JP2020111642A - Olefin-based random copolymer, olefin-based resin composition, olefin-based resin composite material, and member for automobile - Google Patents

Abstract

To improve an affinity between an inorganic filler and an olefin-based matrix resin in an olefin-based resin composite material containing an inorganic filler and solve defects in the conventional modification technology.SOLUTION: An olefin-based random copolymer is one for use in an olefin-based resin composite material containing an inorganic filler, includes (U1) a structural unit derived from one or more kinds of monomers selected from the group consisting of ethylene and a 3-5C α-olefin and (U2) a structural unit derived from one or more kinds of monomers selected from 5-20C α-olefin comonomers having a hydroxyl group, has a content of the structural unit (U2) of 0.5 mol% to 10 mol% based on 100 mol% of the total of the structural units and has a weight average molecular weight as measured by gel permeation chromatography (GPC) of 40,000 to 500,000.SELECTED DRAWING: None

Description

The present invention relates to an olefin-based random copolymer, an olefin-based resin composition, an olefin-based resin composite material, and a vehicle member. More specifically, it relates to an olefin-based resin for improving the affinity between the inorganic filler and the matrix resin in the inorganic-filler-containing resin-based composite material.

BACKGROUND ART A molding material made of a thermoplastic resin reinforced with an inorganic filler is lightweight and has excellent mechanical properties, and thus is widely used in sports equipment applications, aerospace industry applications, and other general industrial applications. In recent years, as a thermoplastic resin as a base material, lightness and economical efficiency have been required, and a lightweight olefin resin, particularly polypropylene has come to be used. Since polypropylene has a low specific gravity among thermoplastic resins, it can be expected to obtain a lightweight molded product having high strength and high elastic modulus by combining it with an inorganic filler having high strength and high elastic modulus. For example, a polypropylene resin composition in which mechanical strength is enhanced by using glass fiber is described (Non-Patent Document 1). However, since polypropylene has poor interfacial adhesion with an inorganic filler, it is difficult to obtain a molded product having excellent mechanical properties. In particular, when a reinforcing material having a poor surface reactivity such as a glass filler is used, it is extremely difficult to obtain a molded product having excellent mechanical properties.
So far, for example, a polyolefin glass fiber reinforced resin composition using an acid-modified polyolefin resin has been disclosed as a means for improving the strength of the inorganic filler reinforced olefin resin (for example, Patent Document 1).

However, even with the above disclosure, there is a problem that an inorganic filler-reinforced olefin resin having sufficient mechanical properties cannot be obtained. In order to solve this problem, a method of treating a polyolefin with radiation such as an electron beam or ozone, or in the presence of a radical generator such as an organic peroxide, an ethylenically unsaturated compound such as a vinyl compound or an unsaturated compound is used. There is a method of graft-modifying a carboxylic acid or the like.
The method of the graft reaction is roughly classified into a so-called solution method in which a solvent is used for the reaction and a so-called melting method in which the reaction is performed in a molten state using a kneading extruder. Since the solution method uses a large amount of solvent, the cost is high, and it is not preferable from the viewpoint of global environmental problems. On the other hand, the melting method has attracted attention as a simple method because it does not use such a solvent.
However, the modified polyolefin produced by the melting method contains a large amount of unreacted substances (that is, vinyl compounds that have not undergone graft reaction or ethylenically unsaturated compounds such as unsaturated carboxylic acids) and oligomers (that is, vinyl compounds or unsaturated carboxylic acids). (Low molecular weight products of ethylenically unsaturated compounds such as acids) and other by-products are present, which becomes a factor that inhibits adhesiveness, paintability and printability, and when used as molded products such as sheets and films. There is a drawback that bubbles are generated (Non-Patent Document 2).

Therefore, as a method of removing the unreacted matter from the modified polyolefin produced by the melting method, the modified polyolefin obtained by graft polymerization by melt-kneading an unsaturated carboxylic acid or its acid anhydride in the presence of a catalyst to the polyolefin , A method for producing a modified polyolefin in which the unmodified polyolefin and an unreacted unsaturated carboxylic acid or an acid anhydride thereof are treated in a good solvent in a state in which the modified polyolefin is not substantially dissolved (dissolution reprecipitation method; ) Or a modified polypropylene obtained by melt-kneading a mixture of polypropylene, an unsaturated carboxylic acid or a derivative thereof and an organic peroxide, and heating and drying the modified polypropylene at a temperature of 60° C. or higher (heat drying method; Patent Document 3), a modified polyolefin obtained by melt-kneading an unsaturated carboxylic acid or an acid anhydride thereof into a polyolefin and graft-polymerizing the polyolefin in the presence of a catalyst, has a Vicat softening temperature of the polyolefin or 25° C. from the softening temperature. A method for producing a modified polyolefin that is treated with hot/hot air or hot/hot water in a low temperature range (method of stirring in hot/hot water; Patent Document 4) and the like have been proposed.
However, the dissolution and reprecipitation method has a drawback that the cost is high because a large amount of solvent such as acetone is used and the operation is complicated. Further, the heat-drying method has a drawback that the unreacted matter, particularly the oligomer of the unsaturated compound is not sufficiently removed, and the modified polyolefin resin is colored during the heat-drying. Further, even in the method of stirring in warm/hot water, removal of unreacted substances and oligomers and prevention of coloration are still insufficient.
On the other hand, in the case of using a resin other than the acid-modified polyolefin resin, a technique of introducing a hydroxyl group, which is a polar group, into polypropylene was developed, and a propylene-based polymer composed of propylene and a hydroxyl group-containing olefin (i) The amount of hydroxyl group-containing olefin in the polymer is 10 mol% or less, (ii) the weight average molecular weight (Mw) obtained by gel permeation chromatography (GPC) measurement of the polymer is 5,000 or more, and (iii) The value (Mw/Mn) of the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) is in the range of 1.0 to 3.5, and (iv) the melting point of the polymer measured by DSC ([[ Tm]; °C) and the amount of hydroxyl group-containing olefin ([-OH]; mol%) measured by nuclear magnetic resonance (NMR) satisfy a specific relational expression, and a propylene-based polymer is disclosed in Patent Documents 5 and 6. Has been done. However, in these patent documents, although the catalyst component and the polymerization method for producing a polypropylene-based polymer having a hydroxyl group are described in detail, the characteristics and applications are only described as a paintable material. No other suggestions have been made.

JP-A-3-121146 JP-A-54-99193 JP-A-56-95914 JP-A-56-118411 JP, 2006-2072, A JP, 2009-84578, A

Fumio Ide "Interface Control and Composite Material Design", Sigma Publishing, 1995, Chapter 6 Vol. 49, No. 2 (1992), pages 87-95 and 97-104.

Looking at the conventional technology as described above, in producing a composite material of a polypropylene resin and an inorganic filler, the development of an olefin resin for obtaining better physical properties is still vigorously carried out. However, there is still room for improvement.
The object of the present invention is to improve the affinity between the inorganic filler and the olefinic matrix resin in the olefinic resin composite material containing the inorganic filler, and solve the drawbacks of the conventional modification techniques. Another object of the present invention is to provide an olefin-based random copolymer that can be used, and an olefin-based resin composite material containing an inorganic filler containing the olefin-based random copolymer.

As a result of intensive studies to achieve the above objects, the present inventors have found that an olefin-based random copolymer having a specific amount of a specific structure excellent in affinity with an inorganic filler on a polymer main chain is an inorganic filler and an olefin. It has been found that it has an affinity for both matrix resins and that the affinity between the inorganic filler and the olefin matrix resin can be improved by a technical approach different from the conventional modification technology. The present invention has been completed based on the above.
That is, according to the present invention, there are provided an olefin random copolymer, an olefin resin composition, an olefin resin composite material, and an automobile member as described below.

[1]
An olefin-based random copolymer used in an olefin-based resin composite material containing an inorganic filler,
A structural unit (U1) derived from ethylene and at least one monomer selected from the group consisting of α-olefins having 3 to 5 carbon atoms;
A structural unit (U2) derived from at least one monomer selected from α-olefin comonomers having a hydroxyl group and having 5 to 20 carbon atoms,
The content of the structural unit (U2) is 0.5 mol% or more and 10 mol% or less with respect to 100 mol% of the total of structural units,
An olefin-based random copolymer having a weight average molecular weight of 40,000 or more and 500,000 or less as measured by gel permeation chromatography (GPC).

[2]
The olefin-based random copolymer according to [1], wherein the α-olefin comonomer is a linear α-olefin comonomer.

[3]
The olefin-based random copolymer according to [1] or [2], which has a molecular weight distribution (Mw/Mn) measured by GPC of 3.5 or less.

[4]
The olefin-based random copolymer according to any one of [1] to [3], wherein the structural unit (U1) includes a structural unit derived from propylene.

[5]
An olefin resin composition comprising the olefin random copolymer (A) according to any one of [1] to [4] and an inorganic filler (B).

[6]
The olefin-based random copolymer (A) according to any one of [1] to [4], the inorganic filler (B), and the olefin-based according to any one of [1] to [4]. An olefin-based resin composite material comprising an olefin-based random copolymer (C) other than the random copolymer.

[7]
The olefin random copolymer (C) other than the olefin random copolymer according to any one of [1] to [4] is selected from the group consisting of a propylene homopolymer and a propylene copolymer. The olefin resin composite material according to [6], which is a resin.

[8]
A member for an automobile, which is a molded product using the olefin resin composite material according to [6] or [7].

