KR102191329B1 - Foaming agent and foam formed using the same - Google Patents

Abstract

The present invention relates to a foaming agent comprising a foaming compound that decomposes to generate ammonia during foaming and an ammonia reducing agent including calcium chloride.By effectively reducing ammonia gas generated during foaming of the foaming compound, it is excellent in terms of economy and environment. It is possible to provide a foaming agent and a foam formed using the same.

Description

Foaming agent and foam formed using the same

The present invention relates to a foaming agent and a foam formed using the same.

Herein, background art related to the present disclosure is provided, and these do not necessarily mean known art.

The foaming agent is a synthetic resin additive for producing a porous foam by being blended with a synthetic resin, and is a material that supplies gas for forming bubbles in foam molding, and is roughly classified as a chemical foaming agent and a physical foaming agent. It is added to plastic or rubber and thermally decomposed according to a specific temperature, pressure and time to form a fine foam structure.

Among the above chemical foaming agents, azodicarbonamide has a high gas generation rate during pyrolysis, a large amount of gas generated, and thus a foamed foam having excellent foaming ratio can be produced, and the decomposition temperature can be easily controlled by using a decomposition temperature accelerator. There is this. However, there is a problem in the working environment due to a large amount of ammonia generated during foaming, and it is a problem due to the smell of ammonia when commercialized. There is a method of using a physical adsorbent to remove ammonia, but since the foaming temperature of azodicarbonamide is 200℃ and 230℃, ammonia is adsorbed to the physical adsorbent and then desorbed again at a high temperature, reducing ammonia. Is very low. There is also a method of using a strong acid to increase the reduction efficiency of ammonia, but this has a problem in that the shape of the foam is damaged or the foaming ratio is low, and the color of the foam is foamed to black.

The present invention has been made to solve the above problems, and an object of the present invention is to provide a foaming agent capable of reducing the emission of ammonia gas generated during foaming of a foaming agent such as an azo foaming agent, and a foam formed using the same.

However, the objects of the present invention are not limited to the above-mentioned objects, and other objects that are not mentioned will be clearly understood by those skilled in the art from the following description.

As a means to achieve the above object,

An embodiment of the present invention is a foaming compound that is decomposed during foaming to generate ammonia; And it provides a foaming agent comprising a; and ammonia reducing agent containing calcium chloride.

In addition, the foaming compound provides a foaming agent comprising at least one of azo-based foaming compounds including azodicarbonamide (ADCA) and azobisisobutyronitrile (AIBN).

In addition, the ammonia reducing agent provides a foaming agent contained within the range of 10 to 20 parts by weight based on 100 weight of the foaming compound.

In addition, the ammonia reducing agent provides a foaming agent in which calcium chloride is adsorbed on a porous carrier.

In addition, the porous carrier provides a foaming agent of aluminum oxide or zeolite.

In addition, 0.5 to 3 parts by weight of calcium chloride is adsorbed on the porous carrier, and the porous carrier on which the calcium chloride is adsorbed provides a foaming agent contained within a range of 10 to 20 parts by weight based on 100 weight of the foaming compound.

In addition, the ammonia reducing agent provides a foaming agent coated on a foaming compound.

In addition, the ammonia reducing agent provides a foaming agent coated in the range of 0.1 to 2 parts by weight based on 100 weight of the foaming compound.

The present invention also provides a resin to be foamed; And it provides a foaming composition comprising the foaming agent.

The present invention also provides a foam that is foamed with a foaming agent that decomposes during foaming to generate ammonia, wherein the foam of 10cm X 10cm is placed in a 5L sealed container and ammonia detected when left to stand for 1 hour is 120ppm or less.

The present invention provides a foaming agent and a foam capable of dramatically reducing the generation of ammonia while maintaining the foaming performance of the foaming agent by using an ammonia reducing agent containing calcium chloride.

The above effects and additional effects are described in detail below.

Before describing the present invention in detail below, it is understood that the terms used in the present specification are for describing specific embodiments and are not intended to limit the scope of the present invention, which is limited only by the scope of the appended claims. shall. All technical and scientific terms used in the present specification have the same meaning as commonly understood by those of ordinary skill in the art unless otherwise stated.

Throughout this specification and claims, unless otherwise stated, the term "comprise, comprises, comprising" means to include the recited object, step or group of objects, and steps, and any other object It is not used in the sense of excluding a step, a group of objects, or a group of steps.

Meanwhile, various embodiments of the present invention may be combined with any other embodiments unless there is a clear opposite point. Any feature indicated to be particularly preferred or advantageous may be combined with any other feature and features indicated to be preferred or advantageous. Hereinafter, embodiments of the present invention and effects thereof will be described.

The foaming agent according to an embodiment of the present invention includes a foaming compound that is decomposed during foaming to generate ammonia, and an ammonia reducing agent including calcium chloride.

