KR20210067338A - Composite resin composition comprising polypropylene and ethylene alpha-olefin copolymer - Google Patents

Abstract

According to the present invention, provided is a composite resin composition having improved impact resistance, heat resistance and rigidity by including an ethylene-alpha copolymer having a high repeating ratio of ethylene structural units in a molecule.

Description

Composite resin composition comprising polypropylene and ethylene alpha-olefin copolymer {COMPOSITE RESIN COMPOSITION COMPRISING POLYPROPYLENE AND ETHYLENE ALPHA-OLEFIN COPOLYMER}

The present invention relates to a composite resin composition comprising polypropylene and an ethylene alpha-olefin copolymer.

Thermoplastic resins, especially polyethylene and polypropylene, which are polyolefin resins, have a low specific gravity, are cheaper than other resins, and have excellent mechanical properties and processability. resin being used. However, these polyolefin-based resins have limitations in the physical properties that can be expressed by themselves, so it is difficult to apply them to fields requiring special functions.

In order to overcome these disadvantages, by mixing the above two types of resins or adding a mineral filler, etc., a polyolefin-based composite resin with a new function that was not previously present was manufactured, and it was applied to various fields where it was impossible to apply only with the existing polyolefin-based resin. can be applied.

In particular, a polyolefin-based resin composition using polypropylene, a kind of polyolefin-based resin, as a base material, and adding an ethylene α-olefin copolymer or elastomer as an impact reinforcing material or adding an inorganic filler as a rigidity reinforcing material to express the necessary properties is an automobile part can be widely used for As described above, various methods for improving various physical and thermal properties by changing the type of polypropylene resin and various types of impact modifiers and rigidity reinforcing materials have been proposed and are being put to practical use.

In particular, low-density ethylene α-olefin copolymers are used to improve impact resistance in various environments, but in this case, there is a problem in that the mechanical strength of polypropylene is rather reduced.

On the other hand, the physical properties of polyolefin-based resins are greatly affected by changes in processing conditions. In order to prevent deterioration of physical properties due to deformation and aging of the polyolefin-based resin in a high-temperature and high-pressure atmosphere in the extruder during processing, a heat-resistant stabilizer, weather resistance Additives such as stabilizers have been prescribed. However, there is an interface between the components between the polymer base material and materials having different properties, such as additives, and there is a problem in that the physical properties of the resin depend on the size of the interfacial adhesive at this interface.

Korean Patent Publication No. 10-1998-0075880

An object of the present invention is to provide an ethylene alpha-olefin copolymer having superior impact resistance, heat resistance and rigidity compared to a copolymer having the same density and the same content of alpha-olefin by controlling the distribution of ethylene structural units in the copolymer. .

In addition, it is to provide a composite resin composition comprising the ethylene alpha-olefin copolymer and having excellent impact resistance, heat resistance and rigidity.

According to one embodiment of the present invention,

In the composite resin composition comprising a polypropylene resin and an ethylene alpha-olefin copolymer,

The ethylene alpha-olefin copolymer includes an ethylene structural unit and an alpha-olefin structural unit,

Ethylene monomer reactivity ratio (r ₁ ) and alpha-olefin monomer reactivity ratio (r ₂ ) are represented by the following formula (1):

식 (1)

Formula (1)

[In formula (1),

r ₁ and r ₂ are calculated according to the following formula (2),

,

식 (2)

,

Equation (2)

where X is the ratio of the amount of alpha-olefin monomer _{fed (mol) to the amount of ethylene monomer fed (mol), and P 11} , P ₁₂ , P ₂₁ and P ₂₂ are calculated according to the following formula (3),

식 (3)

Equation (3)

E is an ethylene structural unit, O is an alpha-olefin structural unit,

When A is E or O, [A], [AA] and [AAA] are the ^{values determined by 13} C NMR spectroscopy analysis, respectively, meaning the proportion of A, AA and AAA structures present in the copolymer,

The [EE], [E], [OO] and [O] are calculated according to the following formula (4)

식 (4)]

formula (4)]

Formed under a metallocene catalyst that satisfies

^The ethylene structural unit repeat ratio (D) determined by 13 C NMR spectroscopy analysis is represented by the following formula (5):

10 < Ethylene structural unit repeat ratio (D) < 14 Equation (5)

이다][In Equation (5),

to be]

A composite resin composition satisfying the

Since the ethylene-alpha copolymer according to the present invention has a high repeating ratio of ethylene structural units in the molecule, it exhibits a higher melting temperature and lower glass transition temperature than a copolymer having the same density and the same alpha-olefin content, and has impact resistance, heat resistance and Excellent rigidity.

Furthermore, when the ethylene-alpha copolymer and the polypropylene resin according to the present invention are mixed, it is possible to provide a composite resin without deterioration of other physical properties while improving impact resistance, heat resistance and rigidity.

Hereinafter, preferred embodiments of the present invention will be described. However, the embodiment of the present invention may be modified in various other forms, and the scope of the present invention is not limited to the embodiments described below.

As used herein, the term “alkyl” refers to a monovalent straight-chain or branched saturated hydrocarbon radical composed only of carbon and hydrogen atoms, and examples of such alkyl radicals include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t- butyl, pentyl, hexyl, octyl, dodecyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, and the like.

In addition, as used herein, the term "alkenyl" refers to a straight-chain or branched hydrocarbon radical containing one or more carbon-carbon double bonds, and includes ethenyl, propenyl, butenyl, pentenyl, and the like, However, the present invention is not limited thereto.

In addition, the term "alkynyl" as used in the present invention refers to a straight-chain or branched hydrocarbon radical containing at least one carbon-carbon triple bond, and methynyl, ethynyl, propynyl, butynyl, pentynyl, hexy nyl, heptynyl, octynyl, and the like.

In addition, the term "aryl" described in the present invention is an organic radical derived from an aromatic hydrocarbon by removal of one hydrogen, and includes a single or fused ring system. Specific examples include, but are not limited to, phenyl, naphthyl, biphenyl, anthryl, fluorenyl, phenanthryl, triphenylenyl, pyrenyl, peryleneyl, chrysenyl, naphthacenyl, fluoranthenyl, and the like.

