JPS5829337B2 - Flame retardant resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a resin composition that is flame retardant and has good physical properties.
- One or more salts of tris(4,6-diamitu-1゜3.5-1-riazin-2-yl)hexane and cyanuric acid, isocyanuric acid, cyanuric acid derivatives, or isocyanuric acid derivatives. The object of the present invention is to provide a flame-retardant resin composition with good moldability.

Generally, organic polymer substances have excellent properties in terms of strength, weather resistance, abrasion resistance, dyeability, etc., and are widely used in general industrial fields as resin molded products or fibers. There is.

However, these organic polymeric materials have the disadvantage of being extremely flammable, and as their range of use expands, they increasingly become a powerful ignition source or fuel source in the event of a fire.

In recent years, as higher safety standards have been set for products,
Flame retardancy and heat resistance are strongly required for organic polymer substances.

Conventional techniques and methods for making flame retardant resins include: (1) blending flame retardant resins;

Q Add flame retardant.

■Manufacturing resin with flame-retardant monomers, ■Making flame retardant through post-treatment, and ■Others.

Among these methods, the one commonly used for resins is the method of adding flame retardant Q. In this method, flame retardants include halogen-containing compounds, phosphorus-containing compounds, inorganic compounds, and nitrogen-containing compounds. There are compounds etc.

Each of these additive flame retardants has drawbacks, and halogen-containing compounds generally have poor heat resistance, poor sublimation bleed, and are often ineffective unless used together with antimony trioxide. Furthermore, phosphorus-containing compounds have little effect on resins that do not contain oxygen, and are often used together with halogens.

Depending on the resin, decomposition and deterioration may occur.

Generally, they are liquid, and the flame retardant that plasticizes the resin bleeds out.

There are disadvantages such as many of them are colored yellowish brown.

Among inorganic compounds, antimony trioxide is a scarce resource, and raw material availability and cost are unstable, and systems such as aluminum hydroxide have little effect and require large amounts of addition, resulting in decreased physical properties, poor moldability, and surface There are drawbacks such as deterioration and increased specific gravity, and materials that have a flame retardant effect by emitting water during decomposition, such as aluminum hydroxide, generally have poor heat resistance, and the flame retardant effect and heat resistance are inversely proportional. It has the following disadvantages.

Next, nitrogen-containing compounds are typified by melamine, etc., but melamine has poor heat resistance, sublimes during molding, and bleeds easily, and other materials with good heat resistance are difficult to manufacture. However, the price is very high (for example, several tens of thousands of yen/kg), and resins to which these are added cannot be manufactured industrially.

Therefore, the present inventors conducted intensive research to resolve the drawbacks of these flame retardants, and found that 1,3,6-tris (4,6-diami2-1), which has three triazine rings in one molecule,
, 3,5-triazin2-yl)hexane and a salt of cyanuric acid, isocyanuric acid, or a derivative thereof as a flame retardant, the flame retardant effect can be improved. It has been found that it is possible to provide a flame-retardant resin that has better heat resistance than melamine and is free from drawbacks such as sublimation and bleed.

That is, the present invention provides (1) 1,3,6-tris(4,6
-Diami2-1,3,5-)riazin-2-yl)hexane and a salt of cyanuric acid, isocyanurate, or a derivative thereof at 3 to 50 weight φ, preferably 4 to 3
The present invention relates to a resin composition containing 0% by weight and having excellent twist resistance.

Cyanuric acid and cyanuric acid derivatives constituting the salt used in the present invention are compounds represented by the following formula (A),
Isocyanuric acid and isocyanuric acid derivatives are expressed by the following formula (
B).

(However, 1, R is hydrogen, an alkyl group having 1 to 3 carbon atoms, an oxyalkyl group having 1 to 3 carbon atoms, or a phenyl group,
H is at least one hydrogen or an oxyalkyl group having 1 to 3 carbon atoms.

) Compounds represented by the general formula (N) include, for example, cyanuric acid, methyl cyanurate, phenyl cyanurate, diphenyl cyanurate, tris(2-hydroxyethyl) cyanurate, and compounds represented by the general formula , for example, isocyanuric acid, methyl isocyanurate, phenyl isocyanurate, diphenyl isocyanurate, tris(2-hydroxyethyl) cyanurate, and the like.

