JPH09268236A - Flame-retardant composition, thermoplastic resin composition compound with the flame-retardant composition and flame-retardant molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a flame-retarding agent to be compounded to a thermoplastic resin and having water-resistance and flame-retardance. SOLUTION: A modified ammonium polyphosphate treated with a triazine derivative and used as a flame-retarding main agent is produced by treating a melamine-coated ammonium polyphosphate with a triazine derivative. The objective flame-retarded thermoplastic resin composition contains 18wt.% of the flame-retarding main agent, 7wt.% of a homopolymer containing a nitrogen- containing compound consisting of 2-piperazinylene-4-morpholino-1,3,5-triazine as a monomer unit and 73.7wt.% of a thermoplastic resin consisting of a crystalline propylene-ethylene copolymer [having an ethylene content of 8.5wt.% and an MFR of 20g/10min (230 deg.C; 21.2N). The above flame-retarded composition may further be compounded with a polyhydric alcohol. The composition has a flame-retardancy of UL 94V-O, an oxygen index of 34.1, a heat-resistance of class A and a bleeding resistance of >=30 days.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a flame retardant composition having excellent heat resistance and imparting excellent flame retardancy when added to a thermoplastic resin, and a flame retardant heat containing the flame retardant. It relates to a plastic resin composition. Specifically, the present invention relates to ammonium polyphosphate (A) obtained by treating melamine-coated ammonium polyphosphate with a triazine derivative obtained by reacting a specific triazine compound with formaldehyde, a nitrogen-containing organic compound (B), and a polyvalent ammonium salt. Alcohol (C)
A flame retardant composition formed of one or more selected from the above, and a thermoplastic resin containing one or more selected from (B) and (C) in combination with the above (A). The present invention relates to a flame-retardant thermoplastic resin composition containing a flame retardant composition, and various flame-retardant molded articles molded from the flame-retardant thermoplastic resin composition.

[0002]

2. Description of the Related Art Conventionally, thermoplastic resins have been
Taking advantage of workability, chemical resistance, weather resistance, electrical characteristics, mechanical strength, and other advantages, it can be used in a variety of fields such as buildings, upholstery and automobile parts, including the field of industrial and household electrical products. It is widely used in the field and the applications in which thermoplastic resins are used are also expanding. With the expansion of such applications, thermoplastic resins are beginning to be required to have flame retardancy, and the required performance is becoming stricter year by year.

Particularly recently, a flame-retardant resin composition in which a halogen-containing compound, which is the mainstream of conventional flame-retarding techniques, is used alone or in combination with an antimony compound such as antimony oxide to form a flame-retardant, which is blended with a thermoplastic resin. It is regarded as a problem that a substance emits a halogen-based gas at the time of burning or molding. Therefore, there is a demand for flame-retardant resin compositions that do not generate these halogen-based gases during combustion or molding.

In order to meet these demands, recently, as a specific combustion suppressing formulation, in addition to causing an endothermic reaction at the combustion temperature of the resin, a specific metallic water capable of suppressing the combustion of the resin by its own decomposition and dehydration reaction. Measures for blending Japanese products have been proposed. However, it is necessary to add a large amount of the metal hydrate used in this method in order to make up for the weakness of the flame retardancy-imparting effect.
As a result, it has been recognized that the flame-retardant resin composition obtained has a decrease in molding processability and various characteristics such as a decrease in mechanical strength of a molded product obtained from the composition.

In order to solve this problem, recently, a method has been proposed in which a specific triazine derivative and a specific phosphorus compound are combined and blended with a thermoplastic resin to make it flame-retardant (for example, Japanese Patent Laid-Open Publication No. Hei 10 (1999) -242242). 3-149262, JP-A-3-215564).

Also proposed is a method of flame-retarding a thermoplastic resin by using a flame retardant in which a nitrogen-containing compound obtained by condensing a specific triazine derivative with an aldehyde such as formalin is combined with a specific phosphorus compound. (For example, European Patent Nos. 0542370 and 05).
No. 42376).

However, in the flame-retardant thermoplastic resin prepared by blending the flame-retardant agent described in the above-mentioned known literature with a thermoplastic resin, the amount of the flame-retardant agent to be blended is relatively low, but
The flame retardancy is still insufficient, and there has been a demand for a flame retardant exhibiting a higher flame retardancy and a flame retardant resin composition containing the flame retardant.

[0008] The present inventors have also reported that active hydrogen belonging to the amino group in the melamine unit already present in the coating layer of the melamine-coated ammonium polyphosphate particles and an organic compound having a functional group capable of reacting with the active hydrogen. Flame-retardant thermoplastic polymer composition containing, as an active ingredient, water-insoluble ammonium polyphosphate particles whose surface is cross-linked by the method described in JP-A-7-196842 and JP-A-7-196845.
Issue gazette).

However, the thermoplastic resin (polymer)
The flame retardant composition, which is a combination of the water-insoluble ammonium polyphosphate and the nitrogen-containing organic compound added to the composition, is inferior in heat resistance at high temperature, and thus the flame retardant composition was blended. Molded articles using the thermoplastic resin composition also have a problem of being colored at high temperatures.

[0010]

Therefore, in order to obtain a non-halogen flame retardant excellent in heat resistance in addition to being able to impart high flame retardancy when compounded with a thermoplastic resin, the present inventors Diligent research was conducted. As a result, a flame retardant comprising ammonium polyphosphate obtained by treating a melamine-coated ammonium polyphosphate with a triazine derivative obtained by reacting a specific triazine compound with formaldehyde and a nitrogen-containing organic compound and / or a polyhydric alcohol. The present invention was completed as a result of discovering that a composition solves the above-mentioned problems and further proceeding with research based on these findings. Here, "formaldehyde" in the present invention means "formaldehyde monomer"
However, it also includes multimers such as "dioxane" which is a dimer and "trioxane" which is a trimer, and "polyoxane".

As is apparent from the above, the object of the present invention is to provide a melamine-coated ammonium polyphosphate (A) treated with a specific triazine derivative, a specific nitrogen-containing organic compound (B) and a polyhydric alcohol (C). It is to provide a flame retardant which is a combination of one or more selected. Further, the object of the present invention is to impart a high degree of flame retardancy when blended with a thermoplastic resin, and yet to prevent coloring even at high temperatures, a non-halogen flame retardant and a flame retardant of the thermoplastic resin ( The purpose of the present invention is to provide a flame-retardant thermoplastic resin composition blended with D). In addition to the above, an object of the present invention is to provide various flame-retardant molded articles molded from the above flame-retardant thermoplastic resin composition.

[0012]

The present invention has the following constitutions: 1) Formed from the following components (A) and (B), the weight ratio B / A between the two components is 0.1 to 10. Flame retardant composition: (A) Modified ammonium polyphosphate treated with triazine derivative (B) Nitrogen-containing organic compound. 2) Flame retardant composition formed of the following components (A) and (C), in which the weight ratio C / A between the two components is 0.1 to 10: (A) Modified polyphosphoric acid treated with a triazine derivative Ammonium (C) polyhydric alcohols. 3) In addition to the following components (A), (B) and (C), the weight ratio (B + C) / A between the three components is 0.1 to 10, and the weight ratio B between the two components is B. / C is 0.1-10 flame retardant composition: (A) Modified ammonium polyphosphate treated with triazine derivative (B) Nitrogen-containing organic compound (C) Polyhydric alcohol. 4) The modified ammonium polyphosphate treated with the triazine derivative is represented by the following general formula (1) with respect to 100 parts by weight of the melamine-coated ammonium polyphosphate containing 0.5 to 20% by weight of the melamine unit based on the melamine monomer. A modified ammonium polyphosphate obtained by reacting formaldehyde with a composition containing 0.1 to 30 parts by weight of a mixture of one or more kinds selected from the group of triazine derivatives described above. The flame retardant composition according to any one of Items 1 to 3 below:

