JPH0539330A - Production of thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To produce a thermoplastic resin composition having the properties of both polyamide and polyolefin and excelling in mechanical properties, surface properties and environmental properties. CONSTITUTION:The process for producing the objective thermoplastic resin composition by mixing a polyamide (a) with a polyolefin (b), at least one polymerizable compound (c) containing at least one glycidyloxy group in the molecule and a polymerization initiator (d) in such amounts that the (a)/(b) weight ratio is 1/99 to 99/1, 0.01-5 pts.wt. component (c) is present per 100 pts.wt. total of components (a) and (b), and 0.001-0.5 pt.wt. component (d) is present per 100 pts.wt. total of components (a) and (b), and melt-kneading the mixture at 200-300 deg.C.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a thermoplastic resin composition containing a polyamide and a polyolefin. More specifically, polyamide and polyolefin are well compatible with each other and have excellent mechanical properties such as impact resistance and mechanical strength, water deterioration resistance, chemical resistance, heat resistance, and surface properties such as appearance. The present invention relates to a method for producing a thermoplastic resin composition suitable for exterior products, electrical components, home appliances, sports goods, furniture, office articles, and other molded articles.

[0002]

2. Description of the Related Art Polyamide is a resin having excellent heat resistance, mechanical strength and insulating properties. On the other hand, polyolefin has the features of being lightweight and excellent in impact resistance, and having good environmental characteristics such as moldability, water resistance, and chemical resistance. Therefore, attempts have been made to prepare a resin composition having the advantages of both by blending a polyamide and a polyolefin, each of which has excellent characteristics. However, since polyamide and polyolefin have poor compatibility with each other, there is a problem that impact resistance and mechanical strength of the thermoplastic resin composition containing them are deteriorated. Therefore, for the purpose of improving the compatibility between the polyamide and the polyolefin, the polyamide is blended with a polyolefin obtained by adding an unsaturated carboxylic acid or a derivative thereof, particularly an anhydride of an unsaturated dicarboxylic acid such as maleic anhydride (MAH). It is known that the melt-kneading is performed to improve the compatibility dispersibility of polyamide and polyolefin, improve impact resistance, and prevent deterioration due to water absorption. However, in this method, when the dicarboxylic acid is added to the polyolefin, alteration and deterioration occur due to crosslinking of the polyolefin, and the physical properties are not sufficiently improved by compatibilization. In addition, the unreacted acid added to the polyolefin reacts with the polyamide to cause coloration, which may impair the appearance. Therefore, an object of the present invention is to provide a method for producing a thermoplastic resin composition in which polyamide and polyolefin are well compatibilized and which have excellent mechanical properties, surface properties and environmental properties.

[0003]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that polyamide and polyolefin contain a specific polymerizable compound different from the unsaturated compound such as maleic anhydride and a polymerization initiator. By blending with and melt-kneading, it was found that the polyamide and the polyolefin are well compatibilized, and a thermoplastic resin composition having excellent mechanical properties, surface properties and environmental properties can be obtained, and the present invention has been reached. It was done. That is, the present invention uses (a) a polyamide, (b) a polyolefin, (c) one or more polymerizable compounds having at least one glycidyloxy group in the molecule, and (d) a polymerization initiator. The mixing ratio of the component (a) and the component (b) is (a) / weight ratio.
Under the condition of (b) = 1/99 to 99/1, the component (c) was added to the total of 100 parts by weight of (a) + (b), and
01 to 5 parts by weight are added, and 0.001 to 0.5 parts by weight of the component (d) is added to 100 parts by weight of (a) + (b), and
The present invention provides a method for producing a thermoplastic resin composition, which comprises melt-kneading at a temperature of 00 to 300 ° C.

