JP2622614B2 - Thermoplastic resin composition and method for producing the same - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a thermoplastic resin composition comprising a modified polyolefin polymer and a polyamide, and a method for producing the same. More specifically, the present invention relates to a resin composition having excellent compatibility, mechanical properties, heat resistance, and the like, and a method for producing the same.

[Conventional technology and problems]

Mechanical properties, heat resistance, dyeability,
In order to improve the paintability, etc., on the other hand, in order to improve the water absorption of the polyamide resin and the reduction in various physical properties due to this, a resin composition having both characteristics by blending / alloying both resins. Attempts to obtain it have received attention in recent years.
However, since the compatibility between the polyolefin resin and the polyamide resin is generally low, even if the two are simply blended by a method such as melt-kneading, they are not well compatible with each other, resulting in poor mechanical strength and poor surface properties.

In order to improve the compatibility of both, a method is known in which an unsaturated carboxylic anhydride is copolymerized with a polyolefin to modify the polyolefin. As the unsaturated carboxylic acid, maleic anhydride and its analogs are generally used.For example, JP-A-60-177073 discloses an improved resin composition obtained by graft-polymerizing an unsaturated carboxylic acid to a polyolefin resin. A method of obtaining is disclosed. JP-A-62-241938 discloses a process for producing a resin composition comprising an unsaturated carboxylic acid-modified polyolefin, a polyolefin, a polyamide and a metal compound.

Thus, maleic anhydride and its analogs are used as modifiers in conventional modified polyolefin resins. However, a resin composition produced using such a modified polyolefin resin does not always show a sufficient improvement in properties, and further improvement in properties is required for practical use.

An object of the present invention is to provide a new modifier that replaces maleic anhydride and its analogs, and to improve the properties of the obtained resin composition.

[Means for solving the problem]

That is, the first aspect of the present invention is that (A) per 2-1,000 repeating units of olefin, the following general formula (I) (In the formula, Ar represents a C ₆ -C ₂₀ aromatic hydrocarbon group having at least one glycidyloxy group, and R represents a hydrogen atom or a methyl group.) One structural unit having a glycidyl group represented by the following formula: (B) 1-99 parts by weight of a polyamide (provided that (A) + (B)
= 100 parts by weight] A second aspect of the present invention is a method for producing a thermoplastic resin composition characterized by melt-kneading both the components (A) and (B). Each is a content.

 Hereinafter, the present invention will be described in detail.

The modified polyolefin-based polymer as the component (A) of the present invention has the following general formula (I) per 2-1,000, preferably 5-200, repeating units of olefin. (In the formula, Ar represents a C ₆ -C ₂₀ aromatic hydrocarbon group having at least one glycidyloxy group, and R represents a hydrogen atom or a methyl group.) One structural unit having a glycidyl group represented by the following formula: It contains. The structural unit represented by the general formula (I) is an important component of the present invention, and has the following general formula (III) (Wherein, Ar and R are the same as in the case of the general formula (I)). Such a modifying agent can be produced by a method as described in JP-A-60-130580. For example, when 2,6-xylenol and N-methylolacrylamide are used as starting materials, the following structural formula (IV) Can be obtained.

The amide bond in the structural unit of the general formula (I) improves the affinity for the polyolefin in addition to the dyeability and coating properties of the polyolefin. The glycidyl group is expected to react with active hydrogen in the polyamide, and contributes to the improvement in mechanical strength, heat resistance, and compatibility of the resin composition.

In order to balance various properties, the proportion of the structural unit of the general formula (I) contained in the polyolefin is important. If the proportion is less than the above, the properties of the resin composition cannot be sufficiently improved. On the other hand, if the amount is too large, the original properties of the resin composition will be lost, such as loss of thermoplasticity, which is not preferable.

The method for producing the modified polyolefin polymer used in the present invention is not particularly limited, but the following two methods can be suitably used. The first is a graft modification method of a polyolefin resin, wherein (A) a polyolefin and
(B) radical-adding a composition comprising two components with a modifier having a glycidyl group represented by the above general formula (III) using a radical initiator (C). At this time, a solvent that dissolves or swells the polyolefin, for example, tetralin, decalin, toluene, xylene, or chlorobenzene may be used. In addition, the reaction can be performed in a state where the polyolefin resin is melted by using a melt kneading device such as an extruder, a kneader, a heating roll or the like without using a solvent.

The second production method is a method of copolymerizing an olefin monomer and a modifier having a glycidyl group represented by the above general formula (III). The copolymerization method is not particularly limited, and a general radical polymerization method, a cationic polymerization method, an anion polymerization method, a coordination polymerization method using a transition metal, or the like can also be used.

Modified polyolefin polymer used in the present invention,
For example, it can be produced from the following polyolefin or olefin monomer. (polyethylene,
(Poly) propylene, (poly) 1-butene, (poly) 1
-Pentene, (poly) isobutene and the like. In addition, these random and / or block copolymers or mixtures may be used.

