteriorate the physical properties of the composition, so it is necessary to decide the amount to be used by comprehensively considering these physical properties. In the case of thermoplastic resins, conventional compounding methods can be utilized to prepare the compositions of the invention.

That is, synthetic resin powder or pellets and halogenated diphenyl sulfides can be mixed and melt-blended using a kneader, a screw type extruder, a Banbury mixer, a mixing roll, or the like. In the case of thermosetting resins such as epoxy resins and phenolic resins, they can be manufactured by mixing them with the raw materials used prior to curing. Similarly, it is often possible to make it present during the polymer production reaction, such as by mixing it with monomers, and then mixing it at the same time as the polymer production. Furthermore, when molding a synthetic resin into a porous body, there is also a method of adding the foaming agent at the same time. The composition of the present invention can be molded into films, tapes, ribbon plates, tubes, pipes, fibers, foams, and other various shapes, and these can be used for construction materials, electrical equipment materials, interior goods, clothing items, and other miscellaneous goods. It can be used as supplies.

Example 1 100 parts of commercially available polystyrene pellets (in the following examples,
(parts indicate parts by weight) and 5 parts of bisdibromopropyl ether of 3,5,3',5'-detrapromo-4,4'-dihydroxydiphenyl sulfide were heated at 160 to 170°C using a mixing roll. Knead with 180-19
It was pressed at 0° C. (pressure: 50 kg/Cfii) and molded into a flat plate with a thickness of 3 mm.

This molded product gradually burned when exposed to flames, but immediately self-extinguished when the flames were removed. The oxygen index was 25.2. The one without the addition of flame retardant was completely burnt out and had an oxygen index of 18.5.

The combustion test in the above test was conducted in accordance with ASTM D635-56T.

Moreover, the oxygen index was measured by the method of ASTM D2863-70. (Hereinafter, measurements were made using the same method as in this example unless otherwise specified.) Example 2 10 parts of the same flame retardant as in Example 1 and 5 parts of diantimony trioxide were mixed with 100 parts of commercially available ABS resin powder. Rolled at 170-180℃ using a roll, 190-180℃
Pressed at 200℃ (pressure 50kg/Cwi), thickness 3
It was molded into a flat plate of m1.

This molded product gradually burned when exposed to flames, but immediately self-extinguished when the flames were removed. The oxygen index was 28.0. The one without the addition of flame retardant was completely burnt out and had an oxygen index of 18.5.

Example 3 5 parts of the same flame retardant as in Example 1 and 100 parts of styrene monomer
The mixture was mixed with 1 part of benzoyl peroxide and polymerized at 80° C. into a rod having a diameter of 1011 mm.

This rod-shaped molded product gradually burned when it came into contact with flame, but
The fire self-extinguished as soon as the flames were moved away. Oxygen index is 25.
It was 5. The one to which no flame retardant was added was completely burnt out, and the oxygen index was 18.9. Example 4 To 100 parts of commercially available polyvinyl chloride powder, 5 parts of the same flame retardant as in Example 1, 45 parts of dioctyl phthalate, and 2 parts of stabilizer (1.5 parts of dibutyltin dilaurate, 0 parts of cadmium stearate) .3 parts and 0.2 parts of barium stearate), mixed using a mixing roll at 160°C, and press-molded to a thickness of 3 m7! It was made into a L sheet.

This molded product gradually burned when brought into contact with a flame, but immediately extinguished itself when the flame was removed, and the oxygen index was 36.
The oxygen index was 25 when no flame retardant was added. Example
5 10 parts of the same flame retardant as in Example 1 and 5 parts of diantimony trioxide were kneaded into 100 parts of commercially available acrylonitrile styrene resin powder using a mixing roll at 160 to 170°C, and pressed at 180 to 190°C. , thickness 3mm
It was molded into a flat plate.

This molded product gradually burned when exposed to flames, but self-extinguished as soon as the flames were removed. The oxygen index was 26. The one to which no flame retardant was added was completely burnt out, and the oxygen index was 18.3. Example 6 5 parts of the same flame retardant as in Example 1 were mixed with 200 parts of a 50% solution of polyvinyl acetate in ethyl acetate, 2.5 parts of diantimony trioxide was uniformly dispersed, and ethyl acetate was poured into a petri dish. Evaporated to a thickness of 2m7! I made an L sheet.

