JP2005060592A - Polyolefin composite material, production method thereof and molded body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyolefin composite material in which all of heat distortion temperature, impact resistance and elongation at break are achieved at a high level in a balanced manner, a production method thereof, and a molded body obtained by melt-molding it.
A non-modified polyolefin resin, a modified polyolefin resin having a polar group, a lamellar clay mineral, and a low molecular compound having a functional group having reactivity with the polar group. Polyolefin composite material.
[Selection figure] None

Description

  The present invention relates to a composite material containing a polyolefin-based resin and a layered clay mineral, a method for producing the same, and a molded body obtained by melt-molding the composite material.

In the past, attempts have been made to mix layered clay minerals as fillers for the purpose of improving the mechanical properties of polyolefin resins such as polypropylene. In JP-A-10-182892 (Patent Document 1), they are familiar with each other. In order to satisfactorily disperse the layered clay mineral in the poor polyolefin, a clay composite material comprising a polyolefin oligomer containing a functional group, an organized layered clay mineral hydrogen bonded to the functional group, and a polyolefin resin is disclosed. ing. However, in the clay composite material described in the publication, maleic anhydride group, hydroxyl group, carboxyl group, amide group, amino group, urethane group, ester group, imide group, maleimide group, halogen group, ether group, thiol group, Although polyolefin-based oligomers containing a functional group such as an epoxy group are used, the effect of improving the heat distortion temperature is small, and the impact resistance and elongation at break are still insufficient.
Japanese Patent Laid-Open No. 10-182892

  The present invention has been made in view of the above-mentioned problems of the prior art. A polyolefin composite material in which all of the heat distortion temperature, impact resistance and elongation at break are achieved at a high level in a balanced manner, a method for producing the same, and An object of the present invention is to provide a molded product obtained by melt-molding.

  As a result of intensive studies to achieve the above object, the inventors of the present invention have added the polar group to a polyolefin composite material containing an unmodified polyolefin resin, a modified polyolefin resin having a polar group, and a layered clay mineral. By adding a low molecular weight compound having a functional group having the following reactivity, the thermal deformation temperature, impact resistance and elongation at break were all improved in a balanced manner, and the present invention was completed.

  That is, the polyolefin composite material of the present invention comprises an unmodified polyolefin resin, a modified polyolefin resin having a polar group, a layered clay mineral, and a low molecular compound having a functional group having reactivity with the polar group. It is characterized by containing.

  The molded article of the present invention contains an unmodified polyolefin resin, a modified polyolefin resin having a polar group, a layered clay mineral, and a low molecular compound having a functional group having reactivity with the polar group. The polyolefin composite material is melt-molded.

  Furthermore, the method for producing a polyolefin composite material according to the present invention includes an unmodified polyolefin-based resin, a modified polyolefin-based resin having a polar group, a lamellar clay mineral, and a low molecular weight having a functional group having reactivity with the polar group. It is a method characterized by melt-kneading a compound.

  In the polyolefin composite material according to the present invention, the content of the modified polyolefin resin is 0.01 to 100 parts by weight with respect to 100 parts by weight of the unmodified polyolefin resin, and the content of the layered clay mineral Is 0.1 to 40 parts by weight, and the content of the low molecular compound is preferably 0.01 to 50 parts by weight.

  In addition, as the modified polyolefin resin, as the polar group, maleic anhydride group, hydroxyl group, carboxyl group, amide group, amino group, urethane group, ester group, imide group, maleimide group, halogen group, ether group, thiol group And those having at least one group selected from the group consisting of epoxy groups, and the low molecular compound is preferably a carbodiimide group, isocyanate group, isocyanurate group, carboxyl group, epoxy group, amino group as the functional group. Those having at least one group selected from the group consisting of a hydroxyl group, a maleic anhydride group and a thiol group are preferred.

