JPS6043372B2 - 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, synthetic resins such as vinyl resins such as polyolefin resins, polyvinyl acetate, their saponified products, polyacrylic acid esters, polyacrylonitrile, polystyrene, etc. are strong, lightweight, and have water resistance, chemical resistance, and electrical insulation properties. Because it has excellent properties and is easy to mold,
It is widely used as a building material, a material for electrical equipment, a household product, or an auxiliary material for these materials. However, these resins all have the disadvantage of being easily combustible, although this varies 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 to date has been the addition of 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 into the polyolefin resin, and as a result, the polyolefin resin composition The disadvantage is that physical properties such as strength, whiteness, gloss, and electrical insulation properties are reduced. Similarly, in the case of vinyl resin, it is necessary to mix an extremely large amount of flame retardant in order to make it sufficiently flame retardant.
It has the disadvantage that the physical properties of the resin, such as strength, whiteness, gloss, and electrical insulation properties, are reduced. 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 halogenated diphenyl sulfides used in the present invention have the following general formula [
Here, X represents a halogen atom and may be the same or different.

Moreover, Ml and m2 each represent 0 or an integer of 1 to 5. However, both Ml and m2 are never 0. ] 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. Some of these compounds are dipromodiphenyl sulfide, dichlorodiphenyl sulfide, chlorobromodiphenyl sulfide, tetrabromodiphenyl sulfide, tetrachlorodiphenyl sulfide, dichlorodibromodiphenyl sulfide, monochlorotripromodiphenyls. hexabromodiphenyl sulfide, hexachlorodiphenyl sulfide, trichlorotribromodiphenyl sulfide, octabromodiphenyl sulfide, octachlorodiphenyl sulfide, tetrachlorotetrabromodiphenyl sulfide, decabromodiphenyl sulfide, decachlorodiphenyl sulfide, and pentachloropentabromo Examples include diphenyl sulfide. There are various compounds in which these halogen atoms are present not only in two phenyl groups in the same way, but also in only one phenyl group. These halogenated diphenyl sulfides may be used alone or in combination of two or more.

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, -COOC2H5 group, -COOC3H7 group, -COO
C4H9 group, -CN group, -COCH3 group, -NCO group,
-αX℃H3 group, -0H group, -0CH3 group, or CH
represents an O group, R3 is a hydrogen atom, a chlorine atom, a bromine atom, a fluorine atom, -CH3 group, -COOCH3 group, -COOC6
It represents a Hll 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, polypentene-1, ethylene vinyl acetate copolymer, saponified ethylene vinyl acetate copolymer, polyacrylonitrile, polyvinyl chloride, polystyrene, polyvinyl acetate, polyvinyl alcohol. ，
These include 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 derephthalate, polybutylene terephthalate, 6-,
Examples include polyamide resins such as 6.6-, 6.10-, 11-, and 12-nylon, polycarbonate resins, epoxy resins, phenolic resins, and polyurethane resins.

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 flammable synthetic resin and the halogenated diphenyl sulfides, the composition of the present invention may also contain other flame retardants and flame retardant aids, especially when antimony oxide is used in combination with the halogenated diphenyl sulfides. In some cases, the amount used can be significantly reduced by about 5 parts by weight per 10 parts 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 sulfide per 10 parts by weight of the combustible synthetic resin. A composition containing at least one of the following.

When this content is less than 0.1 part by weight, the resulting composition has insufficient flame retardancy, and even if this content is greater than 4 parts by weight, no improvement in flame retardant effect is observed. In addition, increasing the amount from 25 parts to 10 parts improves the flame retardant effect, but on the other hand, it may reduce the physical properties of the composition, so it is necessary to decide the amount to use by taking these physical properties into consideration comprehensively. .
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, screw extruder, Panbury mixer, 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 used as films, tapes, ribbons, plates, tubes, vibrators, fibers, foams, and other molded products in various shapes and as adhesives for construction-related, electrical equipment-related, interior-related, clothing-related, and other miscellaneous goods. It can be used in relationships etc.

Example 1 100 parts of commercially available polystyrene pellets (in the following examples,
(parts indicate parts by weight) and 15 parts of tetrabromodiphenyl sulfide were mixed using a mixing roll to form 160 to 17 parts of
Knead at 0℃, press at 180-190℃ (pressure 50℃)
kg/Clt) and molded into a flat plate with a thickness of 3 gourds.

This molded product gradually burned when exposed to flames, but immediately self-extinguished when the flames were removed. The oxygen index was 23.5. 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 20 parts of dipromodiphenyl sulfide and 5 parts of diantimony trioxide were added to 10 parts of commercially available ABS resin powder using a mixing roll. Te170-18
Knead at 0℃, press at 190-200℃ (pressure 50℃)
kg/d) and molded into a flat plate with a thickness of 3TfrIIL.

