JPS6017314B2 - 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.
By adding tris(4,6-diamino-1,3,5-triazin-2-yl)hexane and a phosphorus compound in combination, a flame-retardant resin composition with good physical properties is provided.

The resin may also contain 1,3,6-tris(4,6-diamino-1,3,5-triazin-2-yl)hexane, a phosphorus compound, and one or two of cyanuric acid, isocyanuric acid, or derivatives thereof. The object is to provide a flame-retardant resin composition with even better physical properties by adding at least one of these types.

In general, organic polymer substances have excellent properties such as strength, weather resistance, abrasion resistance, and dyeability, and are widely used in general industry, clothing, etc. 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 resin flammability technologies and methods include: ■ Blending flame retardant resin, ■ Adding a flame retardant, ■
There are several methods: producing resin using flame-retardant monomers, (2) making the resin key flammable through post-treatment, (2) and others.

Among these methods, the most commonly used method for resins is the method (2) of adding scale flame retardants.The flame retardants used in this method include halogen-containing compounds, phosphorus-containing compounds, inorganic compounds, and nitrogen-containing compounds. There are compounds etc. Each of these additive-type retardants has drawbacks, and halogen-containing compounds generally have poor heat resistance, poor sublimation bleed properties, and are often ineffective unless used together with antimony trioxide. In addition, phosphorus-containing compounds have little effect on resins that do not contain oxygen, are often used together with halogens, decompose and deteriorate depending on the resin, and are generally liquid.
There are disadvantages such as plasticizing the resin, bleeding of scale retardant, and many of them are colored yellowish brown.

Among inorganic compounds, antimony trioxide is a rare resource, and raw material availability and cost are unstable. Systems such as aluminum hydroxide have little effect and require large amounts of addition, leading to decreased physical properties, poor formability, and surface roughness. Materials that have a flame retardant effect by emitting water when aluminum hydroxide is divided into equal parts and have disadvantages such as deterioration and increased specific gravity generally have poor heat resistance, and the flame retardant effect and heat resistance are inversely proportional. It has the following disadvantages. Next, melamine is a typical nitrogen-containing compound, but melamine has poor heat resistance, sublimates during moldability, and bleeds easily. It is difficult and extremely expensive (for example, tens of thousands of yen/kg), and resins to which these are added have drawbacks such as being impossible to manufacture industrially. Therefore, the present inventors
We should solve the drawbacks of these surfactants. As a result of intensive research, we found that 1, 3, 6, which has three triazine rings in one molecule.
- By using tris(4,6-diamino-1,3,5-triazin-2-yl)hexane and a phosphorus compound together as a flame retardant, the heat resistance is better than when the phosphorus compound is used alone. A flammable resin composition can be provided, and 1
・In addition to 3,6-tris(4,6-diami/1,3,5-triazin-2-yl)hexane and a phosphorus compound, cyanuric acid, isocyanuric acid, or their derivatives are used together as an elutriation agent. Furthermore, it has been found that it is possible to provide a flame-retardant resin composition with few defects such as sublimability and bleedability and excellent moldability.

That is, the present invention provides (1) resin, (b) 1,3,6 tris(4,6-diamino-1,3,5-triazin-2-yl)hexane, and (m) phosphorus other than phosphate ester. The total content of (0) and (m) is 3 to 5.
(W) cyanuric acid, isocyanuric acid, or isocyanuric acid represented by the following formula (1) or [BI]. The present invention relates to a resin composition with further excellent flame retardancy, which is obtained by adding a derivative. (However, R in the formula may be the same or different and represents hydrogen, an alkyl group having 1 to 3 carbon atoms, an oxyalkyl group having 1 to 3 carbon atoms, or a phenyl group) As the phosphorus compound used in the present invention, ,for example,
Red phosphorus, calcium phosphide, phosphorus tribromide, phosphorus oxybromide, phosphorus pentoxide, phosphorus oxychloride, phosphorus trichloride, ammonium phosphate, potassium phosphate, calcium phosphate, iron phosphate, sodium phosphate, magnesium phosphate , lithium phosphate, phosphotungstic acid, phosphomolybdic acid,
Guanidine phosphate, potassium polyphosphate, sodium polyphosphate, potassium metaphosphate, sodium metaphosphate, diphenyldecyl phosphite, diphenyl isodecyl phosphite, diphenyl isooctyl phosphite, distearylbentaerythrityl diphosphite, diisodecyl Bentaerythritol diphosphite, di(
2-ethylhexyl) octylphenyl phosphite,
Dipropylene glycol, phosphite, diphenyl phosphite, tridecyl phosphite, tri(2-ethylhexyl) phosphite, trimethyl phosphite,
Triphenyl phosphite, triisodecyl phosphite, triisooctyl phosphite, tris(dipropylene glycol) phosphite, tris(nonylphenyl) phosphite, tricresyl phosphite, phenyldecyl phosphite, phenyl diisodecyl phosphite, bis (neobentylglycyl) triethyleneglycyl diphosphite, tetrakis (hydroxymethyl)
Phosphonium chloride, Pis(dipropylene glycol) hydroxymethanephosphonate, Bentaxi dipropylene glycol triphosphite, Bis(dipropylene glycol) 1q-hydroxy-B.8.3-trichloroethanephosphonate, Tris(polypropylene glycol 425) phosphonate , etc., and phosphorus compounds represented by the following structural formulas, and one or more of these phosphorus compounds are used.

