JPH07165982A - Flame retardant composition and flame retardant resin composition using the same - Google Patents

Abstract

PURPOSE:To obtain the composition, comprising a compound containing phosphors, a compound containing the triazine ring and a specific resin, excellent in flame retardancy and good in mechanical properties and moldability. CONSTITUTION:This composition comprises (A) a compound containing phosphorus (preferably ammonium polyphosphate having <=1.0g dissolved portion when dispersing 10g thereof in 90g pure water at 25 deg.C for 30min), (B) a compound, containing the triazine ring and selected from compounds (salts) containing the triazine ring in which >=2 amino groups bound to the triazine ring are unsubstituted and guanamine compounds (salts) having >=2 triazine rings in one molecule and (C) a resin which is a resin, comprising neither heterocyclic ring containing nitrogen nor C(=O)N< recurring unit in the main chain and having an amine compound (preferably dimethylamine, etc.) as a terminal group of the resin and/or a side chain thereof and/or a cross-linking agent fixed with a chemical bond.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame retardant composition and a flame retardant resin composition using the same. More specifically, it relates to a halogen-free flame retardant composition containing a phosphorus-based flame retardant, a triazine ring-containing compound and an amino group-containing compound as main components, and a flame-retardant resin composition using the flame retardant composition.

[0002]

2. Description of the Related Art Conventionally, halogen-based flame retardants have been mainly used for flame-retarded resins. However, recently, due to problems of environmental pollution and environmental destruction, a strict review has been made on the use of halogenated compounds, and various regulations have been put in place. Regarding halogen-based flame retardants, some countries have come to regulate the production and use of diphenyl ether-based halogen flame retardants.
Even in countries where regulations are not officially established, at the user stage,
There is a movement to voluntarily refrain from using the flame retardant. Furthermore, a flame-retardant resin composition using a halogen-based flame retardant generates a large amount of corrosive harmful gas when burned, and also produces black smoke, which causes many problems during a fire or incineration of resin. Is causing. Therefore, it has been strongly desired to provide a flame-retardant agent having higher safety in place of the halogen-based flame-retardant agent and a flame-retardant resin composition using the flame-retardant agent.

A flame retardant composition for forming a foamed carbonized layer, which is a combination of a phosphorus flame retardant and a nitrogen-containing compound or a polyvalent hydroxyl group-containing compound, has been developed as a flame-retardant having a higher safety level, which replaces the halogen-based flame retardant. In addition, a flame-retardant resin composition using the flame-retardant composition has been developed and provided. For example, an example of combining a phosphorus-based flame retardant and a nitrogen-containing compound is a flame retardant composition that uses a triazine ring-containing compound as the nitrogen-containing compound. More specifically, a flame retardant composition (USP 4, comprising a 1,3,5-triazine derivative oligomer containing a nitrogen-containing heterocycle in the main chain in which a triazine ring derivative is linked with a polyamine and ammonium polyphosphate is used. 504, 610), and a flame retardant composition (U.S.P. S.P. 4, 312, 805).

Further, ammonium polyphosphate and tris-
Flame-retardant composition (USP 4,7) comprising (2-hydroxyethyl) isocyanurate or its oligomer
27, 102) and the like, each of which uses a nitrogen-containing compound having a polymer structure as a flame retardant component. More recently, ammonium polyphosphate,
Synthesized from cyanuric chloride and various amines,
Flame retardant composition containing 2,4,6-triamino-1,3,5-triazine derivative (EP-415,371A)
2), a flame retardant composition (USP.5, comprising ammonium polyphosphate and a bistriazinylpiperazine derivative)
116,891) and the like, wherein a triazine ring-containing compound having no polymer structure is used as the nitrogen-containing compound.

Further, amine phosphates and amine pyrophosphates (USP 4,599,3) are used as nitrogen-containing compounds exhibiting excellent flame retardant performance in combination with phosphorus-based flame retardants.
75), amine / hydrogen halide salt (USP 4,
136, 082, U.S.S. S. P. 4,096,113) and the like are disclosed. The nitrogen-containing compound having a polymer structure having a triazine ring or —C (═O) N <repeating unit in the main chain and exhibiting excellent flame retardancy when combined with a phosphorus-based flame retardant is It has problems such as lack of affinity with resins derived from the structure and high softening temperature.When these flame retardants are added to olefin-based or styrene-based resins with relatively low processing temperatures, the flow of resin composition Deteriorates the workability, impairs the processability, and significantly deteriorates the physical properties of the resin product. Further, in the polymer having the above-mentioned structure, even if it is used as an oligomer or a low molecular weight compound, its drawbacks are not improved.

Further, the triazine ring-containing compounds used in combination with the phosphorus-based flame retardants in these prior arts are special ones obtained through complicated synthetic processes using cyanuric acid chloride or isocyanuric acid as a starting material. However, when used in combination with a phosphorus-based flame retardant, it exhibits excellent flame retardancy, but on the other hand, it is expensive, which is an obstacle to substitution of halogen-based flame retardants.

Inorganic acid salts of amines are usually highly hygroscopic and water-soluble, and when used as a flame retardant for molding resins, they are dissolved and extracted by environmental moisture and bleed out on the surface of the molded product. In addition, there is a problem that the flame retardant effect decreases with time.