[0013]

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[Wherein R ¹ is a methyl group, a phenyl group or a group represented by the following general formula (2) or general formula (3)],

[0015]

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[0016]

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[Wherein R ² is a phenyl group and has 1 to 1 carbon atoms]
A straight-chain alkyl group having 12 or a branched alkyl group having 1 to 12 carbon atoms, and R ³ is hydrogen or a methyl group]. 5) Ammonium polyphosphate treated with a triazine derivative has a melamine unit of 0.5 based on the melamine monomer.
0.1 to 30 parts by weight of a mixture of one or two or more kinds selected from the group of triazine derivatives represented by the following general formula (1) with respect to 100 parts by weight of melamine-coated ammonium polyphosphate containing 20 to 20% by weight, And melamine and methylolmelamine having 4 to 9 carbon atoms [C ₃ H _6-n N ₆ (CH ₂ OH)
Reformation obtained by reacting formaldehyde with a composition containing 1 or more and 0.1 to 30 parts by weight selected from the group represented by _n (where n is a number of 1 to 6)] Item 5. The flame retardant composition according to any one of items 1 to 4, which is ammonium polyphosphate:

[0018]

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[Wherein R ¹ is a methyl group, a phenyl group,
A group represented by the following general formula (2) or general formula (3)],

[0020]

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[0021]

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[Where R ² is a phenyl group or 1 carbon atom]
Is a straight-chain alkyl group having 12 to 12 carbon atoms or a branched alkyl group having 1 to 12 carbon atoms, and R ³ is hydrogen or a methyl group]. 6) The nitrogen-containing organic compound is selected from homopolymers and copolymers consisting of structural units represented by the following general formula (4) 1
The flame retardant composition according to any one of Items 1 to 5 above:

[0023]

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[In the formula, X and Z are both groups bonded to the triazine skeleton through a nitrogen atom, and X is -NHR.
⁴ or —NR ⁵ R ⁶ is an alkylamino group, a morpholino group or a piperidino group, and R ⁴ , R ⁵ and R ⁶
Are both linear alkyl groups having 1 to 6 carbon atoms or branched alkyl groups (wherein R ⁵ and R ⁶ may be different from each other), and X is —NHR ⁷ or —NR ⁸ R ⁹ A hydroxyalkylamino group represented by R ⁷ , R ⁸ and R
⁹ is a straight-chain hydroxyalkyl group having 2 to 6 carbon atoms or a branched hydroxyalkyl group having 2 to 6 carbon atoms (wherein R ⁸ and R ⁹ may be different groups from each other). Z is a divalent piperazine group, of the formula —HN (CH ₂ ) _m
A divalent group represented by NH- (where, m is a number of 2 to 6) or _{^{-NR 10 (CH 2) p R}} 11 2 represented by N-
A valence group, at least one of R ¹⁰ and R ¹¹ is a hydroxyethyl group, and when either is a hydroxyethyl group, the other is a hydrogen atom or a linear alkyl group or branched alkyl group having 1 to 6 carbon atoms. It is a base]. 7) The nitrogen-containing organic compound is a product obtained by the reaction of cyanuric chloride and diamines, 1 to
The flame retardant composition according to item 6. 8) The flame retardant composition according to item 7, wherein the diamine is one or more selected from ethylenediamine, 1,3-diaminopropane, hexamethylenediamine and piperazine. 9) Nitrogen-containing compounds are melamine, melem, melam, ammeline, melamine phosphate, melamine polyphosphate, melamine cyanurate, tris (2-hydroxyethyl) isocyanurate, reaction products of ethylene urea and formaldehydes, ethylene thiourea Item 1 to 8 which is one or more selected from reaction products with formaldehydes, reaction products with ethylene urea, melamine and formaldehydes, reaction products with ethylene thiourea, melamine and formaldehydes. Combustion composition. 10) The polyhydric alcohols are one or more selected from pentaerythritol, dipentaerythritol, polypentaerythritol, neopentyl glycol, trimethylolpropane, mannitol, sorbitol, and complexes thereof with metal borate salts. 9. The flame retardant composition according to any of 9. 11) 99 to 50% by weight of the thermoplastic resin (D) is added to the above item 1
10. A flame-retardant thermoplastic resin composition containing 1 to 50 wt% of the flame retardant composition according to any one of 10 to 10 based on the weight of the final composition. 12) The thermoplastic resin is one or more selected from olefin resins, styrene resins, polyamide resins, polycarbonate resins, polyethylene terephthalate resins, polybutylene terephthalate resins, polysulfone resins, polyurethane resins and polyphenylene ether resins, and thermoplastic elastomers. Item 12. The flame-retardant thermoplastic resin composition according to item 11. 13) The thermoplastic resin (D) in an amount of 99 to 50% by weight is added to the above item 1
10. A flame-retardant thermoplastic resin molded article molded from the flame-retardant thermoplastic resin composition containing 1 to 50% by weight of the flame retardant composition according to any one of 10 to 10 based on the weight of the final composition.

[0025]

BEST MODE FOR CARRYING OUT THE INVENTION Ammonium polyphosphate treated with a triazine derivative which is one of the essential components constituting a flame retardant composition or a flame retardant thermoplastic resin composition containing the flame retardant according to the present invention ( A) is an amino group of a melamine unit present in the coating layer of melamine-coated ammonium polyphosphate, an amino group present in melamine, or a carbon number of 4 to 4
The ammonium polyphosphate produced by reacting the amino group present in the methylolmelamine of 8 or the amino group present in the specific triazine compound with the active hydrogen of the amino group and formaldehydes. According to such a treatment, it is presumed that the surface of the ammonium polyphosphate powder forms a crosslinked structure by the reaction with the triazine derivative, and such surface-crosslinked ammonium polyphosphate can be obtained by, for example, the following method.

100 parts by weight of ammonium polyphosphate coated with melamine having a melamine unit content of 0.5 to 20% by weight and 100 parts by weight of ammonium polyphosphate coated with melamine in a reactor having a heating and stirring function or a heating and kneading function. An aqueous solution of formaldehyde corresponding to 0.5 to 6 equivalent times with respect to the number of moles of the melamine unit is charged, and the inside of the reactor is mixed.

In the reaction between the melamine-coated ammonium polyphosphate and formaldehydes, the temperature is 10 to 120 ° C., which is a temperature at which the melamine-containing ammonium polyphosphate can easily react with the amino group of the melamine unit to form a methylol group. Both are reacted preferably at 20 to 90 ° C. for 1 min to 48 h to obtain a product in which the melamine molecule contained in the melamine-coated ammonium polyphosphate is methylolated. At this time, it should be noted that 12
It can be mentioned that when the reaction is carried out at a temperature higher than 0 ° C., dehydration condensation of the methylol group occurs violently, and conversely, at 10 ° C. or lower, the methylolation reaction becomes very slow.

On the other hand, 0.1 to 30 parts by weight of melamine or methylolmelamine having 4 to 9 carbon atoms and a triazine derivative represented by the above general formula (4) are placed in another reaction vessel having a heating and stirring function or a heating and kneading function. Charge 0.1 to 30 parts by weight of a mixture with one or more selected from the group.

Next, an aqueous solution of formaldehyde is
0.1 to 10 equivalent times, preferably 0.5 to 8 equivalent times the amount of the active hydrogen equivalent of the amino group contained in the triazine derivative or the like to be added are charged and mixed. At this time, it should be noted that the effect of improving the hydrolysis stability is poor when the addition amount of the aqueous formaldehyde solution is less than 0.1 equivalent times the triazine derivative, and more than 10 equivalent times. It can be mentioned that even if added in an amount, the amount of unreacted formaldehyde only increases.

