KR102118942B1 - Polyolefin-polymeric acid resin foaming composition, foam sheet using the same and manufacturing method thereof - Google Patents

Abstract

One embodiment of the present invention to provide a polyolefin-based polymer asset foam composition comprising a polyolefin-based resin, a blowing agent and a polymer acid, and a foam sheet using the same, to remove harmful odors by reducing harmful gases emitted from the foam sheet and the human body It has the effect of blocking harmfulness and improving the working environment of workers engaged in the foaming process.

Description

Polyolefin-polymer asset foam composition, foam sheet using the same, and manufacturing method thereof {Polyolefin-polymeric acid resin foaming composition, foam sheet using the same and manufacturing method thereof}

The present invention relates to a polyolefin-based solid asset foam composition, a foam sheet using the same, and a method for manufacturing the same, more specifically, foaming by adding a polymer acid to a mixture of a polyolefin resin and a foaming agent, and remains harmful inside the foam sheet It relates to a technology for reducing gas.

The most frequently used polymer materials in the production of foamed sheets are polyurethane, polyolefin, and polyvinyl chloride. A foaming agent is added to foam the polymers. Examples of the foaming agent include azo compounds, nitroso compounds, and sulfonylhydrazide compounds. In particular, among the azo-based compounds, azodicarbonamide is known to be an excellent foaming agent due to rapid generation of nitrogen gas by heating, non-combustible decomposition products, and no toxicity.

When the blowing agent has a lot of gas, the foaming magnification is improved, but there is a problem that harmful gases such as ammonia and formamide are generated and remain inside the foam sheet after foaming.

As a conventional technique for solving this problem, a method of dehydrating the gaseous formamide and converting it to hydrogen cyanide (HCN) has been disclosed, but the method must be performed at a high temperature (350 to 600°C) for a long time. There is a disadvantage. A method for converting formamide to hydrogen cyanide in a short time (20 seconds) and a relatively low temperature (220-240°C) has also been proposed, but it is not economical because it requires the use of a special heat surface device facility coated with a catalyst and is not applicable The disadvantage is that it is limited.

In addition, although the technique of mixing the blowing agent and the inorganic deodorant during the foaming process has been proposed, there is a problem of poor compatibility with the polyolefin-based resin composed of the organic material which is the main component of the foamed sheet, and the existing defoaming of the existing foam sheet There is a problem that the physical properties are not lowered or the foaming magnification is not maintained, and a high deodorizing effect on the harmful gas remaining inside the foamed sheet is not exhibited.

The technical problem to be achieved by the present invention is to solve the above problems, it is highly compatible with deodorant materials without lowering the foaming magnification or physical properties of the existing foamed sheet, and significantly reduces the harmful gas emitted from the inside of the foamed sheet. It is to provide a polyolefin-based high-molecular-weight foam composition that can be reduced, a foam sheet using the same, and a method for manufacturing the same.

The technical problem to be achieved by the present invention is not limited to the technical problems mentioned above, and other technical problems not mentioned can be clearly understood by those skilled in the art from the following description. There will be.

In order to achieve the above technical problem, an embodiment of the present invention is a polyolefin-based resin; blowing agent; And a polymer acid, wherein the polymer acid neutralizes ammonia generated by the decomposition of the foaming agent to produce an ammonium salt.

In one embodiment of the present invention, the polyolefin-based resin is polyethylene, polypropylene, polyisoprene, polybutadiene, polystyrene, polystyrene butadiene, polychloroprene, polyethylene-vinyl acetate, polyvinyl chloride, polyethylene terephthalate and polypropylene terephthalate It may be any one or more selected from.

In one embodiment of the present invention, the blowing agent is azodicarbonamide (azodicarbonamide), N,N'- dinitrosopentamethylenetetramine, p-toluenesulfonyl hydrazide, p,p'-oxybis (benzene Sulfonylhydrazide), p-toluenesulfonyl semicarbazide, azobisisobutyronitrile, and diazoamino azobenzene.

In one embodiment of the present invention, the foaming agent may include 0.1 to 10 parts by weight based on 100 parts by weight of the polyolefin-based resin.