1, 3, 6 Tris (4
,6-diamitu-1,3,5-triazin-2-yl)
Hexane is a normally white non-powdered guanamine compound that can be obtained by the reaction of dicyandiamide with 1,3,6-11J cyanohexane obtained from electrolytic trimerization of acrylonitrile, and is represented by the following structural formula.

The salt used in the present invention generally has the following formula (C) or (D)
It is expressed as

R6: alkyl group having 1 to 3 carbon atoms, or phenyl group R7
: Alkylene group having 1 to 3 carbon atoms These salts are 1,3,6-tris(4,6-cyami2 1°3.
The base of hexane is the amino group, and the acid contained in cyanuric acid, isocyanuric acid, or their derivatives is hydrogen (the hydrogen of H or the hydroxyl group of the oxyalkyl group). The composition varies depending on the base group and the number of acidic hydrogen atoms.

These salts contain the basic substance 1,3,6-tris(4
,6-diamitsu-1,3,5-triazin--2-yl)hexane and one or more of the acidic substances cyanuric acid, isocyanuric acid, or derivatives thereof are dissolved or dispersed in a solvent, After the reaction, the produced salt is separated and filtered, and then it is obtained by recrystallization, washing with water, etc.

The solvent used here is dimethyl sulfoxide,
Dialkyl sulfoxide compounds such as diethyl sulfoxide, or β-methoxyethanol, β-ethoxyethanol, β-butoxycetanol, β-methoxypropanol, β-ethoxypropanol, β-butoxypropanol, β-methoxyethanol, β -Ethoxybutanol, isoamyl alcohol, primary amyl alcohol, secondary amyl alcohol, benzyl alcohol, dimethylformamide, dimethylacetamide, N-
These include methyl-2-pyrrolidone, pyridine, water, and the like.

The reaction temperature is 50 to 180°C, preferably 10
It is carried out at 0 to 160°C.

If the reaction temperature is below 500℃, the formation of salt will be slow,
A reaction temperature of 180° C. or higher is not preferable because deterioration of the amino group occurs.

The reaction time generally requires 10 to 180 minutes.

The reaction pressure may be reduced pressure, normal pressure, or increased pressure.

Further, the reaction may be a homogeneous reaction or a heterogeneous reaction, but from the viewpoint of yield, a homogeneous reaction is preferable.

The resin used in the present invention includes, for example, nylon 6,
Polyamides such as nylon 66, nylon 610, or copolymers and mixtures thereof, linear saturated aromatic polyesters such as polyethylene terephthalate, poly, litetramethylene terephthalate, polyhexamethylene terephthalate, polyphelene oxide, noryl, polyethylene, polypropylene and polyolefins such as polystyrene, polyacrylic acid esters such as polymethyl acrylate, polymethyl methacrylate, poly(styrene-
butadiene) copolymers, ABS resins, polycarbonates, polyacetal homopolymers, polyacetal copolymers, as well as diallyl phthalate, diallyl teretocrate, diallyl-2,6-naphthalene dicarboxylate, etc., and thermosetting polyesters, polyurethanes, Although thermosetting resins such as epoxy resins can be used, preferable effects can be obtained when polyamide resins are used.

The amount of these resins used is 50% for the composition of the present invention.
-97 weight range, preferably 70-96 weight range.

If the resin amount exceeds 97 weight φ, the flame retardant effect will be reduced, and if it is less than 50 weight φ, the bottom shape of the composition or the resin will deteriorate, resulting in a decrease in physical properties, which is not preferable.

The flame retardant of the present invention, 1,3,6-IJ (4°6-
Although any known technique can be applied to the method of blending diami2-1,3,5-1-riazin-2-yl)hexane and a salt of cyanuric acid, isocyanuric acid, or a derivative thereof into a resin, the method used in the present invention In order to obtain a flame-retardant resin that takes advantage of the advantages of flame retardants, internal blending through kneading is preferred.

In other words, in the case of thermoplastic resin, resin pellets or powder and the flame retardant may be mixed at room temperature and then molded using a melt molding machine such as an extruder, or after mixing and pelletizing, the pellets may be molded. A method of melt molding may also be used.

In addition, a resin containing a high concentration of the flame retardant is manufactured in advance,
In addition to this method, a conventional method of melting and milling resin and then molding the resin can also be applied.

