JPS6042826B2 - Phosphorus-containing flame-retardant resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel resin composition that is flame retardant and has excellent physical properties.

More specifically, the present invention provides 1,3,6-tris(4
・6-diamino-1.3 ・5-triazin-2-yl)hexane and cyanuric acid (or isocyanuric acid)
The present invention relates to a novel flame-retardant resin composition in which a combination of a phosphorus compound or a derivative thereof and a phosphorus compound is blended into a synthetic resin as a flame retardant. In general, organic polymer substances have excellent properties in terms of strength, weather resistance, abrasion resistance, dyeability, etc., and are widely used as resin molded products or fibers in general industry, clothing, etc. has been done.

However, these organic polymeric substances 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.

Conventionally, flame-retardant technologies and methods for resins include blending flame-retardant resins, adding flame retardants, manufacturing resins with flame-retardant monomers, and making flame-retardant resins through post-treatment. ing.

Among these methods, the method commonly used for resins is the method of adding flame retardants, and flame retardants include halogen-containing compounds, phosphorus-containing compounds, inorganic compounds, nitrogen-containing compounds, and the like. However, among these additive flame retardants, halogen-containing compounds generally have drawbacks such as poor heat resistance, poor sublimation bleed properties, and are often ineffective unless used together with antimony trioxide. The compound is
Resins that do not contain oxygen have little effect and must be used together with halogens, some resins may deteriorate due to decomposition, are generally liquid and may plasticize the resin, flame retardants may bleed, yellow-brown There are disadvantages such as many of them are colored.

Among inorganic compounds, antimony trioxide is a rare resource, and raw material availability and cost are unstable.
Furthermore, systems such as aluminum hydroxide have little effect and require addition in large amounts, and have drawbacks such as decreased physical properties, poor moldability, poor surface properties, and increased specific gravity. Substances such as aluminum hydroxide, which exhibit a flame retardant effect by emitting water during decomposition, generally have poor heat resistance, and have the disadvantage that the flame retardant effect and heat resistance are inversely proportional. Next, as nitrogen-containing compounds,
Melamine is a typical example, but melamine has poor heat resistance, sublimes during molding, and bleeds easily, and other products with good heat resistance are difficult to manufacture.
The price is very high (for example, tens of thousands of yen/K9), and resins to which these are added have disadvantages such as being impossible to manufacture industrially. Therefore, the present inventors conducted intensive research to solve the drawbacks of these flame retardants, and as a result, they developed 1,3,6-tris (4,6-diamino-1,3-tris), which has three triazine rings in one molecule.・5-triazin-2-yl)hexane and cyanuric acid, isocyanine. It is a guanamine compound that has the effect of using a phosphorus compound alone as a flame retardant, and is usually in the form of a white powder. It is.

In addition, the resin composition has better heat resistance than when used to form a salt with this compound, has fewer drawbacks such as sublimation and bleed, and has sufficient flame retardancy. We have discovered that it is possible to provide

The present invention has been made based on this knowledge. That is, the present invention provides CA) 1,3,6-tris(4,6-
Diamino-1,3,5-triazin-2-yl)hexane with the general formula (R in the formula may be the same or different, at least one of which is a hydrogen atom or has 1 carbon number)
-3 oxyalkyl groups, the others are alkyl groups having 1 to 3 carbon atoms or phenyl groups) and (B) at least one phosphorus compound; The weight ratio of (B) is 10:1 to 1:10
and the total amount of (4) and (B) is 3 of the total.
The present invention provides a flame-retardant resin composition characterized in that it is blended into a synthetic resin so that the amount is 5% by weight.

1 and 3, which are the raw materials for component (4) of the flame retardant in the present invention
・6-Tris(4,6-diamino-1,3,5-triazin-2-yl)hexane is obtained by reacting dicyandiamide with 1,3●6-tricyanohexane obtained by electrolytic trimerization of acrylonitrile. Examples of the cyanuric acid (or isocyanuric acid) of the above general formula (1) or (■) or its derivatives corresponding to general formula (1) that can be produced by the method include cyanuric acid, methyl Examples of cyanurate, phenyl cyanurate, diphenyl cyanurate, tris(2-hydroxyethyl) cyanurate, dimethylphenyl cyanurate, etc. that correspond to general formula (■) include isocyanuric acid, methyl isocyanurate, phenyl isocyanurate, etc. nurate, tris(2-hydroxyethyl) cyanurate, dimethylphenylisocyanurate, and the like.

