KR101442128B1 - Organophosphorus-nitrogen compound, preparation method thereof, and flame retardant composition comprising same - Google Patents

Abstract

The present invention relates to an organic phosphorus-nitrogen compound useful as a flame retardant for an organic polymer material or a raw material for the production thereof, a process for producing the phosphorus-nitrogen compound, and a flame retardant composition containing the organophosphorus compound. The organophosphorus compound according to the present invention has heat resistance and water resistance Is excellent in flame retardancy because it has a phosphorus-nitrogen bond and is capable of producing an additive type flame retardant in a form suitable for the characteristics of the resin, and is useful as a flame retardant for general-purpose polymers, particularly polymer resins for electric and electronic materials.

Organic phosphorus-nitrogen compounds, flame retardants, polymers, heat resistance, water resistance

Description

TECHNICAL FIELD [0001] The present invention relates to an organic phosphorus-nitrogen compound, a method for producing the phosphorus-nitrogen compound, and a flame retardant composition containing the phosphorus-nitrogen compound.

The present invention relates to a flame retardant of an organic polymer material or an organic phosphorus-nitrogen compound useful as a raw material for the production thereof, a process for producing the same, and a flame retardant composition containing the same.

BACKGROUND ART Conventionally, as a flame retardant for a flammable polymer material, a halogen-based flame retardant excellent in a flame retarding effect and an economical view has been widely used. Among them, a bromine-based compound having excellent flame retardancy is used in most general-purpose resins, and a flame retardant is used together with a bromine-based flame retardant or an antimony-based flame retardant such as antimony trioxide as an adjuvant in order to improve flame retardancy. However, brominated flame retardants may generate toxic gases such as HBr in the event of a fire, which may cause aquaculture and may generate dioxine, which is a strong carcinogen when burned. Furthermore, antimony flame retardants used in combination with brominated flame retardants also have their own carcinogenic properties, leading to restrictions on their use in Europe.

Accordingly, studies on non-halogen flame retardants have been actively conducted recently, and various environmentally friendly flame retardants have been developed.

Non-halogen flame retardants include phosphorus, nitrogen compounds, silicones, boron-based flame retardants, metal oxides and metal hydroxide flame retardants. Of these, organophosphorous compounds which are considered most positively as flame retardants capable of replacing halogen flame retardants are monomolecular types such as phosphates or phosphonates, condensation type thereof, and the like.

As the most basic compound among the phosphates, triphenyl phosphate (TPP) is known. However, since TPP has a small molecular weight, there is a problem that it is easily volatilized during the molding process of a polymer material carried out at a high temperature, and also has a problem of deteriorating the softening point of the resin and the mechanical properties by acting as a plasticizer of the polymer material. Further, since the flame retardant is easily eluted from the resin, there is a problem that the flame retardancy is lowered and secondary contamination is generated.

In order to solve such problems, JP-A-59-202240 and JP-A-2-18336 disclose the use of a condensed phosphorus flame retardant containing two phosphorus elements in a molecule by using hydroquinone, resorcinol, bisphenol derivative, . However, such a condensed phosphorus flame retardant also has a problem that the flame retardancy is lowered with the lapse of time, and the effect is significantly lowered in comparison with the conventional halogen flame retardant in terms of heat resistance, hydrolysis resistance and flame retardancy. When TPP or a condensed phosphorus flame retardant is added to an ester type polymer resin (PET, PC, etc.), there is a problem that resin properties are deteriorated due to an ester exchange reaction.

Accordingly, in order to solve the problems such as heat resistance, it is necessary to increase the molecular weight of the flame retardant agent or to strengthen the molecular structure, and in order to have hydrolysis property and ester interchangeability, it is necessary to introduce a hydrophobic group or a steric hindrance substituent group into the flame- It is desirable to design the molecule in such a direction as to reduce the number of phosphorus-oxygen bonds and to increase the number of phosphorus-carbon bonds or phosphorus-nitrogen bonds.

It is known that the stability and flame retardancy of the flame retardant can be improved by having a phosphorus-nitrogen covalent bond in the molecule of the flame retardant compound. As such flame retardants, there are ammonium polyphosphate and melamine phosphate. However, most of the phosphorus-containing compounds containing nitrogen are low in water resistance, and in particular, melamine phosphate has a low flame retardancy and requires an additional flame retardant additive. There is a drawback to drop. Ethylenediamine phosphate is also used, but it also has a problem of low water resistance and heat resistance.