  According to the polyolefin composite material and the method for producing the same of the present invention, the heat distortion temperature, impact resistance and elongation at break of the polyolefin composite material containing the polyolefin resin and the layered clay mineral are all improved to a high level in a balanced manner. Is possible. Therefore, by using the polyolefin composite material of the present invention, it is possible to obtain a molded body made of a polyolefin composite material having a sufficiently high thermal deformation temperature, impact resistance and elongation at break in a well-balanced manner.

  Hereinafter, the present invention will be described in detail with reference to preferred embodiments thereof.

  The polyolefin composite material of the present invention contains an unmodified polyolefin resin, a modified polyolefin resin having a polar group, a layered clay mineral, and a low molecular compound having a functional group having reactivity with the polar group. It is characterized by this.

  First, the polyolefin resin according to the present invention will be described. The polyolefin resin used in the present invention is a chain (straight chain or branched chain) high molecular polymer that is almost composed of a combination of carbon atoms and hydrogen atoms and does not contain an aromatic chemical group. Α, olefin homopolymers such as polyethylene, polypropylene, polybutene, polypentene, polyhexene; ethylene copolymers such as ethylene-propylene copolymer, ethylene-α olefin copolymer; polydienes such as polybutadiene, polyisoprene; their water An additive etc. are mentioned, and a polypropylene is especially preferable. In the present invention, the polyolefin resin may be used alone, but may be a blend or copolymer of two or more thereof.

  The unmodified polyolefin resin according to the present invention refers to the above-described polyolefin resin that does not have a polar group described later. The molecular weight (weight average molecular weight) of the unmodified polyolefin used in the present invention is preferably about 30,000 to 1,000,000. If the molecular weight is less than the above lower limit, the strength of the resulting molded product tends to be insufficient. On the other hand, if the molecular weight exceeds the upper limit, the flow characteristics at the time of melting tend to be insufficient, and the molding tends to be impossible.

  The polar group possessed by the modified polyolefin resin according to the present invention refers to a chemical modification group having a relatively highly polar chemical structure covalently bonded to the polyolefin resin. Such polar groups include maleic anhydride groups, hydroxyl groups, carboxyl groups, amide groups, amino groups, urethane groups, ester groups, imide groups, maleimide groups, halogen groups, ether groups, thiol groups and epoxy groups. In view of the tendency to impart higher intercalation ability, maleic anhydride groups, hydroxyl groups, carboxyl groups, amide groups, urethane groups, imide groups, maleimide groups and thiol groups are preferred, and in particular maleic anhydride Acid groups are particularly preferred. Such a modified polyolefin resin is not limited as long as the polar group is bonded to the aforementioned polyolefin resin, and the bonding site is in the middle of the molecular chain even at the end of the polyolefin resin. Also good. Moreover, the polar group which modified polyolefin resin has may be 1 type, or may be 2 or more types. In addition, the manufacturing method of such a modified polyolefin resin is not particularly limited, and the polar group can be introduced into the polyolefin resin and modified by a known method.

  The molecular weight (weight average molecular weight) of the modified polyolefin resin according to the present invention is preferably about 5000 to 1000000. If the molecular weight is less than the above lower limit, the strength of the resulting molded product tends to be insufficient, whereas if it exceeds the upper limit, the fluidity of the kneaded product during melt kneading tends to decrease and the uniform dispersibility tends to decrease. is there. In addition, it is preferable to use a modified polyolefin resin having the same repeating unit as the unmodified polyolefin resin to be used from the viewpoint of mutual compatibility. For example, when polypropylene is used as the former, it is preferable to use modified polypropylene as the latter. .

  In the polyolefin composite material of the present invention, the content of the modified polyolefin resin is preferably 0.01 to 100 parts by weight with respect to 100 parts by weight of the unmodified polyolefin resin, and 0.5 to 50 parts by weight. It is more preferable that If the content of the modified polyolefin resin is less than the above lower limit, the heat distortion temperature, bending strength and bending elastic modulus or tensile strength and tensile elastic modulus of the resulting polyolefin composite material tend not to be sufficiently improved, while exceeding the above upper limit. And impact resistance and elongation at break may be reduced.

