KR101164928B1 - A MATERIAL FOR REDUCING THE PRODUCTION OF tVOC AND ACRYL OR STYREN BASED RESIN COMPRISING THE SAME - Google Patents

Abstract

An object of the present invention is to provide a material capable of effectively removing volatile organic compounds generated from a resin without affecting the physical properties of an acrylic resin or a styrene resin and an acrylic resin or a styrene resin using the same. Specifically, the present invention provides a material capable of physically as well as chemically removing volatile organic compounds generated from acrylic resins or styrene resins by using a medium having less influence on the physical properties of acrylic resins or styrene resins. It is an object of the present invention to provide an acrylic resin or a styrene-based resin in which the generation of volatile organic compounds is reduced while maintaining physical properties.

Acrylic resin, styrene resin, volatile organic compound, VOC

Description

A material for reducing the occurrence of total volatile organic compounds and acrylic or styrene resins containing the same {A MATERIAL FOR REDUCING THE PRODUCTION OF tVOC AND ACRYL OR STYREN BASED RESIN COMPRISING THE SAME}

The present invention relates to a new material that suppresses the generation of total volatile organic compounds (tVOC) in acrylic resins or styrene resins such as ABS resins, and to acrylic resins or styrene resins containing the same to reduce the generation of total volatile organic compounds. will be.

Generally, acrylic resins or styrene resins are widely used within a very close range, and polystyrene resins represented by ABS are frequently used. ABS resin is a ternary copolymer composed of 3 kinds of Monomer (monomer) of AN (Acrylonitrile), BD (Butadiene) and SM (Styrene Monomer), and adjusts the composition ratio of three main monomers, And because it has the advantage that can be developed in various forms through additive reinforcement, heat-resistant agent addition, flame retardant addition, molecular weight control and the like. Typical products using ABS resins include synthetic resin bags, helmets, etc., which require impact resistance, home appliances such as telephones, refrigerators, exteriors, TVs, VTRs, computers with added flame retardants, monitors, and automotive interiors that require heat resistance. However, these polymer resin compositions are usually problematic for generating harmful volatile organic compounds (VOCs). In particular, volatile organic compounds generated from peripheral devices that are closely related to daily life may not only be harmful to health but also cause a decrease in the image of the product.

In order to reduce the amount of such volatile organic compounds, conventionally, activated carbon, zeolite, and the like are compounded together with the raw materials of the resin to achieve an adsorption effect. However, when using activated carbon in compounding, it is difficult to implement color, and when using zeolite, water absorption is very easy due to the characteristics of the material of zeolite. Problems such as poor appearance such as streaks and deterioration of physical properties can occur.

In addition, as another study, Korean Patent Laid-Open Publication No. 10-2004-0066335 relates to a deodorized impregnated carbon nanoball having a multi-pore structure, and a carbon nanoball having a multilayer structure and a transition metal and a transition metal attached thereto. Disclosed is a carbon nanoball deodorant characterized by having a deodorant component alone or in a mixture selected from two or more kinds in the group consisting of an oxide and an alkali metal salt, and Korean Patent Publication No. 10-2004-0059265 discloses a core-shell structure. Although a carbon nanoball deodorant is disclosed, the documents describe only deodorants for removing odors in external air, and external generation of volatile organic compounds from a resin compounded including such deodorants It does not describe the technique for reducing the Physical properties are not considered.

In addition, Korean Patent Publication No. 10-2007-0098279 discloses a thermoplastic resin composition comprising a polypropylene resin, a thermoplastic elastomer, an inorganic filler, and a deodorant having a porous nanoball structure. Only the physical adsorption of volatile organic compounds has been suggested, and the results are not satisfactory in adsorption performance.

An object of the present invention is to provide a material capable of effectively adsorbing volatile organic compounds generated from plastics without affecting the physical properties of the plastics and general purpose plastics using the same. Specifically, the present invention provides a material capable of physically and chemically removing volatile organic compounds generated from them by using a medium having less influence on the physical properties of acrylic resins or styrene resins and physical properties thereof. It is an object of the present invention to provide an acrylic resin or a styrene resin with reduced generation of volatile organic compounds.

