WO2016013819A1

WO2016013819A1 - Composition comprising at least two resins, fiber glass and olefin-based rubber resin

Info

Publication number: WO2016013819A1
Application number: PCT/KR2015/007481
Authority: WO
Inventors: 조윤숙; 신양재
Original assignee: 한국컨테이너풀 주식회사
Priority date: 2014-07-25
Filing date: 2015-07-20
Publication date: 2016-01-28
Also published as: TW201604230A; TWI613242B

Abstract

Provided is a composition comprising: at least two resins; fiber glass; and an olefin-based rubber resin and, more specifically, a composition comprising: 100% by weight of a mixed resin consisting of at least two unit resins; 3 to 30% by weight of fiber glass having a length of 10 mm to 50 mm; and 0.5 to 25% by weight of an olefin-based rubber resin.

Description

Composition comprising two or more resins, glass filaments and olefinic rubber resins

The present invention relates to a composition comprising two or more kinds of resins, glass filaments and olefinic rubber resins, and more particularly, adding glass filaments together with olefinic rubber resins to waste resins having low impact resistance and low bending characteristics when mixed. By improving the dispersion of glass filaments, the impact resistance and bending properties of glass filaments can be improved at the same time, and the compatibility and property degradation problems caused by the use of two or more types of mixed resins having different elongation at break can be solved. The present invention relates to a composition comprising two or more kinds of mixed resins, glass long fibers and olefin rubber resins solved using an olefin resin and a glass long fiber.

Waste resins can be used as recycled raw materials, so they are collected separately, crushed, melted and provided for reuse. However, since the physical properties of these waste resins are very different depending on the type of polymer, various kinds of waste resins must be accurately separated according to the type of waste resin for recycling.

In general, the waste resin is separated using a difference in specific gravity, but the problem is that polyethylene (PE) and polypropylene (PP) having a lower specific gravity than water are difficult to separate in this manner. When using resins of different physical properties that are not accurately separated in this manner at the same time, compatibility between the resins is poor and sufficient affinity between the respective resin polymers is degraded, so that physical properties such as impact resistance are lowered.

For example, Utility Model Application No. 20-2001-24176 discloses a technique for manufacturing a pallet using recycled plastic to achieve cost reduction. However, the recycled pallet of the cited invention is produced by pulverizing the waste resin material into a pallet shape. In this case, due to the compatibility and affinity between different waste resin materials, there is a problem that the impact resistance is inferior.

Therefore, the problem to be solved by the present invention is to provide a composition comprising a heterogeneous waste resin, and a plastic product using the same, improved physical properties such as impact resistance, flexural strength.

In order to solve the above problems, the present invention is a composition comprising two or more resins, glass filament, olefin rubber resin, 100 parts by weight of a mixed resin consisting of two or more unit resins; 1 to 30 parts by weight of the glass filament having a length of 10 mm to 50 mm; And it provides a composition comprising a 0.5 to 25 parts by weight of olefinic rubber resin.

In one embodiment of the present invention, the composition further comprises 5 to 35 parts by weight of LDPE, the LDPE is contained in the olefin-based rubber resin of the pellet form, it is incorporated into the composition.

In one embodiment of the present invention, the mixed resin is made of waste polyethylene (PE) and waste polypropylene (PP).

In one embodiment of the present invention, the mixed resin comprises a first resin and a second resin, wherein the first resin is a resin having an elongation at break of 100% or more, the second resin is 20% or less at break The weight average molecular weight of the rubber resin is 1,000 to 500,000.

Further, the weight ratio of the first resin and the second resin is 20 to 59: 30 to 50.

In one embodiment of the present invention, one of the first resin and the second resin is polyethylene (PE), the other is polypropylene (PP), and the present invention provides a plastic product comprising the composition described above. .

In one embodiment of the invention, the plastic product is a pallet or box.

The present invention also provides a method for producing a plastic product using the composition described above, comprising the steps of preparing the composition by mixing the mixed resin, the glass fiber and an olefinic rubber resin having a molecular weight of 1,000 to 500,000; Melting the mixed composition; And molding the molten composition to produce a plastic product.