After that, the reaction with the amino group can easily occur to form a methylol group at a temperature of 10 to 120.
The triazine derivative and the formaldehyde are reacted at 0 ° C, preferably 20 to 90 ° C for 1 min to 48 hours to prepare an aqueous solution or suspension (slurry) of the methylolated triazine derivative.

During the methylolation reaction of the melamine-coated ammonium polyphosphate or the methylolation reaction of the triazine derivative, an optional amount of a basic compound can be added as a catalyst.

The thus obtained methylolated melamine-coated ammonium polyphosphate and a mixed aqueous solution or suspension of melamine or a methylol melamine and a methylolated triazine derivative are provided in a reaction vessel equipped with a heating stirring device or a heating kneading device. 50 to 150 ° C., preferably 70 to 1 which is a temperature at which the condensation reaction can easily occur.
Both are reacted at 20 ° C. for 10 minutes to 10 hours. At this time, it should be noted that the condensation reaction rate is low at a reaction temperature of lower than 50 ° C., and ammonia is desorbed from ammonium polyphosphate at a temperature of higher than 150 ° C.

In the condensation reaction, a single solvent or a mixed solvent composed of water and / or an organic solvent can be used, and a water / alcohol mixed solvent can be preferably used. Further, in the condensation reaction, an optional amount of acidic compound can be added as a catalyst at any time. By such a method, a modified ammonium polyphosphate treated with a triazine derivative can be obtained. Other than this, there is a method of mixing each of the raw materials as described above after mixing them with each other, and then co-condensing them.Other than that, by mixing the respective raw materials in a specific ratio in advance, It can also be produced by a method in which a predetermined amount of formaldehyde is added to the active hydrogen of the amino group contained in the raw material mixture, and a methylolation reaction and then a cocondensation reaction are performed.

Examples of the above-mentioned triazine derivative include the following: acetoguanamine, benzoguanamine, succinylguanamine (succinylguanamine), 3,9-bis [2- (3,5-diamino-2,4, 6-Triazaphenyl) ethyl] -2,4,8,10-tetraoxaspiro [5.
5] Undecane, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-1,3,5-triazine, 2,4-diamino-6- [2'-ethylimidazolyl- (1 ')]-Ethyl-1,3,5
-Triazine, 2,4-diamino-6- [2'-propylimidazolyl- (1 ')]-ethyl-1,3,5-triazine, 2,4-diamino-6- [2'-butylimidazolyl- ( 1 ')]-Ethyl-1,3,5
-Triazine, 2,4-diamino-6- [2'-pentylimidazolyl- (1 ')]-ethyl-1,3,5-triazine, 2,4-diamino-6- [2'-hexylimidazolyl- ( 1 ')]-Ethyl-1,
3,5-triazine, 2,4-diamino-6- [2'-heptylimidazolyl- (1 ')]-ethyl-1,3,5-triazine, 2,4-diamino-6- [2'-octyl Imidazolyl- (1 ')]-ethyl-
1,3,5-triazine, 2,4-diamino-6- [2'-nonylimidazolyl- (1 ')]-ethyl-1,3,5-triazine, 2,4-diamino-6- [2' -Decyl imidazolyl- (1 ')]-ethyl-1,
3,5-triazine, 2,4-diamino-6- [2'-undecylimidazolyl- (1 ')]-ethyl-1,3,5-triazine, 2,4-diamino-6- [2'- Phenylimidazolyl- (1 ')]-ethyl
-1,3,5-triazine, 2,4-diamino-6- [2'-ethyl-4'-
Methylimidazolyl- (1 ')]-ethyl-1,3,5-triazine, 2,4-diamino-6- [2'-phenyl-4'-methylimidazolyl- (1')]-ethyl-1,3 , 5-Triazine, 2,4-diamino-6- [2'-undecyl-4'-methylimidazolyl-
(1 ')]-Ethyl-1,3,5-triazine, 2,4-diamino-6-
[2'-Methylimidazolyl- (1 ')]-ethyl-1,3,5-triazine / isocyanuric acid adduct and the like.

The melamine-coated ammonium polyphosphate used in the present invention is ammonium polyphosphate obtained by sublimating a melamine monomer and adding and / or adhering it to the surface of ammonium polyphosphate particles, and can be obtained, for example, by the following method.

Ammonium polyphosphate is charged into a heating kneader such as a heated kneader so that the ammonium polyphosphate is not melted and the ammonia added to the ammonium polyphosphate easily desorbs. Melamine is added and / or attached to the surface of the ammonium polyphosphate particles by adding melamine and heating at a temperature of 350 ° C. or lower, preferably 200 to 300 ° C., at which sublimation can be sublimated.

The proportion of melamine added at this time is 0.5 to 20% by weight, preferably 2 to 15% by weight, based on the ammonium polyphosphate, and most of the added melamine when produced by the above-mentioned method is A melamine-coated ammonium polyphosphate in the state of being added to and / or attached to the ammonium polyphosphate is obtained.

The term "addition" as used herein means a state in which melamine is chemically bound to a hydroxyl group on the surface in a state where ammonia is desorbed from ammonium polyphosphate, and the added melamine is stable even when heated and is removed again. Never let go.
Further, the adhesion means a state in which melamine is adsorbed on the surface of ammonium polyphosphate particles, and melamine is repeatedly sublimated and adsorbed on the surface of ammonium polyphosphate particles by continuing heating.

As the raw material of the melamine-coated ammonium polyphosphate, ammonium polyphosphate may be a commercially available product or one obtained by a known method, and as the commercially available product, a trade name (trademark registration pending) "TERRAJU" is used. ) S1
0 "(manufactured by Chisso), trade name (pending trademark registration)" TERRAJU S20 "(manufactured by Chisso), product name" Sumisafe-P "(manufactured by Sumitomo Chemical Co., Ltd.), product name" Exorit (E
xolit) -422 "(made by Hoechst), product name" FOSCEK "
(Phos-chek) P / 30 "(manufactured by Monsanto), trade name" Phos-chek P / 40 "(manufactured by Monsanto), and the like.

As a known method, for example, ammonium orthophosphate and phosphorus pentoxide in substantially equimolar amounts are heated to a temperature of 1 in the presence of gaseous ammonia and simultaneously with the reaction mixture.
It can be obtained by heating to 70 to 350 ° C.

Commercially available melamine can be used. Methylolmelamine having a carbon number of 4 to 9 [general formula C ₃ H
_6-n N ₆ (CH ₂ OH) _n , where n is a number from 1 to 6] is obtained by reacting 1 to 6 moles of formaldehyde with respect to 1 mole of the melamine. Besides being obtainable, a commercially available product may be used.