In addition, the term "alkylaryl" as used in the present invention refers to an organic group in which one or more hydrogens of the aryl group are substituted by an alkyl group, and methylphenyl, ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl, iso butylphenyl, t-butylphenyl, and the like.

In addition, the term "arylalkyl" described in the present invention refers to an organic group in which one or more hydrogens of the alkyl group are substituted by an aryl group, and includes, but is not limited to, phenylpropyl, phenylhexyl, and the like.

In addition, the term "amido" described in the present invention refers to an amino group (-NH ₂ ) bonded to a carbonyl group (C=O), and “alkylamido” is an alkyl group in which at least one hydrogen in _{-NH 2 of the amido group is an alkyl group.} means an organic group substituted with, "arylamido" means an organic group _{in which at least one hydrogen is substituted with an aryl group in -NH 2} of the amido group, an alkyl group in the alkylamido group, and an aryl group in the arylamido group It may be the same as the examples of the above-described alkyl group and aryl group, but is not limited thereto.

In addition, the term "alkylidene" as used in the present invention refers to a divalent aliphatic hydrocarbon group in which two hydrogen atoms have been removed from the same carbon atom of the alkyl group, and ethylidene, propylidene, isopropylidene, butylidene, pentylidene and the like.

In addition, the term "acetal" described in the present invention refers to an organic group formed by the bond between alcohol and aldehyde, that is, a substituent having two ether (-OR) bonds on one carbon, methoxymethoxy, 1-meth ethoxy, 1-methoxypropyloxy, 1-methoxybutyloxy, 1-ethoxyethoxy, 1-ethoxypropyloxy, 1-ethoxybutyloxy, 1-(n-butoxy)ethoxy, 1-(iso-butoxy)ethoxy, 1-(sec-butoxy)ethoxy, 1-(tert-butoxy)ethoxy, 1-(cyclohexyloxy)ethoxy, 1-methoxy -1-methylmethoxy, 1-methoxy-1-methylethoxy, and the like.

In addition, the term "ether" described in the present invention is an organic group having at least one ether bond (-O-), 2-methoxyethyl, 2-ethoxyethyl, 2-butoxyethyl, 2-phenoxyethyl , 2- (2-methoxyethoxy) ethyl, 3-methoxypropyl, 3-butoxypropyl, 3-phenoxypropyl, 2-methoxy-1-methylethyl, 2-methoxy-2-methylethyl , 2-methoxyethyl, 2-ethoxyethyl, 2-butoxyethyl, 2-phenoxyethyl, and the like.

In addition, the term "silyl" described in the present invention refers to a -SiH ₃ radical derived from silane, and at least one of the hydrogen atoms in the silyl group may be substituted with various organic groups such as alkyl and halogen, and specifically as trimethylsilyl, triethylsilyl, t-butyldimethylsilyl, vinyldimethylsilyl, propyldimethylsilyl, triphenylsilyl, diphenylsilyl, phenylsilyl, trimethoxysilyl, methyldimeroxysilyl, ethyldiethoxysilyl, triethoxysilyl, vinyldimethoxysilyl, triphenoxysilyl, and the like.

In addition, as used herein, the term “alkoxy” refers to an —O-alkyl radical, where “alkyl” is as defined above. Examples of such alkoxy radicals include, but are not limited to, methoxy, ethoxy, isopropoxy, butoxy, isobutoxy, t-butoxy, and the like.

In addition, as used herein, the term "aryloxy" refers to an -O-aryl radical, where 'aryl' is as defined above. Examples of such aryloxy radicals include, but are not limited to, phenoxy, biphenoxy, naphthoxy, and the like.

In addition, the term "halogen" described in the present invention means a fluorine, chlorine, bromine or iodine atom.

In addition, the term "C _n " described in the present invention means that the number of carbon atoms is n.

The present invention provides a composite resin composition in which an ethylene alpha-olefin copolymer and a polypropylene resin are mixed with a higher melting temperature and a lower glass transition temperature than a copolymer having the same density and the same alpha-olefin content by controlling the distribution of ethylene structural units. to provide.

According to an embodiment, the ethylene alpha-olefin copolymer may be prepared under a metallocene catalyst, and in this case, the metallocene catalyst may include a transition metal compound represented by Formula 1 below.

In Formula 1,

M is selected from the group consisting of a Group 4 transition metal;

Q ¹ and Q ² are each independently halogen, (C ₁ -C ₂₀ )alkyl group, (C ₂ -C ₂₀ )alkenyl group, (C ₂ -C ₂₀ )alkynyl group, (C ₆ -C ₂₀ )aryl group, (C ₁ -C ₂₀ )alkyl(C ₆ -C ₂₀ )aryl group, (C ₆ -C ₂₀ )aryl(C ₁ -C ₂₀ )alkyl group, (C ₁ -C ₂₀ )alkylamido group, (C ₆ - C ₂₀ ) an arylamido group or a (C ₁ -C ₂₀ )alkylidene group;

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently hydrogen; _{A (C 1} -C ₂₀ )alkyl group unsubstituted or substituted with an acetal group, a ketal group, or an ether group; _{A (C 2} -C ₂₀ )alkenyl group unsubstituted or substituted with an acetal group, a ketal group, or an ether group; _{a (C 1} -C ₂₀ )alkyl(C ₆ -C ₂₀ )aryl group unsubstituted or substituted with an acetal group, a ketal group, or an ether group; _{a (C 6} -C ₂₀ )aryl(C ₁ -C ₂₀ )alkyl group unsubstituted or substituted with an acetal group, a ketal group, or an ether group; _{or a (C 1} -C ₂₀ ) silyl group unsubstituted or substituted with an acetal group, a ketal group, or an ether group; R ¹ and R ² may be connected to each other to form a ring, R ³ and R ⁴ may be connected to each other to form a ring, and ^{two or more of R 5} to R ¹⁰ may be connected to each other to form a ring can;

R ¹¹ , R ¹² and R ¹³ are each independently hydrogen; _{A (C 1} -C ₂₀ )alkyl group unsubstituted or substituted with an acetal group, a ketal group, or an ether group; _{A (C 2} -C ₂₀ )alkenyl group unsubstituted or substituted with an acetal group, a ketal group, or an ether group; _{a (C 1} -C ₂₀ )alkyl(C ₆ -C ₂₀ )aryl group unsubstituted or substituted with an acetal group, a ketal group, or an ether group; _{a (C 6} -C ₂₀ )aryl(C ₁ -C ₂₀ )alkyl group unsubstituted or substituted with an acetal group, a ketal group, or an ether group; _{A (C 1} -C ₂₀ )silyl group unsubstituted or substituted with an acetal group, a ketal group, or an ether group; _{A (C 1} -C ₂₀ )alkoxy group unsubstituted or substituted with an acetal group, a ketal group, or an ether group; _{or a (C 6} -C ₂₀ )aryloxy group unsubstituted or substituted with an acetal group, a ketal group, or an ether group; The R ¹¹ and R ¹² or R ¹² and R ¹³ may be connected to each other to form a ring.