According to the present invention, since it has an affinity for both the inorganic filler and the olefinic matrix resin, it is possible to improve the affinity between the inorganic filler and the olefinic matrix resin, and moreover, the olefinic resin. It is possible to obtain an olefin-based random copolymer which does not have the drawbacks associated with the conventionally known modification technique for improving the interfacial adhesion to the inorganic filler. Further, by using the olefin-based random copolymer, an olefin-based resin composite material containing an inorganic filler having excellent adhesiveness between the inorganic filler and the olefin-based matrix resin can be obtained. It is possible to produce a molded product having excellent mechanical properties.

1. Olefin-based Random Copolymer The olefin-based random copolymer of the present invention is an olefin-based copolymer for inorganic filler-olefin-based resin composites, which is used for an olefin-based resin composite containing an inorganic filler. The olefin-based random copolymer is a structural unit (U1) derived from ethylene and one or more kinds of monomers selected from the group consisting of α-olefins having 3 to 5 carbon atoms, and 5 carbon atoms having a hydroxyl group. A structural unit (U2) derived from one or more kinds of monomers selected from the above α-olefin comonomer of 20 or less, and the content of the structural unit (U2) is 0. It is 5 mol% or more and 10 mol% or less, and the weight average molecular weight measured by gel permeation chromatography (GPC) is 40,000 or more and 500,000 or less.
That is, in the olefin-based random copolymer of the present invention, structural units (U1) derived from main ethylene and α-olefin monomers occupy most of the structural units, and derived from α-olefin comonomer containing a hydroxyl group. The content of the structural unit (U2) to be contained is 0.5 mol% or more and 10 mol% or less of the entire structural unit, and has a polymer structure in which these structural units are linked.

In the olefin-based random copolymer of the present invention, the hydroxyl group portion present on the polymer main chain of the olefin-based copolymer has excellent interfacial adhesion to the inorganic filler.
Further, since the olefin random copolymer of the present invention has a polyolefin polymer skeleton that is common or similar to the polymer skeleton of the olefin matrix resin, it has excellent affinity with the olefin matrix resin. There is.
Therefore, the olefin-based random copolymer of the present invention exhibits excellent interfacial adhesion with respect to the inorganic filler in the hydroxyl group portion, and the skeleton portion of the polyolefin-based polymer has excellent affinity with the olefin-based matrix resin. It is considered that the affinity between the inorganic filler and the olefinic matrix resin can be improved in the composite material in which the inorganic matrix resin contains the inorganic filler. That is, it is considered that the olefin random copolymer of the present invention can be suitably used as an affinity improver between an inorganic filler and an olefin matrix resin.
The olefin-based random copolymer of the present invention may be used as a matrix resin for a composite material containing an inorganic filler.
Further, the olefin random copolymer of the present invention can be synthesized by copolymerizing a main α-olefin monomer and an α-olefin comonomer having a hydroxyl group. Since this copolymerization reaction is a reaction scheme which is completely different from the above-mentioned conventional modification technique, the drawbacks associated with the above-mentioned conventional modification technique do not occur when synthesizing the olefin random copolymer of the present invention.

In the olefin-based random copolymer of the present invention, the structural unit derived from the α-olefin comonomer having a hydroxyl group, that is, the α-olefin comonomer having a hydroxyl group and having 5 to 20 carbon atoms is the olefin-based random copolymer of the present invention. Is a component necessary for imparting interfacial adhesiveness with an inorganic filler.

The hydroxyl group may be bonded to carbon at any position in the hydrocarbon chain of the α-olefin comonomer, but is preferably positioned at the terminal carbon as viewed from the ω position, that is, the position of the double bond. When the hydroxyl group is bonded to the hydrocarbon chain of the α-olefin comonomer, that is, at a position other than the ω position, the hydroxyl group may be directly bonded to the hydrocarbon chain of the α-olefin comonomer, or the hydrocarbon chain. It may be bound via a linker such as.
Further, two or more hydroxyl groups may be bonded on the hydrocarbon chain of the α-olefin comonomer. For example, a hydroxyl group is directly bonded to the ω position on the hydrocarbon chain of the α-olefin comonomer, and another hydroxyl group is bonded near the α position on the same hydrocarbon chain via a linker such as a hydrocarbon chain. It may be.

In the present invention, the structure of the α-olefin portion of the structural unit derived from the α-olefin comonomer having a hydroxyl group is not particularly limited, but the carbon number is 5 or more in order to impart adhesiveness to the inorganic filler. It is preferable. The hydrocarbon chain of the α-olefin comonomer is preferably linear. The olefin-based random copolymer of the present invention has excellent interfacial adhesion to an inorganic filler, as shown in Examples below. The reason is speculated as follows.
When the number of carbon atoms of the α-olefin comonomer having a hydroxyl group in the olefin-based random copolymer is smaller than 5, the interaction between the hydroxyl group and the polyolefin main chain to which the hydroxyl group is bound becomes strong, so that the mobility of the hydroxyl group is increased. It is considered that the hydroxyl groups and the surface of the inorganic filler are constrained, and it becomes difficult to take an optimal arrangement, and as a result, strong interaction between the hydroxyl group and the surface of the inorganic filler is unlikely to occur. On the other hand, when the α-olefin comonomer having a hydroxyl group in the olefin-based random copolymer has 5 or more carbon atoms, the constraint on the mobility of the hydroxyl group is relaxed, the mobility of the hydroxyl group is improved, and the hydroxyl group and the inorganic filler surface are It is thought that strong interaction with is likely to occur. That is, it is presumed that making the movement of the hydroxyl group independent of the polyolefin main chain and increasing the mobility of the hydroxyl group is an effective mechanism for maximizing the interaction with the surface of the inorganic filler. In order to make the hydroxyl group independent of the movement of the polyolefin main chain itself and enhance the mobility of the hydroxyl group, it is necessary to enhance the mobility of the carbon atom near the end of the α-olefin to which the hydroxyl group is directly bonded. The direct restraining force that the carbon atom near the terminal receives from the polyolefin main chain is the expansion and contraction of interatomic bonds (interaction between two atoms), the bending angle (interaction between three atoms), the dihedral angle of bonds (four atoms). Interaction) is known (see, for example, J. Phys. Chem. Vol. 94, p8897, 1990).
Therefore, in order to release the carbon atoms near the end of the α-olefin from the direct restraining force from the polyolefin main chain, it is preferable that at least the interaction of the bond dihedral angle is not exerted. That is, it is assumed that it is preferable to use an α-olefin having 5 or more carbon atoms.
On the other hand, since the main monomer that occupies most of the structural units contained in the olefin-based random copolymer is a monomer having a small number of carbon atoms such as propylene and ethylene in many cases, the α-olefin comonomer having a hydroxyl group is As the carbon number increases, the difference in carbon number between the different structural units contained in the olefin random copolymer increases, leading to a decrease in the glass transition temperature of the olefin random copolymer (dynamics of polymer and composite material). By LE Nielsen, Kagaku Dojin Co., Ltd., 1984, Chapter 1), the deterioration of heat resistance of the composite material and the softening of the resin itself make it impossible to play a role as a stress transmitting material at the adhesive interface. There is concern that this may lead to a decrease in rigidity.
Therefore, the number of carbon atoms of the α-olefin comonomer having a hydroxyl group capable of improving adhesiveness while maintaining heat resistance and rigidity is preferably 5 or more and 20 or less, and more preferably 5 or more and 12 or less.

As the main olefin monomer occupying most of the structural units contained in the olefin-based random copolymer of the present invention, in order to make it the same structural unit as the structural unit of the olefin-based matrix resin of the composite material, the number of carbon atoms is usually Less olefin monomers, more specifically, olefin monomers having 5 or less carbon atoms such as propylene and ethylene are used.
As the main olefin monomer, it is preferable to select one having a high affinity with the matrix resin of the composite material combined with the olefin resin of the present invention. From this viewpoint, it is preferable to use a monomer that produces the same structural unit as the main structural unit contained in the matrix resin of the composite material. For example, when the matrix resin of the composite material is a propylene resin, it is preferable to use propylene as the main α-olefin monomer.

Regarding the molecular weight of the olefin-based random copolymer of the present invention, the weight average molecular weight measured by gel permeation chromatography (GPC) is 40,000 or more and 500,000 or less, more preferably 50,000 or more and 300,000. It is as follows.
When the molecular weight of the olefin random copolymer of the present invention is larger than the upper limit of the above range, the fluidity as a composite material is insufficient, and a molding machine having a large mold clamping force when molding a thin molded product is required. Alternatively, it is necessary to raise the molding temperature, which adversely affects the productivity. On the other hand, when the molecular weight is less than the lower limit of the above range, mechanical properties such as impact resistance are poor.