  Next, the layered clay mineral blended in the polyolefin composite material of the present invention will be described. As the layered clay mineral according to the present invention, a general layered clay mineral can be used and is not particularly limited. Specifically, the smectite group such as montmorillonite, beidellite, saponite, hectorite; kaolinite, halosite, etc. Kaolinite group of the above; vermiculite group such as dioctahedral vermiculite, trioctahedral vermiculite; These layered clay minerals may be natural minerals or synthetic minerals by hydrothermal synthesis, melting method, solid phase method or the like. Moreover, in this invention, 1 type in said layered clay mineral may be used independently, and may be used in combination of 2 or more type. Moreover, it is preferable that the cation exchange capacity | capacitance of a layered clay mineral is 30-300 meq / 100g.

  Furthermore, in the present invention, it is more preferable to use a layered clay mineral obtained by organizing with an organic onium salt. Such an organized layered clay mineral is commercially available, and commercially available products include those sold by Southern Clay Products, Corp Chemical Co., Nanocor, and the like. In addition, such organicization means that organic substances are adsorbed and / or bonded to the interlayer and / or surface of the layered clay mineral by a physical or chemical method (preferably a chemical method). An organic onium salt is used for such organic formation. The organic onium salt is an organic layered clay mineral that increases the interlayer distance, thereby improving the dispersion uniformity between the polyolefin resin and the layered clay mineral.

Specific examples of such organic onium salts include organic ammonium salts, organic phosphonium salts, organic pyridinium salts, and organic sulfonium salts. As such an organic ammonium salt, for example, NR ₄ ⁺ X ⁻ [4 Rs may be the same or different and each represents a hydrogen atom, an alkyl group, an alkyl ether group or an aryl group, and X ⁻ represents a counter Represents an ion]. Here, it is preferable that the carbon number of the organic onium salt (the total number of carbon atoms of four R) is 6 or more. If the organic onium salt has less than 6 carbon atoms, the interlayer distance of the layered clay mineral cannot be sufficiently increased, and it tends to be difficult to uniformly disperse the layered clay mineral in the polyolefin resin. When R is an alkyl group or an alkyl ether group, the alkyl group or alkyl ether group may have a substituent, and the substituent is preferably a hydroxyl group. Furthermore, examples of counter ions represented by X ⁻ include halogen ions such as Cl ⁻ and Br ⁻ .

Particularly preferred examples of the organic ammonium ion represented by the above NR ₄ ⁺ include those represented by the following general formula (1). These may be used alone or in combination. May be.

［式中、Ｒ⁶、Ｒ⁷、Ｒ⁸及びＲ⁹は同一でも異なっていてもよく、それぞれ水素原子、アルキル基又はアリール基を表し、Ｒ⁶、Ｒ⁷、Ｒ⁸及びＲ⁹の合計の炭素数は６以上である。］
上記のアルキル基としては、具体的には、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、直鎖又は分岐鎖状のペンチル基、直鎖又は分岐鎖状のヘキシル基、直鎖又は分岐鎖状のヘプチル基、直鎖又は分岐鎖状のオクチル基、直鎖又は分岐鎖状のノニル基、直鎖又は分岐鎖状のデシル基、直鎖又は分岐鎖状のウンデシル基、直鎖又は分岐鎖状のドデシル基、直鎖又は分岐鎖状のトリデシル基、直鎖又は分岐鎖状のテトラデシル基、直鎖又は分岐鎖状のペンタデシル基、直鎖又は分岐鎖状のオクタデシル基等が挙げられるが、当該アルキル基の炭素数は１〜４であることが好ましい。アルキル基の炭素数が前記上限値を超えると有機オニウム塩の合成が困難となる傾向にある。また上記のアリール基として具体的には、フェニル基、ベンジル基等が挙げられる。

[Wherein R ⁶ , R ⁷ , R ⁸ and R ⁹ may be the same or different and each represents a hydrogen atom, an alkyl group or an aryl group, and the total of R ⁶ , R ⁷ , R ⁸ and R ⁹ Carbon number is 6 or more. ]
Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, and a linear or branched pentyl group. A linear or branched hexyl group, a linear or branched heptyl group, a linear or branched octyl group, a linear or branched nonyl group, a linear or branched decyl group , Linear or branched undecyl group, linear or branched dodecyl group, linear or branched tridecyl group, linear or branched tetradecyl group, linear or branched pentadecyl group , A linear or branched octadecyl group, and the like. The alkyl group preferably has 1 to 4 carbon atoms. When the carbon number of the alkyl group exceeds the upper limit, synthesis of the organic onium salt tends to be difficult. Specific examples of the aryl group include a phenyl group and a benzyl group.