The present invention provides a material for reducing the generation of volatile organic compounds, characterized in that the core made of porous inorganic particles, and an organic polymer polymer coated on the surface of the core. Reducing material of the present invention is 70 to 95% by weight, preferably 80 to 90% by weight of the inorganic particles, 5 to 30% by weight, preferably 10 to 20% of the organic polymer polymer and other small amounts relative to the total weight It is characterized by containing an impurity. If the content ratio of the organic polymer polymer is more than 30% by weight, the coating ratio is not efficient and economically disadvantageous. On the contrary, if the content ratio is less than 5% by weight, the dispersion or fluidity of the material is not satisfactory, and the function to remove volatile organic compounds may be sufficient. It becomes impossible.

In addition, the present invention provides an acrylic resin or styrene-based resin is reduced generation of volatile organic compounds, characterized in that it comprises a material for reducing the generation of the volatile organic compounds.

In general, in the production of acrylic resins or styrene resins, a technique of compounding by adding porous inorganic particles to remove harmful volatile organic compounds is known, but the target acrylic resin or styrene resin is an organic compound. Therefore, the inorganic particles are not effectively mixed, resulting in an undesirable effect on the physical properties of the acrylic resin or styrene resin, such as weak durability of the acrylic resin or styrene resin. The present inventors have found through the careful examination and experiment that the above-mentioned disadvantages can be overcome by coating the organic polymer polymer on the surface of the porous inorganic particles as the core. When the surface of the inorganic material is coated with an organic compound as described above, the coated organic compound forms an organic bond with the surrounding monomers in the acrylic resin or the styrene resin, and thus is fused with the surrounding acrylic resin or the styrene resin. The physical properties of the product can not be reduced. In addition, when the surface of the inorganic particles is coated with an organic compound, the volatile organic compounds generated from the acrylic resin or the styrene resin are not only physically adsorbed by the hollow and / or pores of the porous inorganic particles, but also the surface of the core. Because the chemical reaction with the organic polymer compound coated on the metal is consumed, there is a synergistic effect that the generation of harmful volatile organic compounds as a whole is further reduced.

In the present invention, the porous inorganic particles are preferably selected from the group of porous materials used as zeolites (3A, 4A, 13X zeolites), silica, alumina or other fillers, and particularly preferably zeolites. When the zeolite is used as a core, it has a low specific gravity and excellent dispersibility in acrylic resin or styrene resin to which the material is to be provided, and thus has good miscibility, and is economically advantageous, so that it is suitable for mass production at low cost. In particular, the nature of the material is preferred because it does not affect the physical properties of the original acrylic resin or styrene resin.

In addition, the average particle size of the porous inorganic particles is preferably 1 to 10㎛. If the size exceeds 10㎛ it is not preferable because the efficiency is lowered in the compounding process with the acrylic resin or styrene resin and the mechanical strength and the like deteriorate. On the contrary, although the particle size is actually smaller, there is an advantage in dispersibility, but considering the technical difficulty of nanoparticles of inorganic matters, it is disadvantageous in workability and economic efficiency when pulverizing below 1 μm, and also coating of polymer. Since efficiency worsens, it is preferable to set it as the size of 1 micrometer or more.

The organic polymer to be coated on the surface of the porous inorganic particle is preferably selected from an aromatic polymer, a styrene polymer or an acrylic polymer, but is not limited thereto. It is preferable that the polymer is a polymer obtained by polymerizing a monomer selected from divinylbenzene, styrene, methyl methacrylate (MMA) or acrylonitrile (AN). Among these, aromatic polymers, in particular, polymers of divinylbenzene (DVB) More preferred. In this case, it is possible to effectively remove the gas of the styrene-based compound that is organically excellent in the acrylic resin or styrene-based resin and occupies a large proportion of the volatile organic compounds generated.

As a method for producing a material for reducing a volatile organic compound according to the present invention, a porous inorganic particle as a raw material and an organic monomer for coating the same are dissolved in a suitable solvent, and a polymerization initiator for polymerizing the organic monomer is further added. To react in the reactor. At this time, a reactor of 2L jacket was used as the reactor, and the reaction conditions were to be reacted for about 6 hours at a reaction temperature of 95 ° C. Thereafter, the reaction was filtered and washed with N-hexane and dried at 100 ℃.

