KR101257289B1 - Flame resistant composition containing Phosphor-Nitrogen compound and thermoplastic resin composition containing the same - Google Patents

Abstract

상기 식에서, X는

이며; Y는 H, NH₄ 또는

이고; Z는 H 또는 NH₄이다.The present invention relates to a biguanide phosphate compound represented by the following general formula (1), a flame retardant composition and a thermoplastic resin composition using the same, and more specifically, a biguanide represented by the following general formula (1) obtained by reacting dicyanamide and ammonium phosphate The present invention relates to a phosphate compound, a flame retardant composition comprising the same, and a thermoplastic resin composition having excellent flame retardancy. The flame retardant composition according to the present invention is environmentally friendly because it does not contain a halogen element, has excellent heat resistance, contains phosphorus and nitrogen at the same time, and is excellent in flame retardancy and can be used as a flame retardant of various polymer resins.
[Formula 1]

In which X is

; Y is H, NH ₄ or

ego; Z is H or NH ₄ .

Description

Flame resistant composition containing Phosphor-Nitrogen compound and thermoplastic resin composition containing the same

The present invention relates to a phosphorus-nitrogen biguanide phosphate salt compound obtained by reacting dicyandiamide and ammonium phosphate, and a flame retardant composition or thermoplastic resin composition comprising the same.

Conventional halogen-based flame retardants, particularly bromine-based compounds, have been used effectively in most thermoplastic resins together with antimony flame retardant, antimony trioxide. 302102), bromine-based flame retardants are known to produce toxic fumes and strong carcinogen dioxine in the event of fire is increasingly regulated.

Some of the active flame retardants that can replace halogen-based flame retardants include monomolecular organophosphorus compounds such as phosphates, phosphonates, or triphenyl phosphate (TPP). It tends to be easy, and since the flame retardant is easily eluted from the resin, there is a problem of lowering flame retardancy and generating secondary pollution.

In order to improve this problem, condensed phosphorus-based flame retardants using resorcinol, bisphenol derivatives and the like have been used (Japanese Patent Laid-Open Nos. 59-202240 and 2-18336). However, the condensed phosphorus-based flame retardant is significantly less effective than conventional halogen-based flame retardants in terms of heat resistance, hydrolysis resistance and flame retardancy, and is difficult to use in styrene resins and ester type polymer resins (PET, PC, etc.). If added, there is a problem that the resin physical properties are lowered due to the transesterification reaction.

As flame retardants to increase the stability and flame retardancy of the flame retardant, there are ammonium polyphosphate, melamine phosphate, and the like, which have phosphorus-nitrogen covalent bonds. Examples of the non-halogen flame retardant include phosphorus, inorganic oxides and hydroxides, nitrogen compounds, and silicones. However, even nitrogen compounds and silicones are hardly imparted with flame retardancy alone, and there has been no development of flame retardants that can keep up with the performance of halogen flame retardants.

Dicyandiamide reacts with phosphoric acid to produce guanylurea phosphate (GUP), and it is a water-soluble flame retardant by adding boric acid to GUP. It is known to use for softening (USP 4,373,010, WO 02/070215, USP 4,073,617). However, the flame retardant has a strong acidity and poor storage stability, there is a problem such as corrosion of the metal, in particular can not be used in thermoplastic resins.

Accordingly, the present inventors have studied and tried to solve the above-mentioned problems. As a result, when the composition containing insoluble phosphorus-nitrogen-based condensate is reacted with dicyandiamide and ammonium phosphate, various flame retardancy is excellent. By discovering that the polymer resin can be used as a flame retardant, the present invention has been completed.

Therefore, the present invention forms an phosphorus-nitrogen bond and has excellent heat resistance, and can be added in a form suitable for the properties of the thermoplastic resin to be used as a flame retardant and a synergist, and a phosphorus-nitrogen-based compound and a thermoplastic resin composition comprising the same. The purpose is to provide.

The present invention is characterized by providing a flame-retardant composition comprising a phosphorus-nitrogen biguanide phosphate compound represented by the following formula (1) obtained by reacting dicyanamide and ammonium phosphate.

[Formula 1]

이며; Y는 H, NH₄ 또는

이고; Z는 H 또는 NH₄이다.In which X is

; Y is H, NH ₄ or

ego; Z is H or NH ₄ .