Flame retardant compositions containing a polyvalent hydroxyl group-containing compound instead of a nitrogen-containing compound have also been developed. This is to react the phosphoric acid and the polyvalent hydroxyl group-containing compound in advance,
A spiro-ring-type phosphoric acid ester is synthesized, and then a salt is formed with a triazine ring-containing compound (U.
S. P. 4,154,930). Although this flame retardant composition also has excellent flame retardant performance, it has been pointed out that when it is made into a composition with a resin, it bleeds out because of its hydrophilicity and lack of affinity with the resin.

[0009]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide a flame-retardant composition exhibiting excellent flame retardancy and suppressing deterioration of processability and physical properties of resin products, and the flame-retardant composition. It is an object of the present invention to provide a flame-retardant resin composition using a substance at a low cost by using a phosphorus-based flame retardant or a triazine ring-containing compound that is relatively inexpensive and easily available.

[0010]

DISCLOSURE OF THE INVENTION The inventors of the present invention have solved the problems of the above-mentioned prior art in cost, imbalance in performance and deterioration of moldability, and are flame retardant compositions which can be substituted for halogen flame retardants. And further to provide a flame-retardant resin composition using the same. As a result, in a flame retardant composition comprising a phosphorus-based flame retardant and a triazine ring-containing compound, it was found that the inclusion of a small amount of an amine compound significantly improves the flame retardant performance of the flame retardant composition,
Furthermore, it has been found that the object of the present invention can be achieved by combining this amine compound with an optimum resin and resin component.

That is, the present invention provides (a) a phosphorus-containing compound,
(B) one or more kinds selected from a triazine ring compound in which two or more amino groups bonded to the triazine ring are unsubstituted or a salt thereof, a guanamine compound having two or more triazine rings in a molecule or a salt thereof Triazine ring-containing compound, (c) nitrogen-containing heterocycle in main chain and -C (= O)
A flame retardant composition comprising a resin containing no N <repeating unit and having an amine compound fixed by a chemical bond as a terminal group and / or a side chain and / or a cross-linked chain of the resin is excellent. It has been found that the flame-retardant resin composition has a flame-retardant property and can solve the problems of the prior art, and can sufficiently oppose a flame-retardant resin composition using a halogen-based flame-retardant agent in terms of cost. .

Examples of the (a) phosphorus-containing compound that can be used in the present invention include inorganic phosphorus compounds such as ammonium polyphosphate and red phosphorus, salts of melamine phosphate, melamine pyrophosphate and the like, trioctyl phosphate, trilauryl phosphate, tristearyl. Organic phosphates such as phosphate, tricresyl phosphate, trixylenyl phosphate, trimethyl phosphite, tris- (2
Examples include organic phosphites such as -ethylhexyl) phosphite and tristearyl phosphite, and phosphonates such as diethyl phenylphosphonate and dioctyl phenylphosphonate diallylphenylphosphonate. When using these phosphorus-containing compounds to make the resin flame-retardant, it is necessary to include a certain amount or more of phosphorus element in the resin, so it is necessary to use a compound with a high phosphorus content to reduce the addition amount. This is suitable because it can reduce the demerits in physical properties due to the addition of the phosphorus-containing compound. In this respect, the inorganic phosphorus-containing compound is suitable for use, but ammonium polyphosphate is most suitable in consideration of safety. Further, as the ammonium polyphosphate used for flame retarding the resin, 25 g of ammonium polyphosphate is used.
When dispersed in 90 g of water for 30 minutes as a slurry,
It is preferable that the amount of ammonium polyphosphate dissolved is 1.0 g or less in order to avoid problems such as bleed-out when the resin composition is used under high temperature and high humidity.

The triazine ring-containing compound (b) used in the present invention does not need to have a special functional group introduced therein for improving the flame retardant performance as disclosed in the prior art. It is possible to use a triazine ring-containing compound that is available at a relatively low cost. For example, triazine ring-containing compounds suitable for use in the present invention include melamine, ammeline, melamine cyanurate, melam, melem, benzoguanamine, phthalodiguanamine, butylene diguanamine, spiro diguanamine, bis (4,6-diamino-1, 3,5
-Triazin-2-yl) -cyclohexane, JP-A-5-
8-179263, methylene dimelamine, ethylene dimelamine, trimethylene dimelamine, tetramethylene dimelamine, hexamethylene dimelamine,
Examples of 1,3-hexylenedimelamine, p-xylenedimelamine, and the like, which do not undergo any substitution reaction on the —NH ₂ group bonded to the triazine ring, are exemplified, and phosphorus of the above-exemplified triazine ring-containing compound is exemplified. Acid salts, pyrophosphates, sulfates, hydrogen halides and the like can also be used in the present invention. Further, for example, a so-called amino resin, which is a polymer of melamine and formalin, can be used in combination with these triazine ring-containing compounds or alone.

While the inventors of the present invention have studied in detail the flame retardant performance of a flame retardant composition comprising a phosphorus-based flame retardant and a triazine ring-containing compound, the presence of an amine compound causes the phosphorus-based flame retardant and the triazine ring compound to intervene. It has been found that the flame retardant performance of the flame retardant composition consisting of the above is remarkably improved, and that the addition effect of the amine compound can be best expressed by fixing this to the optimum resin component, and the present invention has been achieved. .

