JP2932114B2 - Manufacturing method of recycled resin from waste material - Google Patents

Description

[Detailed description of the invention]

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for recycling waste nylon pile carpet.

[0002]

2. Description of the Related Art Carpets with polypropylene pile and polyethylene backing are polypropylene (hereinafter referred to as "PP").
abbreviated as ) and polyethylene (hereinafter abbreviated as "PE") are polyolefin resins of the same family and are compatible with each other, and the waste carpet material is recycled as a recycled resin by remelting and extrusion. However, nylon (hereinafter abbreviated as "PA") pile, polyester (hereinafter abbreviated as "PET") base fabric, and PE backing carpet are not used as recycled resins due to the poor compatibility of these three resins. not It is generally landfilled or incinerated. In some cases, a part of the carpet is reused. In this case, the carpet is crushed into small pieces, melted in an extruder, and the solidified lumps are pulverized and mixed with polyethylene at 10 to 20% by weight as a backing material. are used as In this case, the pulverized carpet material is used only in the form of a filler, and does not work as a resin by being compatible with PE.

[0003]

SUMMARY OF THE INVENTION The object of the present invention is to compatibilize and strengthen the three components of nylon pile carpet, PA, PET and PE, to obtain a recycled resin with practical physical properties (strength, elongation). It is to be

[0004]

SUMMARY OF THE INVENTION The present invention provides PA, PET and
The gist of the present invention is a method for producing recycled resin from waste material, comprising pulverizing a composite material consisting essentially of PE, and melt-kneading the pulverized material with maleic anhydride-modified polyolefin and a peroxide compound.

The composite consisting essentially of PA, PET and PE is typically the nylon pile carpet commonly used in automobiles, which carpet consists essentially of P
Consists of A-pile, PET base fabric and PE backing. The PET base fabric is often latex-coated,
The PE backing may contain a small amount of polyvinyl acetate or the like, and the composite material used in the present invention also includes these.

The composition ratios of PA, PET and PE in nylon pile carpets for automobiles, which are typical composite materials, are PA: 30-65 parts by weight, PET: 8-20 parts by weight, PE: 25-20 parts by weight.
Although it is 60 parts by weight, it is not particularly limited to these proportions.

[0007] The composite material is pulverized in order to facilitate subsequent charging into kneading equipment and kneading itself. At this time, the size of the pulverized product should be approximately 3 to 15 mm. If it is too large, it becomes uneconomical in terms of equipment and power. This pulverized product may be preliminarily kneaded and crushed in order to facilitate introduction into a kneader in later kneading and to make it quantitative.

The maleic anhydride-modified polyolefin is added to compatibilize the three polymers PA, PET and PE. Examples of the maleic anhydride-modified polyolefin include a terpolymer composed of 1 to 3% by weight of maleic anhydride, 3 to 30% by weight of acrylic acid ester and ethylene, and styrene, methyl methacrylate or acrylic styrene in addition to this terpolymer. etc., gives particularly excellent properties.

The maleic anhydride-modified polyolefin is added in an amount of 0.5-10% by weight, preferably 2-5% by weight, based on the total amount of the composite material, maleic anhydride-modified polyolefin, peroxide compound and other additives. %
is. If this amount is too small, compatibility with the recycled material will be poor. On the other hand, if the amount is too large, the effect is improved, but the technical idea of recycling waste materials is not met, and the use of this expensive resin is not worthwhile.

[0010] PA, PET and PE can be obtained by using a peroxide in combination with the maleic anhydride-modified polyolefin.
greatly improves the compatibility of As the peroxide, it is preferable to use a peroxide of the type on which free radicals act effectively at a temperature of 260 to 280° C. during heating and kneading.

Examples include 1,3-bis(t-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, t
-butylcumyl peroxide, diisopropylbenzene hydroxide, di-t-butyl peroxide, p-menthane hydroperoxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexene-3 and the like. be done.

[0012] Since the addition of a small amount of peroxide shows its effect, it is preferable to use a masterbatch so that the amount can be added as accurately as possible. A product obtained by dispersing 10% by weight of peroxide in polypropylene resin is commercially available, and it is convenient to use this product. This masterbatch contains 0.01 to 5% by weight, preferably 0.1 to 1% by weight (0.001 to 0.5% by weight, preferably 0.01 to 0.5% as peroxide).
1% by weight) (based on the total amount of the composite and additives)
is good. If it exceeds 5% by weight as a masterbatch, the elongation property is rather deteriorated, which is not preferable.