According to the present invention, an olefinic rubber resin is used to recycle waste resin, thereby improving the resinous dispersion of glass filament in the waste resin containing polyethylene, and can solve the problem of precipitation of the rubber resin on the surface. Furthermore, the problem of odor generation by carbonization of rubber resin can be solved. According to the present invention, the problem of compatibility and physical property deterioration caused by the use of two or more kinds of mixed resins having different elongation at break is solved using an olefin resin and a glass filament having a specific molecular weight range. In particular, olefinic rubber resins having a specific molecular weight range are used in recycling mixed resins having extremely low elongation at break, such as waste resins, to solve the problem of deterioration of mixing characteristics due to the use of recycled and new materials generated during the melting process.

1 and 2 are pallet surface photographs of the above Examples and Comparative Examples, respectively.

3 is an impact strength test result according to the present experimental example.

Figure 4 is a SEM image after molding of the composition using an olefin rubber resin containing LDPE.

Figure 5 is a step diagram of a plastic product manufacturing method according to an embodiment of the present invention.

Hereinafter, with reference to the drawings of the present invention will be described in detail. The following embodiments are provided as examples to ensure that the spirit of the present invention can be fully conveyed to those skilled in the art. Therefore, the present invention is not limited to the embodiments described below and may be embodied in other forms. In the drawings, the width, length, thickness, etc. of the components may be exaggerated for convenience. Like numbers refer to like elements throughout. In addition, the abbreviations shown throughout this specification should be interpreted to the level understood in the art, unless otherwise indicated herein.

MEANS TO SOLVE THE PROBLEM In order to solve the problem mentioned above, this inventor provides the composition which mixed the glass fiber and olefinic rubber resin which are glass fiber of a predetermined length (10 mm or more) with 2 or more types of waste resin mixture materials. In one embodiment of the present invention, the olefin rubber resin was an ethylene-butene copolymer, but the scope of the present invention is not limited thereto.

The present invention uses an olefinic rubber resin to recycle waste resin, and improves the resinous dispersibility of the glass fiber in the waste resin containing polyethylene in addition to the impact resistance by a high carbon polymer such as butane. The problem of precipitation on the surface of the final product can be solved. Furthermore, it solves the problem of odor generated by carbonization of rubber resin added to enhance impact resistance.

That is, the present invention is a non-olefin rubber-based resin such as SBS, SEBS in general in the melting process in the plastic product using waste resin, the carbonization phenomenon occurs by heat (carbide and odor generation), and also the decomposition rate during the melting process In order to solve this problem, an olefinic rubber resin was used in the composition to reduce the possibility of agglomeration of the rubber resin during melting of the waste resin, and also a smell generated during the carbonization process. Reduced.

Composition according to an embodiment of the present invention comprises a composition comprising two or more resins, glass fiber, LDPE and olefinic rubber resin, 100 parts by weight of a mixed resin consisting of two or more unit resins; 1 to 30 parts by weight of the glass filament having a length of 10 mm to 50 mm; 0.5 to 25 parts by weight of olefinic rubber resin.

In another embodiment of the present invention, the LDPE is added to the olefinic rubber resin, in which the LDPE is 5 to 35 parts by weight, and in particular, the dispersion degree of the glass fiber is greatly increased by using an olefinic rubber resin and LDPE mixed. It is improved, which is explained in more detail below.

In one embodiment of the present invention, the two or more unit resins were polyethylene (PE) and polypropylene (PP) having a specific gravity lower than that of water, and the two kinds of resins were waste resins disposed of after use. In particular, the present invention uses two or more waste resins having different structures, physical properties and molecular weights together, but also suffers from a decrease in compatibility caused by the simultaneous use of two or more waste resins, namely, brittleness, impact resistance, Problems such as weakening of flexural strength were solved by using glass fibers having a specific length and an olefinic rubber resin.

In particular, the present inventors solve the problem that when the long glass fiber is mixed with the molten resin, the dispersion of the long glass fiber is low, and thus it is difficult to achieve uniform strength of the plastic product. It is made to contain in resin, and it mixes with the mixed resin which consists of two or more waste resins. LDPE mixed with the olefinic rubber resin improves the dispersibility of the glass fiber, thereby improving the strength of the finally obtained plastic product. The effect of improving the glass fiber dispersion degree by using the LDPE-containing olefinic rubber resin is described in more detail in the following experimental example.