Ordinary amine compounds sublime or evaporate more or less at the processing temperature of the resin, which causes deterioration of the working environment, and many of them have a high hydrophilicity, and are extracted from the resin by water in the environment during use. Tends to lose its effect of addition over time, and many of them have a large rate of being evaporated and lost when exposed to high temperatures during combustion,
It has the problem that it does not work sufficiently during combustion when flame retardant performance must be exhibited. As a result of intensive studies to solve the problems of the amine compound, the present inventors have (c) a nitrogen-containing heterocycle or -C in the main chain.
(= O) N <resin containing no repeating unit,
It has been found that a resin having an amine compound fixed by a chemical bond as a terminal group and / or a side chain and / or a cross-linked chain of the resin is effective in solving such a problem. Further, in the present invention, the resin in which the amine compound is chemically bonded is chemically bonded to the polymer or oligomer having an affinity for the flame-retardant resin or the flame-retardant resin itself. It has been found that a fixed one is suitable. Thus, by fixing the amine compound to the polymer or oligomer by a chemical bond,
Even an amine compound that cannot be directly used for a molding resin that requires heat processing can be sufficiently used as a flame retardant composition component.

Therefore, the amine compound which can be used in the present invention may be a compound having one or more amino groups in one molecule, such as an aliphatic amine, an aromatic amine, an alicyclic amine, a heterocyclic amine and a silicon. Any of the contained organic compound amine and the like can be used.

By reacting one or more of these amines with a polymer or oligomer having a functional group capable of easily forming a chemical bond with the amine, a resin in which the amine compound used in the present invention is chemically bonded is produced. It is possible. Further, a copolymer having an amine-containing monomer as a copolymerization component can also be used as the resin obtained by chemically bonding the amine compound of the present invention. In the present invention, since the amine particularly exhibits a special function, it is necessary to have an amino group that still has the characteristics of the amine after the immobilization reaction of the amine. For example, when monoamine is used as the amine compound, a polymer having a glycidyl group as a functional group may be used.

As the aliphatic amine, t-butylamine,
Monoamines such as n-amylamine, dimethylamine and diethylamine, diamines such as ethylenediamine, trimethylenediamine, 1,2-diaminopropane, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine and other triamines Aromatic amines such as polyamines of aniline, benzylamine,
Phenylenediamine, diaminodiphenylmethane, diaminodiphenyl sulfone, xylylenediamine, N,
N'-phenyl-phenylenediamine, bis (3,4-
Diaminophenyl) sulfone, etc., cyclohexylamine as alicyclic amine, 2-methyl-1-aminocyclohexane, cyclohexenediamine, 3,3′-dimethyl-4,4′-diaminocyclohexylmethane, etc., heterocyclic amines, piperidine, piperazine And those having a lower alkyl group at the carbon atoms constituting the ring, 2,2
6,6-Tetramethylpiperidine, 2,3,5,6-tetramethylhyperazine and 4-aminopiperidine having an amino group bonded thereto, morpholine, 2,6-diaminopyridine and 1,3,5-tris (2- Hydroxyethyl)-
2,4,6-hydrotriazine and the like can be mentioned. Further, as the amine compound, an amino group-containing organic silane compound such as γ-aminopropyltriethoxysilane, an amine having a functional group other than the amino group such as hydroxyamine such as ethanolamine and propanolamine can be used, and a functional group other than the amine is used. It is also possible to fix the amine compound to the resin. Further, an adduct of an epoxy resin and an aliphatic polyamine such as an adduct of propylene glycol diglycidyl ether and diethylenetriamine, a modified aliphatic polyamine such as an adduct of bisphenol-A epoxy resin and ethylenediamine, EP4000 (Asahi Denka Co., Ltd.), EH651 (Asahi Denka Co., Ltd.) Modified aromatic polyamines such as) are also included in the amine compounds usable in the present invention. In some cases, these adducts can be directly used as a resin in which the amine compound of the present invention is fixed by a chemical bond.

Basically, use of a resin having these amine compounds fixed thereon can provide a flame retardant composition having a flame retardant performance equivalent to or better than that of the prior art, but having a small carbon / nitrogen atomic ratio. , Cycloalkyl, heterocyclic amine compounds such as dimethylamine, diethylamine, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, aniline, benzylamine, diaminodiphenylmethane, xylylenediamine, cyclohexylamine, piperidine, piperazine, 1,3,5-Tris (2
-Hydroxyethyl) -2,4,6-hydrotriazine, ethanolamine, propanolamine and the like are used in the resin, excellent flame retardancy can be obtained with a smaller amount of addition, and the flame retardant composition is used. It is preferable in that the workability of the resin composition and the deterioration of the physical properties of the molded article can be suppressed.
As a resin for fixing an amine compound by a chemical bond, a polymer having a functional group capable of easily reacting with a functional group such as an amino group, for example, a glycidyl group, an anhydrous carboxyl group, a maleimide group, a carboxyl group, a methylol group, for example, ethylene / Glycidyl methacrylate copolymer, styrene / glycidyl methacrylate copolymer, ethylene / acrylic acid copolymer, styrene / maleic anhydride copolymer, maleated polyolefin, epoxy resin, maleimide resin, N-methylolation (meth ) Acrylamide copolymers and oligomers thereof.