In addition to the above maleic anhydride-modified polyolefins and peroxides, EPR and ultra-low density ethylene copolymers (VLDPE), etc., which are generally used to improve the impact resistance and elongation properties of polyolefin resins. Addition of olefinic thermoplastic polymer leads to PA/PET/
It is preferable because the impact resistance and elongation properties of the PE compatibilized recycled material can be improved.

The amount of the thermoplastic olefinic polymer added is preferably 0-20% by weight, preferably 1-10%, based on the total amount of the composite material and additives (including the thermoplastic olefinic polymer). % by weight. At 2 to 5% by weight, a recycled material having particularly good elongation properties can be obtained. Even if the amount is 20% by weight or more, the effect is improved, but it is not preferable for the same reason as the maleic anhydride-modified polyolefin.

The melt-kneading is carried out at a temperature higher than the melting point (about 260°C) of PET, which has the highest melting point among PA, PET and PE, preferably at a temperature of 270-280°C. A known apparatus can be used for melt-kneading. These include, for example, mixing rolls, Σ-vane kneaders, Banbury mixers, high-speed continuous twin-screw mixers, extruder-type kneaders. Among them, a twin-screw extruder is particularly convenient, and the resin can be well mixed and dispersed.

In melt-kneading, the pulverized composite material and the additive may be mixed in a batch, or the additive may be sprinkled on the pulverized composite material on a conveyor. When a screw extruder is used for melt-kneading, it is preferable to perform heat treatment and dehumidification in the hopper of the extruder as necessary, and to pressurize the material so that it flows smoothly. The additive may be introduced from the middle of the extruder cylinder.

The recycled material obtained by the method of the present invention can be used again as a backing material for carpet lining, etc., and can also be used for flowerpots, fences, car wheel stoppers, nursery boxes, U-shaped grooves, and U-shaped grooves. It can also be used for general molded articles such as lids.

[0018]

EXAMPLES Examples are shown below, but the present invention is not limited to them. The ratios and percentages shown below are by weight unless otherwise specified.

Example 1 Nylon 6 pellets, PET pellets, and low-density PE pellets used as raw materials for tufted carpet were
A:PET:PE was mixed at a ratio of 48:12:40 to prepare mixed pellets assuming a tufted carpet. Add additives such as maleic anhydride-modified polyolefin (hereinafter sometimes referred to as "compatibility agent") shown in Table 1 to the compounded pellets (addition % is the total amount of compounded pellets and additives)
100%. ) Melt-extrusion temperature The mixture was placed in a twin-screw extruder set at 270°C, stranded, passed through a cooling water tank, and then pelletized with a pelletizer. then this pellet 2
It was placed in an injection molding machine at 70°C and molded into a JIS K 7113 type (tensile) test piece. Tensile speed of 10mm/min for this test piece
A tensile test was performed at The results are shown in Table 1.

Table 1 Olefin Tensile test data Experiment No. Compatibilizer Peroxy thermoplastic Tensile strength Elongation at break; Side ^*1 ) Polymer kgf/cm2 ^% 1 - - - 260 4.3 2 A8100 ^*2) ;5% - - 237 10.2 3 TX8030 ^*3) ;10% - - 156 14.2 4 TX8030;5% 0.5% - 311 85 5 TX8030; 5% 1% − 305 18 6 TX8030; 5% 0.5% PO280 ^*4) ; 5% 304 137 7 A8100; 5% 0.25% PO280; 5% 266 27 8 Same as above 0.5% Same as above 291 74 9 Same as above 0.75% Same as above 289 25 10 Same as above 1% Same as above 296 19 11 Same as above − Same as above 238 5.7 12 Same as above 0.5% − 309 18.9 13 TX8030; 5% 0.5% VLDPE ^*5) 5% 314 35 14 TX8030; 10% − PO280; 5% 177 14.2 15 TX8030; 2.5% 0.5% VLDPE; 5% 318 31 16 same as above same PO280; ^*6) ;2.5% Same as above VLDPE;5% 325 99.6 18 Same as above Same as above LDPE;5% 318 39 19 HX8210 ^*7) ;5% Same as above PO280;5% 314 76 20 HX8210;2.5% Same as above VLDPE; 5% 327 40 21 Same as above PO280; 5% 313 81 22 Same as above PO280; 2.5% 323 60.8 ────────────────── ──────────────────

