JPH05202233A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a new thermoplastic resin composition which is very good in the balance among various properties such as moldability, rigidity, heat resistance, impact resistance, oil resistance, chemical resistance and water resistance and can give a molding such as a film or a sheet excellent in appearance and trans-parency by mixing a reactive monomer containing a specified functional group so that the dispersed particles may be uniformly microdispersed with their diameters of 1mum or smaller. CONSTITUTION:The title composition comprises 100 pts.wt. resin composition comprising 5-95wt.% polyolefin and 95-5wt.% aromatic polyester and/or polyamide, 0.1-20 pts.wt. at least either a beta-carboxyalkyl acrylate monomer or an alkylureido monomer, and 0.01-10 pts.wt. organic peroxide.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel thermoplastic resin composition which can be used as a molded product, a sheet, a film or the like by injection molding, extrusion molding or the like. More specifically, it relates to a composition in which the compatibility of the polyolefin with the polyester and / or the polyamide is remarkably improved.

[0002]

2. Description of the Related Art Polyolefin has a good moldability, toughness,
Since it has excellent water resistance, organic solvent resistance, chemical resistance, low specific gravity and low cost, it has been widely used for various molded products, films, sheets and the like. However, polyolefins are not so high in heat resistance and rigidity, and it has been desired to further improve these in order to develop new applications. On the other hand, polyester is used in a wide range of fields such as electric and electronic device parts and automobile parts due to its excellent properties. However, since polyester is inferior in impact resistance, particularly notched impact strength, many improvement methods have been conventionally proposed. For example, aromatic polyester is blended with a modified ethylene polymer obtained by graft-polymerizing α, β-unsaturated dicarboxylic acid or a derivative thereof with a copolymer of ethylene and an α-olefin having 3 or more carbon atoms. Although the impact resistance is somewhat improved, it is still insufficient for use in applications where demands for impact resistance are high. However, there is a problem that the appearance is poor. Further, attempts have been made so far to blend a polyethylene and a polyamide to produce a thermoplastic resin having both characteristics. However, this composition generally has poor compatibility, and when a film, sheet, bottle, etc. is formed by extrusion molding, non-uniform phase separation is likely to occur, which significantly impairs the appearance and is insufficient in terms of transparency. I only got it.

[0003]

DISCLOSURE OF THE INVENTION According to the present invention, a dispersion particle diameter of 1 μm is obtained by blending a polyolefin, a polyester and / or a polyamide with an acrylic monomer.
Even if it is formed into a film or sheet, it has a very good balance of physical properties such as moldability, rigidity, heat resistance, impact resistance, oil resistance, chemical resistance, and water resistance. It is an object of the present invention to provide a novel thermoplastic resin composition having excellent appearance and transparency.

[0004]

The present invention provides a resin composition 100 comprising (A) 5 to 95% by weight of polyolefin and (B) 95 to 5% by weight of polyester and / or polyamide.
At least 1 part of the (C) carboxyalkyl acrylate monomer and the allyl ureido monomer based on parts by weight.
The present invention relates to a thermoplastic resin composition comprising 0.1 to 20 parts by weight of a seed monomer and 0.01 to 10 parts by weight of (D) an organic peroxide.

As the polyolefin (A) used in the present invention, for example, ethylene, propylene, butene-1, pentene-1, hexene-1, 3-methylbutene-1, octene-1, etc. Coalescing,
Random or block copolymers, random or block or graft copolymers of a majority weight of these α-olefins with other unsaturated monomers, or oxidation, halogenation or sulfonation of these polymers. Is something
It is at least partially crystalline. Examples of the other unsaturated monomer include acrylic acid, methacrylic acid, maleic acid, itaconic acid, methyl acrylate, ethyl acrylate, methyl methacrylate, maleic anhydride aryl maleic imide, and alkyl maleic imide. Unsaturated organic acids or derivatives thereof, and vinyl acetate,
Vinyl esters such as vinyl butyrate, styrene, aromatic vinyl compounds such as methylstyrene, vinyltrimethylmethoxysilane, vinylsilane such as γ-methacryloyloxypropyltrimethoxysilane, dicyclopentadiene,
A non-conjugated diene such as 4-ethylidene-2-norbornene can be used. In the case of copolymerization, the α-olefin and other monomers are not limited to two types, and may be a plurality of types.