In addition, the present invention 100 parts by weight of thermoplastic resin; And 1 to 50 parts by weight of a biguanide phosphate compound represented by Formula 1 obtained by reacting dicyanamide and ammonium phosphate.

The flame-retardant composition comprising the phosphorus-nitrogen biguanide phosphate compound according to the present invention is environmentally friendly because it does not contain a halogen element, has excellent heat resistance, and contains phosphorus and nitrogen at the same time. Can be used as a flame retardant. In addition, synergistic effect with the flame retardant of the alkyl phosphinate metal salt system to impart superior flame retardant performance to the thermoplastic resin than when used alone, in particular can be useful in the production of styrene-based flame retardant resin composition.

The present invention provides a phosphorus-nitrogen biguanide phosphate salt compound obtained by reacting dicyandiamide and ammonium hydrogen phosphate, and a flame retardant composition or a flame retardant thermoplastic resin composition having excellent flame retardancy. It is about.

More specifically, 1 to 50 parts by weight of a biguanide phosphate compound represented by the following formula (1) based on 100 parts by weight of a biguanide phosphate compound represented by the following formula (1) and a flame retardant composition or thermoplastic resin comprising the same It relates to a thermoplastic resin composition excellent in flame retardancy.

[Formula 1]

이며; Y는 H, NH₄ 또는

이고; Z는 H 또는 NH₄이다.In which X is

; Y is H, NH ₄ or

ego; Z is H or NH ₄ .

The biguanide phosphate compound may be represented by, for example, the following Chemical Formulas 2 to 5.

Hereinafter, the present invention will be described in detail.

The biguanide phosphate compound obtained from dicyandiamide and ammonium phosphate used in the present invention is a condensate containing nitrogen and phosphorus, which has high nitrogen content and foamability, and contains phosphorus, which is advantageous in forming a film of the resin and thus flame retardant. When used in compositions or thermoplastics, it provides excellent flame retardant effects.

Dicyandiamide (or cyanoguanidine) of the present invention has the advantage of being inexpensive and easy to handle and commercially useful. In addition, the conventional flame retardant ammonium polyphosphate (APP) has a limit in processing and use because ammonia is generated at 170 ℃ or more, whereas the dicyandiamide of the present invention has a high melting point (220 ℃ or more) for resin processing It is advantageous and has a feature of generating less ammonia during processing.

The biguanide phosphate compound according to the present invention is prepared by heat condensation reaction of dicyandiamide and ammonium phosphate.

In particular, the present invention is characterized in that monoammonium phosphate (MAP) or diammonium phosphate (Diammonium phosphate, DAP) is reacted with dicyanamide to obtain biguanide phosphate. That is, the present invention reacts dicyandiamide with monoammonium phosphate (MAP) or diammonium phosphate (DAP) to prepare biguanide phosphate, an insoluble phosphorus / nitrogen condensate that is difficult to dissolve in water.

In the preparation of the biguanide phosphate compound, the amount of the ammonium phosphate compound is preferably used in an amount of 0.5 to 3 equivalents based on 1 equivalent of the dicyandiamide compound. If the amount of ammonium phosphate is less than 0.5 equivalent, unreacted CN group remains, and if it exceeds 3 equivalent, water-soluble condensation has a problem in compatibility with thermoplastic resins.

The method for preparing the biguanide phosphate compound includes a method of preparing without a solvent and a method of using a solvent. When prepared using a solvent, butanol, toluene, dioxane, xylene or mesitylene may be selected and used. In the above method for preparing biguanide phosphate, the reaction is performed by stirring at 80 ° C. to 200 ° C. for 2 to 6 hours, and monitoring the completion of the reaction is performed by FT-IR. It is desirable to monitor to determine the completion of the reaction.

The biguanide phosphate compound obtained by the above method is neutral, and it is preferable to prepare it as a crystalline white solid which does not dissolve in water and is not viscous.

The biguanide phosphate does not need to be completely pure, and the obtained biguanide phosphate is preferably obtained by reacting the same moles in the condensation reaction of dicyanamide and ammonium phosphate for heat resistance, but the molar ratio thereof is 2 or more. Thus, a small amount of melam, melem, melon, etc., which are cyclic melamine or a polymer form of melamine, may be contained. In addition, unreacted dicyandiamide or ammonium phosphate (Ammonium hydrogen phosphate (AHP)), dihydrogen phosphate (dihydrogen phosphate, DHP) may be included remaining. Among biguanide phosphates, containing 8 to 20% by weight of phosphorus atoms is preferred because it can express the flame retardant effect most effectively. Such biguanide phosphate may be used by modification, but may be used by itself.