The nitrogen-containing organic compound (B), which is one of the constituents of the flame retardant composition according to the present invention or the flame retardant thermoplastic resin composition obtained by blending the flame retardant composition, is involved in the present invention. When present in a thermoplastic resin together with ammonium polyphosphate treated with a triazine derivative, it generates a non-flammable gas by heat due to ignition or ignition or contact with a flame, and also produces a carbonaceous residue or A compound that promotes the formation thereof, specifically exemplified by any of the following (1) to (3): (1) Basically based on the monomer structure represented by the general formula (4) It is one or more selected from homopolymers and copolymers as a unit, and X in the formula is a monovalent group, and examples thereof include the following: monomethylamino group,
Dimethylamino group, methylethylamino group, methylethylamino group, monoethylamino group, diethylamino group,
Monopropylamino group, dipropylamino group, methylpropylamino group, ethylpropylamino group, diisopropylamino group, mono-n-butylamino group, di-n-propylamino group, methyl-n-butylamino group, ethyl- n-butylamino group, propyl-n-butylamino group, isopropyl-
n-Butylamino group, monoisobutylamino group, diisobutylamino group, methylisobutylamino group, ethylisobutylamino group, propylisobutylamino group, isopropylisobutylamino group, monopentylamino group, dipentylamino group, methylpentylamino group, ethyl Pentylamino group, propylpentylamino group, isopropylpentylamino group, n-butylpentylamino group, isobutylpentylamino group, monohexylamino group, dihexylamino group, methylhexylamino group, ethylhexylamino group, propylhexylamino group, isopropyl Hexylamino group, n-butylhexylamino group, isobutylhexylamino group, pentylhexylamino group, monohydroxyethylamino group, dihydroxyethylamino group, monohydride Propyl group, dihydroxypropyl group, monohydroxy isopropylamino group, dihydroxypropyl group, monohydroxy -n- butylamino group, dihydroxy -n- butylamino group, monohydroxy -i- butylamino group, dihydroxy -
i-butylamino group, monohydroxypentylamino group,
Dihydroxypentylamino group, monohydroxyhexylamino group, dihydroxyhexylamino group, N-methylhydroxyethylamino group, morpholino group, piperidino group and the like. Among these groups, preferred X is a morpholino group and a piperidino group.

Z in the above formula is a divalent group, and examples thereof include ethylenediamine residue, N, N'-dimethylethylenediamine residue, N, N'-diethylethylenediamine residue and 1,3-diamino. Propane residue, tetramethylenediamine residue, pentamethylenediamine residue, hexamethylenediamine residue, piperazine residue (piperazinylene group) and trans-2,5-dimethylpiperazine residue (trans-2,5-dimethylpiperazine And a len group). Among these groups, Z is preferably a piperazine residue (piperazinylene group).
And trans-2,5-dimethylpiperazine residue (trans-2,5-dimethylpiperazinylene group). (2) Examples of the product obtained by the reaction of cyanuric chloride and diamines are as follows: ◆ Molar ratio of cyanuric chloride and ethylenediamine (former / latter =) 1/5 to 1/1, Preferably from 1/3
Product obtained by reaction in 2/3; ◆ Molar ratio of cyanuric chloride and 1,3-diaminopropane (former / latter =) 1/5 to 1/1, preferably 1 /
Product obtained by reaction in 3 to 2/3; ◆ Molar ratio of cyanuric chloride and hexamethylenediamine (former / latter =) 1/5 to 1/1, preferably 1
The product obtained by the reaction at / 3 to 2/3; ◆ Molar ratio of cyanuric chloride and piperazine (former / latter =) 1/5 to 1/1, preferably 1/3 to 2/3
The product obtained by the reaction in. (3) In addition to the nitrogen-containing organic compounds described above, the following nitrogen-containing organic compounds can also be used. That is, melamine, melem, melam, ammeline, melamine phosphate, melamine polyphosphate, melamine cyanurate, tris (2-hydroxyethyl) isocyanurate, a reaction product of ethylene urea and formaldehydes, ethylene thiourea and formaldehydes Examples thereof include a reaction product, a reaction product of ethylene urea, melamine and formaldehydes, and a reaction product of ethylene thiourea, melamine and formaldehydes.

Further, in order to obtain a homopolymer having the above-mentioned 2-piperazinylene-4-morpholino-1,3,5-triazine as a constitutional unit which is one of the nitrogen-containing organic compounds (B), for example, To operate: ◆ Equimolar 2,6-dihalo-4-morpholino-1,3,5-triazine (eg 2,6-dichloro-4-morpholino-1,3,5-triazine or 2,6-dibromo) -4-morpholino-1,3,5-triazine and piperazine are combined with an organic base such as triethylamine or tributylamine, or an inorganic base such as xylene in the presence of sodium hydroxide, potassium hydroxide or sodium carbonate React in a solvent with heating.
After the completion of the reaction, the reaction product is filtered to separate and collect a solid, and the solid is washed with boiling water to remove a by-product salt, and then the solid is dried.

2-Piperazinylene-4-morpholino-obtained
The homopolymer containing 1,3,5-triazine as a constituent unit was insoluble in ordinary organic solvents, its melting point was not observed, and it had a decomposition temperature of about 304 ° C and a true specific gravity of 1.3 g / cc. .

In the case of obtaining a homopolymer having 2-piperazinylene-4-bis (2-hydroxyethyl) amino-1,3,5-triazine as a constituent unit, 2,6-dihalo-4-morpholino- The same method as described above can be applied using 1,3,5-triazine as a raw material.

In order to obtain a reaction product of cyanuric acid chloride and ethylenediamine, the molar ratio of cyanuric acid chloride and ethylenediamine (the former / the latter =) is 1/5 to 1
/ 1, preferably 1/3 to 2/3, in the presence or absence of an organic base such as triethylamine, tributylamine, or an inorganic base such as sodium hydroxide, potassium hydroxide or sodium carbonate (in this case, The raw material ethylenediamine itself functions as a dehydrochlorinating agent)
The reaction is performed with water or an inert organic solvent as the solvent.

The reaction is started from a temperature of 10 ° C. or lower and gradually heated to the reflux temperature of the solvent. After the completion of the reaction, the reaction product is filtered to collect a solid matter, and the solid matter is washed with boiling water to remove the salt as a by-product, and the solid matter remaining is dried. The obtained solid reaction product was insoluble in an organic solvent, the solubility in water at room temperature was 0.1% or less, and the decomposition temperature was 324 ° C.

To obtain the reaction product of ethylene urea and formaldehyde, the reaction vessel is charged with an aqueous solution of ethylene urea and formaldehyde in a molar ratio of about 1, and water is used as a solvent to adjust the pH of the reaction system. Was maintained at 7-8. After that, the reaction system is reacted under heating while keeping the pH at 3 to 4, and the reaction product is filtered to collect a solid matter,
The solid was washed several times with boiling water and then dried. The decomposition temperature of the obtained solid reaction product was 311 ° C.

Examples of the polyhydric alcohol (C) which is one of the constituents of the flame retardant composition according to the present invention or the flame retardant thermoplastic resin composition obtained by blending the flame retardant composition are: Examples thereof include pentaerythritol, dipentaerythritol, polypentaerythritol, neopentyl glycol, trimethylolpropane, mannitol and sorbitol, and a complex of boric acid (boric acid) metal salt with one or more selected from polyhydric alcohols.

To obtain a complex of a polyhydric alcohol and a metal borate, for example, pentaerythritol and boric acid are usually used in a molar ratio of the former / latter = 0.8 to 1.2, preferably in substantially equimolar amounts. It is usually heated to 70 to 100 ° C. in a water solvent, and then aluminum, calcium, cobalt, nickel,
A water-soluble salt of at least one metal selected from barium, magnesium, zinc and manganese, for example, an aqueous solution of acetate or carbonate is gradually added while maintaining the same temperature, followed by further reaction under heating, and after cooling. The product is filtered and dried.

Suitable as the thermoplastic resin which is the component (D) which is the base material of the flame-retardant thermoplastic resin composition of the present invention are various ones exemplified below: ◇ Polyolefin resin For example, polyethylene Resin, polypropylene resin, poly-1-butene resin, poly-4-methyl-1
-Pentene resin, poly-1-hexene resin, poly-1-octene resin and poly-1-decene resin, or at least one resin or a mixture (composition) of two or more thereof, ◇ vinyl polymer resin For example, polystyrene (PS), poly
Examples include -α-methylstyrene, polymethyl (meth) acrylate resin (PMMA), acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-styrene copolymer (AS resin) and the like. ◇ Condensation polymerization type resins such as nylon (NY), polyester (PET, PBT, etc.), polycarbonate (P
C), thermoplastic polyurethane (PU), polysulfone,
Polyphenylene ether (PPE), ◇ thermoplastic elastomer (TPE or TPR) For example,
Examples of the olefin-based thermoplastic elastomer and the styrene-based thermoplastic elastomer include the following: ◆ 1-olefin-based thermoplastic crystalline resin (PO) and ethylene-propylene copolymer elastomer (EPM) Polymer composition or partially cross-linked product of the polymer composition, ◆ Polymer composition of 1-olefin thermoplastic crystalline resin (PO) and ethylene-propylene-non-conjugated diolefin copolymer elastomer (EPDM) Alternatively, a partially crosslinked product of the polymer composition.