The salt of component (4) used in the present invention is a basic substance 1,3,6-tris (4,6-diamino-1,3,5
- Triazin-2-yl)hexane and at least one acidic substance selected from cyanuric acid, isocyanuric acid, and their derivatives are dissolved or dispersed in an appropriate solvent and brought into contact with each other, and then Separately filter the salt, recrystallize it if necessary, or wash it with water etc.
It can be obtained by purification.

The reaction at this time may be a homogeneous reaction or a heterogeneous reaction, but
A homogeneous reaction is advantageous because it gives a higher yield. Also,
The reaction pressure is not particularly limited and may be reduced pressure, normal pressure, or increased pressure. The solvent used here includes dialkyl sulfoxide compounds such as dimethyl sulfoxide and diethyl sulfoxide, or β-methoxyethanol,
β-monoethoxyethanol, β-butoxyethanol, β
-methoxypropanonyl, β-monoethoxypropanol,
β-Butoxypropanol, β-methoquibutanol, β
These include monoethoxybutanol, isoamyl alcohol, primary amyl alcohol, secondary amyl alcohol, benzyl alcohol, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, pyridine, and water. The reaction temperature is 50 to 180°C, preferably 100°C.
Perform at ~160°C.

If the reaction temperature is below 50°C, the formation of salt will be slow,
A reaction temperature of 180'C or higher is not preferred because deterioration of the amino group occurs.

Although the reaction time depends on other reaction conditions, 10 to 18 powders is usually sufficient.

The salt obtained in this way is 1,3,6-tris(4
・6-diamino-1,3,5-triazin-2-yl)
The amino group, which is the basic group of hexane, and the cyanuric acid (
or isocyanuric acid) or its derivatives with acidic hydrogen, and since both components have a plurality of salt-forming units, various bonding forms can be considered. For example, it can be represented by the following general formula. Can be done.

However, R1 is a group represented by the formula, R2 is a group represented by the formula, R3 is an alkyl group having 1 to 3 carbon atoms or a phenyl group, R4 is an alkylene group having 1 to 3 carbon atoms, and ~a)b~CS. d) k to I) m) and n are 0≦a≦
3, 0≦b≦3, 1≦k≦6, 1≦1≦3, 0kn≦6
, 0km≦1, a+b=1. ．． c+d=MlO≦c≦A
lO≦d≦Bl6≧Knll≧Km) or (where R1, R3, R4, Kll, N..ml have the same meanings as above, and R5 is a group expressed when f=0) , a group expressed when f=1, a group expressed when f=2, and F..g..h,.i is O≦
f≦2, 0≦g≦3, f+g=1, h+i=MlO≦h
≦f, 0≦i≦g) Examples of the phosphorus compound used in the present invention include 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, potassium polyphosphate, sodium polyphosphate, Inorganic phosphorus compounds such as potassium metaphosphate, sodium metaphosphate, diphenyldecyl phosphite, diphenyl isodecyl phosphite, diphenyl isooctyl phosphite, distearyl pentaerythrityl diphosphite, diisodecyl pentaerythritol diphosphite, di(2 -ethylexyl)octylphenyl phosphite, dipropylene glycol, phosphite, diphenyl phosphite, tridecyl phosphite, tri(2-ethylhexyl) phosphite, trimethyl phosphite, triphenyl phosphite, triisodecyl phosphite, tri- Isooctyl phosphite, tris(dipropylene glycol) phosphite, tris(nonylphenyl) phosphite, tricresyl phosphite, phenyldecyl phosphite, phenyl diisodecyl phosphite, bis(neopentylglycyl) triethylene glycyl diphosphite organic phosphites, such as pentakis dipropylene glycol triphosphite, tetrakis(
hydroxymethyl)phosphonium chloride, bis(dipropylene glycol)hydroxymethanephosphonate, bis(dipropylene glycol)-α-hydroxy-β●β●β-trichloroethanephosphonate, tris(
These include organic phosphorus compounds such as polypropylene glycol 425) phosphonate, and aromatic organic phosphorus compounds represented by the following structural formula.