The olefin-based random copolymer of the present invention is an α-olefin monomer which is a main monomer of the copolymer, and the content of structural units in the copolymer is 0.5 mol% or more and 10 mol% or less. It can be produced by charging an α-olefin comonomer having a hydroxyl group and using various known catalysts used in the synthesis of polypropylene or the like, for example, a Ziegler-Natta catalyst or a metallocene catalyst, and copolymerizing.
In general, the Ziegler-Natta catalyst tends to have a wide monomer composition distribution in the random copolymer produced from the non-uniformity of active sites, which may reduce rigidity and impact strength due to a wide molecular weight distribution. .. The content ratio of the constituent unit of the α-olefin comonomer having a hydroxyl group in the copolymer is preferably 0.55 mol% or more and 7.5 mol% or less, more preferably 0.6 mol% or more and 6 mol% or less, and It is preferably 0.6 mol% or more and 5 mol% or less.
The molecular weight distribution (Mw/Mn) of the olefin-based random copolymer of the present invention is preferably 3.5 or less, more preferably 3.0 or less. By using a metallocene catalyst, an olefin-based random copolymer having a narrow molecular weight distribution can be easily obtained. The molecular weight distribution (Mw/Mn) is set to 1.0 or more.
The metallocene catalyst referred to here is (i) a transition metal compound of Group 4 of the periodic table (so-called metallocene compound) containing a ligand having a cyclopentadienyl skeleton, (ii) an aluminumoxy compound, and the above transition metal compound. At least one cocatalyst selected from the group consisting of an ionic compound or Lewis acid capable of reacting with and converting to a cation, a solid acid fine particle, and a compound group consisting of an ion-exchange layered silicate, and if necessary, iii) Any known catalyst that is a catalyst composed of an organoaluminum compound and is capable of producing a propylene-based resin can be used.

<Method for producing olefin random copolymer>
The olefin-based random copolymer used for the olefin-based resin composite material containing an inorganic filler is an α-olefin monomer having 3 to 5 carbon atoms, which is a main monomer, and an α-olefin monomer having 5 to 20 carbon atoms, which has a hydroxyl group. In addition to the olefin comonomer, it is possible to add an organoaluminum compound if necessary, and use various known catalysts for α-olefin polymerization, particularly polypropylene polymerization.

The α-olefin comonomer having a hydroxyl group and having 5 to 20 carbon atoms used in the present invention is preferably 3-methyl-2-buten-1-ol, 2-methyl-3-buten-1-ol, 3 or -Methyl-3-buten-1-ol, 2-methyl-3-buten-2-ol, 2-penten-1-ol, 4-penten-1-ol, 3-penten-2-ol, 4-pentene 2-ol, 1-penten-3-ol, 4-methyl-3-penten-1-ol, 3-methyl-1-penten-3-ol, 2-hexen-1-ol, 3-hexene-1. -Ol, 4-hexen-1-ol, 5-hexen-1-ol, 1-hexen-3-ol, 1-hepten-3-ol, 6-methyl-5-hepten-2-ol, 1-octene -3-ol, citronellol, dihydromyrcenol, 3-nonen-1-ol, 5-decen-1-ol, 9-decen-1-ol, 10-undecen-1-ol, oleyl alcohol, 2-methylene. -1,3-propanediol, 7-octene-1,2-diol, 1,4-pentadiene-3-ol, 2,4-hexadiene-1-ol, 1,5-hexadiene-3-ol, 2, 4-dimethyl-2,6-heptadien-1-ol, dihydrocarbeol, isopregool, 5-norbornen-2-ol, 5-norbornene-2-methanol, 5-norbornene-2,2-dimethanol, etc. Can be mentioned.
More preferably, 4-penten-1-ol, 5-hexen-1-ol, citronellol, dihydromyrcenol, 10-undecen-1-ol, 7-octene-1,2-diol, 5-norbornene-2. -Ol, 5-norbornene-2-methanol.
Particularly preferred are 5-hexen-1-ol and 10-undecen-1-ol.

The organoaluminum compound used in the present invention is preferably trialkylaluminum, triisopropylaluminum, triisobutylaluminum, trialkylaluminum such as trioctylaluminum, dialkylaluminum halide, alkylaluminum sesquihalide, alkylaluminum dihalide, alkylaluminum. Hydride, such as aluminum oxy compounds such as methylalumoxane and butylalumoxane, and the like, more preferably, triethylaluminum, triisopropylaluminum, triisobutylaluminum, methylalumoxane, particularly preferably, triisobutylaluminum, methyl. Alumoxane is mentioned.

The polymerization catalyst used in the production of the olefin-based random copolymer of the present invention reacts with (i) a transition metal compound of Groups 4 to 10 of the periodic table, and (ii) an aluminumoxy compound and the above transition metal compound, if necessary. Cation compound capable of being converted into a cation by means of at least one promoter selected from the group of compounds consisting of Lewis acid, solid acid fine particles, and ion-exchange layered silicate, and optionally (iii) organoaluminum Any known catalyst that is a catalyst composed of a compound and is capable of producing an olefin resin can be used.

Examples of the transition metal compound of Groups 4 to 10 of the periodic table include Group 4 metallocene compounds, Group 10 phosphine phenolate compounds, Group 10 phosphine sulfonate compounds, and the like, and Group 4 metallocene compounds are particularly preferable.
The Group 4 metallocene compound is a cross-linking metallocene compound capable of stereoregular polymerization of propylene, and preferably a metallocene compound capable of isoregular polymerization of propylene.
For example, JP-A-2-131488, JP-A-2-76887, JP-A-4-211694, JP-A-4-300887, JP-A-5-43616, JP-A-6-100579, and JP-A-5-2090113. The metallocene compounds described in JP-A-6-239914, JP-A-11-240909, JP-A-6-184179, JP-A-2003-533550 and the like.

Specific examples of the Group 4 metallocene compound include the following.
Dimethylsilylenebis[1-(2-methyl-4-phenylindenyl)]zirconium dichloride, Dimethylsilylenebis[1-(2-ethyl-4-phenylindenyl)]zirconium dichloride, Dimethylsilylenebis[1-(2 -Methyl-4-(1-naphthyl)-indenyl)]zirconium dichloride, dimethylsilylene bis[1-(2-methyl-4,5-benzoindenyl)]zirconium dichloride, dimethylsilylene[1-(2-methyl- 4-(4-t-butylphenyl)indenyl)][1-(2-i-propyl-4-(4-t-butylphenyl)indenyl)]zirconium dichloride, dimethylsilylenebis[1-(2-methyl- 4-phenyl-4H-azurenyl)]zirconium dichloride, dimethylsilylenebis[1-(2-ethyl-4-(4-chlorophenyl)-4H-azurenyl)]zirconium dichloride, dimethylsilylenebis[1-(2-ethyl- 4-(2-fluorobiphenylyl)-4H-azurenyl)]zirconium dichloride, dimethylgermylene bis[1-(2-ethyl-4-(4-chlorophenyl)-4H-azurenyl)]zirconium dichloride, dimethylgermylene bis Examples thereof include zirconium compounds such as [1-(2-ethyl-4-phenylindenyl)]zirconium dichloride.

A compound in which zirconium is replaced by hafnium in the above metallocene compound can be used as well. Also, two or more kinds of complexes can be used. Further, chloride can be replaced with other halogen compounds, hydrocarbon groups such as methyl and benzyl, amide groups such as dimethylamide and diethylamide, alkoxide groups such as methoxy group and phenoxy group, and hydride groups. Of these, metallocene compounds having substituents at the 2- and 4-positions and having a bisindenyl group or an azulenyl group crosslinked with a silicon or germyl group as a ligand are preferable.
The above complex may be isolated and extracted for use as a catalyst, or may be used for a catalyst without isolation. Further, one kind may be used alone, or plural kinds of catalyst compositions may be used in combination. In particular, for the purpose of broadening the molecular weight distribution and the comonomer content distribution, the combined use of such plural kinds of catalyst compositions is useful.

In the polymerization for producing the α-olefin having 3 to 5 carbon atoms and the α-olefin comonomer copolymer having 5 to 20 carbon atoms having a hydroxyl group, which is used as the olefin random copolymer of the present invention, the polymerization type is , Not particularly limited.
Polymerization methods include slurry polymerization in which at least a part of the produced polymer becomes a slurry in a medium, bulk polymerization using a liquefied monomer itself as a medium, gas phase polymerization performed in a vaporized monomer, and liquefaction at high temperature and high pressure. High pressure ionic polymerization in which at least a part of the produced polymer is dissolved in the monomer can be used. Further, any of batch polymerization, semi-batch polymerization and continuous polymerization may be used.
In the slurry polymerization in which at least a part of the produced polymer becomes a slurry in the medium, a hydrocarbon solvent such as propane, n-butane, isobutane, n-hexane, n-heptane, toluene, xylene, cyclohexane, and methylcyclohexane, Liquids such as liquefied α-olefins and polar solvents such as diethyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, dioxane, ethyl acetate, methyl benzoate, acetone, methyl ethyl ketone, formamide, acetonitrile, methanol, isopropyl alcohol, ethylene glycol, etc. It is performed in the presence or absence.
Also, mixtures of the liquid compounds described herein may be used as the solvent.
The above-mentioned hydrocarbon solvents are more preferable for obtaining high polymerization activity and high molecular weight. Further, upon copolymerization, the copolymerization can be carried out in the presence or absence of a known additive.

As the additive, a radical polymerization inhibitor or an additive having a function of stabilizing the produced copolymer is preferable. Examples of preferable additives include quinone derivatives and hindered phenol derivatives. Specifically, monomethyl ether hydroquinone, 2,6-di-t-butyl 4-methylphenol (BHT), a reaction product of trimethylaluminum and BHT, a reaction product of alkoxide of tetravalent titanium and BHT, and the like. Can be used.
Inorganic and/or organic fillers may be used as additives, and polymerization may be carried out in the presence of these fillers.