In the flame-retardant thermoplastic resin composition of the present invention, various additives usually added to the thermoplastic resin, such as an antioxidant, a heat resistance stabilizer, an anti-UV agent, an antistatic agent, and copper. Anti-harmful agent, lubricant, neutralizing agent (higher fatty acid metal salt such as calcium stearate, zinc stearate, metal oxide / metal hydroxide complex salt such as hydrotalcite or manaceite), nucleating agent, pigment, etc. Can be used together.

The flame-retardant thermoplastic resin composition of the present invention can be produced, for example, by the following procedure. That is, the thermoplastic resin (D) as the base (base material) is treated with ammonium triphosphate treated with a triazine derivative.
(A), a nitrogen-containing organic compound (B) and / or a polyhydric alcohol (C) or a complex of them with a metal salt of boric acid and, if necessary, other additives (E) in predetermined amounts respectively. The mixture is put into a mixing device such as a Henschel mixer (trade name), a super mixer (trade name), or a tumbler mixer, and then mixed with stirring for 1 to 10 minutes.

The obtained mixture is melt-kneaded at a temperature of usually 170 to 260 ° C. using an extruder equipped with a vent, if necessary, such as a roll kneader or a screw extruder, and then extruded in a strand form and cut. The target flame-retardant thermoplastic resin composition can be obtained by pelletizing.

<Thermoplastic Thermoplastic Resin Molded Article> Further, the flame-retardant thermoplastic resin composition of the present invention is usually in the form of pellets by various molding means such as injection molding method, vacuum molding method and pressure molding. Or flame molding (compression molding method) or the like to form various flame-retardant molded articles. There are a wide variety of flame-retardant resin moldings of this kind,
For example, it can be widely used as various casings or housings for various devices or containers described below: ◆ Household products, particularly casings, housings for home appliances,
Rotating blades, etc., such as TVs, VTRs, video cameras, vacuum cleaners, air conditioners, washing machines, dryers, dishwashers, household container; ◆ Gardening equipment, such as irrigation pumps, rain dew ) Etc. ◆ Vehicles, especially automobile interior and exterior parts or materials, such as instrument panels, meter casings, front and rear cowls, center consoles, ceiling core materials, front, rear and side bumpers, rear stabilizers, fuel containers (storage tanks), Coolant container (storage tank; reservoir), etc.

The flame-retardant thermoplastic resin composition of the present invention means that the thermoplastic resin (D) is contained in an amount of 99 to 50% by weight.
The flame-retardant composition according to any one of 10 to 10 is a flame-retardant thermoplastic resin composition containing 1 to 50% by weight based on the weight of the final composition.

[0058]

EFFECTS OF THE INVENTION The flame retardant composition of the present invention and the flame retardant thermoplastic resin composition containing it exhibit the following various effects: (1) The flame retardant composition has excellent heat resistance at high temperatures. (2) The flame-retardant thermoplastic resin composition exhibits excellent flame retardancy and also has excellent bleeding resistance for a long time. (3) Molded articles using the flame-retardant thermoplastic resin composition It is nontoxic and capable of exhibiting excellent flame retardancy for a long period of time in both household and business use, and can be widely used for furniture, office equipment, vehicles, ships, aircrafts, storages and the like.

[0059]

EXAMPLES In order to specifically explain the present invention, examples and comparative examples are shown below, but the present invention is not limited thereto. The evaluations in Examples and Comparative Examples were performed by the following methods. (1) Flame retardance: UL94V Test method: Based on the vertical combustion test specified in "Combustion test of plastic material for parts of equipment" of UL Subject 94 (Underwriter Laboratories, Inc.). Thickness of test piece 1.6 mm (1/16 inch) Flame retardance evaluation criteria: (2) Flame retardancy: Oxygen index (O.I.) Japanese Industrial Standard JIS K7201 (combustion of polymer material by oxygen index method) Test method). (3) Heat resistance About 10 g of the flame retardant composition well mixed by a mixing device was placed in a petri dish and visually observed when left standing in an oven set at 150 ° C for 3 days. It was rated in 5 stages (A to E: A is the least colored) according to the degree of coloring. (4) Bleed resistance test A test piece (100 mm in length x 100 mm in width x 2 mm in thickness) was molded by an injection molding machine, and the surface electric resistance of this test piece was measured by a vibration capacitance type microcurrent potentiometer (Takeda Riken Kogyo Co., Ltd. ). Then, the test piece was placed in a constant temperature and humidity chamber (temperature: 80 ° C, humidity: 80).
% RH) and the test pieces were taken out at predetermined time intervals. The taken-out test piece was dried for 2 hours in a constant temperature dryer adjusted to a temperature of 80 ° C., and allowed to stand at room temperature in a desiccator, and then the surface electric resistance of the test piece was measured.

When the surface electric resistance value of the test piece significantly decreased after being taken out from the constant temperature and humidity chamber, the bleeding resistance under the high temperature and high humidity condition was poor, and the surface was exposed under the high temperature and high humidity condition. The number of days until the electric resistance value decreased was examined.

The melamine-coated ammonium polyphosphate used in each Example of the present invention was obtained by the following method. Content 5 preheated to 270-300 ℃
An L (liter) kneader was charged with 2000 parts by weight of ammonium polyphosphate [trade name (trademark registration pending): TERRAJU S20 (manufactured by Chisso Corporation)]. When the temperature of the ammonium polyphosphate reached 250 to 280 ° C, a predetermined amount of melamine was charged and mixed by heating for 6 hours to obtain a melamine-coated ammonium polyphosphate.

As a result of observing the obtained product with an electron microscope, it was confirmed that the particle surface of ammonium polyphosphate was uniformly coated with melamine, and elemental analysis thereof confirmed that most of melamine was polyphosphoric acid. It was confirmed that it was added to ammonium.

[0063]

Example 1 100 parts by weight (pbw) of melamine-coated ammonium polyphosphate (containing 5% by weight of melamine units based on product) and aqueous formaldehyde solution (concentration 35%) 3.
4 parts by weight (pbw) was stored in a trade name "Kenmix Mixer" [manufactured by Aikosha Seisakusho] and stirred at room temperature for 5 minutes. It was placed in a plastic bag, sealed, and then allowed to react in an oven (maintained at 28 ° C.) for 24 hours.

500 ml reactor [stirrer, thermometer,
Attach the inlet and condenser] to 3,9-bis [2- (3,5-diamino-2,4,6-triazaphenyl) ethyl] -2,4,8,10-
5.3 parts by weight of tetraoxaspiro [5.5] undecane, 10.5 parts by weight of formaldehyde aqueous solution (concentration 35%),
Urotropin (0.2 parts by weight) and water (10 parts by weight) were added as a catalyst, and the mixture was stirred at a temperature of 80 to 90 ° C. for 10 minutes while heating to obtain an aqueous solution of a triazine derivative.

