KR102355601B1 - Eco-friendly blowing agent composition and eco-friendly foam manufactured using the same - Google Patents

Abstract

The present invention relates to an environmentally friendly foam manufactured by using a foaming agent composition which does not generate harmful substances by comprising a hydrazide-based foaming agent which is pyrolyzed to generate gas, heat expandable microspheres, and a material which collects harmful gas generated during foaming and removes the same.

Description

Eco-friendly blowing agent composition and eco-friendly foam manufactured using the same

The present invention relates to an eco-friendly foam manufactured using a foaming agent composition that does not generate harmful components, including a hydrazide foaming agent that generates gas by thermal decomposition, thermally expandable microspheres, and a material that traps and removes harmful gases generated during foaming. it's about

A foaming agent is an additive for producing a porous foam by mixing with a synthetic resin, and is a substance that supplies a gas for forming bubbles for foam molding. These materials can be divided into organic foaming agents and inorganic foaming agents according to their properties, and can be divided into chemical foaming agents and physical foaming agents according to phase change.

Among the chemical foaming agents, azodicarbonamide is widely used because it produces a high amount of thermal decomposition gas and can obtain a foam with a high foaming ratio. However, when azodicarbonamide is thermally decomposed, a small amount of harmful components such as formamide and ammonia are generated.

In Korea Patent Publication No. 10-2017-0140236, aminoguanidine oxalate was synthesized and used as a foaming agent, but there was a problem in substantially replacing azodicarbonamide because the specific gravity of the foam was high and the foaming ratio was small.

Korea Patent No. 10-1915690 is a foaming agent in which azodicarbonamide is mixed with a metal oxide and a silane coupling agent, and suggests an effect of reducing the amount of ammonia generated in the foam, but does not completely remove the ammonia concentration.

In the case of Korean Patent No. 10-1966289, hydrotalcite and sodium bicarbonate were used for OBSH to reduce sulfur oxides and ammonia, but the sodium bicarbonate mixed foaming agent produced ammonia, so it was difficult to apply.

Korean Patent Publication No. 10-2017-0140236 Korean Patent No. 10-1915690 Korean Patent No. 10-1966289

According to the present invention, it is an object to provide an eco-friendly foaming agent composition that can suppress the generation of harmful components in the foaming process.

According to the present invention, it is an object of the present invention to provide an environmentally friendly foam excellent in whiteness, yellowing degree, hardness, compression deformation and split tear strength.

The object of the present invention is not limited to the object mentioned above. The object of the present invention will become clearer from the following description, and will be realized by means and combinations thereof described in the claims.

According to the present invention, a hydrazide-based foaming agent; physical blowing agents including thermally expandable microspheres; and additives; It provides an eco-friendly foaming agent composition comprising a.

The hydrazide-based foaming agent may include any one selected from the group consisting of p,p'-oxybis(benzenesulfonylhydrazide), p-toluenesulfonylhydrazide, benzenesulfonylhydrazide, and combinations thereof. .

The hydrazide-based foaming agent may include p,p'-oxybis(benzenesulfonylhydrazide).

The thermally expansible microspheres may include a shell comprising a thermoplastic resin; And it may include a foaming compound contained in the outer shell.

The thermoplastic resin is acrylonitrile (Acrylonitrile, AN), methacrylonitrile (Methacrylonitrile, MAN), methyl methacrylate (Methylmethacrylate, MMA), methacrylic acid (Methacrylicacid, MAA), acrylic acid (Acrylic acid, AA) and any one selected from the group consisting of combinations thereof, and the foaming compound may include hydrocarbon.

The physical foaming agent may be included in an amount of 10 to 30 parts by weight based on 100 parts by weight of the hydrazide-based foaming agent.

The additive may include at least one of aluminum and titanium.