Hereinafter, the method for producing the thermoplastic resin composition of the present invention will be described in detail. The (a) polyamide of the thermoplastic resin composition component used in the present invention is a thermoplastic resin having an amide bond, and examples thereof include hexamethylenediamine, decamethylenediamine, dodecamethylenediamine,
2,2,4- or 2,4,4-trimethylhexamethylenediamine, 1,3- or 1,4-bis (aminomethyl) cyclohexane, bis (p-aminocyclohexylmethane), m- or p-xylylenediene Aliphatic, alicyclic or aromatic diamines such as amines and aliphatic, alicyclic or aromatic dicarboxylic acids such as adipic acid, suberic acid, sebacic acid, cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid Polyamides produced from, 6-aminocaproic acid, polyamides produced from aminocarboxylic acids such as 11-aminoundecanoic acid, 12-aminododecanoic acid, ε-caprolactam, ω
-Polyamides produced from lactams such as dodecalactam, copolyamides composed of these components, mixtures of these polyamides and the like.

Specific examples of the polyamide include nylon 6, nylon 66, nylon 610, nylon 9, nylon 6/66, nylon 66/610, nylon 6 /
11, nylon 6/12, nylon 12, nylon 4
6, amorphous nylon and the like. Among these,
Nylon 6 and nylon 66, which have particularly good rigidity and heat resistance, are preferable. In the present invention, the molecular weight of the polyamide is not particularly limited, but polyamides having a relative viscosity [η] of 0.5 or more, measured in 98% sulfuric acid based on JIS K6810, of which 2.0 or more are preferably used.

The (b) polyolefin as a component of the thermoplastic resin composition used in the present invention means ethylene and propylene, butene-1, hexene-1,3-methylbutene-.
Homopolymers of α-olefins having 3 or more carbon atoms such as 1,4-methyl-pentene-1, heptene-1, octene-1, and decene-1, random of these two or more monomers,
Copolymers such as blocks and grafts, mixtures thereof, copolymers such as random, block and graft copolymers of ethylene or α-olefins having 3 or more carbon atoms with other unsaturated monomers. Among these polyolefins,
A homopolymer of ethylene or propylene, a copolymer of ethylene and propylene, and a copolymer of ethylene or propylene and another α-olefin are preferable. Particularly preferred is a copolymer of propylene and ethylene having an ethylene content of 20% by weight or less, and such polypropylene usually has a melt flow rate (MFR, JISK7210, load of 2.16 kg) of about 0.1 to 200 g / 10 minutes. , 230 ° C.). As a homopolymer of ethylene, high pressure low density polyethylene (LDPE) and low pressure high density polyethylene (H
DPE) is preferable, and linear low-density polyethylene (LLDPE) known as a low-pressure ethylene copolymer can also be used.

In the present invention, the polyolefin also includes an olefin elastomer. Here, the olefin elastomer means ethylene, propylene, butene-
Α-, such as 1, hexene-1, 4-methyl-pentene-1
It means a copolymer rubber of two or more kinds of olefins, or a copolymer of α-olefin and another kind of monomer. Specific examples of the copolymer rubber of two or more kinds of α-olefins include ethylene-propylene copolymer rubber (EPR), ethylene-butadiene copolymer rubber (EBR) and ethylene-propylene-diene copolymer. Coated rubber (EPDM) can be mentioned.

In the present invention, in order to improve the compatibilization of the above components (a) and (b), one or more polymerizable compounds (c) having at least one glycidyloxy group in the molecule and a polymerization initiator. Use (d). Examples of the preferable (c) polymerizable compound of the thermoplastic resin composition component in the present invention include a glycidyl compound having an unsaturated group capable of copolymerizing with an olefin and a glycidyloxy group in the molecule, and specifically, Unsaturated glycidyl esters,
In addition to unsaturated glycidyl ethers, those represented by the following general formula (1) having an acrylamide group and an epoxy group are preferably used.