In the transition metal compound represented by Formula 1, an amido ligand and ortho-phenylene form a condensed ring, and a five-membered ring pi-ligand bonded to the ortho-phenylene is fused by a thiophene hetero ring. a ligand of the structure. Accordingly, the transition metal compound has an advantage in that the copolymerization activity of ethylene alpha-olefin is higher than that of the transition metal compound to which the thiophene hetero ring is not fused.

According to an embodiment, in the transition metal compound represented by Formula 1, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ may each independently be substituted with a substituent including an acetal, ketal or ether group. When substituted with the above substituents, it may be more advantageous to support the transition metal compound on the surface of the carrier.

In addition, in the transition metal compound represented by Formula 1, M is preferably titanium (Ti), zirconium (Zr), or hafnium (Hf).

In addition, in the transition metal compound represented by Formula 1, Q ¹ and Q ² are each independently a halogen or a (C ₁ -C ₂₀ )alkyl group, and more preferably a chlorine or methyl group.

In addition, in the transition metal compound represented by Formula 1, R ¹ , R ² , R ³ , R ⁴ and R ⁵ may each independently be hydrogen or a (C ₁ -C ₂₀ )alkyl group, preferably Each independently may be a hydrogen or a methyl group. More preferably, the R ¹ , R ² , R ³ , R ⁴ and R ⁵ may each independently be a hydrogen or a methyl group, provided ^{that at least one of R 3} and R ⁴ is a methyl group, and R ⁵ may be a methyl group. have.

In addition, in the transition metal compound represented by Formula 1, R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ are each preferably hydrogen.

It is preferred that the transition metal compound represented by Formula 1 includes the above-described substituents for controlling the electronic and steric environment around the metal.

In one embodiment, the metallocene catalyst may include a co-catalyst compound. The co-catalyst compound activates the catalyst, and an aluminoxane compound, an organo-aluminum compound, or a bulky compound that activates the catalyst compound may be used. Specifically, the promoter compound may be selected from the group consisting of compounds represented by the following Chemical Formulas 3 to 5.

In Formula 2,

Al is aluminum,

O is oxygen,

Ra is halogen; Or a halogen-substituted or unsubstituted (C ₁ -C ₂₀ )hydrocarbyl group, for example, a (C ₁ -C ₁₀ )alkyl group,

n is an integer greater than or equal to 2;

In Formula 3,

Q is aluminum or boron,

Rb are the same as or different from each other, and each independently halogen; Or a halogen-substituted or unsubstituted (C ₁ -C ₂₀ )hydrocarbyl group.

In Formula 4,

[W] ⁺ is a cationic Lewis acid; or a cationic Lewis acid to which a hydrogen atom is bound,

Z is a group 13 element,

Rc is the same as or different from each other, and each independently halogen, (C ₁ -C _{20 ) A (C 6} -C ₂₀ )aryl substituted with one or two or more substituents selected from the group consisting of a hydrocarbyl group, an alkoxy group and a phenoxy group. group; halogen, (C ₁ -C _{20 ) A (C 1} -C ₂₀ )alkyl group substituted with one or two or more substituents selected from the group consisting of a hydrocarbyl group, an alkoxy group and a phenoxy group.

The cocatalyst compound is included in the catalyst together with the metallocene compound represented by Formula 1 to activate the metallocene compound. Specifically, in order for the metallocene compound to become an active catalyst component used for olefin polymerization, a counterion having a weak binding force while cationizing ^{the central metal (M 1} or M ^{2 ) by extracting a ligand in the metallocene compound,} That is, the compound including the unit represented by Formula 2, which can act as an anion, the compound represented by Formula 3, and the compound represented by Formula 4 act together as a cocatalyst.

The 'unit' represented by Formula 2 is a structure in which n structures in [ ] are connected in the compound, and if it includes a unit represented by Formula 2, other structures in the compound are not particularly limited, and repeating Formula 2 The unit may be a cluster type, such as a globular compound, connected to each other.

In order for the promoter compound to exhibit a better activation effect, the compound represented by Formula 2 is not particularly limited as long as it is an alkylaluminoxane, but preferred examples thereof include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, and butylaluminoxane. and the like, and a particularly preferred compound is methylaluminoxane.

In addition, the compound represented by Formula 3 is not particularly limited as an alkyl metal compound, and non-limiting examples thereof include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, and triiso. Propyl aluminum, tri-s-butylaluminum, tricyclopentylaluminum, tripentylaluminum, triisopentylaluminum, trihexylaluminum, trioctylaluminum, ethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl boron, triethyl boron, triisobutyl boron, tripropyl boron, tributyl boron, and the like. Considering the activity of the metallocene compound, one or two or more selected from the group consisting of trimethylaluminum, triethylaluminum and triisobutylaluminum may be preferably used.

When the compound represented by Formula 4 considers the activity of the metallocene compound, when [W] ⁺ is a cationic Lewis acid to which a hydrogen atom is bonded, it is a dimethylanilinium cation, and when [W] ⁺ is a cationic Lewis acid, It is [(C ₆ H ₅ ) ₃ C] ⁺ , and [Z(Rc) ₄ ] ^- is [B(C ₆ F ₅ ) ₄ ] ^- It may be preferably used.

