KR20170049255A - Heat-decomposed compound and method for gasification using the same - Google Patents

Abstract

Disclosed are a thermolysis compound and a gas generation method using the same wherein the thermolysis compound can foam resin as the thermolysis compound is decomposed by heat and generates nitrogen gas. The thermolysis compound is represented by chemical formula 1, x-(-R-D)n. In chemical formula 1, X is an alkyl group having 1-10 carbon atoms, an aryl group having 4-10 carbon atoms, a heterocycle ring having 3-10 carbon atoms, or a group 3, 4, or 5 element, R is a single bond or a double bond, D is a group including hydrazine moiety, and n is an integer of 3-6.

Description

TECHNICAL FIELD The present invention relates to a heat decomposition compound and a gas generating method using the heat decomposition compound.

The present invention relates to a heat decomposition compound and a gas generating method using the same, and more particularly, to a heat decomposition compound capable of foaming a resin by pyrolysis to generate nitrogen gas and a gas generating method using the same.

The blowing agent is a resin additive for blending with a resin to prepare a porous foam. Azodicarbonamide (ADCA) is used as a foaming agent for thermoplastic resins such as polyethylene, polypropylene, ethylene-vinyl acetate copolymer (EVA), polyvinyl chloride, styrene-butadiene rubber, acrylonitrile- , p, p'-oxybis (benzenesulfonyl hydrazide), dinitroso pentamethylene tetramine (DPT), p-toluenesulfonyl hydrazide a variety of organic compound blowing agents such as ptoluenesulfonylhydrazide, benzenesulfonyl hydrazide and 5-phenyl tetrazole are known (Korean Patent No. 10-1518698, Japanese Patent Laid-Open No. 2001-139928, Japanese Patent No. 3872961 , U. S. Patent No. 4885316, etc.).

Among the above blowing agents, azodicarbonamide (ADCA) is a general-purpose product because nitrogen gas is rapidly generated by heating, decomposition products are incombustible, and toxicity is low. However, when a foam is produced using azodicarbonamide, the azodicarbonamide is not completely decomposed and yellowish remnants remain, and the whiteness of the foam is lowered. Further, as shown in Reaction Scheme 1 below, harmful components such as formamide, ammonia, and carbon monoxide which may cause reproductive toxicity may be generated when azodicarbonamide is pyrolyzed.

[Reaction Scheme 1]

Accordingly, an object of the present invention is to provide a heat decomposition compound which does not generate harmful components such as formamide and ammonia and which is pyrolyzed to generate mainly nitrogen gas, and a gas generating method using the same. It is another object of the present invention to provide a heat decomposition compound which is eco-friendly, which can avoid regulation of harmful substances, and which has a foaming capability higher than that of the conventional ADCA, and a gas generating method using the same.

In order to achieve the above object, the present invention provides a foaming agent represented by the following general formula (1).

[Chemical Formula 1]

X is an alkyl group having 1 to 10 carbon atoms, an aryl group having 4 to 10 carbon atoms, a heterocyclic group having 3 to 10 carbon atoms, or a Group 3, 4, or 5 group atom, and R is a single bond or a double bond , D is a hydrazine containing group (group including hydrazine moiety), and n is an integer of 3 to 6.

The foaming agent according to the present invention does not generate harmful components such as formamide and ammonia and is pyrolyzed to generate mainly nitrogen gas. Therefore, it is eco-friendly and can avoid the regulation of harmful substances, .

1 and 2 are electron micrographs showing the internal pore shape of a foam obtained by foaming a polypropylene (PP) and an ethylene-vinyl acetate copolymer (EVA), respectively, using a blowing agent according to an embodiment of the present invention.

Hereinafter, the present invention will be described in detail.

The heat decomposition compound according to the present invention is represented by the following general formula (1).

[Chemical Formula 1]

X is an alkyl group having 1 to 10 carbon atoms (specifically 1 to 6 carbon atoms), an aryl group having 4 to 10 carbon atoms (specifically 5 to 8 carbon atoms), an aryl group having 3 to 10 carbon atoms, A heterocyclic group having 1 to 10 carbon atoms (specifically 5 to 8 carbon atoms), a Group 3 element such as aluminum (Al), a Group 4 element such as silicon (Si) or nitrogen (N) D is a hydrazine containing group, and n is an integer of 3 to 6. If necessary, D may be bonded to an aluminum containing an alkyl group having 2 to 5 carbon atoms in the adjacent groups.

