JPH0621206B2 - Resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a resin composition containing soft polypropylene.

[Prior Art] Compositions of various resins, elastomers or rubbers and organic fillers have been conventionally known. However, for example, a composition of polypropylene and an organic filler is hard, and a composition of urethane, various elastomers or rubber is expensive. Further, the composition with polyvinyl chloride has a problem such as bleeding of the plasticizer.

[Problems to be Solved by the Invention] In the present invention, when a special soft polypropylene is used, it exhibits elastic and elastic behavior and exhibits excellent moisture absorption and desorption (the difference between the time of moisture absorption and the time of moisture release is large). It was found that a resin composition having The present invention is based on this finding.

[Means for Solving the Problems] Accordingly, the present invention provides a soft polypropylene of 95 to 40% by weight and one kind selected from the group consisting of leather powder, gelatin, casein, silk powder, cellulose powder, bamboo powder and chitin powder. Organic filler 5
60% by weight of the resin composition.

In the present specification, the "soft polypropylene" means a homopolymer or a copolymer described in (1) to (4) below:
Furthermore, it means any of the compositions containing these polymers.

(1) (i) 10 to 90% by weight of boiling heptane-soluble polypropylene having an intrinsic viscosity of 1.2 dl / g or more, and (ii) 90-boiling boiling heptane-insoluble polypropylene having an intrinsic viscosity of 0.5 to 9.0 dl / g. 10% by weight of the polypropylene-based polymer (a), (2) (i) the α-olefin unit content is 0.1 to 5 mol%, and (ii) the intrinsic viscosity is 1.2 dl / g or more. Some boiling hexane solubles are 20-99.9% by weight, and (i
ii) Random copolymer (b) of propylene and α-olefin having 4 to 30 carbon atoms, having a tensile elastic modulus of 5000 kg / cm ² or less, (3) (i) the polypropylene polymer (a) 10 ~ 9
5% by weight, and (ii) ethylene having an ethylene unit content of 10 to 60 mol% and an intrinsic viscosity of 0.5 to 7.0 dl / g.
Propylene copolymer (c) and / or (ii) ethylene unit content is 10 to 60 mol%, polyene unit content is 1 to 10 mol%, and intrinsic viscosity is 0.5 to
Propylene composition (d) consisting of ethylene-propylene-polyene copolymer (c ') 90 to 5 wt% of 7.0 dl / g, and (4) (i) the random copolymer (b). Propylene composition (e) consisting of 10 to 95% by weight and (ii) 90 to 5% by weight of the ethylene-propylene copolymer (c) and / or the ethylene-propylene-polyene copolymer (c '). .

The polypropylene-based polymer (a) has the following properties.
Those having (i) to (iv) are particularly preferable.

(i) ¹³ C-NMR pentad fraction, rrrr / 1-mmm
m is 20% or more.

(ii) The melting peak temperature (Tm) measured by a differential calorimeter (DSC) is 150 ° C. or higher.

(iii) The melting enthalpy (ΔH) measured by DSC is 100 J / g or less.

(iv) Upon observation with a transmission electron microscope, a domain structure is observed.

Among the soft polypropylenes used in the present invention, the above polypropylene-based polymer (a) and random copolymer (b)
Can be prepared, for example, by either the gas-phase one-step polymerization method or the slurry one-step polymerization method described below.
Hereinafter, their preparation methods will be described in order.

Gas-Phase One-Step Polymerization Method The catalyst system used in the gas-phase one-step polymerization method is, for example, (I) (i) a crystalline polyolefin and (ii) a solid catalyst component composed of magnesium, titanium, a halogen atom and an electron-donating compound. And a solid component (II), an organic aluminum compound (II), an alkoxy group-containing aromatic compound (III), and an electron donating compound (IV).

The solid component (I) is a crystalline polyolefin (i) 1.
The solid catalyst component (ii) is contained in an amount of 0.005 to 30 parts by weight (preferably 0.02 to 10 parts by weight) with respect to parts by weight.

The solid component (I) can be prepared, for example, by a method of prepolymerizing an olefin in the presence of a solid catalyst component (ii), an organoaluminum compound, and optionally an electron donating compound (preliminary polymerization method). ).

Here, the solid catalyst component (ii) is magnesium, titanium,
It contains a halogen atom and an electron donating compound as essential components, and can be prepared by contacting a magnesium compound, a titanium compound and an electron donating compound.