The solvent may be N-heptane, N-decane, ethanol, isopropyl alcohol, acetonitrile and the like, but is not limited thereto. Among these, N-heptane is preferable.

As the polymerization initiator, benzoyl peroxide (BPO) or azobisisobutyronitrile (AIBN) may be used, and it is particularly preferable to use BPO.

The reduced material thus produced has a powdery shape with excellent dispersibility and fluidity as a result of coating the organic polymer on the surface of the inorganic core. Electron scanning micrographs and thermogravimetric analysis graphs of the reducing material coated with the organic polymer are shown in FIGS. 2 and 3, respectively.
Looking at Figure 2, it can be seen that the surface state of the particles after the coating of the organic polymer polymer is different by introduction of the functional group, that is, compared to the coating of the organic polymer. This is because the organic polymer is coated on the surface of the inorganic material is different appearance. Due to the coating of the organic polymer, the reducing material of the present invention has excellent dispersibility and fluidity.

Figure 3 is a graph of the instrument analysis of the abatement material by the thermogravimetric analyzer (TGA). TGA is a device that measures the change in weight while raising the temperature in air and nitrogen atmospheres, and as shown in the graph, the difference in mass between the coated and the organic polymer is obvious.
Referring to the graph disclosed in FIG. 3 in detail, first, in the case of zeolite 4A, which is a comparative standard, the weight loss first appeared as the temperature evaporated and the moisture existing on the surface of the zeolite evaporated. As the number of crystals, etc., that they had left out, the secondary weight loss appeared. The zeolite according to the present invention is coated with an organic polymer polymer, and as the temperature increases, weight loss occurs as much as the mass loss caused by the combustion of the organic polymer material in addition to the above-described reduction effect. In other words, more mass loss was observed in the coated particles according to the invention.

The present invention also provides an acrylic resin or a styrene resin to which a volatile organic compound reducing material according to the present invention is added during compounding. The content of the reducing material is preferably 0.2 to 5% by weight based on the total weight. The acrylic resin or styrene resin is preferably acrylonitrile-butadiene-styrene resin (ABS).

Reducing material and acrylic resin or styrene resin including the same according to the present invention is a synthetic resin bag, a helmet, etc. requiring impact resistance; Household appliances such as telephones, refrigerators, interiors and exteriors, TVs, and VTRs; Computers, monitors with added flame retardants; And it can be used effectively, such as automotive interior materials, adhesive tape, acrylic foam double-sided tape that requires heat resistance, but is not limited thereto.

According to the present invention, it is possible to obtain a material and a plastic composition using the same that can effectively adsorb volatile organic compounds generated from the plastic with little effect on the plastic properties. Specifically, a material capable of physically and chemically removing volatile organic compounds generated from an acrylic resin or a styrene resin using a medium having a low influence on physical properties and a volatile organic compound while maintaining physical properties thereof. Acrylic resin or styrene resin in which generation | occurrence | production of a compound was reduced can be obtained.

Hereinafter, preferred embodiments are provided to help understanding of the present invention, but these are only for illustrating the present invention, and the present invention is not particularly limited to these embodiments.

(Production of the material for the reduction)

210 g of 4A zeolite and 30.6 g of DVB monomer, each of which was tested for raw materials, were added to 1.5 L of N-heptane with 7.35 g of a polymerization initiator BPO (benzoyl peroxide). The mixture was then reacted for 6 hours at a temperature of 95 ° C. with stirring in a 2 L jacketed reactor. The reaction product was then filtered and washed with 1.5 L of N-hexane. After drying at a temperature of 100 ℃ to obtain a material for reducing the volatile organic compounds.
Electron scanning micrographs and thermogravimetric analysis graphs of the obtained materials are shown in FIGS. 2 and 3. The temperature of the thermogravimetric analysis was carried out in units of 20 ° C, and the analysis showed that the coating ratio of the organic polymer coated on the inorganic surface was about 10 to 12% by weight.