Hereinafter, the components of the thermoplastic resin composition excellent in flame retardancy of the present invention will be described in detail.

Since the biguanide phosphate compound of the present invention forms a phosphorus-nitrogen bond, its melting point is 220 ^o C or more, which is excellent in heat resistance, and has a form suitable for addition processing to thermoplastic resins such as high-impact polystyrene resin (HIPS) and ABS. It can be used as an additive flame retardant. Accordingly, the present invention provides a thermoplastic resin composition excellent in flame retardancy comprising a thermoplastic resin and biguanide phosphate.

The content of biguanide phosphate used in the thermoplastic resin composition according to the present invention varies greatly depending on the type of the polymer resin to be blended and the target flame retardant performance, but is generally 1 part by weight to 100 parts by weight based on 100 parts by weight of the thermoplastic resin. It is preferable to use 50 parts by weight, more preferably 5 to 40 parts by weight. When included in less than 1 part by weight is not sufficient to improve the flame retardancy, when included in excess of 50 parts by weight it is preferable to maintain the above range because the physical properties of the resin due to excessive addition is not changed.

The thermoplastic resin used in the present invention is polyethylene, polypropylene, polybutylene, polyisobutylene, polybutadiene, polyacrylonitrile, polystyrene, styrene / butadiene copolymer, acrylonitrile / butadiene air Copolymer, styrene / acrylonitrile copolymer, ABS resin, polyacetal, polyphenyl oxide resin, polyphenylene sulfide resin, polysulfone resin, polyethylene terephthalate, polybutylene terephthalate, polyethylene dynaphthoate, terephthalic acid / 1, 4-butanediol / polybutylene ether co-condensation elastomer, polycarbonate, polyamide, polyimide, polyurethane, epoxy resin, phenol resin, melamine resin, urea resin, liquid crystalline polymer compound, cellulose acetate, etc. One or two or more selected from may be used, but is not limited thereto. is. More preferably, the use of polystyrene, styrene / butadiene copolymer, acrylonitrile / butadiene copolymer, styrene / acrylonitrile copolymer, and ABS resin in the thermoplastic resin is similar to the heat resistance.

In particular, the thermoplastic resin composition excellent in flame retardancy according to the present invention may preferably further include an alkyl phosphinate metal salt in the thermoplastic resin, and more preferably include an alkyl phosphinate metal salt represented by the following formula (6). .

[Formula 6]

Wherein M is a metal ion such as Al, Zn, Ca, Ba, Mg; d is 1 to 4; R ₁ and R ₂ are each independently H or C ₁ C ₁₈ alkyl; m and n are each independently 0 or 1. In this case, d is set to 1, 2, 3 or 4 depending on the type of M and its oxidation state.

When the alkyl phosphinate metal salt is added to the thermoplastic resin composition, it is preferable to use 10 parts by weight to 50 parts by weight based on 100 parts by weight of the thermoplastic resin. More preferably, 20 to 40 parts by weight is used. When included in less than 10 parts by weight it is not sufficient to improve the flame retardancy, when included in excess of 50 parts by weight it is preferable to maintain the above range because the physical properties of the resin is not changed due to excessive addition.

The thermoplastic resin composition having excellent flame retardancy of the present invention includes a flame retardant and a flame retardant aid commercialized such as inorganic organ salts such as magnesium, aluminum, inorganic metal salt flame retardants, fluorinated polyolefins, organic metal compounds, etc. You can use it to get synergy effect.

The flame-retardant thermoplastic resin composition according to the present invention may also be used by further adding an inorganic additive such as zinc borate as an adjuvant.

In addition, a polymer or copolymer of tetrafluoroethylene (PTFE) or vinylidene fluoride, which is a fluorine resin, may be used as a drip inhibitor to prevent the resin from dropping during combustion. The amount of the anti-dripping agent is preferably used in an amount of 0.1 parts by weight to 3 parts by weight based on 100 parts by weight of the thermoplastic resin, and more preferably 0.3 to 2 parts by weight. If the amount of use is less than 0.1 part by weight, the desired non-dropping property is insufficient. If the amount is more than 3 parts by weight, the viscosity of the material rises to deteriorate formability.