Therefore, an object of the present invention is to provide an additive type flame retardant which is excellent in heat resistance and water resistance, forms a phosphorus-nitrogen bond, is excellent in flame retardancy, To provide a novel organic phosphorus-nitrogen compound useful as a flame retardant.

Another object of the present invention is to provide a method for producing the organic phosphorus-nitrogen compound.

It is still another object of the present invention to provide a flame retardant composition comprising the organic phosphorus-nitrogen compound.

In order to accomplish the above object, the present invention provides an organic phosphorus-nitrogen compound represented by the following formula (1)

In this formula,

A represents -NX ₁ NX ₂ or N = N and, X ₁ and X ₂ are each independently hydrogen, C _1-50 alkyl, C _3-50 cycloalkyl, C _6-50 aryl, or nuclear atoms of 5 to 50 X ₁ and X ₂ are each independently selected from the group consisting of C _1-50 alkyl, C _6-50 aryl, heteroaryl having 5 to 50 nucleus atoms, and C _7-50 aralkyl group Which may be substituted with one or more groups,

R ₁ to R ₄ are each independently hydrogen, cyano, nitro, amino, thio, Four spokes reel, phosphinylmethyl, carbonyl, silyl, borane yl, C _1-50 alkyl, C _2-50 alkenyl, C _2-50 alkynyl, C _1-50 alkoxy, C _3-50 cycloalkyl, C _6-50 aryl, 5- to 50-membered heteroaryl, C _6-50 aryloxy or C _6-50 arylperoxy group Wherein R ₁ to R ₄ are each independently selected from the group consisting of substituted or unsubstituted cyano, nitro, amino, thio, hydroxy, carbonyl, carboxy, carbamoyl, epoxy, phosphoryl, phosphinyl, one, C _1-50 alkyl, C _2-50 alkenyl, C _2-50 alkynyl, C _1-50 alkoxy, C _3-50 cycloalkyl, C _6-50 aryl, the number of nuclear atoms of 5 to 50 heteroaryl group , C _6-20 aryloxy, and C _7-50 aralkyl group.

The present invention also provides a process for preparing an organophosphorous-based compound of Formula 1, comprising reacting a compound of Formula 2 with a compound of Formula 3:

(X ₁ X ₂ N) ₂

In the above formula

X ₁ and X ₂ are as defined above,

R 'and R "are each independently hydrogen, cyano, nitro, amino, thio, phosphoryl, phosphine sulfinyl, carbonyl, silyl, borane yl, C _1-50 alkyl, C _2-50 alkenyl, C C _2-50 alkynyl, C _1-50 alkoxy, C _3-50 cycloalkyl, C _6-50 aryl, 5-50 heteroaryl, C _6-50 aryloxy or C _{6-50 arylperoxy} group , R 'and R "are each independently selected from the group consisting of substituted or unsubstituted cyano, nitro, amino, thio, hydroxy, carbonyl, carboxy, carbamoyl, epoxy, phosphoryl, phosphinyl, silyl, , C _1-50 alkyl, C _2-50 alkenyl, C _2-50 alkynyl, C _1-50 alkoxy, C _3-50 cycloalkyl, C _6-50 aryl, 5-50 heteroaryl, C _6-20 aryloxy, and C _7-50 aralkyl group, which may be substituted with one or more groups selected from the group consisting of

Y is a halogen atom or a hydroxy group.

The organophosphorus compound according to the present invention is environmentally friendly, has excellent heat resistance and water resistance, contains phosphorus and nitrogen at the same time, and is excellent in flame retardancy and stability. Thus, the organophosphorus compound according to the present invention can be used as a flame retardant for various polymer resins .

Hereinafter, the present invention will be described in more detail.

In the present specification, "substituted" means, cyano, nitro, amino, thio, hydroxy, carbonyl, carboxy, carbamoyl, epoxy, phosphoryl, phosphine sulfinyl, silyl, borane yl, C _{1 -50} alkyl, C _{2 -50} alkenyl, C _{2 -50} alkynyl, C _{1 -50} alkoxy, C _{3 -50} cycloalkyl, C _{6 -50} aryl, nuclear atoms of 5 to 50 heteroaryl, C _{6 -20} aryloxy and C _{7 -50} aralkyl group substituted with at least one substituent selected from the group consisting of C _{7 -50} aralkyl groups.