(Added to acrylic resin or styrene resin)

Example  1-3

The prepared volatile organic compound reducing material was added to the ABS resin by 0.2, 0.5, and 1 wt%, respectively, based on the total weight. ABS resin used the thing whose AN is 15-30 weight%, BD is 5-30 weight%, and SM is 45-70 weight%.

Example  4 ~ 7

To the acrylic foam used as a double-sided tape was added 1, 2, 3, 4% by weight to the total weight of the prepared volatile organic compound reducing material, respectively, to prepare a product.

Comparative example

The same process as in Examples 4 to 7 was conducted except that no volatile organic compound reducing material was added.

Emission Test of Volatile Organic Compounds

The test was carried out through normal GC / MS measurements. Specimens of the same size were taken in a weight range of 0.7-1.0 g, accommodated in a micro-chamber, and high purity nitrogen was flowed at a flow rate of 50 ml / min at a temperature of 70 ° C. Thereafter, gas was collected in a solid adsorption tube (Tanex-TA) for 5 minutes, and the adsorbed organic compound was measured by GC / MS. The equipment used was Clarus 600 GC / MS (Perkin Elmer, USA), and the thermal desorber (ATD) was TurboMatrix, Perkin Elmer, USA. The column used for GC / MS was HP-1, 60 m (320 μm), and the residence time was within 36 minutes. The quantitative analysis of the adsorbed organic compounds was carried out by TO-14 STD gas quantitative analysis and the qualitative analysis by NIST & Wiley Library. The results are shown in Tables 1 and 2 below.

Table 1

Material content (% by weight) Generation amount (ng / l) Reduction rate% Styrene Removal Efficiency% Example 1 0.2 441.9 36.4 32.4 Example 2 0.5 551.6 20.6 12.8 Example 3 One 429.5 38.2 16

The most frequently occurring materials in the ABS resin were styrene-based materials, and their removal efficiencies were 32.4, 12.8, and 16% in Examples 1 to 3, respectively.

Table 2

Material content (% by weight) Generation amount (ng / l) Reduction rate% Example 4 One 36877 56.4 Example 5 2 33971 59.8 Example 6 3 31401 62.9 Example 7 4 28039 66.9 Comparative example 0 84587 -

1 is a synthetic process chart of the material for reducing volatile organic compounds according to the present invention.

2 is an electron scanning micrograph before and after the organic polymer is coated on the inorganic particle core according to the present invention.

3 is a comparative graph of the mass loss measurements by combustion between coated inorganic particles and uncoated inorganic particles.

Claims (10)

Comprising a core consisting of a porous inorganic particles selected from zeolite, silica or alumina, and an organic polymer polymer coated on the surface of the core, The core is 70 to 95% by weight relative to the total weight of the material for reducing, The organic polymer is a volatile organic compound reducing material, characterized in that it comprises 5 to 30% by weight. The method of claim 1, The average particle size of the porous inorganic particles is a material for reducing volatile organic compounds, characterized in that 1 to 10㎛. The method of claim 1, The organic polymer is a material for reducing volatile organic compounds, characterized in that selected from an aromatic polymer, styrene polymer or acrylic polymer. The method of claim 1, The organic polymer is a volatile organic polymer which is a polymer obtained by polymerizing a monomer selected from the group consisting of MMA (methyl methacrylate), DVB (divinylbenzene), SM (styrene monomer) and AN (acrylonitrile). Compound Reduction Material. delete The method of claim 1, The core is 80 to 90% by weight relative to the total weight of the material for reduction, the organic polymer is a volatile organic compound reduction material, characterized in that it comprises 10 to 20% by weight. An acrylic resin comprising 0.2 to 5 wt% of the volatile organic compound reducing material according to any one of claims 1 to 4 or 6, based on the total weight. Styrene-based resin comprising 0.2 to 5% by weight of the total weight of the material for reducing the volatile organic compounds according to any one of claims 1 to 4. The method of claim 7, wherein The acrylic resin is an acrylic resin, which is a polymer resin obtained by polymerizing an MMA (methyl methacrylate) monomer. 9. The method of claim 8, The styrene-based resin is an styrene-based resin, characterized in that the ABS resin.

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