The polymerization temperature, the polymerization pressure and the polymerization time are not particularly limited, but usually, the optimum setting can be made from the following ranges in consideration of productivity and process capability.
The polymerization temperature is usually -20°C to 290°C, preferably 0°C to 250°C, more preferably 20°C to 200°C, further preferably 25°C to 150°C, particularly preferably 30°C. To 100°C.
The polymerization pressure is usually 0.1 MPa to 100 MPa, preferably 0.3 MPa to 90 MPa, more preferably 0.35 MPa to 10 MPa, and further preferably 0.4 MPa to 5 MPa.
The polymerization time is usually 0.1 minutes to 10 hours, preferably 0.5 minutes to 7 hours, more preferably 1 minute to 6 hours.

There is no particular limitation on the supply of the catalyst and the monomer to the polymerization reactor, and various supply methods can be adopted depending on the purpose.
For example, in the case of batch polymerization, it is possible to supply a predetermined amount of monomer to the copolymerization reactor in advance and supply the catalyst thereto. In this case, additional monomer or additional catalyst may be fed to the copolymerization reactor.
Further, in the case of continuous polymerization, it is possible to employ a method in which a predetermined amount of a monomer and a catalyst are continuously or intermittently supplied to a copolymerization reactor to continuously carry out the copolymerization reaction.
A conventionally known method can be used for controlling the molecular weight of the polymer. That is, by controlling the polymerization temperature to control the molecular weight, controlling the monomer concentration to control the molecular weight, controlling the molecular weight using a chain transfer agent, and controlling the ligand structure of the catalyst. Examples thereof include a method of controlling the molecular weight.

Regarding the composition control of the polymer, a method of supplying a plurality of monomers to a reactor and controlling the composition by changing the supply ratio can be generally used.
Other methods include controlling the copolymerization composition by utilizing the difference in monomer reactivity ratio due to the difference in catalyst structure, and controlling the copolymerization composition by utilizing the polymerization temperature dependency of the monomer reactivity ratio. To be

2. Olefin Resin Composition The olefin resin composition of the present invention is a composition containing the olefin random copolymer (A) of the present invention and an inorganic filler (B) as essential components.
The olefin resin composition of the present invention is suitably used as an additive for reinforcing an olefin molding resin with an inorganic filler. The olefin resin composition may be an olefin resin composition for an inorganic filler-olefin resin composite material used for an olefin resin composite material containing an inorganic filler.
As the inorganic filler used in the olefin resin composition of the present invention, glass, talc, mica, clay, montmorillonite, bentonite, activated clay, sepiolite, imogolite, sericite, wollastonite and the like silicates, calcium carbonate, magnesium carbonate. , Carbonates such as zinc carbonate, barium carbonate, dawsonite, hydrotalcite, hydroxides such as aluminum hydroxide, magnesium hydroxide, calcium hydroxide, zinc oxide, titanium oxide, silica, diatomaceous earth, alumina, magnesium oxide, etc. Examples of the filler include oxides.
Among them, glass fillers which are generally used for the purpose of reinforcing a thermoplastic resin or the like, and glass fillers having a scaly, fibrous, powdery, or beaded shape are preferably used. As the glass constituting the glass filler, non-alkali silicate glass such as E glass, alkali-containing silicate glass such as C glass, or ordinary soda lime glass is used.

Among glass fillers, glass fiber not only excels in mechanical properties such as specific strength and specific elastic modulus, but also in functional properties such as thermal stability, chemical stability, and electromagnetic wave properties, It is preferable because it can be expected to have a wide range of application fields as a filler for use.
Although the size of the glass fiber is not particularly limited, the average fiber diameter is usually 3 μm or more and 30 μm or less, preferably 8 μm or more and 20 μm or less, and the average fiber length is usually 0.05 mm or more and 200 mm or less, preferably 0.2 mm or more and 50 mm or less. Hereafter, it is more preferably 2 mm or more and 20 mm or less.
The aspect ratio (average fiber length/average fiber diameter) of the glass fibers is usually 5 or more and 6000 or less, preferably 10 or more and 2000 or less.

Alumina fibers are also preferably used as the inorganic filler other than the glass filler. Although the size of the alumina fiber is not particularly limited, the average fiber diameter is usually 0.5 μm or more and 30 μm or less, preferably 1 μm or more and 20 μm or less, and the average fiber length is usually 0.05 mm or more and 200 mm or less, preferably 0.2 mm. It is 50 mm or less and more preferably 2 mm or more and 20 mm or less.

The olefin resin composition of the present invention may contain an olefin (co)polymer other than the olefin random copolymer of the present invention as a diluting resin. As the olefin (co)polymer as the diluting resin, it is desirable to use an olefin resin for molding, that is, one having a high affinity with the olefin matrix resin used in the olefin resin composite material containing an inorganic filler. .. From this point of view, the olefin-based (co)polymer for dilution is preferably a homopolymer or a copolymer containing a monomer that forms a main structural unit of the polymer which is the olefin-based matrix resin. The olefin (co)polymer for dilution preferably contains 50 mol% or more of the main structural unit of the polymer which is the olefin matrix resin.
For example, when the olefin-based matrix resin is a propylene-based resin, the olefin-based (co)polymer for dilution is preferably a propylene homopolymer or a propylene copolymer, and the propylene unit content is 50 mol. % Or more is preferable.

The content of the inorganic filler and the olefin-based random copolymer is not particularly limited, but the inorganic filler is usually 5% by mass or more and 40% by mass when the entire olefin-based resin composition of the present invention is 100% by mass. The following content is preferably 10% by mass or more and 40% by mass or less. The olefin-based random copolymer is usually contained in an amount of 60% by mass or more and 95% by mass or less, preferably 60% by mass or more and 90% by mass or less, based on 100% by mass of the entire olefin resin composition of the present invention.

The olefin resin composition of the present invention is obtained by melt-kneading an inorganic filler, an olefin random copolymer, and, if necessary, an olefin (co)polymer for dilution, and other additives, and pellets. The shape can be a shape such as a shape, a powder shape, or a flake shape.
The step of melt-kneading can be performed, for example, by a roll mill, a Banbury mixer, a kneader or the like. Moreover, after mixing with a tumbler type blender, a Henschel mixer, a ribbon mixer, etc., you may knead with a single screw extruder, a twin screw extruder, etc.
When using long glass fibers as the glass fibers, a bundle of long glass fiber monofilaments is introduced into an impregnation die, and after impregnating the resin component in a molten state in the die, the pellets are cut into the required length. A composition of the form is obtained.

3. Olefin Resin Composite Material Containing Inorganic Filler of the Present Invention The olefin resin composite material containing an inorganic filler of the present invention comprises, as essential components, an inorganic filler (A), the olefin random copolymer (B) of the present invention, And a composition containing an olefin resin (C) other than the olefin random copolymer of the present invention.
INDUSTRIAL APPLICABILITY The composite material of the present invention is suitably used as a resin material for molding an inorganic filler-reinforced resin molded body that is lightweight and has excellent mechanical properties.
Since the olefin random copolymer of the present invention is an olefin resin having excellent interfacial adhesion with an inorganic filler, it may be used as a matrix resin for a composite material. In that case, a molded product can be produced by using an inorganic filler as an essential component and an inorganic filler-reinforced composite material containing the olefin random copolymer of the present invention.
The olefin resin composite material of the present invention uses an olefin resin other than the olefin resin of the present invention as the olefin matrix resin of the composite material. As the matrix resin, an olefin resin that has been conventionally used as a molding resin can be used. From the viewpoint of lightness and economy, a propylene resin is preferably used as the matrix resin. As the propylene-based resin, propylene homopolymer, and, may be used any of the propylene copolymer, from the viewpoint of sufficiently bringing out the mechanical properties of the propylene-based resin, it is preferable that the polymerization ratio of the propylene monomer is large, Specifically, usually, a propylene-based resin in which the content ratio of the structural units derived from the propylene monomer is 50 mol% or more based on 100 mol% of the total structural units in the polymer is used.

The composite material of the present invention may contain various additives as required. For example, dispersants, lubricants, plasticizers, flame retardants, antioxidants (phenolic antioxidants, phosphoric antioxidants, sulfur antioxidants), antistatic agents, light stabilizers, UV absorbers, crystallization acceleration Agents (nucleating agents), foaming agents, crosslinking agents, modifying additives such as antibacterial agents, colorants such as pigments and dyes, carbon black, titanium oxide, red iron oxide, azo pigments, anthraquinone pigments, phthalocyanines, talc, carbonic acid Examples thereof include particulate fillers such as calcium, mica and clay, short fibrous fillers such as wollastonite, whiskers such as potassium titanate.

The content of the inorganic filler, the olefin random copolymer, and the olefin matrix resin in the olefin resin composite material is not particularly limited, but the inorganic filler is usually 100% by mass of the entire olefin resin composite material. In this case, the content is 5% by mass or more and 40% by mass or less, preferably 10% by mass or more and 30% by mass or less. The olefin-based random copolymer is usually contained in an amount of 1% by mass or more and 20% by mass or less, preferably 3% by mass or more and 10% by mass or less, based on 100% by mass of the entire olefin resin composite. The olefin-based matrix resin is usually contained in an amount of 40% by mass or more and 94% by mass or less, preferably 60% by mass or more and 87% by mass or less, based on 100% by mass of the entire olefin resin composite.

The olefin resin composite of the present invention is an inorganic filler, the olefin random copolymer of the present invention, an olefin matrix resin, and, obtained by melt-kneading other additives, pellets, powder, The shape may be a flake shape or the like. As the method and apparatus for melt-kneading, the same one as in the case of producing the above-mentioned olefin resin composition of the present invention can be used.
Further, the olefin resin composite material of the present invention may be manufactured by mixing the olefin matrix resin and the above-mentioned olefin resin composition of the present invention. In this case, the olefin resin composite material of the present invention may be manufactured by mixing the pellets of the olefin matrix resin and the pellets of the olefin resin composition of the present invention.