Preferably, X ₁ and X ₂ in the above formula (1) are each independently hydrogen, C _1-18 alkyl, C _3-20 cycloalkyl or C _6-20 aryl group,

R ₁ to R ₄ are each independently, C _{1 -18} alkyl, C _{1 -18} alkoxy, C _{3 -20} cycloalkyl, C _6-20 aryl, 4 to 20 nuclear atoms heteroaryl, C _{6 -20} aryl Oxy, or a C _{6 -50} aryl peroxy group, or is independently selected from the group consisting of substituted or unsubstituted, cyano, nitro, amino, thio, hydroxy, carbonyl, carboxy, carbamoyl, epoxy, C _1-20 alkyl, C _1-18 alkoxy, C _4-20 cycloalkyl, C _6-20 aryl, heteroaryl having 4 to 20 nuclear atoms, C _6-20 aryloxy and C _7-20 arylene the with one or more groups selected from the group consisting of alkyl substituted, C _1-18 alkyl, C _1-18 alkoxy, C _3-20 cycloalkyl, C _6-20 aryl, 4 to 20 nuclear atoms heteroaryl, C _{6 -20} aryloxy or a C _{6-50 arylperoxy} group.

More preferably, the organophosphorous-based compound is a compound of the following formula 4 or 5:

In this formula,

X ₁ and X ₂ are each independently hydrogen, C _1-18 alkyl, C _3-20 cycloalkyl or C _6-20 aryl group,
n is an integer of 0 to 2, preferably 0 or 1.

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The organic phosphorus-nitrogen compound according to the present invention preferably has a melting point of 100 ° C to 250 ° C as measured by a differential scanning calorimeter (DSC).

The present invention also provides a process for preparing an organophosphorous-based compound of Formula 1, comprising reacting a compound of Formula 2 with a compound of Formula 3:

(2)

(X ₁ X ₂ N) ₂

(3)

In the above formula

X ₁ , X ₂ , R ', R "and Y are as defined above

Specifically, examples of the compound of Formula 2 include hydrazine monohydrate, 1,2-diphenylhydrazine (or hydrazobenzene), and the like.

The compound of Formula 3 may be diphenyl chlorophosphate, diphenylphosphate, diphenylphosphinic chloride, or the like. The compound of Formula 3 may be used in an amount of 2 to 10 moles per mole of the compound of Formula 2 desirable.

The reaction of the compound of Formula 2 with the compound of Formula 3 is preferably carried out in chloroform, tetrahydrofuran, dimethylformamide, distilled water or a mixed solvent thereof.

Further, tertiary amines such as triethylamine, bases such as sodium carbonate, potassium carbonate, sodium hydrogencarbonate, and sodium hydroxide may be further used to improve the reaction yield and shorten the reaction time during the reaction. In this case, the base is preferably used in an amount of 2 to 10 moles per 1 mole of the compound of the formula (2).

The reaction is preferably carried out at room temperature to 100 ° C for 2 to 48 hours.

Subsequently, a step of selectively dehydrogenating the compound formed by the reaction of the compound of formula (2) with the compound of formula (3) may be further performed.

The dehydrogenation reaction is N-chlorosuccinimide can be carried out by using a radical generator such as a mid-bromosuccinimide, N.

The radical generator is preferably used in an amount of 0.5 to 3 moles per mole of the compound obtained.

The dehydrogenation reaction may be carried out using a chlorinated hydrocarbon such as methylene chloride; Ketones such as acetone and butanone; Ethers such as tetrahydrofuran and dioxane; It is preferably carried out in an inert solvent such as dimethylformamide, dimethylsulfoxide or the like.

The organophosphorus compound according to the present invention produced by the above method can solve problems such as heat resistance, hydrolysis and ester interchangeability of the conventional phosphoric acid ester system, has excellent heat resistance and water resistance, Nitrogen-bonded, excellent flame retardance and stability, and can be used in the production of additive type flame retardant in a form suitable for the characteristics of the resin, and can be used for general purpose polymers in a wide range of fields, particularly polymer resins for electric and electronic materials.