  Moreover, it is preferable that it is 10-150 weight part with respect to 100 weight part of layered clay minerals, and, as for content of organic onium salt, it is more preferable that it is 20-100 weight part. If the content of the organic onium salt is less than the lower limit, the interlayer distance of the layered clay mineral is not sufficiently widened, and the dispersion uniformity between the aliphatic polyester and the layered clay mineral tends to decrease, When the upper limit is exceeded, the amount of the organic onium salt introduced by physical adsorption tends to increase and the physical properties of the aliphatic polyester composition tend to be impaired (for example, embrittlement).

  The content of the layered clay mineral is preferably 0.1 to 40 parts by weight, and more preferably 1 to 30 parts by weight with respect to 100 parts by weight of the unmodified polyolefin resin. If the content of the layered clay mineral is less than the lower limit value, the degree of improvement in rigidity and crystallization rate tends to be insufficient. On the other hand, if the content exceeds the upper limit value, the aliphatic polyester is brittle. And the impact strength tends to decrease significantly.

  Next, the specific low molecular weight compound mix | blended with the polyolefin composite material of this invention is demonstrated. The low molecular weight compound according to the present invention needs to have a functional group having reactivity with the polar group of the modified polyolefin resin described above, and the low molecular weight compound having such a functional group (hereinafter, depending on circumstances). By blending “functional group-containing low molecular weight compounds”), the modified polyolefin resins are bonded to each other to increase the molecular weight, and the heat distortion temperature, impact resistance and elongation at break of the resulting polyolefin composite material are improved in a well-balanced manner. It becomes. The functional group having reactivity with the polar group refers to a chemical modification group that can form a bond (preferably a covalent bond) by reacting with the polar group in a kneading step described later. Examples of such functional groups include carbodiimide groups, isocyanate groups, isocyanurate groups, carboxyl groups, epoxy groups, amino groups, hydroxyl groups, maleic anhydride groups, and thiol groups, which are highly reactive and react in a short time. From the viewpoint of termination, a carbodiimide group, an isocyanate group, an isocyanurate group, a carboxyl group and an epoxy group are preferred. Further, such a functional group is more preferably selected according to the polar group of the modified polyolefin resin used together. For example, when the polar group is a maleic anhydride group, the functional group may be a carbodiimide group, an isocyanate group, an epoxy group. Group and isocyanurate group are preferred, and when the polar group is a hydroxyl group, a carbodiimide group, an isocyanate group, an isocyanurate group and a carboxyl group are preferred as the functional group. In addition, the functional group which a low molecular compound has may be 1 type, or may be 2 or more types.

  Specific examples of such a functional group-containing low molecular weight compound include polycarbodiimide, N-ethyl-N ′-(3-dimethylaminopropyl) carbodiimide, N, N′-dicyclohexylcarbodiimide, and N, N′-diisopropylcarbodiimide. Carbodiimide compounds such as diphenylmethane diisocyanate; hexamethylene diamine, ethylene glycol, propylene glycol, hexamethylene dithiol, etc., among which polycarbodiimide, N-ethyl-N ′-(3-dimethylaminopropyl) carbodiimide, Diphenylmethane diisocyanate is preferred.

  The molecular weight (number average molecular weight) of the functional group-containing low molecular weight compound according to the present invention is preferably 50,000 or less, more preferably about 50 to 10,000. When the molecular weight of such a low molecular weight compound exceeds 50,000, it is not compatible with the olefin resin and tends to lower the mechanical properties.