Examples of the magnesium compound include magnesium dihalide such as magnesium dichloride, magnesium oxide, magnesium hydroxide, hydrotalcite, magnesium carboxylate, alkoxy magnesium such as diethoxy magnesium, aryloxy magnesium, alkoxy magnesium halide, and aryloxy magnesium. Alkyl magnesium such as halide and ethyl butyl magnesium, alkyl magnesium halide, or organic magnesium compound and electron donor, halosilane,
Examples thereof include alkoxysilane, silanol, and a reaction product with an aluminum compound. Among these, magnesium halide, alkoxymagnesium,
Alkyl magnesium and alkyl magnesium halide are preferable. In addition, these magnesium compounds are 1
They may be used alone or in combination of two or more.

Examples of the titanium compound include tetramethoxy titanium, tetraethoxy titanium, tetra-n-propoxy titanium, tetraisopropoxy titanium, tetra-n-butoxy titanium, tetraisobutoxy titanium, tetracyclohexyloxy titanium, and tetraphenoxy titanium. Titanium tetrahalides such as tetraalkoxytitanium, titanium tetrachloride, titanium tetrabromide and titanium tetraiodide, methoxytitanium trichloride, ethoxytitanium trichloride, propoxytitanium trichloride, n-
Trihalogenated alkoxytitanium such as butoxytitanium trichloride, ethoxytitanium tribromide,
Dihalogenated dialkoxytitanium such as dimethoxytitanium dichloride, diethoxytitanium dichloride, dipropoxytitanium dichloride, di-n-propoxytitanium dichloride, diethoxytitanium dibromide, trimethoxytitanium chloride, triethoxytitanium chloride, tripropoxytitanium chloride, Examples thereof include mono-hagogenized trialkoxy titanium such as tri-n-butoxytitanium chloride, and among these, a high halogen content titanium compound, particularly titanium tetrachloride, is preferable. These titanium compounds may be used alone or in combination of two or more.

The electron-donating compound is an organic compound containing oxygen, nitrogen, phosphorus, sulfur, silicon and the like, and can basically improve the regularity in the polymerization of propylene.

Examples of such an electron-donating compound include esters, thioesters, amines, ketones, nitriles, phosphines, ethers, thioethers, acid anhydrides, acid halides, acid amides, aldehydes, Examples thereof include organic acids. Furthermore, for example, diphenyldimethoxysilane, diphenyldiethoxysilane, dibenzyldimethoxylane, tetramethoxysilane, tetraethoxysilane, tetraphenoxysilane,
Organosilicon compounds such as methyltrimethoxysilane, methyltriethoxysilane, methyltriphenoxysilane, phenyltrimethoxysilane and benzyltrimethoxysilane, aromatic dicarboxylic acid esters such as n-butyl phthalate and diisobutyl phthalate, benzoic acid , P-
Alkyl ester having 1 to 4 carbon atoms of aromatic monocarboxylic acid such as methoxybenzoic acid, p-ethoxybenzoic acid and toluic acid, isopropyl methyl ether, isopropyl ethyl ether, t-butyl methyl ether, t-butyl ethyl ether, t Asymmetric ethers such as -butyl-n-propyl ether, t-butyl-n-butyl ether, t-amyl methyl ether and t-amyl ethyl ether, 2,2'-azobis (2-ethylpropane),
2,2-azobis (2-ethylpropane), 2,2'-
Azobis (2-methylpentane), a, a'-azobisisobutyronitrile, 1,1'-azobis (1-cyclohexanecarboxylic acid), (1-phenylmethyl) -azodiphenylmethane, 2-phenylazo-2, Examples thereof include azo compounds in which a sterically hindering substituent is bonded to an azo bond such as 4-dimethyl-4-trixypentanenitrile. These may be used alone or in combination of two or more. Good.