In addition, in the case of thermosetting resins, generally the monomer before curing,
A preferred method is to add and mix into a prepolymer or a dope or compound made by adding a reinforcing agent or the like to the prepolymer, and then mold the material.

The flame retardant land resin composition of the present invention may contain conventional flame retardants or flame retardant aids (for example,
Third components such as antimony oxide, barium metaborate, zirconium dioxide, iron oxide, zinc borate, etc.), matting, pigments, dyes, stabilizers, plasticizers, dispersants, etc. may also be added, and glass fibers. , carbon fiber, tarnish, clay,
Calcined clay, mica, calcium silicate, calcium sulfate, calcium carbonate, glass peas, molybdenum disulfide,
It is also possible to include fillers such as internal reinforcing agents such as graphite, antistatic agents such as various phosphoric acid esters, sulfonic acids, quaternary ammonium salts, polyhydric alcohols, esters, alkylamides, alkylamine conductive carbon black, etc. .

The present invention will be explained in more detail below by way of examples.

In addition, regarding the flame retardancy test method in the example, the flame test method specified in the UL standard was adopted.

Example 1 1.3,6-tris (4,6-cyami2 1°3.
0.24 mol of 5-1-IJ azin-2-yl)hexane (hereinafter abbreviated as TG) and 1.44 mol of cyanuric acid were added to 500 g of dimethyl sulfoxide (hereinafter abbreviated as DMSO), and the mixture was heated in an oil bath. The temperature was raised to 160'C without stirring, and after reacting at the same temperature for about 30 minutes, it was cooled to room temperature to precipitate the salt, which was then separated and filtered, and an additional 500 g of DM was added.
Recrystallize at 140'C in SO and pass through separation filter, Honsuri 11
The salt was synthesized by washing with water and drying.

The salt was identified by IR1 elemental analysis and quantification of primary amino groups and hydroxyl groups.

Elemental analysis C: 33.6% N: 39.3 H: 3.
6 coefficient 0: 23.5 coefficient (theoretical value C: 33.4φ N: 38.9 coefficient H: 3.
5 ratio 0:24.2%) 1, R, 3400C:wL, 1330CrrL 7
The ammonium ion salt was converted into commercially available nylon 66 (hereinafter abbreviated as N66).
The dry pellets were blended with the amounts shown in Table 1, kneaded using a conventional extruder, and extruded as a monofilament.

After pelletizing this, using an injection molding machine, 127 mm
×12.7 mm×O, 8 mm UL combustion test test was created.

For comparison, test pieces of N66 alone, cyanuric acid alone as a flame retardant, and test pieces of compositions in which N66 was blended with a mixture of cyanurate and TG were prepared.

Table 1 shows the test results conducted on these test pieces.

From the results in Table 1, it can be seen that the composition of the present invention exhibits excellent twist resistance and also has excellent molding stability.

Examples 2 to 3 The flame retardant used in Example 1 was mixed with N66 in the formulation shown in Table 1.
After pelletizing, UL test pieces were prepared and tested in the same manner as in Example 1.

From the results in Table 1, it can be seen that the composition of the present invention exhibits excellent twist resistance and excellent molding stability.Example 4 TGo, 24 mol and cyanuric acid 0.72 mol Example 1 The salt was synthesized by reaction and purification under the same conditions.

The analysis results of this salt are as follows.

Elemental analysis C: 35.8%, N: 41.7%.

H: 3.8 yen, 0: 18.7% 1, R, absorption 3400crrL, 1.330cr
fL' Primary amine group 2.8 pcs/mole Hydroxyl group 6.1 pcs/mode From the above, this salt is [R1(NI2)3(NH3)3]
It can be seen that the ratio is 3+[R2(OH)20]3-.

Next, UL test pieces were prepared using the formulations listed in Table 2 in the same manner as in Example 1.

Example 5 A salt was synthesized in the same manner as in Example 1 using 24 mol of TGo and 0.24 mol of cyanuric acid.

Elemental analysis C: 40.0%, N: 46.7% H: 4.8
0:8.5% ■, Specific absorption 3400cIrL, 1330cIIL' Primary amine group 5.2/mode Hydroxyl group 1.7/mode From the above, this salt is (R1(NI2)5(NH3)
) ” [R2(OH)20]-.