  In the polyolefin composite material of the present invention, the content of the functional group-containing low molecular weight compound is preferably 0.01 to 50 parts by weight with respect to 100 parts by weight of the unmodified polyolefin resin, and 0.5 to 10 parts. More preferred are parts by weight. When the content of the functional group-containing low molecular weight compound is less than the above lower limit, the heat distortion temperature, impact resistance and elongation at break of the resulting polyolefin composite material tend not to be sufficiently improved. The balance tends to be lost and molding tends to be difficult.

  Furthermore, in the polyolefin composite material of the present invention, fillers, plasticizers, pigments, stabilizers, antistatic agents, ultraviolet absorbers, antioxidants, flame retardants, mold release agents, lubricants, as long as the properties are not impaired. Additives such as dyes, antibacterial agents, and end-capping agents may be further added. The content of such an additive is preferably 20% by weight or less in the polyolefin composite material of the present invention.

  Next, the manufacturing method of the polyolefin composite material of this invention is demonstrated. The method for producing a polyolefin composite material of the present invention comprises the above-mentioned unmodified polyolefin resin, a modified polyolefin resin having a polar group, a lamellar clay mineral, and a low molecule having a functional group having reactivity with the polar group. The present invention as described above, wherein the compound (functional group-containing low molecular weight compound) is melt-kneaded, whereby the heat distortion temperature, impact resistance and elongation at break are all achieved at a high level in a balanced manner. The polyolefin composite material can be obtained efficiently and reliably.

Thus, the specific method for obtaining the polyolefin composite material by melt-kneading the above-mentioned components is not particularly limited, and for example, a method of kneading using a roll or a twin screw extruder is suitably employed. Further, the procedure for melting and kneading the above-mentioned various components is not particularly limited, and the following procedure:
(i) A method of obtaining a polyolefin composite material by simultaneously melt-kneading an unmodified polyolefin resin, a modified polyolefin resin, a layered clay mineral, and a functional group-containing low molecular weight compound;
(ii) An unmodified polyolefin resin, a modified polyolefin resin, and a layered clay mineral are first melt-kneaded, and then a functional group-containing low-molecular compound is added to the resulting kneaded material to further melt-knead to obtain a polyolefin composite material. Method;
(iii) First, melt-kneaded the unmodified polyolefin resin and the layered clay mineral, and then add the modified polyolefin resin and the functional group-containing low molecular weight compound to the resulting kneaded material, and further melt-knead to obtain a polyolefin composite material Method;
(iv) A method of obtaining a polyolefin composite material by first melt-kneading an unmodified polyolefin-based resin, and then adding a modified polyolefin-based resin, a layered clay mineral and a functional group-containing low molecular weight compound to the resulting kneaded material and further melt-kneading. ;
(v) In the above methods (i) to (iv), an organic solvent is further added to the kneaded product, the above components are melted and kneaded, and then degassed to remove the organic solvent to obtain a polyolefin composite material. Method;
Is preferably employed.

  In the case of using an unorganized layered clay mineral, in the above methods (i) to (iv), water is further added to the kneaded product, and the above components are melted and kneaded. Thus, it is preferable to remove water to obtain a polyolefin composite material. If it does in this way, a layered clay mineral will be organized by the reaction product of a modified polyolefin resin and a functional group containing low molecular weight compound, and a layered clay mineral will be more uniformly disperse | distributed in the polyolefin composite material obtained. In addition, although the addition amount in particular of this water is not restrict | limited, It is preferable that the addition amount of water is 2-50 weight part with respect to 100 weight part of unmodified polyolefin resin.

  The temperature in the kneading step is appropriately selected within a temperature range in which the resin to be used melts and does not thermally decompose depending on the type of the unmodified polyolefin resin and the modified polyolefin resin to be used. About 300 degreeC is preferable. The organic solvent used in the above method (iv) is preferably an aromatic compound such as toluene and xylene, and the amount used is 0 with respect to 100 parts by weight of the unmodified polyolefin resin. It is preferably 0.01 to 10 parts by weight.