Specifically, dimethyl phthalate, diethyl phthalate, dipropyl phthalate, diisobutyl phthalate,
Methyl ethyl phthalate, methyl propyl phthalate,
Methyl isobutyl phthalate, ethyl propyl phthalate, ethyl isobutyl phthalate, propyl isobutyl phthalate, dimethyl terephthalate, diethyl terephthalate, dipropyl terephthalate, diisobutyl terephthalate, methyl ethyl terephthalate, methyl propyl terephthalate, methyl isobutyl terephthalate, ethyl propyl terephthalate, ethyl isobutyl terephthalate, propyl Isobutyl terephthalate,
Aromatic such as dimethylisophthalate, diethylisophthalate, dipropylisophthalate, diisobutylisophthalate, methylethylisophthalate, methylpropylisophthalate, methylisobutylisophthalate, ethylpropylisophthalate, ethylisobutylisophthalate and propylisobutylisophthalate Dicarboxylic acid diester, methyl formate, ethyl acetate,
Vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, ethyl acetate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl pivalate,
Dimethyl maleate, ethyl cyclohexanecarboxylate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, ethyl toluate,
Monoesters such as amyl toluate, ethyl anisate, ethyl ethoxybenzoate, ethyl p-butoxybenzoate, ethyl o-chlorobenzoate and ethyl naphthoate,
γ-valerolactone, coumarin, phthalide, esters having 2 to 18 carbon atoms such as ethylene carbonate, benzoic acid, p-
Organic acids such as oxybenzoic acid, acid anhydrides such as succinic anhydride, benzoic anhydride and p-toluic anhydride, and ketones having 3 to 15 carbon atoms such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone and benzoquinone Aldehydes having 2 to 15 carbon atoms such as acetaldehyde, octyl aldehyde, benzaldehyde, tolualdehyde and naphthyl aldehyde,
C2 to C15 acid halides such as acetyl chloride, benzyl chloride, toluic acid chloride, and anisic acid chloride, methyl ether, ethyl ether, isopropyl ether, n-butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether,
2 to 2 carbon atoms such as ethylene glycol butyl ether
0 ethers, acetic acid amides, benzoic acid amides, acid amides such as toluic acid amides, tributylamine, N,
Examples thereof include amines such as N′-dimethylpiperazine, tribenzylamine, aniline, pyridine, picoline and tetramethylethylenediamine, and nitriles such as acetonitrile, benzonitrile and tolunitrile.

Among these, esters, ethers, ketones and acid anhydrides are preferable, and especially di-n-butyl phthalate,
Aromatic dicarboxylic acid diesters such as diisobutyl phthalate, benzoic acid, p-methoxybenzoic acid, p-ethoxybenzoic acid and alkyl esters of aromatic monocarboxylic acids such as toluic acid having 1 to 4 carbon atoms are preferable. Aromatic dicarboxylic acid diesters are particularly preferred because they improve catalyst activity and activity persistence.

The solid catalyst component (ii) can be prepared by a known method (JP-A-
53-43094, JP-A-55-135102, JP-A-55-13
5103, JP-A-56-18606). For example, (1) a method of pulverizing a magnesium compound or a complex compound of a magnesium compound and an electron donor in the presence of an electron donor and a pulverization aid optionally used and reacting with a titanium compound, (2 ) A method of reacting a liquid material of a magnesium compound having no reducing ability and a liquid titanium compound in the presence of an electron donor to precipitate a solid titanium complex, (3) the above (1) or (2) ) A method of reacting a titanium compound with the product obtained in), (4) a method of further reacting the product obtained in (1) or (2) with an electron donor and a titanium compound,
(5) A magnesium compound or a complex compound of a magnesium compound and an electron donor is crushed in the presence of an electron donor, a titanium compound, and a crushing aid optionally used, and then treated with halogen or a halogen compound. It can be prepared by a method, (6) a method of treating the compound obtained in the above (1) to (4) with halogen or a halogen compound, and the like.

Furthermore, methods other than these methods (JP-A-56-166205, JP-A-57-63309, JP-A-57-190004, JP-A-57-300407, and JP-A-58-58) (47003 publication)
The solid catalyst component (ii) can also be prepared by

Further, oxides of elements belonging to Groups II to IV of the periodic table, for example,
Oxides such as silicon oxide, magnesium oxide, and aluminum oxide, or composite oxides containing at least one oxide of an element belonging to Groups II to IV of the periodic table, for example, a solid product obtained by supporting the magnesium compound on silica alumina or the like. And an electron donor and a titanium compound in a solvent in an amount of 0 to 200
The solid catalyst component (ii) can be prepared by contacting at a temperature of 0 ° C, preferably 10 to 150 ° C for 2 minutes to 24 hours.

In preparing the solid catalyst component (ii), an organic solvent inert to the magnesium compound, the electron donor and the titanium compound as a solvent, for example, an aliphatic hydrocarbon such as hexane or heptane, or an aromatic solvent such as benzene or toluene. Group hydrocarbons or halogenated hydrocarbons such as mono- or polyhalogen compounds of saturated or unsaturated aliphatic, alicyclic and aromatic hydrocarbons having 1 to 12 carbon atoms can be used.

The composition of the solid catalyst component (ii) thus prepared is
Usually, the magnesium / titanium atomic ratio is in the range of 2 to 100, the halogen / titanium atomic ratio is in the range of 5 to 200, and the electron donor / titanium molar ratio is in the range of 0.1 to 10.