This sheet gradually burned when exposed to flames, but self-extinguished as soon as the flames were removed. Those without added flame retardants were completely burnt down. Example 7 8 parts of the same flame retardant as in Example 1 were mixed into a mixture of 80 parts of styrene monomer and 20 parts of methyl methacrylate monomer, and 70-130
It was polymerized into a rod shape with a diameter of 10 mm at ℃.

This rod-shaped molded product gradually burned when it came into contact with flame, but
The fire self-extinguished as soon as the flames were moved away. The oxygen index was 27. Those without flame retardant were completely burnt down and had an oxygen index of 18.
It was hot. Example 8 10 parts of 3,5,3',5'-tetraflowo-4-dipromopropoxyl-dichloropropoxydiphenyl sulfide, 5 parts of diantimony trioxide, and 100 parts of commercially available ABS resin powder were mixed on a mixing roll. using 170-180
Knead at ℃, press at 190-200℃, thickness 3mm
It was made into a flat plate.

This molded product gradually burned when exposed to flames, but self-extinguished as soon as the flames were removed. The oxygen index was 26.5. In addition, those without flame retardant were completely burnt down and had an oxygen index of 1.
It was 8.5. Example 9 3, 5, 3', 100 parts of commercially available polystyrene pellets
Add 6 parts of bismonobromopropyl ether of 5'-tetrabromo-4,4'-dihydroxydiphenyl sulfide, knead at 160-170°C using a mixing roll, and press at 180-190°C to form a thick Sa37IEm
It was made into a flat plate.

This molded product gradually burned when exposed to flames, but immediately extinguished itself when the flames were removed. The oxygen index was 24.1. In addition, those without flame retardant were completely burnt down and had an oxygen index of 1.
It was 8.5.

Example 10 5 parts of 3,5,3',5'-tetrabromo-4-bromoethoxy-l-dipromopropoxydiphenyl sulfide were mixed with 200 parts of a 50% solution of polyvinyl acetate in ethyl acetate, and trioxide Uniformly disperse 2.5 parts of antimony,
Evaporate ethyl acetate on a sieve to a thickness of 2ml/L.
I made a sheet.

This sheet gradually burned when exposed to flames, but self-extinguished as soon as the flames were removed. The one without added flame retardant was completely burnt down. Example 11 3,5,3',5'-tetrapromo-4-butoxy-4
10 parts of '-dipromopropoxydiphenyl sulfide, 100 parts of commercially available acrylonitrile styrene resin powder, and 5 parts of diantimony trioxide were kneaded using a mixing roll at 160 to 170°C, and pressed at 180 to 190°C. Thickness 3m7! It was made into a L flat plate.

This molded product gradually burned when exposed to flames, but immediately self-extinguished when the flames were removed. The oxygen index was 25.2. In addition, those without flame retardant were completely burnt down and had an oxygen index of 1.
It was 8.3. Example 12 A flat plate with a thickness of 3 mm was prepared in the same manner as in Example 1, except that tribromomonochloro 2,4/dihydroxydifenino sulfide bis dibromopropyl ether was used as the flame retardant. Ivy.

This molded product gradually burned when exposed to flames, but immediately self-extinguished when the flames were removed.

The oxygen index of this molded product was 24.5. Example 1
3 Example 1 except that 10 parts of octabromo-4·l-dihydroxydiphenyl sulfide was used as the flame retardant.
I made a flat plate with a thickness of 3 fins using the same process and method.

This molded product gradually burned when exposed to flames, but immediately self-extinguished when the flames were removed. The oxygen index of this molded product was 23.8. Example 14 100 parts of commercially available polyethylene for molding and 15 parts of the same flame retardant as in Example 1 were kneaded at 160 to 170°C using a mixing roll.
It was pressed at 0°C and molded into a flat plate with a thickness of 3 mm.