In the thermoplastic resin composition according to the present invention, the method of mixing the biguanide phosphate with the thermoplastic resin is not particularly limited. For example, a roll mill, a brabender mixer, a super mixer, a Henschel mixer, a high speed mixer, a ball mill, Mixing equipment such as steel mill, sand mill, progress mill, homo mixer, homogenizer, jet mill, batch kneader, twin screw extruder, single screw extruder can be mixed. You may use together above.

Hereinafter, the present invention will be described in more detail with reference to the following examples, but the following examples are intended to illustrate the invention and are not intended to limit the invention.

Example  One : Biguanide  Synthesis of Phosphate Compounds

Dry ammonium phosphate and dicyandiamide at 120 ^o C for at least 1 hour, add 84 g of dicyandiamide to a three-necked flask reactor equipped with a mechanical stirrer, condensation condenser and thermometer and place it at 140 ^o C to 160 ^o C. While stirring, 73 g of ammonium phosphate were added over 1 hour. After addition, the mixture was stirred at 140 ^° C. to 160 ^° C. for 2 to 4 hours, and then cooled to obtain a white solid of biguanide phosphate. As a result of confirming the completion of the reaction by IR, there was no characteristic peak indicated by CN triple bond.

Example  2 to 5: preparation of the thermoplastic resin composition

As shown in the following Table 1, the biguanide phosphate solid according to the preparation example as a flame retardant, polytetrafluoroethylene (PTFE) as an anti-dripping, a mineral as a flame retardant (synergist) (zinc borate) And organic-phosphinate (organic-phosphinate) was added to the stirrer (monoaxial mixer) of 1 kg of contents by adding as shown in Table 1 below, stirred for 10 minutes to give a preliminary dispersion (premixed) fair). At this time, the rotation speed of the stirring blade which a stirrer had was made into 2000 rpm.

Subsequently, HIPS (weight average molecular weight 100,000, manufactured by BASF), which is a thermoplastic resin, was added to the first mixture obtained by the preliminary mixing process, and then, at a temperature range of 200 ° C. to 260 ° C. in a brabender mixer, at a rotational speed of 20 rpm. Mixing for minutes prepared a thermoplastic resin composition. The prepared composition was molded for 3 to 20 at an molding temperature of 170 to 240 ° C. using an extruder to prepare a specimen for evaluation of flame retardancy. At this time, the specimens were manufactured in a size of 12.7 × 127 × 1.58 (mm), and five specimens were prepared for each sample. The composition ratios are summarized in Table 1 below.

Comparative example  1 to 2

A resin composition having a composition shown in Table 1 below was prepared for comparison with the above Examples according to the present invention using the same conditions as the above Examples. At this time, the specimens were manufactured in the same size as 12.7 × 127 × 1.58 (mm), and five specimens were prepared for each sample. The composition ratios are summarized in Table 1 below.

Test Example  : Flame Retardant Evaluation

In order to evaluate the flame retardancy of the resin composition, specimens were prepared according to Examples and Comparative Examples, and flame retardancy evaluation was performed using a UL-94 V test method set by the US Underwriters Laboratories.

When evaluating the flame retardancy of the manufactured specimens, the test standard is adjusted to 20 mm according to IEC 60695-11-10 using small flames (50 W), and the burner is removed from the bottom of the specimen by 10 mm when ignited. It was positioned mm apart. Set up the specimen and light it with a burner for 10 seconds, then remove the burner, time t1 before the fire on the specimen goes out, t2 time after removing the burner after the fire for 10 seconds, remove the burner, and turn off the light on the specimen. The time t3 until the fire glow disappeared was measured.

[Evaluation standard]

The flame retardancy rating of UL 94 V-0 is when the specimens have t1 and t2 less than 10 seconds each, when five specimens have t1 + t2 less than 50 seconds each t2 + t3 is less than 30 seconds,

UL 94 V-1 is when t1 and t2 are less than 30 seconds each, and when t1 + t2 of five specimens is less than 250 seconds, each t2 + t3 is less than 60 seconds and no flaming occurs due to sparks. ,

UL 94 V-2 is when t1 + t2 is less than 30 seconds each, and when t1 + t2 of five specimens is less than 250 seconds, each t2 + t3 is less than 60 seconds, and sparking occurs due to sparking.

The results are summarized in Table 1 below. The unit is parts by weight.