When a resin having a sufficiently small molecular weight such as an oligomer is used as the resin, the resin having the amine compound fixed thereon not only improves the flame retardancy but also improves the fluidity of the flame retardant resin composition. It is also used as an agent. As a method of fixing an amine compound by a chemical bond to a resin having a functional group capable of easily reacting with the amino group, a method of dissolving the resin in a solvent and carrying out an immobilization reaction of the amine compound in a solution state, A method of reacting with an amine compound in a molten state in a suitable kneading machine such as an extruder or a Banbury mixer, and a method of kneading a flame-retardant resin, the above polymer, and an amine compound in a molten state in a suitable kneading machine. and so on.

In addition to the method of fixing an amine compound to the functional group using a polymer or oligomer having a functional group which easily reacts with an amino group as described above, 2- (dimethylamino) ethyl acrylate, 2 −
The amine compound of the present invention is also chemically bonded by copolymerizing an amino group-containing monomer such as (dimethylamino) ethyl methacrylate with other radically polymerizable olefin-based, styrene-based, or acrylic-based monomers. A resin can be manufactured.

When the amount of the amine compound in the resin in which the amine compound is fixed by a chemical bond is excessive with respect to the resin portion, the resin itself in which the amine compound is fixed tends to be hygroscopic and water-soluble, The property which is not preferable as a flame retardant for molding resin becomes stronger. On the other hand, if the amount of the fixed amine compound is too small, when this is used as a component of the flame retardant composition, the effect of using the resin obtained by fixing the amine compound by a chemical bond as a component is lost. Therefore, the ratio of the amine compound to the resin fixing the amine compound is usually preferably 1: 1 to 1:10.

The phosphorus-based flame retardant described above, particularly ammonium polyphosphate, a triazine ring-containing compound, a resin containing no nitrogen-containing heterocycle or -C (= O) N <repeating unit in the main chain, and the terminal group of the resin. And / or a side chain and / or a cross-linking chain, which has a flame-retardant effect more than that of a halogen-based flame retardant, and is a harmful gas by forming a resin containing an amine compound bonded by a chemical bond at an appropriate ratio. It is possible to obtain a highly safe flame retardant with a small amount of black smoke and black smoke. The optimum composition ratio varies depending on the phosphorus-based flame retardant used, the triazine ring-containing compound, the type of resin in which an amine compound is chemically bonded, and the type of resin to be flame retarded, but generally polyphosphoric acid is used. Ammonium 1
10 to 6 parts by weight of triazine ring-containing compound
The range of 0 parts by weight and 5 to 40 parts by weight of the fixed amine compound shows excellent flame retardancy. When the phosphorus element or the triazine ring compound in the flame retardant composition is too small, when used as a flame retardant for a thermoplastic resin, the effect of preventing the drip that melts down while the resin is ignited during the combustion of the resin becomes small. , Flame retardant performance is reduced. When the nitrogen element weight ratio of the fixed amine compound in the flame retardant composition is too small, when the flame retardant composition of the present invention is used as the flame retardant of the resin, the resin in which the amine compound is chemically bonded becomes difficult. The effect of being used as one component of the flame retardant composition is lost, and the self-extinguishing property of the burning resin deteriorates. On the contrary, the flame retardant composition containing a large amount of amine compound does not improve the flame retardant performance even if the amount is large, and when used as a flame retardant for a resin, there is a demerit that causes deterioration of the hue of the resin due to heat or light. come.

The present invention also includes a flame retardant resin composition comprising the above flame retardant composition and a resin. The flame-retardant resin is, for example, an olefin resin, a styrene resin, an acrylic resin, a thermoplastic polyester resin, a polycarbonate resin, a polyphenylene oxide resin, or another thermoplastic resin that is usually used for molding, an unsaturated polyester. Thermosetting resins such as resins, epoxy resins and polyurethane resins may be mentioned. More specifically, as the olefin resin, polyethylene, polypropylene, polybutene-1,
Polymethylpentene, ethylene-propylene copolymer,
Examples thereof include ethylene-vinyl acetate copolymers, ethylene-acrylic acid copolymers, ethylene-acrylic acid ester copolymers, maleated polyolefins and polycycloolefin copolymers. Polystyrene as styrene resin,
High impact polystyrene (HIPS), styrene-acrylonitrile copolymer, styrene-methyl methacrylate copolymer, ABS resin, MBS resin, block SBR and the like can be mentioned. Representative examples of the acrylic resin are polymethylmethacrylate and acrylonitrile copolymer. As the polycarbonate resin, C, H, O containing bisphenol-A, bisphenol-S, etc. as components
Polycarbonate containing only is typical, and halogen-containing polycarbonate containing tetrabromobisphenol-A as a component is excluded from the present invention. A typical polyphenylene oxide resin is poly- (2,6-dimethylphenylene) -ether, which also includes those modified with HIPS. As the thermoplastic polyester, polyethylene terephthalate, polybutylene terephthalate and the like are typical, maleic acid as the unsaturated group source as the unsaturated polyester, those using an unsaturated polycarboxylic acid such as fumaric acid, polybutadiene glycol,
Examples include those using unsaturated polyhydroxy such as trimethylolpropane monoallyl ether. The flame retardant composition of the present invention imparts excellent flame retardancy to the resins listed above, but particularly has a remarkable effect on flame retardancy of flammable resins such as olefin resins and styrene resins. Show.
Further, it can be used not only as a molding resin but also as a flame retardant for paint resins.

