JPS6021624B2 - Resin composition with excellent flame retardancy - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a flame-retardant resin composition with little plexus, excellent heat resistance and mechanical properties, and excellent moldability.

Several methods have been proposed for making secondary resin flame retardant.

The most widely used method is to add and mix a scale retardant to a resin, and known examples of this type of scale retardant include halogen-based retardants and nitrogen-based compounds.
Among these, halogen-based elutriants have problems in terms of toxicity and molding process. On the other hand, nitrogen-based compounds have relatively few toxicity problems, but they do cause the so-called mold deposit phenomenon, in which they sublimate and adhere to the mold during the molding process, and the molded product absorbs moisture and precipitates a retardant on the surface. There are problems such as the so-called bleed-out phenomenon, and in order to meet the social demand for improving the safety of electrical and electronic products, there are strong expectations for the development of flame-retardant resins that are free from practical problems. The present inventors have arrived at the present invention as a result of intensive studies in view of the above circumstances.

That is, the present invention provides a flame-retardant resin composition comprising a resin and a salt of diguanamine and isocyanuric acids, the content of the salt of diguanamine and isocyanuric acids being 3 to 5% by weight. It is something. Attempts to add cyanuric acid to resins have been made for a long time for the purpose of improving heat resistance and imparting flame retardancy. In particular, the addition of cyanuric acid for the purpose of imparting flame retardancy was disclosed in Japanese Patent Application Laid-Open No. 51-39750.
, No. 51-39751. However, none of the polyamide compositions provided in these publications have solved the problems such as mold deposit and bleed-out as described above, and are extremely unsatisfactory for practical use. However, the composition of the present invention has no problems such as mold deposits or lead-out, and can truly meet social needs. The present invention provides diguanamine represented by the formula,
Low toxicity, heat resistance, mechanical properties containing 3 to 5% by weight of isocyanuric acid represented by the formula {B), i, /cyanuric acid converter, cyanuric acid or a salt consisting of cyanuric acid converter The present invention also provides a flammable resin composition with excellent moldability.

(However, in the formula, R is as follows, n and m are 0 or a positive integer, and OS(n+m)mi10.

R, is hydrogen, 1CN, 1COOR2, 1C mother NR3R
4, R2, R3. R4, R5, R6, R7 are the same or different groups, and are hydrogen or an alkyl group having 1 to 20 carbon atoms) (wherein R' is hydrogen, an alkyl group having 1 to 3 carbon atoms, It represents 1 to 3 oxyalkyl groups or phenyl groups, and at least one is hydrogen or an oxyalkyl group having 1 to 3 carbon atoms.

R's in the same molecule may be the same or different. ) The diguanamine compound constituting the salt of the present invention is 1,6-bis(4,6-diamino-1,3,5-triazine-2)
Hexane, 1,6-pisu (4,6-diamino-1,3
,5-triazine-2)-3-hexanenitrile,1,
6-bis-(4,6-diamino-1,3,5-triazine-2)-3-hexanenitrile, 1,6-bis-(4
,6-diamino-1,3,5-triazine-2)-3-hexanecarboxylic acid, 1,6-bis-(4,6-diamino-1,3,5-triazine-2)-3-hexaneamide, 1,6-bis- (4,6-diamino-1,3,5-
triazine-2)-3-(aminomethyl)hexane, 1
, 4-bis-(4,6-diamino-1,3,5-triazine-2)butane, 1,2-pis-(4,6-diamino-1,3,5-triazine-2)ethane, 1,6-bis-(4 ,6-diamino-1,3,5-triazine-2)
-3-hexaneaminomethylcarboxylic acid, 1,6-bis-(4,6-diamino-1,3,5-triazine-2)
-3-hexaso-2-benzimidazole) and the like.

Examples of the isocyanuric acids or cyanuric acids constituting the salt of the present invention include isocyanuric acid, tris(2-hydroxyethyl)isocyanurate, cyanuric acid, methyl cyanurate, phenyl cyanurate, diphenyl cyanurate, tris(2-hydroxyethyl)isocyanurate, and tris(2-hydroxyethyl)isocyanurate. (hydroxyethyl) cyanurate, etc. The amount of the salt consisting of the diguanamine compound of the present invention and isocyanuric acids or cyanuric acids added to the resin is 3 to 5% by weight, preferably 4 to 3% by weight. If it is less than 3% by weight, the flame retardance is insufficient, and if it exceeds 5% by weight, the fluidity will be poor and the mechanical properties will be deteriorated, so that it is not practical.

Examples of the salt include an equimolar reaction salt of diguanamine and isocyanuric acid, a reaction salt of 1 mol of diguanamine and 2 mol of isocyanuric acid, or a mixture of these two types of reaction salts. These reaction salts are neutralized salts produced by a neutralization reaction between diguanamine, which is a base, and isocyanuric acid, which is an acid. These salts can be obtained by dissolving or dispersing diguanamine and isocyanuric acid in water or a suitable organic solvent and subjecting them to a heating reaction. The resin used in the present invention includes homobolyamides represented by nylon 60, nylon 610, nylon 612, nylon 6, nylon 11, nylon 12, etc., mixtures thereof, copolyamides, linear saturated resins such as polynethylene terephthalate, polytetramethylene terephthalate, etc. Polyolefins such as polyester, polyethylene and polypropylene, polyacrylic acid esters such as polymethyl methacrylate and polymethyl methacrylate, polyphenylene oxide, modified polyphenylene oxide, polystyrene, Amo resin, styrene acryl nitrile copolymer, polycarbonate,
Thermoplastic resins such as polyacetal homopolymer and polyacetal copolymer, furthermore, diallyl phthalate,
Examples include thermosetting resins such as thermosetting polyesters derived from diallyl terephthalate and diallyl-2,6 naphthalene dicarboxylate, polyurethane, and epoxy resins.