This molded product burned when exposed to flames, but self-extinguished as soon as the flames were moved away. This molded product is 3cm wide! Cut into 10 mm long pieces, leave in a constant temperature dryer at 100℃ for 7 days, and calculate the weight loss before and after that as the amount of flame retardant reduction.The reduction rate of flame retardant content is 10% or less. No change in flame retardant effect was observed before and after heat treatment, and self-extinguishing properties were maintained. (Measurements were made in the same manner as in this example unless otherwise specified) Example 15 5 parts of the same flame retardant as in Example 1, 2 parts of diantimony trioxide.
After kneading 5 parts and 100 parts of commercially available polyethylene for molding at 160 to 170°C using a mixing roll,
It was pressed at ℃ to form a flat plate with a thickness of 31 tm.

This molded product gradually burned when exposed to flames, but self-extinguished as soon as the flames were removed. The reduction rate of the flame retardant content in this molded product was less than 10%, and there was no change in the flame retardant effect.
It maintained self-extinguishing properties. Example 16 Using a mixing roll, 15 parts of the same flame retardant as in Example 1 and 100 parts of commercially available molding polypropylene were mixed into 170-1
Knead at 80℃ and press at 200℃ to a thickness of 3m71L
It was made into a flat plate.

This molded product burned when exposed to flames, but self-extinguished as soon as the flames were moved away. The rate of decrease in the flame retardant content of this molded product was 10% or less, no change was observed in the flame retardant effect, and self-extinguishing properties were maintained. Example 17 3 parts of the same flame retardant as in Example 1, 1 part of diantimony trioxide.
5 parts and 100 parts of commercially available polypropylene for molding were kneaded at 170 to 180°C using a mixing roll.
It was pressed at 0°C to form a flat plate with a thickness of 3 m1.

This molded product burned when exposed to flames, but self-extinguished as soon as the flames were moved away. The rate of decrease in the flame retardant content of this molded product was 10% or less, no change was observed in the flame retardant effect, and self-extinguishing properties were maintained. Example 18 10 parts of 3,5,3',5'-tetrabromo-4,4-dihydroxydiphenyl sulfide, 5 parts of diantimony trioxide, and 85 parts of commercially available molding polypropylene were added to Example 16.
A flat plate with a thickness of 3 mm was made using the same method as above.

This molded product caught fire when it came into contact with flames, but immediately self-extinguished when the flames were moved away. Example 19 5 parts of the same flame retardant as in Example 8, 2. diantimony trioxide.
5 parts and 100 parts of commercially available polyethylene for molding were kneaded at 160 to 170°C using a mixing roll.
It was pressed at ℃ to form a flat plate with a thickness of 3 m1.

This molded product burned when exposed to flames, but self-extinguished as soon as the flames were moved away. The rate of decrease in the flame retardant content of this molded product was 10% or less, no change was observed in the flame retardant effect, and self-extinguishing properties were maintained. Example 20 6 parts of the same flame retardant as in Example 9, 3 parts of diantimony trioxide, and 100 parts of commercially available polypropylene for molding were kneaded at 170 to 180°C using a mixing roll, and
It was pressed at ℃ and molded into a flat plate with a thickness of 31 m1.

What is this molded product? It burned when touched, but self-extinguished as soon as the flame was moved away. The rate of decrease in the flame retardant content of this molded product was 10% or less, no change was observed in the flame retardant effect, and self-extinguishing properties were maintained. Example 21 5 parts of the same flame retardant as in Example 10, 2 parts of diantimony trioxide
．． 5 parts and 100 parts of commercially available moldable polyethylene were treated in the same manner as in Example 14 to form a flat plate with a thickness of 311 mm.

This molded product gradually burned when exposed to flames, but self-extinguished as soon as the flames were removed. The reduction rate of the flame retardant content in this molded product was less than 10%, and there was no change in the flame retardant effect.
It maintained self-extinguishing properties. Example 22 6 parts of the same flame retardant as Example 11, 3 parts of diantimony trioxide
and 100 parts of commercially available molding polypropylene were treated in the same manner as in Example 14 to obtain a thickness of 3 m77! It was made into a flat plate.

This molded product gradually burned when exposed to flames, but immediately self-extinguished when the flames were removed. The rate of decrease in the flame retardant content of this molded product was 10% or less, no change was observed in the flame retardant effect, and self-extinguishing properties were maintained. Example 23 After molding 10 parts of the same flame retardant as in Example 1 and 90 parts of commercially available polyethylene for molding in the same manner as in Example 14, the tensile strength and flame retardance were measured to be 300 kg/Crii, self-extinguishing property. I got the result.

