KR20240043879A - Eco-friendly foam composition with shell powder - Google Patents

Abstract

The present invention relates to an eco-friendly foam composition containing shells, and more specifically, isocyanate, TMP (trimethylolpropane), acrylic acid, and shell powder mixed with a foam composition based on EVA or PU to form a foam. By adding a polar group to the composition, the adhesive strength of the foam product can be improved, and by adding and recycling previously discarded shells, the physical properties of the O-ring can be further improved while solving the cost and environmental pollution problems caused by the disposal of conventional shells. It relates to an eco-friendly foam composition containing shells, which allows providing an eco-friendly foam composition.

Description

Eco-friendly foam composition containing shell {ECO-FRIENDLY FOAM COMPOSITION WITH SHELL POWDER}

The present invention not only improves the adhesive strength of foam products by modifying a foam composition based on EVA (ethylene vinyl acetate) or PU (polyurethane), but also recycles previously discarded shells to reduce the cost incurred due to shell disposal. and an eco-friendly foam composition containing shells that can solve environmental pollution problems.

In general, the scope of use of polymer materials such as EVA (ethylene vinyl acetate) or PU (polyurethane) has been limited due to poor adhesion to other materials.

To solve this problem, Patent Document 1 describes a method of continuous grafting in the presence of maleic anhydride, focusing on rheological properties, and describes the type and content of the component, and in Patent Document 2, maleic anhydride and A method of grafting is described by dissolving an initiator in a solvent and injecting it into a twin-screw extruder using a liquid injection device. In addition, a technique to improve adhesiveness by polymerizing methyl methacrylate was also used.

However, the conventional method as described above has the disadvantage of consuming a lot of processing time and cost, and also having a complicated manufacturing process, resulting in high manufacturing costs.

In addition, the method of modifying by introducing maleanhydride or methyl methacrylate still had many limitations in adhesion as moldability was significantly reduced due to the high molecular weight.

Meanwhile, more than 300,000 tons of marine waste shells (e.g., shells of oysters, petrified abalone, blood clams, clams, scallops, pearl clams, pearl mussels, cockles, etc.) are generated annually.

Moreover, in most cases, shells are neglected or illegally dumped, and abandoned or illegally dumped shells are the main cause of damage to the coastal environment, that is, they cause unbearable odor and various environmental pollution problems, leading to complaints from local residents. is emerging as an environmental and social problem that is difficult to solve.

In general, shells are made up of about 94% calcium carbonate, and due to their high adsorption of heavy metals and organic matter and the ability for microorganisms to easily attach and grow, some are attempting to recycle and process them, mainly using the shells as fertilizers or fertilizers. It is used as feed or applied to various soil cover materials, soil conditioners, neutralizers, etc.

However, despite recycling as described above, not only is it not actively utilized due to negative perceptions about its effectiveness and method, but more than 100,000 tons are still difficult to dispose of due to the Marine Dumping Prevention Act.

In other words, the recycling rate of shells is currently very low, and shells that are not recycled are the main culprit of environmental pollution. Therefore, there is an urgent need for a plan to recycle shells classified as marine waste.

Patent Document 1: U.S. Patent Registration No. 4,612,155 “Process for the grafting of monomers onto polyolefins” Patent Document 2: U.S. Patent Publication No. 4,762,890 “Method of grafting maleic anhydride to polymers”

The present invention is intended to solve the above problems, by mixing isocyanate, TMP (trimethylolpropane), acrylic acid, and shell powder with a foam composition based on EVA or PU to impart a polar group to the foam composition. This not only improves the adhesive strength of foam products, but also improves the physical properties of O-rings by adding and recycling previously discarded shells, and solves the cost and environmental pollution problems caused by disposal of conventional shells, making it an eco-friendly foam. The task is to provide a composition.

The present invention provides an eco-friendly foam composition containing shells, which is characterized in that it is made by mixing isocyanate, trimethylolpropane (TMP), acrylic acid, and shell powder in the foam composition. Do it as

Here, the foam composition is preferably based on ethylene vinyl acetate (EVA) or polyurethane (PU).

