JPH0987476A - Thermoplastic polymer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermoplastic polymer composition which comprises a mixture of a modified olefin polymer having a specific chemical structure and a polar thermoplastic polymer and shows excellent mechanical characteristics and oil resistance in a variety of applications for resin molded products and elastomers. SOLUTION: This composition is produced by admixing (B) 99-1 pts.wt. of a modified olefin polymer to which at least one selected from the group consisting of ethylenically unsaturated group-containing carboxylic acids (derivatives) is bonded in an amount of 0.05-20 pts.wt. per 100 pts.wt. of a component A and (C) 1-99 pts.wt. of a polar thermoplastic polymer to (A) a main olefin polymer which comprises ethylene and at least one of α-olefins of 3-12C, preferably 6-12C, has a density of 0.858-0.885g/cm<3> and <=3.0Mw/Mn where Mw is a weight-average molecular weight and Mn is a number-average molecular weight calculated from a gel permeation chromatography.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a modified olefin polymer composition containing an ethylenically unsaturated group-containing carboxylic acid or a derivative thereof, and the modified olefin polymer has a polar functional group. For example, a thermoplastic polymer composition having excellent impact resistance is provided for the polar thermoplastic polymer having

[0002]

2. Description of the Related Art Conventionally, in applications such as rubber, films, sheets, and molded articles which are polymeric materials, when the use of a single polymeric material is not sufficient for the purpose of the final product, a plurality of materials are used. There have been many attempts to achieve the object by forming a composition of components, and a large number of composite alloy blend materials are on the market.

However, in the case of mixing different types of polymer substances to form a composition, the specific examples of combinations that control the phase structure and achieve the purpose are limited. For example, polypropylene resin with ethylene-propylene rubber (EPR), ethylene-butylene rubber (EBR), styrene-ethylene / butylene-styrene rubber (SEBS)
Conventionally, attempts have been made to impart impact resistance by appropriately dispersing elastomers such as the above with an extruder.

Further, in order to improve the impact resistance of engineering plastics such as polyamide and polyester having a polar group, an elastomer obtained by introducing a functional group such as a carboxylic acid derivative into the above elastomer is used.
Attempts have been made to impart impact resistance.

For example, JP-A-63-254119 contains a dicarboxylic acid group or a derivative group thereof,
Techniques relating to vinyl aromatic-olefin compound block copolymers are disclosed. According to the present proposal, the compatibility of the modified block copolymer with the polar resin is dramatically improved as compared with the unmodified block copolymer, and, for example, the impact resistance of polyamide is significantly improved. It is clearly stated that

However, since the modified block copolymer in the proposal has a styrene block, many volatile components such as styrene monomers and dimers contained in the modified block copolymer are generated during resin kneading, which is not preferable. .
Further, since the solvent resistance is poor, for example, the modified block copolymer is easily extracted by contacting the resin composition using the modified block copolymer with an organic solvent such as toluene or chloroform. There is a problem. Also,-
The fact that the impact resistance modifying effect in the low temperature region around 30 ° C. sharply decreases is also mentioned as a problem, which is an obstacle to the development of applications in the market.

Further, in JP-A-2-160812 or Japanese Patent Publication No. 7-42339, glycidyl methacrylate is substantially added to an ethylene-propylene copolymer rubber and / or an ethylene-propylene-diene copolymer rubber. There is disclosed an epoxy-containing impact modifier for a thermoplastic resin, which is obtained by bulk-reacting a free radical-polymerizable monomer having epoxy functionality as described above in the presence of an organic peroxide at a high temperature. According to the proposal, epoxy-modified ethylene-propylene (-diene) with specific gel content, epoxy functionality and degree of grafting
It has been suggested that blending 20% by weight of a copolymer rubber with a thermoplastic resin such as polybutylene terephthalate dramatically improves Izod impact strength and knit line strength.

However, the unmodified ethylene-propylene (-diene) copolymer rubbers used in these proposals are all polymerized by a Ziegler type catalyst using a vanadium compound or the like.

The conventional Ziegler-type ethylene-α-olefin copolymer elastomers as described above have a very wide molecular weight distribution, and accordingly, a very low molecular weight component is also contained in a considerable proportion. However, by itself, the balance between flexibility and mechanical strength is poor. For example, even if the flexibility is excellent, the mechanical strength is low, which is not preferable. This tendency has a significant adverse effect, especially in elastomer-rich compositions.

With respect to the Ziegler-type ethylene-α-olefin copolymer elastomer, particularly EPR, the polymer structure of pellets is limited, and the EPR having other structures is veil-like and complicated in handling, which is preferable. Absent. Further, even in the pellet form, there is a problem of blocking, which is not preferable.