The foaming compound is not limited as long as it is decomposed during foaming to generate ammonia. As an example, the foaming compound is an azo-based compound that can be represented by the general formula RN=N-R', for example, azodicarbonamide (ADDA), azobisisobutyronitrile (AIBN). Can be mentioned. Azo compounds may be used alone, but other pyrolytic compounds such as oxybisbenzenesulfonyl hydrazide (4,4'-Oxydibenzenesulfonyl Hydrazide, OBSH) compounds together with the azo compounds to the extent that the effects of the invention are not impaired. You may use together.

As the foaming compound, a foaming compound having an average particle diameter of 1 to 30 μm is used. If it is less than 1 μm, there is a problem of early decomposition of the foaming agent, and if it is more than 30 μm, there is a problem that the foam cell is made uneven. It is preferable to use a foaming compound having an average particle diameter of 2 to 20 μm.

The ammonia reducing agent containing calcium chloride may reduce ammonia generated outside the foam by trapping ammonia generated during thermal decomposition of the foaming compound. Here, collection includes meanings such as collection by a chemical reaction, the form of complex compounds, adsorption, and absorption, but is not limited thereto, and includes a state that is not separated by being combined with a material to be collected. Calcium chloride may be in anhydrous form or in monohydrate, dihydrate, tetrahydrate, or hexahydrate form.

It is not clear how calcium chloride reduces ammonia, but ammonia is captured in the form of CaCl ₂ ·4NH ₃ or CaCl ₂ ·8NH ₃ or CaCl ₂ + 2NH ₃ + H ₂ O -> 2NH ₄ Cl + CaO It is assumed that the ammonia concentration is reduced by the reaction.

The ammonia reducing agent may be used alone, and may be used simply by mixing with a foaming compound. At this time, the ammonia reducing agent is preferably included in the range of 10 to 20 parts by weight based on 100 parts by weight of the foaming compound. If the ammonia reducing agent is less than 10 parts by weight, the ammonia reduction efficiency is insignificant, and if it exceeds 20 parts by weight, the foaming properties deteriorate and it is difficult to obtain a high-quality foam.

As another example, the ammonia reducing agent may be a form in which calcium chloride is adsorbed on a porous carrier. Since the porous carrier can physically adsorb ammonia, calcium chloride present on the surface of the carrier helps to more efficiently capture ammonia. Examples of the porous carrier include porous aluminum oxide or zeolite. In the case of using only the porous carrier without the presence of calcium chloride, the adsorption power of ammonia is weak and the desorption of ammonia occurs reversibly, resulting in insufficient ammonia reduction effect.

The porous carrier adsorbed by 0.5 to 3 parts by weight of calcium chloride based on 100 parts by weight of the foaming compound is preferably used within the range of 10 to 20 parts by weight. By using a porous carrier and calcium chloride within the above range, the amount of calcium chloride used can be reduced and a high-quality foam can be obtained.

If the amount of calcium chloride based on 100 parts by weight of the blowing agent compound is less than 0.5 parts by weight, the ammonia reduction effect is insignificant, and if it exceeds 3 parts by weight, the acidity is strong and the magnification is low, pinholes may occur, and discoloration may occur. In addition, when the content of the carrier is less than 10 parts by weight, the ammonia effect is insignificant as when the amount of calcium chloride is small, and when the amount of the carrier exceeds 20 parts by weight, the magnification is lowered.

As another example, the ammonia reducing agent may be in a form coated on a foaming compound, for example, a foamed compound coated with calcium chloride. By directly coating the foaming compound with calcium chloride, ammonia generated during foaming of the foaming compound can be immediately collected, and the ammonia reduction efficiency can be remarkably improved.

The content of the ammonia reducing agent to be coated is preferably contained within the range of 0.1 to 2 parts by weight based on 100 parts by weight of the foaming compound. If the amount is less than 0.1 parts by weight, the ammonia reduction efficiency is insignificant, and if it is added in excess of 2 parts by weight, the ammonia reduction effect is not better, the acidity becomes stronger, the magnification decreases, a pinhole occurs, and discoloration proceeds.

The foaming agent according to the present invention may further include an additive for further enhancing the ammonia reduction effect. As an example, magnesium sulfate, magnesium chloride, etc. are mentioned.

Other additives include calcium compounds such as calcium stearate and calcium carbonate, and zinc compounds such as zinc oxide and zinc stearate. , Titanium dioxide, titanium or tin compounds such as tin methoxy maleate, barium stearate, barium ricinoleate, etc. Magnesium compounds such as barium compounds, magnesium oxide, talc, monosodium citrate, urea, silica, dicyclohexylphthalate ( Dicyclohexyl phthalate) and stearic acid (stearic acid) includes any one or more selected from the group consisting of.