*1) "Akzobisbreak P" (trademark) manufactured by Nippon Kayaku Co., Ltd., 1,3-bis(t-butylperoxyisopropyl)benzene was used. *2) A8100: “Modiper A8100” manufactured by NOF Corporation
(Trademark) *3) TX8030: “Bondyne TX8030” manufactured by Sumitomo Chemical Co., Ltd.
(Trademark) *4) P0280: Mitsui Petrochemical Co., Ltd. “Tafmer P028
0” (trademark); EPR *5) VLDPE: manufactured by Sumitomo Chemical Co., Ltd. *6) LX4110: manufactured by Sumitomo Chemical Co., Ltd. “Bondyne LX4110”
(trademark) *7) HX8210: “Bondyne HX8210” manufactured by Sumitomo Chemical Co., Ltd.
(trademark)

It is clear from Table 1 that the lack of either one or both of the compatibilizer and peroxide results in a decrease in tensile strength and/or elongation properties. In addition, it is clear that the addition of a thermoplastic elastomer in addition to the above two components greatly improves the elongation properties in many cases (N
4: No. 6; No. 12: No. 8; No. 13: No. 10).

Example 2 Scrap tufted carpet (PA: 50%; PET: 12%; PE: 38
%) was crushed to a size of 5 to 10 mm and introduced into an extruder to 270
°C. The extruded product did not form strands, but formed short strands or long lumps of several cm to 5 cm in length. This product was crushed with a crusher having a mesh filter with a hole size of 5 mm. Additives shown in Table 2, such as a compatibilizing agent, were blended with the resulting pulverized product, and then introduced into a twin-screw extruder, extruded into strands, and pelletized. Using these pellets, JIS K 7113 No. 1 (tensile) test pieces were prepared by injection molding at a temperature of 270° C., and tensile tests were conducted at a tensile speed of 10 mm/min. The result is the second
shown in the table.

Table 2 Olefin Tensile Test Data Experiment No. Compatibilizer Peroxy Thermoplastic Tensile Strength Break Elongation; Side ^*1 ) Polymer kgf/cm2 ^% 1 A8100 ^*2) ;5% - - 237 10.2 2 Same as above - PO280 ^*4) ;5% 213 6.8 3 Same as above 0.3% Same as above 361 48 4 Same as above Same as above Top - 320 31 5 TX8030 ^*3) ; 5% - PO280; 5% 210 7 6 LX4110 ^*6) ; 2.5% 0.5% VLDPE ^*5) ; 2.5% 284 49 ^* 7 TX8030; 5% Same as above - 286 33 8 Same as above Same as above PO280; 5% 302 41 9 LX4110; 5% - VLDPE; 5% 246 9.3 10 Same as above 0.5% - 295 38 11 Same as above Same as above VLDPE;

From Table 2 it is clear that the tensile strength and elongation properties are degraded in the absence of peroxide even in the presence of compatibilizer. In this case, fold the test piece in two and
°If you bend it, it will break. Further, when an olefinic thermoplastic polymer is further added to the above two components, No. 4,7,
10 and No. As can be seen by comparing Nos. 3, 6 and 11, the elongation characteristics are greatly improved. These specimens are 2
No cracks even when folded 180°.

FIG. 1 is a cross-sectional photograph showing the particle structure of the resin of Example 1, Experiment No. 5 (enlarged about 1000 times; the white line on the lower right indicates a length of 10 μm). 2, 3, and 4 are cross-sectional photographs showing the particle structure of the resin of Example 1 and Experiment No. 1 (comparative example) (magnifications of 200, 1000, and 3000, respectively; 10μ and 10μ are shown.). 5, 6, and 7 show the same carpet as in Example 2, compatibilizer (maleic anhydride-modified polyolefin: 5% Bondine LX4110 (trademark) manufactured by Sumitomo Chemical Co., Ltd., and 0.5 peroxide).
%, showing the particle structure of the resin of the test piece prepared in the same manner as in Example 2 (magnifications of 200, 1000 and 3000, respectively; the lengths of the white lines in the lower right are 100 µ, 10 µ and 10 µ, respectively. )
is. 8, 9, and 10 are the same blended pellets as in Example 1, compatibilizer (maleic anhydride-modified polyolefin: Sumitomo Chemical Co., Ltd. "Bondine LX4110" (trademark) 5% and peroxide 0.5% Cross-sectional photographs showing the particle structure of the resin of the test piece prepared in the same manner as in Example 1 (each 200, 1
000, 3000 times; the length of the white line on the lower right indicates 100μ, 10μ and 10μ, respectively. ).