[0011]

SUMMARY OF THE INVENTION The object of the present invention is to overcome all the problems of the conventional modified polymers.
It is an object of the present invention to provide a novel modified olefin polymer composition having improved compatibility with a polar thermoplastic polymer.

[0012]

Means for Solving the Problems As a result of intensive studies in view of the above points, the present inventor has found that the following thermoplastic polymer compositions solve all of the above-mentioned problems, The present invention has been completed.

That is, the density is 0.858 to 0.885.
Ethylene having a molecular weight distribution (Mw / Mn) of less than 3.0, which is in the range of g / cm ³ and is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) calculated by GPC. And at least one compound selected from the group consisting of ethylenically unsaturated group-containing carboxylic acids or derivatives thereof in the basic olefin polymer consisting of at least one α-olefin having 3 to 12 carbon atoms, Characterized by mixing 99 to 1 part by weight of a modified olefin polymer obtained by combining 0.05 to 20 parts by weight per 100 parts by weight of a basic olefin polymer and 1 to 99 parts by weight of a polar thermoplastic polymer. And a thermoplastic polymer composition.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.

Basic Olefin Polymer The basic olefin polymer used as a starting material for the modified olefin polymer of the present invention is ethylene and has 3 carbon atoms.
Of at least one α-olefin having Examples of the α-olefin having 3 to 12 carbon atoms include propylene, butene-1, pentene-1, hexene-1, 4-methylpentene-1, heptene-1, octene-1, nonene-1, decene-1, Undecene-1, dodecene-1, etc. are mentioned. As α-olefin,
An α-olefin having 6 to 12 carbon atoms is more preferable.
In this case, further improvement of the modifying effect and mechanical strength is expected.

The basic olefin polymer has a density of 0.8.
It is in the range of 58 to 0.885 g / cm ³ . By using a basic olefin polymer having a density within this range, it is highly flexible and has a low low-temperature modulus, and if it is modified with a specific functional group, it is an excellent modifier for each application of the thermoplastic polymer. Functions as a material.

The basic olefin polymer has a molecular weight distribution (Mw / Mn) of 3, which is the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) calculated by GPC.
It is less than 0. When the molecular weight distribution is less than 3.0, the low molecular weight component is extremely small, mechanical properties and processability are excellent,
High quality and preferable. The GPC apparatus and the measuring method are not particularly limited, but the present inventors used the following apparatus and measuring method. 1. Equipment: Waters 150C GPC. 2. Column: Shodex, AT-807S, 1 piece, Tosoh, TSK-GEL, GMH-H6, 2 pieces, 3 pieces in total. 3. Solvent: 1,2,4-trichlorobenzene. 4. Measurement temperature: 140 ° C. 5. Reference material: polystyrene.

The melt index of the backbone olefin polymer used in the present invention is not particularly limited, but is 0.01 to 300 g / 10 minutes (190 ° C., 2.16).
It is preferably used in the range of (kg load), and more preferably 0.05 to 100 g / 10 minutes.

The basic olefin polymer can be produced, for example, by using a metallocene catalyst. The metallocene-based catalyst is composed of a cyclopentadienyl derivative of a group IV metal such as titanium and zirconium and a co-catalyst, and is not only highly active as a polymerization catalyst, but also compared with conventional catalysts such as Ziegler-based catalysts. The molecular weight distribution of the obtained polymer is narrow, and the number of carbon atoms of the comonomer in the copolymer is 3 to
The distribution of 12 α-olefins is uniform, and the catalyst species are uniform.

By using the catalyst, the comonomer composition ratio can be increased more than in the prior art, and an elastomeric polymer having excellent flexibility and low modulus can be obtained.

Also, ethylene and α by Ziegler catalyst
-Olefin-based polymer, which is a copolymer of olefins, has a temperature of 190 ° C specified by ASTM D1238.
The melt index (I10) at 10 kgf,
The ratio (I10 / I2) to the melt index (I2) at 190 ° C./2.16 kgf and the molecular weight distribution show an almost linear proportional relationship, and the molecular weight distribution tends to increase as the melt index ratio increases. . The molecular weight distribution is about 3-10. On the other hand, in the olefin polymer using a metallocene catalyst, the molecular weight distribution becomes a sharp value of less than 3.0, regardless of the value of the melt index ratio, and the low molecular weight component is extremely small.

Therefore, when the basic olefin polymer, which is the base of the modified olefin polymer of the present invention, is polymerized by using a metallocene catalyst, the mechanical strength and processability are very excellent.