The additive is aluminum triethoxide, aluminum triisopropoxide, aluminum ethylacetoacetate diisopropoxide, aluminum tris- (ethylacetoacetate) (Aluminum tris) -(ethylacetoacetate)), aluminum mono-acetylacetonate bis-(ethylacetoacetate)), aluminum alkylacetylacetonate diisopropoxide, titanium acetylacetonate Titanium acetylacetonate, Titanium tetra-acetylacetonate, Titanium Ethyl Acetoacetate, Tetra-N-Butyl Titanate, Tetra-Isopropyl Titanium (Tetra-Isopropyl Titanate), titanium phosphate complex (Titanium phosphate complex), titanium octylene glycolate (Titanium octyleneglycolate), and may include any one selected from the group consisting of combinations thereof.

The additive is more preferably titanium acetylacetonate (Titanuim acetylacetonate), titanium tetra-acetylacetonate (Titanium tetra-acetylacetonate), titanium ethyl acetoacetate (Titanium Ethyl Acetoacetate), tetra-N-butyl titanate (Tetra-N- Butyl Titanate), tetra-isopropyl titanium (Tetra-Isopropyl Titanate), titanium phosphate complex (Titanium phosphate complex), titanium octylene glycolate (Titanium octyleneglycolate) and may include any one selected from the group consisting of combinations thereof .

The additive may be included in an amount of 0.5 parts by weight to 1.5 parts by weight based on 100 parts by weight of the hydrazide-based foaming agent.

According to the present invention, preparing a mixed slurry by mixing the base polymer resin, the crosslinking agent, and the blowing agent composition of any one of claims 1 to 10; and coating the slurry on a substrate and foaming it to prepare a foam; provides an eco-friendly foam manufacturing method comprising a.

According to the present invention, there is provided an eco-friendly foam, characterized in that manufactured by the above manufacturing method.

The foam may have an emission amount of sulfur dioxide (SO ₂ ) of 5 ppm or less, and an emission amount of ammonia (NH ₃ ) of 0.1 ppm or less.

According to the present invention, it is possible to provide an environmentally friendly foaming agent composition capable of suppressing the generation of harmful components in the foaming process.

According to the present invention, it is possible to provide a foam that is environmentally friendly and has excellent whiteness, yellowness, hardness, compression deformation and split tear strength.

The effects of the present invention are not limited to the above-mentioned effects. It should be understood that the effects of the present invention include all effects that can be inferred from the following description.

The above objects, other objects, features and advantages of the present invention will be easily understood through the following preferred embodiments in conjunction with the accompanying drawings. However, the present invention is not limited to the embodiments described herein and may be embodied in other forms. Rather, the embodiments introduced herein are provided so that the disclosed content may be thorough and complete, and the spirit of the present invention may be sufficiently conveyed to those skilled in the art.

In this specification, terms such as "comprise" or "have" are intended to designate that a feature, number, step, operation, component, part, or a combination thereof described in the specification exists, but one or more other features It is to be understood that it does not preclude the possibility of the presence or addition of numbers, steps, operations, components, parts, or combinations thereof. Also, when a part of a layer, film, region, plate, etc. is said to be "on" another part, this includes not only the case where it is "on" another part, but also the case where there is another part in between. Conversely, when a part of a layer, film, region, plate, etc. is said to be “under” another part, this includes not only cases where it is “directly under” another part, but also a case where another part is in the middle.

Unless otherwise specified, all numbers, values, and/or expressions expressing quantities of ingredients, reaction conditions, polymer compositions and formulations used herein, contain all numbers, values and/or expressions in which such numbers essentially occur in obtaining such values, among others. Since they are approximations reflecting various uncertainties in the measurement, it should be understood as being modified by the term "about" in all cases. Also, where the present disclosure discloses numerical ranges, such ranges are continuous and inclusive of all values from the minimum to the maximum inclusive of the range, unless otherwise indicated. Furthermore, when such ranges refer to integers, all integers inclusive from the minimum to the maximum inclusive are included, unless otherwise indicated.