The compound represented by Formula 4 is not particularly limited, but ^{non-limiting examples of the case where [W] +} is a cationic Lewis acid to which a hydrogen atom is bonded include triphenylcarbenium borate, trimethylammonium tetraphenylborate, methyldioctadecylammonium tetraphenyl Borate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri(n-butyl)ammonium tetraphenylborate, methyltetradecyclooctadecylammonium tetraphenylborate, N,N-dimethylaninium tetraphenylborate, N ,N-diethylaninium tetraphenylborate, N,N-dimethyl(2,4,6-trimethylaninium)tetraphenylborate, trimethylammonium tetrakis(pentafluorophenyl)borate, methylditetradecylammonium tetrakis (Pentaphenyl)borate, methyldioctadecylammonium tetrakis(pentafluorophenyl)borate, triethylammonium tetrakis(pentafluorophenyl)borate, tripropylammonium tetrakis(pentafluorophenyl)borate, tri(n -Butyl)ammonium tetrakis(pentafluorophenyl)borate, tri(sec-butyl)ammonium tetrakis(pentafluorophenyl)borate, N,N-dimethylaninium tetrakis(pentafluorophenyl)borate, N ,N-diethylaninium tetrakis(pentafluorophenyl)borate, N,N-dimethyl(2,4,6-trimethylaninium)tetrakis(pentafluorophenyl)borate, trimethylammonium tetrakis(2, 3,4,6-tetrafluorophenyl)borate, triethylammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate, tripropylammonium tetrakis(2,3,4,6-tetrafluoro Rophenyl)borate, tri(n-butyl)ammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate, dimethyl(t-butyl)ammonium tetrakis(2,3,4,6-tetrafluoro Rophenyl) borate, N,N-dimethylaninium tetrakis(2,3,4,6-tetrafluorophenyl)borate, N,N-diethylaninium tetrakis(2,3,4,6-tetra Fluorophenyl)borate, N,N-dimethyl-(2,4,6-trimethylaninium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate, dioctadecylammonium tetrakis(pentadecyl) Fluorophenyl) borate, ditetradecylammonium tetra Kis(pentafluorophenyl)borate, dicyclohexylammonium tetrakis(pentafluorophenyl)borate, triphenylphosphonium tetrakis(pentafluorophenyl)borate, methyldioctadecylphosphonium tetrakis(pentafluorophenyl) ) borate, tri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)borate, methyldi(octadecyl)ammonium tetrakis(pentafluorophenyl)borate, methyldi(tetradecyl)-ammonium tetra kiss (pentafluorophenyl) borate, triethyl tetrakis (pentafluorophenyl) borate, and the like.

Meanwhile, the addition amount of the promoter compound may be determined in consideration of the addition amount of the transition metal compound and an amount required to sufficiently activate the promoter compound. According to one embodiment, the promoter compound may be included in a molar ratio of 1:1 to 100,000, preferably 1:1 to 10,000, more preferably 1:1 to 5,000 with respect to the transition metal compound. More specifically, the promoter compound represented by Formula 2 or 3 is 1:1 to 100, preferably 1:1 to 10, more preferably 1:1 to the transition metal compound represented by Formula 1 It may be included in a molar ratio of 4.

Meanwhile, in one embodiment, the metallocene catalyst may be supported on a carrier. Here, as the carrier, a carrier of an inorganic or organic material generally used for the preparation of a catalyst may be used without limitation, for example, silica (SiO ₂ ), alumina (Al ₂ O ₃ ), magnesia (MgO), magnesium chloride ( MgCl ₂ ), calcium chloride (CaCl ₂ ), zirconia (ZrO ₂ ), titania (TiO ₂ ), boron trioxide (B ₂ O ₃ ), calcium oxide (CaO), zinc oxide (ZnO), barium oxide (BaO), dioxide Thorium (ThO ₂ ), silica-alumina (SiO ₂ -Al ₂ O ₃ ), silica-magnesia (SiO ₂ -MgO), silica-titania (SiO ₂ -TiO ₂ ), silica-vanadium pentoxide (SiO ₂ -V _{2 )} O ₅ ), silica-chromium oxide (SiO ₂ -Cr ₂ O ₃ ), silica-titania-magnesia (SiO ₂ -TiO ₂ -MgO), bauxite, zeolite, starch, cyclodextrin, synthesis Polymers and the like may be used. Preferably, the carrier includes a hydroxyl group on the surface, and may be at least one carrier selected from the group consisting of silica, silica-alumina, and silica-magnesia.

As a method of supporting the catalyst including the transition metal compound and the cocatalyst compound on the carrier, a method of directly supporting the transition metal compound on a dehydrated carrier; a method of supporting the transition metal compound after pretreating the carrier with the cocatalyst compound; a method of supporting the transition metal compound on the carrier and then post-treatment with the cocatalyst compound; A method of reacting the transition metal compound with the cocatalyst compound and then reacting by adding the carrier may be used.

The solvent usable in the supporting reaction may be an aliphatic hydrocarbon-based solvent, an aromatic hydrocarbon-based solvent, a halogenated aliphatic hydrocarbon-based solvent, or a mixture thereof. Here, the aliphatic hydrocarbon-based solvent is a non-limiting example, pentane (Pentane), hexane (Hexane), heptane (Heptane), octane (Octane), nonane (Nonane), decane (Decane), undecane (Undecane) or dodecane (Undecane) or dodecane and Dodecane. In addition, the aromatic hydrocarbon-based solvent may include, but is not limited to, benzene (Benzene), monochlorobenzene (Monochlorobenzene), dichlorobenzene (Dichlorobenzene), trichlorobenzene (Trichlorobenzene), or toluene (Toluene). In addition, the halogenated aliphatic hydrocarbon-based solvent may include, but is not limited to, dichloromethane, trichloromethane, dichloroethane, or trichloroethane.

In addition, it is advantageous in terms of efficiency of the loading process that the supporting reaction is carried out at a temperature of -70 to 200 °C, preferably -50 to 150 °C, more preferably 0 to 100 °C.

In an embodiment, an ethylene alpha-olefin copolymer may be prepared by reacting an ethylene monomer and an alpha-olefin monomer under the metallocene catalyst represented by Formula 1; In this case, the alpha-olefin monomer may be a (C ₃ -C ₁₀ )alpha-olefin monomer, for example, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 1-hexene, 1-heptene, It may be at least one selected from the group consisting of 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, and 1-tetradecene.