In addition, the shell powder is surface-modified after firing the shell at 800-1000°C for 3-5 hours, pulverizing it to a particle size of 300-500 mesh, and adding 5-15 weight of silane coupling agent per 100 parts by weight of shell powder. The surface is modified by mixing parts, and the silane coupling agent is bis(triethoxy silylpropyl)tetrasulfide or bis(triethoxy silylpropyl)disulfide. ) It is preferable to use disulfide).

Meanwhile, the eco-friendly foam composition containing the shell contains 1 to 5 parts by weight of zinc oxide, 0.1 to 3 parts by weight of stearic acid, and 1 to 30 parts by weight of shell powder, based on 100 parts by weight of EVA or PU. parts, 0.1 to 3 parts by weight of crosslinking agent, 0.5 to 3 parts by weight of foaming agent, 1 to 5 parts by weight of isocyanate, 0.5 to 6 parts by weight of TMP, and 3 to 20 parts by weight of acrylic acid.

The present invention not only improves the adhesive strength of foam compositions based on EVA or PU, but also improves the physical properties of O-rings by adding and recycling conventionally discarded shells, while reducing the cost and environmental pollution caused by disposal of conventional shells. It has the effect of providing an eco-friendly foam composition that can solve problems.

The present invention to achieve the above effects relates to an eco-friendly foam composition containing shells. Only the parts necessary to understand the technical structure of the present invention are described, and the description of other parts is omitted so as not to confuse the gist of the present invention. It should be noted that this will happen.

Hereinafter, the eco-friendly foam composition containing shells according to the present invention will be described in detail as follows.

The eco-friendly foam composition containing shell according to the present invention contains 1 to 5 parts by weight of zinc oxide, 0.1 to 3 parts by weight of stearic acid, 1 to 30 parts by weight of shell powder, and 0.1 to 3 parts by weight of crosslinking agent, based on 100 parts by weight of EVA or PU. , 0.5 to 3 parts by weight of foaming agent, 1 to 5 parts by weight of isocyanate, 0.5 to 6 parts by weight of TMP, and 3 to 20 parts by weight of acrylic acid.

The zinc oxide is added to improve the processing characteristics and physical properties of the foam. If the content is less than 1 part by weight, the processing characteristics of the foam may become weak, and if it exceeds 5 parts by weight, the dispersion characteristics may become weak.

The stearic acid is added to improve cross-linking and foaming characteristics. If the content is less than 0.1 parts by weight, there is a risk that the cross-linking and foaming characteristics may be insufficient, and if it exceeds 3 parts by weight, there is a risk that the mechanical properties of the foam may deteriorate. .

The shell powder is added to improve physical properties in addition to recycling conventionally discarded shells. If the content is less than 1 part by weight, the efficiency of improving physical properties may be insufficient, and if it exceeds 30 parts by weight, dispersibility is weak. There is a risk of sunset.

On the other hand, the shell powder uses the shells of shells (e.g., oysters, petrified abalone, blood clams, clams, scallops, pearl clams, pearl mussels, cockles, etc.) that are commonly available on the market as marine waste resources, Wash thoroughly to remove unnecessary foreign substances before use.

In addition, the shell powder is used by calcining the shell at 800 to 1000°C for 3 to 5 hours to further improve physical property improvement efficiency and dispersibility, then grinding it to a particle size of 300 to 500 mesh, and adding 100 parts by weight of the shell powder. It is used for surface modification by mixing 5 to 15 parts by weight of a silane coupling agent.

Here, the silane coupling agent can be used as bis(triethoxy silylpropyl)tetrasulfide or bis(triethoxy silylpropyl)disulfide, but must be used. It is not limited to this, and various already known silane coupling agents can be used.

On the other hand, if the sintering temperature and time, particle size, and content of the silane coupling agent are outside the above range, there is a risk that the efficiency of improving physical properties may be insufficient or the dispersibility may be insufficient.