The calcium compound may improve the flowability of the foaming agent, the zinc compound may accelerate the decomposition temperature, and the titanium or tin compound may improve the whiteness of the foam.

The foaming agent according to the present invention is polyethylene (PE), polypropylene (PP), ethylene vinyl acetate copolymer (EVA), polycarbonate (PC), ethylene propylene diene monomer (Ethylene). Propylene Diene Monomer: EPDM), polystyrene (PS), Thermoplastic Elastomer (TPE), Thermoplastic polyurethane (TPU), Polyvinyl chloride (PVC), ABS resin (acrylonitrile butadiene styrene) copolymer), polyamide (PA), acetal, rubber, etc. It can be usefully used as a foaming agent for various synthetic or natural resins.

The method for producing a foam according to the present invention includes a step of mixing and heating the foaming agent and the resin to be foamed. The heating temperature may vary depending on the type of the resin to be foamed, but is, for example, 100 to 250°C, preferably 130 to 200°C.

In the foam produced by using the foaming agent according to the present invention, ammonia content of 120 ppm or less is detected when ammonia is analyzed by the following method.

<Ammonia analysis method>

After keeping the foam at room temperature for 1 hour, cut it into 10cm X 10cm, put it in a sealed container, for example, a 5L Tedler bag, and inject 4.5L air and seal it. After leaving the 5L Tedler bag at 80℃ for 1 hour using the following convention oven, check the ammonia concentration in the 5L Tedler bag using an ammonia detector.

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

Experimental method

Foam production method

In this example, a foam was manufactured using PVC as an example, and other resins may also be applied.

After adding 1.7 phr of foaming agent to 100 weight of PVC sole, stir at 3000 rpm for 1 minute using a mechanical stirrer. After that, the mixed PVC sol is spread out using a 1.7T bar, and then foamed at 230°C for 2 minutes and 50 seconds using a matis oven.

Ammonia analysis method

After maintaining the prepared PVC foam at room temperature for 1 hour, cut it into 10cm X 10cm, put it in a sealed container, for example, a 5L Tedler bag, and inject 4.5L of air and seal it. After leaving the 5L Tedler bag at 80℃ for 1 hour using the following convention oven, check the ammonia concentration in the 5L Tedler bag using an ammonia detector.

<Example 1>

Azodicarbonamide (ADCA) dry product purity 100g particle size 3~6 um (Unicell D300 manufacturer: Dongjin Semichem) mixed with 5g CaCl ₂ anhydrus, and then sieved using a 100 mesh sieve. A foam was prepared using the obtained foaming agent, and the ammonia concentration was analyzed, and the results are shown in Table 1. It showed a 10% ammonia reduction effect compared to Comparative Example 1.

<Example 2>

In Example 1, except for using CaCl ₂ anhydrus 10g, it was carried out in the same manner, and the results are shown in Table 1. It showed a 40% ammonia reduction effect compared to Comparative Example 1.

<Example 3>

In Example 1, except for using CaCl ₂ anhydrus 20g, the same was carried out, and the results are shown in Table 1. It showed a 70% ammonia reduction effect compared to Comparative Example 1.

<Example 4>

In Example 1, except that 30 g of CaCl ₂ anhydrus was used, the same was carried out, and the results are shown in Table 1. Compared to Comparative Example 1, the ammonia reduction effect was achieved by 70%, but the foaming ratio was low, the surface was rough, and the foamed foam state performance was deteriorated.

<Example 5>

Dissolve 5 g of CaCl _{2 in} 50 g of water in a 250 mL beaker, add 50 g of an aluminum oxide carrier, stir at room temperature for 1 hour, and dry in a vacuum dryer at 90° C. for 24 hours to obtain an adsorbed material. Thereafter, the present compound was mixed by adding 5 parts by weight relative to 100 parts by weight of ADCA, and then sieved using a 100 mesh sieve to prepare a foaming agent. Then, it was carried out in the same manner as in Example 1, and the results are shown in Table 1. It showed a 13% ammonia reduction effect compared to Comparative Example 1.

<Example 6>

In Example 5, it was carried out in the same manner, except that 10 parts by weight of the aluminum oxide carrier adsorbed with CaCl ₂ was added relative to 100 parts by weight of ADCA, and the results are shown in Table 1. It showed 43% ammonia reduction effect compared to Comparative Example 1.

<Example 7>

In Example 5, an aluminum oxide carrier adsorbed with CaCl ₂ was carried out in the same manner, except that 20 parts by weight of ADCA was added, and the results are shown in Table 1. It showed 71% ammonia reduction effect compared to Comparative Example 1.