The flame retardant-free product had a combustibility of 3061<9/Cd. Example 24 4 parts of the same flame retardant as in Example 1, 2 parts of diantimony trioxide, and 94 parts of commercially available polyethylene for molding were treated in the same manner as in Example 23, resulting in 303 kg/Cd, self-extinguishing property, and no afterflame. I got the result.

Example 25 After molding 10 parts of the same flame retardant as in Example 1 and 90 parts of commercially available molding polypropylene in the same manner as in Example 16, the tensile strength and flammability were measured, and the result was 3301<9/Cd, self-extinguishing property. The results were as follows.

The flame retardant-free product had a combustibility of 350 kg/CrA. Example 26 4 parts of the same flame retardant as in Example 1, 2 parts of diantimony trioxide, and 94 parts of commercially available molding polypropylene were added to Example 25.
It was treated in the same manner as above, and a result of 335 kg/Cd, self-extinguishing property, and no afterflame was obtained.

Example 27 For comparison with known flame retardants, 4 parts of flame retardant, 2 parts of diantimony trioxide and 100 parts of commercially available moldable polyethylene were treated in the same manner as in Example 15, and a thickness of 3 m7! It was made into a L flat plate.

The flammability of this molded product and the rate of decrease in flame retardant content and flammability after 7 days of treatment at 100°C were measured. It is also self-extinguishing, and the flame retardant content decreases by 10%.
The following results were obtained. On the other hand, hexabromobenzene, brominated diphenyl (bromine content 70%), chlorinated diphenyl (chlorine content 60%), bisethyl ether of tetrapromobisphenol A, and tetrabromobutane were tested for comparison. It is also flammable after 7 days of treatment at 100℃, and the flame retardant content decreases by 30%.
The above results were obtained.

Example 28 The same measurements as in Example 27 were carried out and the same results were obtained, except that commercially available moldable polypropylene was used instead of commercially available moldable polyethylene and the molding method was changed to the same method as in Example 17. Obtained.

Example 29 100 parts of commercially available molding polypropylene, 5 parts of bismonobromopropyl ether of tribromomonochloro-4·l-dihydroxydiphenyl sulfide, and 2.5 parts of diantimony trioxide were added in the same manner as in Example 17. The mixture was kneaded and pressed according to the method and molded into a flat plate with a thickness of 3 mT1L.

This molded product gradually burned when exposed to flames, but immediately self-extinguished when the flames were removed. The rate of decrease in the flame retardant content of this molded product was 10% or less, no change was observed in the flame retardant effect, and self-extinguishing properties were maintained. Example 30 A flat plate with a thickness of 311 mm was prepared using the same recipe and method as in Example 1, except that 3 parts of the flame retardant of Example 1 and 7 parts of the flame retardant of Example 8 were used as flame retardants. Ivy.

This molded product gradually burned when exposed to flames, but self-extinguished when the flames were removed.

Example 31 100 parts of polybutylene terephthalate having an intrinsic viscosity of 1.04 and a softening point of 222° C. and 15 parts of the same flame retardant as in Example 1 were mixed in a blender for 5 minutes.

Next, the mixture was heated to 270°C using an extruder, melt-kneaded,
I made pellets. This pellet was put into an injection molding machine to prepare a test piece with a thickness of 31'', width of 12.5 m, and length of 12711 mm. This test piece had a tensile strength of 560 kg/Cd and gradually burned when brought into contact with a flame, but extinguished within 1 second when the flame was removed. Those without flame retardant additives are
It had a tensile strength of 580 kg/Cd, and it took more than a minute to extinguish the flame after it was removed. Example 32 Vinyl acetate unit content 10% by weight instead of polyethylene
The same test as in Example 14 was conducted using an ethylene monovinyl acetate copolymer having a melt index of 6, and similar results were obtained.

Example 33 Vinyl acetate unit content 10% by weight instead of polyethylene
The same test as in Example 14 was conducted using a saponified ethylene monovinyl acetate copolymer having a melt index of 6, and similar results were obtained.