In summary, the characteristics of the basic olefin polymer when the metallocene polymerization catalyst is used are listed below.

1. Since the polymerization catalyst has an extremely high activity, it is possible to significantly increase the composition of the α-olefin comonomer as compared with the conventional one, and a polymer having a high flexibility can be obtained even without containing a plasticizer.

2. Compared to the Ziegler-based catalyst, the metallocene-based catalyst has more uniform active sites (single site), and the metallocene-based polymer has more uniform comonomer distribution than the Ziegler-based polymer.

3. Compared with the Ziegler-based polymer, the metallocene-based polymer has an extremely sharp molecular weight distribution, contains very few low-molecular weight components, has excellent mechanical properties and processability, and is of high quality.

4. When the long chain branch is introduced, the melt index ratio (I10 / I2) is large and the processing characteristics are excellent even though the molecular weight distribution is sharp.

5. Excellent transparency.

Modified olefin-based polymer The modified olefin-based polymer according to the present invention has at least one selected from the group consisting of the above-mentioned basic olefin-based polymer and an ethylenically unsaturated group-containing carboxylic acid or a derivative thereof.
It is a combination of different types of compounds.

Examples of such an ethylenically unsaturated group-containing carboxylic acid or derivative thereof include maleic acid, halogenated maleic acid, fumaric acid, itaconic acid and cis-4-.
Examples thereof include cyclohexene-1,2-dicarboxylic acid, endo-cis-bicyclo (2,2,1) -5-heptene-2,3-dicarboxylic acid and the like, and anhydrides, esters, amides and imides of these dicarboxylic acids. , And acrylic acid,
Methacrylic acid, crotonic acid, etc. and esters of these monocarboxylic acids, for example, methyl acrylate, methyl methacrylate, ethyl methacrylate, glycidyl acrylate,
Examples thereof include derivatives such as glycidyl methacrylate and amide.

Further, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate,
3-hydroxypropyl methacrylate, 3-chloro-
2-hydroxypropyl acrylate, 3-chloro-2
-Hydroxypropyl methacrylate, 3-hydroxy-2-phenoxypropyl acrylate, 3-hydroxy-2-phenoxypropyl methacrylate and the like are also exemplified.

Of these, maleic anhydride, glycidyl methacrylate and 2-hydroxyethyl methacrylate are particularly preferably used.

These compounds may be used alone or in combination of two or more. When modifying the basic olefin polymer, in addition to the above compounds, vinyl aromatics such as styrene and α-methylstyrene may be used as long as the characteristics of the modified olefin polymer of the present invention are not impaired. Group compounds can be used in combination.

The addition amount of the carboxylic acid containing an ethylenically unsaturated group or its derivative compound is 0.05 to 20 parts by weight, preferably 0.1 to 10 parts by weight, relative to 100 parts by weight of the basic olefin polymer. Parts, more preferably 0.1 to 5 parts by weight. If the addition amount is less than 0.05 parts by weight, the improvement in composition as compared with the unmodified olefin-based polymer is slight, which is not preferable. Further, even if the added amount exceeds 20 parts by weight, the improvement effect is hardly increased as compared with the addition amount less than 20 parts by weight, and the gel content is increased, which is not preferable.

The modified olefin polymer of the present invention is, for example, a basic olefin polymer containing at least one compound selected from the group consisting of a carboxylic acid containing an ethylenically unsaturated group or a derivative thereof in a solution state or a molten state. In, it is obtained by adding with or without a radical initiator.

As the radical initiator used for preparing the modified ethylene polymer, an organic peroxide, an azo compound or the like is usually preferably used.

As a concrete example of the above organic peroxide,
1,1-bis (t-butylperoxy) -3,5,5-
Trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (t-butylperoxy) octane, n-butyl-4,4-bis (t-butylperoxy) paralate and 2 , 2-bis (t-butylperoxy) butane, etc .; peroxyketals; di-t-butylperoxide, dicumylperoxide, t-butylcumylperoxide, α,
α'-bis (t-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-bis (t-
Butyl peroxy) hexane and 2,5-dimethyl-
Dialkyl peroxides such as 2,5-bis (t-butylperoxy) hexyne-3; acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5 -Diacyl peroxides such as trimethylhexanoyl peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide and m-trioyl peroxide; t-butyl peroxyacetate, t-butyl peroxyisobutyrate, t -Butylperoxy-2-ethylhexanoate, t-butylperoxylaurylate, t-butylperoxybenzoate, di-t-butylperoxyisophthalate, 2,5-dimethyl-2,5-di (benzoyl) Peroxy Peroxyesters such as hexane, t-butylperoxymaleic acid, t-butylperoxyisopropyl carbonate and cumylperoxyoctate; and t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide and 1,
Hydroperoxides such as 1,3,3-tetramethylbutyl hydroperoxide can be mentioned.