In addition, the kneading step is preferably performed according to the method disclosed in International Publication WO99 / 50340 by the applicant. That is, using a biaxial kneader equipped with a screw capable of applying high resin conversion pressure, high total shear amount, and high shear energy, the average value of the resin conversion pressure is 5 × 10 ⁴ Pa or more, and the maximum value is 1 ×. By dispersing and kneading the above components under the conditions of 10 ⁵ Pa, total shear amount of 10 ⁵ to 10 ⁷ , and total shear energy of 10 ¹⁰ to 10 ¹⁴ Pa, the dispersion uniformity can be further improved. There is a tendency.

  Next, the molded product of the present invention will be described. That is, the molded article of the present invention is a low molecular compound having a functional group having reactivity with the aforementioned unmodified polyolefin resin, a modified polyolefin resin having a polar group, a layered clay mineral, and the polar group ( A polyolefin composite material containing a functional group-containing low molecular weight compound) is melt-molded.

  When manufacturing the molded object of this invention, it is preferable that the temperature at the time of melting a polyolefin composite material is 150-300 degreeC. When this temperature is less than the above lower limit, the polyolefin composite material is not sufficiently melted and molding tends to be difficult. On the other hand, if this temperature exceeds the upper limit, the physical properties of the molded product obtained by reducing the molecular weight of the polyolefin tend to be impaired. Thus, when producing the molded article of the present invention, the specific molding method is not particularly limited, and injection molding, extrusion molding, blow molding, inflation molding, profile extrusion molding, injection blow molding, vacuum pressure molding, spinning Any of these methods may be used, and the injection molding method is particularly preferable. Moreover, the shape, thickness, etc. of the molded product of the present invention are not particularly limited, and any of injection molded products, extrusion molded products, compression molded products, blow molded products, sheets, films, yarns, fabrics, and the like may be used.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example.

(Examples 1-2 and Comparative Examples 1-2)
Using the following unmodified polyolefin resin, modified polyolefin resin, layered clay mineral, and functional group-containing low molecular weight compound, a polyolefin composite material having the composition shown in Table 1 is provided with a twin screw extruder (Nippon Steel) TEX30α, L (screw length) / D (screw diameter) = 45.5). The melt kneading was performed under the conditions of a screw rotational speed of 300 rpm, a cylinder set temperature (resin temperature) of 200 ° C., and a resin supply speed of 10 kg / hr.
(Unmodified polyolefin resin: Unmodified PP)
Homopolypropylene resin (MA2 manufactured by Nippon Polychem)
(Modified polyolefin resin: Modified PP)
Maleic anhydride-modified polypropylene (Yumex 1001, Sanyo Chemical Co., Ltd., weight average molecular weight 40,000)
(Layered clay mineral: Organized clay)
Organized montmorillonite (octadecylamine treated montmorillonite, NANOCOR ODA-CWC)
(Functional group-containing low molecular weight compound)
Polycarbodiimide (Nisshinbo Carbodilite 8CA).

  That is, first, an unmodified polyolefin resin, a modified polyolefin resin, and a functional group-containing low molecular weight compound are mixed (dry blended) so as to have the composition shown in Table 1, and charged into a twin screw extruder to melt both. . Next, from the middle of the twin-screw extruder (cylinder position after the resin is melted), a layered clay mineral is added so as to have the composition shown in Table 1, and further melt-kneaded to obtain the desired polyolefin composite material. It was. The resulting polyolefin composite material was extruded in the form of a strand from the tip of a twin screw extruder, quenched and solidified in a water tank, and then cut with a strand cutter to obtain polyolefin composite material pellets.