This molded product gradually burned when exposed to flames, but immediately self-extinguished when the flames were removed. The oxygen index was 30.0. The one without the addition of flame retardant was completely burnt out and had an oxygen index of 18.5. Example 3 A plate having a thickness of 3 TWL was prepared using the same recipe and method as in Example 1, except that 15 parts of monochlorotetrapromodiphenyl sulfide was used as the flame retardant.

This molded product gradually burned when exposed to flames, but immediately self-extinguished when the flames were removed. The oxygen index was 23.8. Example 4 The same formulation and method as in Example 2 was used, except that 1 width of hexabromodiphenyl sulfide was used as the flame retardant, and the thickness was 3Tn! I made a flat plate of n.

This molded product gradually burned when exposed to flames, but immediately self-extinguished when the flames were removed. The oxygen index was 24.5. Example 5 The same formulation and method as in Example 1 was used to prepare a 3.5 mm thick film, except that m parts of octachlorodiphenyl sulfide were used as the flame retardant. I made a flat plate.

This molded product gradually burned when exposed to flames, but immediately self-extinguished when the flames were removed. The oxygen index was 24.0. Example 6 A 3wn thick plate was made using the same recipe and method as in Example 1, except that 5 parts of nonapromodiphenyl sulfide was used as the flame retardant.

This molded product gradually burned when exposed to flames, but immediately self-extinguished when the flames were removed. The oxygen index was 25.5. Example 7 100 parts of commercially available polystyrene pellets, 1 part of decabromodiphenyl sulfide and 5 parts of diantimony trioxide were kneaded by the method of Example 1.

This kneaded material was tested for flammability according to the method specified in UL94. ■I got the result that I passed 1/0. Example 8 200 (4) parts of water, 6 parts of a copolymer consisting of 95% N-vinylpyrrolidone and 5% methyl acrylate, 2 parts of sodium pyrophosphate, 19,400 parts of styrene, 15 (4) parts of pentane.
Part, benzoyl peroxide 6? , and 16 (4) parts of octabromodiphenyl sulfide were placed in a pressure vessel equipped with a stirring device, and after pressurizing 2 atm of nitrogen, 7 parts of octabromodiphenyl sulfide were added while stirring.
When polymerized for 1 hour at 0°C and 80°C, 0.5 to 3
A spherical polymer with a diameter of wft was obtained.

This was separated, washed and dried in a stream of air at 50°C. A predetermined amount of the produced polymer particles was placed in a mold, and when heated with steam or boiling water, it expanded to 40 times its original volume. This foam had an apparent specific gravity of 0.015 to 0.025, was difficult to burn after the foaming agent evaporated, and naturally extinguished when the flame was removed. Example 9 GP polystyrene part, HI polystyrene 3 (2), blend oil 01 part, azodicarbonamide 0.4 part,
m parts of decabromodiphenyl sulfide and 5 parts of diantimony trioxide were blended, and low foaming profile extrusion with a cross-sectional area of 2d and an apparent specific gravity of 0.65 was carried out using a 65φ extruder.

The flame retardancy of the resulting foam was found to pass UL94 standard 94V-1. Example 10 Example 1 was added to 1 (4) parts of commercially available polyvinyl chloride powder.
m parts of the same flame retardant as above, 45 parts of dioctyl phthalate and 2 parts of stabilizer (1.5 parts of dibutyltin dilaurate, 0.3 parts of cadmium stearate and 0.1 part of barium stearate) were added, and the mixture was heated at 160°C using a mixing roll. The mixture was mixed and press-molded to form a sheet with a thickness of 3 mm.

This molded product gradually burned when brought into contact with a flame, but immediately self-extinguished when the flame was removed, and the oxygen index was 37. The oxygen index was 25 when no flame retardant was added. Example 11 W 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 kneaded at 180 to 190°C. Blessed, thickness 37r0n
It was molded into a 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. The one to which no flame retardant was added was completely burnt out, and the oxygen index was 18.3. Example 12 w 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 the ethyl acetate was evaporated on a shear plate to form a sheet with a thickness of 2 TWL.

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 13 Using a mixing roll, 1 (1) part of commercially available polyethylene for molding and 20 parts of the same flame retardant as in Example 1 were mixed into 1 (1) part of commercially available polyethylene for molding.
The mixture was kneaded at 70°C, pressed at 190°C, and formed 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 was cut into pieces 3 cm wide and 10 α long, and left in a constant temperature dryer at 100°C for 7 days. The weight loss before and after that was calculated as the amount of flame retardant reduction. The rate of decrease in flame retardant content was At 10% or less, no change was observed in the flame retardant effect before and after the main heat treatment, and self-extinguishing properties were maintained.
(Hereinafter, measurements were made using the same method as in this example unless otherwise specified). Example 14 5 parts of the same flame retardant as in Example 1, 2 parts 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=.