The cross-linking agent uses a peroxide-based cross-linking agent. If the content is less than 0.1 parts by weight, there is a risk that cross-linking will not be carried out properly, and if it exceeds 3 parts by weight, there is a risk that the appearance of the foam may be poor due to over-cross-linking. There is. Meanwhile, the peroxide-based crosslinking agent includes t-butylperoxyisopropylcarbonate, t-butylperoxylaurylate, and t-butylperoxyacetate. , di-t-butylperoxyphthalate, etc. can be applied.

The foaming agent includes azo-based compounds such as azodicarbonamide, nitroso-based compounds such as N, N'- dinitrosopenta methylenetetraamine, etc. can be applied, and if the content is less than 0.5 parts by weight, there is a risk that the hardness and specific gravity will be excessively high, and if it exceeds 3 parts by weight, there is a risk that the hardness will be excessively low and the mechanical properties will be deteriorated.

The isocyanate is intended to improve adhesive strength by imparting a polar group to the foam composition. If the content is less than 1 part by weight, the effect may be insufficient, and if it exceeds 5 parts by weight, there is a limit to the efficiency of improving adhesive strength relative to the amount used. There are concerns that it may be uneconomical. Meanwhile, the isocyanates include aromatic isocyanates such as tolylene-2,4-diisocyanate, methylene diphenyl diisocyanate, and 1,5-naphthalene diisocyanate (1, 5-Naphthalene diisocyanate), 4,6-Xylylene diisocyanate, or aliphatic isocyanates such as isoprene diisocyanate (isophorone diisocyanate), 4,4'-methylenebis (cyclohexyl isocyanate) ( 4,4′-Methylenebis(cyclohexyl isocyanate)), Hexamethylene diisocyanate, Meta-Tetramethylxylylene Diisocyanate, Para-Tetramethylxylylene Diisocyanate, etc. You can use it.

The TMP is a material that allows mixing of isocyanate with EVA or PU. If the content is less than 0.5 parts by weight, there is a risk that the isocyanate may not be mixed properly, and if the content exceeds 6 parts by weight, it may be uneconomical.

The acrylic acid is intended to improve adhesive strength by imparting a polar group to the foam composition. If the content is less than 3 parts by weight, the effect may be insufficient, and if it exceeds 20 parts by weight, there is a limit to the efficiency of improving adhesive strength relative to the amount used. There are concerns that it may be uneconomical.

Hereinafter, the present invention will be described in detail by giving examples, but the present invention is not necessarily limited to the following examples.

1. Preparation of foam composition

(Example 1)

Based on 100 parts by weight of EVA, 1 part by weight of zinc oxide, 0.1 part by weight of stearic acid, 1 part by weight of shell powder, 0.1 part by weight of crosslinking agent (t-butyl peroxyacetate), 0.5 part by weight of foaming agent (azodicarbonamide), isocyanate ( After kneading 1 part by weight of isoprene diisocyanate for 10 minutes at an internal temperature of 90℃ in the reader, 0.5 parts by weight of TMP was added and kneaded again for 3 minutes, then 3 parts by weight of acrylic acid was added and kneaded on an open roll (temperature of 80℃) for 7 minutes. It was prepared by sufficiently dispersing it.

Here, the shell powder is surface-modified after baking the shell at 800°C for 5 hours, pulverizing it to a particle size of 300 mesh, and using a silane coupling agent (bis(triethoxysilyl propyl)tetrasulfide for 100 parts by weight of the shell powder. ) 5 parts by weight were mixed and surface modified.

(Example 2)

Based on 100 parts by weight of PU, 5 parts by weight of zinc oxide, 3 parts by weight of stearic acid, 30 parts by weight of shell powder, 3 parts by weight of crosslinking agent (t-butyl peroxyacetate), 3 parts by weight of foaming agent (azodicarbonamide), isocyanate ( After mixing 5 parts by weight of isoprene diisocyanate for 8 minutes at the internal temperature of the reader at 100℃, 6 parts by weight of TMP was added and kneaded again for 4 minutes, then 20 parts by weight of acrylic acid was added and kneaded on an open roll (temperature of 110℃) for 10 minutes. It was prepared by sufficiently dispersing it.

