JPS5950183B2 - 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.
- Physical properties obtained by adding together tris(4,6-diamino-1,3,5-triacin-2-yl)hexane and one or more compounds selected from cyanuric acid, cyanuric acid derivatives, or isocyanuric acid derivatives. The present invention provides a good flame-retardant resin composition.

Generally, organic polymer substances have excellent properties in terms of strength, weather resistance, abrasion resistance, dyeability, etc., 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 flame retardant technologies and methods include: 1. Blending flame retardant resins, 2. Adding flame retardants, 3.
There are 4 methods for producing resins using flame-retardant monomers, 4 for making them flame-retardant through post-treatment, and 5 for others.

Among these methods, the method most commonly used for resins is the method of adding flame retardants (2).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 flame 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 the flame retardant, and many products are colored yellowish brown.

Among inorganic compounds, antimony trioxide is a rare 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 formability, and Substances 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 the manufacturing method for other compounds with good heat resistance is difficult. However, these resins are very expensive (for example, tens of thousands of yen/kg), and resins containing them cannot be manufactured industrially. Therefore, the present inventors conducted intensive research to solve the drawbacks of these flame retardants, and found that 1,3,6-
Tris(4,6-diamino-1,3,5-triazine-
By using 2-yl)hexane and cyanuric acid, isocyanuric acid, or their derivatives together as a flame retardant, the flame retardant effect can be improved, and the resulting flame retardant has higher heat resistance than melamine. Good, sublimable,
It has been found that it is possible to provide a flame-retardant resin without drawbacks such as bleeding.

That is, the present invention provides (I) 1,3,6-tris(4,6.-
diamino-1,3,5-triazin-2-yl)hexane and () cyanuric acid, isocyanuric acid, or derivatives thereof, and the total content of (I) and () is 3 to 3.
50% by weight, preferably 4 to 30% by weight, of a resin composition with excellent flame retardancy. The cyanuric acid and cyanuric acid derivatives used in the present invention are of the following formula (
It is a compound represented by ^, and isocyanuric acid and isocyanuric acid derivatives are represented by the following formula.

(However, 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.

) Examples of the compound represented by the general formula (au) include cyanuric acid, methyl cyanurate, phenyl cyanurate, diphenyl cyanurate, tris(2-hydroxyethyl) cyanurate, triphenyl cyanurate, trimethyl cyanurate, Dimethylphenyl cyanurate, etc., and the compounds represented by the general formula (BI) include:
For example, isocyanuric acid, methyl isocyanurate,
Phenyl isocyanurate, diphenyl isocyanurate, tris(2-hydroxyethyl) cyanurate,
These include triphenyl isocyanurate, trimethyl isocyanurate, and dimethyl phenyl isocyanurate.

1,3,6-tris(4,6-diamino-1,3,5-triazin-2-yl)hexane used in the present invention is a 1,3,
It is a normally white, unpowdered guanamine compound that can be obtained by the reaction of 6-tricyanohexane and dicyandiamide, and is represented by the following structural formula.

(1) 1,3,6-tris(4,6
The composition ratio ()/(1) of -diamino-1,3,5-triazin-2-yl)hexane and ()cyanuric acid, isocyanuric acid, or their derivatives is (molar ratio) 0
．． 05, preferably 0.1-3.

If this composition ratio is less than 0.05, the flame retardant effect will be insufficient, and if it exceeds 6, it will cause deterioration of the resin and cause problems such as a decrease in physical properties, so it is not practical. It's inappropriate. The resin used in the present invention includes, for example, polyamides such as nylon 6, nylon 66, and nylon 610, or copolymers and mixtures thereof, and linear saturated aromatic resins such as polyethylene terephthalate, polytetramethylene terephthalate, and polyhexamethylene terephthalate. polyesters, polyphelene oxides, polyolefins such as noryl, polyethylene, polypropylene and polystyrene, polyacrylic esters such as polymethyl acrylate, polymethyl methacrylate, poly(styrene-butadiene) copolymers, ABS resins, polycarbonates, polyacetal homopolymers Examples include thermosetting polyesters derived from polymers, polyacetal copolymers, diallyl phthalate, diallyl terephthalate, diallyl-2,6-naphthalene dicarboxylate, etc., and thermosetting resins such as polyurethane and epoxy resins. More preferable effects can be obtained when polyamide resin is used.