Among these compounds, 1,1-bis (t-butylperoxy) -3,5,5-trimethylcyclohexane, di-t-butylperoxide, dicumyl peroxide, 2,5-dimethyl -2,5-bis (t-butylperoxy) hexane and 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3 are particularly preferred.

As a specific example of the azo compound used as a radical initiator, azoisobutyronitrile or the like can be mentioned.

Such radical initiators can be used alone or in combination of two or more kinds.

The amount of the radical initiator is 0 to 10 parts by weight, preferably 0.05 to 5 parts by weight, more preferably 0.05 to 3 parts by weight, based on 100 parts by weight of the basic olefin polymer. Is.

The method for producing these modified olefin-based polymers is not particularly limited in the present invention, but the modified olefin-based polymer obtained may contain undesired components such as insoluble and infusible gels, A method in which the melt viscosity is remarkably increased and the workability is deteriorated is not preferable.
A method preferably used is, for example, a method of reacting a basic olefin polymer with an ethylenically unsaturated group-containing carboxylic acid or a derivative thereof in the presence of a radical initiator in an extruder.

Since the modified olefin polymer of the present invention has an improved compatibility with a polar thermoplastic polymer having a polar functional group, the composition of the present invention obtained by combining it with the polar thermoplastic polymer has It has extremely excellent mechanical properties and workability.

Further, an unmodified basic olefin polymer may be added to the modified olefin polymer of the present invention within a range that does not impair the improvement result of the resin composition.

Polar Thermoplastic Polymer In the polar thermoplastic polymer used in the thermoplastic polymer composition of the present invention, the polar functional group is a carboxylic acid containing an ethylenically unsaturated group added to a modified olefin polymer. Or a functional group that chemically bonds with its derivative or exhibits a physically strong interaction, and examples thereof include amino group, hydroxyl group, isocyanate group, thiol group, and means such as heating. Examples thereof include a urethane group, an ester group, an amide group, and an ammonium base that easily generate the above functional group. The functional group may be bound to the end of the polymer used or to the side chain.

Examples of the polar thermoplastic polymer having a polar functional group include polyamide, thermoplastic polyester, polycarbonate, thermoplastic polyurethane, vinyl ester polymer, polyvinyl alcohol polymer and the like.

The above polar thermoplastic polymers will be individually described below.

Polyamides include polycondensates of dicarboxylic acids and diamines, polycondensates of α-aminocarboxylic acids,
It is a ring-opening polymer of a cyclic lactam, and specifically, nylon 6, nylon 66, nylon 610, nylon 1
1, nylon 12, nylon 46, 6-T nylon, aromatic nylon containing aromatic hydrocarbon in the main chain, and copolymers thereof, that is, nylon 6-nylon 66 copolymer, nylon 6-nylon 12 copolymers and the like.

The thermoplastic polyester is a polycondensate of dicarboxylic acid and glycol, or a ring-opening polymer of a cyclic lactone. These are obtained by polycondensation of dicarboxylic acid, or its lower ester, or its acid halide or acid anhydride, and glycol, or by ring-opening polymerization of cyclic lactone. Specific examples include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyetherester block copolymer (PTEE), poly (ε-caprolactone), and the like.

As the polycarbonate, an aromatic polycarbonate generally derived from bisphenol A can be mentioned, and typical examples thereof include the phosgene method and the melt method.

The thermoplastic polyurethane is classified into a complete thermoplastic type and an incomplete thermoplastic type depending on its synthesis conditions, and these are determined by the molar ratio of the bifunctional polyol as a raw material, the hydroxyl group of glycol and the NCO group of isocyanate. The one synthesized at about 0.95 <NCO / OH ≦ 1 is the complete thermoplastic type, and the one synthesized at about 1 <NCO / OH <1.1 is the incomplete thermoplastic type. As the thermoplastic polyurethane, there is, for example, one in which a block of polyol (polyester or polyether) and diisocyanate is a soft segment and a block of diisocyanate and glycol is a hard segment.

Examples of the polyester diol as the above-mentioned raw material include poly (1,4-butylene adipate), poly (1,6-hexane adipate), polycaprolactone, and the like, and polyether diols include polyethylene glycol and polypropylene. Examples thereof include glycol and polyoxytetramethylene glycol. Further, as glycols, ethylene glycol, 1,4-
Examples thereof include butanediol and 1,6-hexanediol. Examples of the diisocyanate include aromatic, alicyclic and aliphatic diisocyanates such as tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate,
Hexamethylene diisocyanate, isophorone diisocyanate and the like can be mentioned.