Examples of the resin used in the present invention include nylon 6
, polyamides such as nylon 610, or copolymers and mixtures thereof, linear saturated aromatic polyesters such as polyethylene terephthalate, polytetramethylene terephthalate, polyhexamethylene terephthalate, polyphenylene oxide, noryl, polyethylene, polypropylene and Polyolefins such as polystyrene, polyacrylic esters such as polymethyl acrylate and polymethyl methacrylate, poly(styrene-butadiene) copolymers, ABS resins, polycarbonates, polyacetal homopolymers, polyacetal copolymers, diallyl phthalate, diallyl terephthalate, Examples include thermosetting polyesters derived from diaryl-2,6-naphthalene dicarboxylate, and thermosetting resins such as polyurethane and epoxy resins, but more favorable effects can be obtained when noryl resins are used. .

The amount of these resins used is 50% for the composition of the present invention.
~97% by weight, preferably 70-9% by weight.

If the amount of resin exceeds 9% by weight, the flame retardant 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. 1,3,6-tris (4,6
-Diamino-1,3,5-triazin-2-yl)hexane, a salt of cyanuric acid, isocyanuric acid, or a derivative thereof, and a phosphorus compound can be blended into the resin using any known technique, but the present invention In order to obtain flame-retardant resin that takes advantage of the advantages of flame retardants used in
Internal compounding by 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.

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 melt-kneaded and then molded. 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 flame retardant resin composition of the present invention may contain conventional flame retardants or flame retardant aids (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, stabilizers, plasticizers, and dispersants may be added, as well as glass fibers, carbon fibers, talc, clays, fired clays, mica, calcium silicate, Calcium sulfate, calcium carbonate, glass beads, molybdenum disulfide,
It is also possible to include fillers such as internal reinforcing agents such as glassphite, and antistatic agents such as various phosphoric acid esters, sulfonic acids, quaternary ammonium salts, polyhydric alcohols, esters, alkylamides, alkylamine conductive carbon black, etc. be.

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

As for the flame retardancy test method in the examples, the flame retardant test method specified in the UL standard was used. Example 11.3.6-tris(4.6-diamino-1.3.5-triazine-2-
yl) 0.24 mol of hexane (hereinafter abbreviated as TG) and 1.44 mol of cyanuric acid were added in DMSO5OOy,
Heat to 160℃ while stirring in an oil bath, approx.
After reacting at the same temperature as the powder, cooling to room temperature to precipitate the salt, followed by fractional filtration, and further 500y(7) DMS.
After recrystallization in O at 140'C and fractional filtration, washing with about 11 g of water and drying, a salt was synthesized.

The salt was identified by 11R1 elemental analysis and quantification of primary amino groups and hydroxyl groups.

Elemental analysis values: C: 33.6%, N: 39.3%, H: 3
．． 6%, 0:23.5% (calculated value C when all reacted)
:33.4%, N:38.9%, H:3.5%, O:2
4.2%) 1-R34OO礪-1, 1330c7n-1
, ammonium ion primary amino group determination 0 pieces 1 mole Hydroxyl group determination 11.8 pieces 1 mole or more According to the result, the product becomes [R1(NH3)6]6+[R2(0H)20]6- I know that there is.

Next, this mixture of salt and trimethyl phosphite was mixed with commercially available nolyl pellets in the proportions shown in Table 1, and the mixture was kneaded using a conventional extruder and extruded as a monofilament.

After pelletizing this, using an injection molding machine, 127Tf$
A test piece for UL flame retardancy test of t×12.7T$L×0.8T was prepared. For comparison, a test piece made of Noryl alone was prepared.

It can be seen from the results in Table 1 that the composition of the present invention is excellent. Example 2 A salt was synthesized by reaction and purification using 0.24 mol of TG and 0.72 mol of cyanuric acid under the same conditions as in Example 1.