Thus obtained solid catalyst component (ii), in the presence of an organoaluminum compound and optionally an electron donating compound,
The solid component (I) can be prepared by prepolymerizing an olefin.

Examples of the organoaluminum compound used here include AlR ³ pX _3-p (1) (wherein R ³ is an alkyl group having 1 to 10 carbon atoms, X is a halogen atom such as chlorine or bromine, and p is 1 to 1). A number represented by 3). Examples of such an aluminum compound include, for example, trialkyl aluminum such as trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, and trioctyl aluminum, diethyl aluminum monochloride, diisopropyl aluminum monochloride, diisobutyl aluminum monochloride, dioctyl aluminum. Dialkylaluminum monohalides such as monochloride and alkylaluminum sesquihalides such as ethylaluminum sesquichloride can be preferably used. These aluminum compounds may be used alone or in combination of two or more.

Further, as the electron-donating compound that can be optionally present, the compounds described in connection with the solid catalyst component (ii) can be used.

In the method for preparing the solid component (I), as the olefin, an α-olefin having 2 to 10 carbon atoms such as ethylene, propylene, butene-1, and 4-methylpentene-1 is used, and usually 30 to 80 ° C, preferably 55-70 ° C
Prepolymerization is carried out at a temperature within the range to form a crystalline polyolefin having a melting point of 100 ° C. or higher. At this time, the aluminum / titanium atomic ratio of the catalyst system is usually selected in the range of 0.1 to 100, preferably 0.5 to 5, and the electron donating compound / titanium molar ratio is 0 to 50.
It is preferably selected in the range of 0.1 to 2.

The solid component (I) comprises crystalline powder such as crystalline polypropylene or polyethylene having a uniform particle size, the solid catalyst component (ii), an organoaluminum compound, an electron donating compound (having a melting point of 100 ° C. or higher). Can also be prepared by a method of dispersing (dispersion method).

Furthermore, the solid component (I) can be prepared by combining the above-mentioned prepolymerization method and dispersion method.

As described above, the catalyst system used in the gas-phase one-step polymerization method comprises bringing the solid component (I), the organoaluminum compound (II), the alkoxy group-containing aromatic compound (III) and the electron donating compound (IV) into contact with each other. The organoaluminum compound (II) and the electron-donating compound (IV) may be the compounds described above.

Further, the alkoxy group-containing aromatic compound (III) has, for example, a compound represented by the general formula: [In the formula, R ¹ is an alkyl group having 1 to 20 carbon atoms, R ² is a hydrocarbon group having 1 to 10 carbon atoms, a hydroxyl group or a nitro group, m is an integer of 1 to 6, and n is 0 to (6-m. Is an integer]], and specifically, for example, m-methoxytoluene, o-methoxyphenol, m-methoxyphenol, 2-methoxy-4-methylphenol, vinylanisole, p- ( 1-propenyl) anisole,
p-allylanisole, 1,3-bis (p-methoxyphenyl) -1-pentene, 5-allyl-2-methoxyphenol, 4-allyl-2-methoxyphenol, 4-
Monoalkoxy compounds such as hydroxy-3-methoxybenzyl alcohol, methoxybenzyl alcohol, nitroanisole and nitrophenetole, o-dimethoxybenzene, m-dimethoxybenzene, p-dimethoxybenzene, 3,4-dimethoxytoluene, 2,6- Dialkoxy compounds such as dimethoxyphenol, 1-allyl-3,4-dimethoxybenzene and 1,3,5-trimethoxybenzene, 5-allyl-1,2,3-trimethoxybenzene, 5-allyl-1,2. , 4-trimethoxybenzene, 1,2,3-trimethoxy-5- (1-propenyl) benzene, 1,2,4-trimethoxy-5- (1
-Propenyl) benzene, 1,2,3-trimethoxybenzene, 1,2,4-trimethoxybenzene, and other trialkoxy compounds, and the like. Among these, dialkoxy compounds and trialkoxy compounds are preferable. . These alkoxy group-containing aromatic compounds may be used alone or in combination of two or more.

In the above catalyst system, the solid component (I) is used in an amount of 0.0005 to 1 mol per 1 reaction volume in terms of titanium atom. The amount of the alkoxy group-containing aromatic compound (III) used is 0.01 to 500 mol, preferably 1 to 300 mol, based on 1 mol of the titanium atom in the solid component (I). If the amount used is less than 0.01 mol, the physical properties of the resulting polymer deteriorate, and if it exceeds 500 mol, the catalytic activity decreases, which is not preferable. In this catalyst system, the atomic ratio of aluminum to titanium is 1 to 1 to 3000. (Preferably 1:40 to 800). If the atomic ratio is out of this range, sufficient catalytic activity cannot be obtained. Furthermore, the molar ratio of the alkoxy group-containing aromatic compound (III) and the electron donating compound (IV) is 1: 0.01 to 100 (preferably 1 :).
0.2-100).