The polymerization reaction of ethylene and alpha-olefin may be carried out in a slurry phase, a solution phase, a gas phase, or a bulk phase. When the polymerization reaction is carried out in a liquid phase or a slurry phase, a solvent may be used or ethylene and alpha-olefin monomer itself may be used as a medium.

The solvent that can be used in the polymerization reaction may be an aliphatic hydrocarbon-based solvent, an aromatic hydrocarbon-based solvent, a halogenated aliphatic hydrocarbon-based solvent, or a mixture thereof. The aliphatic hydrocarbon-based solvent is a non-limiting example, butane, isobutane (Isobutane), pentane (Pentane), hexane (Hexane), heptane (Heptane), octane (Octane), nonane (Nonane), decane (Decane) ), undecane, dodecane, cyclopentane, methylcyclopentane, or cyclohexane. The aromatic hydrocarbon-based solvent is a non-limiting example, benzene (Benzene), monochlorobenzene (Monochlorobenzene), dichlorobenzene (Dichlorobenzene), trichlorobenzene (Trichlorobenzene), toluene (Toluene), xylene (Xylene), or chlorobenzene (Chlorobenzene) and the like. The halogenated aliphatic hydrocarbon solvent includes, but is not limited to, dichloromethane, trichloromethane, chloroethane, dichloroethane, trichloroethane, or 1,2-dichloroethane. (1,2-Dichloroethane) and the like.

Meanwhile, the amount of the metallocene catalyst added in the polymerization reaction is not particularly limited, since it may be determined within a range in which the polymerization reaction of the monomers can sufficiently occur depending on the slurry phase, solution phase, gas phase, or bulk process.

^{However, the amount of the metallocene catalyst added is 10 -8} to 1 mol/L, preferably 10 ^-7 to 10, based on the concentration of the central metal (M) in the metallocene catalyst compound per unit volume (L) of the monomer. ^-1 mol/L, more preferably 10 ^-7 to 10 ^-2 mol/L.

In addition, the polymerization reaction is made of a batch type, semi-continuous type, or continuous type reaction, preferably a continuous type reaction.

In one embodiment, the temperature and pressure conditions of the polymerization reaction may be determined in consideration of the efficiency of the polymerization reaction according to the type of reaction and the type of reactor to be applied, but the polymerization temperature is 100 to 200 °C, preferably 120 to 160 °C. may be, the pressure may be 1 to 3000 atmospheres, preferably 1 to 1000 atmospheres.

The ethylene alpha-olefin copolymer prepared by the polymerization reaction of an ethylene monomer and an alpha-olefin monomer under the catalyst represented by Formula 1 has a high repeating ratio of ethylene structural units compared to a copolymer having the same density and the same alpha-olefin content ( D) has The ethylene alpha-analyzed by ¹³ C NMR spectroscopy for the olefin copolymers of ethylene structural unit of alpha-analyzed the peak (Peak) represents the triad sequence (Triad sequence) structure of the olefin structural unit, with less than ¹³ C NMR spectroscopy Describe the content of the analysis.

The metallocene catalyst used for preparing the ethylene alpha-olefin copolymer according to an embodiment has an ethylene monomer reactivity ratio (r ₁ ) and an alpha-olefin monomer reactivity ratio (r ₂ ) satisfying the following formula (1). and r ₁ and r ₂ may be calculated according to Equation (2) below.

식 (1)

Formula (1)

,

식 (2)

,

Equation (2)

In formula (2), P ₁₁ means the probability that an ethylene monomer exists after the ethylene monomer, and P ₁₂ means the probability that the alpha-olefin monomer exists after the ethylene monomer. In addition, P ₂₁ means the probability that the ethylene monomer exists after the alpha-olefin monomer, and P ₂₂ means the probability that the alpha-olefin monomer exists after the alpha-olefin monomer.

Here, X is the ratio (mol) of the alpha-olefin monomer to the amount (mol) of the ethylene monomer, and P ₁₁ , P ₁₂ , P ₂₁ and P ₂₂ may be calculated according to the following formula (3).

식 (3)

Equation (3)

Also, in Formula (3), E is an ethylene structural unit present in the copolymer, and O is an alpha-olefin structural unit present in the copolymer.

Also, when A is E or O, [A], [AA] and [AAA] are ^{values calculated using the values of each peak according to 13} C NMR spectroscopy analysis, respectively, A, AA and [AAA] present in the copolymer AAA means the proportion of structures. In Equation (3), [EE], [E], [OO] and [O] may be calculated according to Equation (4) below.

식 (4)

Equation (4)

The repetition ratio (D) of the ethylene structural unit of the ethylene alpha-olefin copolymer prepared under such a metallocene catalyst can be calculated. The value of the repeating ratio (D) of the ethylene structural unit satisfies the following formula (5), and D may be represented by the following formula (6).

10 < Ethylene structural unit repeat ratio (D) < 14 Equation (5)

식 (6)

Equation (6)

In the ethylene alpha-olefin copolymer according to an embodiment, the repeating length of the ethylene structural unit may be expressed as L=[EEE]/([EEO]+[OEE]). However, since the higher the total ethylene content in the copolymer, the higher the repeating ratio of the ethylene structural unit, so the L value is ^{corrected for the ethylene content ([E] 6} ) to relate to the repeating ratio (D) of the ethylene structural unit Equation (6) was derived.

When the repeat ratio (D) of the ethylene structural unit satisfies Formula (5), a higher melting point and a lower glass transition temperature than a copolymer having the same density and the same alpha-olefin content are exhibited. This is because the region with high crystallinity becomes harder and the region with low crystallinity becomes softer because the ethylene structural unit repeat ratio (D) in the ethylene alpha-olefin copolymer is high. That is, heat resistance and rigidity are improved due to the high melting point of the ethylene alpha-olefin copolymer, and impact strength is improved due to a low glass transition temperature. However, if the repeating ratio (D) of the ethylene structural unit exceeds 14, regions with high crystallinity are excessively large, and when mixed with other resins, the elastic properties such as elongation and impact strength of the mixed resin may be reduced, and the repeating ratio of the ethylene structural unit If (D) is less than 10, mechanical properties, thermal properties, and restoring force may be deteriorated during manufacturing of the mixed resin due to the low crystallinity region.