Specific examples of X include a heteroaryl group such as a carbon atom (methyl group), a phenyl group, and a 1,3,5-triazine group. The hydrazine containing group (D) is a group containing a hydrazine moiety, i.e., -NN- group, which can be converted into nitrogen by heating, and includes a hydrazine group (-NHNH ₂ ), a nitroamine group (-NHNO ₂ And a -NH- group. Examples of the heterocyclic group containing the hydrazine moiety include a tetrazole group, a tetrazole amine group and the like.

In addition, if necessary, the hydrazine containing group (D) may be substituted with a carbonyl group (-CO- or -COR ₁ , wherein R ₁ represents a hydrocarbon group having 1 to 10 carbon atoms), an amide group (-CONH ₂ ), a hydrocarbon group having 1 to 20 carbon atoms (specifically having 1 to 10 carbon atoms) with or without a hetero atom, an amine group, and combinations thereof.

For example, the hydrazine containing group (D) includes a hydrazine moiety such as a semydicarbazide group, a benzohydrazide group, a hydrazinecarbonyl group and the like and at least one substituent substituted therewith. The hydrocarbon group having 1 to 20 carbon atoms, which may or may not contain a hetero atom, is a linear, branched, or cyclic hydrocarbon group, and may be an iso or branched alkyl group having 1 to 10 carbon atoms or a linear alkyl group having 2 to 10 carbon atoms An alkenyl group having 2 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, a cycloalkenyl group or a cycloalkynyl group, an aryl group having 4 to 10 carbon atoms, or an aryl group having 1 to 5 heteroatoms A heteroaryl group or a heterocyclic group having 4 to 10 carbon atoms, and combinations thereof.

For example, X may be an alkyl group (for example, the following formulas 1d, 1p, 1q and 1r), an aryl group (for example, a phenyl structure, the following formula 1b and 1h), a heterocyclic group ) Or a Group 5 compound (for example, silicon, the following Formula 1s).

The foaming agent according to the present invention is excellent in the structural stability and foaming performance of the foaming agent, and can be usefully used as a high-temperature or low-temperature foaming agent when necessary, can generate nitrogen gas upon decomposition, and can control the decomposition temperature .

Specific examples of the blowing agent according to the present invention include compounds represented by the following formulas.

(화학식 1a),

(화학식 1b),

(Formula 1a),

(1b),

(화학식 1c),

(화학식 1d),

(Formula 1c),

(1d),

(화학식 1e),

(화학식 1f),

(1e),

(1f),

(화학식 1g),

(화학식 1h),

(Formula 1g),

(1h),

(화학식 1i),

(화학식 1j),

(1i),

(1j),

(화학식 1k),

(화학식 1l),

(Ik),

(Formula l),

(화학식 1m),

(화학식 1n),

(1m),

(1n),

(화학식 1o),

(화학식 1p),

(Io),

(Formula 1p),

(화학식 1q),

(화학식 1r),

(Formula 1q),

(1R),

(화학식 1s)

(화학식 1t)

(Formula 1s)

(Formula 1t)

The foaming agent of the present invention contains three or more nitrogen-nitrogen functional groups in a star-shape, and can produce more nitrogen gas. Compared to the ADCA foaming agent used in general use, It is advantageous in that it has low foaming performance and less generation of formamide and ammonia gas during thermal decomposition. For example, the pyrolysis mechanism of the blowing agent represented by the formula (1d) is as shown in the following reaction formula (2).

[Reaction Scheme 2]

The foaming agent according to the present invention is not only economical but also generates a small amount of carbon monoxide because the amount of generated gas is usually about 25 to 40% larger than that of the conventional ADCA foaming agent. Therefore, There is also a small amount of formamide generated.

The foaming agent according to the present invention can be produced by a variety of conventional organic synthesis methods, and specifically, as shown in the following examples, (i) by reacting guanidine with hydrazine or a derivative thereof, (Ii) reacting a compound containing three reactive halogens with hydrazine or a derivative thereof (Examples 2 and 3), (iii) reacting three cyano groups (-CN) with NaN ₃ (Example 7) or the like. Therefore, the foaming agent according to the present invention can be synthesized by a one-pot reaction, so that the synthesis is easy and economical.

