KR102129227B1 - Nature - friendly soft MBS resin composition - Google Patents

Abstract

The present invention relates to an eco-friendly soft MBS resin composition, and more specifically, it is eco-friendly and does not generate environmental hormones unlike conventional PVC, including methyl methacrylate butadiene styrene resin, vegetable oil, and thermoplastic polyester elastomer resin. , Cold-resistance, heat resistance, tensile strength, elongation, scratch resistance, adhesive and abrasion resistance environment-friendly soft MBS resin composition.

Description

Eco-friendly soft MBS resin composition {Nature-friendly soft MBS resin composition}

The present invention relates to an eco-friendly soft MBS resin composition, and more particularly, to an eco-friendly soft MBS resin composition comprising methyl methacrylate butadiene styrene resin, vegetable oil, and thermoplastic polyester elastomer resin.

Polyvinyl chloride (PVC) has been used as a raw material for typical artificial leather (vinyl leather) with excellent physical properties and processability such as weatherability, tensile strength, elongation, scratchability, adhesion, and abrasion resistance.

Recently, due to environmental problems, the use of polyvinyl chloride is gradually restricted and prohibited, but it is still widely used for bags, construction, advertising, etc. as an absence of alternative raw materials.

In particular, when used in combination with fabrics, such as artificial leather, recycling becomes more difficult, and most of them must be incinerated, thereby causing environmental and cost problems.

There have been many attempts to replace soft PVC, but it is extremely partial and no complete replacement has been made.

Meanwhile, methylmethacrylate butadiene styrene (MBS) resin is grafted with styrene and butadiene-based rubber latex monomers such as styrene and methylmethacrylate. It is manufactured in powder form and is mainly used as an impact modifier for hard PVC or engineering plastics or a processing aid for other resins.

PVC is one of the most commonly used resins because it is easy to mix with liquid raw materials such as plasticizers, has good compatibility, and has good physical properties and excellent workability through softening, so it can produce soft, high-quality products. In the case of MBS resin, the softening process is not easy, and even after softening, physical properties are deteriorated and commercialization is impossible.

Therefore, there is a need for further research on a method of replacing various soft PVC products by supplementing the problems of the MBS resin.

Domestic Publication No. 10-2008-0037904

In order to solve the problems of the prior art as described above, the present invention aims to provide an environmentally friendly soft MBS resin composition that does not generate environmental hormones, unlike conventional PVC.

In addition, the present invention is excellent in weather resistance, cold resistance, heat resistance, tensile strength, elongation, scratch resistance, adhesiveness and abrasion resistance, as well as bags, construction, and advertisements used in existing PVC material artificial leather, films, sheets, toys, medical, It is an object of the present invention to provide an eco-friendly soft MBS resin composition suitable for use in place of other soft PVC.

In order to achieve the above object, the present invention is 100 parts by weight of methyl methacrylate butadiene styrene resin; 20 to 130 parts by weight of vegetable oil; And 3 to 150 parts by weight of a thermoplastic polyester elastomer resin and 30 to 600 parts by weight of a glycol-modified polyethylene terephthalate (PETG) resin; provides an environment-friendly soft MBS resin composition.

The methyl methacrylate butadiene styrene resin preferably has a rubber content of 60 to 85 parts by weight.

The thermoplastic polyester elastomer resin has a Showa hardness of 35 to 50D.

The soft MBS resin composition may further include 10 to 30 parts by weight of a filler selected from calcium carbonate (CaCO ₃ ), silica, and mixtures thereof.

In addition, the soft MBS resin composition is characterized by adding one more lubricant, modifier or flame retardant.

In addition, the present invention comprises the steps of mixing methyl methacrylate butadiene styrene resin and vegetable oil; And mixing a thermoplastic polyester elastomer resin in the mixture. It provides a method for producing an eco-friendly soft MBS resin comprising a.