Next, using an injection molding machine (manufactured by Nissei Plastic Industry Co., Ltd., PS40E2ASE), the obtained polyolefin composite material was injection molded under the conditions of a mold temperature of 40 ° C. and a cooling time of 35 seconds, and a test piece for the following test was prepared. Produced. The following tests were performed on the polyolefin composite materials obtained in each Example and each Comparative Example, and the results obtained are shown in Table 1.
(Bending elastic modulus test)
The flexural modulus and breaking strain were measured according to the bending test method specified in IS0 178: 1993. The distance between the fulcrums was 64 mm. The measurement conditions were 23 ° C. and a deflection rate of 5 mm / min.
(Heat deformation temperature test)
The heat distortion temperature was measured according to the test method specified in IS0 75-2: 1993. In addition, it was set as flatwise, high load: 1.8MPa, low load: 0.45MPa.

(Examples 3-6 and Comparative Examples 3-6)
A polyolefin composite material pellet and a test piece were prepared in the same manner as in Example 1 except that the layered clay mineral and the functional group-containing low molecular weight compound shown below were used and the composition of each component was changed as shown in Table 2. Each of the above tests was conducted. The obtained results are shown in Table 2.
(Layered clay mineral: Organized clay)
Organized hectorite (Benton 38 by Elementis)
(Functional group-containing low molecular weight compound)
(i) Epoxy-containing compound 1 (epoxidized product of SBR elastomer, Epofriend A1005 manufactured by Daicel Chemical Industries)
(ii) Epoxy-containing compound 2 (alicyclic epoxy compound, EHPE manufactured by Daicel Chemical Industries, weight average molecular weight 1000).

(Examples 7-8 and Comparative Examples 7-8)
The following are used as layered clay minerals and functional group-containing low molecular weight compounds, the composition of the various components is changed as shown in Table 3, and water is added to the kneaded product from the middle of the twin screw extruder at 1 kg / h. Pellets and test pieces of polyolefin composite material were prepared in the same manner as in Example 1 except that the water was removed by deaeration after charging at a supply amount, melt-kneading, and the above tests were performed. The obtained results are shown in Table 3. In Comparative Examples 7 to 8, instead of the functional group-containing low molecular weight compound, the following low molecular weight compound was added so as to have the composition shown in Table 3.
(Layered clay mineral: Clay)
Sodium Montmorillonite (Kunimine Industries Kunipia F)
(Functional group-containing low molecular weight compound)
N-ethyl-N ′-(3-dimethylaminopropyl) carbodiimide hydrochloride (manufactured by Toyo Kasei Kogyo Co., Ltd., molecular weight 191.5)
(Low molecular compound)
OTM hydrochloride (octadecyltrimethylammonium chloride, manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 347.5).

(Example 9 and Comparative Example 9)
Unmodified polyolefin resin, modified polyolefin resin, layered clay mineral and functional group-containing low molecular weight compounds shown below are used, and the composition of each component is changed as shown in Table 4, and the cylinder set temperature (resin temperature) In the same manner as in Example 1 except that the functional group-containing low molecular weight compound was added from the middle of the twin-screw extruder to the final kneaded product. And the following tensile elastic modulus test and breaking elongation test were carried out. Table 4 shows the obtained results.
(Unmodified polyolefin resin: Unmodified PE)
Polyethylene resin (Nippon Polychem KF380)
(Modified polyolefin resin: Modified PE)
Maleic anhydride modified polyethylene (FUSABOND 226D manufactured by DuPont Chemical)
(Layered clay mineral: Organized clay)
Organized montmorillonite (NANOCOR I28T)
(Functional group-containing low molecular weight compound)
Diphenylmethane diisocyanate (Cosmonate PH, Mitsui Takeda Chemical Co., Ltd., molecular weight 250).
(Tensile modulus test)
The tensile elastic modulus and elongation at break were measured according to the test method specified in ISO 547-1, 2 (1993). Measurement conditions were 23 ° C. and a tensile speed of 10 mm / min.

  As is clear from the results shown in Tables 1 to 4, all of the molded bodies made of the polyolefin composite material of the present invention had a sufficiently high thermal deformation temperature, impact resistance and elongation at break in a well-balanced manner. . On the other hand, a molded article made of a polyolefin composite material to which the functional group-containing low molecular weight compound according to the present invention is not added is clearly inferior to that of the present invention in terms of heat distortion temperature, impact resistance, and elongation at break. It was.