The aromatic polyester (B) used in the present invention is a polyester having an aromatic ring as a chain unit of a polymer and is usually an aromatic dicarboxylic acid (or its ester-forming derivative) and a diol (or its And an ester-forming derivative) as a main component. The aromatic dicarboxylic acid as used herein is usually terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid. Acid, 3,3′-biphenyldicarboxylic acid, 4,4′-diphenyletherdicarboxylic acid, 4,4′-diphenylmethanedicarboxylic acid, 4,4′-diphenylsulfonedicarboxylic acid, 4,4′-diphenylisopropylidenedicarboxylic acid, 1,2-bis (phenoxy) ethane-4,
4'-dicarboxylic acid, 2,5-anthracene dicarboxylic acid, 2,6-anthracene dicarboxylic acid, 4,4'-p
-Terphenylenedicarboxylic acid, 2,5-pyridinedicarboxylic acid and the like, and terephthalic acid can be preferably used. Two or more kinds of these aromatic dicarboxylic acids may be mixed and used. If the amount is small, adipic acid, azelaic acid, sebacic acid, aliphatic dicarboxylic acids such as dodecanedicarboxylic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid may be used in combination with one or more of these aromatic dicarboxylic acids. it can. The diol component is usually ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, 2-methyl-1,3-
Aliphatic diols such as propane diol, diethylene glycol and triethylene glycol, alicyclic diols such as 1,4-cyclohexanedimethanol, and the like, and mixtures thereof are preferable. In addition, as long as it is a small amount, one or more long chain diols having a molecular weight of 400 to 6000, that is, polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol and the like may be copolymerized. Examples of preferred aromatic polyester (B) used in the present invention include polyethylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polyethylene-2,6.
-Naphthalate, polyethylene-1,2-bis (phenoxy) ethane-4,4'-dicarboxylate, copolyester obtained by copolymerizing terephthalic acid with ethylene glycol and 1,4 cyclohexanedimethanol (PET)
-G) and so on.

Examples of the polyamide (B) include polylactams such as nylon 6, nylon 11 and nylon 12, nylon 6,6, nylon 6,10 and nylon 6,
Polyamides obtained from dicarboxylic acids such as 12 and diamines, nylon 6 / 6,6, nylon 6 / 6,1
2, nylon 6/6, 6/6, 10, nylon 6/6,
Examples include copolymerized polyamides such as 6/6, 12 and nylon 6 / 6T (T; terephthalic acid component), or high amino-terminated polyamides such as a mixture thereof.

Next, the reactive monomers having a specific functional group used in the present invention are carboxyalkyl acrylate monomers and allylureido monomers, which have the following structures. Carboxyalkyl acrylate monomer (CA
A) R: (CHX ₂ ) _n (n = 1 to 10) X ₁ : H or CH ₃ X ₂ : H, CH ₃ or a mixture thereof When n = 11 or more among CAA, the effect as a compatibilizer disappears. Therefore, those having n = 1 to 10 are preferable, and among them, β-carboxyethyl acrylate monomer (β-CEA) of the following chemical formula is particularly preferable. _{CH 2 = CH-COO-CH} 2 CH 2 -COOH ( molecular weight: 144) allyl ureido monomer (WAM) (N = 1 or 2)