<Example 8>

In Example 5, an aluminum oxide carrier adsorbed with CaCl ₂ was carried out in the same manner except that 30 parts by weight of ADCA was added, and the results are shown in Table 1. Compared to Comparative Example 1, ammonia reduction effect of 70% was exhibited, but the foaming ratio was lowered.

<Example 9>

In Example 6, except that zeolite was used instead of aluminum oxide as a carrier, it was carried out in the same manner, and the results are shown in Table 1. Compared to Comparative Example 1, it exhibited a 40% ammonia reduction effect, thus exhibiting the same effect as aluminum oxide.

<Example 10>

In Example 6, it was carried out in the same manner, except that 1 g was used instead of 5 g of CaCl ₂ , and the results are shown in Table 1. Compared to Comparative Example 1, the ammonia reduction effect was shown to be 7%, indicating that the ammonia reduction efficiency was somewhat inferior.

<Example 11>

In Example 6, it was carried out in the same manner except that 20g was used instead of CaCl ₂ 5g, and the results are shown in Table 1. Compared to Comparative Example 1, ammonia reduction effect of 70% was exhibited, but the foaming ratio was low, pinholes were generated, and discoloration proceeded.

<Example 12>

In a 250 mL beaker, 0.05 g of CaCl ₂ was dissolved in 50 g of water, and 100 g of ADCA was added, stirred at room temperature for 1 hour, and dried in a vacuum dryer at 90° C. for 24 hours to obtain a coating material. Then, the present compound was sieved using a 100 mesh sieve to prepare a foaming agent. Then, it was carried out in the same manner as in Example 1, and the results are shown in Table 1. It showed a 10% ammonia reduction effect compared to Comparative Example 1.

<Example 13>

In Example 12, CaCl ₂ was carried out in the same manner except that 0.10 g was used instead of 0.05 g, and the results are shown in Table 1. It showed a 60% ammonia reduction effect compared to Comparative Example 1.

<Example 14>

In Example 12, CaCl ₂ was carried out in the same manner except that 2.0g was used instead of 0.05g, and the results are shown in Table 1. Compared to Comparative Example 1, it exhibited a 95% ammonia reduction effect.

<Example 15>

In Example 12, CaCl ₂ was carried out in the same manner except that 2.5g was used instead of 0.05g, and the results are shown in Table 1. Compared to Comparative Example 1, the ammonia reduction effect was exhibited by 95%, but the foaming ratio was low, pinholes were generated, and discoloration proceeded.

<Comparative Example 1>

In Example 1, except that only Azodicarbonamide (ADCA) blowing agent was used, it was carried out in the same manner, and the results are shown in Table 1. The foaming properties of the foaming agent were at the same level as in Example 1, and the ammonia concentration was as high as 200 ppm.

division DT Gas volume (mL/g) Ammonia concentration (ppm) ammonia
Reduction effect (%) Example 1 206 246 180 10% Example 2 206 240 120 40% Example 3 206 231 60 70% Example 4 206 200 60 70% Example 5 206 244 174 13% Example 6 206 242 114 43% Example 7 206 231 58 71% Example 8 206 198 60 70% Example 9 206 241 123 40% Example 10 206 242 186 7% Example 11 206 242 61 70% Example 12 206 247 180 10% Example 13 206 247 70 65% Example 14 206 242 10 95% Example 15 206 241 10 95% Comparative Example 1 206 245 200 0%

Features, structures, effects, and the like illustrated in each of the above-described embodiments can be combined or modified for other embodiments by a person having ordinary knowledge in the field to which the embodiments belong. Accordingly, contents related to such combinations and modifications should be interpreted as being included in the scope of the present invention.

Claims (10)

A foaming compound that is decomposed during foaming to generate ammonia; And
Containing an ammonia reducing agent,
The ammonia reducing agent is a foaming agent in the form of calcium chloride alone or a porous carrier adsorbed with calcium chloride.
The method of claim 1,
The foaming compound is a foaming agent containing at least one or more of azo-based foaming compounds including azodicarbonamide (ADCA) and azobisisobutyronitrile (AIBN).
The method of claim 1,
The ammonia reducing agent is a foaming agent contained within the range of 10 to 20 parts by weight based on 100 weight of the foaming compound.
delete The method of claim 1,
The porous carrier is a foaming agent of aluminum oxide or zeolite.
The method of claim 1,
The porous carrier is adsorbed by 0.5 to 3 parts by weight of calcium chloride,
The porous carrier adsorbed with calcium chloride is a foaming agent contained within the range of 10 to 20 parts by weight based on 100 weight of the foaming compound.
delete delete Resin to be foamed; And
Foaming composition comprising the foaming agent according to claim 1.
A foam prepared from the foam composition according to claim 9,
A foam having 120 ppm or less of ammonia detected when the foam of 10 cm X 10 cm is placed in a 5 L sealed container and left for 1 hour.