Preferably, the alpha-olefin content in the ethylene alpha-olefin copolymer is 3 to 20 mol%, and the density of the ethylene alpha-olefin copolymer may be 0.850 to 0.915 g/cm 3 . In addition, the ethylene alpha-olefin copolymer may have a melting point (Tm) of 40 to 100°C, a glass transition temperature (Tg) of -70 to -40°C, and a melt index of 0.1 to 50 g/10min.

In addition, the ethylene alpha-olefin copolymer may have a weight average molecular weight (Mw) of 10,000 to 1,000,000 g/mol, preferably 50,000 to 800,000 g/mol, and more preferably 230,000 to 500,000 g/mol. In addition, the ethylene alpha-olefin copolymer may have a molecular weight distribution (Mw/Mn) of 1.5 to 4.

In one embodiment, the propylene resin is not particularly limited, and may preferably be a highly crystalline homopolypropylene, an ethylene-containing block copolymer, or a mixture thereof.

In one embodiment, the composite resin composition may include 50 to 90% by weight of a polypropylene resin and 5 to 30% by weight of an ethylene alpha-olefin copolymer. If the content of the ethylene alpha-olefin copolymer is less than 5% by weight, flexibility, flexibility, impact resistance, and cold resistance of the composite resin composition may decrease, and if it exceeds 30% by weight, heat resistance and mechanical strength are lowered, which is not preferable.

In addition, the composite resin composition may further include an inorganic filler to improve strength. As the inorganic filler, talc, calcium carbonate, mica, clay, etc. may be used, but the present invention is not limited thereto.

In addition, the composite resin composition may further include an additive for improving physical properties, for example, may further include an antioxidant, a UV stabilizer, a slip agent, and the like.

Example

Hereinafter, embodiments of the present invention will be described in detail. The following examples are only for the understanding of the present invention, but do not limit the present invention.

[Example 1]

1. Preparation of catalyst compounds

2,3,4,5-tetramethyl-6-(2-methyl-2,3,4,5-tetrahydroquinolin-8-yl)-4-H-cyclopenta[b]thi represented by the following formula Opene (2,3,4,5-tetramethyl-6-(2-methyl-2,3,4,5-tetrahydroquinolin-8-yl)-4-H-cyclopenta[b]thiophene) 0.58 g (1.79 mmol) To 10 mL of the dissolved diethyl ether solution, 1.63 g (3.55 mmol, 1.6 M solution in diethyl ether) of methyl lithium was added dropwise at -30°C. The solution was stirred at room temperature for 24 hours, cooled to -30 °C, and 0.37 g (1.79 mmol) of _{Ti(NMe 2} ) ₂ Cl _{2 was added at once.} After the solution was stirred for 3 hours, all solvents were removed using a vacuum pump. The resulting solid was dissolved in 8 mL of toluene, and 1.16 g (8.96 mmol) _{of Me 2} SiCl _{2 was added to this solution.} After the solution was stirred at 80° C. for 3 days, the solvent was removed using a vacuum pump.

As a result, 2,3,4,5-tetramethyl-6-(2-methyl-2,3,4,5-tetrahydroquinolin-8-yl)-cyclopenta[b as a red solid represented by the following formula ]thiophene dimethyl titanium (2,3,4,5-tetramethyl-6-(2-methyl-2,3,4,5-tetrahydroquinolin-8-yl)-cyclopenta[b]thiophene dimethyl titaniun) 0.59 g was obtained. (yield 75%). As a result of analyzing the solid compound through ¹ H NMR spectrum, it was confirmed that two steric compounds were present in a ratio of 2:1.

¹ H NMR (C ₆ D ₆ ): δ 7.10 (t, J = 4.4 Hz, 1H), 6.90 (d, J = 4.4 Hz, 2H), 5.27 and 5.22 (m, 1H, NCH), 2.54-2.38 ( m, 1H, CH ₂ ), 2.20-2.08 (m, 1H, CH ₂ ), 2.36 and 2.35 (s, 3H), 2.05 and 2.03 (s, 3H), 1.94 and 1.93 (s, 3H), 1.89 and 1.84 (s, 3H), 1.72-1.58 (m, 2H, CH ₂ ), 1.36-1.28 (m, 2H, CH ₂ ), 1.17 and 1.14 (d, J = 6.4, 3H, CH ₃ ) ppm.

¹³ C NMR (C ₆ D ₆ ): 162.78, 147.91, 142.45, 142.03, 136.91, 131.12, 130.70, 130.10, 128.90, 127.17, 123.39, 121.33, 119.87, 54.18, 26.48, 21.74, 17.28, 14.4680, 14.28 13.27 ppm.

2. Preparation of ethylene 1-octene copolymer

After replacing the inside of the 2 L stainless steel high-pressure reactor with nitrogen at room temperature, 1 L of n-hexane and 2 mL of triisobutylaluminum were added. Then, 100 g of ethylene gas and 100 g of 1-octene were injected. Thereafter, the reactor temperature was preheated to 140 ° C., and a dimethylanilinium tetrakis (pentablue orophenyl) borate promoter (45.0 μmol) was added to a mixed solution of the synthesized catalyst compound (1.5 mol) and triisobutylaluminum (187.5 μmol). ) solution was mixed and injected into the reactor, and then polymerization was carried out for 5 minutes.

After the polymerization reaction was completed, the reaction was terminated using ethanol diluted with 10% HCl, the temperature was lowered to room temperature, and the excess gas was discharged. Then, the copolymer solution dispersed in the solvent was transferred to a container and dried in a vacuum oven at 80° C. for 15 hours or more to prepare an ethylene 1-octene copolymer.

[Example 2]

An ethylene 1-octene copolymer was prepared in the same manner as in Example 1, except that 95 g of ethylene gas and 120 g of 1-octene were added in the 2. ethylene 1-octene copolymer preparation step of Example 1.

[Example 3]

An ethylene 1-octene copolymer was prepared in the same manner as in Example 1, except that 80 g of ethylene gas and 140 g of 1-octene were added in the 2. ethylene 1-octene copolymer preparation step of Example 1.

[Comparative Example 1]

Ethylene 1-octene copolymer (product name: ENGAGE8003) commercially available from DOW was obtained and the physical properties were analyzed.

[Comparative Example 2]

Ethylene 1-octene copolymer (product name: ENGAGE8200) commercially available from DOW was obtained and the physical properties were analyzed.