Example 34 The same test as in Example 14 was conducted using an ethylene ethyl acrylate copolymer having a melt index of 1 and having an ethyl acrylate unit content of 20% by weight in place of polyethylene, and similar results were obtained.

Example 35 The same test as in Example 14 was conducted using an ethylene-acrylic acid copolymer having an acrylic acid unit content of 20% by weight and a melt index of 10 in place of polyethylene, and similar results were obtained.

Example 36 Methyl acrylate unit content 25 instead of polyethylene
ethylene with a vinyl acetate unit content of 10% by weight
The same test as in Example 14 was conducted using a methyl acrylate monovinyl acetate terpolymer, and similar results were obtained.

Example 37 0.75 part of α·α5-azobisinbutyronitrile was added to 500 parts of methyl methacrylate, which was obtained by distilling a commercially available product once under reduced pressure, and mixed.

The temperature was raised to 75 DEG C., maintained at that temperature for about 40 minutes, and then cooled to give a semi-polymerized syrup with a viscosity of about 100 centipoise. To 300 parts of this syrup were added 100 parts of 3,5,3ξ5'-tetrabromo-4,l-bisbutoxydiphenyl sulfide and mixed. 1001 of the mixed syrup
111! After suction dehydration under reduced pressure of about Hg, 30
0X300] 11! Injected into a 3-fin thick glass cell assembled with two pieces of square tempered glass, heated at 50°C for 20 hours and then at 70°C.
Polymerization was carried out for 5 hours to obtain a cast plate. When this casting board was brought into contact with the flame, it gradually burned, but when the flame was moved away,
The fire self-extinguished within 0 seconds.

Example 38 50 parts of commercially available polycarbonate resin, 50 parts of commercially available ABS resin, 10 parts of the flame retardant of Example 1, and 5 parts of diantimony trioxide were premixed in a crusher and then mixed in an extruder to form pellets.

A flat plate with a thickness of 3 U was made from this pellet by the repress method. This molded product gradually burned when exposed to flames, but immediately self-extinguished when the flames were removed. In addition, when the flame retardant was not added, it took more than 60 seconds for the flame to go out when the flame was removed. Example 39 200 parts of ε-caprolactam were placed in a glass flask equipped with a stirrer and heated to 150° C. under a nitrogen stream, and 1 part of fine powder of sodium malonate was added thereto as a catalyst and dissolved under stirring.

The mixture was heated to 180° C. and 8 parts of cocatalyst hexamethylene diincyanate and 20 parts of the same flame retardant as in Example 1 were added.
After polymerization and foaming, the mixture was cooled to room temperature to obtain a foam having an apparent specific gravity of 0.25. U for this foam
Flammability was tested according to the method specified in L94, and 94V-
I got a result that passed 1. In addition, it was found that a product without added flame retardant did not pass 94V-1.

Example 40 100 parts of bisphenol A type epoxy resin, 20 parts of decachlorodiphenyl sulfide, and 10 parts of diantimony trioxide were mixed at a temperature of 120° C., and then 12 parts of diethylenetriamine was added with stirring. A rod-shaped object with a diameter of 1011 mm was made by keeping it for 2 hours.

The oxygen index of this rod-shaped molded product was 31. It was 22 for the flame retardant-free product. Example 41 In a separable flask equipped with a reflux condenser, thermometer, and stirrer, 100 parts of distilled phenol and 74% aqueous formaldehyde solution were added.
1 part and 0.1 part of 35% concentrated hydrochloric acid as a catalyst were added, and the mixture was heated with stirring.

When the temperature of the reaction system reached 85° C., the heating was adjusted to maintain a reflux state. After continuing this state for about 1.5 hours, the resin layer was precipitated by cooling with water. Once the upper water layer was no longer turbid, the water layer was poured out at an angle. The mixture was heated again while stirring to remove volatile components such as water and unreacted phenol. When the temperature of the resin reached 170 to 175°C, heating was stopped and the resin was poured into a vat and solidified. 10 parts of the flame retardant of Example 1 and 10 parts of hexamethylenetetramine were added to 100 parts of this pulverized resin, and the mixture was pulverized and mixed in a mixer mill. This was placed in a test tube with an inner diameter of 1011, and immersed in an oil bath at 140°C to solidify. Solidification was completed in about 30 minutes. The oxygen index of this product was 26.

