JPH0752159A - Recovery method of resin composite - Google Patents

Abstract

(57) [Summary] [Object] To provide a method for obtaining a recycled resin composition having excellent physical properties such as moldability, mechanical strength, and cold resistance from a recovered resin composite. [Structure] (A) 95 to 50 parts by weight of a resin composite containing polyethylene, polyamide and polyester, and (B)
5 to 50 parts by weight of an epoxy group-containing polyolefin and 5 to 90 parts by weight of (C) polyethylene are added to 95 to 10 parts by weight of (A) + (B) and melt-kneaded.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for recovering a resin composite containing polyethylene, polyamide and polyester to obtain a recycled resin composition.

[0002]

2. Description of the Related Art Resin composites containing polyethylene, polyamide and polyester are widely used for interior and exterior parts of automobiles, home electric appliances and the like, for example, as a multilayer sheet for carpets. Such a resin composite is discarded as waste after use, but the amount is enormous. Therefore, in recent years, there has been an increasing trend to collect and regenerate such resin composites and use them as regenerated resin compositions. As a method for recycling, a method of diluting by adding polyethylene is conceivable. However, in such a method, since the compatibility of the three components is poor, the moldability, mechanical strength and cold resistance of the obtained recycled resin composition are high. Inferior in physical properties and cannot be reused.

[0003]

Therefore, the present invention provides a method for recovering and regenerating the above resin composite to obtain a regenerated resin composition having excellent physical properties such as moldability, mechanical strength and cold resistance. The purpose is to

[0004]

The present invention relates to a method for obtaining a recycled resin composition from a resin composite containing polyethylene, polyamide and polyester, wherein the resin composite containing (A) polyethylene, polyamide and polyester is contained in an amount of 95 to 50% by weight. Parts, (B) 5 to 50 parts by weight of an epoxy group-containing polyolefin, and (C) polyethylene 5 to 90 with respect to a total of 95 to 10 parts by weight of (A) and (B).
The present invention provides a method characterized by melt-kneading parts by weight.

In the method of the present invention, as the resin composite (A) to be recovered and regenerated, any resin composite containing polyethylene, polyamide and polyester can be used. The composite includes, for example, a laminated body of each component (including a sheet shape, a rod shape, a spherical shape, etc.), a fiber structure in which threads of each component are entangled, a structure in which other components are dispersed in a one-component matrix, and the like. Including. The shape is not particularly limited. Examples of polyethylene include high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE) and ultra low density polyethylene (VLDPE).
A polymer containing at least one of the above, and butene-1, hexene and the like may be copolymerized with the polymer.
It may also be a mixture. As polyamide, nylon-6, nylon-66, nylon-612, nylon-12,
Examples include nylon-46, nylon-11, aromatic nylon and amorphous nylon. It may be a homopolymer or a copolymer, or a mixture thereof. Examples of polyesters include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and the like, or a mixture thereof. The content of the above three components in the resin composition is not particularly limited, and the resin composition can be blended in any ratio. For example, in the case of multilayer sheets used for carpets, the weight ratio of polyethylene, polyamide and polyester is about 4: 4: 1.

Next, the component (B) epoxy group-containing polyolefin will be described. Here, the epoxy group-containing polyolefin is a random or block copolymer of a compound (unsaturated epoxy compound) containing both an unsaturated bond and an epoxy group and an olefin (ethylene, propylene, etc.), or an unsaturated epoxy compound in the polyolefin. Is graft-copolymerized. Examples of unsaturated epoxy compounds include glycidyl methacrylate.
(GMA), glycidyl acrylate (GA), allyl glycidyl ether, the following formula (Formula 1):

[0007]

[Chemical 1] (In the formula, R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Ar represents at least one glycidyloxy substituent.
Having 6 to 20 carbon atoms, which may have other substituents
Is an aromatic hydrocarbon group, and n represents an integer of 1 to 4)
And a glycidyl compound represented by In the above formula (Formula 1), R is preferably a hydrogen atom or CH.
₃ and Ar is preferably a mononuclear aromatic hydrocarbon group having 6 to 10 carbon atoms (alkyl-substituted or not) having 1 or 2 glycidyloxy substituents or a bisphenol A residue. Other optional substituents on the aromatic ring include alkyl groups such as methyl and ethyl groups, and halogen atoms.
Among them, a glycidyl compound represented by the following formula (Formula 2) is particularly preferable.