The method of preparing the thermoplastic flame-retardant resin composition is as follows.
A method of melt-kneading the flame retardant composition together with a flame retardant resin using a Banbury mixer, a mixing roll, a twin screw extruder, and the like, a phosphorus-based flame retardant that is a component of the flame retardant composition, a triazine ring-containing compound, There is a method in which a compound containing an amino group and a resin to be flame-retarded are charged into the same kneader and melt-kneaded.However, due to the difference in the preparation method, the flame-retardant resin composition obtained has a flame-retardant property. Since there is no difference in various physical properties such as the beginning, either method can be adopted. Further, in the present invention, when preparing the flame-retardant resin composition, pigments such as titanium oxide, zinc oxide, silica, hindered amine-based, hindered phenol-based, phosphite-based, phosphine-based stabilizers, silane coupling Agents, silicone resin oils, fluidity improvers such as silicone resins, and release agents can be added within a range that does not impair the effects of the present invention.

The ratio of the flame-retardant composition to the resin to be flame-retarded is not particularly limited, but is usually 10 to 30: 100 by weight.
Is. The flame retardant composition according to the present invention is particularly suitable as a flame retardant for polyolefins and styrene resins, and can impart the same or higher flame retardancy with a smaller addition amount than conventional flame retardant compositions, Since the addition amount may be small, deterioration of various physical properties of the resin composition due to the addition of the flame retardant can be minimized. That is, to give an example,
When a flame retardant composition composed of ammonium polyphosphate and melamine cyanurate is used as a flame retardant in the flame retardation of polypropylene, even if 35 parts by weight of the flame retardant is added to 100 parts by weight of polypropylene, UL94V-
Although the flame retardancy of 0 is not obtained, according to the method of the present invention in which a small amount of an amino group-containing compound is intervened in this flame retardant composition, UL94 is used even when the amount of the flame retardant used is about 20 to 25 parts by weight.
The flame retardancy of V-0 is obtained, and it is possible to improve various problems associated with the addition of the flame retardant, such as deterioration of processability of the resin composition, deterioration of mechanical properties, and deterioration of appearance.

The flame-retardant resin composition of the present invention containing the amino group-containing resin as one component is a flame-retardant composition using a conventional phosphorus-based flame retardant and a flame retardant composition containing a triazine ring-containing compound as a component. It has better flame retardancy than the resin composition, and it is possible to reduce the amount used to obtain the same flame retardancy, and the mechanical properties and appearance physical properties of the flame retardant resin composition accompanying the use of the flame retardant can be reduced. The decrease can be suppressed. Furthermore, since a resin containing an amino group can be used as a fluidity improving agent, it is possible to suppress deterioration of moldability of the flame-retardant resin composition.

[0028]

EXAMPLES The present invention will be described in more detail with reference to the following examples. Reference Example 1 Synthesis of resin in which amine compound is fixed by chemical bond Styrene / glycidyl methacrylate copolymer (trade name: ALMATEX AP2024, Mitsui Toatsu Chemicals, Inc.)
5 g) was dissolved in 30 ml of benzene, 4 g of pentaethylenehexamine was added thereto, and the mixture was reacted at 60 ° C. for 6 hours under stirring. The reaction was carried out without significant thickening due to crosslinking. After completion of the reaction, reprecipitation operation was performed using methanol, and the resin to which the amine compound was fixed was separated by filtration to collect 7.5 g of the resin.

Reference Example 2 Synthesis of Resin with Amine Compound Fixed by Chemical Bonding 5 g of styrene / glycidyl methacrylate copolymer (trade name: Armatex AP2024) was added to 30 m of benzene.
Dissolve in 1 l, add 3 g of piperazine to this, and stir under stirring 6
The reaction was carried out at 0 ° C for 6 hours. The reaction was carried out without significant thickening due to crosslinking. After the completion of the reaction, reprecipitation operation was performed using methanol, and the resin to which the amine compound was fixed was separated by filtration to recover 7.0 g of the resin.

Reference Example 3 Synthesis of Resin with Amine Compound Fixed by Chemical Bond 200 g of ethylene / glycidyl methacrylate copolymer (15% of glycidyl methacrylate) was added to xylene 2000.
It was dissolved in ml at 120 ° C. The temperature of the solution was lowered to 100 ° C., 200 ml of piperidine was added, and the reaction was carried out at 100 ° C. for 5 hours. After completion of the reaction, unreacted amine was removed at 90 ° C. under reduced pressure, and then reprecipitation operation with methanol was performed to separate the resin on which the amine compound was fixed by filtration.
0 g of the resin was obtained.

Reference Example 4 Synthesis of Resin Combining Amine Compound by Chemical Bond Styrene / maleic anhydride copolymer (trade name: Dailark 332 MT TC ACO Co., Ltd.) 200 g
Was dissolved in 2000 ml of toluene, 60 g of pentaethylenehexamine was added thereto, and the mixture was reacted at 100 ° C. for 5 hours with stirring. After completion of the reaction, reprecipitation operation was performed with methanol to obtain 240 g of a resin having an amine compound fixed thereon.