Specifically, when the organic phosphorus-nitrogen compound of the present invention is used as a flame retardant, the organic polymer material that can be used includes polyethylene, polypropylene, polybutylene, polyisobutylene, polybutadiene, polyacrylonitrile, polystyrene , Styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, styrene-acrylonitrile copolymer, acrylonitrile butadiene styrene (ABS) resin, polyacetal, polyphenyl oxide resin , Polyphenylene sulfide resin, polysulfone resin, polyethylene terephthalate, polybutylene terephthalate, polyethylene dynaphthoate, terephthalic acid-1,4-butanediol-polybutylene ether copolymer elastomer, polycarbonate, polyamide, Polyimide, polyurethane, epoxy resin, phenol resin, melamine resin, urea resin, liquid crystalline polymer Compounds, cellulose acetate, and the like, but are not limited thereto.

The method of mixing the phosphorus-nitrogen-based compound and the organic polymer material according to the present invention is not particularly limited and may be carried out using a roll mill, a super mixer, a Henschel mixer, a high speed mixer, a ball mill, a steel mill, a sand mill, , A homogenizer, a jet mill, a batch mixer, a twin screw extruder, a single screw extruder, etc. These mixing devices may be used alone or in combination of two or more.

When the organophosphorus compound of the present invention is used as a flame retardant, its content differs greatly depending on the kind of the organic polymer material to be blended and the desired flame retardant performance. Generally, the organophosphorus compound is used in an amount of 1 to 99 By weight, preferably 1 to 40% by weight, more preferably 1 to 20% by weight. When the content is less than 1% by weight, the effect of improving the flame retardancy is not sufficient. If the content is more than 40% by weight, the effect of improving the flame retardancy with the increase of the addition amount is small.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples are intended to illustrate the present invention, but the scope of the present invention is not limited thereto.

Example  One : Organic phosphorus - Preparation of nitrogen compound (Compound 1)

A solution of hydrazine monohydrate (0.93 mol, 45.6 g), triethylamine (1.87 mol, 190 g) and chloroform (500 ml) as a solvent were placed in a 2 L, round bottom three-necked flask equipped with a reflux condenser and a dropping funnel. And the solid content was completely dissolved while stirring at room temperature. Diphenylchlorophosphate (1.86 mol, 500 g) was then added dropwise over about 1 hour using a dropping funnel at room temperature, and the reaction solution was allowed to react at room temperature (25 캜) for about 24 hours. After the reaction was completed, the resulting suspension was filtered, and the filtrate was reprecipitated in n -hexane and filtered to obtain a white powder. Then, the obtained powder was washed with a large amount of water several times, and then dried to obtain 423 g of Compound 1.

¹ H-NMR (CDCl ₃ , 500 MHz) ₁₆ H (C ₆ H ₅ -O-, m, 7.278-7.341), 4 H (C ₆ H ₅ -O-, t, 7.162-7.190) , < / RTI > d, 6.605, 6.549)

EI-MS: m / z 496 (M < + >).

Example 2 : Preparation of organic phosphorus-nitrogen compound (compound 2)

(0.93 mol, 172 g), triethylamine (1.87 mol, 190 g) and chloroform (500 ml) as a solvent were placed in a 2 L volumetric round bottom three-necked flask equipped with a reflux condenser and a dropping funnel. And the solid content was completely dissolved while stirring at room temperature. Diphenylchlorophosphate (1.86 mol, 500 g) was then added dropwise over about 2 hours using a dropping funnel at room temperature, and the reaction solution was allowed to react at room temperature (25 캜) for about 24 hours. After the completion of the reaction, the resulting suspension was filtered, and the filtrate was reprecipitated in n -hexane and filtered to obtain a solid. The resulting solid was washed with a large amount of water several times and dried to obtain 489 g of Compound 2 .

_{^{1 H-NMR (CDCl 3,}} 500MHz) 16H (C 6 H 5 -O-, m, 7.289-7.353), 4H (C 6 H 5 -O-, t, 7.173-7.199), 6H (C 6 H 5 _{-N-, 6.915-6.988) 4H (C 6} H 5 -N-, 7.410-7.418)

EI-MS: m / z 649 (M < + >).