In the gas-phase one-stage polymerization method, the polypropylene-based polymerization (a) is obtained by homopolymerizing propylene, and the random copolymerization is performed by copolymerizing propylene with an α-olefin having 4 to 30 carbon atoms. A combination (b) is obtained. The molecular weight can be adjusted by known means (for example, adjustment of hydrogen concentration). The polymerization temperature is generally 40 to 90 ° C.
(Preferably 60 to 75 ° C.), and the polymerization pressure is 10 to
45 kg / cm ² (preferably 20 to 30 kg / cm ² ), and the polymerization time is 5 minutes to 10 hours.

Slurry One-Step Polymerization Method In the slurry one-step polymerization method, for example, either of the following two types of catalyst systems can be used. That is, (1) a catalyst comprising a combination of (a) a solid component containing magnesium, titanium, a halogen atom and an electron donor as essential components, (b) an alkoxy group-containing aromatic compound, and (c) an organoaluminum compound. System, or (2) (A) a solid catalyst obtained by reacting the above (a) solid component and (b) an alkoxy group-containing aromatic compound in the presence or absence of (c) an organoaluminum compound A catalyst system comprising a combination of components and (B) an organoaluminum compound.

First, the catalyst system of (1) above will be described. The solid component (a) contains magnesium, titanium, a halogen atom and an electron donor as essential components, and a magnesium compound, a titanium compound and an electron donor are contacted with each other. Can be prepared.

In preparing the solid component (a), an organic solvent inert to the magnesium compound, the electron donor and the titanium compound as a solvent, such as an aliphatic hydrocarbon (hexane, heptane, etc.), an aromatic hydrocarbon ( benzene,
Toluene, etc.) or halogenated hydrocarbons (mono- and polyhalogen compounds of saturated or unsaturated aliphatic, alicyclic and aromatic hydrocarbons having 1 to 12 carbon atoms) alone or in combination of two or more kinds. Can be used.

The magnesium compound, titanium compound and electron donating compound used in preparing the solid component (a) of the catalyst system (1) are each compound described in relation to the catalyst system of the gas phase one-step polymerization method described above. Can be the same. From these compounds, the solid component (a) can be prepared by a known method (for example, the method described in the gas-phase one-step polymerization method).

As the alkoxy group-containing aromatic compound (b) and the organoaluminum compound (c) which are brought into contact with the solid component (a) thus obtained, the compounds described in connection with the catalyst system of the gas phase one-step polymerization method can be used. Can be used.

Regarding the amount of each component constituting the catalyst system (1) used, the solid component (a) is usually converted into titanium atoms to give a reaction volume of 1
The amount of the alkoxy group-containing aromatic compound (b) is usually 0.01 to 500 (preferably 1 to 300) with respect to the titanium atom of the solid component (a). It is used in proportion. If this molar ratio is less than 0.01, the physical properties of the produced polymer deteriorate,
When it exceeds 500, the catalytic activity is lowered, which is not preferable. The organoaluminum compound (C) has a magnesium / titanium atomic ratio of usually 1 to 3000 (preferably 4).
0-800). If this amount deviates from the above range, the catalytic activity will be insufficient.

Next, the catalyst system (2) will be described. The solid catalyst component (A) in the catalyst system (2) includes the solid component (a) of the catalyst system (1) and the alkoxy group-containing aromatic compound (ro). ) With the organoaluminum compound (c) in the presence or absence of the organoaluminum compound (c). For this preparation, a hydrocarbon solvent (for example, a hydrocarbon solvent used for preparing the catalyst system (1)) is generally used.

The reaction temperature is usually 0 to 150 ° C. (preferably 10 to 50).
If the temperature is lower than 0 ° C, the reaction does not proceed sufficiently, and if it exceeds 150 ° C, a side reaction occurs and the activity decreases.

The reaction time varies depending on the reaction temperature, but is usually 1 minute to 20 hours, preferably 10 to 60 minutes.

When the solid catalyst component (A) is prepared in the presence of the organoaluminum compound (C), the concentration of the aluminum compound (C) is usually 0.05 to 100 mmol /
(Preferably 1 to 10 mmol /). If the concentration is less than 0.05 mmol / min, the effect of carrying out the reaction in the presence of the organoaluminum compound (c) is not sufficiently obtained, and if it exceeds 100 mmol / min, the reduction of titanium in the solid component (ii) is caused. As it progresses, the catalytic activity decreases.

