JPS6042825B2 - Metal-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-triazine-2-
A novel flame-retardant resin composition in which a combination of hexane, cyanuric acid (or isocyanuric acid), or a derivative thereof, and a metal salt, metal oxide, or metal hydroxide is blended into a synthetic resin as a flame retardant. It is. In general, 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 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. There is.

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/Kg), and resins containing these compounds have drawbacks 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.・A salt of 5-triazin-2-yl)hexane and one or more compounds selected from cyanuric acid, isocyanuric acid, or their derivatives, and a metal salt, metal oxide, or metal hydroxide as a flame retardant. When used in combination, it is possible to provide a resin composition that has better heat resistance, fewer drawbacks such as sublimation and bleed properties, and has sufficient flame retardancy compared to when a phosphorus compound is used alone. I discovered that.

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) metal salts, metal oxides and metal hydroxides. The weight ratio of (4) and (B) is in the range of 10:1 to 1:10, and the total amount of (4) and (B) is 3 to 5% of the total amount of at least one selected from among them. The present invention provides a flame-retardant resin composition characterized in that it is blended into a synthetic resin so as to have a nominal weight of %.

1●3 which is the raw material 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. It is a guanamine compound with a structural formula that can be produced by.It is usually in the form of a white powder.

In addition, as the cyanuric acid (or isocyanuric acid) of the general formula (1) or (■) or its derivatives that are used to form a salt with this compound, examples of cyanuric acid corresponding to the general formula (1) include cyanuric acid Acid, methyl cyanurate, phenyl cyanurate, diphenyl cyanurate, tris(2-hydroxyethyl) cyanurate, dimethylphenyl cyanurate, etc., as those corresponding to general formula (■), such as isocyanuric acid, methyl isocyanurate, Phenyl isocyanurate, 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 the yield is higher. Further, the reaction pressure is not particularly limited and may be reduced pressure, normal pressure, or increased pressure.
Solvents used here include dialkyl sulfoxide compounds such as dimethyl sulfoxide and diethyl sulfoxide, or β-methoxyethanol, β-ethoxyethanol, β-butoxyethanol, β-methoxypropanol, β-ethoxypropanol, and β-butoxypropanol. , β-methoxybutanol, β-ethoxybutanol, isoamyl alcohol, primary amyl alcohol, secondary amyl alcohol, benzyl alcohol, dimethylformamide, dimethylacetamide, N-
Methyl-2-pyrrolidone, pyridine, water, etc. j
The reaction temperature is 50-180°C, preferably 100-160°C.
Perform at 0°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 preferable 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 multiple salt-forming units, various bond formations can be considered, for example, as represented by the following general formula. I can do it.

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~c'Sd)k) 1) m and n are 0≦a≦3
, 0≦b≦3, 1≦k≦6, 1≦1≦3, 0kn≦6,
0≦m≦1, a+b=1, c+d=MlO≦c≦AlO
≦d≦Bl6≧Knll≧Km)
or (but R1, R3, R4, Kll, N..m
has the same meaning as above, R5 is a group represented when f=0, a group represented when f=1, a group represented when f=2, and F. ．． g. ．． h. ．． i is 0≦
f≦2, 0≦g≦3, f+g=1, h+i=MlO≦h
≦FlO≦i≦g) On the other hand, examples of metal salts, metal oxides, and metal hydroxides used as component (B) of the present invention include zirconium antimonate, zirconium oxide, and calcium carbonate. , hydrated alumina,
Antimony glycol, quartz powder, silica sand, boric acid, dimethylsiloxane, phenyl silicate, triphenylantimony, zinc carbonate, antimony potassium tartrate, alum, etc.

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, polymethyl methacrylate, poly('X.
(ethylene-butadiene) copolymer, ABS resin, polycarbonate, polyacetal homopolymer, polyacetal copolymer, thermosetting polyester derived from diallyl phthalate, diallyl terephthalate, diaryl-2,6-naphthalene dicarboxylate, etc., and polyurethane, Examples include thermosetting resins such as epoxy resins, but more preferable effects can be obtained when noryl resins are used.

The amount of these resins used is 50% for the composition of the present invention.
~9% heel weight, preferably 70-9% heel 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
- A method for blending a salt of diamino-1,3,5-triazin-2-yl)hexane with cyanuric acid, isocyanuric acid, or a derivative thereof, and a metal salt, metal oxide, or metal hydroxide into a resin is known. Although any technique can be applied, internal compounding 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.