Example 3: Preparation of Organophosphorous-Nitride Compounds (Compound 3)

Compound 2 (20.0 g, 40 mmol) obtained in Example 1 was dissolved in methylene chloride (120 ml) into a 2 L volume round bottom flask equipped with a reflux condenser. Then, pyridine (3.51 g, 44 mmol) and N -bromosuccinimide (7.17 g, 40 mmol) were added successively and reacted at room temperature for 24 hours. After completion of the reaction, methylene chloride (100 ml) and distilled water (100 ml) were added to the reaction mixture, followed by washing with 200 ml of 5% sodium hydroxide aqueous solution twice. Thereafter, the methylene chloride was removed and the resultant solid was dried to obtain 12 g of the compound 3.

¹ H-NMR (CDCl ₃ , 500 MHz) ₁₆ H (C ₆ H ₅ -O-, m, 7.321-7.365), 4H (C ₆ H ₅ -O-, t, 7.185-7.199)

EI-MS: m / z 649 (M < + >).

Comparative Example 1

For comparison with the organic phosphorus-nitrogen compound of the present invention, a compound having the following formula (SP-703 of Shikoku Chemical Co., Ltd.) was prepared as a conventional flame retardant.

Test Example 1: Evaluation of physical properties

Compounds prepared according to Example 1 were analyzed by gas chromatography-mass spectrometer (GC-MS; JMS-600W, manufactured by JEOL) and differential scanning calorimeter (DSC; DSC 823e, manufactured by METTLER TOLEDO) was used for mass spectrometry and thermal properties were evaluated. The results are shown in Fig. 1 and Fig. 2, respectively.

As shown in FIG. 1 and FIG. 2, it was confirmed that the compound prepared was the target compound of the formula (1), and that the molecular weight was 496 and the melting point was 146 ° C to 147 ° C.

Test Example 2: Evaluation of flame retardancy

In order to evaluate the flame retardancy of the compounds according to the present invention, flakes were prepared as described below, and the flame retardancy was evaluated using the UL-94 V test method set by the American Underwriter's Laboratory.

First, 10 parts by mass of each of the compounds prepared in Examples 1 to 3 and Comparative Example 1 was added to 100 parts by mass of a bisphenol A-type polycarbonate (weight average molecular weight (Mw): 25,000, L1250 AP, And extruded in a twin-screw extruder at a temperature in the range of 230 to 280 ° C to prepare a flame retardant composition. The resulting composition was dried at 80 ° C for 3 hours and then molded by an injection molding machine at a molding temperature of 200 to 280 ° C and a mold temperature of 50 to 70 ° C To prepare specimens for evaluation of flame retardancy. At this time, specimens were fabricated with dimensions of 5 × 0.5 × 1/16 (inches) and 5 specimens were prepared for each specimen.

The flame retardancy of the prepared specimens was tested by adjusting the flame size to 20 mm according to IEC 60695-11-10 using small flames (50 W) mm. After burning the specimen with a burner for 10 seconds, the burner is removed, and the time t1 until the flame on the specimen is turned off is t1, the flame is again applied for 10 seconds, the burner is removed and the time t2, The time t3 until the glow (fire glow) disappears was measured, and the flame retardancy was evaluated according to the following criteria. The results are shown in Table 1 below.

<Flammability Evaluation Standard>

V-0: t1 and t2 of each specimen are less than 10 seconds, t1 + t2 of 5 specimens is less than 50 seconds, t2 + t3 of each specimen is less than 30 seconds, If not

V-1: t1 and t2 of each specimen are less than 30 seconds, t1 + t2 of less than 250 seconds, and t2 + t3 of less than 60 seconds of each specimen, Occation

V-2: When t1 and t2 of each specimen are less than 30 seconds, t1 + t2 of five specimens is less than 250 seconds, t2 + t3 of each specimen is less than 60 seconds,

Example 1 Example 2 Example 3 Comparative Example 1 Flammability V-1 V-1 V-1 V-2

As shown in Table 1, t1 in Example 1 was measured at 20 seconds, and the flame retardancy was evaluated as V-1. In Example 2, t1 was 22 seconds and flame retardancy was V-1. In Example 3, t1 was 12 seconds and flame retardancy was V-1. Further, all of Examples 1 to 3 were not ignited by sparks. On the other hand, in the case of Comparative Example 1, t1 was measured at 28 seconds, but flammability was evaluated by V-2.

