JPS6042824B2 - 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-
The present invention relates to a novel flame-retardant resin composition in which a combination of hexane, cyanuric acid (or isocyanuric acid) or a derivative thereof, and a halogen 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 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. 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. Compounds have little effect on resins that do not contain oxygen and must be used together with halogens. Depending on the resin, decomposition and deterioration may occur.
In general, most of them are liquids, which have drawbacks such as plasticizing the resin, bleeding of flame retardants, and many of them being colored yellowish brown.

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 found that 1,3,6-tris (4,6-diamino-1, By using a salt of 3,5-triazin-2-yl)hexane and one or more compounds selected from cyanuric acid, isocyanuric acid, or their derivatives together with a halogen compound as a flame retardant, a halogen compound. It is a guanamine compound that has better heat resistance than guanamine, sublimation property, and free* properties, and is usually in the form of a white powder.

In addition, as cyanuric acid (or isocyanuric acid) or its derivatives of the general formula (1) or (■) used to form a salt with this compound, there are few drawbacks such as deterioration, and there is sufficient difficulty. It has been found that it is possible to provide a resin composition that has flammability.

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 halogen compound; The weight ratio of (B) is 10:1 to 1:
10, and the total amount of (4) and (B) is 3 to 5% of the total weight of the total weight of the flame retardant resin composition. There is.

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. Structural formulas that can be produced by formula (1) include, for example, cyanuric acid, methyl cyanurate, phenyl cyanurate, diphenyl cyanurate, tris(2-hydroxyethyl) cyanurate, dimethylphenyl cyanurate, etc. Examples of the compounds corresponding to the general formula (■) include isocyanuric acid, methyl isocyanurate, phenyl isocyanurate, tris(2-hydroxyethyl) cyanurate, and dimethylphenylisocyanurate.

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 It can be obtained by separately filtering the salt, recrystallizing it if necessary, or washing it with water, etc., and purifying it.

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
-methoxypropanol, β-monoethoxypropanol,
β-butoxyp C]/gunol, β-methoxybutanol, β-ethoxybutanol, isoamyl alcohol,
Primary amyl alcohol, secondary amyl alcohol, benzyl alcohol, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, pyridine,
Water etc.

The reaction temperature is 50-180°C, preferably 100-160°C.
Perform at °C. If the reaction temperature is 50° C. or lower, the formation of the salt will be slow, and if the reaction temperature is 180° C. or higher, amino groups will be degraded, which is not preferable.

Although the reaction time depends on other reaction conditions, 10 to 18 reactions 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 are possible.For example, it is represented by the following general formula. ! I can do three things.

(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~c ~d) k) I) m and n are O≦a≦3,
0≦b≦3, 1≦k≦6, 1≦I≦3, 0<n≦6, 0
<m≦1,. a+b=1. ．． c+d=MlO≦c≦Al
is an integer that satisfies O≦d≦B6≦Kmll≦Km)
or (where R1, R3, R4, k, l, n, m have the same meanings as above, R5 is a group expressed when f=0, a group expressed when f=1, a group expressed when f=2) is a group represented by F..g..h..i, 0≦
f≦2, 0≦g≦3, f+g=1, . h+i=MIO≦
h≦FlO≦i≦g)Next, examples of the halogen compound used as component (B) of the present invention include ammonium bromide, ammonium chloride, antimony trichloride, antimony oxychloride, and dichloride. Antimony perchloropentacyclodecane, 2-chlortetrabromobutane, 2●2-bis[p-(chloroformyloxy)
Phenyl-3]propane, 1●2-dibromo3-chloropropane, 1●23-tribromopropane, 11●2
●2-tetrabromoethane, tetrabromobutane, hexabromocyclododecane, hexabromooctane, hexabromobutane, pentab-heptamocyclohexane, tribromotrichlorocyclohexane, pentabromochlorocyclohexane, 1●2-dibromo1・1●2●2 -tetrachloroethane, 2●2-bis(4-hydroxy-3
●5-dibromophenyl)propane, 2,2-bis(4
-Hydroxyethoxy(3,5-dibromophenyl)propane, vinylchloroacetate, 2,4,6-tribromophenyl methacrylate, 2●3,3″-tripromoallylformate, 2,2-dibromopropyl methacrylate, bis (2●3-dibromopropyl)-2●3
-dibromofumarate, tribromophenyl acrylate, diallyl chloroendoic acid, bromostyrene, chloroendoic acid, chloroendoic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, chloropropanediol, 3-bromo22-bis(bromomethyl) Propanol, 2●2-dibromobutene-1●4-diol,
Tribromophenol, dipromoneopentyl glycol, tribromoneopentyl alcohol, 23-dibromopropanol, 2.3.3″-tribromoallyl alcohol, chloropentabromophenyl allyl ether,
Pentachlorophenoxyglycerin ether, bromophenyl allyl ether, tribromophenol allyl ether, pentabromophenol allyl ether, tetrabromobisphenol A allyl ether, pentabromophenyl allyl ether, bromoalkenyl ether, sorbitol-1●6-bis(2) ●3-dibromopropyl) ether, decabromodiphenyl ether, hexabromodiphenyl ether, dipromocresyl glycidyl ether, pentabromoallyl ether, 1,2-dibromopropyl tribromophenyl ether, decachlorodiphenyl carbonate, decabromodiphenyl carbonate, 2,3,3-tripromoallylcarboxylate, 2356, 2″, 3″, 5″, 6″-octachloro-4,4″-dioxydiphenyl, decabromobiphenyl, tetrabromobenzene, α◆β-dibromoethylbenzene, 2-bromo α◆β-dibromoethylbenzene, hexabromobenzene, tetrabromobisphenol A1 tetrabromobisphenol A diethoxylate, bis(2-hydroxyethyl ether)tetrabromobisphenol A1 decabromodiphenyl oxide,
decabromophenyl oxide, pentabromotoluene,
Tribromoaniline, acetylenetetrapromide, 1-
These are inorganic and organic halogen-containing compounds such as (p-tosyl)-3-(2-bromo444-trichlorobutyl)urea, 23-dibromopropanol ester, and dechlorane.