On the other hand, when the solid catalyst component (A) is prepared by reacting the solid component (a) with the alkoxy group-containing aromatic compound (b) in the absence of the organoaluminum compound (c), the alkoxy group-containing compound (B) is used in such a ratio that the molar ratio to the titanium atom in the solid component (A) is usually 0.1 to 200 (preferably 1 to 50), and the compound (B) has a molar ratio of The concentration is usually selected in the range of 0.01 to 10 mmol / (preferably 0.1 to 2 mmol /). If the molar ratio to the titanium atom is out of the above range, it is difficult to obtain a catalyst having a desired activity. On the other hand, if the concentration is less than 0.01 mmol / ml, the volumetric efficiency is low, which is not practical, and if it exceeds 10 mmol / mol, overreaction is apt to occur and the catalytic activity is lowered.

As the organoaluminum compound (B) in the catalyst system (2), it is possible to use the organoaluminum compounds exemplified for the catalyst in the gas phase one-step method.

Regarding the amount of each component used in the catalyst system (2), the solid catalyst component (A) is converted into titanium atoms and the reaction volume is 1
Therefore, the organoaluminum compound (B) usually has an aluminum / titanium atomic ratio of 1 to 3 per unit.
It is used in an amount so as to be in the range of 000 (preferably 40 to 800). If this atomic ratio deviates from the above range, the catalytic activity will be insufficient.

When the homopolymerization of propylene is carried out in the slurry one-step polymerization method of the present invention, the above polypropylene-based polymer (a) can be obtained, and the propylene and the carbon number of 4 to 30 are obtained.
The above random copolymer (b) can be obtained by copolymerization with α-olefin.

In the case of slurry one-stage polymerization, the polymerization temperature is usually 0 to 200 ° C.
(Preferably 60 to 100 ° C.), and the propylene pressure is usually selected in the range of 1 to 50 kg / cm ² . A polymerization time of about 5 minutes to 10 hours is sufficient, and the molecular weight of the polymer can be adjusted by known means, for example, by adjusting the hydrogen concentration in the polymerization vessel.

Next, among the soft polypropylenes used in the present invention, the propylene composition (d) {the polypropylene polymer (a) and the ethylene-propylene copolymer (c) or the ethylene-propylene-polyene copolymer (c '). And a propylene-based composition (e) {a composition of the random copolymer (b) and an ethylene-propylene copolymer (c) or an ethylene-propylene-polyene copolymer (c '). } Can be prepared, for example, by any of the following gas phase multi-step method, slurry multi-step method or blending method.

Gas phase multi-stage polymerization method The catalyst used in the gas phase multi-stage polymerization method is the same as the catalyst used in the gas phase one-stage polymerization method.

In the gas phase multi-stage polymerization method, the first polymerization (first stage polymerization) is the same as the above-mentioned gas phase one stage polymerization. Therefore, the molecular weight can be adjusted by known means (for example, adjustment of hydrogen concentration). The polymerization temperature is generally 40 to 90 ° C (preferably 60 to 75 ° C), and the polymerization pressure is 10 to 45 Kg / cm.
² (preferably 20 to 30 kg / cm ² ), and the polymerization time is 5 minutes to 10 hours.

The second to the final polymerization (nth stage polymerization) is carried out with ethylene-
Propylene copolymerization or ethylene-propylene-polyene copolymerization.

Examples of the non-conjugated polyene that can be used in the copolymer include dicyclopentadiene, tricyclopentadiene, 5-methyl-2,5-norbornadiene, 5-
Methylene-2-norbornene, 5-ethylidene-2-norbornene, 5-isopropylidene-2-norbornene, 5-isopropenyl-2-norbornene, 5- (1
-Butenine) -2-norbornene, cyclooctadiene, vinylcyclohexene, 1,5,9-cyclododecatriene, 6-methyl-4,7,8,9-tetrahydroindene, 2-2'-dicyclopentenyl, trans −
1,2-divinylcyclobutane, 1,4-hexadiene, 4-methyl-1,4-hexadiene, 1,6-octadiene, 1,7-octadadiene, 1,8-nonadiene, 1,9-decadiene, 3,6 -Dimethyl-1,7-
Octadiene, 4,5-dimethyl-1,7-octadiene, 1,4,7-octatriene, 5-methyl-1,8
-Nonadiene, norbornadiene, vinyl norbornene and the like can be mentioned. Among these non-conjugated polyenes, especially dicyclopentadiene, 5-ethylidene-2-
Norbornene and 1,7-octadiene are preferred.