The methylolated melamine-coated ammonium polyphosphate and a water / methanol mixed solution as a solvent (a mixed solution of 110 parts by weight of water and 35 parts by weight of methanol).
Is introduced into the reactor, heated and stirred to adjust the pH of the liquid phase to 3 to 4
The reaction was allowed to proceed at the reflux temperature for 1.5 hours while adjusting the temperature. After the reaction was completed, the inside of the reactor was rapidly cooled to 25 to 30 ° C., the solid matter collected after vacuum filtration was washed with water and methanol, dried in an oven (100 ° C.) for 2 h, and treated with a triazine derivative. Modified ammonium polyphosphate
105 parts by weight of (A1) was obtained.

18% by weight of this triazine-modified ammonium polyphosphate (A1), a homopolymer containing 2-piperazinylene-4-morpholino-1,3,5-triazine as its monomer unit as the nitrogen-containing compound (B) ( B1) 7% by weight and a crystalline propylene-ethylene crystalline copolymer (D1) as the thermoplastic resin (D) [ethylene content 8.5% by weight, MFR
(230 ° C; 2.16kgf) 20g / 10min] 73.7% by weight, various additives (E) as hydrotalcite (E1) 0.8% by weight,
2,6-di-t-butyl-p-cresol (E2) 0.2% by weight, dimyristyl-β, β'-thiodipropionate (E3) 0.2% by weight, calcium stearate (E4) 0.1 The weight% was charged into a Henschel mixer (trade name) and mixed by stirring for 3 minutes.

The resulting mixture was melt-kneaded (temperature: 200 ° C.) using a screw type extruder (diameter: 30 mm) and then extruded to form pellets of a flame-retardant resin composition (abbreviated as “flame-retardant pellets” in the present invention). Sometimes there is). After drying the obtained flame-retardant pellets (temperature 100 ° C; 3h), the flame-retardant pellets were injected into an injection molding machine (cylinder temperature 220 ° C).
Each of the predetermined test pieces was prepared by charging the test pieces to the test pieces, and the flame retardancy, heat resistance and bleeding resistance of each test piece were tested. Table 1 shows the results.

[0068]

Example 2 Reactor having a capacity of 500 ml (stirrer, thermometer,
Melamine-coated ammonium polyphosphate (melamine unit content 3% by weight) 10 in the inlet and the condenser)
0 parts by weight, 3,9-bis [2- (3,5-diamino-2,4,6-triazaphenyl) ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane 15 parts by weight , 30 parts by weight of a formaldehyde aqueous solution having a concentration of 35% and a water / methanol mixed solution (a mixed solution of 135 parts by weight of water and 20 parts by weight of methanol) as a solvent are gradually heated and stirred to adjust the pH of the liquid phase to 3 ~.
The reaction was carried out for 1.5 h at reflux temperature while adjusting to 4.

After completion of the reaction, the contents of the reactor were heated to a temperature of 25 to
It was rapidly cooled to 30 ° C., then filtered under reduced pressure, and the collected solid matter was washed with water and methanol and then dried in an oven (100
It was dried at (° C.) for 2 hours to obtain 110 parts by weight of triazine derivative-treated ammonium polyphosphate (A2).

20% by weight of this triazine-treated modified ammonium polyphosphate (A2), and 2-piperazinylene-4-N, N-bis (2-hydroxyethyl) -1,3,2 as the nitrogen-containing compound (B)
Homopolymer (B2) 5 containing 5-triazine as a monomer unit
% By weight and crystalline propylene as thermoplastic resin (D)
Ethylene block copolymer (D1) [ethylene content 8.5% by weight, MFR (230 ° C; 2.16kgf) 20g / 10min] 7
3.7 wt%, hydrotalcite (E1) 0.8 wt% as various additives (E), 2,6-di-t-butyl-p-cresol
(E2) 0.2% by weight, dimyristyl-β, β'-thiodipropionate (E3) 0.2% by weight and calcium stearate
(E4) 0.1% by weight was charged into a Henschel mixer (trade name) and mixed by stirring for 3 minutes.

The resulting mixture was melt-kneaded (temperature: 200 ° C.) using an extruder (diameter: 30 mm) and then extruded to obtain pellets of a flame-retardant resin composition. The obtained flame-retardant pellets were dried at a temperature of 100 ° C for 3 hours, and then the pellets were made into predetermined test pieces by using an injection molding machine (cylinder temperature was set to 220 ° C). The heat resistance, heat resistance and bleeding resistance were tested. Table 1 shows the results.

[0072]

Example 3 Reactor having a capacity of 500 ml (stirrer, thermometer,
Melamine-coated ammonium polyphosphate (melamine content 10% by weight) 100
Parts by weight, 3,9-bis [2- (3,5-diamino-2,4,6-triazaphenyl) ethyl] -2,4,8,10-tetraoxaspiro [5.
5] Add 3 parts by weight of undecane, 26 parts by weight of formaldehyde aqueous solution (concentration 35% by weight), and a water / methanol mixed solution (a mixed solution of 135 parts by weight of water and 20 parts by weight of methanol) as a solvent, heat and stir the liquid phase. The reaction was carried out at the reflux temperature for 1.5 hours while adjusting the pH of the solution to 3-4. After completion of the reaction, the temperature was rapidly cooled to 25 to 30 ° C., the solid matter collected after vacuum filtration was washed with water and methanol, dried in an oven (100 ° C.) for 2 h, and then treated with a triazine derivative. 103 parts by weight of ammonium (A3) was obtained.

19% by weight of this triazine-modified ammonium polyphosphate (A3), and 2-piperazinylene-4-morpholino-1,3,5-triazine as a nitrogen-containing compound (B) and 2-
Piperazinylene-4-N, N-bis (2-hydroxyethyl) -1,
Copolymer having a molar ratio of 1,5-triazine component of 1: 1
(B3) 6 wt% and a crystalline propylene-ethylene block copolymer (D1) as the thermoplastic resin (D) [ethylene content 8.5% by weight, MFR (230 ° C; 2.16 kgf) 20 g /
10min] 73.7% by weight, various additives (E) as hydrotalcite (E1) 0.8% by weight, 2,6-di-t-butyl-p-cresol (E2) 0.2% by weight, dimyristyl -β, β'-thiodipropionate (E3) 0.2 wt%, calcium stearate (E4) 0.1 wt% Henschel mixer (trade name)
The mixture was charged into and mixed with stirring for 3 minutes. The flame-retardant resin composition thus obtained is melt-kneaded (temperature: 20 mm) using an extruder (diameter 30 mm).
(0 ° C.) and then extruded to obtain pellets of the flame-retardant resin composition.

After drying the obtained flame-retardant pellets at a temperature of 100 ° C. for 3 hours, the pellets were loaded into an injection molding machine (cylinder temperature was set at 220 ° C.) to prepare predetermined test pieces. The test pieces were tested for flame retardancy, heat resistance and bleed resistance. The results are shown in Table 1.

[0075]

Examples 4 and 5 In preparing thermoplastic resin compositions, the following modifications were made in both examples: ◆ In Example 4, as the nitrogen-containing compound (B), cyanuric chloride and ethylenediamine were used in a molar ratio. (Former / latter =) The reaction product (B4) reacted at 1/3 was used. In Example 5, tris (2-hydroxyethyl) isocyanurate (B5) was used as the nitrogen-containing compound (B).

Except for the above, the flame-retardant pellets were obtained in the same manner as in Example 1 except that melt-kneading was followed by extrusion. Predetermined test pieces were prepared using the obtained flame-retardant pellets, and each test piece was tested for flame retardancy, heat resistance and bleed resistance. The results are shown in Table 1.

[0077]

Example 6 When obtaining an aqueous solution of a triazine derivative,
11 parts by weight of 3,9-bis [2- (3,5-diamino-2,4,6-triazaphenyl) ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane The procedure of Example 1 was repeated except that the amount of the aqueous formaldehyde solution (concentration: 35%) was changed to 21.7 parts by weight and urotropine as a catalyst to 0.4 parts by weight. Parts by weight were obtained.