[Comparative Example 3]

Ethylene 1-octene copolymer (product name: ENGAGE8180) commercially sold by DOW was obtained and the physical properties were analyzed.

[Evaluation of copolymer properties]

Table 1 below shows the copolymer structure analysis results for the ethylene 1-octene copolymers according to each of the Examples and Comparative Examples. In Table 1, r ₁ and r ₂ values of Comparative Examples 1 to 3 are known values. In addition, the density, 1-octene content, melt index, weight average molecular weight, molecular weight distribution, melting point, glass transition temperature, and shore hardness of the ethylene 1-octene copolymer were measured as follows, and the measurement results are shown in the table below. 2 is shown.

(1) Structural analysis of ethylene 1-octene copolymer

After analyzing the peaks represented by the triad sequence structure of ethylene and 1-octene through ¹³ _{C NMR spectroscopy, r 1} , r ₂ , L and D were calculated using the values of each peak.

(2) density

It was measured based on ASTM D1505.

(3) 1-octene content in the copolymer

400 MHz NMR (device name: Ascend 400, manufacturer: Bruker) spectrum analysis method was measured at 100 ℃ using a tetrachloroethane-d2 solvent.

(4) Melt Index (MI),

ASTM D-1238 (Condition E, 190 °C, 2.16 kg load) method was applied, and measurements were made with an instrument (device name: SD-120L, manufacturer: Mirage).

(5) Weight average molecular weight (Mw), molecular weight distribution (Mw/Mn)

GPC (Gel Permeation Chromatography, device name: PL-GPC220, manufacturer: Agilent) analysis method was measured at 160 ℃ using a 1,2,4-trichlorobenzene solvent.

(6) Melting point (Tm), glass transition temperature (Tg)

Differential Scanning Calorimeter (DSC), device name: DSC 2920, manufacturer: TA) was used. After reaching equilibrium at the temperature of 0 °C, DSC is increased by 10 °C per minute to 200 °C, decreased by 10 °C per minute to -90 °C, and then increased again by 10 °C per minute to increase the temperature to 200 °C. method was measured. The melting point is obtained by taking the top region of the endothermic curve during a second temperature rise.

(7) Shore A hardness

After preparing a specimen using a 190°C hot-press, hardness was measured with a Durometer according to ASTM D2240 conditions.

OOO
(%) OOE+EOO
(%) OEO
(%) OEE+EEO
(%) EOE
(%) EEE
(%) r ₁ r ₂ L D Example 1 0.0 2.1 1.5 10.3 8.1 78.0 2.63 0.53 7.57 13.29 Example 2 0.0 2.9 2.2 11.9 9.4 73.6 2.64 0.48 6.18 12.40 Example 3 0.0 4.7 3.4 13.3 11.4 67.2 2.71 0.45 5.05 12.71 Comparative Example 1 0.0 1.6 1.3 14.6 7.8 74.7 2.33 0.45 5.12 9.25 Comparative Example 2 0.0 2.9 1.1 17.2 8.8 70.0 2.39 0.44 4.07 8.43 Comparative Example 3 0.0 4.2 2.2 18.3 9.9 65.4. 2.42 0.44 3.57 8.70

density
(g/cm ³ ) 1-octene
(mol%) MI
(g/10min.) Mw
(g/mol) Mw/Mn Tm
(℃) Tg
(℃) Shore A Example 1 0.882 9.1 1.0 293K 2.0 78 -55 82 Example 2 0.875 11.5 5.2 201K 2.0 69 -61 65 Example 3 0.862 14.6 2.0 272K 2.0 56 -63 60 Comparative Example 1 0.885 9.4 1.0 359K 2.2 72 -52 84 Comparative Example 2 0.870 12.1 5.0 212K 2.2 60 -56 67 Comparative Example 3 0.863 14.2 0.5 389K 2.3 49 -58 63

In the case of the ethylene 1-octene copolymers of Examples 1 to 3 prepared according to the present invention, the melting temperature was higher and the glass transition compared to the ethylene 1-octene copolymers of Comparative Examples 1 to 3 having a similar density and a similar 1-octene content. It can be seen that the temperature is low. This is because the region with high crystallinity becomes harder and the region with low crystallinity becomes softer because the repeating ratio of ethylene structural units in the copolymer is high.

[Examples 4-6 and Comparative Examples 4-6]

Ethylene 1-octene air of Examples 1 to 3 and Comparative Examples 1 to 3 using a twin screw extruder including an internal mixer and an extruder and having a length/outer diameter ratio of 52 To 20 parts by weight of the coalescing, 70 parts by weight of polypropylene having a melt index (190° C., 2.16 kg) of 60 g/10 min and 10 parts by weight of talc (KCM-6300, Kotsu Corporation) are added and melted at a reaction temperature of 160 to 220° C. By kneading, a polypropylene-based composite resin composition in the form of pellets was prepared.

[Evaluation of composite resin properties]

After leaving the composite resins prepared in Examples 4 to 6 and Comparative Examples 4 to 6 in a constant temperature and humidity room (25 ℃, 50% humidity) for 24 hours or more, tensile strength, tensile elongation, flexural strength, flexural modulus, IZO The strength and heat deflection temperature were measured as follows, and the measurement results are shown in Table 3 below.

(1) Tensile strength, tensile elongation, flexural strength and flexural modulus

Measurements were made according to ASTM D790 using a universal material testing machine (INSTRON 4466).

(2) IZOD impact strength

It was carried out according to ASTM D256, the impact strength was measured at room temperature under the conditions of room temperature (23 ℃), and the low temperature impact strength was measured after standing in a low temperature chamber (-30 ℃) for 12 hours or more.