In each polymerization step, the molecular weight can be adjusted by a known means (for example, adjustment of hydrogen concentration). In the case of an ethylene-propylene copolymer, the ethylene unit content can be adjusted by adjusting the composition of the charged gas. Also in the case of an ethylene-propylene-polyene copolymer, the polyene unit content can be adjusted by adjusting the charged amount of the polyene compound. Polymerization temperature is 2
The temperature is 0 to 90 ° C. (preferably 40 to 50 ° C.), the polymerization pressure is 5 to 30 kg / cm ² (preferably 10 to 20 kg / cm ² ), and the polymerization time is 5 minutes to 10 hours.

Slurry multi-stage polymerization method In the slurry multi-stage polymerization method, either the catalyst system (1) or (2) used in the above-mentioned slurry one-stage polymerization method can be used.

The polymerization order and the number of polymerization stages in the slurry multi-stage polymerization method are not particularly limited and can be arbitrarily selected. For example, propylene homopolymerization or a copolymer of propylene and an α-olefin having 4 to 30 carbon atoms is performed in the first and third stage polymerizations, and ethylene-propylene copolymerization is performed in the second and fourth stage polymerizations. Alternatively, ethylene-propylene-polyene polymerization can be carried out. As for the number of polymerization stages (the number of n), the optimum number of stages may be selected in order to obtain a desired product, as in the case of the gas-phase multi-stage method. As the polymerization mode, either a continuous polymerization method or a discontinuous polymerization method is used. be able to.

In the case of propylene homopolymerization or copolymerization of propylene and an α-olefin having 4 to 30 carbon atoms, the polymerization temperature is usually 0 to
The range of 200 ° C. (preferably 60 to 100 ° C.) and the propylene pressure are usually selected in the range of 1 to 50 kg / cm ² . In the case of ethylene-propylene copolymerization or ethylene-propylene-polyene copolymerization, the polymerization temperature is usually in the range of 0 to 200 ° C (preferably 40 to 80 ° C),
The olefin pressure is usually selected in the range of 1 to 50 kg / cm ² .

In any of the above-mentioned polymerizations, a reaction time of about 5 minutes to 10 hours is sufficient, and the molecular weight of the polymer can be adjusted by known means, for example, by adjusting the hydrogen concentration in the polymerization vessel.

In the case of ethylene-propylene copolymer, the ethylene unit content can be adjusted by adjusting the feed gas composition, and in the case of ethylene-propylene-polyene copolymer, the adjustment of the polyene unit content can be performed by adjusting the charge amount. You can As the polyene monomer, the polyene monomer described in the vapor phase multi-stage method can be used.

Blending Method The propylene-based compositions (d) and (e) are the polypropylene-based polymer (a) or the random copolymer (b) and the ethylene-propylene copolymer (c) or the ethylene-
It can be prepared by blending the propylene-polyene copolymer (c ') by a known method (for example, dry blending or kneading). The polypropylene polymer (a) and the random copolymer (b) can be obtained by the gas phase one-step polymerization method or the slurry one-step polymerization method, and the ethylene-propylene copolymer (c) or The ethylene-propylene-polyene copolymer (c ') can be obtained by a known method.

The post-treatment after the polymerization can be performed by a conventional method. That is, in the gas-phase one-stage polymerization method or the gas-phase multi-stage polymerization method, after polymerization, the polymer powder discharged from the polymerization vessel is passed through a nitrogen stream or the like in order to remove unreacted olefins and the like contained therein. You may let me. If desired, pelletization may be carried out by an extruder, and in that case, a small amount of water, alcohol, etc. may be added in order to completely deactivate the catalyst. Further, in the slurry one-stage polymerization method or the slurry multi-stage polymerization method, after the polymerization, the monomer can be completely separated from the polymer discharged from the polymerization vessel, and then pelletized.

The resin composition of the present invention is the above-mentioned soft polypropylene 95.
-40% by weight (preferably 80-50% by weight) and 5-60% by weight of one kind of organic filler selected from the group consisting of leather powder, gelatin, casein, silk powder, cellulose powder, bamboo powder and chitin powder (preferably 20 to 50% by weight). If the content of the organic filler is less than 5% by weight, the moisture absorption and desorption property becomes insufficient, and if it exceeds 60% by weight, the heat generated during kneading becomes large and the organic filler easily deteriorates. If you make, the surface will become rough.