18% by weight of this triazine-treated modified ammonium polyphosphate (A4) and tris (2-hydroxyethyl) isocyanurate (B5) 4 as the nitrogen-containing compound (B)
% By weight and 3% by weight of melamine (B6), polyhydric alcohol
Using pentaerythritol as (C), 2% by weight of its complex with zinc borate (C1) and a crystalline propylene-ethylene copolymer (D1) [thermoplastic resin (D1) [ethylene content 8.5 wt. %, MFR (230 ℃; 2.16lkgf)
20g / 10min] 51.8% by weight and high density polyethylene
(D2) [MI (190 ℃; 2.16kgf) 6.5g / 10min; Density 0.9
52 g / cc] 10% by weight, ethylene-propylene copolymer lastomer (D3) [trade name: EP-02P (manufactured by Japan Synthetic Rubber Co., Ltd.)] 10% by weight, and various additives (E) as hydrotalcite (E1) 0 0.7% by weight, 2,6-di-t-butyl-p-cresol (E2) 0.2% by weight, dimyristyl-β, β'-thiodipropionate (E3) 0.2% by weight and calcium stearate ( E4) 0.1% by weight was charged into a Henschel mixer (trade name) and mixed by stirring for 3 minutes.

The obtained flame-retardant resin composition was extruded (caliber:
After melt-kneading (temperature 200 ° C.) in 30 mm), it was extruded to obtain pellets of flame-retardant resin composition. After drying the obtained flame-retardant pellets at a temperature of 100 ° C. for 3 hours, the pellets were loaded into an injection molding machine (cylinder temperature was set to 220 ° C.) to make predetermined test pieces, and Tests for flame retardancy, heat resistance and bleed resistance were conducted. The results are shown in Table 1.

[0080]

Examples 7 to 9 The following points were changed in the following examples: ◆ In Example 7, as the nitrogen-containing organic compound (B), 2-piperazinylene-4-morpholino-1,3,5-triazine was used. 7% by weight of a homopolymer (B1) containing 10% as a monomer unit and a polyhydric alcohol
2% by weight of polypentaerythritol (C2) was used as (C). ◆ In Example 8, as the nitrogen-containing organic compound (B), cyanuric chloride and ethylenediamine were reacted at a molar ratio (former / latter =) 1/3. 7% by weight of the reaction product (B4) was used. In Example 9, 7% by weight of melamine cyanurate (B7) was used as the nitrogen-containing organic compound (B).

In all cases other than the above, the raw material components were melt-kneaded according to Example 6 and then extruded to obtain flame-retardant pellets. Predetermined test pieces were produced using the obtained flame-retardant pellets, and the test pieces were tested for flame retardancy, heat resistance and bleed resistance. Table 1 shows the results.

[0082]

Example 10 100 parts by weight of melamine-coated ammonium polyphosphate (content of melamine unit: 7% by weight) and 7.2 parts by weight of aqueous formaldehyde solution (concentration: 35%) were put in a polybag and carefully washed by hand. The polybag was sealed and allowed to react for 36 h in an oven (held at 28 ° C.) to give a methylolated melamine coated ammonium polyphosphate.

500 ml reactor (stirrer, thermometer,
2,4-diamino-6- [2'-on the inlet and condenser attached)
Methylimidazolyl- (1 ')]-ethyl-S-triazine 5.3 parts by weight, aqueous formaldehyde solution (concentration 35%)
Charge 4.3 parts by weight and 10 parts by weight of water at a temperature of 80-9.
The mixture was stirred at 0 ° C. for 30 minutes under heating to obtain an aqueous solution of triazine derivative.

The above methylolated melamine-coated ammonium polyphosphate and a water / methanol mixed solution as a solvent (a mixed solution of 110 parts by weight of water and 35 parts by weight of methanol).
Was introduced into the reactor, and the mixture was heated and stirred at reflux temperature for 5 hours.
Reacted. After the reaction, the temperature in the reactor is 25 to 30
After being rapidly cooled to ℃, filtered under reduced pressure, the collected solids are washed with methanol, and then the solid is dried in an oven (105 ℃) for 2 hours.
After drying for 100 hours, 100 parts by weight of triazine derivative-treated ammonium polyphosphate (A5) was obtained.

20% by weight of the obtained triazine-treated modified ammonium polyphosphate (A5), 2 as the nitrogen-containing compound (B)
-Piperazinylene-4-morpholino-1,3,5-triazine as a monomer unit, 9% by weight of a homopolymer (B1) and a low density polyethylene (D4) [MI (190
℃; 2.16kgf) 3g / 10min; trade name: Petrosen 186 (manufactured by Tosoh Corporation)] 69.8% by weight and various additives (E) 0.7% by weight of hydrotalcite (E1), 2,6-di -t-butyl-p-cresol (E2) 0.2% by weight, dimyristyl-β,
0.2% by weight of β'-thiodipropionate (E3) and 0.1% by weight of calcium stearate (E4) were charged into a Henschel mixer (trade name) and mixed with stirring for 3 minutes.

The obtained flame-retardant resin composition was extruded (caliber:
Melt kneading (temperature: 200 ° C.) was used to obtain pellets of the flame-retardant resin composition. After drying the obtained flame-retardant pellets at a temperature of 100 ° C. for 3 hours, the pellets were loaded into an injection molding machine (cylinder temperature was set to 220 ° C.) to make predetermined test pieces, and The flame resistance, heat resistance, and bleed resistance were tested.
Table 1 shows the results.

[0087]

Example 11 When obtaining an aqueous solution of a triazine derivative,
The amount of 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-S-triazine was 11 parts by weight, the amount of formaldehyde aqueous solution (concentration 35%) was 8.9 parts by weight, and the catalyst As in Example 10, except that 5 ml of an aqueous solution of sodium carbonate (concentration: 1%) was added, 110 parts by weight of triazine derivative-treated ammonium polyphosphate (A6) was obtained.

The obtained triazine-treated modified ammonium polyphosphate (A6) (25% by weight) and the nitrogen-containing organic compound (B), 2-piperazinylene-4-morpholino-1,3,5-triazine as a single unit 5% by weight of combined (B1) and 5% by weight of dipentaerythritol (C3) and thermoplastic resin (D)
Polystyrene resin (D5) [MI (190 ℃; 2.16kgf)
1.7 g / 10 min; trade name: Styron 475S (manufactured by Asahi Kasei)] 62.8% by weight and various additives (E) as hydrotalcite (E1) 0.7% by weight, 2,6-di-t- Butyl-p-
Charge 0.2% by weight of cresol (E2), 0.2% by weight of dimyristyl-β, β'-thiodipropionate (E3) and 0.1% by weight of calcium stearate (E4) into a Henschel mixer (trade name). Then, the mixture was stirred for 3 minutes.

The obtained flame-retardant resin composition was extruded (caliber:
45 mm) was melt-kneaded (temperature: 220 ° C.) and then extruded to obtain pellets of the flame-retardant resin composition. After drying the obtained flame-retardant pellets at a temperature of 100 ° C. for 3 hours, the pellets were loaded into an injection molding machine (cylinder temperature was set to 220 ° C.) to prepare predetermined test pieces, and Tests for flame retardancy, heat resistance and bleed resistance were conducted. Table 1 shows the results.

[0090]

[Comparative Example 1] Instead of triazine-treated modified ammonium polyphosphate (A6), untreated ammonium polyphosphate (A6)
7) [Product name (trademark registration pending): TERRAJU S10
(Manufactured by Chisso Corp.)] was used to prepare flame-retardant pellets in accordance with Example 1, and predetermined test pieces were prepared using the pellets. And bleed resistance were tested. Table 1 shows the results.