In one embodiment of the present invention, the decomposition temperature of the blowing agent may be 130 to 250 ℃.

In one embodiment of the present invention, the polymer acid may be any one or more selected from polyacrylic acid, polystyrene sulfonic acid and polyphosphoric acid.

In one embodiment of the present invention, the polymer acid may include 1 to 500 parts by weight based on 100 parts by weight of the blowing agent.

In order to achieve the above technical problem, another embodiment of the present invention is a foam sheet obtained by foaming a composition comprising a polyolefin-based resin, a foaming agent, and a polymer acid, and neutralizing ammonia generated by decomposition of the foaming agent with the polymer acid Provided is a polyolefin-based foam sheet comprising an ammonium salt produced, characterized in that the residual ammonia concentration inside the foam sheet is 25 ppm or less.

In another embodiment of the present invention, the specific gravity of the foam sheet may be 0.10 to 0.25.

In another embodiment of the present invention, the foaming ratio of the foamed sheet may be less than 10% of a difference from the foaming ratio in another identical foamed sheet without the polymer acid in the composition.

In another embodiment of the present invention, the polyolefin-based resin is polyethylene, polypropylene, polyisoprene, polybutadiene, polystyrene, polystyrene butadiene, polychloroprene, polyethylene-vinyl acetate, polyvinyl chloride, polyethylene terephthalate and polypropylene terephthalate It may be any one or more selected from.

In another embodiment of the present invention, the blowing agent is azodicarbonamide (azodicarbonamide), N,N'- dinitrosopentamethylenetetramine, p-toluenesulfonyl hydrazide, p,p'-oxybis (benzene Sulfonylhydrazide), p-toluenesulfonyl semicarbazide, azobisisobutyronitrile, and diazoamino azobenzene.

In another embodiment of the present invention, the foaming agent may include 0.1 to 10 parts by weight based on 100 parts by weight of the polyolefin-based resin.

In another embodiment of the present invention, the decomposition temperature of the blowing agent may be 130 to 250 ℃.

In another embodiment of the present invention, the polymer acid may be any one or more selected from polyacrylic acid, polystyrene sulfonic acid and polyphosphoric acid.

In another embodiment of the present invention, the polymer acid may include 1 to 500 parts by weight based on 100 parts by weight of the blowing agent.

In another embodiment of the present invention, the foam sheet may further include at least one of an antioxidant, a light stabilizer, a lubricant, an antistatic agent, and a colorant.

In order to achieve the above technical problem, another embodiment of the present invention comprises the steps of mixing a polyolefin-based resin and a blowing agent; Forming a sol by adding a polymer acid dissolved in a solvent to the mixture of the polyolefin-based resin and the blowing agent; Coating the sol on release paper and foaming to form a foam sheet; And cooling the foamed sheet to room temperature, wherein the foamed sheet has a residual ammonia concentration of 25 ppm or less.

In another embodiment of the present invention, in the step of forming the foam sheet, the polymer acid may be to neutralize ammonia generated by decomposition of the foaming agent.

In another embodiment of the present invention, ammonium salt may be produced by the neutralization.

According to an embodiment of the present invention, by reducing harmful gases emitted from the inside of the foam sheet, it is possible to remove odors, block human body hazards, and improve the working environment of workers engaged in the foaming process.

It should be understood that the effects of the present invention are not limited to the above-described effects, and include all effects that can be deduced from the configuration of the invention described in the detailed description or claims of the present invention.

1 is a flow chart showing a method of manufacturing a polyolefin-based solid asset foam sheet according to the present invention.

Hereinafter, the present invention will be described with reference to the accompanying drawings. However, the present invention may be implemented in various different forms, and thus is not limited to the embodiments described herein. In addition, in order to clearly describe the present invention in the drawings, parts irrelevant to the description are omitted, and like reference numerals are assigned to similar parts throughout the specification.

Throughout the specification, when a part is "connected (connected, contacted, coupled)" with another part, it is not only "directly connected" but also "indirectly connected" with another member in between. "It also includes the case where it is. Also, when a part “includes” a certain component, this means that other components may be further provided instead of excluding other components, unless otherwise stated.