The resins used in the present invention include, for example, polyamides such as nylon 6, nylon 65s and nylon 610, or copolymers and mixtures thereof, linear saturated resins such as polyethylene terephthalate, polytetramethylene terephthalate, and polyhexamethylene terephthalate. Aromatic polyesters, polyphenylene oxides, noryl, polyolefins such as polyethylene, polypropylene and polystyrene, polyacrylic acid esters such as polymethyl acrylate, polymethyl methacrylate, poly(styrene-butadiene) copolymers, ABS resins, polycarbonates , polyacetal homopolymers, polyacetal copolymers, thermosetting polyesters derived from diallyl phthalate, diallyl terephthalate, diaryl-2,6-naphthalene dicarboxylate, and the like;
Examples include thermosetting resins such as polyurethane and 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 undesirable. 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 halogen compound can be blended into the resin using any known technique, but the present invention In order to obtain a flame-retardant resin that takes advantage of the advantages of flame retardants used in Internal blending by kneading is preferred.

That is, 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, they may be pelletized and then 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 melt-kneaded and then molded. In addition, in the case of thermosetting resins, monomers and
A preferred method is to add and mix into a prepolymer or a dope or compound made by adding a reinforcing agent or the like to the prepolymer, and then mold the material.

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 these 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
internal reinforcing agents, fillers such as aluminum, calcium carbonate, glass beads, molybdenum disulfide, and graphite, various phosphoric acid esters, sulfonic acids, quaternary ammonium salts, polyhydric alcohols, esters, alkylamides, alkylamines, conductive carbon black It is also possible to include antistatic agents such as.

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 building standards was adopted. Example 11 0.24 mol of 3,6-tris(4,6-diamino-1,3●5-triazin-2-yl)hexane (hereinafter abbreviated as TG) and 1.44 mol of cyanuric acid were added to DMSO5OOy. The temperature was raised to 160℃ while stirring in an oil bath, and the temperature was increased to about 3℃.
After reacting at the same temperature, the mixture was cooled to room temperature to precipitate the salt, then filtered separately, recrystallized in DMSO5OOy at 140°C, filtered separately, washed with water for about 1 minute, and dried. Synthesized salt.

The identity of this salt is 1. ．． This was performed using 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%, O: 23.5%, (calculated value when all reacted C: 33.4%, N: 38.9%, H: 3.5%
, O; 24.2%)1. R3400cm-1, 1330
cTrL-1, ammonium ion, primary amino group determination 0 pieces 1 mole hydroxyl group determination 1. From the results of more than 1 mol of pits, the product is [R1(NH3)6][R2
(0H)2]6-.

Next, this mixture of salt and dechlorane was mixed with commercially available noryl 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, 127Tn! n×12.7
Test pieces for UL combustion test were prepared in the order of wm x 0.8. 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 *
[R1(NH2)3(NH3)3]3+[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 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 value C: 40.0%, N: 46.7%, H: 4.
3%, O; 8.5%1. R3400cm-1, 1330
cm-1 5.2 primary amino groups 1 mol 1.7 hydroxyl groups 1 mol or more, this salt is [R1(NH2)5(NH3)]+[R2(0H)20
]-.

Next, 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%, O: 2.9%1. R3400cTn-1, 133
h-1 5.2 primary amino groups 1 mol*TGO. 24 moles of cyanuric acid and 0.72 moles of cyanuric acid were reacted and purified under the same conditions as in Example 1 to synthesize a salt.

The analysis results of this salt are as follows. Elemental analysis value C; 3
5.8%, N; 41.7%, H; 3.8%,
0; 18.7%, 1. R3400d-1, 1330[-
1 2.8 primary amino groups 1 mol Hydroxyl group From 1 mol or more, this salt is: From 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 value C: 44.4%, N: 46.6%, H: 5.
7%, 0; 3.3%1. R3400cTn-1, 133
0c! n-1 primary amino group5. Since 1 mole of brass has 0.2 hydroxyl groups 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%, O; 5.1%1. R3400α6133
0α-1 5.1 primary amino groups 1 mole 0.1 hydroxyl groups 1 mole or more This salt is [R1(NH2)5(NH3)]1[R2ph(0H)
It can be seen that it becomes O]-.

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 superior*2.

Examples 10-13. Comparative Examples 2 to 5 For the thermoplastic and thermosetting resins shown in Table 2, Table 2
A test piece was prepared by mixing a predetermined amount of the flame retardant shown below.

(However, the salt used here is the same as the salt used in Example 4) After mixing the epoxy resin, bisphenol A type epoxy resin, curing agent (HI (PA) and 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 halogen compound, 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% of the total amount. A flame-retardant resin composition, characterized in that it is blended with a synthetic resin in an amount of ~50% by weight.