By using the olefin-based resin composite material of the present invention, it is possible to manufacture a lightweight molded article having excellent mechanical properties such as bending strength, bending elastic modulus, impact strength, and rigidity. As the molding method, known molding methods such as an injection molding method, an extrusion molding method, a hollow molding method, a compression molding method, an injection compression molding method, a gas injection injection molding method, and a foam injection molding method can be applied.
Molded articles in various fields can be produced using the olefin resin composite material of the present invention. For example, automobile members, automobile parts, automobile materials, furniture, house-related interior/exterior materials, tools and other machine parts can be molded.
Examples of automobile members include interior parts such as instrument panels, door panels and console boxes, and exterior parts such as radiator grills, spoilers, side garnishes and lamp covers. Examples of bicycle parts include frames and wheels. Examples of furniture include chairs, legs of tables, and storage containers. Examples of housing-related interior and exterior materials include bathroom parts, valves around water, toilet seats, etc. Examples of tools and other mechanical parts include electric tool parts, hose joints, and resin bolts.
In particular, in a composite material using a propylene-based resin as a matrix resin, the olefin-based resin of the present invention containing a structural unit derived from a hydroxyl group-containing comonomer imparts excellent adhesiveness between the inorganic filler and the propylene-based matrix resin. Therefore, the physical properties such as rigidity, heat resistance, and moldability originally possessed by the propylene-based matrix resin are not impaired, and the deterioration of durability due to peeling of the bonding interface, which is usually a problem in composite materials, is improved, It can be expected to have a physical property balance.
In particular, it can be suitably used in the field of automobile materials that require a high balance of physical properties such as large size of products, thin and lightweight, diversification of shapes, recyclability, and economic efficiency.

Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited to these Examples as long as the gist thereof is not exceeded.

1. Evaluation method (1) Molecular weight (Mw) and molecular weight distribution (Mw/Mn)
The weight average molecular weight (Mw) was determined by gel permeation chromatography (GPC). The specific measurement method is as follows. As for the molecular weight distribution parameter (Mw/Mn), the number average molecular weight (Mn) was further determined by GPC, and the ratio of Mw and Mn, Mw/Mn was calculated.
[Measurement condition]
-Device: Waters GPC (ALC/GPC 150C)
・Detector: MIRAN 1A IR detector manufactured by FOXBORO (measurement wavelength: 3.42 μm)
・Column: Showa Denko AD806M/S (3)
・Mobile phase solvent: Orthodichlorobenzene (ODCB)
・Measuring temperature: 140℃
・Flow rate: 1.0 ml/min
・Injection volume: 0.2 ml
[Sample preparation]
ODCB (containing 0.5 mg/mL of 2,6-di-t-butyl-4-methylphenol (BHT)) was used as a sample to prepare a 1 mg/mL solution, and it took about 1 hour at 140°C. And dissolved.
[Calculation of molecular weight]
The conversion from the retention capacity obtained by GPC measurement into the molecular weight was performed using a calibration curve prepared in advance using standard polystyrene (PS). The standard polystyrenes used are all the following brands manufactured by Tosoh Corporation.
F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000
A calibration curve was prepared by injecting 0.2 mL of a solution dissolved in ODCB (containing 0.5 mg/mL BHT) so that each was 0.5 mg/mL. As the calibration curve, a cubic expression obtained by approximation by the least square method was used.
The following numerical values were used for the viscosity formula [η]=K×M ^α used for conversion into the molecular weight.
PS: K=1.38×10 ⁻⁴ , α=0.7
PP: K=1.03×10 ⁻⁴ , α=0.78
That is, the weight average molecular weight (Mw) of the olefin resin used in the olefin resin composite material containing an inorganic filler was determined from the polypropylene-converted molecular weight by the method described above. The definition of Mw is described in "Basics of Polymer Chemistry" (edited by The Polymer Society of Japan, Tokyo Kagaku Dojin, 1978) and the like.

(2) Hydroxyl group-containing comonomer content (mol%)
The content (mol %) of the α-olefin comonomer having a hydroxyl group was determined using the signal intensity of 1H-NMR spectrum.
[Sample preparation]
A 200 mg sample was placed in an NMR sample tube with an inner diameter of 10 mmφ together with O-dichlorobenzene/deuterated benzene bromine (C6D5Br)=4/1 (volume ratio) 2.4 ml and hexamethyldisiloxane which is a chemical shift reference substance. After substituting with nitrogen, the tube was sealed, heated, dissolved and subjected to NMR measurement as a uniform solution.
[Measurement condition]
For the NMR measurement, an NMR apparatus AVANCE (III) 400 manufactured by Bruker BioSpin Co., Ltd. equipped with a 10 mmφ cryoprobe was used. The measurement conditions of 1 H-NMR were as follows: the sample temperature was 120° C., the pulse angle was 4.5°, the pulse interval was 2 seconds, and the number of integration was 512 times. The chemical shift was set with the proton signal of hexamethyldisiloxane set to 0.09 ppm, and the chemical shifts of signals due to other protons were based on this. The comonomer content was assigned based on the comonomer signal of the 1H-NMR spectrum, and calculated based on the signal intensity.

2. Production of Olefin Resin As the olefin resin used for the olefin resin composite material containing the inorganic filler, the following A-1 to A-15 were used.

<Production of A-1>
A propylene/10-undecen-1-ol copolymer was produced by the following method.
2 μmol of rac-dimethylsilylenebis(2-methyl-4-phenylindenyl)zirconium dichloride was weighed into a 30 mL flask that had been sufficiently replaced with nitrogen, and dehydrated heptane (10 mL) was added. To this heptane solution, a methylaluminoxane toluene solution (20 mmol as methylaluminoxane (MAO)) manufactured by Nippon Alkyaluminum Co., Ltd. was added to prepare a catalyst solution.
Next, under a purified nitrogen atmosphere, a purified heptane (500 mL), 10-undecen-1-ol (60 mmol) and triisobutylaluminum (66 mmol) were introduced into a stainless steel autoclave with an internal volume of 2.4 L and equipped with an induction stirrer, hydrogen (200 mL) and propylene pressure. Stabilized at 0.5 MPa and 80°C.
Then, the catalyst solution prepared above was added into the autoclave to start the polymerization.
After completion of the polymerization for 15 minutes, ethanol (10 mL) was added, the pressure was released, the atmosphere was replaced with nitrogen, and the autoclave was cooled to room temperature.
The copolymer was reprecipitated from the recovered polymerization slurry liquid using ethanol (1 L), and the copolymer was obtained by filtration.
The copolymer was washed with a hydrochloric acid (2N, 200 mL)/ethanol (1 L) solution, and then further washed with ethanol (1 L).
After drying under reduced pressure at 70° C. for 6 hours, a propylene/10-undecen-1-ol copolymer was finally recovered. The yield was 36.7 g, Mw 110,000, Mw/Mn 2.4, 10-undecen-1-ol content 4.30 mol %.

<Production of A-2>
A propylene/10-undecen-1-ol copolymer was produced by the following method.
7 μmol of rac-dimethylsilylenebis(2-methyl-4-phenylindenyl)zirconium dichloride was weighed into a 30 mL flask that had been sufficiently replaced with nitrogen, and dehydrated heptane (10 mL) was added. To this heptane solution, a methylaluminoxane toluene solution (1.8 mmol as methylaluminoxane (MAO)) manufactured by Nippon Alkyl Aluminum Co., Ltd. was added to prepare a catalyst solution.
Then, under a purified nitrogen atmosphere, a purified heptane (500 mL), 10-undecen-1-ol (60 mmol) and triisobutylaluminum (80 mmol) were introduced into a stainless steel autoclave with an internal volume of 2.4 L and equipped with an induction stirrer, hydrogen (22 mL), and propylene pressure. Stabilized at 0.5 MPa and 70°C.
Then, the catalyst solution prepared above was added into the autoclave to start the polymerization.
After completion of the polymerization for 20 minutes, ethanol (10 mL) was added, the pressure was released, the atmosphere was replaced with nitrogen, and the autoclave was cooled to room temperature.
The copolymer was reprecipitated from the recovered polymerization slurry liquid using ethanol (1 L), and the copolymer was obtained by filtration.
The copolymer was washed with a hydrochloric acid (2N, 200 mL)/ethanol (1 L) solution, and then further washed with ethanol (1 L).
After drying under reduced pressure at 70° C. for 6 hours, a propylene/10-undecen-1-ol copolymer was finally recovered. The yield was 28.9 g, Mw 254,000, Mw/Mn 3.0, and 10-undecen-1-ol content 3.00 mol %.