[0008]

[Chemical 2] (In the formula, R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, preferably a hydrogen atom or a methyl group.) Such a glycidyl compound is described in, for example, JP-A-60-1.
It can be manufactured by the method shown in Japanese Patent No. 30580.

The compound of R = H in the above formula (Formula 2) is commercially available from Kanegafuchi Chemical Industry Co., Ltd.

Next, in the case of a graft copolymer, the base polyolefin is a polymer or copolymer containing at least one selected from polyethylene, polypropylene and ethylene-containing copolymers, or a mixture thereof. . As polyethylene, HDPE, LDPE, LLDP
Either E or VLDPE can be used, or they can be used together. Homopolymer as polypropylene,
Alternatively, any of other components such as a random copolymer and a block copolymer with ethylene or the like may be used, and these may be used in combination. Examples of the ethylene-containing copolymer include ethylene-propylene rubber (EPR), ethylene-butadiene rubber (EBR), ethylene-propylene-diene terpolymer (EPDM), ethylene-ethyl acrylate copolymer (EEA). ), Ethylene-vinyl acetate copolymer (EVA)
Etc. can be used, and these can also be used together.

The above-mentioned reaction between the polyolefin and the unsaturated epoxy compound can be carried out by either a solution method or a melt-kneading method, preferably a melt-kneading method. Further, as a catalyst, a usual radical polymerization catalyst (for example, an organic peroxide such as benzoyl peroxide) can be used. In this reaction, the unsaturated epoxy compound is graft-polymerized with the polyolefin. Generally, 70-95%, especially 80-90%, of the unsaturated epoxy compound used is actually grafted. It is generally preferred to have 0.1 to 25 parts by weight of unsaturated epoxy compound grafted to 100 parts by weight of polyolefin.

The details of the reaction between the glycidyl compound represented by the above formula (Formula 1) and the polyolefin can be as described in Japanese Patent Application No. 3-166231.

The amount of the unsaturated epoxy compound blended with the olefin or the polyolefin is 0.1 to 30 with respect to 100 parts by weight of the olefin or the polyolefin.
Parts by weight, preferably 0.3 to 10 parts by weight. When the amount of the unsaturated epoxy compound is less than 0.1 part by weight, the copolymerization reaction is difficult to be sufficiently achieved, while when it is more than 30 parts by weight, gelation occurs between the modified polyolefin and the component (A) obtained. It tends to occur and the moldability tends to deteriorate.

As the component (B), the above-mentioned epoxy group-containing polyolefin may be used alone or in combination of two or more kinds.

The component (B) epoxy group-containing polyolefin is an unmodified polyolefin (epoxy group-free polyolefin such as EPR, EBR, EPDM, EEA, EVA, etc.) in an amount of up to 80% by weight of the whole component (B). Can be included.

The component (B) is blended in an amount of 5 to 50 parts by weight with respect to 95 to 50 parts by weight of (A), preferably 10 to 40 parts by weight with respect to 90 to 60 parts by weight of (A). If the amount of (B) is less than the above range, the compatibilization of the three components will be poor, and if it is too large, not only gelation will occur, but also the cost balance will deteriorate.

As the component (C) polyethylene, any of the above-mentioned high-density polyethylene (HDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE) and ultra-low-density polyethylene (VLDPE) can be used. Can also be used together.

Component (C) is 5 to 90 parts by weight, preferably (A) + (B) 95 to 15 parts by weight, based on the total of 95 to 10 parts by weight of (A) and (B). Add 5 to 85 parts by weight. If the amount of (C) is too small, it cannot be used as recycled polyethylene, and if it is too large, the recycling efficiency decreases.

In the method of the present invention, the above-mentioned (A), (B) and (C) are melt-kneaded. The order of adding each component is not particularly limited. For example, (B) is added to (A) and melt-kneaded, and then (C) is added and melt-kneaded. The addition order of (B) and (C) is reversed.
(A), (B) and (C) are simultaneously melt-kneaded,
Any method such as melt-kneading (B) and (C) and then adding (A) thereto and melt-kneading can be employed.