From the experimental results, it can be seen that the organophosphorus compound according to the present invention has excellent flame retardancy as compared with the conventional organophosphorous compound flame retardant according to the comparative example.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is clearly understood that the same is by way of illustration and example only and is not to be construed as limiting the present invention. It should be understood that it can be performed within a range.

FIG. 1 is a graph showing the results of GC-Mass measurement for Compound 1. FIG.

2 is a graph showing the results of DSC measurement for Compound 1. Fig.

Claims (11)

delete delete An organic phosphorus-based flame retardant represented by the following formula (4) or (5). [Chemical Formula 4]

[Chemical Formula 5]

(Wherein X ₁ and X ₂ are each independently hydrogen or a C _6-20 aryl group, and n is an integer of 1) The method of claim 3, Wherein X ₁ and X ₂ are each independently hydrogen or a phenyl group. Reacting a compound of formula (2) with a compound of formula (3); And Subjecting the compound produced by the reaction to a dehydrogenation reaction; Wherein the organic phosphorus-nitrogen compound is represented by the following formula (1): &lt; EMI ID = (2) (X ₁ X ₂ N) ₂ (3)

[Chemical Formula 1]

In the above formula (1), (2) or (3) A is N = N, X ₁ and X ₂ are each independently hydrogen, R ₁ to R ₄ are each independently hydrogen, cyano, nitro, amino, thio, phosphoryl, phosphine sulfinyl, carbonyl, silyl, borane yl, C _1-50 alkyl, C _2-50 alkenyl, C C _2-50 alkynyl, C _1-50 alkoxy, C _3-50 cycloalkyl, C _6-50 aryl, 5- to 50-membered heteroaryl, C _6-50 aryloxy or C _{6-50 arylperoxy} group , R ₁ to R ₄ are each independently selected from substituted or unsubstituted cyano, nitro, amino, thio, hydroxy, carbonyl, carboxy, carbamoyl, epoxy, phosphoryl, phosphinyl, , C _1-50 alkyl, C _2-50 alkenyl, C _2-50 alkynyl, C _1-50 alkoxy, C _3-50 cycloalkyl, C _6-50 aryl, 5-50 heteroaryl, C _6-20 aryloxy, and C _7-50 aralkyl group, which may be substituted with one or more groups selected from the group consisting of R 'and R "are each independently hydrogen, cyano, nitro, amino, thio, phosphoryl, phosphine sulfinyl, carbonyl, silyl, borane yl, C _1-50 alkyl, C _2-50 alkenyl, C C _2-50 alkynyl, C _1-50 alkoxy, C _3-50 cycloalkyl, C _6-50 aryl, 5- to 50-membered heteroaryl, C _6-50 aryloxy or C _{6-50 arylperoxy} group , R 'and R "are each independently selected from the group consisting of substituted or unsubstituted cyano, nitro, amino, thio, hydroxy, carbonyl, carboxy, carbamoyl, epoxy, phosphoryl, phosphinyl, silyl, , C _1-50 alkyl, C _2-50 alkenyl, C _2-50 alkynyl, C _1-50 alkoxy, C _3-50 cycloalkyl, C _6-50 aryl, 5-50 heteroaryl, C _6-20 aryloxy, and C _7-50 aralkyl groups, which may be substituted with one or more groups selected from the group consisting of Y is a halogen atom or a hydroxy group. 6. The method of claim 5, Wherein the compound of Formula 2 is hydrazine monohydrate. 6. The method of claim 5, Wherein the compound of Formula 3 is selected from the group consisting of diphenyl chlorophosphate, diphenyl phosphate, diphenylphosphinic chloride, and mixtures thereof. 6. The method of claim 5, Wherein the compound of Formula 3 is used in an amount of 2 to 10 moles relative to 1 mole of the compound of Formula 2. [ delete 6. The method of claim 5, A method being carried out using a mid-chlorosuccinimide and a radical generating agent selected from the group consisting of mixtures thereof is the dehydrogenation of N-bromosuccinimide, N. A flame retardant composition comprising an organophosphorus-based flame retardant according to claim 3 or 4.

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