In one embodiment of the present invention, the mixed resin includes any one of waste polyethylene (PE) and waste polypropylene (PP) as a unit resin, and the molecular weight of the unit resin is generally used in the molecular weight of general PE and PP. Follow. In addition, the unit resin of the mixed resin has a specific gravity of less than 1, it is difficult to separate the resin of PE and PP by the conventional waste resin separation method using the specific gravity difference with water. Furthermore, when using these resins mixed, due to different chain lengths, structures, branch shapes and the like. The compatibility between the resin and the chemical bonding strength is lowered, as a result, there is a problem that the molded article made of the mixed resin is easily broken by the impact applied to the outside.

However, in the present invention, the glass filaments of a certain length are physically mixed before melting and then melted, so that the glass filaments function as a kind of main chain to which the unit resin of the mixed resin is bonded. As a result, different types of unit resins are combined with glass filaments, and the glass filaments function as a linkage connecting two types of unit resins. In particular, the present inventors, in the case of glass filaments connecting different types of waste resins, the effect varies depending on the length and the degree of dispersion, and by dispersing the glass filaments by containing LDPE in an olefinic rubber resin which improves impact resistance characteristics. To improve the degree, the strength of the composition was greatly improved.

The present invention further recognizes the problems of compatibility and physical property degradation caused by the use of two or more kinds of mixed resins having different elongation at break, and solves this problem by using olefinic resins and glass filaments in a specific molecular weight range.

In one embodiment of the present invention, the mixed resin is mixed with a first resin having an elongation at break of 100% or more and a second resin having an elongation at break of 20% or less at a weight ratio of 20 to 59:30 to 50. At this time, when the weight average molecular weight of the rubber resin is 1,000 to 500,000, more preferably 10,000 to 200,000, the compatibility of the first resin and the second resin having an excessively different chain length and the lowering of compatibility due to impact strength reduction Solve the problem. Furthermore, glass fibers of a specific length or more are used together with the rubber resins in the above-described molecular weight range, so that the glass latent fibers function as a skeleton that allows two different elongation-breaking resins and molten rubber resins to be bonded at the same time. In one embodiment of the present invention, the elongation at break is a result measured according to ASTM D638 in the tensile elongation at the point of breaking the specimen.

The first resin of the present invention is a new material, the second resin may be a reclaimed material, the first resin, a new material and the reclaimed material is a polyolefin-based resin, polyethylene, polypropylene may be the new material and reclaimed material. In particular, the present invention uses a mixture of at least one of polyethylene and polypropylene new material, and recycled material recycled for the other one.

As a result of analyzing the properties of the second resin such as the reclaimed material, the present inventors have found that the general-purpose regenerated material used for other purposes has a breakage elongation of 20% or less. I found out that this is abnormal. This means that the recycled material has a shorter chain length compared to the new material, and in particular, it has been recognized that the bending strength and the impact strength of the recycled plastic product (for example, the container) fall due to the excessively short chain length during melting.

Therefore, the present invention is to solve the problem arising from the difference in the chain length when using a recycled material having a break elongation of only 20% or less and a new material having a break elongation of 100% or more, the glass fiber and olefin resin Using a mixed solution solves the problem of excessively different chain lengths between new and recycled materials.

Glass filaments used in the present invention, according to the man-made vitreos fibers (MMVF) specified by the World Health Organization (WHO), the average diameter is 6 ~ 15㎛.

Hereinafter, the present invention will be described in more detail with reference to specific experimental examples.

Experimental Example 1

Odor Reduction Effect of Olefin Rubber Resin

Ethylene-butene copolymer which is a glass filament (10 parts by weight) and an olefinic rubber resin in a mixed resin in which the ratio (weight ratio) of PP and PE is 5: 5 to 9: 1 according to an embodiment of the present invention. (Average molecular weight 2000, 10 parts by weight) was added, followed by melting to prepare a pallet (Example). On the contrary, instead of the olefinic rubber resin, SBS was added in the same weight part to prepare a pallet in the same manner as in Example 1 (comparative example).

The following table shows the results of three experiments sensoryly determined by placing the pallets of the Examples and Comparative Examples prepared according to the present invention in a closed room for 10 hours.

	실시예Example	비교예Comparative example
실험자 1Experimenter 1	냄새 없음 No smell	냄새 있음Smelly
실험자 2Experimenter 2	냄새 없음No smell	냄새 있음Smelly
실험자 3Experimenter 3	냄새 없음No smell	냄새 있음Smelly

Referring to the experimental results, it can be seen that when the olefin-based rubber resin is used for remelting the waste resin according to the present invention, it is possible to suppress the occurrence of odor due to carbonization of the rubber.