In this specification, when a range is described for a variable, the variable will be understood to include all values within the stated range including the stated endpoints of the range. For example, a range of “5 to 10” includes the values of 5, 6, 7, 8, 9, and 10, as well as any subranges such as 6 to 10, 7 to 10, 6 to 9, 7 to 9, etc. It will be understood to include any value between integers that are appropriate for the scope of the recited range, such as 5.5, 6.5, 7.5, 5.5 to 8.5 and 6.5 to 9, and the like. Also for example, ranges from "10% to 30%" include values of 10%, 11%, 12%, 13%, etc. and all integers up to and including 30%, as well as 10% to 15%, 12% to It will be understood to include any subrange, such as 18%, 20% to 30%, etc., and also include any value between reasonable integers within the scope of the stated range, such as 10.5%, 15.5%, 25.5%, and the like.

The present invention relates to an eco-friendly foaming agent composition and an eco-friendly foam manufactured using the same.

Hereinafter, each configuration of the eco-friendly foaming agent composition of the present invention will be described, and the results of comparative experiments on foams prepared through Examples and Comparative Examples will be described later.

Eco-friendly foaming agent composition

The eco-friendly foaming agent composition of the present invention is characterized by including a hydrazide-based foaming agent, a physical foaming agent including thermally expandable microspheres, and additives.

Hereinafter, each configuration will be described.

hydrazide foaming agent

The hydrazide-based foaming agent of the present invention includes any one selected from the group consisting of p,p'-oxybis(benzenesulfonylhydrazide), p-toluenesulfonylhydrazide, benzenesulfonylhydrazide, and combinations thereof. . Preferably p,p'-oxybis(benzenesulfonylhydrazide) is included.

The hydrazide-based foaming agent is characterized in that it does not release ammonia gas and formamide during decomposition.

physical blowing agent

The physical blowing agent of the present invention preferably comprises thermally expansible microspheres comprising a shell comprising a thermoplastic resin and a foaming compound encapsulated in the shell.

The thermoplastic resin is acrylonitrile (Acrylonitrile, AN), methacrylonitrile (Methacrylonitrile, MAN), methyl methacrylate (Methylmethacrylate, MMA), methacrylic acid (Methacrylicacid, MAA), acrylic acid (Acrylic acid, AA) and any one selected from the group consisting of combinations thereof.

The foaming compound includes hydrocarbons.

The physical foaming agent is included in an amount of 10 to 30 parts by weight based on 100 parts by weight of the hydrazide-based foaming agent. Preferably, the physical foaming agent is included in an amount of 15 to 25 parts by weight.

additive

The additive of the present invention is characterized in that it includes at least one of aluminum and titanium.

The additive has an effect of removing sulfur dioxide (SO ₂ ) emitted while the hydrazide-based foaming agent contained in the foaming agent composition foams.

The additive is preferably aluminum triethoxide, aluminum triisopropoxide, aluminum ethylacetoacetate diisopropoxide, aluminum tris-(ethylacetoacetate) ( Aluminum tris-(ethylacetoacetate)), Aluminum mono-acetylacetonate bis-(ethylacetoacetate)), Aluminum alkylacetylacetonate diisopropoxide, Titanium Acetylacetonate (Titanuim acetylacetonate), Titanium tetra-acetylacetonate (Titanium Ethyl Acetoacetate), Tetra-N-Butyl Titanate (Tetra-N-Butyl Titanate), Tetra-Iso It includes any one selected from the group consisting of propyl titanium (Tetra-Isopropyl Titanate), titanium phosphate complex, titanium octyleneglycolate, and combinations thereof. More preferably, the additive is titanium acetylacetonate (Titanuim acetylacetonate), titanium tetra-acetylacetonate (Titanium tetra-acetylacetonate), titanium ethyl acetoacetate (Titanium Ethyl Acetoacetate), tetra-N-butyl titanate (Tetra-N- Butyl Titanate), tetra-isopropyl titanium (Tetra-Isopropyl Titanate), titanium phosphate complex (Titanium phosphate complex), titanium octylene glycolate (Titanium octyleneglycolate) and any one selected from the group consisting of combinations thereof.

The additive may be included in an amount of 0.5 parts by weight to 1.5 parts by weight, preferably 0.8 parts by weight to 1.2 parts by weight, based on 100 parts by weight of the hydrazide-based foaming agent.