In addition to the above-mentioned thermoplastic polyurethane, polyurethane polymers used for adhesives, foams, paints, etc., which have sufficient compatibility with the modified olefin polymer of the present invention, are also available. The modified olefin polymer of the present invention can be used and suitably used in combination with it.

Examples of the vinyl ester-based polymer include vinyl ester homopolymers, olefin-vinyl ester copolymers such as polyvinyl acetate, ethylene-vinyl acetate copolymer (EVA), propylene-vinyl acetate copolymer. Etc.

As the polyvinyl alcohol polymer,
It is a polymer composed of vinyl alcohol units or a copolymer containing vinyl alcohol units, which is a polymer obtained by partially or completely saponifying a vinyl ester polymer with an alkali. In the present invention, various polyvinyl alcohols or olefin-vinyl alcohol copolymers can be used, but ethylene-vinyl alcohol copolymers are preferred from the viewpoints of processability and mechanical properties.

Thermoplastic Polymer Composition The thermoplastic polymer composition of the present invention comprises an olefin polymer modified with an ethylenically unsaturated group-containing carboxylic acid or its derivative as an olefin polymer component.
By using a modified olefin-based polymer, which is one of the constituent requirements, in the case of a combination with a polar thermoplastic polymer having a polar functional group, compared with the case of using an unmodified olefin-based polymer, , And has a characteristic that the composition has a significantly improved compatibility.

The composition of the unmodified olefin polymer and the polar thermoplastic polymer having a polar functional group has poor compatibility with each other and thus has poor dispersibility. For example, impact modifying effect is obtained. On the other hand, the thermoplastic polymer composition of the present invention has good dispersibility and is expected to have a significant effect of modifying impact resistance, for example.

The thermoplastic polymer composition of the present invention has a mechanical property from rubber-like or leather-like to resin-like depending on the composition ratio of the modified olefin polymer and the polar thermoplastic polymer. There is a wide variety of polar thermoplastic polymers to be mixed.

For example, a polymer composition containing 80 parts by weight of the modified olefin polymer and 20 parts by weight of nylon 66 has a higher hardness and a higher modulus than the basic and / or modified olefin polymer alone. A leather-like polymer composition showing high heat resistance and high oil resistance. Then, as the composition ratio of the thermoplastic polymer is increased, the composition changes to a tough resin state, and in the composition ratio of a large amount of the thermoplastic resin component, for example, 20 parts by weight of the modified olefin polymer and nylon are used. The polymer composition in which 66 is 80 parts by weight exhibits a remarkable modification effect in impact resistance, bending fatigue resistance, surface modification, etc., as compared with nylon 66 alone.

The modified olefin polymer of the present invention is
The basic olefin polymer has good weather resistance, and its high weather resistance is maintained even after modification.

In the thermoplastic polymer composition of the present invention,
Its composition is 99 to 1 part by weight of the modified olefin polymer,
The range is from 1 to 99 parts by weight of the polar thermoplastic polymer. Outside the ranges of these composition ratios, no remarkable change in characteristics is recognized as compared with each polymer itself.

Further, the modified olefin polymer 99 to about 5
In the range of 0 parts by weight, polar thermoplastic polymer 1 to about 50 parts by weight, it is useful as an improved composition of modified olefinic polymer, while modified olefinic polymer 1 to about 50 parts by weight.
In the range of 99 parts by weight to about 50 parts by weight of the polar thermoplastic polymer, it is useful for modifying the polar thermoplastic polymer, especially for improving impact resistance.

In addition, the thermoplastic polymer composition of the present invention contains a non-polar compound in a range that does not significantly impair compatibility, mechanical properties, processability, etc. in the combination of the polar thermoplastic polymer and the modified olefin polymer. A thermoplastic polymer may be further added. Examples of these nonpolar thermoplastic polymers include high-density polyethylene, low-density polyethylene, polypropylene-based polymers (homopolymers, other α such as ethylene, etc.).
-Including a block or random copolymer with olefin), poly (butene-1) resin, poly (4-methylpentene-1) resin, polystyrene (including both atactic and syndiotactic), rubber-reinforced polystyrene, Polyphenylene ether, polyoxymethylene, polyphenylene sulfide, aromatic vinyl compound-conjugated diene compound block copolymer and hydrogenated product thereof,
Alternatively, a combination of these arbitrary components may be used.