According to the present invention, unlike conventional PVC, it is eco-friendly because it does not generate environmental hormones, and it is excellent in weather resistance, cold resistance, heat resistance, tensile strength, elongation, scratch resistance, adhesion, and abrasion resistance. It is suitable for use as a substitute for construction, advertisement, as well as film, sheet, toy, medical, and other soft PVC.

Hereinafter, the present invention will be described in detail.

The present invention is an invention for developing a soft resin having physical properties and processability to replace soft PVC, film, sheet, toy, medical, and other soft PVC to which existing PVC resin has been applied.

MBS resin is made of powder and is mainly used as a hardening agent for hard PVC or engineering plastics. It has good mixing properties and compatibility with other resins, and is mainly used to improve the properties and processability of other resins. , MBS resin itself does not have the properties to be used alone, so commercialization is impossible.

Accordingly, in the present invention, to prepare a soft MBS resin by mixing and using a thermoplastic polyester elastomer resin to produce a soft resin having physical properties and processability to replace soft PVC while using the MBS resin as a base resin.

The present invention provides an eco-friendly soft resin composition comprising methyl methacrylate butadiene styrene resin, vegetable oil, and thermoplastic polyester elastomer resin.

The methyl methacrylate butadiene styrene (MBS) resin is used as a base resin.

The MBS resin is mainly used for opacity, but it is preferable to use a type having a large amount of butadiene synthetic rubber, and specifically, the content of butadiene synthetic rubber (60 to 85 parts by weight) is absorbent and compatible with vegetable oil. It is more preferable in (compatibility), and since the state after mixing with vegetable oil is good, since it is easy to mix with a thermoplastic polyester elastomer resin and a soft MBS resin excellent in physical properties and processability can be prepared, it is more preferable.

MBS resin is a methyl methacrylate-butadiene-styrene resin produced by using 60 parts by weight or less of synthetic rubber (butadiene), and has a small impact reinforcing effect, so an excessive amount of impact modifier is added to improve the impact strength of the resin It has to be done so that it is not suitable economically.

The MBS resin can be mixed with oil to control the hardness. In this process, the mixing property and compatibility of the resin and the oil are important. If the mixing property and the compatibility are poor, the physical properties and processability of the resin may be lowered.

Therefore, it is preferable to use vegetable oil as the oil added to soften the MBS resin.

As the vegetable oil, oil extracted from a plant or a seed of a plant, palm oil, coconut oil, castor oil, grape seed oil, jojoba oil, safflower oil, macadamia nut oil, olive seed oil, etc. may be used. It is preferred to use palm oil.

The vegetable oil is preferably contained in 20 to 130 parts by weight based on 100 parts by weight of the MBS resin, more preferably 40 to 100 parts by weight. If the content is less than 20 parts by weight, the softening of the MBS resin may be insignificant, and when it exceeds 130 parts by weight, the mixture and compatibility with the MBS resin deteriorate due to the excessive oil content, and the oil is exposed to the sheet surface. Blooming occurs, which can degrade the physical properties and processability of the resin.

After mixing the MBS resin and vegetable oil, a thermoplastic polyester elastomer resin is added to the mixture and mixed.

The thermoplastic polyester elastomer (TPEE) resin is an eco-friendly resin, has good physical properties and processability, and has excellent compatibility, thereby compensating for physical properties of the MBS resin.

In other words, TPEE resin has excellent compatibility and compatibility with MBS resin, has good compatibility with palm oil, has good compatibility, has good tensile strength at high temperatures, and has a compression set. It has low, chemical resistance, low temperature resistance, weatherability, heat resistance, and good physical properties such as tensile strength, so that it can form a high-quality composition when mixed with MBS resin, and can also inhibit palm oil leaching. It is recommended to use TPEE resin with low hardness and low melting point.

The TPEE resin may be one obtained by melt-polymerizing an aromatic dicarboxylic acid or its ester-forming derivative, an aliphatic diol, and polyalkylene oxide according to a conventional method, or one prepared by solid-phase polymerization of the TPEE resin prepared by the melt polymerization again. have.

It is preferable that the TPEE resin has a Shore hardness of 35-50D for sufficient expression of physical properties.