Thermoplastic
Suzy Biguanide Phosphate Alkyl phosphinate metal salt Flame Retardant Supplements Anti-drip Burning time (s) HIPS OP-930 ¹⁾ ZnBrO ₃ PTFE ^{2 )} t1 t2 Flame Retardant Grade Example 2 100 20 - - One 23.1 29.0 V-2 Example 3 100 20 15 - - 21.0 17.2 V-1 Example 4 100 20 20 5 One 5.4 4.8 V-0 Example 5 100 20 20 - - 6.1 8.6 V-0 Comparative Example 1 100 - 20 - One 230.7 0 NC Comparative Example 2 100 - 40 125.7 0 NC

¹⁾ OP930: Aluminum diethylphosphinate

²⁾ PTPE: Tetrafluoroethylene

* Combustion time: average value of five specimens (NC: cannot classify)

As a result, as shown in Table 1, in Example 4, t1 was measured at 5.4 seconds, t2 was measured at 4.8 seconds, and flame retardancy was evaluated as V-0. In Example 5, t1 was measured at 6.1 seconds and t2 at 8.6 seconds. The flame resistance was evaluated as V-0. In the case of Example 3, t1 was 21.0 seconds, t2 was 17.2 seconds, and the flame retardancy was evaluated as V-1, but the results were slightly lower than those of Examples 4 and 5, but the results were still excellent. In addition, in Examples 2 to 5, cotton wool did not ignite due to residual salt. On the contrary, in the case of Comparative Example 1 and Comparative Example 2, t1 was measured as 230.7 seconds and 125.7 seconds, respectively, and there was no grade, and it was determined that ignition due to residual flame did not occur.

From the above experimental results, it was found that the formulation having a synergistic effect with the flame retardant according to the present invention had excellent flame retardancy.

Claims (9)

Biguanide phosphate compound represented by following formula (1).
[Formula 1]

(In Formula 1, X and Y are simultaneously

ego; Z is H or NH ₄ )
The compound of claim 1, wherein the biguanide phosphate compound is obtained by reacting dicyanamide and ammonium phosphate.
The compound of claim 1, wherein the biguanide phosphate compound is neutral and water-insoluble.
Flame retardant composition comprising a biguanide phosphate compound represented by the formula (1).
[Formula 1]

(In Formula 1, X and Y are simultaneously

ego; Z is H or NH ₄ )
A thermoplastic resin composition having excellent flame retardancy, comprising 100 parts by weight of thermoplastic resin and 1 to 50 parts by weight of biguanide phosphate compound represented by the following Chemical Formula 1.
[Formula 1]

(In Formula 1, X and Y are simultaneously

ego; Z is H or NH ₄ )
6. The composition according to claim 5, wherein the composition is selected from the group consisting of polymers or copolymers of organophosphorous ester compounds, magnesium, aluminum, fluorinated polyolefins, organometallic compounds, zinc borate, tetrafluoroethylene and vinylidene fluoride. A thermoplastic resin composition excellent in flame retardancy, further comprising the above additive.
The thermoplastic resin composition of claim 5, further comprising an alkyl phosphinate metal salt in the composition.
8. The thermoplastic resin composition of claim 7, wherein the alkyl phosphinate metal salt is a compound represented by the following formula (6).
[Chemical Formula 6]

Wherein M is Al, Zn, Ca, Ba or Mg; d is 1 to 4; R ₁ and R ₂ are each independently H or C ₁ C ₁₈ alkyl; m and n are each independently 0 or 1.
9. The thermoplastic resin according to claim 5, wherein the thermoplastic resin is polyethylene, polypropylene, polybutylene, polyisobutylene, polybutadiene, polyacrylonitrile, polystyrene, styrene / butadiene Copolymer, acrylonitrile / butadiene copolymer, styrene / acrylonitrile copolymer, ABS resin, polyacetal, polyphenyl oxide resin, polyphenylene sulfide resin, polysulfone resin, polyethylene terephthalate, polybutylene tere Phthalates, polyethylene dynaphthoates, terephthalic acid / 1,4-butanediol / polybutylene ether co-condensers elastomers, polycarbonates, polyamides, polyimides, polyurethanes, epoxy resins, phenolic resins, melamine resins, urea resins, Characterized in that one or two or more selected from the group consisting of a liquid crystalline polymer compound and cellulose acetate It is excellent in flame-retardant thermoplastic resin composition.