As the polystyrene, in addition to amorphous polystyrene which is atactic generally used in general,
Crystalline polystyrene that is syndiotactic is included. In particular, the latter is drawing attention as an engineering plastic.

Examples of the aromatic vinyl compound-conjugated diene compound block copolymer and hydrogenated products thereof include styrene-butadiene block copolymers and hydrogenated products thereof, and styrene-isoprene block copolymers and hydrogenated products thereof. To be

Further, in the thermoplastic polymer composition of the present invention, a reactive group contained in the modified olefin polymer,
The present invention also includes a graft copolymer formed by reaction with a reactive group contained in a polar thermoplastic polymer, the graft copolymer consisting of a modified olefin polymer and a polar thermoplastic polymer as a part of the composition. Included in the range of the thermoplastic polymer composition.

The thermoplastic polymer composition of the present invention can be prepared by an apparatus which is usually used for kneading a polymeric substance depending on the composition ratio of each component. Examples of the kneading device used here include a single-screw extruder, a twin-screw extruder, a mixing roll, a Banbury mixer, a kneader, and the like. In the present invention, the melt-kneading method using an extruder is particularly preferable.

Specific examples of the method for obtaining the thermoplastic polymer composition of the present invention include: A modified olefin polymer is obtained by a twin-screw extruder using a basic olefin polymer, a modifier and an organic peroxide.
A method of obtaining a composition by pelletizing, blending and blending with pellets of a desired thermoplastic polymer, and kneading again with a twin-screw extruder.

2. A basic olefin polymer, a modifier and an organic peroxide are used to perform kneading in the front part of the twin-screw extruder, and then the desired thermoplastic polymer is added in the middle and rear parts of the extruder. And a method of obtaining the composition.

3. A method in which a basic olefin polymer, a modifier, an organic peroxide, and a desired thermoplastic polymer are added all at once and kneaded by a twin-screw extruder to obtain a composition.

Although any of the methods for producing the above-mentioned composition is different in terms of the production method, the purpose of controlling the performance of the composition by using the modifier is the same, and the concept is the same. To consider.

Further, it is possible to add an inorganic filler and a plasticizer to the thermoplastic polymer composition of the present invention to the extent that the characteristics thereof are not impaired. Examples of the inorganic filler used here include calcium carbonate, magnesium carbonate, silica, carbon black, glass fiber, titanium oxide, and clay. As a plasticizer,
For example, paraffin oil, polyethylene glycol,
Examples thereof include phthalic acid esters such as dioctyl phthalate (DOP). Further, other additives such as heat stabilizers, antioxidants, ultraviolet absorbers, colorants, pigments, antistatic agents, lubricants and the like may be added in appropriate amounts. It is also possible to

Taking advantage of the various characteristics described above, the thermoplastic polymer composition of the present invention can be used for automobile parts such as automobile connectors and wire harnesses, mechanical parts, electric parts,
It can be widely used for applications such as cables, hoses, belts, toys, sundries, daily necessities, building materials, sheets and films.

[0074]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In addition, in these Examples and Comparative Examples, the test methods used for the preparation of the modified olefin polymer and various evaluation methods are as follows.

(1) Melt index [g / 10 minutes] Measured under a load of 2.16 kg and a temperature of 190 ° C. according to ASTM D1238.

(2) Graft amount [wt%] After the reaction, the polymer was dissolved in 1,2,4-trichlorobenzene at 140 ° C and allowed to cool, and then the polymer was precipitated with acetone to remove unreacted substances. And purified. The grafted amount of the purified polymer was calculated by oxygen analysis.

(3) Grafting rate [%] The case where the amount of unreacted material to the charge is 0 is defined as 100%.
The ratio of the graft amount obtained in (2) was calculated.

(4) Gel amount [wt%] 5 g of the modified polymer was added to 500 ml of 1,2,4 at 140 ° C.
The mixture was shaken with trichlorobenzene for 4 hours, the undissolved polymer was filtered through glass wool, the filtrate was separated into a solvent and a polymer component, and the difference was calculated from the weight of the polymer component to calculate the gel content.

(5) Notched Izod impact strength [k
J / m ² ] Using a test piece having a thickness of 1/8 inch, ASTM D256
It measured at 23 degreeC and -30 degreeC according to

(6) Flexural modulus [MPa] Using a test piece having a thickness of 1/8 inch, ASTM D790
Was measured at 23 ° C.

(7) For hardness, a sheet of 2 mm thick was produced by compression molding, and four sheets of this sheet were piled up to ASTM D2240.
According to the above, the measurement was performed with an A type in an atmosphere of 23 ° C.

(8) Tensile strength [MPa] Measured at 23 ° C. according to JIS K6251.