  As described above, in the polyolefin composite material of the present invention, all of the heat distortion temperature, impact resistance and elongation at break are achieved at a high level with good balance. Elongation is high enough with good balance. Therefore, the molded body made of the polyolefin composite material of the present invention includes bumpers, radiator grills, side moldings, garnishes, wheel covers, aero parts, instrument panels, door trims, seat fabrics, door handles, floor mats and other automotive parts, home appliances. It is useful as a product housing, product packaging film, waterproof sheet, various containers, bottles and the like. Moreover, when using the molded object of this invention as a sheet | seat, you may laminate | stack with paper or another polymer sheet, and may use it as a laminated body of a multilayer structure.

Claims (9)

  A polyolefin composite material comprising an unmodified polyolefin resin, a modified polyolefin resin having a polar group, a layered clay mineral, and a low molecular compound having a functional group having reactivity with the polar group .   The content of the modified polyolefin resin is 0.01 to 100 parts by weight with respect to 100 parts by weight of the unmodified polyolefin resin, and the content of the layered clay mineral is 0.1 to 40 parts by weight, The polyolefin composite material according to claim 1, wherein the content of the low molecular compound is 0.01 to 50 parts by weight.   The polar group is selected from the group consisting of maleic anhydride groups, hydroxyl groups, carboxyl groups, amide groups, amino groups, urethane groups, ester groups, imide groups, maleimide groups, halogen groups, ether groups, thiol groups and epoxy groups. And at least one group, wherein the functional group is selected from the group consisting of a carbodiimide group, an isocyanate group, an isocyanurate group, a carboxyl group, an epoxy group, an amino group, a hydroxyl group, a maleic anhydride group, and a thiol group. The polyolefin composite material according to claim 1 or 2, wherein   A polyolefin composite characterized by melt-kneading an unmodified polyolefin resin, a modified polyolefin resin having a polar group, a lamellar clay mineral, and a low molecular compound having a functional group having reactivity with the polar group Material manufacturing method.   The content of the modified polyolefin resin is 0.01 to 100 parts by weight with respect to 100 parts by weight of the unmodified polyolefin resin, and the content of the layered clay mineral is 0.1 to 40 parts by weight, And the content of the said low molecular compound is 0.01-50 weight part, The manufacturing method of the polyolefin composite material of Claim 4 characterized by the above-mentioned.   The polar group is selected from the group consisting of maleic anhydride groups, hydroxyl groups, carboxyl groups, amide groups, amino groups, urethane groups, ester groups, imide groups, maleimide groups, halogen groups, ether groups, thiol groups and epoxy groups. And at least one group, wherein the functional group is selected from the group consisting of a carbodiimide group, an isocyanate group, an isocyanurate group, a carboxyl group, an epoxy group, an amino group, a hydroxyl group, a maleic anhydride group, and a thiol group. The method for producing a polyolefin composite material according to claim 4 or 5, wherein:   A polyolefin composite material containing an unmodified polyolefin resin, a modified polyolefin resin having a polar group, a layered clay mineral, and a low molecular compound having a functional group having reactivity with the polar group was melt-molded. A molded product characterized by being a thing.   The content of the modified polyolefin resin is 0.01 to 100 parts by weight with respect to 100 parts by weight of the unmodified polyolefin resin, and the content of the layered clay mineral is 0.1 to 40 parts by weight, And the content of the said low molecular compound is 0.01-50 weight part, The molded object of Claim 7 characterized by the above-mentioned.   The polar group is selected from the group consisting of maleic anhydride groups, hydroxyl groups, carboxyl groups, amide groups, amino groups, urethane groups, ester groups, imide groups, maleimide groups, halogen groups, ether groups, thiol groups and epoxy groups. And at least one group, wherein the functional group is selected from the group consisting of a carbodiimide group, an isocyanate group, an isocyanurate group, a carboxyl group, an epoxy group, an amino group, a hydroxyl group, a maleic anhydride group, and a thiol group. The molded article according to claim 7 or 8, wherein