The polyamide as the component (B) used in the present invention includes:
Usually called "nylon", acid amide bond (-CONH-)
Can be used as long as it has a repeating unit. Depending on the type of polymerization reaction, (1) reaction by ring-opening polymerization of lactam, (2) reaction of aliphatic diamine with at least one compound selected from aliphatic dicarboxylic acids, acid anhydrides and acid halides thereof By,
(3) Polycondensation of aminocarboxylic acid, and the like.

A specific example is polycaprolactam (nylon-
6), polyhexamethylene adipamide (nylon-6
6), nylon-610, nylon-12, nylon-9, nylon-11 and the like. Further, two or more copolymers may be used, or a mixture of two or more copolymers may be used.

The resin composition of the present invention can be produced by melt-kneading the above-mentioned modified polyolefin polymer (A) and polyamide (B). A known device can be used for the melt kneading. For example, a hot roll, an extruder, a Banbury mixer, a Brabender and the like. The melting temperature and the power required for kneading can be appropriately adjusted depending on the molecular weight of the resin used.

At the time of kneading, a heat stabilizer, an ultraviolet absorber, an antioxidant, a filler, an antistatic agent, a lubricant, a coloring agent, a flame retardant, and an organic / inorganic reinforcing material can be added as required.

[Action / Effect]

According to the method of the present invention, a strong affinity is generated at the interface between the polyolefin and the polyamide, and a composition having mechanical properties such as impact properties and good surface properties can be obtained.
Taking advantage of such features, the resin composition of the present invention can be widely used for molded articles in addition to fibers and films. Injection molding used for ordinary thermoplastics,
A desired molded product can be obtained by applying a method such as extrusion molding, blow molding, or compression molding. These molded articles are useful as various mechanical parts, electric / electronic parts, and the like.

〔Example〕

Hereinafter, the present invention will be described by way of examples, but the present invention is not limited to only these examples.

Reference Example 1: Synthesis of denaturing agent A mixture of 4-acrylamidomethyl-2,6-dimethylphenol 102.6 parts, epichlorohydrin 181 parts and benzyltriethylammonium chloride 2.27 parts at 100 ° C.
Stirred for 0 minutes. The reaction mixture was cooled to 50 ° C, and 147 parts of 5N sodium hydroxide was added dropwise with stirring over 10 minutes, and then stirred at 45 to 50 ° C for 1 hour.

This is cooled to room temperature, and methyl isobutyl ketone 120
And 500 parts of water. The organic layer was washed three times with 300 parts of water, dehydrated with anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to give N- {4- (2,3-epoxypropoxy)-.
3,5-Dimethylphenylmethyl acrylamide was obtained. The epoxy equivalent measured by the method of JIS K 7236 is 271,
Melting point was 90-92 ° C.

Reference Example 2: Synthesis of modified polyolefin polymer 100 parts of polypropylene having an average molecular weight of 5,000, 1 part of the modifier synthesized in Reference Example 1, and benzoyl peroxide 0.1
The portion was extruded and melt-kneaded at 200 ° C. for 1 minute.
When the resulting pellets were measured molded infrared absorption spectrum of the film, absorption due to amide group near 3300 cm ^-1, observed absorption due to an epoxy group in the vicinity of 910 cm ^-1, modifier is introduced I confirmed that.

Example 1 100 parts of modified polypropylene synthesized in Reference Example 2 and 30 parts of nylon-66 were melted and kneaded at 230 ° C. for 1 minute in an extruder. Injection molding temperature 220 from the obtained pellets
Injection molding was performed at 50 ° C and a mold temperature of 50 ° C to obtain a molded product. The surface properties of the molded product were good, and it was found that both resins were well micro-dispersed.

Claims (7)

(57) [Claims] (A) The number of repeating units of an olefin is 2-10.
The following general formula (I) (In the formula, Ar represents a C ₆ -C ₂₀ aromatic hydrocarbon group having at least one glycidyloxy group, and R represents a hydrogen atom or a methyl group.) One structural unit having a glycidyl group represented by the following formula: (B) 1-99 parts by weight of a polyamide (provided that (A) + (B)
= 100 parts by weight]. The structural unit having a glycidyl group contained in the modified polyolefin polymer is represented by the following formula (II): The composition according to claim 1, which is represented by the formula: 3. The polyolefin moiety contained in the modified polyolefin polymer is polyethylene, polypropylene,
3. The composition according to claim 1, wherein the composition is selected from poly (1-butene), poly (1-pentene), polyisobutene, a copolymer thereof, and a mixture thereof. 4. The composition according to claim 1, wherein the polyamide is produced by ring-opening polymerization of a lactam. 5. The polyamide according to claim 1, wherein the polyamide is produced by reacting an aliphatic diamine with at least one compound selected from aliphatic dicarboxylic acids, acid anhydrides and acid halides thereof. 3. The composition according to 3. 6. The composition according to claim 1, wherein the polyamide is produced by a polycondensation reaction of an aminocarboxylic acid. (A) according to each of claims 1 to 6,
(B) A method for producing a thermoplastic resin composition, comprising melting and kneading both components.