[0009]

[Chemical 2]

[In the formula, R represents a hydrogen atom or a carbon number of 1 to 6]
Of Ar, Ar is an aromatic hydrocarbon group having 6 to 20 carbon atoms and having at least one glycidyloxy group, and n represents an integer of 1 to 4. Among the glycidyl compounds represented by the above general formula, a glycidyl compound represented by the following general formula (2) is particularly preferable.

[0011]

[Chemical 3]

[In the formula, R represents a hydrogen atom or a carbon number of 1 to 6]
Is an alkyl group. Such a glycidyl compound can be produced, for example, by the method described in JP-A-60-130580, and these polymerizable compounds can be used alone or in combination of two or more kinds.

As the (d) polymerization initiator of the thermoplastic resin composition component used in the present invention, various peroxides and diazo compounds used as catalysts in ordinary radical polymerization can be used. Specifically, benzoyl peroxide, lauroyl peroxide, ditertiary butyl peroxide, acetyl peroxide, tert-butyl peroxybenzoic acid, dicumyl peroxide, peroxybenzoic acid, peroxyacetic acid, tert-butyl peroxypivalate,
Examples thereof include peroxides such as 2,5-dimethyl-2,5-ditertiarybutylperoxyhexyne and diazo compounds such as azobisisobutyronitrile. These may be used alone or in combination of two or more kinds. You can also do it.

In the present invention, each of the above components, that is, (a) polyamide and (b) polyolefin as main resin components, is compounded with a specific amount of (c) a polymerizable compound and (d) a polymerization initiator. According to the present invention, the component (a) and the component (b) are satisfactorily compatibilized with each other and have the characteristics of polyamide and polyolefin. The thermoplastic resin composition can be obtained. As the melt-kneading method, various conventionally known methods can be adopted. That is, a batch kneading method using a batch type kneading machine, a kneading method using a kneading machine such as a Banbury mixer, a Brabender, a kneading roll, a single-screw extruder, or a twin-screw extruder can be exemplified. The kneading temperature is in the range of 200 to 300 ° C, preferably 210 to 250 ° C. If the kneading temperature is lower than 200 ° C, the compatibility of the polyamide and the polyolefin is insufficient, and if the temperature exceeds 300 ° C, the original properties of the resin may be impaired.

In carrying out the present invention, the kneading order of each component is not particularly limited, and various orders can be adopted. For example, (i) the component (a), the component (b) and the component (c) and the component (d), the batch-type kneader described above,
Brabender or a method of batch-kneading into a kneader such as a single-screw or twin-screw extruder at the same time, and (ii) component (a), component (b) and component (d) are simultaneously charged into the extruder. After that, the component (c) is charged from the middle of the barrel and kneaded. (Iii) The component (b), the component (c), and the component (d) are simultaneously charged into the extruder, and then the component ( A method of charging a) halfway, a method of charging component (a) and component (b) into the extruder at the same time, and then charging component (c) and component (d) halfway.

In the present invention, the mixing ratio of the above components is such that the weight ratio of the component (a) (polyamide) and the component (b) (polyolefin) is 1/99 to 99/1, preferably 5 /.
It is 95 to 95/5. If the weight ratio is less than 1/99, the amount of polyamide is too small, and if it is 99/1, the amount of polyolefin is too small, so that a thermoplastic resin composition having both properties cannot be obtained.

The component (c) (polymerizable compound) is the total amount of the components (a) and (b) (that is, (a) +
(B)) 0.01 to 5 parts by weight, preferably 0.1 to 3 parts by weight, based on 100 parts by weight. If it is less than 0.01 part by weight, the effect of improving the compatibility of the polyamide and the polyolefin by the use of the polymerizable compound is not recognized, and if it exceeds 5 parts by weight, the original properties of the resin of the polyamide and the polyolefin may be impaired.