The method for foaming a resin according to the present invention includes a step of mixing and heating the foaming agent of the present invention with a resin to be foamed. The foaming agent may be mixed with the resin to be foamed by a conventional resin mixing means such as a stirrer or a press roll. The heating may be carried out using a conventional resin such as an extruder, a press mold or a hot air circulating oven Heating means can be used. The operation conditions of the resin mixing means and the resin heating means can be appropriately operated according to the kind of the resin to be foamed, the type of the foaming agent, the kind of the additive, and the state. Typical operating conditions include the use of the foaming agent in the form of powder And master batch (master batch means that the foaming agent is concentrated and dispersed in the resin at a high concentration, for example, 10 to 55% by weight) The masterbatch may be prepared by mixing in a resin mixing means having a temperature of 90 to 120 캜 for 10 to 30 minutes and heating in a resin heating means having a temperature of 90 to 250 캜. The foamable resin and the foaming agent (in the form of a powder or a master batch) are mixed in a resin mixing means having a temperature of 25 to 120 캜 for 1 to 30 minutes and then heated at 150 to 250 캜 (specifically 170 to 230 캜) And a resin heating means having a pressure of 100 to 160 kg / cm ² (specifically, 100 to 150 kg / cm ² ) for 20 seconds to 30 minutes. The amount of the blowing agent to be used may vary depending on the type of the resin to be foamed, the type of the blowing agent, the desired degree of foaming, etc. For example, the powdered blowing agent may be used in an amount of 1 to 40 parts by weight 1 to 20 parts by weight, more specifically, 1.5 to 10 parts by weight, and more specifically 2 to 6 parts by weight) of the blowing agent in the form of a master batch may be used in an amount of 10 to 100 parts by weight, 80 parts by weight (specifically, 20 to 70 parts by weight, more specifically 30 to 55 parts by weight) may be used.

Examples of the resin to be foamed in which the foaming agent of the present invention is used include polyethylene, polypropylene (PP), polyvinyl chloride (PVC), polycarbonate (PC), polystyrene (PS), polyamide, acetal, styrene butadiene rubber (SBR), an ethylene vinyl acetate copolymer (EVA), an ethylene propylene rubber (EPDM), a thermoplastic elastomer (TPE), a thermoplastic polyurethane (TPU), a thermoplastic rubber Various synthetic or natural resins such as thermoplastic rubber (TPR), ABS resin (acrylonitrile butadiene styrene copolymer), rubber, epoxy resin and acrylic resin may be used. In the foaming step, various additives such as calcium carbonate, zinc oxide, stearic acid, and dicyclohexyl phthalate may be used.

The blowing agent according to the present invention can be applied to engineering plastics such as vehicle seat, tire and roof tec cover, garnish cover device, weather strip, air duct for air conditioner, automobile products such as interior / , Footwear products such as wallpaper, flooring, artificial leather, sneakers and slippers, infant and children's mats, household appliances such as TVs, PCs (personal computers), foam molding products such as sashes, sponges, , Children's products such as toys, synthetic wood, accessory ornaments, and other plastic containers.

Hereinafter, the present invention will be described in more detail by way of examples. The following examples are provided to illustrate the present invention, and the scope of the present invention is not limited by these examples.

[Example 1] Production of blowing agent represented by the formula (1d)

19.1 g (0.2 mol, Guanidine hydrochloride) of guanidine hydrochloride and 100 mL of dioxane as a solvent were placed in a flask and stirred, as shown in the following Reaction Scheme 3. To the flask, 40.0 g (0.8 mol) of 80% hydrazine monohydrate was slowly added dropwise at room temperature, and the mixture was refluxed and stirred for 2 hours. Finally, the reaction mixture was washed with dioxane and ethanol (EtOH) at room temperature to synthesize a white compound represented by the formula 1d (yield: 82%, DT: 224 ° C, GV: 300 ml / 4.50 (2H, NH 2),? 8.60 (1H, NH)).

[Reaction Scheme 3]

[Example 1-1] Preparation of blowing agent represented by the formula 1p

As shown in Reaction Scheme 4, 24.4 g (0.2 mol, guanidine nitrate) of guanidine nitrate and 100 mL of ethanol as a solvent were placed in a flask and stirred. To the flask, 40.0 g (0.8 mol) of 80% hydrazine monohydrate was slowly added dropwise at room temperature, and the mixture was refluxed and stirred for 2 hours. (Yield: 80%, DT: 214 캜, GV: 300 ml / g, NMR: δ 4.46 (2H, NH ₂ ) ,? 8.56 (1H, NH).