Reference Example 5 Synthesis of Resin with Amine Compound Fixed by Chemical Bond Styrene / glycidyl methacrylate copolymer (trade name: Almatex AP2024, manufactured by Mitsui Toatsu Chemicals, Inc.) 1
0 g was dissolved in 50 ml of toluene, and piperidine 5 was added to it.
g was added and the reaction was carried out at 100 ° C. for 5 hours. After completion of the reaction, unreacted piperidine and the solvent were removed at 70 ° C. under reduced pressure, and when half of the solvent was removed, reprecipitation operation was performed with methanol. The recovered resin on which the amine compound was fixed was 12 g.

Example 1 Preparation and Evaluation of Flame Retardant Resin Composition Polypropylene (trade name: Noblene BJHH manufactured by Mitsui Toatsu Chemicals, Inc.) 97 g, ammonium polyphosphate (EXO
LIT422 Hoechst Co., Ltd.) 20 g, melamine cyanurate 5 g (manufactured by Nissan Kagaku Co., Ltd.), and 6 g of the resin having the amine compound of Reference Example 1 fixed thereon were well mixed in a powder state, and then at a temperature condition of 200 ° C. Knead with a mixing roll, then pulverize, melt at 220 ° C, then 5 kg / c
12.5 mm x 125 m by press molding with a pressure of m ^2.
A test piece measuring m × 3.2 mm was prepared. Using the above test piece, a flame retardancy test based on the UL94 test piece vertical combustion test method was carried out, and the result was V-0. The results are shown in Table 1.

Example 2 Preparation and Evaluation of Flame Retardant Resin Composition 6 g of resin prepared by fixing the amine compound prepared in Reference Example 1,
Ammonium polyphosphate (EXOLIT422) 20
g, 5 g of melamine cyanurate well mixed with 97 g of polypropylene (Nobrene BJHH), then 200 ° C
The same test piece as in Example 1 was prepared by kneading with a mixing roll under the temperature conditions of 1, then crushing and press molding. Using this test piece, a flame retardancy test based on the UL94 test piece vertical combustion test method was carried out, and the evaluation was V-0. The results are shown in Table 1.

Example 3 Preparation and Evaluation of Flame Retardant Resin Composition The resin prepared by fixing the amine compound prepared in Reference Example 2 was used instead of the resin prepared by fixing the amine compound used in Example 2. A flame-retardant resin composition was prepared and flame-retardant was evaluated in the same manner as in Example 2. Flame retardant rating is V
It was -0. The results are shown in Table 1.

Example 4 Preparation and Evaluation of Flame Retardant Resin Composition Resin 200 fixed with amine compound prepared in Reference Example 3
g, ammonium polyphosphate (manufactured by EXOLIT422 Hoechst) 200 g, spirodiguanamine 50 g, and polypropylene (Mitsui Noblene BJHH Mitsui Toatsu Chemicals, Inc.) 820 g were thoroughly mixed, and then a small biaxial shaft under a temperature condition of 200 ° C. The mixture was kneaded with an extruder (made by Ikegai Tekko Co., Ltd.) and pelletized. After that, a molding test piece having the same size as that of Example 1 was produced with a small injection molding machine (manufactured by Yamashiro Seiki). When flame retardancy was evaluated according to the UL94 test piece vertical combustion test method, a rating of V-0 was obtained.
The results are shown in Table 1.

Example 5 Preparation and Evaluation of Flame Retardant Resin Composition Epoxy resin curing agent (diethylenetriamine was added to propylene glycol diglycidyl ether) obtained by adding amine to epoxy resin as a resin bound with amine compound. Compound) was used. 6 g of resin bound with the above amine compound, ammonium polyphosphate (E
XOLIT 422) 20 g, benzoguanamine (manufactured by Nippon Shokubai Kagaku Co., Ltd.) 5.0 g, polypropylene (Mitsui Noblene BJHH Mitsui Toatsu Chemical Co., Ltd.) 97 g
A flame-retardant resin composition was produced by kneading with a mixing roll under a temperature condition of 00 ° C. After crushing the resin composition,
The same test piece as in Example 1 was produced by press molding, and UL9
When the flame retardancy evaluation based on the test piece vertical combustion method of 4 was performed, the evaluation of V-0 was obtained. The results are shown in Table 1.

Example 6 Using Melamine Pyrophosphate as Phosphorus Flame Retardant 20 g of melamine pyrophosphate (manufactured by Mitsui Toatsu Chemicals Inc.) as a phosphorus flame retardant, 2 g of benzoguanamine, 4 g of dipentaerythritol, amine compound of Reference Example 3 20 g of resin fixing polypropylene, polypropylene (Mitsui Noblen BJHH) 8
2 g was kneaded with a mixing roll at a temperature of 200 ° C. to prepare a flame-retardant resin composition. The flame-retardant resin composition was crushed and press-molded to produce the same test piece as in Example 1. Flame retardant product evaluation according to UL94 V-
A rating of 0 was obtained. The results are shown in Table 1.