The TPEE resin is preferably included in 3 to 150 parts by weight based on 100 parts by weight of the MBS resin. If the content is less than 3 parts by weight, the effect of complementing the physical properties of the MBS resin is negligible, and if it exceeds 150 parts by weight, the physical properties of the soft MBS resin may be adversely affected due to excessive use.

In addition, the environment-friendly soft MBS resin composition of the present invention may further include a glycol-modified polyethylene terephthalate (PETG) resin, if necessary.

The PETG resin is preferably included in 30 to 600 parts by weight based on 100 parts by weight of the MBS resin. When the content is less than 30 parts by weight, the effect of complementing the physical properties of the MBS resin is negligible, and when it exceeds 600 parts by weight, the hardness of the soft MBS resin rises and there is no effect of the softness. There is an oil surface leaching (blooming or migration).

The PETG resin is relatively inexpensive and has a cost reduction effect, and is used together with the TPEE resin to improve physical properties of the MBS resin. The PETG resin is more preferably mixed with a kind having a low melting point to produce a good quality MBS resin, and specifically, the PETG resin preferably has a melting point of 80 to 180°C.

The eco-friendly soft MBS resin composition of the present invention comprising the above components may further include one additional filler, lubricant, flame retardant, or modifier.

The filler may include calcium carbonate (CaCO ₃ ), silica, and the like, and may be used in an amount of 10 to 30 parts by weight based on 100 parts by weight of the MBS resin mixture.

The lubricant may use various lubricants such as paraffin wax, polyolefin wax, polypropylene wax, steamide, oleic acid amide, ercinic acid amide, erucamide, but it is preferable to use a lubricant.

The flame retardant includes zinc oxide (ZnO), zinc borate (ZnBO ₃ ), Ca-Mo, tristriazine, decabromoniphenyl ethane, octabromodiphenyl oxide, antimony trioxide, antimony pentoxide , Aluminum hydroxide, magnesium hydroxide, polyphosphate and the like can be used.

In addition, the eco-friendly soft MBS resin of the present invention may further include additives such as plasticizers, antioxidants, ultraviolet absorbers, modifiers, and the like.

Hereinafter, the present invention will be described in more detail with reference to examples. These examples are for illustrative purposes only and are not intended to limit the protection scope of the present invention.

Example 1

In order to confirm the mixing property according to the content of the vegetable oil mixed with the methyl methacrylate butadiene styrene (MBS) resin, mixing was evaluated by mixing at the ratios shown in Table 1 below. In this case, MB838 and MB872 (manufactured by LG Chemical Co., Ltd.) were used as the methyl methacrylate butadiene styrene resin, and palm oil was used as the vegetable oil. (Units in Table 1 below are kg)

division One 2 3 4 5 6 7 8 MBS resin MB838 1.0 1.0 1.0 1.0 - - - - MB872 - - - - 1.0 1.0 1.0 1.0 Palm oil 0.4 0.6 0.8 1.0 0.4 0.6 0.8 1.0

MBS resin (MBS resin: methyle methacrylate butadiene styrene) is manufactured by LG Chem, product numbers MB872 and MB838.

When mixing MBS resin and vegetable oil, the amount of vegetable oil was increased from 0.4 kg to 0.2 kg step by step from 1.0 kg to 1.0 kg of MBS resin, and the mixture was similar, and the palm oil content was more than 0.8 kg 3 , 4, 7, 8 it was confirmed that the gel state.

However, Tables 1 and 5 of Table 1 have the form of a resin, but even if the amount of palm oil absorption is small, the properties of the MBS resin itself include properties such as tensile strength, elongation, and surface finish, which are not sufficient to be possessed by the resin. The product could not be commercialized due to the phenomenon (blooming or migration), and the properties of Table 1 and 4 were improved compared to those of Table 1, but the leaching and adhesion properties were not significantly improved. In the case of MBS resin, MB838 absorbed oil more than MB872. And better mixing properties.