The melt-kneading can be carried out using a known method, for example, a single-screw or twin-screw extruder, a Banbury mixer, a kneading roll, a Brabender, a kneader, a Henschel mixer, a batch kneader and the like. The melt-kneading conditions are not particularly limited, but usually 200 to 300 ° C., preferably 220
It is carried out at ˜260 ° C. for 1 to 60 minutes, preferably 1 to 20 minutes.

In addition to the above-mentioned components, conventional additives,
For example, pigments, dyes, fillers, reinforcing materials, heat stabilizers, light stabilizers, antioxidants, plasticizers, flame retardants, antistatic agents, mold release agents, foaming agents, nucleating agents and the like may be added.

The regenerated resin composition thus obtained is excellent in moldability, mechanical properties, cold resistance and the like, because the respective components are well compatibilized. Therefore, it can be preferably used for applications such as interior and exterior parts of automobiles and home electric appliance parts.

[0023]

The present invention will be described in more detail by the following examples.

The raw materials used in each example and comparative example are as follows. (A) Resin composite: A three-layer sheet (weight ratio of each component: 4: 4: 1) of a nylon pile carpet obtained by sequentially laminating polyethylene, polyamide and polyester was ground and used. Hereinafter, this is referred to as H-1. (B) Epoxy group-containing polyolefin: Each was manufactured as follows. M-PO-1: Linear low density polyethylene (LLDPE) (G 5391; Nippon Unicar Co., Ltd., melt flow rate (MFR) (19
Measured at 0 ° C. and a load of 2160 g) 60.0 g / 10 min) 100 parts by weight, the following formula (Formula 3):

[0025]

[Chemical 3] 2 parts by weight of a glycidyl group-containing unsaturated compound (manufactured by Kanegafuchi Chemical Industry Co., Ltd., hereinafter abbreviated as AXE) and 0.03 part by weight of Perhexin 25B (manufactured by NOF Corporation) as a peroxide catalyst. Was added and dry-blended with a Henschel mixer, and then melt-kneaded using a single-screw extruder (diameter 30 mm, L / D = 25) at 200 ° C. and 60 rpm to cause a reaction. The obtained epoxy group-containing polyethylene had an AXE graft ratio of 1.5% by weight and an MFR (190 ° C., 2160 g load) of 50.0 g / 10 minutes. M-PO-2: Low Density Polyethylene (LDPE) (G 8360; Nippon Unicar Co., Ltd., MFR (190 ° C, 2160g load) 65.0g
/ 10 minutes) 2 parts by weight of AXE and 0.03 parts by weight of Perhexin 25B (manufactured by NOF CORPORATION) as a peroxide catalyst were added to 100 parts by weight, and after dry blending with a Henschel mixer, a single screw extruder (diameter: 30mm, L / D = 2
The reaction was carried out by melt-kneading the above (5) under the conditions of 200 ° C. and 60 rpm. The epoxy group-containing polyethylene obtained had an AXE graft ratio of 1.6% by weight and an MFR (19
It was 52.5 g / 10 minutes. M-PO-3: Ethylene-Propylene Rubber (EPR) (P0180; manufactured by Mitsui Petrochemical Co., Ltd., MFR (230 ° C, 2160g load)
8.0 g / 10 minutes) 2 parts by weight of AXE and 0.03 parts by weight of Perhexin 25B (manufactured by NOF CORPORATION) as a peroxide catalyst were added to 100 parts by weight, dry blended with a Henschel mixer, and then a single screw extruder. (Diameter 30 mm, L /
The reaction was carried out by melt-kneading (D = 25) at 200 ° C. and 60 rpm. The epoxy group-containing polyolefin obtained had an AXE graft ratio of 1.8% by weight and an MFR of
(230 ° C., 2160 g load) 3.5 g / 10 minutes. M-PO-4: Ethylene-butadiene rubber (EBR) (EBM2041P;
Made by Nippon Synthetic Rubber Co., Ltd., 100 parts by weight of MFR (230 ° C., 2160 g load) 6.0 g / 10 minutes), 2 parts by weight of AXE and 0.03 parts by weight of Perhexin 25B (made by NOF CORPORATION) as a peroxide catalyst. After adding and dry blending with a Henschel mixer, a single screw extruder (diameter 30 m
m, L / D = 25), and the reaction was carried out by melt-kneading at 200 ° C. and 60 rpm. The obtained epoxy group-containing polyolefin has an AXE graft ratio of 1.4% by weight,
The MFR (230 ° C., load of 2160 g) was 2.3 g / 10 minutes. M-PO-5: Ethylene-butadiene rubber (EBR) (EBM2041P;
Made by Nippon Synthetic Rubber Co., Ltd., 100 parts by weight of MFR (230 ° C., 2160 g load) 6.0 g / 10 minutes), 2 parts by weight of glycidyl methacrylate (GMA) and Perhexin 25B as a peroxide catalyst (made by NOF CORPORATION) 0 After adding 0.03 part by weight and dry blending with a Henschel mixer, 200 using a single screw extruder (diameter 30 mm, L / D = 25)
The reaction was carried out by melt-kneading at 60 ° C. and 60 ° C. The epoxy group-containing polyolefin obtained is GMA
The graft ratio was 1.3% by weight and MFR (230 ° C., 2160 g load) was 3.1 g / 10 minutes. M-PO-6: Ethylene-glycidyl methacrylate (GM
A) Random copolymer (BF-E; manufactured by Sumitomo Chemical Co., Ltd., M
FR (190 ° C, 2160g load) 2.0g / 10min, GMA content 12% by weight) Unmodified polyolefin used as (B): EEA: ethylene-ethyl acrylate copolymer, DPDJ
6169; manufactured by Nippon Unicar Co., Ltd., EBR: ethylene-butadiene rubber, EBM2041P; manufactured by Nippon Synthetic Rubber Co., Ltd., EPR: ethylene-propylene rubber, P0180; manufactured by Mitsui Petrochemical Co., Ltd., (C) Polyethylene: LDPE-1: low Density polyethylene, DNDV0405; Nippon Unicar Co., Ltd., MFR (190 ℃, 2160g load) 32.0
g / 10 minutes, LDPE-2: low density polyethylene, NUC-8009; manufactured by Nippon Unicar Co., Ltd., MFR (190 ° C, 2160g load) 9.0
g / 10 minutes. Examples 1 to 17 and Comparative Examples 1 to 8 Components (A) and (B) were dry blended in the weight ratios shown in Tables 1 and 2, and then twin-screw extruder (diameter 30 mm) at 280 ° C. and 300 rpm. Were melt-kneaded and pelletized under the conditions. This was used as a masterbatch (hereinafter referred to as M / B).