The terms used herein are only used to describe specific embodiments, and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this specification, terms such as “include” or “have” are intended to indicate that a feature, number, step, operation, component, part, or combination thereof described in the specification exists, and that one or more other features are present. It should be understood that the existence or addition possibilities of fields or numbers, steps, operations, components, parts or combinations thereof are not excluded in advance.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

Hereinafter, the foaming composition of a polyolefin-based tomb asset will be described.

The present invention is a polyolefin-based resin; blowing agent; And a polymer acid, wherein the polymer acid neutralizes ammonia generated by the decomposition of the foaming agent to produce an ammonium salt.

The polyolefin-based resin can be obtained by mixing a foaming agent and foaming a polymer upon heating. The polyolefin-based resin may be any one or more selected from polyethylene, polypropylene, polyisoprene, polybutadiene, polystyrene, polystyrene butadiene, polychloroprene, polyethylene-vinyl acetate, polyvinylchloride, polyethylene terephthalate, and polypropylene terephthalate. These mixtures and other thermoplastic resins or rubbers may be further included, but are not limited thereto, and any foamable polymer capable of obtaining a foam may be used. It may also include a functionalized version of the polyolefin-based resin, such as, for example, maleated polypropylene.

The polyolefin-based resin may include linear low density polyethylene. It may also include medium density polyethylene, which is measured by ASTM D-792, for example, from about 0.92 g/cc to about 0.94 g/cc or from about 0.926 g/cc to about 0.94 g/cc Refers to an ethylene-based polymer having a density of. The polyolefin-based resin may also include high-density polyethylene. High density polyethylene refers to an ethylene-based polymer having a density of about 0.94 g/cc to about 0.97 g/cc as measured by ASTM D-792.

The foaming agent is azodicarbonamide, N,N'-dinitrosopentamethylenetetramine, p-toluenesulfonylhydrazide, p,p'-oxybis(benzenesulfonylhydrazide), p-toluene Sulfonyl semicarbazide, azobisisobutyronitrile, and diazoamino azobenzene.

The foaming agent is used in combination with the polyolefin-based resin, and is decomposed upon heating to form a porous foam. Azodicarbonamide may be used alone, two or more of the above-mentioned blowing agents may be mixed or used, or a conventional blowing agent such as sodium hydrogen carbonate or sodium carbonate may be further mixed and used. In the case of mixing different blowing agents, the mixing amount may vary depending on the purpose of adjusting the expansion ratio, for example, it may be used by mixing 0.01 to 50 parts by weight of another blowing agent with respect to 100 parts by weight of azodicarbonamide, but is not limited thereto. .

The blowing agent may include 0.1 to 10 parts by weight based on 100 parts by weight of the polyolefin-based resin. If it is less than 0.1 part by weight, foaming does not occur sufficiently, and thus the hardness and specific gravity of the produced foam sheet may be very high, which is undesirable, and when it exceeds 10 parts by weight, the structure of the foam sheet becomes unstable due to excessive foaming and mechanical properties decrease. It is not desirable.

The decomposition temperature of the blowing agent may be 130 to 250 ℃. The decomposition temperature of the blowing agent may also determine the process temperature of the foaming process, and if it exceeds 250°C, the polyolefin-based resin is partially decomposed or the energy input to the process is excessive, which is undesirable. At a temperature of less than 130°C, the gas generated by decomposition of the blowing agent is not sufficiently spread, and thus the foaming efficiency is reduced, which is undesirable.

The polymer acid may be any one or more selected from polyacrylic acid, polystyrene sulfonic acid and polyphosphoric acid. As the blowing agent is thermally decomposed, it releases traces of formamide and ammonia as harmful gases. Formamide can be decomposed again into carbon monoxide and ammonia, so ammonia accounts for most of the harmful gases. The polymer acid is included in the foaming composition for the removal of harmful gases, and may be 1 to 500 parts by weight based on 100 parts by weight of the blowing agent. The mixing amount may vary depending on the type of the polymer acid and the purpose of adjusting the expansion ratio, but when it is contained in less than 1 part by weight, it is not preferable because the removal of harmful gas does not occur sufficiently, and when it is included in excess of 500 parts by weight, a polyolefin-based resin It is not preferable because the content of the foam is reduced to weaken the physical properties of the foam sheet.