Example 2

As shown in Table 2 below, the thermoplastic polyester elastomer (TPEE) resin 0.28 was added to a mixture of 0.4 kg, 0.6 kg, 0.8 kg, and 1.0 kg of palm oil in 1.0 kg of the MB838 and MB872 resins, respectively. , 0.32, 0.36, and 0.40 kg were mixed, heated and cooled to confirm the change state. (Units in Table 2 below are kg)

division One 2 3 4 5 6 7 8 MBS resin MB838 1.0 1.0 1.0 1.0 - - - - MB872 - - - - 1.0 1.0 1.0 1.0 Palm oil 0.4 0.6 0.8 1.0 0.4 0.6 0.8 1.0 TPEE resin 0.28 0.32 0.36 0.4 0.28 0.32 0.36 0.4

(1) TPEE (Thermoplastic polyester elastomer) is item number KP3340 manufactured by Cologne Co., Ltd.

As shown in Table 2, as a result of mixing the TPEE resin with the mixture of MBS resin and palm oil, in the case of 1, 2, 3, 5, 6, 7 of Table 2 with a palm oil content of less than 0.8 kg, A hardness is about 90 In the case of 4 and 8 of Table 2, in which the palm oil content was formed and the palm oil content was 1.0 kg, a low hardness composition having an A hardness of 70 or less was formed, and a high quality composition could not be obtained by containing an excessive amount of palm oil. In addition, the composition results of MB838 or MB872 were similar.

Example 3

After mixing 1.0 kg of palm oil with 1.0 kg of MB838 resin as MBS resin, the content of TPEE resin was varied to 0.6, 1.0, 1.3, 1.5 kg, mixed, heated and cooled to observe the quality improvement effect. The results are shown in Table 3 below. The results of quality improvement in Table 3 were confirmed in comparison with soft PVC (plasticizer content of 100 phr, A hardness of about 70). The unit of Table 3 below is kg.

division One 2 3 4 MB838 resin 1.0 1.0 1.0 1.0 Palm oil 1.0 1.0 1.0 1.0 TPEE resin 0.6 1.0 1.3 1.5 Quality improvement results Good Good Good Very good

As shown in Table 3, in the case of 1, 2, and 3 of Table 3, improvement effects such as heat resistance, cold resistance, and weather resistance were similar to those of soft PVC, but the abrasion and adhesiveness of the inner surface were slightly decreased. It was confirmed that the elasticity was rather better. In addition, in the case of 4 in Table 3, it could be confirmed that the tensile strength and elongation showed significantly better results compared to soft PVC.

Example 4

As shown in Table 4, after mixing palm oils having different weights to 1 kg of MB838 resin, a TPEE resin and PETG resin were mixed to prepare soft MBS resin, and A hardness, quality improvement results, specific gravity, tensile strength And the elongation was measured, and the results are shown in Table 4 below. The unit of Table 4 below is kg.

division 1-1 1-2 One 2 3 4 5 6 7 8 MB838 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Palm oil 1.6 1.3 1.3 1.0 0.7 1.0 1.0 1.3 1.3 1.3 TPEE resin 0.03 0.03 0.03 0.03 0.147 06 1.3 1.5 1.5 1.5 PETG resin 7.0 6.0 5.0 4.0 3.0 2.5 2.0 One 0.69 0.46 A hardness 95±3 D60±3 97±3 98±3 93±3 87±3 72±3 65±3 54±3 51±3 Quality improvement results Good Good Good Good Good Good Good Good importance - 1.16 1.13 1.12 1.10 1.13 1.18 - Tensile strength (㎏f/㎠) - 209 157 133 58 59 28 - Elongation (%) - 270 330 350 280 255 150 -

In the case of Table 4, in the case of 2, the plasticizer 30phr soft PVC with a composition of high hardness, the plasticizer 40phr soft PVC in the case of 3, the plasticizer 60phr soft PVC in the case of 4, the plasticizer 80phr soft PVC in the case of 5, and 6 In the case of 90 phr, it showed a similar level of hardness to soft PVC, and in the case of 7, it showed a hardness similar to that of 100 phr of plasticizer (DOP) of soft PVC (about A51±3). In the case, it was confirmed that the hardness was similar to that of Table 4, but the tensile strength was poor and the physical properties were not good. table

On the other hand, the main purpose of PETG added to the composition is to use as a filler to reduce the cost of the composition as a concept of reducing the cost of the composition to reduce the cost as shown in Table 4, 1,1-1,1-2 of PETG resin Experiment was carried out by mixing a large amount.