[Reaction Scheme 4]

[Example 2] Production of foaming agent represented by the formula (1b)

30.0 g (0.165 mol, Trichloro benzene) of trichlorobenzene and 150 mL of water (H ₂ O) were placed in a flask and stirred as shown in Reaction Scheme 5 below. To the flask, 46.5 g (0.74 mol) of 80% hydrazine monohydrate was slowly added dropwise at room temperature and then refluxed and stirred for 2 hours. Finally, at room temperature, water (H ₂ O) with three to synthesize white compound represented by the general formula 1b (yield: 74%, DT: 300 ℃ , GV: 160ml / g, NMR: δ 5.21 (2H, NH ₂ ) ,? 7.37 (1H, Ph), 7.67 (2H, Ph) ,? 9.67 (1H, NH).

 [Reaction Scheme 5]

[Example 3] Preparation of blowing agent represented by the formula (1c)

18.4 g (0.1 mol, Cyanuric chloride) of cyanuric chloride and 276 mL of water (H ₂ O) were placed in a flask and stirred as shown in Scheme 6 below. To the flask, 31.25 g (0.5 mol) of 60% hydrazine monohydrate was slowly added dropwise, and the mixture was refluxed and stirred for 2 hours. Finally, at room temperature, washed with water (H ₂ O), was synthesized in the white compound of formula 1c (yield: 91%, DT: 270 ℃ , GV: 220ml / g, NMR: δ 4.64 (1H, NH), 8 8.81 (2H, NH ₂ ).

 [Reaction Scheme 6]

[Example 4] Production of blowing agent represented by the formula (1m)

20.0 g (0.21 mol) of the compound represented by the formula (1d) synthesized in Example 1, 63.0 g (1.05 mol, acetic acid) of acetic acid and 200 mL of water (H ₂ O) were placed in a flask Lt; / RTI > To the flask was slowly added 61.2 g (0.942 mol) of NaOCN dropwise at room temperature and then stirred overnight at 75 ° C. Finally, at room temperature, water (H ₂ O) and ethanol and washed with (EtOH), was synthesized in the white compound of formula 1m (yield: 88%, DT: 295 ℃ , GV: 166ml / g, NMR: ? 7.22 (1H, NH) ,? 8.87 (1H, NH) ,? 9.99 (2H, NH2).

 [Reaction Scheme 7]

[Example 5] Preparation of a blowing agent represented by the formula (1n)

5.0 g (0.05 mol, Guanidine hydrochloride) of guanidine hydrochloride and 100 mL of dioxane as a solvent were added to a flask and stirred, as shown in the following reaction formula (8). To the flask, 15.6 g (0.18 mol, tetrazole amine) of tetrazole amine was added dropwise at room temperature, and the mixture was refluxed and stirred for 2 hours. Finally, at room temperature, washed with dioxane (Dioxane) and ethanol (EtOH), was synthesized in the white compound of formula 1n (yield: 51%, DT: 280 ℃ , GV: 80ml / g, NMR: δ 6.45 (1H, NH), 8 14.35 (1H, NH)).

 [Reaction Scheme 8]

[Example 6] Production of blowing agent represented by formula (Io)

As shown in Reaction Scheme 9, 20.0 g (0.2 mol, Guanidine hydrochloride) of guanidine hydrochloride and 200 mL of dioxane as a solvent were placed in a flask and stirred. To the flask, 100.0 g (0.73 mol, benzoic acid hydrazide) of benzoic acid hydrazide was added dropwise, and the mixture was refluxed and stirred overnight. (Yield: 77%, DT: 110 캜, GV: 100 ml / g NMR: δ 6.99 (1H, NH). The reaction mixture was stirred at room temperature for 1 hour, and then washed with dioxane at room temperature. , 7.33 (5H, pH), 8 11.13 (1H, NH)).

 [Reaction Scheme 9]

[Example 7] Production of blowing agent represented by the formula (1k)

As shown in following Reaction Scheme 10, potassium Tricia furnace methide 1.29 g (10 mmol, Potassium tricyanomethide ), NaN 3 2.2 g (33 mmol), ZnBr 2 6.76 g (30 mmol) and water (H ₂ O) 50 as a solvent mL was placed in a flask and refluxed and stirred overnight. The reaction was washed with water at room temperature to give a brown compound which was added to 4N HCl and stirred for 18 hours. The reaction mixture was filtered, and the resulting solid compound was dissolved again in 25 mL of 1 M NaOH and filtered. Filtered and neutralized with water (filterate) in 4N HCl, washed, it was synthesized white compound represented by formula 1k (yield: water: 46%, DT: 310 ℃ , GV: 84ml / g NMR: δ 7.01 (1H, CH), [ delta] 12.01 (1H, NH)).