Eco-friendly foam manufacturing method

The eco-friendly foam manufacturing method of the present invention comprises the steps of preparing a mixed slurry by mixing a base polymer resin, a crosslinking agent, and the foaming agent composition of the present invention, and coating the slurry on a substrate and foaming it to prepare a foam to be.

More specifically, a mixed slurry prepared by mixing a base polymer resin, a crosslinking agent and a foaming agent composition is applied to a substrate to form a sheet, which is heated at a certain pressure and at a certain temperature to foam it to prepare a foam. At this time, 0.1 to 5.0 parts by weight of the crosslinking agent, 1 to 10 parts by weight of the foaming agent composition of the present invention is added based on 100 parts by weight of the polymer resin.

The base polymer resin is a material constituting the basic skeleton of the foam, and the present invention will not specifically limit it. For example, the base polymer resin may include an EVA resin.

The crosslinking agent is sufficient as long as it is a material that can be commonly used in the field of blowing agent technology, and the present invention will not specifically limit it.

Eco-friendly foam

In the present invention, the eco-friendly foam manufactured by the above manufacturing method is characterized in that there is little emission of harmful gas and high physical strength.

Specifically, the eco-friendly foam has an emission amount of sulfur dioxide (SO ₂ ) of 5 ppm or less, ammonia (NH ₃ ) emission of 0.1 ppm or less, a whiteness (White index, WI) of 95 or more, and a yellowing degree (b) of 3.0 or less, the hardness is 45C or more, the compression set (C/S) is 56% or less, and the split tear strength (S/T) is 2.30kg/cm or more.

Hereinafter, the present invention will be described in more detail through specific examples. However, these examples are for illustrating the present invention, and the scope of the present invention is not limited thereto.

How to measure

Expansion factor: Measure the coefficient of linear expansion and use it as the expansion factor

Emission amount of harmful gas: After cutting the foam and measuring 112g, put it in a 9L airtight container. And after storage at 70 ℃ for 1 hour, the concentration of harmful gas inside was measured through the detection tube.

Whiteness (WI) and yellowness (b): White index (WI) and b were measured for the whiteness of the expanded specimen using SPECTROPHOTOMETER CM-2500d. The higher the WI, the better the whiteness, and the smaller the b, the less yellowing.

Crosslinking degree: After measuring about 7.5 g of the sheet prepared in Experimental Method 1, Tmax and Tmin were measured at 175° C. for 10 min using a rheometer, and the difference value was used as the degree of crosslinking.

Hardness: Measured using Asker CL-150.

Compression set (C/S): The thickness of the specimen was measured for the foam using a specimen cutter (6 cm X 10 cm). Then, put it in a compression set and fix it with a nut 1cm. After leaving it in a dry oven at 50°C for 6 hours, take it out and cool the specimen at room temperature for 30 minutes. After that, measure the reduced thickness of the specimen and calculate as follows.

Actual preferred thickness/reduced thickness X 100

Split Tear (S/T): After cutting the specimen to a thickness of about 1 cm with a specimen cutter (6 cm X 10 cm), cut the cut specimen with a tip of 3 cm with a knife to make a 3 cm X 10 cm specimen. makes Cut the scratches with a cutter about 3.5cm along the baseline, and fix it on a tensioner with a height of at least 150cm. After set zero, set the speed to about 80mm/min and start cutting. After measuring the maximum load at the time of final tearing based on the baseline, [maximum load ÷ 3 cm (-0.35 (correction value))] S/T value was calculated.

Example 1

20 g of thermally expansible microspheres (T _s 165 ° C, T _m 195 ° C) and 1 g of additive (titanium tetra-acetylacetonate) were mixed in 100 g of OBSH for about 10 minutes and sieved through 100 mesh to prepare a foaming agent composition .

Then, 0.8 parts by weight of a crosslinking agent (BIBP) and 5 parts by weight of a foaming agent composition were mixed with 100 parts by weight of the EVA resin, and a sheet was prepared using a mixing roll. The prepared sheet was put into a mold of 10cmX15cmX1cm and foamed for 9 minutes at a temperature of 175° C. and a pressure of 150 kgf/cm ³ to prepare a foam.