<Production of A-3>
A propylene/10-undecen-1-ol copolymer was produced by the following method.
22 μmol of rac-dimethylsilylenebis(2-methyl-4-phenylindenyl)zirconium dichloride was weighed into a 30 mL flask that had been sufficiently replaced with nitrogen, and dehydrated heptane (10 mL) was added. To this heptane solution, a methylaluminoxane toluene solution (5.8 mmol of methylaluminoxane (MAO)) manufactured by Nippon Alkylaluminum Co., Ltd. was added to prepare a catalyst solution.
Next, under a purified nitrogen atmosphere, a purified heptane (500 mL), 10-undecen-1-ol (60 mmol) and triisobutylaluminum (80 mmol) were introduced into a stainless steel autoclave with an internal volume of 2.4 L and equipped with an induction stirrer, hydrogen (242 mL) and propylene pressure. Stabilized at 0.5 MPa and 70°C.
Then, the catalyst solution prepared above was added into the autoclave to start the polymerization.
After completion of the polymerization for 20 minutes, ethanol (10 mL) was added, the pressure was released, the atmosphere was replaced with nitrogen, and the autoclave was cooled to room temperature.
The copolymer was reprecipitated from the recovered polymerization slurry liquid using ethanol (1 L), and the copolymer was obtained by filtration.
The copolymer was washed with a hydrochloric acid (2N, 200 mL)/ethanol (1 L) solution, and then further washed with ethanol (1 L).
After drying under reduced pressure at 70° C. for 6 hours, a propylene/10-undecen-1-ol copolymer was finally recovered. The yield was 40.2 g, Mw 64,000, Mw/Mn 2.6, 10-undecen-1-ol content 3.70 mol %.

<Production of A-4>
A propylene/10-undecen-1-ol copolymer was produced by the following method.
11 μmol of rac-dimethylsilylenebis(2-methyl-4-phenylindenyl)zirconium dichloride was weighed in a 30 mL flask that had been sufficiently replaced with nitrogen, and dehydrated heptane (10 mL) was added. A methylaluminoxane toluene solution (2.5 mmol as methylaluminoxane (MAO)) manufactured by Nippon Alkyl Aluminum Co., Ltd. was added to this heptane solution to prepare a catalyst solution.
Next, under a purified nitrogen atmosphere, a purified heptane (500 mL), 10-undecen-1-ol (60 mmol) and triisobutylaluminum (80 mmol) were introduced into a stainless steel autoclave with an internal volume of 2.4 L and equipped with an induction stirrer, hydrogen (66 mL), and propylene pressure. Stabilized at 0.5 MPa and 70°C.
Then, the catalyst solution prepared above was added into the autoclave to start the polymerization.
After completion of the polymerization for 20 minutes, ethanol (10 mL) was added, the pressure was released, the atmosphere was replaced with nitrogen, and the autoclave was cooled to room temperature.
The copolymer was reprecipitated from the recovered polymerization slurry liquid using ethanol (1 L), and the copolymer was obtained by filtration.
The copolymer was washed with a hydrochloric acid (2N, 200 mL)/ethanol (1 L) solution, and then further washed with ethanol (1 L).
After drying under reduced pressure at 70° C. for 6 hours, a propylene/10-undecen-1-ol copolymer was finally recovered. The yield was 7.6 g, Mw 111,000, Mw/Mn 2.2, and 10-undecen-1-ol content was 3.10 mol %.

<Production of A-5>
A propylene/10-undecen-1-ol copolymer was produced by the following method.
2 μmol of rac-dimethylsilylenebis(2-methyl-4-phenylindenyl)zirconium dichloride was weighed into a 30 mL flask that had been sufficiently replaced with nitrogen, and dehydrated heptane (10 mL) was added. To this heptane solution, a methylaluminoxane toluene solution (20 mmol as methylaluminoxane (MAO)) manufactured by Nippon Alkyaluminum Co., Ltd. was added to prepare a catalyst solution.
Next, 900 mL of purified heptane, 25 mmol of 10-undecen-1-ol, and 28 mmol of triisobutylaluminum were introduced into a stainless steel autoclave with an internal volume of 2.4 L and equipped with an induction stirrer under a purified nitrogen atmosphere, hydrogen of 400 mL, and propylene pressure. Stabilized at 0.5 MPa and 100°C.
Then, the catalyst solution prepared above was added into the autoclave to start the polymerization.
After completion of the polymerization for 15 minutes, ethanol (10 mL) was added, the pressure was released, the atmosphere was replaced with nitrogen, and the autoclave was cooled to room temperature.
The copolymer was reprecipitated from the recovered polymerization slurry liquid using ethanol (1 L), and the copolymer was obtained by filtration.
The copolymer was washed with a hydrochloric acid (2N, 200 mL)/ethanol (1 L) solution, and then further washed with ethanol (1 L).
After drying under reduced pressure at 70° C. for 6 hours, a propylene/10-undecen-1-ol copolymer was finally recovered. The yield was 78.9 g, Mw 65,000, Mw/Mn 3.5, 10-undecen-1-ol content 1.10 mol %.

<Production of A-6>
A propylene/10-undecen-1-ol copolymer was produced by the following method.
0.5 μmol of rac-dimethylsilylenebis(2-methyl-4-phenylindenyl)zirconium dichloride was weighed into a 30 mL flask that had been sufficiently replaced with nitrogen, and dehydrated heptane (10 mL) was added. To this heptane solution, a methylaluminoxane toluene solution (10 mmol as methylaluminoxane (MAO)) manufactured by Nippon Alkyl Aluminum Co., Ltd. was added to prepare a catalyst solution.
Next, 900 mL of purified heptane, 20 mmol of 10-undecen-1-ol and 22 mmol of triisobutylaluminum were introduced into a stainless steel autoclave with an internal volume of 2.4 L and equipped with an induction stirrer under a purified nitrogen atmosphere, and 400 mL of hydrogen and propylene pressure were applied. Stabilized at 0.5 MPa and 80°C.
Then, the catalyst solution prepared above was added into the autoclave to start the polymerization.
After the completion of polymerization for 26 minutes, ethanol (10 mL) was added, the pressure was released, the atmosphere was replaced with nitrogen, and the autoclave was cooled to room temperature.
The copolymer was reprecipitated from the recovered polymerization slurry liquid using ethanol (1 L), and the copolymer was obtained by filtration.
The copolymer was washed with a hydrochloric acid (2N, 200 mL)/ethanol (1 L) solution, and then further washed with ethanol (1 L).
After drying under reduced pressure at 70° C. for 6 hours, a propylene/10-undecen-1-ol copolymer was finally recovered. The yield was 79.0 g, Mw 88,000, Mw/Mn 2.9, and 10-undecen-1-ol content was 0.80 mol %.

<Production of A-7>
A propylene/10-undecen-1-ol copolymer was produced by the following method.
1.7 μmol of rac-dimethylsilylenebis(2-methyl-4-phenylindenyl)zirconium dichloride was weighed in a 30 mL flask that was sufficiently replaced with nitrogen, and dehydrated heptane (10 mL) was added. To this heptane solution, a methylaluminoxane toluene solution (0.4 mmol as methylaluminoxane (MAO)) manufactured by Nippon Alkyl Aluminum Co., Ltd. was added to prepare a catalyst solution.
Then, under a purified nitrogen atmosphere, a purified heptane (500 mL), 10-undecen-1-ol (10 mmol) and triisobutylaluminum (13 mmol) were introduced into a stainless steel autoclave with an internal volume of 2.4 L and equipped with an induction stirrer, hydrogen (22 mL) and propylene pressure. Stabilized at 0.5 MPa and 70°C.
Then, the catalyst solution prepared above was added into the autoclave to start the polymerization.
After completion of the polymerization for 20 minutes, ethanol (10 mL) was added, the pressure was released, the atmosphere was replaced with nitrogen, and the autoclave was cooled to room temperature.
The copolymer was reprecipitated from the recovered polymerization slurry liquid using ethanol (1 L), and the copolymer was obtained by filtration.
The copolymer was washed with a hydrochloric acid (2N, 200 mL)/ethanol (1 L) solution, and then further washed with ethanol (1 L).
After drying under reduced pressure at 70° C. for 6 hours, a propylene/10-undecen-1-ol copolymer was finally recovered. The yield was 12.6 g, Mw 170,000, Mw/Mn2.5, 10-undecen-1-ol content 0.60 mol%.

<Production of A-8>
A propylene/10-undecen-1-ol copolymer was produced by the following method.
5 μmol of rac-dimethylsilylenebis(2-methyl-4-phenylindenyl)zirconium dichloride was weighed in a 30 mL flask that was sufficiently replaced with nitrogen, and dehydrated heptane (10 mL) was added. To this heptane solution, a methylaluminoxane toluene solution (1.2 mmol as methylaluminoxane (MAO)) manufactured by Nippon Alkyaluminum Co., Ltd. was added to prepare a catalyst solution.
Next, 750 mL of purified heptane, 30 mmol of 10-undecen-1-ol, and 40 mmol of triisobutylaluminum were introduced into a stainless steel autoclave with an internal volume of 2.4 L and equipped with an induction stirrer under a purified nitrogen atmosphere, and the propylene pressure was 0.5 MPa. Stabilized at 70°C.
Then, the catalyst solution prepared above was added into the autoclave to start the polymerization.
After completion of the polymerization for 40 minutes, ethanol (10 mL) was added, the pressure was released, the atmosphere was replaced with nitrogen, and the autoclave was cooled to room temperature.
The copolymer was reprecipitated from the recovered polymerization slurry liquid using ethanol (1 L), and the copolymer was obtained by filtration.
The copolymer was washed with a hydrochloric acid (2N, 200 mL)/ethanol (1 L) solution, and then further washed with ethanol (1 L).
After drying under reduced pressure at 70° C. for 6 hours, a propylene/10-undecen-1-ol copolymer was finally recovered. The yield was 37.1 g, Mw 295,000, Mw/Mn 2.4, 10-undecen-1-ol content 0.90 mol %.