The polymer acid neutralizes ammonia generated by the decomposition of the blowing agent. Ammonium salt is produced by the neutralization. The ammonium salt may vary depending on the type of polymer acid, and the ammonium phosphate salt is known to impart some flame retardancy. Although imparting flame retardance is not the main object of the present invention, if the type of polymer acid is appropriately selected, a foam sheet having flame retardancy can be produced by removing ammonium phosphate and generating ammonium phosphate.

The polymer acid may be selected from the above-mentioned polyacrylic acid, polystyrenesulfonic acid and polyphosphoric acid, and may be a mixture thereof, but is not limited as long as it can effectively remove harmful gases inside the foam sheet.

Another embodiment of the present invention is a foam sheet obtained by foaming a composition comprising a polyolefin-based resin, a foaming agent, and a polymer acid, and includes an ammonium salt produced by neutralizing ammonia generated by decomposition of the foaming agent with the polymer acid, and Provided is a polyolefin-based pulverized foam sheet characterized in that the concentration of residual ammonia in the foam sheet is 25 ppm or less.

The residual ammonia concentration in the foam sheet is 25 ppm or less, and more preferably 0 ppm. According to an embodiment of the present invention, it is possible to manufacture a foam sheet in which residual ammonia inside the foam sheet is completely removed.

The specific gravity of the foam sheet may be 0.10 to 0.25. If it is less than 0.10, the stiffness as a sheet cannot be sufficiently secured, which is undesirable, and if it exceeds 0.25, the flexibility and elasticity of the sheet decreases, which is undesirable.

The foaming magnification of the foam sheet may be less than 10% of the difference from the foaming magnification in the same foam sheet without the polymer acid in the composition. In the foam sheet, the foaming magnification can be measured by specific gravity, and the difference between specific gravity with and without polymer acid is less than 10%. If the difference in specific gravity exceeds 10%, the physical properties of the foam sheet are weakened, which is not preferable. The present invention is characterized in that the ammonia remaining in the interior is reduced while maintaining the physical properties of the foam sheet as the specific gravity difference is less than 10%.

The foam sheet may be prepared by adding other additives in addition to the polyolefin-based resin, foaming agent, and polymer acid. The other additives may be antioxidants, light stabilizers, lubricants, antistatic agents, colorants or combinations thereof. The content of the other additives may be added in an amount of 0.01 to 5 parts by weight, more preferably 0.5 to 2 parts by weight of the total weight of the foam sheet. The above range is a range that does not impair other properties of the foamed sheet, and if it exceeds the above-mentioned range, the properties of the foamed sheet may be deteriorated, which is not preferable.

Hereinafter, a method of manufacturing a polyolefin-based torn-sheet foam sheet will be described with reference to FIG. 1.

The present invention is a step of mixing a polyolefin-based resin and a blowing agent (S100); Forming a sol by adding a polymer acid dissolved in a solvent to the mixture of the polyolefin-based resin and the blowing agent (S200); Forming a foam sheet by coating and foaming the sol on release paper (S300); And a step (S400) of cooling the foamed sheet to room temperature, wherein the foamed sheet has an internal ammonia concentration of 25 ppm or less.

In step S300 of forming the foam sheet, the polymer acid neutralizes ammonia generated by the decomposition of the foaming agent. Ammonium salt may be produced by the neutralization. Ammonia has high solubility in water accepts a proton in aqueous solution, hydroxide ions (OH ^-) taking place. Water than the pKa value of greater ammonia water acts as a proton acid to water is supplied to the ammonia and hydroxide ions (OH ^-) it will lay out a. The polymeric acid pKa value smaller than that of water taking place more protons in an aqueous solution, to accept a proton ammonia to produce the ammonium salt The binding when the NH ₄ ^+.