Comparative Examples 1 to 11

As shown in Tables 1 and 2 below, the foams of Comparative Examples 1 to 11 were prepared by differently controlling each composition and the content of each composition.

Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 A1 - 100 - - - - - A2 100 - 100 100 100 100 100 A3 - - - 20 - - - B 20 - - - 10 20 30 C1 - - - - - - - C2 1.0 - - - - - - C3 - - - - - - - C4 - - - - - - - A1: azodicarbonamide (ADCA)
A2: p,p'-oxybis(benzenesulfonylhydrazide) (OBSH)
A3: sodium bicarbonate (sodium bicarbonate)
B: Capsule foaming agent ()
C1: Titanium Ethyl acetoacetate
C2: Titanium tetra-acetylacetonate
C3: Aluminum triethoxide
C4: Aluminum tris-(ethylacetoacetate)

Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 Comparative Example 11 A1 - - - - - A2 100 100 100 100 100 A3 - - - - - B 20 20 20 20 20 C1 1.0 - - - - C2 - - - 0.3 1.9 C3 - 1.0 - - - C4 - - 1.0 - - A1: azodicarbonamide (ADCA)
A2: p,p'-oxybis(benzenesulfonylhydrazide) (OBSH)
A3: sodium bicarbonate (sodium bicarbonate)
B: Capsule foaming agent ()
C1: Titanium Ethyl acetoacetate
C2: Titanium tetra-acetylacetonate
C3: Aluminum triethoxide
C4: Aluminum tris-(ethylacetoacetate)

Experimental example (expansion magnification and harmful gas emission)

For the foams prepared in Example 1 and Comparative Examples 1 to 11, the expansion ratio and the harmful gas emission degree were measured and shown in Tables 3 and 4 below.

Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Expansion ratio (%) 168 166 178 170 175 165 157 NH ₃ (ppm) N.D. 220 N.D. 24 N.D. N.D. N.D. SO ₂ (ppm) N.D. N.D. 58 47 38 13 11

Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 Comparative Example 11 Expansion ratio (%) 163 165 164 171 162 NH ₃ (ppm) N.D. N.D. N.D. N.D. N.D. SO ₂ (ppm) 3 One 2 5 N.D.

When examining the results of Tables 3 and 4, Comparative Example 1 to which only ADCA was applied had the highest ammonia emission amount of 220 ppm. Comparative Example 2 in which only OBSH was applied did not generate ammonia gas, but sulfur dioxide gas was generated, and when OBSH and sodium bicarbonate were mixed and applied, the sulfur dioxide gas tended to be somewhat reduced, but it can be seen that ammonia gas was emitted.

When thermally expansible microspheres were applied, there was an effect of reducing the generation of sulfur dioxide. In the case of Comparative Example 6, although the amount of sulfur dioxide reduction was high, it can be seen that the expansion ratio was very low.

When the additive was applied, the sulfur dioxide reduction efficiency was greatly increased, and in particular, in Example 1 and Comparative Example 11, the emission of sulfur dioxide gas was not detected. However, in the case of Comparative Example 11, the expansion ratio was measured to be rather low.

Experimental example (measurement of foam properties)

Among the foams of Example 1, Comparative Example 1 and Comparative Example 2 and other foams, the expansion ratio was 160% or more, the ammonia emission was not detected, and the comparative examples showing a value of less than 20 ppm in the sulfur dioxide emission (Comparative Example 5, Comparative Example 5) For Example 10 and Comparative Example 11), whiteness, yellowing degree, hardness, crosslinking degree, C/S and S/T were measured, and the results are shown in Table 5 below.

Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 5 Comparative Example 10 Comparative Example 11 whiteness 95.22 92.15 95.83 95.59 95.32 93.87 yellowness 2.57 4.96 2.38 2.80 2.62 2.78 Hardness 46 45 33 41 42 49 degree of crosslinking 12.3 12.1 7.5 8.7 11.1 14.3 C/S 55 57 74 62 58 56 S/T 2.31 2.35 1.79 2.05 2.13 1.98

Looking at the results of Table 5, the foam of Comparative Example 1 to which only ADCA was applied had poor whiteness and yellowness values due to the slow foaming rate, but Comparative Example 2 showed relatively excellent whiteness and yellowingness in the case of OBSH. . However, Comparative Example 2 can be expected to be difficult to apply to applications to which ADCA is applied due to low degree of crosslinking and hardness. Comparative Example 5 shows a tendency to increase the degree of crosslinking and hardness, but it can be seen that the physical properties are inferior compared to the physical properties of the ADCA foam. On the other hand, in the case of Example 1, it can be seen that very excellent values are shown in whiteness, yellowing degree, and hardness, and high values are also shown in crosslinking degree, C/S and S/T, so that it can be confirmed that a foam with excellent physical properties is prepared. can

As a result, in the case of Example 1, it can be seen that not only ammonia and sulfur dioxide are hardly discharged, but also very excellent effects are exhibited when the foam is applied.

Claims (13)

hydrazide-based foaming agent;
physical blowing agents including thermally expandable microspheres; and
additive; including,
The hydrazide-based foaming agent includes any one selected from the group consisting of p,p'-oxybis(benzenesulfonylhydrazide), p-toluenesulfonylhydrazide, benzenesulfonylhydrazide, and combinations thereof,
The thermally expandable microspheres may include a shell comprising a thermoplastic resin; and
Containing hydrocarbons contained in the outer shell,
The additive is titanium acetylacetonate, titanium tetra-acetylacetonate, titanium ethyl acetoacetate, tetra-N-butyl titanate. , tetra-isopropyl titanium (Tetra-Isopropyl Titanate), titanium phosphate complex (Titanium phosphate complex), titanium octylene glycolate (Titanium octyleneglycolate) and any one selected from the group consisting of combinations thereof,
The physical foaming agent is included in 10 parts by weight to 30 parts by weight based on 100 parts by weight of the hydrazide-based foaming agent,
The additive is an eco-friendly foaming agent composition, characterized in that it is included in 0.5 parts by weight to 1.5 parts by weight based on 100 parts by weight of the hydrazide-based foaming agent. delete According to claim 1,
The hydrazide-based foaming agent is an eco-friendly foaming agent composition comprising p,p'-oxybis(benzenesulfonylhydrazide). delete According to claim 1,
The thermoplastic resin is acrylonitrile (Acrylonitrile, AN), methacrylonitrile (Methacrylonitrile, MAN), methyl methacrylate (Methylmethacrylate, MMA), methacrylic acid (Methacrylicacid, MAA), acrylic acid (Acrylic acid, AA) and an eco-friendly foaming agent composition comprising any one selected from the group consisting of combinations thereof. delete According to claim 1,
The additive is an eco-friendly foaming agent composition comprising at least one of aluminum and titanium (Titanuim). According to claim 1,
The additive is aluminum triethoxide, aluminum triisopropoxide, aluminum ethylacetoacetate diisopropoxide, aluminum tris- (ethylacetoacetate) (Aluminum tris) -(ethylacetoacetate)), aluminum mono-acetylacetonate bis-(ethylacetoacetate)), aluminum alkylacetylacetonate diisopropoxide, titanium acetylacetonate Titanium acetylacetonate, Titanium tetra-acetylacetonate, Titanium Ethyl Acetoacetate, Tetra-N-Butyl Titanate, Tetra-Isopropyl Titanium (Tetra-Isopropyl Titanate), titanium phosphate complex (Titanium phosphate complex), titanium octylene glycolate (Titanium octyleneglycolate), and eco-friendly foaming agent composition comprising any one selected from the group consisting of combinations thereof. delete delete Preparing a mixed slurry by mixing the base polymer resin, the crosslinking agent, and the blowing agent composition of any one of claims 1, 3, 5, and 7 to 8; and
and coating the slurry on a substrate and foaming it to prepare a foam. An eco-friendly foam, characterized in that produced by the manufacturing method of claim 11. 13. The method of claim 12,
The foam has an emission amount of sulfur dioxide (SO ₂ ) of 5 ppm or less,
Ammonia (NH ₃ ) The emission amount of 0.1ppm or less eco-friendly foam.