<Production of A-9>
A propylene/10-undecen-1-ol copolymer was produced by the following method.
1 μmol of rac-dimethylsilylenebis(2-methyl-4-phenylindenyl)zirconium dichloride was weighed in a 30 mL flask that had been sufficiently replaced with nitrogen, and dehydrated heptane (10 mL) was added. To this heptane solution, a methylaluminoxane toluene solution (20 mmol as methylaluminoxane (MAO)) manufactured by Nippon Alkyaluminum Co., Ltd. was added to prepare a catalyst solution.
Next, 900 mL of purified heptane, 10 mmol of 10-undecen-1-ol, and 11 mmol of triisobutylaluminum were introduced into a stainless steel autoclave with an internal volume of 2.4 L and equipped with an induction stirrer under a purified nitrogen atmosphere. Stabilized at 0.5 MPa and 70°C.
Then, the catalyst solution prepared above was added into the autoclave to start the polymerization.
After completion of the polymerization for 30 minutes, ethanol (10 mL) was added, the pressure was released, the atmosphere was replaced with nitrogen, and the autoclave was cooled to room temperature.
The copolymer was reprecipitated from the recovered polymerization slurry liquid using ethanol (1 L), and the copolymer was obtained by filtration.
The copolymer was washed with a hydrochloric acid (2N, 200 mL)/ethanol (1 L) solution, and then further washed with ethanol (1 L).
After drying under reduced pressure at 70° C. for 6 hours, a propylene/10-undecen-1-ol copolymer was finally recovered. The yield was 115.7 g, Mw 39,000, Mw/Mn 2.2, 10-undecen-1-ol content 0.30 mol %.

<Production of A-10>
A propylene/3-buten-1-ol copolymer was produced by the following method.
1 μmol of rac-dimethylsilylenebis(2-methyl-4-phenylindenyl)zirconium dichloride was weighed in a 30 mL flask that had been sufficiently replaced with nitrogen, and dehydrated heptane (10 mL) was added. To this heptane solution, a methylaluminoxane toluene solution (20 mmol as methylaluminoxane (MAO)) manufactured by Nippon Alkyaluminum Co., Ltd. was added to prepare a catalyst solution.
Next, 900 mL of purified heptane, 60 mmol of 3-buten-1-ol, 66 mmol of triisobutylaluminum were introduced into a stainless steel autoclave with an induction stirrer having an internal volume of 2.4 L under a purified nitrogen atmosphere, and 200 mL of hydrogen and propylene pressure were introduced. Stabilized at 0.5 MPa and 70°C.
Then, the catalyst solution prepared above was added into the autoclave to start the polymerization.
After completion of the polymerization for 60 minutes, ethanol (10 mL) was added, the pressure was released, the atmosphere was replaced with nitrogen, and the autoclave was cooled to room temperature.
The copolymer was reprecipitated from the recovered polymerization slurry liquid using ethanol (1 L), and the copolymer was obtained by filtration.
The copolymer was washed with a hydrochloric acid (2N, 200 mL)/ethanol (1 L) solution, and then further washed with ethanol (1 L).
After drying under reduced pressure at 70° C. for 6 hours, a propylene/3-buten-1-ol copolymer was finally recovered. The yield was 13.9 g, Mw 192,000, Mw/Mn 1.9, and 3-buten-1-ol content of 0.10 mol %.

<Production of A-11>
A propylene/3-buten-1-ol copolymer was produced by the following method.
5 μmol of rac-dimethylsilylenebis(2-methyl-4-phenylindenyl)zirconium dichloride was weighed in a 30 mL flask that was sufficiently replaced with nitrogen, and dehydrated heptane (10 mL) was added. To this heptane solution, a methylaluminoxane toluene solution (20 mmol as methylaluminoxane (MAO)) manufactured by Nippon Alkyaluminum Co., Ltd. was added to prepare a catalyst solution.
Then, under a purified nitrogen atmosphere, a purified heptane (500 mL), 3-buten-1-ol (60 mmol), and triisobutylaluminum (66 mmol) were introduced into a stainless steel autoclave with an internal volume of 2.4 L and equipped with an induction stirrer, hydrogen (100 mL), and propylene pressure. Stabilized at 0.2 MPa and 70°C.
Then, the catalyst solution prepared above was added into the autoclave to start the polymerization.
After completion of the polymerization for 60 minutes, ethanol (10 mL) was added, the pressure was released, the atmosphere was replaced with nitrogen, and the autoclave was cooled to room temperature.
The copolymer was reprecipitated from the recovered polymerization slurry liquid using ethanol (1 L), and the copolymer was obtained by filtration.
The copolymer was washed with a hydrochloric acid (2N, 200 mL)/ethanol (1 L) solution, and then further washed with ethanol (1 L).
After drying under reduced pressure at 70° C. for 6 hours, a propylene/3-buten-1-ol copolymer was finally recovered. The yield was 9.8 g, Mw 78,000, Mw/Mn 2.1, and 3-buten-1-ol content of 0.50 mol %.

<Production of A-12>
A propylene/3-buten-1-ol copolymer was produced by the following method.
40 μmol of rac-dimethylsilylenebis(2-methyl-4-phenylindenyl)zirconium dichloride was weighed into a 30 mL flask that had been sufficiently replaced with nitrogen, and dehydrated heptane (10 mL) was added. To this heptane solution, a methylaluminoxane toluene solution (20 mmol as methylaluminoxane (MAO)) manufactured by Nippon Alkyaluminum Co., Ltd. was added to prepare a catalyst solution.
Then, under a purified nitrogen atmosphere, a purified heptane (500 mL), 3-buten-1-ol (40 mmol) and triisobutylaluminum (44 mmol) were introduced into a stainless steel autoclave with an internal volume of 2.4 L and equipped with an induction stirrer, hydrogen (100 mL) and propylene pressure. Stabilized at 0.2 MPa and 75°C.
Then, the catalyst solution prepared above was added into the autoclave to start the polymerization.
After completion of the polymerization for 15 minutes, ethanol (10 mL) was added, the pressure was released, the atmosphere was replaced with nitrogen, and the autoclave was cooled to room temperature.
The copolymer was reprecipitated from the recovered polymerization slurry liquid using ethanol (1 L), and the copolymer was obtained by filtration.
The copolymer was washed with a hydrochloric acid (2N, 200 mL)/ethanol (1 L) solution, and then further washed with ethanol (1 L).
After drying under reduced pressure at 70° C. for 6 hours, a propylene/3-buten-1-ol copolymer was finally recovered. The yield was 38.6 g, Mw 43,000, Mw/Mn 2.5, and 3-buten-1-ol content of 1.10 mol %.

<Production of A-13>
A propylene/3-buten-1-ol copolymer was produced by the following method.
20 μmol of rac-dimethylsilylenebis(2-methyl-4-phenylindenyl)zirconium dichloride was weighed into a 30 mL flask that was sufficiently replaced with nitrogen, and dehydrated heptane (10 mL) was added. To this heptane solution, a methylaluminoxane toluene solution (20 mmol as methylaluminoxane (MAO)) manufactured by Nippon Alkyaluminum Co., Ltd. was added to prepare a catalyst solution.
Next, under a purified nitrogen atmosphere, 400 mL of purified heptane, 120 mmol of 3-buten-1-ol, and 132 mmol of triisobutylaluminum were introduced into an autoclave made of stainless steel with an induction stirrer having an internal volume of 2.4 L, hydrogen 100 mL, and propylene pressure. Stabilized at 0.1 MPa and 70°C.
Then, the catalyst solution prepared above was added into the autoclave to start the polymerization.
After completion of the polymerization for 30 minutes, ethanol (10 mL) was added, the pressure was released, the atmosphere was replaced with nitrogen, and the autoclave was cooled to room temperature.
The copolymer was reprecipitated from the recovered polymerization slurry liquid using ethanol (1 L), and the copolymer was obtained by filtration.
The copolymer was washed with a hydrochloric acid (2N, 200 mL)/ethanol (1 L) solution, and then further washed with ethanol (1 L).
After drying under reduced pressure at 70° C. for 6 hours, a propylene/3-buten-1-ol copolymer was finally recovered. The yield was 13.2 g, Mw 35,000, Mw/Mn 2.2, and 3-buten-1-ol content of 1.80 mol %.

<A-14>
A commercially available maleic anhydride (MAH) modified polypropylene resin (manufactured by Sanyo Kasei Co., Ltd.: trade name: Umex 1001) was used.

<A-15>
A maleic anhydride (MAH) modified polypropylene resin (trade name: CMPP2) manufactured by Mitsubishi Chemical Corporation was used.

3. Evaluation of Adhesiveness with Glass Material The adhesiveness between the olefin resin used in the olefin resin composite material containing an inorganic filler and the glass material is the slide glass manufactured by Matsunami Glass Industry Co., Ltd. “S2215” (width 21 mm×length 76 mm×thickness 1 mm) was melt-pressed by sandwiching it between two sheets and evaluated by the following method.
(A) The copolymer resin is sandwiched between Kapton sheets, and the sample is melt-pressed by sandwiching it with a mirror-finished stainless steel press plate having a thickness of 5 mm to form a film of 50 μm. Molding conditions include preheating at 210° C. for 3 minutes, pressurizing at a pressure of 10 MPa for 3 minutes, and then cooling and pressurizing at a normal temperature of 10 MPa.
(B) The formed film is cut into a piece having a width of 1 mm and a length of 21 mm, which is placed on one end face of a slide glass, and one end face of another slide glass is placed on it and fixed with a double clip. Heat the sample with a heat gun for 10 seconds to heat-fuse the sample to the slide glass (c) Remove the double clip, and fix one side of the pair of slide glasses (21 mm wide x 74 mm long) on the laboratory table. To do.
(D) A vertically downward load is intermittently applied to the other end of the fixed slide glass, the load at the time when the fused portion is broken is measured, and the adhesiveness is evaluated by the size as follows. did.
Poor (poor): The load at the time when the fused portion was broken was less than 100 g, and the adhesiveness with the slide glass was not shown.
Δ (Slightly bad): The load at the time when the fused portion was broken exceeds 100 g, but does not exceed 150 g.
◯ (Good): The load at the time when the fused portion was broken exceeds 150 g, but does not exceed 200 g.
⊚ (excellent): The degree of adhesion exceeds the above and shows excellent adhesiveness with the slide glass.