The solvent may be water (H ₂ O). When water is used as a solvent, compatibility with a polyolefin-based resin can be enhanced. The polymer acid may be dissolved in an aqueous solution at 10 to 50 wt%. If it is less than 10 wt%, the amount of the polymer acid is too small, so the effect of removing ammonia may not be sufficient, and when it exceeds 50 wt%, the environment required for neutralization of ammonia is not sufficiently made.

The residual ammonia concentration in the foam sheet is 25 ppm or less, and more preferably 0 ppm. According to an embodiment of the present invention, it is possible to manufacture a foam sheet in which residual ammonia inside the foam sheet is completely removed.

Hereinafter, the present invention will be described in more detail through production examples and experimental examples.

Preparation Example 1

80 parts by weight of polyvinyl chloride and 4 parts by weight of azodicarbonamide were mixed, and 16 parts by weight of polyacrylic acid was dissolved in water at a concentration of 50 wt%, added to the mixture, and stirred. The resulting sol was coated on release paper and foamed at 220° C. for about 2 minutes to form a foam sheet. The foam sheet was cooled to room temperature.

Preparation Example 2

A foam sheet was prepared in the same manner as in Preparation Example 1, except that 92 parts by weight of polyvinyl chloride and 7.3 parts by weight of azodicarbonamide were used and 0.7 parts by weight of polystyrene sulfonic acid dissolved in water at a concentration of 18 wt%.

Preparation Example 3

A foam sheet was prepared in the same manner as in Preparation Example 1, except that 92 parts by weight of polypropylene, 7.3 parts by weight of azodicarbonamide and 0.7 parts by weight of polyphosphoric acid (H ₃ PO ₄ ) were used.

Comparative Examples 1-3

Foam sheets were prepared in the same manner as in Preparation Examples 1 to 3, except that no polymer acid was added.

Experimental Example 1

The foam sheets prepared in Preparation Examples 1 to 3 and Comparative Examples 1 to 3 were put in a Tedler bag and placed in an 80° C. convection oven for 1 hour. Then, the concentration of ammonia emission remaining inside the foam sheet was measured using an ammonia detection tube, and the results are shown in Table 1 below.

Experimental Example 2

The foam sheets prepared in Preparation Examples 1 to 3 and Comparative Examples 1 to 3 were measured using specific gravity meters and are shown in Table 1 below.

division Ammonia emission concentration (ppm) Ammonia emission change rate (%) importance Specific gravity change rate (%) Comparative Example 1 70 - 0.12 - Preparation Example 1 0 -100 0.13 8.3 Comparative Example 2 110 - 0.21 - Preparation Example 2 25 -77.27 0.21 0 Comparative Example 3 95 - 0.13 - Preparation Example 3 15 -84.21 0.13 0

Referring to <Table 1>, when polyacrylic acid was used in Production Example 1, ammonia was reduced by 100%, and also in Production Example 2 and Production Example 3, a high reduction rate was exhibited. However, in Production Example 1, there was a change in specific gravity of 8.3%, while in Production Example 2 and Production Example 3, there was no change in specific gravity.

According to the purpose of use of the foam sheet, it is possible to manufacture a foam sheet with reduced ammonia while maintaining the foaming magnification by controlling the addition amount of the polymer acid to control the ammonia reduction effect and specific gravity change rate.

The above description of the present invention is for illustration only, and a person having ordinary knowledge in the technical field to which the present invention pertains can understand that it can be easily modified to other specific forms without changing the technical spirit or essential features of the present invention. will be. Therefore, it should be understood that the embodiments described above are illustrative in all respects and not restrictive. For example, each component described as a single type may be implemented in a distributed manner, and similarly, components described as distributed may be implemented in a combined form.

The scope of the present invention is indicated by the following claims, and all modifications or variations derived from the meaning and scope of the claims and their equivalent concepts should be interpreted to be included in the scope of the present invention.