[Reaction Scheme 10]

[Example 8] Preparation of blowing agent represented by the formula 1s

16.9 g (0.1 mol, Silicon tetrachloride) of silicon tetrachloride and 200 mL of hexane (Hexane) as a solvent were placed in a flask and stirred at 0 ° C, as shown in Scheme 11 below. 15.6 g of a 100% hydrazine solution (0.4 mol, Hydrazine Hydrate 100%) was added dropwise to the flask at 0 占 폚 and the mixture was stirred overnight at 0 占 폚 to 20 占 폚. Finally, recrystallization was carried out in hexane at -5 ° C to synthesize a white compound represented by the formula (1s) (yield: 65%).

[Reaction Scheme 11]

[Example 9] Preparation of blowing agent represented by the formula (1t)

7.21 g (0.1 mol, trimethylaluminium) of trimethylaluminum and 200 mL of hexane (Hexane) as a solvent were placed in a flask and stirred at 0 ° C, as shown in Scheme 12 below. 7.5 g (0.15 mol, Hydrazine Hydrate 100%) of 100% hydrazine solution was added dropwise to the flask at 0 ° C, and the mixture was stirred at 0 ° C to 20 ° C for 30 minutes. Finally, recrystallization was carried out at -30 ° C in a hexane solution to synthesize a white compound represented by the formula 1t (yield: 85%, mp: 105 ° C).

 [Reaction Scheme 12]

[ Experimental Example  1] Decomposition temperature of foaming agent

The decomposition temperature (DT) and the gas volume (GV) were measured while 500 mg of each of the azodicarbonamide (ADCA) was heated and decomposed as Examples 1 to 7 and Comparative Example. Table 1 shows the results.

Blowing agent compound Decomposition temperature (℃) Gas volume (mL / g) compare Comparative Example Azodicarbonamide (ADCA) 202 220 - Example 1 1d 224 300 Gas amount is high, noxious gas X Example 2 1b 300 160 High temperature process application O
Hazardous gas X Example 3 Formula 1c 270 220 High temperature process application O
Hazardous gas X Example 4 1m 295 166 High temperature process application O
Hazardous gas X Example 5 1n 280 80 High temperature process application O
Hazardous gas X Example 6 1o 110 100 No superiority Example 7 1k 310 84 High temperature process application O
Hazardous gas X

1 and 2 are electron micrographs showing the internal pore shape of a foam obtained by foaming a polypropylene (PP) and an ethylene-vinyl acetate copolymer (EVA), respectively, using the foaming agent according to Example 1 of the present invention. As shown in Figs. 1 and 2 and Table 1, the foaming agent according to the present invention has a decomposition temperature and a gas volume similar or superior to those of azodicarbonamide (ADCA) used in general use, and has uniform pores And it is possible to form a foam which does not generate noxious gas.

[Experimental Example 2] Analysis of noxious gas against PVC sol

3.5 phr of the foaming agent represented by the formula 1d synthesized in Example 1 and 100 gr of PVC sol as a resin to be foamed were mixed for 2 minutes on a mechanical stirrer set at a speed of 3000 rpm. 100 g of the mixed sol was poured into a coating paper and coated with 1.1 mm of a bar-coater, and then put into a hot air circulating oven to prepare a PVC foam. The foaming magnification And the concentration of noxious gas formamide were measured. The results are shown in Table 2 below. At this time, the temperature of the hot air circulating oven was 230 DEG C and the foaming time was 1 minute and 14 seconds. In addition, the concentration of formamide in Table 2 below was examined by the Korea Institute of Industrial Technology (KIT) through the Environmental Hazardous Substance Analysis (SGS). N.D. (Not detected) means that the concentration of formamide has occurred in such a small amount that it can not be measured or has not occurred.

subject Expansion ratio Formamide concentration D300L (ADCA) 7.3 mm 405 ppm Example 1
(1d) 4.5 mm (61.6%) N.D.

As shown in Table 2, a large amount of formamide was generated in the azodicarbonamide (ADCA) used in general use, while the foaming agent according to the present invention had a small amount of formamide that could not be measured, .