Next, UL test pieces were prepared using the formulations listed in Table 2 in the same manner as in Example 1.

Example 6 A salt was synthesized in the same manner as in Example 1 using 24 moles of TGo and o and os moles of cyanuric acid.

Elemental analysis C: 42.3 excellent, N: 49.6%.

H: 5.2 ratio, 0: 2.9% 1, R, absorption 3400CrrL, 1330CIr
L' Primary amine group 5,2 units/mol Hydroxyl group 0.1 units/mol or more, this salt is [R1(NI2)5(NI(3)6[R2O3]5-) I understand.

Next, UL test pieces were prepared using the formulations listed in Table 2 in the same manner as in Example 1.

Example 7 0.24 moles of T G and 0.24 moles of dimethyl cyanurate
A salt was synthesized using the same molar ratio as in Example 1.

Elemental analysis C: 44.4%, N: 46.6%.

H: 5.7 units, 0: 3.3% Primary amine group 5.3 units/mol Hydroxyl group 0.2 units/mol or more, this salt is (R1 (NI2)5 (NH3)
)”(R2(CH3)2 o)-.

Next, UL test pieces were prepared using the formulations listed in Table 3 in the same manner as in Example 1.

Example 8 TGo, 24 malt, monophenyl cyanurate 0.2
A salt of 4 mol was synthesized in the same manner as in Example 1.

Elemental analysis C: 48.1 width, N: 42.0%.

H: 4.8 units, O: 5.1 primary amino group 5.1 units/mol e hydroxyl group 1.1 units/mole From the above, this salt is CR1(NI2)5 (NH3)
] “(R21)h (OH) 0 )−.

Next, UL test pieces were prepared using the formulations listed in Table 3 in the same manner as in Example 1.

Example 9 A salt was synthesized in the same manner as in Example 1 using 24 mol of TGo and 0.24 mol of tris(2-hydroxyethyl)isocyanurate.

Elemental analysis C: 42.3%, N: 37.3%H: 60%
, 0:14.4 primary amino group 51 1 mole hydroxyl group 2.2 1 mole or more, this salt is (R1(NH2)5(NH3))+
It can be seen that [R3(C2R50H)2 (C2R50) )-.

Next, UL test pieces were prepared using the formulations listed in Table 3 in the same manner as in Example 1.

Example 10 A test piece was prepared by mixing a predetermined amount of the flame retardant used in Example 1 with the thermoplastic and thermosetting resins shown in Table 4.

Test specimens were prepared for the thermoplastic resins using the same method applied to the polyamides in Examples 1-9.

The diallyl phthalate resin has a momer of 60 to 80.
After the temperature was raised to .degree. C. and the flame retardant was dissolved therein, 2 g of dicumyl peroxide was added, and the mixture was injected between glass plates and cured.

The obtained cured product was cut into a predetermined shape to prepare a test piece.

For thermosetting, polyester is made by condensing polyglyco-2 remalate from maleic anhydride and ethylene glycol, adding styrene monomer, benzoyl peroxide, a reaction accelerator, and a flame retardant to this, and placing it between glass plates. hardened.

The obtained cured product was cut into a predetermined shape to prepare a test piece.

Polyurethane was prepared by mixing tolylene diisocyanate, polyethylene glycol, and a flame retardant, and hardening and molding the mixture between glass plates.

The obtained molded product was cut into a predetermined shape to prepare a test piece.

The epoxy resin was prepared by mixing a bisphenol large epoxy resin, a curing agent (HHPA), and a flame retardant, and then heating and curing the mixture between glass plates.

The obtained molded product was cut into a predetermined shape to prepare a test piece.

The test results are shown in Table 4, and it can be seen that the various resin compositions of the present invention exhibit good flame retardancy.

Claims (1)

[Claims] 11,3,6-tris (4,6-diami2 1°3.5
-) containing 3 to 50 weight φ of a salt of riazin-2-yl)hexane and dianuric acid, isocyanuric acid, or a derivative thereof represented by the following formula (A) or (B). Flammable resin composition. (However, R in the formula may be the same or different and represent hydrogen, an alkyl group having 1 to 3 carbon atoms, an oxyalkyl group having 1 to 3 carbon atoms, or a phenyl group, and at least one of R is hydrogen or carbon It is an oxyalkyl group of numbers 1 to 3.)