In the thermoplastic resin composition according to the present invention, the polyolefin (A) is 5 to 95% by weight, and the polyester and / or polyamide (B) is 95 to 5% by weight based on 100 parts by weight of the resin composition. Further, 0.1 to 2 of at least one monomer (C) selected from a carboxyalkyl acrylate monomer and an allylureido monomer is added.
0 parts by weight and 0.01 to 10 parts by weight of (D) organic peroxide must be blended. When the content of the component (A) is less than 5% by weight and the content of the component (B) is more than 95% by weight, moldability, water resistance and chemical resistance are insufficient. Further, the content of the component (A) is more than 95% by weight,
When the content of the component (B) is less than 5% by weight, preferable properties in heat resistance and rigidity cannot be obtained. Also,
Regarding the component (C), when the content is less than 0.1 parts by weight, there is a problem in the compatibility dispersibility of the resin composition, the dispersed particle size is as large as several tens to several hundreds μm, and the appearance and transparency are high. Is insufficient, and when the content of the component (C) is more than 20 parts by weight, the heat resistance, impact resistance, rigidity and the like are remarkably lowered, and a desirable result cannot be obtained. When the amount of organic peroxide used is less than 0.01 parts by weight or more than 10 parts by weight, impact resistance is lowered. Further, if necessary, other thermoplastic resin may be added to the extent that the basic properties are not impaired, for example, saponified ethylene-vinyl acetate copolymer for improving gas barrier properties, or other additives such as dyes. Pigments, stabilizers, plasticizers, antistatic agents, ultraviolet absorbers, antioxidants, lubricants, fillers and the like can also be added.

Further, as an application of the present invention, two or more multi-layer films including a polyolefin layer, a nylon layer, a polyester layer, a saponified ethylene-vinyl acetate copolymer layer and an adhesive layer, for example, a low density polyethylene layer / adhesive layer. / Nylon layer, low-density polyethylene layer / adhesive layer / aromatic polyester layer, low-density polyethylene layer / adhesive layer / nylon layer / adhesive layer / aromatic polyester layer, low-density polyethylene layer / adhesive layer / ethylene-vinyl acetate copolymer Saponified material layer / nylon layer / adhesive layer / aromatic polyester layer,
Low density polyethylene layer / adhesion layer / saponified ethylene-vinyl acetate copolymer layer / adhesion layer / aromatic polyester layer, etc. crushed or granulated with scraps or granulators of β-CEA Or W
By kneading AM, a recovered regenerated product having a uniform composition, good transparency, and superior mechanical strength can be obtained. This reclaimed material can be used as one layer of a multi-layer film or as a material for other molding.

[0011]

EXAMPLES The present invention will be described below with reference to examples.
This is merely an example and the present invention is not limited thereto. The resin composition used in the examples was prepared by thoroughly mixing and stirring predetermined amounts of each component with a super mixer,
Φ mm, L / D = 40, using a co-rotating twin-screw kneader, melt kneading at a preset temperature of 240 ° C., extruding into strands and cutting into pellets. Further, a sheet having a thickness of 0.05 mm was prepared at a cylinder temperature of 240 ° C., a T-die portion temperature of 240 ° C., and a roll cooling temperature of 30 ° C. with a 50 Φmm single-screw extruder.
It was measured by TM-D1003. In addition, with an injection molding machine,
Injection molding was performed at a cylinder temperature of 240 ° C. and a mold cooling temperature of 60 ° C. to prepare a tensile test piece and an Izod impact test piece with a notch. Izod impact (with notch) test is A
STM-D256 and tensile test ASTM-D638
It was measured by. The appearance was visually determined. The results of the blended composition and each characteristic value are shown in Tables 1 to 7.

Examples 1 to 7 Low density polyethylene (LDPE) was used as the component (A), and terephthalic acid and two diol components, ethylene glycol and 1,4-cyclohexanediene, were used as the component (B). Copolyester (PET-G) obtained from methanol and polyethylene terephthalate (PE
T) is used, and as component (C), β-carboxyethyl acrylate (β-CEA) and allylureido (WAM) having an average molecular weight of 345 are used, and 2,5-dimethyl-2,5 is used as the organic peroxide. (Tert-butylperoxy) hexane was used.