Photographs of FIGS. 2-4 (comparative example) and FIGS.
(Example of the present invention), it is clear that different resins are better mixed in the resin regenerated by the method of the present invention.

[0028]

INDUSTRIAL APPLICABILITY According to the present invention, a recycled material excellent in both tensile strength and elongation properties can be obtained from a nylon pile carpet containing PA, PET and PE. In particular, if an olefinic thermoplastic polymer is added in addition to the two components added in the method of the present invention, a reclaimed material having even better elongation properties can be obtained.

[Brief description of the drawing]

FIG. 1 is a cross-sectional photograph showing the particle structure of the resin of Example 1, Experiment No. 5 (magnified about 1000 times; the white line on the lower right indicates a length of 10 μm).

[Fig. 2] A cross-sectional photograph showing the particle structure of the resin of Example 1, Experiment No. 1 (comparative example) (200x; the white line on the lower right has a length of 100μ
indicates ).

[Fig. 3] A cross-sectional photograph showing the particle structure of the resin of Example 1, Experiment No. 1 (comparative example) (1000x; the white line on the lower right has a length of 10μ
indicates ).

[Fig. 4] A cross-sectional photograph showing the particle structure of the resin of Example 1, Experiment No. 1 (comparative example) (3000x;
indicates ).

[Fig. 5] The same carpet as in Example 2, compatibilizer (maleic anhydride-modified polyolefin: "Bondine LX4110" (trademark) manufactured by Sumitomo Chemical Co., Ltd.) at 5% and peroxide at 0.5%.
A cross-sectional photograph showing the particle structure of the resin of the test piece prepared in the same manner as in Example 2 (200 times; the white line in the lower right has a length of 100
indicates μ. ).

[Fig. 6] The same carpet as in Example 2, compatibilizer (maleic anhydride-modified polyolefin: Sumitomo Chemical Co., Ltd. "Bondine LX4110" (trademark) 5% and peroxide 0.5%
A cross-sectional photograph showing the particle structure of the resin of the test piece prepared in the same manner as in Example 2 (1000 times; the white line in the lower right is 10
indicates μ. ).

[Fig. 7] Carpet same as in Example 2, compatibilizer (maleic anhydride-modified polyolefin: Sumitomo Chemical Co., Ltd. "Bondine LX4110" (trademark) 5% and peroxide 0.5%
A cross-sectional photograph showing the particle structure of the resin of the test piece prepared in the same manner as in Example 2 (3000 times; the length of the white line on the lower right indicates 10 μm each).

[Fig. 8] The same blended pellets as in Example 1, compatibilizer (maleic anhydride-modified polyolefin: Sumitomo Chemical Co., Ltd. "Bondine LX4110" (trademark) 5% and peroxide 0.5
%, and a cross-sectional photograph showing the particle structure of the resin of the test piece made in the same manner as in Example 1 (200 times; the length of the white line in the lower right is 1
Indicates 00μ. ).

[Fig. 9] The same blended pellets as in Example 1, compatibilizer (maleic anhydride-modified polyolefin: Sumitomo Chemical Co., Ltd. "Bondine LX4110" (trademark) 5% and peroxide 0.5
%, and a cross-sectional photograph showing the particle structure of the resin of the test piece made in the same manner as in Example 1 (1000 times; the length of the white line in the lower right is
Indicates 10μ. ).

[Fig. 10] The same blended pellets as in Example 1, compatibilizer (maleic anhydride-modified polyolefin: Sumitomo Chemical Co., Ltd. "Bondine LX4110" (trademark) 5% and peroxide 0.5
%, and a cross-sectional photograph showing the particle structure of the resin of the test piece made in the same manner as in Example 1 (3000 times; the length of the white line in the lower right is
Indicates 10μ. ).

──────────────────────────────────────────────────── ──Continued from the front page (72) Inventor Norio Sato 41-1 Yokomichi, Nagakute-cho, Aichi-gun, Aichi Prefecture, in Toyota Central R&D Labs. JP-A-3-237143 (JP, A) (58) Researched field (Int.Cl. ⁶ , DB name) C08J 11/00 - 11/28 B29B 17/00 - 17/02

Claims (1)

(57) [Claims] 1. Grinding a composite material consisting essentially of polyamide, polyethylene terephthalate and polyethylene,
A method for producing recycled resin from waste material, characterized by melt-kneading the pulverized material with maleic anhydride-modified polyolefin and a peroxide compound.