Among these resins, polyamide resins are particularly preferred. The flame-retardant resin composition of the present invention may contain beam pigments, lubricants, fillers, reinforcing materials, plasticizers, stabilizers, antistatic agents, and other additives as long as they do not impair the effects of the present invention. .

Reinforcing materials include glass fiber, carbon fiber, etc. Thickeners include higher fatty acids, higher fatty acid metal salts, bisamides, etc. Fillers include talc, clay, fired clay, mica,
Carunum silicate, calcium carbonate, calcium sulfate,
Antistatic agents such as glass beads, molybdenum disulfide, and graphite include various phosphate esters, sulfonic acids, quaternary ammonium salts, polyhydric alcohol esters, alkylamides, alkylamines, and conductive carbon black. In the present invention, there is no particular restriction on the method of mixing the flame retardant into the resin, and the method normally used when mixing powdered additives with the resin can be applied.

However, in order to improve the dispersion of the key fuel agent, it is preferable to knead the key fuel agent into the resin using an extruder or the like.
In addition, in the case of thermosetting resins, the monomer before curing,
Alternatively, a method of adding a prepolymer or a dope or compound made by adding a reinforcing agent or the like to a prepolymer, mixing the wires, and then molding is preferable.

The effects of the present invention will be specifically explained below with reference to Examples.
The present invention is not limited thereby.

Moreover, the test method in each example was carried out as follows. '
1' Flammability: US Under WrMrs.
tories Inc. The vertical combustion test shown in S Risagi CT94 was conducted on a 1/10 inch thick test piece.

[21 Molding processability: Regarding mold deposit,
When molding test pieces for combustion tests using a 1-ounce injection molding machine,
The mold during molding was observed to determine the presence or absence of mold deposits. Regarding bleed-out, a test piece for a combustion test was used, and the molded product surface was observed after being left in a heat and air oven at 15°C and a relative humidity atmosphere of 8°C and 80% relative humidity for 10 days. '3} Mechanical properties: Regarding tensile strength and elongation,
ASTM-D-63 mezod impact strength (with /) was measured according to ASTM-D-256. Example 1 1,4-bis(4,6diami/-1,3,5triazine-2)butane 276m (1 mol) and isocyanuric acid 2
58 ml (2 mol) was mixed with 50 ml of water at 80 pm and allowed to react for 1 hour. white powder 51
I got 0 nights.

Elemental analysis of this powder revealed that C=36.0%
, N-42.0%, 0=18.0%, H=4.0%. Nylon 66 pellet 4.5k9 and the above reaction product (adipoguanamine diisocyanurate) 0.5k
After mixing 9 and 9 in a tumbler, 2
Composition pellets were obtained by drilling and extrusion granulation at 80°C.

This pellet was molded using a 1-ounce injection molding machine, and its flammability, moldability, and mechanical properties were measured. The results are shown in Table 1, and it can be seen from this table that Example 1 has excellent flame retardancy, moldability, and mechanical properties. Examples 2 to 4 Comparative Examples 1 to 4 Similar to Example 1, the content of adipoguanamine diisocyanurate in the nylon 6-stripe composition was changed (Examples 2 to 4, Comparative Example 1)
~2), containing only isocyanuric acid (Comparative Example 3)
was manufactured and evaluated.

The results are shown in Table 1, and from this table it can be seen that at less than 3% by weight,
It can be seen that the flame retardancy is insufficient, and that when the amount exceeds 5% by weight, the mechanical properties are severely deteriorated. Examples 5-1
0 In the same manner as in Example 1, nylon 66 mixed with the retardants shown in Table 2 was manufactured and evaluated.

The results are shown in Table 2, and it can be seen that all the compositions were good. Examples 11 to 21 In the same manner as in Example 1, compounds in which adipoguanamine diisocyanurate was blended with various thermoplastic resins shown in Table 3 were manufactured and evaluated.

Diaryl phthalate resin is manufactured by its monomer (Asahi Yukizai D)
After heating P99 state J) to 50 to 80°C and dissolving the flame retardant therein, 2% dicumyl peroxide was added, and the mixture was injected into the glass slope and hardened.

The obtained cured product was cut into a predetermined shape to prepare a test piece. Epoxy resin is bisphenol A type epoxy resin (
After mixing AER661 (manufactured by Asahi Kasei Corporation), a hardening agent (HHPA), and a retardant, the mixture was heat-cured and molded between glass plates.

The obtained molded product was cut into a predetermined shape to prepare a test piece. The results are shown in Table 3, and good results were obtained in all cases. Table 1 Table 2 Table 3

Claims (1)

[Claims] 1. Diguanamine compound represented by formula (A) and formula (B)
or a resin composition with excellent flame retardancy characterized by containing 3 to 50% by weight of isocyanuric acid, an isocyanuric acid derivative, cyanuric acid, or a salt consisting of a cyanuric acid derivative represented by (C) ▲ Numerical formula, chemical formula, There are tables, etc. ▼ (However, R in the formula is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ where n and m are 0 or positive integers, and 0≦(n+m)≦10. R_1 is hydrogen, -CH, -COOR_2, -CH_2
NR_3R_4, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ -CONR6_R_7 or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ And R_2, R_3, R_4, R_5, R_6,
R_7 is the same or different group, hydrogen or carbon number 1-
20 alkyl groups) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (However, in the formula, R' represents 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 R' is hydrogen or an oxyalkyl group having 1 to 3 carbon atoms.R's in the same molecule may be the same or different.)2 In Claim 1, the resin is polyamide Composition 3, characterized in that the salt in claim 2 is adipoguanamine diisocyanurate, adipoguanamine monoisocyanurate, or a mixture thereof.