The analysis results of this salt are as follows. Elemental analysis value; C:
35.8%, N: 41.7%, H: 3.8%, 0
:18.7%IR34OOcm61330c7n-1
2.8 primary amino groups per mole 6.1 hydroxyl groups equal to or more than 1 mole, this salt is [R1(NH2)3(NH3)3]3+[R2(0H)
20] 3-.

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

Example 3 A salt was synthesized in the same manner as in Example 1 using 0.25 mol of TG and 0.24 mol of cyanuric acid.

Elemental analysis values; C: 40.0%, N: 46.7%, H:
4.8%, O: 8.5%1◆R34OOcm-1
, 1330cm-1 5.2 primary amino groups 1 mol 1.7 hydroxyl groups 1 mol or more, this salt is [R1(NH2)5(NH3)]8[R2(0H)20
] You can see that they are one.

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

Example 4 A salt was synthesized in the same manner as in Example 1 using 0.24 mol of TG and 0.08 mol of cyanuric acid.

Elemental analysis value; C: 42.3%, N: 49.6%,
H:5.2%, 0:2.9%1-R34OOcm-1
, 1330c! n-1 5.2 primary amino groups 1 mole 0.1 hydroxyl groups 1 mole or more, this salt is [R1(Nll,)5(NH3)]3+[R2O3]3
I realized that we are all one.

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

Example 5 A salt was synthesized in the same manner as in Example 1 using 0.24 mol of TG and 0.24 mol of dimethyl cyanurate.

Elemental analysis value; C: 44.4%, N: 46.6%,
H: 5.7%, O: 3.3% 14-R34OOcm-
1,1330cm-1 53 primary amino groups 1 mol 0.2 hydroxyl groups 1 mol or more, this salt is [R1(NH2)5(NH3)]8[R2(CH3)2
0]-.

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

Example 6 0.24 mol of TG and 0.24 monophenyl cyanurate
A salt was synthesized in the same manner as in Example 1 using mol.

Elemental analysis value; C: 48.1%, N: 42.0%,
H: 4.8%, 0: 5.1% 1-R34OOCrfl
-1, 1330cm-1 5.1 primary amino groups 1 mole 0.1 hydroxyl groups 1 mole or more, this salt is [R1(NH2)5(NH3)]8[R2ph(0H)
0]-.

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

Examples 7-9 Using the salts used in Example 1, UL test pieces were prepared using the formulations in Table 2 in the same manner as in Example 1.

Table 1 shows the results of combustion tests performed on the test pieces of Examples 1 to 9 and Comparative Example 1.

It can be seen from the results in Table 1 that the composition of the present invention is excellent.

Examples 10-13. Comparative Examples 2 to 5 Test pieces were prepared by mixing a predetermined amount of the flame retardant shown in Table 2 with the thermoplastic and thermosetting resin shown in Table 2.

(However, the salt used here is the same as the salt used in Example 4.) After mixing the epoxy resin, bisphenol A epoxy resin, hardening agent (HHPA), and flame retardant, it is poured between glass plates. It was heat-cured and molded.

Polyurethane was prepared by mixing tolylene diisocyanate, polyethylene glycol, and a flame 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 flame retardant of the present invention exhibit good flame retardancy.

Claims (1)

[Claims] 1 (A) 1,3,6-tris (4,6-diamino-1
・3,5-triazin-2-yl)hexane and general formula ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ mathematical formulas, chemical formulas,
There are tables, etc.▼ (In the formula, R may be the same or different, at least one of them is a hydrogen atom or an oxyalkyl group having 1 to 3 carbon atoms, and the others are alkyl groups having 1 to 3 carbon atoms.) or a phenyl group) and (B) at least one phosphorus compound.
Seeds, the weight ratio of (A) and (B) is 10:1 to 1:1
1. A flame-retardant resin composition characterized in that the total amount of (A) and (B) is in the range of 3 to 50% by weight based on the total weight of the synthetic resin. 2. The flame-retardant resin composition according to claim 1, wherein the phosphorus compound is an inorganic phosphorus compound. 3. The flame-retardant resin composition according to claim 1, wherein the phosphorus compound is a phosphite ester.