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 15 One concave portion 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. The pellets were put into an injection molding machine to prepare a test piece with a thickness of 3wn, width of 12.5wrIn, and length of 127mm. This test piece has a tensile strength of 550 kg/Clt and burns gradually when brought into contact with flame, but
When the flames were moved away, the fire was extinguished within one second. The flame retardant-free flame retardant had a tensile strength of 580k9/Clt, and it took more than 1 minute to extinguish the flame after it was removed. Example 1
The same test as in Example 13 was conducted using an ethylene-vinyl acetate copolymer having a vinyl acetate unit content of 10% by weight and a melt index of 6 instead of polyethylene 6, and similar results were obtained.

Example 17 Vinyl acetate unit content 10% by weight instead of polyethylene
The same test as in Example 13 was conducted using a saponified ethylene-vinyl acetate copolymer having a melt index of 6, and similar results were obtained.

Example 18 Acrylic acid unit content 20% by weight instead of polyethylene
The same test as in Example 13 was conducted using an ethylene-acrylic acid copolymer having a melt index of 10, and similar results were obtained.

Example 19 Methyl methacrylate 5(1) obtained by vacuum distilling a commercial product once
0.75 part of A,a''-azobisisobutyronitrile was added to the mixture 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. 60 parts of octabromodiphenyl sulfide was added to 3 (1) parts of this syrup and mixed. After removing the mixed syrup by suction under reduced pressure of about 1007mHg, 300×3007707! The mixture was poured into a glass cell with a thickness of 3 mm made up of two pieces of rectangular reinforced glass, and polymerization was carried out at 500 C for 5 hours and at 700 C to obtain a cast plate. This cast plate gradually burned when brought into contact with a flame, but self-extinguished within 3 [phases] when the flame was moved away.

Example 20 50 parts of commercially available polycarbonate resin, 50 parts of commercially available ABS resin, decabromodiphenyl sulfide w
1 part and 5 parts of diantimony trioxide were premixed in a pickling machine, and then mixed in an extruder to form pellets.

From this pellet, the thickness is 377!77! I made a flat plate. 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 6 drinks to extinguish the flame when the flame was removed. Example 21 100 parts of bisphenol A type epoxy resin, 2 Cg of decachlorodiphenyl sulfide) and w parts of diantimony trioxide are mixed at a temperature of 120° C., then diethylenetriamine is added with stirring, and maintained at this temperature for 2 hours. The diameter is 10T! U! I made a stick-shaped object.

The oxygen index of this rod-shaped molded product was 30. It was 22 for the flame retardant-free product. Example 22 In a separable flask equipped with a reflux condenser, a thermometer, and a stirrer, 100 parts of distilled phenol, 74 parts of a 37% formaldehyde aqueous solution, and 35% concentrated hydrochloric acid as a catalyst were added.
．． 1 part was 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 one hour, the resin layer was cooled with water to settle. Once the upper water layer was no longer turbid, the water layer was poured out at an angle. The mixture was heated while stirring again 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 onto a pad and solidified. W parts of hexabromodiphenyl sulfide and m parts of hexamethylenetetramine were added to 1 (1) part of the pulverized resin, and the mixture was pulverized and mixed in a mixer mill. Put this in a test tube with an inner diameter of 10 TWL, and
It was immersed in an oil bath at °C to solidify. Solidification was completed in about 30 minutes. The oxygen index of this product was 25.

The value was 19 for the product without flame retardant additives. Example 23 34 parts of hexamethylene glycol to 1 part of anhydrous anisole
(1) and charged into a three-hole flask equipped with a stirrer, condenser, and dropping funnel.

This was heated with stirring to bring it to a boil, and a solution of tetramethylene diisocyanate dissolved in 1 part of anhydrous anisole was rapidly added via a dropping door. 180～
It was refluxed at 190°C for 4 hours.

Next, add 1 part of tetramethylene diisocyanate to 2? The mixture was dissolved in anhydrous anisole and added, and the reaction was continued for 2 hours. When cooled after the reaction, polyurethane precipitated and was filtered, washed with alcohol, and dried under reduced pressure to obtain polyurethane in the form of colorless powder.

15 parts of the flame retardant of Example 1 was kneaded in 1 part of this polyurethane using a mixing roll and then pressed to form a flat plate with a thickness of 3 wt.

Claims (1)

[Claims] 1 General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [Here, X represents a halogen atom, and each may be the same or different. Further, m_1 and m_2 each represent 0 or an integer from 1 to 5. However, both m_1 and m_2 are never 0.] A flame retardant product containing at least 0.1 part by weight of at least one kind of halogenated diphenyl sulfide represented by Synthetic resin composition. 2. The composition according to claim 1, wherein X is a chlorine atom or a bromine atom. 3. 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. 4. 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.