(3) heat deflection temperature

According to ASTM D648, it was measured with a high load (18.5 kg) using an HDT tester (TOYOSEIKI, 6A-2).

ethylene
1-octene
copolymer The tensile strength
(MPa) tensile elongation
(%) flexural strength
(MPa) flexural modulus
(MPa) IZOD impact strength
(J/m) heat deformation
Temperature
(℃) 23℃ -30℃ Example 4 Example 1 17.9 74 29.0 1325 314 27 121 Example 5 Example 2 17.1 75 27.2 1295 367 28 119 Example 6 Example 3 16.6 78 26.3 1298 401 30 116 Comparative Example 4 Comparative Example 1 17.5 69 28.1 1299 301 24 117 Comparative Example 5 Comparative Example 2 16.9 72 26.9 1265 338 24 115 Comparative Example 6 Comparative Example 3 16.5 73 25.8 1269 374 26 114

It can be seen that the composite resin of Example 4 has higher tensile strength, tensile elongation, flexural strength, flexural modulus, IZOD impact strength, and thermal deformation temperature compared to the composite resin of Comparative Example 4. This is because Example 4 contains an ethylene 1-octene copolymer having a higher melting temperature and a lower glass transition temperature than Comparative Example 4. It was confirmed that the composite resin containing the ethylene 1-octene copolymer has improved heat resistance and impact resistance without changing elastic properties such as elongation and resilience. The above results can also be confirmed through the comparison results of Example 5 and Comparative Example 5, and the comparison results of Example 6 and Comparative Example 6.

Claims (7)

In the composite resin composition comprising a polypropylene resin and an ethylene alpha-olefin copolymer,
The ethylene alpha-olefin copolymer includes an ethylene structural unit and an alpha-olefin structural unit,
Ethylene monomer reactivity ratio (r ₁ ) and alpha-olefin monomer reactivity ratio (r ₂ ) are represented by the following formula (1):

Formula (1)
[In formula (1),
r ₁ and r ₂ are calculated according to the following formula (2),

,

Equation (2)
where X is the ratio of the amount of alpha-olefin monomer _{fed (mol) to the amount of ethylene monomer fed (mol), and P 11} , P ₁₂ , P ₂₁ and P ₂₂ are calculated according to the following formula (3),

Equation (3)
E is an ethylene structural unit, O is an alpha-olefin structural unit,
When A is E or O, [A], [AA] and [AAA] are the ^{values determined by 13} C NMR spectroscopy analysis, respectively, meaning the proportion of A, AA and AAA structures present in the copolymer,
The [EE], [E], [OO] and [O] are calculated according to the following formula (4)

formula (4)]
Formed under a metallocene catalyst that satisfies
^The ethylene structural unit repeat ratio (D) determined by 13 C NMR spectroscopy analysis is represented by the following formula (5):
10 < Ethylene structural unit repeat ratio (D) < 14 Formula (5)
(in formula (5),

to be)
A composite resin composition that satisfies

According to claim 1,
Based on the total weight of the composite resin composition, a composite resin composition comprising 50 to 90% by weight of a polypropylene resin and 5 to 30% by weight of an ethylene alpha-olefin copolymer.
According to claim 1,
The metallocene catalyst is a composite resin composition comprising a transition metal compound represented by the following formula (1):

[Formula 1]

(In Formula 1,
M is selected from the group consisting of a Group 4 transition metal;
Q ¹ and Q ² are each independently halogen, (C ₁ -C ₂₀ )alkyl group, (C ₂ -C ₂₀ )alkenyl group, (C ₂ -C ₂₀ )alkynyl group, (C ₆ -C ₂₀ )aryl group, (C ₁ -C ₂₀ )alkyl(C ₆ -C ₂₀ )aryl group, (C ₆ -C ₂₀ )aryl(C ₁ -C ₂₀ )alkyl group, (C ₁ -C ₂₀ )alkylamido group, (C ₆ - C ₂₀ ) an arylamido group or a (C ₁ -C ₂₀ )alkylidene group;
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently hydrogen; _{A (C 1} -C ₂₀ )alkyl group unsubstituted or substituted with an acetal group, a ketal group, or an ether group; _{A (C 2} -C ₂₀ )alkenyl group unsubstituted or substituted with an acetal group, a ketal group, or an ether group; _{a (C 1} -C ₂₀ )alkyl(C ₆ -C ₂₀ )aryl group unsubstituted or substituted with an acetal group, a ketal group, or an ether group; _{a (C 6} -C ₂₀ )aryl(C ₁ -C ₂₀ )alkyl group unsubstituted or substituted with an acetal group, a ketal group, or an ether group; _{or a (C 1} -C ₂₀ ) silyl group unsubstituted or substituted with an acetal group, a ketal group, or an ether group; R ¹ and R ² may be connected to each other to form a ring, R ³ and R ⁴ may be connected to each other to form a ring, and ^{two or more of R 5} to R ¹⁰ may be connected to each other to form a ring can;
R ¹¹ , R ¹² and R ¹³ are each independently hydrogen; _{A (C 1} -C ₂₀ )alkyl group unsubstituted or substituted with an acetal group, a ketal group, or an ether group; _{A (C 2} -C ₂₀ )alkenyl group unsubstituted or substituted with an acetal group, a ketal group, or an ether group; _{a (C 1} -C ₂₀ )alkyl(C ₆ -C ₂₀ )aryl group unsubstituted or substituted with an acetal group, a ketal group, or an ether group; _{a (C 6} -C ₂₀ )aryl(C ₁ -C ₂₀ )alkyl group unsubstituted or substituted with an acetal group, a ketal group, or an ether group; _{A (C 1} -C ₂₀ )silyl group unsubstituted or substituted with an acetal group, a ketal group, or an ether group; _{A (C 1} -C ₂₀ )alkoxy group unsubstituted or substituted with an acetal group, a ketal group, or an ether group; _{or a (C 6} -C ₂₀ )aryloxy group unsubstituted or substituted with an acetal group, a ketal group, or an ether group; R ¹¹ and R ¹² or R ¹² and R ¹³ may be connected to each other to form a ring).
According to claim 1,
The alpha-olefin monomer is (C ₃ -C ₁₀ ) A composite resin composition, characterized in that it is an alpha-olefin monomer.
According to claim 1,
The composite resin composition further comprises an inorganic filler,
The inorganic filler is a composite resin composition, characterized in that at least one selected from the group consisting of talc, calcium carbonate, mica and clay.
According to claim 1,
The composite resin composition, characterized in that the content of the alpha-olefin monomer in the ethylene alpha-olefin copolymer is 3 to 20 mol%, and the density is 0.850 to 0.915 g/cm 3 .
According to claim 1,
A composite resin composition, characterized in that the melting point (Tm) is 40 to 100 °C, and the glass transition temperature (Tg) is -70 to -40 °C.