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,
A method of melting and kneading this and a conventional resin and then molding 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 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) to the extent that their physical properties are not impaired. etc.), matting agents, pigments, dyes,
Third components such as stabilizers, plasticizers, and dispersants may be added, as well as L-glass fibers, carbon fibers, talc, clay,
Internal reinforcing agents such as fired clay, mica, calcium silicate, calcium sulfate, calcium carbonate, glass beads, molybdenum disulfide, graphite, etc. Fillers Various phosphoric acid esters, sulfonic acids, quaternary ammonium salts, polyhydric alcohols, esters It is also possible to include an antistatic agent such as conductive carbon black, alkyl amide, or alkyl amine.

The present invention will be explained in more detail below using examples.
In addition, regarding the flame retardancy test method in the example, the combustion test method specified in the UL standard was adopted. Example 11.3.6-tris(4.6-diamino-1.3●5-triazine-2-
0.24 mol of hexane (hereinafter abbreviated as TG) and 1.44 mol of cyanuric acid were added in DMSO5OO,
The temperature was raised to 160°C while stirring in an oil bath, and about 3 particles were reacted at the same temperature, then cooled to room temperature to precipitate the salt, filtered separately, and then recrystallized at 140°C in 500g of DMSO. After fractional filtration, the product was washed with about 1' of water and dried to synthesize a salt.

The identity of this salt is 1. This was done by R1 elemental analysis and quantitative determination of primary amino groups and hydroxyl groups.

Elemental analysis value: c: 33.6% N: 39.3%
H: 3.6% 0:23.5% (calculated value when all reacted C: 33.4%, N: 38.9%, H: 3.5%, O
:24.2%)1. R3400cm-1, 1330d-
1 Ammonium ion Primary amino group determination: 0 1 mole Hydroxyl group determination: 11.8 1 mole or more From the results, the product is [R1(NH3)6]6+[
It can be seen that R2(0H20]6] has been completed.

Next, this mixture of salt and trimethyl phosphite was mixed with commercially available nolyl pellets in the proportions shown in Table 1, kneaded using a conventional extruder, and extruded as a monofilament.
After pelletizing this, we used an injection molding machine to produce 1277 T$.
A test piece for UL combustion test of L×12.7×0.8 mg 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 practical example was carried out using 0.24 mol of TG and 0.72 mol of cyanuric acid. A salt was synthesized by reaction and purification 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%1. R3400cm-1, 1330cTn
-1 primary amino group 2.8 1 mole hydroxyl group 6.
From 1 mole or more per piece, this salt is [R1(N)3(NH,)3]
It can be seen that 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 0.24 mol of TG and 0.24 mol of cyanuric acid.

Elemental analysis values: C: 40.0%, N: 46.7%, H: 4
．． 3%, 0:8.5%1. R3400cm-11330
cm-1 5.2 primary amino groups 1 mole 1.7 hydroxyl groups 1 mole or more, this salt is [R1(NH2)5(NH3)]
1 [R2(0H)20]-.

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. R3400cm-
11330cm-1 5.2 primary amino groups 1 mol 0.1 hydroxyl groups 1 mol or more, this salt is [R1(NH2)5(NH3)]
It can be seen that 3+[R2O3]3-.

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 values: C: 44.4%, N: 46.6%, H: 5
．． 7%, O: 3.3%1. R3400CTf1-113
30d-1 primary amino group5. ? From 0.2 hydroxyl groups per mole of 1 mole or more, this salt is [R1(NH2)5(NH3)]
1 [R2(Cll3)20]-.

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. R3400cm-1
1330CTfL-1 5.1 primary amino groups 1 mole 0.1 hydroxyl groups 1 mole or more This salt has [R1(NH2)5(NH3)]8
It can be seen that [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 For the thermoplastic and thermosetting resins shown in Table 2,
A test piece was prepared by mixing a predetermined amount of the flame retardant shown in the table.

(However, the salt used here is the same as the salt used in Example 4) After mixing the epoxy resin with bisphenol A epoxy resin L, a hardening agent (HlIPA), and a flame retardant, The mixture was poured in between and heat-cured and molded.

Polyurethane was prepared by mixing tolylene diisocyanate, polyethylene glycol, and a flame retardant, and hardening and molding 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 the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (R in the formula may be the same or different) and at least one of which is a hydrogen atom or an oxyalkyl group having 1 to 3 carbon atoms, and the others are an alkyl group having 1 to 3 carbon atoms or a phenyl group. and (B) at least one selected from metal salts, metal oxides, and metal hydroxides, (
The weight ratio of A) and (B) is in the range of 10:1 to 1:10, and the total amount of (A) and (B) is 3 to 10% of the total amount.
A metal-containing flame-retardant resin composition, which is blended into a synthetic resin in an amount of 50% by weight.