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

If the amount of resin exceeds 97% by weight, the flame retardant effect will be reduced, and if it is less than 50% by weight, the moldability of the composition or the physical properties will deteriorate due to deterioration of the resin, which is not preferable. The flame retardant of the present invention, 1,3,6-tris(4
,6-diamino-1,3,5-triazin-2-yl)
Any known technique can be applied to blend hexane, cyanuric acid, isocyanuric acid, or their derivatives into the resin, but in order to obtain a flame-retardant resin that takes advantage of the advantages of the flame retardant used in the present invention, , internal compounding by kneading is preferred.

In other words, in the case of Natsumachi plastic 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 flame retardant may be molded. A method of melt-molding pellets may also be used. Alternatively, a method can also be applied in which a resin containing a high concentration of the flame retardant is produced in advance, and this and a normal resin are melted and thickened and then molded. In the case of thermosetting resins, it is generally preferable to add and mix them into a dove or compound made by adding a reinforcing agent to monomers, prepolymers, or these before curing, and then molding.

The flame retardant resin composition of the present invention may contain conventional flame retardants or flame retardants (for example, antimony trioxide, barium metaborate, zirconium dioxide, iron oxide, zinc borate, etc.) to the extent that their physical properties are not impaired. , matting agents, pigments, dyes,
Third components such as stabilizers, plasticizers, and dispersants may be added, as well as glass fibers, carbon fibers, talc, clay, calcined resin, mica, calcium silicate, calcium sulfate,
Internal reinforcing agents such as calcium carbonate, glass beads, molybdenum disulfide, graphite, etc., fillers, various phosphoric acid esters, sulfonic acids, quaternary ammonium salts, polyhydric alcohols, esters, alkylamides, alkylamines, conductive carbon black, etc. It is also possible to include antistatic agents.

The present invention will be explained in more detail below using Examples.

In addition, regarding the flame retardant test method in the example, the flame retardant test method specified in the UL standard was adopted. Examples 1 to 5, Comparative Example 1 to
2 A mixture containing dry pellets of commercially available nylon 66 and the flame retardant of the present invention in the proportions shown in Table 1 was kneaded in a conventional extruder and extruded as a monofilament.

After pelletizing this, a tensile test piece was made using an injection molding machine.
And a 127n x 12.71 x 0.8mm (7) test piece for UL combustion test was prepared. For comparison, a test piece of polyamide alone and a test piece of a composition in which cyanuric acid was blended with polyamide as a flame retardant were prepared.

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

The results in Table 1 show that the composition of the present invention exhibits excellent flame retardancy.

Examples 6 to 11, Comparative Examples 3 to 6 The dried pellets of nylon 66 used in Example 1 were treated with 1,3,6-tris (4,6-diamino-1,3,5-triazine) as a flame retardant. -2-yl)hexane and cyanuric acid in the proportions shown in Tables 2 and 3 in a total of 10% by weight, pelletized in the same manner as in Example 1, and then formed into pellets using an injection molding machine. A UL combustion test piece was prepared in the same manner as in Example 1.

The results of the combustion test conducted using this test piece are shown in Tables 2 and 3.

From the results in Tables 2 and 3, it can be seen that if the amount of cyanuric acid added is less than the claimed range of the present invention, flame retardancy will occur, and if it is increased beyond the claimed range, flame retardancy and mechanical properties will deteriorate.

It can also be seen that, compared to using an untreated flame retardant, the use of a reacted flame retardant as a salt exhibits more favorable moldability and mechanical properties.

Examples 12 to 21, Comparative Examples 7 to 16 Test pieces were prepared by mixing the thermoplastic and thermosetting resins shown in Table 4 with a predetermined amount of the flame retardant shown in the notes of the table.

Test specimens were prepared for Netsucho plastic resin using the same method applied to polyamide in Examples 1-13.

Diaryl phthalate resin has its monomer heated to 60~80℃
After the flame retardant was dissolved therein, 2% 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. Thermosetting polyester is produced by polycondensing polyglycol malate from maleic anhydride and ethylene glycol.
This, styrene monomer, benzoyl peroxide,
A reaction accelerator and a flame retardant were added, and the mixture was cured between glass plates.

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 A type epoxy resin, a curing agent (HHPA), and a flame retardant, and then heating and curing the mixture between glass plates.

Claims (1)

[Claims] 1 1,3,6-tris(4,6-diamino-1,3,
5-triazin-2-yl)hexane and (II) the following formula (
Contains cyanuric acid, isocyanuric acid, or derivatives thereof shown in A) or (B), and contains the above (I) and (
A flame-retardant resin composition characterized in that the total content of II) is 3 to 50% by weight. ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (A) (B) (However, R in the formula may be the same or different, hydrogen, an alkyl group having 1 to 3 carbon atoms) , represents an oxyalkyl group or phenyl group having 1 to 3 carbon atoms)