[0091]

[Comparative Example 2] A reactor having a capacity of 500 (equipped with a stirrer, a thermometer and a condenser) was charged with 6.3 parts by weight of melamine and 12.8 parts by weight of an aqueous formaldehyde solution (concentration 35% by weight), and the temperature was adjusted to 60. A methylolmelamine aqueous solution was obtained by reacting with heating to -80 ° C. Next, ammonium polyphosphate [trade name: Exolit-422 (Hoechst)] was added to the reactor.
100 parts by weight, 35 parts by weight of water and 120 parts by weight of methanol were charged, and the mixture was further reacted at reflux temperature for 4 hours.

After the reaction is completed, the temperature in the reactor is set to 25-30.
After rapidly cooling to ℃, filtered under reduced pressure, the collected solids were washed with methanol, and then oven (110 ℃) for 2h.
After drying, 105 parts by weight of ammonium polyphosphate (A8) treated with a melamine-formaldehyde resin was obtained. Flame-retardant pellets were produced in accordance with Example 1 except that the treated ammonium polyphosphate (A8) was used, and predetermined test pieces were produced using the pellets. The heat resistance and bleed resistance were tested.
Table 1 shows the results.

[0093]

[Table 1]

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08K 5/3492 KBN C08K 5/3492 KBN C08L 23/00 KEE C08L 23/00 KEE KFB KFB 25/04 KFV 25/04 KFV KFZ KFZ 67/02 KJR 67/02 KJR 69/00 KKH 69/00 KKH 71/12 LQM 71/12 LQM 75/04 NFY 75/04 NPHY 77/00 KKR 77/00 KKR 81/06 LRF 81/06 LRF 101/00 101/00

Claims (13)

[Claims] 1. A flame retardant composition which is formed of the following components (A) and (B) and has a weight ratio B / A between the two components of 0.1 to 10: A modified with a triazine derivative (A). Ammonium polyphosphate (B) Nitrogen-containing organic compound. 2. A flame retardant composition which is formed of the following components (A) and (C) and has a weight ratio C / A between the two components of 0.1 to 10: A modified treatment with a triazine derivative (A). Ammonium polyphosphate (C) polyhydric alcohols. 3. Formed by the following components (A), (B) and (C), the weight ratio (B + C) / A between the three components is 0.1 to 10, and the weight ratio between the two components is Weight ratio B / C is 0.1-
Flame retardant composition which is 10. (A) Modified ammonium polyphosphate treated with triazine derivative (B) Nitrogen-containing organic compound (C) Polyhydric alcohol. 4. A modified ammonium polyphosphate treated with a triazine derivative, based on 100 parts by weight of a melamine-coated ammonium polyphosphate containing 0.5 to 20% by weight of a melamine unit based on a melamine monomer, the following general formula:
1 selected from the group of triazine derivatives represented by (1)
4. A modified ammonium polyphosphate obtained by reacting formaldehyde with a composition containing 0.1 to 30 parts by weight of a mixture of two or more kinds. Flame retardant composition described in: [Wherein R ¹ is a methyl group, a phenyl group or the following general formula:
(2) or a group represented by the general formula (3)], Embedded image [Wherein R ² is a phenyl group, a linear alkyl group having 1 to 12 carbon atoms or a branched alkyl group having 1 to 12 carbon atoms,
R ³ is hydrogen or a methyl group]. 5. Ammonium polyphosphate treated with a triazine derivative is represented by the following general formula (1) based on 100 parts by weight of melamine-coated ammonium polyphosphate containing 0.5 to 20% by weight of a melamine unit based on a melamine monomer. 0.1 to 30 parts by weight of a mixture of one or more selected from the triazine derivative group represented, and melamine and methylolmelamine having 4 to 9 carbon atoms [C ₃ H _6-n N
₆ (CH ₂ OH) _n (where n is a number of 1 to 6)], and formaldehydes are reacted with a composition containing 0.1 to 30 parts by weight of 1 or more. A flame retardant composition according to any one of claims 1 to 4, which is a modified ammonium polyphosphate obtained by: [Wherein R ¹ is a methyl group, a phenyl group, the following general formula:
(2) or a group represented by the general formula (3)], [Chemical 6] [Here, R ² is a phenyl group, a linear alkyl group having 1 to 12 carbon atoms or a branched alkyl group having 1 to 12 carbon atoms, and R ³ is hydrogen or a methyl group]. 6. The flame retardant according to claim 1, wherein the nitrogen-containing organic compound is one or more selected from homopolymers and copolymers composed of structural units represented by the following general formula (4). Composition: [In the formula, both X and Z are groups bonded to the triazine skeleton through a nitrogen atom, and X is -NHR ⁴ or-
NR ⁵ R ⁶ is an alkylamino group, a morpholino group or a piperidino group, and R ⁴ , R ⁵ and R ⁶ are both a linear alkyl group having 1 to 6 carbon atoms or a branched alkyl group (wherein , R ⁵ and R ⁶ may be groups different from each other), X is a hydroxyalkylamino group represented by —NHR ⁷ or —NR ⁸ R ⁹ , and R ⁷ , R ⁸ and R ⁹ are all It is a linear hydroxyalkyl group having 2 to 6 carbon atoms or a branched hydroxyalkyl group having 2 to 6 carbon atoms (wherein R ⁸ and R ⁹ may be mutually different groups). Z is a divalent piperazine group of the formula —HN (CH ₂ ) _m N
A divalent group represented by H- (where, m is a number of 2 to 6) or _{^{-NR 10 (CH 2) p R}} 11 is a divalent group represented by N-, R ¹⁰ and At least one of R ¹¹ is a hydroxyethyl group, and when either is a hydroxyethyl group, the other is a hydrogen atom or a linear alkyl group or a branched alkyl group having 1 to 6 carbon atoms]. 7. The flame retardant composition according to claim 1, wherein the nitrogen-containing organic compound is a product obtained by reacting cyanuric chloride with a diamine. 8. The flame retardant composition according to claim 7, wherein the diamine is one or more selected from ethylenediamine, 1,3-diaminopropane, hexamethylenediamine and piperazine. 9. A reaction product of melamine, melem, melam, ammeline, melamine phosphate, melamine polyphosphate, melamine cyanurate, tris (2-hydroxyethyl) isocyanurate, ethylene urea and formaldehyde, wherein the nitrogen-containing compound is, It is 1 or more types chosen from the reaction product of ethylene thiourea and formaldehyde, the reaction product of ethylene urea, melamine, and formaldehyde, and the reaction product of ethylene thiourea, melamine, and formaldehyde. The flame retardant composition described. 10. The polyhydric alcohol is one or more selected from pentaerythritol, dipentaerythritol, polypentaerythritol, neopentyl glycol, trimethylolpropane, mannitol, sorbitol and a complex thereof with a boric acid metal salt. Item 11. A flame retardant composition according to any one of items 2 to 9. 11. Thermoplastic resin (D) 99 to 50% by weight
A flame-retardant thermoplastic resin composition comprising the flame-retardant composition according to any one of claims 1 to 10 added to 1 to 50% by weight based on the weight of the final composition. 12. The thermoplastic resin is one selected from olefin resins, styrene resins, polyamide resins, polycarbonate resins, polyethylene terephthalate resins, polybutylene terephthalate resins, polysulfone resins, polyurethane resins and polyphenylene ether resins, and thermoplastic elastomers. The flame-retardant thermoplastic resin composition according to claim 11, which is the above. 13. Thermoplastic resin (D) 99 to 50% by weight
A flame-retardant thermoplastic formed from a flame-retardant thermoplastic resin composition containing 1 to 50% by weight of the flame-retardant composition according to any one of claims 1 to 10 based on the weight of the final composition. Resin molded product.