Comparative Examples 1 to 7 LDPE was used as the component (A), and PET-G and PET were used as the component (B).

Examples 8 to 11 LDPE is used as the component (A), nylon 6 (Ny6) is used as the component (B), and β-CEA and WAM are used as the component (C). Then, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane was used as the organic peroxide.

Comparative Examples 8 to 11 LDPE was used as the component (A) and Ny6 was used as the component (B).

Examples 12 to 15 LDPE is used as the component (A), PET-G and Ny6 are used as the component (B), and β-CEA and WAM are used as the component (C). Then, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane was used as the organic peroxide.

Comparative Examples 12 to 15 LDPE was used as the component (A), and PET-G and Ny6 were used as the component (B).

Example 16 Thickness ratio of LDPE layer / adhesive layer (olefin type) / PET-G layer = 6
0/10/30 (μ) multilayer film scrap with a total thickness of 100 μ (weight ratio = polyolefin / PET-G
= 67: 33) was crushed and WA was added as the component (C).
M is used and 2,5-dimethyl-2,5 is used as the component (D).
Di (tert-butylperoxy) hexane was used. <Comparative Example 16> The same multilayer film scrap as in Example 16 was used, and the components (C) and (D) were not used.

[0019]

EFFECT OF THE INVENTION The thermoplastic resin composition according to the present invention can be easily processed into molded articles, films, sheets, etc. by the processing methods used for ordinary thermoplastic resin compositions such as injection molding and extrusion molding. The product has a very good balance of molding processability, rigidity, heat resistance, impact resistance, oil resistance, chemical resistance, water resistance, etc., and has excellent appearance and transparency during the molding process such as films and sheets. give. Further, by using the method of producing the composition of the present invention, it becomes possible to recycle and recover scraps of a transparent multilayer film composed of a polyolefin layer and an aromatic polyester layer.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C08L 67/02 LNZ 8933-4J 77/00 LQS 9286-4J

Claims (4)

[Claims] 1. A resin composition comprising (A) 5 to 95% by weight of polyolefin and (B) polyester and / or 95 to 5% by weight of polyamide, and (C) to 100 parts by weight of the resin composition.
0.1-2 at least one monomer selected from carboxyalkyl acrylate monomer and allylureido monomer
A thermoplastic resin composition comprising 0 parts by weight and 0.01 to 10 parts by weight of (D) an organic peroxide. 2. A polyolefin is a homopolymer of α-olefins such as ethylene, propylene, butene-1, pentene-1, hexene-1, 3-methylbutene-1, octene-1, and a copolymerization of random or block copolymers. Random, block or graft copolymers of a majority of these α-olefins and other unsaturated monomers, or those obtained by oxidation, halogenation or sulfonation of these polymers, at least partially The thermoplastic resin composition according to claim 1, which exhibits crystallinity. 3. The aromatic polyester is polyethylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polyethylene-2,6-naphthalate, polyethylene-1,2-bis (phenoxy) ethane-4,4′-dicarboxylate. The thermoplastic resin composition according to claim 1 or 2, which is a copolyester (PET-G) obtained by copolymerizing terephthalic acid with ethylene glycol and 1,4 cyclohexanedimethanol. 4. The polyamide is nylon 6, nylon 1
1, polylactams such as nylon 12, nylon 6,
Polyamides obtained from dicarboxylic acids such as 6, nylon 6,10, nylon 6,12 and diamine, nylon 6 / 6,6, nylon 6 / 6,12, nylon 6 /
Copolymerized polyamides such as 6,6 / 6,10, nylon 6 / 6,6 / 6,12, nylon 6 / 6T (T; terephthalic acid component), or high amino-terminated polyamides such as a mixture thereof. Item 3. The thermoplastic resin composition according to Item 1, 2 or 3.