Here, the shell powder is surface-modified after baking the shell at 1000°C for 3 hours, pulverizing it to a particle size of 500 mesh, and using a silane coupling agent (bis(triethoxysilyl propyl)disulfide) for 100 parts by weight of the shell powder. 15 parts by weight were mixed and surface modified.

(Comparative Example 1)

It was prepared in the same manner as in Example 1, except that isocyanate, TMP, acrylic acid, and shell powder were not added.

(Comparative Example 2)

It was prepared in the same manner as in Example 2, except that isocyanate, TMP, acrylic acid, and shell powder were not added.

2. Adhesion strength evaluation

The adhesive specimen used foam and cross-linked rubber (ethylene-propylene rubber) prepared in Examples 1 to 2 and Comparative Examples 1 to 2, and was measured according to KSM 3725. Cross-linked rubber measuring 20 × 100 × 4 mm was washed in distilled water using an ultrasonic cleaner for 5 minutes, then a surface treatment agent for rubber (LOCTITE BONDACE 007) was applied and dried at 60°C for 10 minutes before use. Next, the 20×120×11mm foam was washed in distilled water using an ultrasonic cleaner for 5 minutes, then a UV curing surface treatment agent (LOCTITE BONDACE P 7-2) was applied, dried at 60°C for 10 minutes, and then placed in a UV processor ( Fusion systems cop.) was processed by passing it twice at a speed of 15 m/min. Then, adhesive (Bond Ace W-01, W-104, Dongdong NSC Co., Ltd.) was applied between the prepared specimens, heated, and then bonded using a pressing roller. After 24 hours at room temperature after adhesion, the peel strength was measured using a universal tensile tester (UTM, Zwick, Zwick-1435) at a peel speed of 200 mm/min. The adhesive strength was determined as the average measurement value of three identical pieces, and the results are shown in the table below. 1].

division Example 1 Example 2 Comparative Example 1 Comparative Example 2 State adhesion
(kgf/cm) 6.8 6.9 3.2 3.2 Adhesion status
(wagwan) foam fracture foam fracture No change No change

As shown in [Table 1], the foam composition according to the example of the present invention not only has very excellent adhesive strength compared to the comparative example due to the addition of a polar group to the foam composition, but also can be used to recycle the O-ring by adding shells that were previously discarded. It can be seen that it is environmentally friendly, as it further improves the physical properties and solves the cost and environmental pollution problems caused by disposal of conventional shells.

As described above, the eco-friendly foam composition containing shells according to the present invention has been explained through the above preferred embodiments and its excellence has been confirmed, but those skilled in the art will It will be understood that various modifications and changes can be made to the present invention without departing from the scope.

Claims (4)

In the foam composition,
An eco-friendly foam composition containing shells, characterized in that it is made by mixing isocyanate, trimethylolpropane (TMP), acrylic acid, and shell powder in a foam composition.
According to clause 1,
The foam composition is,
An eco-friendly foam composition containing shells, characterized in that it is a foam composition based on ethylene vinyl acetate (EVA) or polyurethane (PU).
According to clause 1,
The shell powder is,
The shell is fired at 800 ~ 1000℃ for 3 ~ 5 hours, then ground to a particle size of 300 ~ 500 mesh, and the surface is modified.
For 100 parts by weight of shell powder, 5 to 15 parts by weight of a silane coupling agent is mixed to modify the surface, and the silane coupling agent is bis(triethoxy silylpropyl)tetrasulfide. Or an eco-friendly foam composition containing shells, characterized by using bis(triethoxy silylpropyl)disulfide.
According to clause 2,
The eco-friendly foam composition containing the shell,
For 100 parts by weight of EVA or PU, 1 to 5 parts by weight of zinc oxide, 0.1 to 3 parts by weight of stearic acid, 1 to 30 parts by weight of shell powder, 0.1 to 3 parts by weight of crosslinking agent, 0.5 to 0.5 parts by weight of foaming agent. An eco-friendly foam composition containing shells, characterized in that it is made by mixing 3 parts by weight, 1 to 5 parts by weight of isocyanate, 0.5 to 6 parts by weight of TMP, and 3 to 20 parts by weight of acrylic acid.