In the present invention, the effect of improving the compatibility is recognized only by melt-kneading the above-mentioned component (a), component (b) and component (c), but this is not always sufficient, and in addition to these components, Add (d) (polymerization initiator) to (a) +
When it is blended in an amount of 0.001 to 0.5 parts by weight, preferably 0.005 to 0.1 parts by weight, based on 100 parts by weight of the total amount of (b), the effect of further improving the compatibility can be seen, and the thermoplasticity combining the characteristics of polyamide and polyolefin is obtained. A resin composition can be obtained. The use of component (d) in an amount exceeding 0.5 part by weight is economically disadvantageous.

In the present invention, in addition to the above-mentioned substances, other substances such as fillers and reinforcing materials such as glass fibers, heat stabilizers and light stabilizers are further used for the purpose of strengthening and modifying the thermoplastic resin composition. , Flame retardant, plasticizer, antistatic agent, foaming agent,
A nucleating agent or the like can be added and compounded.

[0020]

According to the present invention, when a composition of (a) polyamide and (b) polyolefin is produced, specific amounts of (c) a polymerizable compound and (d) a polymerization initiator are blended and melt-kneaded. Although it relates to a method for producing a thermoplastic resin composition, according to the present invention, a polyamide and a polyolefin are well compatibilized with each other to obtain a resin composition having excellent mechanical properties, surface properties and environmental properties having both properties. Be done. The reason why the present invention produces such an effect is not always clear, but the polymerizable compound having a glycidyl group, and that the polyamide and the polyolefin are compatibilized through the interaction between the polymerizable compound and the polymerization initiator. It is believed that Moreover, since the polymerizable compound used for compatibilization in the present invention does not contain an acid component for coloring the polyamide, appearance deterioration of the resin composition due to coloring does not occur unlike conventional methods. In addition, the present invention is a method having a very high practicability because it can be industrially carried out easily because the resin composition can be obtained by kneading the above-mentioned respective components at once and the cost associated with the kneading is low.

[0021]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples. In each of the examples and comparative examples, the following materials were used as raw materials and additives. [1] Polyamide Nylon 6: [M28, A28, Melt Flow Rate (MFR) 20 g / 10 min] [2] Polyolefin (1) Polypropylene homopolymer PP: [Y201, Tonen Chemical Co., Melt Flow Rate (MFR) ) 1.5 g / 10 minutes] (2) ethylene-propylene copolymer rubber EPR: [EP912P manufactured by Japan Synthetic Rubber Co., Ltd., melt flow rate (MFR) 7.5 g / 10 minutes] (3) ethylene-butadiene copolymer rubber EBR: [EBM2041P manufactured by Japan Synthetic Rubber Co., Ltd., melt flow rate (MFR) 5.5 g / 10 min] [3] Polymerizable compound AXE: glycidyl compound represented by the following chemical formula [manufactured by Kaneka Corporation]

[0022]

[Chemical 4]

[4] Polymerization initiator POX: Perhexin 25B [made by NOF Corporation]

Examples 1 to 10 and Comparative Examples 1 to 12 Polyamide (nylon 6) and polyolefin (PP,
EPR or EBR) and a polymerizable compound (AXE),
A polymerization initiator (POX) was used in a ratio shown in Table 1, and this was melt-kneaded at a temperature shown in Table 1 by the kneading procedure shown below or to obtain a resin composition (however, in Comparative Examples. Maleic anhydride (MAH) was used instead of AXE.). [Kneading procedure] A polyamide, a polyolefin, a polymerizable compound and a polymerization initiator are simultaneously charged into a uniaxial extruder having a diameter of 60 mm,
The resin composition was obtained by batch kneading. Using a twin-screw extruder having a diameter of 45 mm, which has a first supply port on the upstream side with respect to the outlet direction of the screw and a second supply port (a position of 1/3 to the upstream side of the screw from the outlet), The polyamide, the polyolefin and the polymerization initiator are fed from the first feed port, and the polymerizable compound is fed into the second feed port.
A resin composition was obtained by feeding midway from the supply port. Using the above twin-screw extruder, polyolefin, a polymerizable compound and a polymerization initiator were fed from the first feed port, and polyamide was fed midway from the second feed port to obtain a resin composition. The melt flow rate (MFR, 275 ° C., 2.16 kg load) of the thermoplastic resin composition thus obtained, 23 ° C.
And Izod impact strength at -30 ° C, flexural modulus,
The heat distortion temperature and water absorption were measured. The results are also shown in Table 1.