That is, in order to maintain the hardness of about 30-40 phr of soft PVC, the amount of palm oil was increased from 1.0 kg to 1.3 kg and 1.6 kg in MB838 1 kg, and the content of PETG resin was increased to 4.0 to 7.0 kg.

As a result of the experiment, 1 and 1-1 of Table 4 showed hardness of about 40 phr of soft PVC, 1-2 of Table 4 showed hardness of about 30 phr of soft PVC, and physical properties were similar to 2 of Table 4 above. .

In addition, 1 in Table 4 has a hardness of about 30 phr of soft PVC and good quality, but it costs more than 30 phr of soft PVC.

However, as in the case of 1-1 in Table 4, when a large amount of palm oil is mixed with the composition, even if the PETG resin is increased, the oil added to the resin of MBS occurs due to the leakage of oil appearing on the surface. In many cases, oil leached to the surface.

Example 5

Table 1 of Table 4 of Example 4 has a hardness of about 30 phr of soft PVC and good quality, but is more expensive than 30 phr of soft PVC. The amount of palm oil was increased from 1 kg to 1.6 kg to prepare and maintain the hardness similar to 2 of Table 4, which is a hardness similar to that of soft PVC 30 phr.

The results are shown in Table 5 below. The unit of Table 5 below is kg.

division One 2 3 4 MB838 1.0 1.0 1.0 1.0 Palm oil 1.0 1.3 1.3 1.6 TPEE resin 0.03 0.03 0.03 0.03 PETG resin 4.0 5.0 6.0 7.0 A hardness 98±3 97±3 D60±3 95±3

The experimental results of Table 5 1 and 2 showed hardness of about 40 phr of soft PVC, 3 of Table 5 showed hardness of 30 phr PVC, and 4 of Table 5 showed hardness similar to PVC 50 phr. The physical properties of Tables 1, 2, 3, and Table 5 were similar to those of Table 4, and Table 5, 4, even though PETG was increased by mixing a large amount of oil, leaching occurred. As a result of this experiment, even if the content of oil was increased from 1.0kg to 1.3kg, and the content of PETG was increased up to 6.0kg, there was a significant cost saving effect as a result similar to 2 in Table 4.

As shown in Table 5, even if the content of oil is increased from 1.0 to 1.3 kg to increase the content of PETG resin up to 6.0 kg, it can be seen that there is a significant cost saving effect because it shows similar results to 2 in Table 4 above. there was.

Although the present invention has been described as a preferred embodiment mentioned above, it is possible to make various modifications or variations without departing from the spirit and scope of the invention. Also, the appended claims include such modifications or variations that fall within the spirit of the present invention.

Claims (1)

100 parts by weight of methyl methacrylate butadiene styrene (MBS) resin; 20 to 130 parts by weight of vegetable oil; And 3 to 150 parts by weight of a thermoplastic polyester elastomer (TPEE) resin and 30 to 600 parts by weight of a glycol-modified polyethylene terephthalate (PETG) resin, wherein the environment-friendly soft MBS resin composition comprises:
The methyl methacrylate butadiene styrene resin has a butadiene synthetic rubber content of 60 to 85 parts by weight,
The thermoplastic polyester elastomer resin has a Shore hardness of 35 to 50D,
The soft MBS resin composition further comprises 10 to 30 parts by weight based on 100 parts by weight of the MBS resin mixture with a filler selected from calcium carbonate (CaCO ₃ ), silica, and mixtures thereof.
The soft MBS resin composition is an eco-friendly soft MBS resin composition, characterized in that one more type of lubricant, modifier or flame retardant is added.