(9) Elongation at break [%] Measured at 23 ° C. according to JIS K6251.

(10) Oil resistance According to JIS K6258, the volume swelling ratio [%] after 22 hours at 23 ° C. was calculated using JIS No. 3 oil.

In preparing the modified olefin polymer, the following basic olefin polymer (a) was obtained.

Basic olefin polymer (a-1) ENGAGE available from Dow Chemical Company
-SM8400. Comonomer: Octene-1. Density: 0.870 g / cm ³ . Mw / Mn = 2.6. ASTM D1238: MI = 30. ASTM / D2240: Hardness type A / 72.

Basic olefin polymer (a-2) ENGAGE available from Dow Chemical Company
-EG8200. Comonomer: Octene-1. Density: 0.870 g / cm ³ . Mw / Mn = 2.4. ASTM D1238: MI = 5. ASTM / D2240: Hardness type A / 75.

Basic olefin polymer (a-3) AFFINI available from Dow Chemical Company
TY / PF1140. Comonomer: Octene-1. Density 0.895 g / cm ³ . Mw / Mn = 2.3. ASTM D1238: MI = 1.6. ASTM / D2240: Hardness type A / 93.

(1) Preparation of Modified Olefin Polymer (Production Examples 1 to 4) Each of the above polymers (a-1) to (a-
2) to 100 parts by weight of each, 2.5 parts by weight of maleic anhydride and 0.1 parts by weight of radical initiator Perhexa 25B (manufactured by NOF Corporation) were uniformly blended,
The mixture was fed to a twin-screw extruder to carry out a graft reaction. The twin-screw extruder used and the extrusion conditions were the same direction rotation type, screw diameter 30 mm, L / D = 30, cylinder set temperature 230 ° C., screw rotation speed 200 rpm, and average residence time 40 seconds.

Then, each of the above polymers (a-1) to (a)
-2) to 100 parts by weight of each, 2.5 parts by weight of glycidyl methacrylate, 0.1 parts by weight of perhexa 25
Using B, the graft reaction was performed in the same manner as above.

The polymer after the reaction was purified, and the melt index, graft ratio and gel amount were calculated. Table 1 shows the results
Shown in

[0092]

[Table 1]

In each of the production examples, the target gelled olefin polymer modified with maleic anhydride or glycidyl methacrylate having a low gel content was obtained.

(Examples 1 to 4 and Comparative Examples 1 to 3) Nylon 6 (Toray, Amilan CM10) was used as the polar thermoplastic polymer.
07) was used and 80 parts by weight of this was used for Production Examples 1 to 2.
20 parts by weight of the modified olefin polymer obtained in step 1, or 20 parts by weight of an unmodified basic olefin polymer, 0.5 part by weight of maleic anhydride as a modifier, and Perhexa25B as a radical initiator. After uniformly blending 0.02 part by weight, the mixture was fed to a twin-screw extruder to obtain a composition.
The twin-screw extruder used was the same as in Production Examples 1 to 4, and was carried out under the same conditions except that the cylinder set temperature was 250 ° C.

In order to clarify the effect of the present invention, as a comparative example, a composition was obtained by the same method even in a system using no modified olefin polymer or a system using no modifier.

The obtained composition was injection-molded and the mechanical properties were evaluated. As a comparative example, the mechanical properties of nylon 6 alone were also evaluated. Further, regarding the compositions obtained in each of the examples and comparative examples, the molded pieces were frozen and fractured with liquid nitrogen, and the fracture surface was observed with a scanning electron microscope (SEM), and the average circle-equivalent particle diameter of the dispersed phase was obtained. Was calculated using an image analyzer. The results are shown in Tables 2 and 3.

[0097]

[Table 2]

[0098]

[Table 3]

As the results show, it is clear that the thermoplastic polymer composition of the present invention gives a nylon composition having excellent mechanical properties. Further, it is clear that a composition having desired physical properties can be obtained regardless of the production method.

(Examples 5 to 7, Comparative Examples 4 to 5) The same nylon 6 as the above as the polar thermoplastic polymer, and the polypropylene homopolymer (Mitsubishi Polypro, MA4; MFR = 5) as the nonpolar thermoplastic polymer. .0), while
As the modified olefin-based polymer, the polymer obtained in Production Example 2 was used, and these were kneaded in a nitrogen atmosphere at a temperature of 230 ° C. for 10 minutes using a kneader. The resulting composition was compression molded and evaluated for mechanical properties. As a comparative example, the same evaluation was performed in a system not using the modified olefin polymer. The results are shown in Table 4.