[0025]

[Table 1]

[0026]

[Table 2]

[0027]

[Table 3]

The methods for measuring the physical properties shown in Table 1 above are as follows. (1) Melt flow rate: Measured according to JIS K7210. (2) Izod impact strength: Measured according to JIS K7110. (3) Flexural modulus: Measured according to JIS K7203. (4) Heat distortion temperature: Measured according to JIS K7207. (5) Water absorption rate: The water content was measured by the Karl Fischer method for a sample in which water absorption reached equilibrium in a thermostatic chamber at 23 ° C and a humidity of 50%.

As is apparent from Table 1, the thermoplastic resin composition obtained by the method of the present invention was prepared by using MA instead of AXE.
Compositions using H (Comparative Examples 2-5 and Comparative Example 7),
Compared to the compositions of Comparative Examples 10-12 lacking POX, the compositions consisting only of polyamide and polyolefin (Comparative Examples 1, 6 and 8) and the polyolefin (Comparative Example 9),
Good Izod impact strength, flexural modulus, heat distortion temperature, and excellent water resistance. Further, the compositions of Examples 1 to 10 had no color and had a good appearance, but in Comparative Examples 2 to 5 and Comparative Example 7 in which MAH was used, coloring of the resin compositions was observed.

[0030]

As described in detail above, in the present invention, when a composition of a polyamide and a polyolefin is produced, a polymerizable compound having a glycidyloxy group and a polymerization initiator are added in order to improve the compatibility of the two. Provided is a method for producing a thermoplastic resin composition to be used, wherein the resin composition obtained by the method of the present invention has impact resistance, heat resistance, chemical resistance,
It has excellent mechanical strength and insulation, and has a good appearance. Such a thermoplastic resin composition of the present invention is used as various engineering plastics, especially as a resin composition for interior and exterior parts of automobiles, home electric appliance parts, industrial material parts, sports equipment, furniture, office supplies, packaging materials and the like. It is suitable.

Front page continuation (72) Koichi Yokoyama, 1-3-1, Nishitsurugaoka, Oi-cho, Iruma-gun, Saitama Prefecture Tonen Corporation Research Institute (72) Eiji Kuchiki 1-chome, Nishitsurugaoka, Oi-cho, Iruma-gun, Saitama Prefecture No. 1 Tonen Co., Ltd. Research Institute (72) Inventor Yuji Fujita 1-3-3 Nishitsurugaoka, Oi-cho, Iruma-gun, Saitama Inside Tonen Research Institute

Claims (2)

[Claims] 1. Use of (a) a polyamide, (b) a polyolefin, (c) one or more polymerizable compounds having at least one glycidyloxy group in the molecule, and (d) a polymerization initiator. The mixing ratio of the component (a) and the component (b) is (a) / (b) = 1/99 to 99/1 in weight ratio.
Under the condition that component (c) is (a) + (b) in total 1
0.01 to 5 parts by weight per 100 parts by weight of component (d)
0.001 to 100 parts by weight of (a) + (b)
A method for producing a thermoplastic resin composition, which comprises blending 0.5 part by weight and melt-kneading at a temperature of 200 to 300 ° C. 2. The component (c) has the following general formula: [In the formula, R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Ar represents an aromatic hydrocarbon group having 6 to 20 carbon atoms having at least one glycidyloxy group, and n
Represents an integer of 1 to 4. ] The manufacturing method of the thermoplastic resin composition of Claim 1 which is an unsaturated glycidyl compound represented by these.