[0039]

[Figure 1]

* 1 Modified aliphatic amine: Diethylenetriamine added to propylene glycol diglycidyl ether. * 2 UL94 test piece vertical combustion test method evaluation results after the test piece for flame retardancy evaluation was boiled in hot water at 100 ° C. for 1 hour, dried, and then conditioned for evaluation.

Comparative Example 1 When no resin having an amine compound fixed thereon was used 100 g of polypropylene (Mitsui Noblene BJHH),
Ammonium polyphosphate (EXOLIT422) 20
g and 5.0 g of melamine cyanurate were kneaded with a mixing roll at a temperature of 200 ° C. to prepare a flame-retardant resin composition. After crushing the flame-retardant resin composition, the same molding test piece as in Example 1 was prepared by press molding, and UL94
The flame retardancy was evaluated based on the test piece vertical combustion test method. The evaluation result was V-2. The results are shown in Table 2.

Comparative Example 2 Prior Art Evaluation 100 g of polypropylene (Mitsui Noblene BJHH),
Ammonium polyphosphate (EXOLIT422) 20
g, 1,3,5-triazine derivative oligomer (EP1
Synthesized by the method described in 15871A2) 7.0 g
Was mixed with a mixing roll under a temperature condition of 200 ° C. to prepare a flame-retardant resin composition. After crushing the flame retardant composition, press molding was carried out in Example 1. The same test piece as described in (1) above was prepared, and the flame retardancy was evaluated according to the UL94 test piece vertical combustion test method. The evaluation result was V-0. The results are shown in Table 2.

Comparative Example 3 Prior Art Evaluation 100 g of polypropylene (Mitsui Noblene BJHH),
20 g of ammonium polyphosphate, 6.0 g of acidic piperazine pyrophosphate (synthesized by the method described in EP126,454), and 5.0 g of spirodiguanamine at 200 ° C.
Kneading was performed with a mixing roll under the temperature conditions of, to prepare a flame-retardant resin composition. After crushing the flame-retardant resin composition, the same test piece as in Example 1 was prepared by press molding.
Flame retardant evaluation was carried out in accordance with the test piece vertical combustion test method of L94. At the same time, the flame retardancy was evaluated after the test piece was immersed in hot water at 100 ° C. for 1 hour. It was V-0 before the hot water immersion test, but decreased to V-2 after the immersion.
The results are shown in Table 2.

Comparative Example 4 Prior Art Evaluation 100 g polypropylene (Mitsui Noblene BJHH),
15 g of ammonium polyphosphate, 5 g of melamine cyanurate, nylon 66 (-C (= O) -N <containing resin) 1
0 g was kneaded with a mixing roll at a temperature of 220 ° C. to prepare a flame-retardant resin composition. After crushing the flame-retardant resin composition, a test piece having the same dimensions as in Example 1 was produced by press molding, and the flame-retardant property was evaluated according to the test piece vertical combustion test method of UL94. The flame retardancy rating was V-0, but a finely pulverized product of nylon 66 having an average particle size of 100 microns or less was not available, and it was melted during kneading and regenerated as fine particles in polypropylene. Since it was not dispersed, the dispersibility of nylon 66 in the flame-retardant resin composition after kneading was poor, and the surface appearance, mechanical properties, and fluidity were very poor. The results are shown in Table 2.

[0045]

[Fig. 2] Example 7 Flame-retardant HIPS Impact-resistant polystyrene (Topolex 830, manufactured by Mitsui Toatsu Chemicals, Inc.) 760 g, ammonium polyphosphate (E
XOLIT422) 240g, Spirodiguanamine 60
g, and Irganox 1010 (10 g) were added, and 240 g of the resin obtained by fixing the amine compound obtained in Reference Example 4 was used as 210 g.
Under a temperature condition of ° C, the mixture was kneaded with a small twin-screw extruder to obtain a pelletized flame-retardant resin composition. A test piece having the same dimensions as in Example 1 was produced from the flame-retardant resin composition using a small injection molding machine, and the flame retardancy was evaluated according to the test piece vertical combustion test method of UL94. The evaluation result was V-1.
The results are shown in Table 3.

Comparative Example 5 HIPS Flame Retardant HIPS (Topolex 850 + Block SBR90
/ 10) 50 g, ammonium polyphosphate 12 g, spirodiguanamine 3 g, and Irganox 1010 1.0 g were added, and the mixture was kneaded at 220 ° C. using a mixing roll. After kneading, the mixture was crushed, and the same test piece as in Example 1 was produced by press molding, and a flame retardancy test based on UL94 was carried out. The evaluation was V2. The results are shown in Table 3.

Example 8 Flame Retardation of ABS Resin 80 g of ABS resin (trade name Santac UT62 manufactured by Mitsui Toatsu Chemicals, Inc.), 20 g of ammonium polyphosphate, 6.0 g of spiro diguanamine, 1.0 g of Irganox 1010 and 20 g of the resin having the amine compound fixed thereon obtained in Reference Example 5 was kneaded with a 200 ° C. hot roll to prepare a flame-retardant resin composition. After crushing the composition, a test piece having the same shape as that of Example 1 was produced by press molding, and a flame retardancy test was carried out in accordance with UL94. The flame retardancy evaluation was V-1. The results are shown in Table 3.