1,3,6-tris(4,6-diamino-1,3,5-triazin-2-yl)hexane used in the present invention is a 1,3-tris(4,6-diamino-1,3,5-triazin-2-yl)hexane obtained by electrolytic trimerization of acrylonitrile.
- A guanamine compound usually in the form of a white powder that can be obtained by the reaction of 6-tricyanohexane and dicyandiamide, and is represented by the following structural formula. In the resin composition of the present invention, phosphorus compounds other than (0) 1,3,6-tris(4,6-diamino-1,3,5-triazin-2-yl)hexane and (m) ester phosphate The total content is 3
-5% by weight, preferably 4-3% by weight.

If the content is 3% by weight, the flame retardance is insufficient, and if it exceeds 5% by weight, the mechanical properties will deteriorate.

Moreover, the ratio (m)/(0) (weight ratio) of (0) and (m) is 0.1 to 1, preferably 0.3 to 0.7.

If it is less than 0.1, the flame retardancy, sublimation resistance, and bleed resistance will be insufficient, and if it exceeds 1, the heat resistance will decrease, which is not practical. The resin used in the present invention includes, for example, polyamides such as nylon 6, nylon 60 and nylon 610, or copolymers and mixtures thereof, linear saturated aromatic resins such as polyethylene terephthalate, polytetramethylene terephthalate, and polyhexamethylene terephthalate. polyesters, polyphenylene oxide or mixtures thereof with polystyrene, polyolefins such as polyethylene, polypropylene and polystyrene, polyacrylate esters such as polymethyl acrylate and polymethyl methacrylate, poly(styrene-butadiene) copolymers,
ABS resin, polycarbonate, polyacetal homopolymer, polyacetal copolymer, diallyl phthalate, diallyl terephthalate, diaryl 2/6
Examples include thermosetting polyesters derived from naphthalene dicarboxylate, and thermosetting resins such as polyurethane and epoxy resins, but more favorable effects can be obtained when polyphenylene oxide resins are used. It will be done.

The amount of these resins used is 50 to 9% by weight, preferably 70 to 9% by weight, based on the total amount of the resin composition of the present invention. If the amount of resin exceeds 90% by weight, the flash effect will be reduced, and if it is less than 5% by weight, the moldability of the composition or the physical properties will deteriorate due to deterioration of the resin, which is not preferable. The aforementioned (1) resin, (0) 1,3,5 tris(4o6-diamino-1,3,5 triazine-2
-ylhexane and (m) a resin composition consisting of a phosphorus compound excluding a phosphate ester; and (W) a composition in which cyanuric acid, isocyanuric acid, or a derivative thereof represented by the above-mentioned compound and [B' formula] is added. provides a flame retardant resin composition with low sublimation and bleeding properties of flame retardants.

Further, cyanuric acid, isocyanuric acid, or derivatives thereof represented by the above formula (1) and Tsukuda used in the present invention include the following.

That is, as compounds represented by the general formula, for example, cyanuric acid, methyl cyanurate, phenyl cyanurate, diphenyl cyanurate, tris(2-hydroxyethyl) cyanurate, triphenyl cyanurate, trimethyl cyanurate, dimethylphenyl Examples of compounds represented by the general formula 'B' include cyanurate, etc.
For example, isocyanuric acid, methyl isocyanurate,
Phenyl isocyanurate, diphenyl isocyanurate, tris (2-hydroxyethyl) cyanurate, triphenyl isocyanurate, trimethyl isocyanurate, dimethyl phenyl isocyanurate, etc.
One or more of these compounds may be used. The amounts of these compounds added are (b) 1, 3, and 6 in the composition.
-tris(4,6-diamino-1,3,5-triazin-2-yl)hexane in an amount of 0.05 to 6 times, preferably 0.1 to 3 times, by mole. If it is less than 0.09 moles, the flame retardancy and moldability will be insufficient, and if it exceeds 6 times the mole, the resin will deteriorate and the loom properties will deteriorate.