[Experimental Example 3] Analysis of gas components generated upon decomposition of blowing agent

Pyrolizer was used to weigh a sample (the foaming agent represented by the formula 1d synthesized in Example 1 and the azodicarbonamide (ADCA) as a comparative example) by using Eco-cup LF, Respectively. The sample was treated in a furnace having a temperature of 250 ° C for 1 minute and then analyzed with a gas chromatograph / mass spectrophotometer (GC-MS) containing a decomposition gas. GC-MS analysis equipment (Agilent 7890) was used for the gas analysis of the blowing agent, and Ultra Alloy-5 (30 m * 0.25 mm * 0.25 ㎛) was used for the GC-MS column. The flow rate was 1 ml / min and observed for 30 minutes. The results are shown in Table 3 below.

Component Formula Area% Example 1 (Formula 1d) Comparative Example (ADCA) Ammonia NH ₃ 12.6 41.9 Water H ₂ O 0.0 0.0 Nitrogen N ₂ 85.2 0.0 Nitrogen + Carbon monooxide - 0.0 23.6 Carbon dioxide CO ₂ 2.2 32.7 Formamide H ₂ NCOH 0.0 1.8 SUM 100 100

As shown in Table 3, in the case of azodicarbonamide (ACDA) which is generally used, a large amount of noxious gases such as formamide and ammonia are generated. On the other hand, in the blowing agent according to the present invention, Which is harmless to nitrogen, does not generate formaldehyde, and has an advantage in that the amount of harmful substances such as ammonia is reduced.

Claims (9)

A blowing agent represented by the following formula (1).
[Chemical Formula 1]

X is an alkyl group having 1 to 10 carbon atoms, an aryl group having 4 to 10 carbon atoms, a heterocyclic group having 3 to 10 carbon atoms, or a Group 3, 4, or 5 group atom, and R is a single bond or a double bond , D is a hydrazine containing group (group including hydrazine moiety), and n is an integer of 3 to 6. The method of claim 1, wherein X is selected from the group consisting of a carbon atom, a phenyl group, a 1,3,5-triazine group, nitrogen (N), silicon (Si) ) Is selected from the group consisting of a hydrazine group (-NHNH ₂ ), a nitroamine group (-NHNO ₂ ), and a heterocyclic group containing a -NN- moiety. The blowing agent according to claim 2, wherein the heterocyclic group containing the hydrazine moiety is selected from the group consisting of a tetrazole group and a tetrazolamine group. The compound according to claim 1, wherein the hydrazine-containing group is a substituent substituted on the hydrazine moiety, and includes a carbonyl group (-CO- or -COR ₁ wherein R ₁ represents a hydrocarbon group having 1 to 10 carbon atoms), an amide group (-CONH ₂ ), A hydrocarbon group having 1 to 20 carbon atoms, which may or may not contain a hetero atom, an amine group, and combinations thereof. The hydrocarbon group having 1 to 20 carbon atoms as set forth in claim 4, wherein the hydrocarbon group containing or not containing a hetero atom is a branched or linear alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, A cycloalkyl group, a cycloalkenyl group or a cycloalkynyl group having 5 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 4 to 10 carbon atoms, and a heterocyclic group having 4 to 10 carbon atoms, which may or may not contain 1 to 5 hetero atoms An aryl group or a heterocyclic group. The foaming agent according to claim 1, wherein D is bonded to aluminum containing an alkyl group having 2 to 5 carbon atoms in adjacent groups. 100 parts by weight of a resin; And
A master batch comprising 10 to 80 parts by weight of a blowing agent represented by the following formula (1).
[Chemical Formula 1]

X is an alkyl group having 1 to 10 carbon atoms, an aryl group having 4 to 10 carbon atoms, a heterocyclic group having 3 to 10 carbon atoms, or a Group 3, 4, or 5 group atom, and R is a single bond or a double bond , D is a hydrazine containing group (group including hydrazine moiety), and n is an integer of 3 to 6. The method of claim 7, wherein the resin is selected from the group consisting of polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polycarbonate (PC), polystyrene (PS), polyamide, acetal, styrene butadiene rubber From the group consisting of ethylene-vinyl acetate copolymer (EVA), ethylene propylene rubber (EPDM), thermoplastic elastomer (TPE), thermoplastic polyurethane (TPU), thermoplastic rubber (TPR), ABS resin, rubber, epoxy resin and acrylic resin The master batch, which is selected. A foamed foamed article using the foaming agent represented by the following formula (1).
[Chemical Formula 1]

X is an alkyl group having 1 to 10 carbon atoms, an aryl group having 4 to 10 carbon atoms, a heterocyclic group having 3 to 10 carbon atoms, or a Group 3, 4, or 5 group atom, and R is a single bond or a double bond , D is a hydrazine containing group (group including hydrazine moiety), and n is an integer of 3 to 6.

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