The value was 19 for the product without flame retardant additives.

Example 42 34 parts of hexamethylene glycol to 1 part of anhydrous anisole
00 parts and charged into a three-hole flask equipped with a stirrer, a condenser, and a dropping tube.

This was heated with stirring to bring it to a boil, and a solution of 40 parts of tetramethylene diisocyanate dissolved in 150 parts of anhydrous anisole was rapidly added dropwise via a dropper. 18
It was refluxed at 0-190°C for 4 hours. Next, 1 part of tetramethylene diisocyanate dissolved in 20 parts of anhydrous anisole was added, and the reaction was continued for 2 hours. When cooled after the reaction, polyurethane will precipitate, so filter it thoroughly and wash it with alcohol.
It was dried under reduced pressure to obtain colorless powdery polyurethane.

10 parts of the flame retardant of Example 1 was mixed with 100 parts of this polyurethane using a mixing roll and then pressed to form a flat plate with a thickness of 3 mm. The oxygen index of this molded product was 30. The product without flame retardant additive was 25. Reference Example 1 A plate with a thickness of 3 mm was made using the same recipe and method as in Example 1, except that 15 parts of tetrapromodiphenyl sulfide was used as a flame retardant.

This molded product gradually burned when exposed to flames, but immediately self-extinguished when the flames were removed.

The oxygen index was 23.5.

Reference Example 2 A flat plate with a thickness of 3 mm was produced using the same recipe and method as in Example 1, except that 15 parts of monochlorotetrapromodiphenyl sulfide was used as a flame retardant.

This molded product burned slowly when exposed to flames, but immediately self-extinguished when the flames were removed. The oxygen index was 23.8. Reference Example 3 Using the same formulation and method as in Example 2, except for using 15 parts of hexapromodiphenyl sulfide and 7.5 parts of diantimony trioxide as flame retardants, a 3 m thick
I made a wL flat plate.

This molded product gradually burned when exposed to flames, but immediately self-extinguished when the flames were removed. The oxygen index was 24.5. Reference Example 4 A plate with a thickness of 3 mm was made using the same recipe and method as in Example 1, except that 15 parts of octachlorodiphenyl sulfide was used as a flame retardant.

This molded product gradually burned when exposed to flames, but immediately self-extinguished when the flames were removed. The oxygen index was 24.0. Reference Example 5 A flat plate with a thickness of 3 mm was produced using the same recipe and method as in Example 1, except that 15 parts of nonapromodiphenyl sulfide was used as a flame retardant.

This molded product gradually burned when exposed to flames, but immediately self-extinguished when the flames were removed.

Claims (1)

[Claims] 1. General formula▲ Numerical formulas, chemical formulas, tables, etc.▼ [Here, X is a halogen atom, A is a hydrogen atom, or a hydrocarbon group having 1 to 6 carbon atoms or a halogenated hydrocarbon group may be the same or different. Further, m_1 and m_2 each represent 0 or an integer from 1 to 5, and n_1 and n_2 each represent 0 or 1. However, m_1, m_2 and n_1, n_2 are never 0, and m_1 and n_1 and m_2 and n
At least one of the halogenated diphenyl sulfides represented by
The amount of seeds per 100 parts by weight of combustible synthetic resin is at least 0.
A flame-retardant synthetic resin composition containing 1 part by weight. 2
The composition according to claim 1, wherein the general formula is ▲There are mathematical formulas, chemical formulas, tables, etc.▼. 3. The composition according to claim 1, wherein the general formula is ▲There are mathematical formulas, chemical formulas, tables, etc.▼. 4. The composition according to claim 2 or 3, wherein X is a chlorine atom or a bromine atom. 5. The composition according to claim 4, wherein A is an alkyl group having 1 to 4 carbon atoms or a halogenated alkyl group. 6. The composition according to claim 1, which contains 0.1 to 40 parts by weight of the halogenated diphenyl sulfide based on 100 parts by weight of the combustible synthetic resin. 7. The composition according to claim 1, which contains 0.5 to 25 parts by weight of the halogenated diphenyl sulfide based on 100 parts by weight of the combustible synthetic resin.