Next, the M / B and the component (C) produced above were dry blended in the weight ratios shown in Tables 1 and 2, and then 240 ° C. in a single-screw extruder (diameter 30 mm).
The mixture was melt-kneaded and pelletized at 00 rpm. The obtained pellets were press-molded at 240 ° C. and subjected to the following physical property evaluation test. The results are shown in Tables 1 and 2. (1) Surface Releasability 100 pieces of 1 mm × 1 mm squares were attached to the surface of the test piece with a razor, cellophane tape (manufactured by Nichiban Co., Ltd.) was attached to the squares, and then peeled off. Of the 100 squares, the number of squares remaining on the test piece that did not adhere to the cellophane tape was counted. The larger the number, the better the peeling resistance. (2) Low temperature foldability At −30 ° C., a sheet of 10 × 100 × 1 mm was folded and completely folded at 0 points, partially broken at 1 point, and not broken at all. Was 2 points. The test was performed on 5 samples and evaluated as a total of 10 points. (3) Elongation at break Measured at 23 ° C. according to ASTM D-638.

[0027]

[Table 1]

[0028]

[Table 2]

[0029]

EFFECTS OF THE INVENTION According to the present invention, it is possible to provide a method for obtaining a recycled resin composition having excellent physical properties such as moldability, mechanical strength and cold resistance from the recovered resin composite.

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Claims (1)

[Claims] 1. A method for obtaining a recycled resin composition from a resin composite containing polyethylene, polyamide and polyester, comprising: (A) 95 to 50 parts by weight of a resin composite containing polyethylene, polyamide and polyester; and (B) containing an epoxy group. 5 to 50 parts by weight of polyolefin and
A method comprising melt-kneading 5 to 90 parts by weight of (C) polyethylene with respect to a total of 95 to 10 parts by weight of (A) and (B).