Comparative Example 6 Flame Retardant ABS Resin ABS Resin (Santac ET62 Mitsui Toatsu Chemicals, Inc.)
100 g, ammonium polyphosphate (EXOLIT
422) 20 g, spirodiguanamine 6 g, and Irganox 1010 were kneaded with a 1.0 g mixing roll at 230 ° C., pulverized, and then press-molded to prepare a test piece having the same shape as in Example 1. As a result of conducting the flame retardancy test based on UL94, the evaluation was V-2. The results are shown in Table 3.
Shown in.

[0049]

[Figure 3]

Comparative Example 1 is an example in which a resin having an amine compound fixed by a chemical bond was not used in the flame retardant composition, and Comparative Examples 2 to 4 are polyolefin resin flame-retardant resin compositions. It is an example using the flame retardant disclosed in the prior art. Examples 1 to 8 relate to the present invention using a resin in which an amine compound is fixed by a chemical bond as one component of a flame retardant composition. The flame-retardant resin composition according to the present invention has not only excellent flame retardancy but also excellent properties in fluidity (MFR) and mechanical properties (Izod impact strength) of the resin composition. Further, in Examples 1 to 8, since a low molecular weight amine was fixed to the oligomer or polymer by a chemical bond, almost no amine odor was generated during press molding.

[Flame Retardancy Evaluation Method] The flame retardancy evaluation method is performed according to the UL94 test piece vertical combustion test method. Explanation of terms Drip: A phenomenon in which a test piece burns into droplets while burning while burning. Self-extinguishing property: ability to spontaneously extinguish an ignited test piece when separated from the ignition source: A substance having self-extinguishing property equivalent to UL94V-0 is marked ◎. Physical property measurement method MFR (g / 10 minutes) JIS K
Conforming to 6758 Izod impact strength (Kg · cm / cm ² ) JIS K
6758 Tensile strength (Kg / cm ² ) JIS K
Complies with 6758

[0052]

The flame-retardant resin composition containing the amino group-containing compound of the present invention as one component is a flame-retardant composition using a conventional phosphorus-based flame retardant and a flame retardant composition containing a triazine ring-containing compound as a component. It has better flame retardancy than the resin composition, and the same amount of flame retardancy can be obtained to obtain the same flame retardancy. The decrease can be suppressed. Furthermore, since the amino group-containing compound can also be used as a fluidity improver, it is possible to suppress deterioration in moldability of the flame-retardant resin composition.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08L 33/14 LHT 101/00 LSY 101/02

Claims (8)

[Claims] 1. A (a) phosphorus-containing compound, (b) a triazine ring compound in which two or more amino groups bonded to a triazine ring are unsubstituted or a salt thereof, and guanamine having two or more triazine rings in one molecule. One or more triazine ring-containing compounds selected from compounds or salts thereof,
(C) A resin containing no nitrogen-containing heterocycle or -C (= O) N <repeating unit in the main chain, wherein an amine compound is chemically bonded as a terminal group and / or a side chain and / or a cross-linked chain of the resin. A flame retardant composition comprising a fixed resin. 2. The phosphorus-containing compound comprises 25 g of 10 g thereof.
When it was dispersed in 90 g of pure water at 30 ° C for 30 minutes, the dissolved content was 1.
The flame retardant composition according to claim 1, which is 0 g or less of ammonium polyphosphate. 3. A resin having an amine compound fixed by a chemical bond is an olefin resin, a styrene resin, an acrylic resin,
The flame retardant composition according to claim 1, which is an oligomer or polymer of an epoxy resin, a polymaleimide resin, or a silicone resin. 4. The amine compound fixed by a chemical bond in (c) of claim 1 is dimethylamine, diethylamine, ethylenediamine, 1,2-diaminopropane, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, penta. Ethylenehexamine, aniline, benzylamine, diaminodiphenylamine, xylylenediamine, cyclohexylamine, piperidine, piperazine, 1,3,5-tris (2-hydroxyethyl) -2,4,6-hydrotriazine, γ-amino The flame retardant composition according to claim 1, which is one or more selected from propyltriethoxysilane. 5. The resin having an amine compound fixed by a chemical bond is any one of a glycidyl group-containing resin, an anhydrous carboxyl group-containing resin, a carboxyl group-containing resin, a methylol group-containing resin, and a maleimide group-containing resin. The flame retardant composition according to claim 3, which is characterized in that. 6. An α-olefin / glycidyl (meth)
Acrylate copolymer, styrene / glycidyl (meth)
Acrylate copolymer, maleated polyolefin, styrene / maleic anhydride copolymer, α-olefin /
The flame retardant composition according to claim 5, wherein the amine compound is fixed to any of the (meth) acrylic acid copolymers by a chemical bond. 7. A flame-retardant resin composition comprising the flame-retardant composition according to claim 1 and a resin to be flame-retarded. 8. The flame-retardant resin is an olefin resin, a styrene resin, an acrylic resin, a polycarbonate resin, a polyphenylene oxide resin, a thermoplastic polyester resin, a polyoxymethylene resin, an unsaturated polyester resin, or an epoxy resin. The flame-retardant resin composition according to claim 7, which is a resin or a polyurethane resin.