Table 1 shows the evaluation results of the adhesiveness between A-1 to A-15 and the glass material.

4. Evaluation of Adhesiveness with Aluminum Material The adhesiveness between the olefin resin used in the olefin resin composite material containing the inorganic filler and the aluminum material is determined by using the olefin resin for composite material in two strip-shaped aluminum sheets (width 15 mm, The tensile test was performed using a test piece melt-pressed in such a manner as to be sandwiched between one end faces having a length of 100 mm and a thickness of 0.1 mm. The fusion-bonded portion had a width of 15 mm and a length of 20 mm. Install in the tensile tester so that one of the test pieces that has not been melt-pressed with the olefin resin for composite materials can be firmly gripped by the grip of the tester and the tensile melt-pressed part can be peeled off in a straight line. .. After that, the grip portion of the tester is moved at a predetermined test speed in a direction of peeling off the melt-bonded portion. The load applied when the melt-bonded portion is peeled off is recorded with respect to the distance moved by the grip portion. The adhesiveness was evaluated by the maximum load recorded until the melt-bonded portion was completely peeled off.
[Measurement condition]
・Testing machine: Shimadzu Autograph AG-X plus
-Method for producing test piece: Press molding (preheat at 210°C for 3 minutes, pressurize at 5 MPa for 1 minute, and then water-cool to solidify).
・Number of test pieces: n=5
・Test speed: 500 mm/min
・Evaluation item: Maximum peeling load

Table 2 shows the evaluation results of the adhesiveness between A-1, A-5, A-7, A-9, A-11, A-12, A-14, A-15 and the aluminum material.

5. Evaluation of Mechanical Properties of Glass Fiber Composite Material Polyolefin resin, glass fiber, and olefin resin for composite material were mixed by dry blending in a ratio shown in Table 3 to obtain a resin composition.
[Materials used]
As the polyolefin-based resin, homopolypropylene (grade name MA3) manufactured by Nippon Polypro Ltd. was used. The MFR was 10 g/10 minutes and the melting point was 161°C.
As the glass fiber, T480H (average fiber length 3 mm, average fiber diameter 13 μm) manufactured by Nippon Electric Glass Co., Ltd. was used.
As the olefin resin for composite materials, A-2 and A-8 obtained by the above-mentioned production were used. Based on 100 parts by mass of the obtained resin composition, tetrakis[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]methane( which is a phenolic antioxidant is used. Trade name: IRGANOX1010, manufactured by BASF Japan Ltd. 0.05 parts by mass, phosphite antioxidant tris(2,4-di-t-butylphenyl) phosphite (trade name: IRGAFOS 168, BASF Japan Ltd.) 0.05 parts by mass of calcium stearate and 0.05 parts by mass of calcium stearate were added.
Using a twin-screw extruder (KZW-15 manufactured by Techno Bell Co., Ltd.), the screw rotation speed was set to 400 RPM, and the kneading temperature was set to 120° C., 200° C., 240° C. from the bottom of the hopper (the same temperature up to the die outlet). The mixture was melt-kneaded under the conditions to obtain resin composition pellets.
The above resin composition pellets were injection-molded with an EC20 injection molding machine manufactured by Toshiba Machine Co., Ltd. to form test pieces of 10×80×4t (mm) size.
The injection molding conditions are a molding temperature of 240° C., a mold temperature of 40° C., an injection speed of 52 mm/sec, an injection time of 8 seconds, and a cooling time of 12 seconds.

Using this test piece, flexural modulus, flexural strength, and Charpy impact strength were evaluated.
[Bending elastic modulus and bending strength measurement conditions]
・Standard number: Conforms to JIS K-7171 (ISO 178) ・Testing machine: Bend Graph II manufactured by Toyo Seiki Co., Ltd.
-Shape of test piece: thickness 4 mm, width 10 mm, length 80 mm
・Method of preparing test pieces: Injection molding ・Condition adjustment: Left for 24 hours or longer in a temperature-controlled room controlled to room temperature 23°C and humidity 50% ・Test room: Temperature-controlled room controlled to room temperature 23°C and humidity 50% ・Test Number of pieces: n=3
・Distance between fulcrums: 64 mm
・Test speed: 2.0 mm/min
・Evaluation items: Flexural modulus and bending strength (maximum bending stress)
[Charpy impact strength measurement conditions]
・Standard number: JIS K-7111 (ISO 179/1eA) compliant ・Testing machine: Toyo Seiki's fully automatic Charpy impact tester (with constant temperature bath)
-Shape of test piece: test piece with single notch, thickness 4 mm, width 10 mm, length 80 mm
-Notch shape: Type A notch (notch radius 0.25 mm)
・Impact speed: 2.9 m/s
・Nominal pendulum energy: 4J
・Method of creating test piece: Notch is cut on injection molded test piece (according to ISO 2818)
-Condition adjustment: left for 24 hours or more in a temperature-controlled room controlled to room temperature 23°C and humidity 50%-Test room: temperature-controlled room controlled to room temperature 23°C and humidity 50%-Number of test pieces: n=5
・Test temperature: 23℃
・Evaluation items: absorbed energy

Table 3 shows the evaluation results for the evaluation of the mechanical properties of the glass fiber composite material.

6. Results and Discussion In an adhesiveness evaluation test with a glass material, in Examples 1 to 8, the load at the time when the fused portion was broken exceeded 150 g, but in Comparative Examples 1 to 7, it was 150 g or less. It was From this result, it was confirmed that the adhesiveness between this example and the glass material was good.
In the adhesion evaluation test with an aluminum material, the peeling load of Examples 1, 5, and 7 was larger than the peeling load of Comparative Examples 1, 3, 4, 6, and 7. In detail, although the peeling load of each comparative example is less than 10 N, the peeling load of Examples 1 and 5 is close to 20 N, and the peeling load of Example 7 is over 30 N. A large difference was seen in the peeling load of the examples. From this result, it was confirmed that the adhesiveness between this example and the aluminum material was good.
In the mechanical property evaluation test of the glass fiber composite material, Example 9 had higher flexural modulus and flexural strength than Comparative Example 8. In addition, Example 10 had higher bending strength and Charpy impact strength than Comparative Example 8. From this result, it was found that the glass fiber composite material of the present example had better mechanical properties than the comparative example.

The olefin-based random copolymer of the present invention can improve the affinity between the inorganic filler and the olefin-based matrix resin, and has been conventionally known to increase the interfacial adhesion of the olefin-based resin to the inorganic filler. Since there is no disadvantage associated with the modification technique, it can be preferably used as an affinity improver between the inorganic filler and the olefinic matrix resin.
The olefin-based resin composite material containing an inorganic filler of the present invention can be suitably used for producing a molded body that is lightweight and has excellent mechanical properties, and thus is used in a wide range of fields.
In particular, since the molded product produced from the olefin resin composite material of the present invention has a good balance of rigidity, heat resistance, durability and moldability, it can be suitably used as a member for automobiles.

Claims (8)

An olefin-based random copolymer used in an olefin-based resin composite material containing an inorganic filler,
A structural unit (U1) derived from ethylene and at least one monomer selected from the group consisting of α-olefins having 3 to 5 carbon atoms;
A structural unit (U2) derived from at least one monomer selected from α-olefin comonomers having a hydroxyl group and having 5 to 20 carbon atoms,
The content of the structural unit (U2) is 0.5 mol% or more and 10 mol% or less with respect to 100 mol% of the total of structural units,
An olefin-based random copolymer having a weight average molecular weight of 40,000 or more and 500,000 or less as measured by gel permeation chromatography (GPC). The olefin random copolymer according to claim 1, wherein the α-olefin comonomer is a linear α-olefin comonomer. The olefin-based random copolymer according to claim 1 or 2, which has a molecular weight distribution (Mw/Mn) measured by GPC of 3.5 or less. The olefin-based random copolymer according to claim 1, wherein the structural unit (U1) contains a structural unit derived from propylene. An olefin resin composition comprising the olefin random copolymer (A) according to any one of claims 1 to 4 and an inorganic filler (B). The olefin random copolymer (A) according to any one of claims 1 to 4, an inorganic filler (B), and the olefin random copolymer according to any one of claims 1 to 4. And an olefin-based random copolymer other than (C), and an olefin-based resin composite material. A propylene-based resin in which the olefin-based random copolymer (C) other than the olefin-based random copolymer according to any one of claims 1 to 4 is selected from the group consisting of a propylene homopolymer and a propylene copolymer. The olefin-based resin composite material according to claim 6, wherein A member for an automobile, which is a molded body using the olefin resin composite material according to claim 6 or 7.