[0101]

[Table 4]

As the results show, it is clear that the composition of the present invention has significantly excellent mechanical properties.

(Examples 8 to 12, Comparative Examples 6 to 8) Nylon 66 (Asahi Kasei, Leona 1300) was used instead of nylon 6.
S) and blending at 275 ° C.
Compositions were obtained in the same manner as in Examples 1-2. The evaluation results of mechanical properties of the composition are shown in Tables 5 and 6.

[0104]

[Table 5]

[0105]

[Table 6]

As the results show, it is clear that the composition according to the invention is superior. It is also possible to use the modified olefin polymer and the basic olefin polymer in a preferable combination.

(Examples 13 to 14 and Comparative Examples 9 to 11) 80 parts by weight of polybutylene terephthalate (Toray, PBT1401) as a polar thermoplastic polymer, and modified olefin polymers obtained in Production Examples 3 and 4 were obtained. Thing 20
And parts by weight. The twin-screw extruder used is Production Example 1
The same as Nos. 4 to 4, and the same conditions were used except that the cylinder set temperature was 250 ° C. Then, the obtained composition was injection-molded at 240 ° C., and the mechanical properties of the molded product were evaluated. For comparison, PBT alone was also evaluated. Table 7 shows the results.

[0108]

[Table 7]

As the results show, it is clear that the composition of the present invention has excellent impact resistance.

(Examples 15 to 16 and Comparative Examples 12 to 13)
As the polar thermoplastic polymer, a thermoplastic polyurethane (Dainippon Ink and Chemicals, Pandex T-1180) and a modified olefin polymer were blended in respective composition ratios. The twin-screw extruder used was the same as in Production Examples 1 to 4, and was carried out under the same conditions except that the cylinder set temperature was 200 ° C.
Then, the obtained composition was compression-molded at 200 ° C., and the mechanical properties of the molded product were evaluated. Table 8 shows the results.

[0111]

[Table 8]

As the results show, it is clear that the composition of the present invention has excellent mechanical properties over a wide composition range.

Comparative Examples 14 to 15 2.5 parts by weight of maleic anhydride and 0.1 parts by weight of Perhexa 25B were used with respect to 100 parts by weight of the basic olefin polymer (a-3). The graft reaction was performed in the same manner as in Production Examples 1 to 4. The obtained graft body was purified and the same measurement and analysis were carried out. As a result of the analysis, MI was 1.3, graft ratio was 60%,
The gel amount was 0.03% (symbol Ma-3).

Nylon 6 used in Examples 1 to 4 as the thermoplastic polymer and Nylon 6 used in Examples 8 to 12
6 was used. Next, 80 parts by weight of each of these and 20 parts by weight of (Ma-3) obtained above were blended. The extruder and extrusion conditions used were the same as in the previous example, and the composition obtained was then injection molded at 240 ° C. to evaluate the mechanical properties of the molded product. The results are shown in Table 9.

[0115]

[Table 9]

As the results show, modified olefinic polymers having densities outside the scope of the present invention were tested in Examples 1-2 and 8
It is clear that the effect of modifying impact resistance is insufficient as compared with those of -9.

[0117]

Industrial Applicability The thermoplastic polymer composition of the present invention is an ethylene-α-olefin copolymer having a specific structure,
The modified olefin polymer to which the ethylenically unsaturated group-containing carboxylic acid or its derivative is bonded and the polar thermoplastic polymer are well mixed, and the impact strength and tensile strength are obtained in various fields such as resin molded products and elastomer applications. It has excellent mechanical properties such as strength and elongation, oil resistance, etc., and its utility value is extremely high.

Claims (3)

[Claims] 1. The density is 0.858 to 0.885 g / cm.
^The molecular weight distribution (Mw / Mn), which is the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn), which is in the range of ³ and calculated by gel permeation chromatography (GPC) is less than 3.0. Which is a basic olefin polymer consisting of ethylene and at least one or more α-olefins having 3 to 12 carbon atoms and at least one kind selected from the group consisting of ethylenically unsaturated group-containing carboxylic acids or derivatives thereof. The compound is a mixture of 99 to 1 part by weight of a modified olefinic polymer and 0.05 to 20 parts by weight of a basic olefinic polymer, and 1 to 99 parts by weight of a polar thermoplastic polymer. A thermoplastic polymer composition comprising: 2. The thermoplastic polymer composition according to claim 1, wherein the basic olefin polymer comprises ethylene and at least one α-olefin having 6 to 12 carbon atoms. 3. The thermoplastic polymer composition according to claim 1, wherein the basic olefin-based polymer is polymerized by using a metallocene-based catalyst.