Claims (20)

Polyolefin resins;
blowing agent; And
Contains a polymer acid,
The polymer acid is characterized in that the foaming agent decomposes to neutralize the ammonia generated to produce an ammonium salt,
The polymer acid is a polyolefin-based polymer foam composition characterized in that it comprises a polyacrylic acid or polystyrene sulfonic acid.
According to claim 1,
The polyolefin-based resin is at least one selected from polyethylene, polypropylene, polyisoprene, polybutadiene, polystyrene, polystyrene butadiene, polychloroprene, polyethylene-vinyl acetate, polyvinylchloride, polyethylene terephthalate, and polypropylene terephthalate. Foaming composition for polyolefin-based fine assets.
According to claim 1,
The foaming agent is azodicarbonamide, N,N'-dinitrosopentamethylenetetramine, p-toluenesulfonylhydrazide, p,p'-oxybis(benzenesulfonylhydrazide), p-toluene A polyolefin-based polymer foam composition comprising at least one selected from sulfonyl semicarbazide, azobisisobutyronitrile, and diazoamino azobenzene.
According to claim 1,
The foaming agent is a polyolefin-based polymer foam composition characterized in that it comprises 0.1 to 10 parts by weight based on 100 parts by weight of the polyolefin-based resin.
According to claim 1,
The foaming agent has a decomposition temperature of 130 to 250°C.
delete According to claim 1,
The polymer acid is a polyolefin-based solid asset foaming composition comprising 1 to 500 parts by weight based on 100 parts by weight of the blowing agent.
A foam sheet obtained by foaming a composition comprising a polyolefin-based resin, a blowing agent, and a polymer acid,
The foaming agent includes an ammonium salt produced by neutralizing ammonia generated by decomposition with the polymer acid,
Characterized in that the residual ammonia concentration in the foam sheet is 25 ppm or less,
The polymer acid is a polyolefin-based foam sheet characterized in that it comprises a polyacrylic acid or polystyrene sulfonic acid.
The method of claim 8,
The specific gravity of the foam sheet is 0.10 to 0.25, characterized in that the polyolefin-based foam sheet.
The method of claim 8,
The foaming ratio of the foamed sheet is a polyolefin-based high-assembly foamed sheet characterized in that the difference from the foaming magnification in the same foamed sheet other than the polymer acid in the composition is less than 10%.
The method of claim 8,
The polyolefin-based resin is at least one selected from polyethylene, polypropylene, polyisoprene, polybutadiene, polystyrene, polystyrene butadiene, polychloroprene, polyethylene-vinyl acetate, polyvinylchloride, polyethylene terephthalate, and polypropylene terephthalate. Foam sheet of polyolefin-mold assets.
The method of claim 8,
The foaming agent is azodicarbonamide, N,N'-dinitrosopentamethylenetetramine, p-toluenesulfonylhydrazide, p,p'-oxybis(benzenesulfonylhydrazide), p-toluene A polyolefin-based polymer foam sheet characterized in that it is at least one selected from sulfonyl semicarbazide, azobisisobutyronitrile, and diazoamino azobenzene.
The method of claim 8,
The foaming agent is a polyolefin-based foam sheet characterized in that it comprises 0.1 to 10 parts by weight based on 100 parts by weight of the polyolefin-based resin.
The method of claim 8,
The foaming agent has a decomposition temperature of 130 to 250°C.
delete The method of claim 8,
The polymer acid is a polyolefin-based foam sheet characterized in that it comprises 1 to 500 parts by weight based on 100 parts by weight of the blowing agent.
The method of claim 8,
The foam sheet further comprises at least one of an antioxidant, a light stabilizer, a lubricant, an antistatic agent, and a coloring agent.
Mixing a polyolefin-based resin and a blowing agent;
Forming a sol by adding a polymer acid dissolved in a solvent to the mixture of the polyolefin-based resin and the blowing agent;
Coating the sol on release paper and foaming to form a foam sheet; And
Cooling the foam sheet to room temperature;
Including,
The concentration of the residual ammonia in the foam sheet is 25 ppm or less,
The polymer acid is a method for producing a polyolefin-based foam sheet characterized in that it comprises a polyacrylic acid or polystyrene sulfonic acid.
The method of claim 18,
In the step of forming the foam sheet, the polymer acid is a method for producing a polyolefin-based polymer foam sheet, characterized in that the foaming agent decomposes to neutralize ammonia.
The method of claim 19,
A method for producing a foamed sheet of polyolefin-based powder, characterized in that ammonium salt is produced by the neutralization.

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