1,3,6-tris(4,6-diamino)-1,3,5-triazin-2-yl)hexane, which is the elutriation agent of the present invention, a phosphorus compound, and a resin of cyanuric acid, isocyanuric acid, or a derivative thereof. Although any known technique can be applied to the blending method, internal blending by kneading is preferred in order to obtain a flame-retardant resin that takes advantage of the advantages of the flame retardant used in the present invention.

That is, in the case of a thermoplastic resin, the pellet or powder of the resin and the flame promoter may be mixed at room temperature and then molded using a melt molding machine such as an extruder, or after mixing, it may be made into a pellet and then molded. A method of melt-molding this pellet may also be used.

In addition, a resin containing a high concentration of the key refueling agent is manufactured in advance,
In addition to this method, a conventional method of melting and kneading a resin and then molding the resin can also be applied. In the case of thermosetting resins, it is generally preferable to add and mix them into a monomer, prepolymer, or a dope or compound made by adding a reinforcing agent to these before curing and then molding.

The Nada fuel burner resin composition of the present invention may be used with a subordinate chicken fuel agent or elutriation fuel additive (for example, antimony trioxide, barium metaborate, zirconium dioxide, iron oxide, zinc borate, etc.) to the extent that its physical properties are not impaired. ), matting agents, pigments, dyes,
Third components such as stabilizers, plasticizers, dispersants, etc. may be added, as well as glass fibers, carbon fibers, talc, clay, calcined clay, mica, calcium silicate, calcium sulfate,
Internal reinforcing agents such as calcium carbonate, glass beads, molybdenum disulfide, graphite, etc. Fillers Various phosphate esters, sulfonic acids, quaternary ammonium salts, polyhydric alcohols, esters, alkylamides, alkylamine conductive superpowers - antistatic properties such as bomb black It is also possible to include agents.

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 retardant test method specified in the UL standard was adopted. Examples 1 to 8, Comparative Example 1 A mixture containing commercially available dried pellets of Noryl (polyphenylene oxide polystyrene mixture: GE brand name) and the Nada retardant of the present invention in the proportions shown in Table 1 was heated to The mixture was kneaded with a Ktruder and weighed as a monofilament.

After forming this into pellets, using an injection molding machine, 127 side x 1
A test piece for UL combustion test of 2.7 ribs x 0.8 skin was prepared. For comparison, a test piece made of Noryl alone was prepared.

Table 1 shows the results for these test pieces. It can be seen from the results in Table 1 that the composition of the present invention is superior.

Table 1 Note) 1. The symbols are as shown in the table below.

Examples 9-10 Comparative Examples 2-5 Test pieces were prepared by mixing the thermoplastic and thermosetting resins shown in Table 2 with a predetermined amount of the retardant shown in Table 2.

For thermoplastic resins, test pieces were prepared using the same method as applied in Examples 1-8.

The epoxy resin was prepared by mixing bisphenol A type epoxy gutter resin, a hardening agent (HHPA), and a flame retardant, and then pouring the mixture between glass plates and heat-curing molding.

Polyurethane was prepared by mixing tolylene diisocyanate, polyethylene glycol, and a scale retardant, and hardening the mixture between glass plates. The test results are shown in Table 2, and it can be seen from this table that various resin compositions using the Nada flame agent of the present invention exhibit good flame retardancy.

Table 2 Note) 1 The same flame retardants as in Example 1 were used in Examples 9 to 12.

2 The same flame retardants as in Example 5 were used in Examples 13 to 16.

Claims (1)

[Claims] 1 (I) resin, (II) 1,3,6-tris (4,6-
diamino-1,3,5-triazin-2-yl)hexane and (III) a phosphorus compound (excluding phosphoric acid ester), and the total content of (II) and (III) is 3 to 50
% by weight. 2 (I) Resin, (II) 1,3,6-tris (4,6-
A resin comprising diamino-1,3,5-triazin-2-yl)hexane and (III) a phosphorus compound (excluding phosphoric acid ester), and the total content of (II) and (III) is 3 to 50% by weight. The composition further contains (IV) the following formula (A) or (
A flame-retardant resin composition comprising B) cyanuric acid, isocyanuric acid, or a derivative thereof. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, R in the formula may be the same or different and represents hydrogen, an alkyl group having 1 to 3 carbon atoms, an oxyalkyl group having 1 to 3 carbon atoms, or a phenyl group)