Experimental Example 2

Precipitation prevention effect by using olefin rubber resin

1 and 2, when the olefinic rubber resin is used in the present invention, due to the low decomposition rate, the possibility of aggregation of the rubber resin in the molten waste resin is lowered, and thus the surface of the finally obtained pallet It can be seen that the rubber resin does not precipitate black.

Experimental Example 3

Strengthening Effect According to Molecular Weight of Olefin Rubber Resin

In this Experimental Example, the effect of strengthening the impact strength according to the molecular weight of the same olefin rubber resin (ethylene rubber resin) was tested.

In this Experimental Example, the impact strength of the composition of Example 1 and the composition (Comparative Example 2) using 600,000 ethylene rubber resins having a molecular weight of more than 500,000 of ethylene rubber resins were measured.

Referring to Figure 3, when the molecular weight of the olefinic rubber resin is 500,000 or less, it can be seen that the impact strength is sharply improved in the case of a mixed resin having a large difference in elongation at break. However, if the molecular weight exceeds 500,000, it can be seen that the impact strength is low despite the use of glass filaments.

Experimental Example 4

Effect of Using LDPE-Containing Olefin Rubber

Referring to FIG. 4, when the LDPE-containing olefinic rubber resin is added to the molten resin in the form of pellets, the glass filaments are uniformly dispersed, and in the composition, the cavity is formed to have a uniform size and a small size. have.

From the above results, the glass filaments added together with the olefin-based rubber resin containing LDPE in the molten state are uniformly dispersed in the resin, and thus it can be expected to produce an effect of improving both impact and bending strength.

The present invention provides a plastic product having improved strength, flexural strength and the like by using the composition having the above-described effect. The compositions according to the invention can be used in various forms of products that have to withstand a certain load, for example by loading cargo such as pallets, crates, boxes, all of which are within the scope of the invention.

Referring to FIG. 5, the above-described composition is prepared by mixing the above-described mixed resin, glass filament, and an olefinic rubber resin. When the olefinic rubber resin is used when the waste resin is melted according to the present invention, the problem of agglomeration and precipitation of the rubber resin on the surface of the plastic product can be solved, and generation of odor due to carbonization can be suppressed.

In addition, in another embodiment of the present invention, after LDPE is contained in the olefin-based rubber resin in a pellet form, it is mixed in the mixed resin, and the dispersion of glass filaments is greatly improved according to the use of LDPE as described above. .

Claims

A composition comprising two or more resins, long glass fibers, and an olefinic rubber resin,

100 parts by weight of a mixed resin composed of two or more unit resins;

1 to 30 parts by weight of the glass filament having a length of 10 mm to 50 mm; And

A composition comprising 0.5 to 25 parts by weight of an olefinic rubber resin.
The method of claim 1,

The composition, LDPE composition further comprises 5 to 35 parts by weight.
The method of claim 2,

The LDPE is contained in the olefin-based rubber resin of the pellet form, characterized in that it is incorporated into the composition.
The method of claim 1,

The mixed resin includes a first resin and a second resin,

The first resin is a resin having an elongation at break of 100% or more, the second resin has an elongation at break of 20% or less, and the weight average molecular weight of the rubber resin is 1,000 to 500,000.
The method of claim 4, wherein

The weight ratio of the first resin and the second resin is 20 to 59: 30 to 50, characterized in that the composition.
The method of claim 5,

Any one of the first resin and the second resin is polyethylene (PE), the other is polypropylene (PP) composition.
Plastic product comprising the composition according to claim 1.
The method of claim 7, wherein

Said plastic product being a pallet or a box.
A method for producing a plastic product using the composition according to any one of claims 1 to 6,

Preparing a composition according to any one of claims 1 to 7, by mixing the mixed resin, the glass fiber and an olefinic rubber resin having a molecular weight of 1,000 to 500,000;

Melting the mixed composition; And

Molding the molten composition to produce a plastic product.
The method of claim 9,

The mixed resin includes a first resin and a second resin,

The first resin is a resin having an elongation at break of 100% or more, the second resin has an elongation at break of 20% or less, and the weight average molecular weight of the rubber resin is 1,000 to 500,000, characterized in that the plastic product manufacturing method. .