The organic filler that can be used in the present invention is an organic filler that becomes water-insoluble after molding, specifically, leather powder, gelatin, casein, silk powder, cellulose powder, bamboo powder or chitin powder. Further, an organic filler that can be kneaded with the soft polypropylene is preferable, with the temperature of the soft polypropylene during kneading being in the range of 220 ° C to 170 ° C.

The form of the organic filler is preferably powder fine particles or short fibers. The average particle size of the fine powder organic filler is generally 1 mm or less, preferably 3 to 100 μm.
m. The large-sized organic filler having an average particle diameter of about 1 mm can be used when preparing a thick molded product. Further, when preparing a thin molded product (for example, a sheet or a film), it is necessary to use an organic filler having a small particle size. It is also possible to use a combination of large and small particle size organic fillers. Generally, it is preferable to use an organic filler having a particle diameter of 1/3 or less of the thickness of the molded product. When a short fiber filler is used, it is preferable to use a filler whose major axis is ½ or less of the thickness of the molded product.

The resin composition of the present invention includes, in addition to the above-mentioned soft polypropylene and organic filler, known additives generally used for polypropylene resin moldings (for example, antioxidants, heat stabilizers, lubricants, antistatic agents). Agents, antiblocking agents or flame retardants).

The resin composition of the present invention can be prepared by drying the organic filler and then kneading with the soft polypropylene. It is necessary to dry the organic filler before kneading. This is because when the organic filler contains water, foaming occurs during kneading and thermal decomposition of the organic filler is promoted. The compound after kneading needs to be dried for the same reason.

The organic filler is dried at 100 to 120 ° C for 1 to 24
Time, water content less than 1% (especially less than 0.5%)
Is preferred. When the water content exceeds 1%, foaming and decomposition or discoloration of the organic filler increase. The water content is 0.
When it is 5% or less, particularly stable kneading can be performed. Any dryer can be used, but a vacuum dryer is preferable.

A generally used kneader can be used for kneading the dried organic filler and the soft polypropylene. That is, as the kneader, for example, Banbury mixer, calendar roll, kneader, multi-axis roll,
Examples thereof include a multi-screw extruder and a single-screw extruder.

When the amount of filler is large, it is preferable to generally use a Banbury mixer, a calender roll, a kneader, a multi-screw extruder or a multi-screw roll. When the amount of filler is small, a single screw extruder or the like can also be used.

The temperature of the soft polypropylene during kneading is 170 ° C-
It is 220 ° C. (preferably 180 ° C. to 200 ° C.). If the resin temperature at the time of kneading exceeds 220 ° C., the organic filler may be thermally decomposed to generate a bad odor or discolor. When the resin temperature at the time of kneading is lower than 170 ° C., the soft polypropylene is not sufficiently melted and kneading cannot be performed.

[Examples] Examples 1 to 6 and Comparative Examples 1 to 4 Hereinafter, the present invention will be described in more detail with reference to Examples.
The invention is not limited by these examples.

Production Example of Soft Polypropylene Production Example 1: Preparation of Homo-Soft Polypropylene (1) Fixed Catalyst Component A glass three-necked flask with an internal volume of 500 ml, which had been sufficiently replaced with nitrogen, had 20 ml of purified heptane and Mg (OEt) _2.
4 g and 1.2 g of di-n-butyl phthalate were added, the system temperature was kept at 90 ° C., ₄ ml of TiCl 4 was dropped while stirring, and 111 ml of TiCl ₄ was additionally added, and the temperature was raised to 110 ° C. After reacting for 2 hours at 110 ° C., it was washed with purified heptane at 80 ° C. 115 ml of TiCl ₄ was added to the obtained solid phase portion, and the mixture was further reacted at 110 ° C. for 2 hours. After the reaction was completed, the product was purified into heptane 10
It was washed several times with 0 ml to give a solid catalyst component [corresponding to the solid catalyst component (ii) in the gas phase method].

(2) Preparation of solid components A glass pressure-resistant _three- necked flask with an internal volume of 2.5, which had been sufficiently replaced with nitrogen, had purified heptane 1.7 and AlEt ₃ 0.0.
7 mol, diphenyldimethoxysilane (DPDMS)
0.05 mmol and 120 g of the catalyst component of the above (1)
Was added. The inside of the system was maintained at 30 ° C., a propylene was continuously supplied while stirring, and the internal pressure was maintained at 0.5 Kg / cm ² .
After continuing this reaction for 1 hour, it was washed 5 times with purified heptane 1 to obtain a solid component [corresponding to solid component (I) in the gas phase method].

(3) Gas-phase first-stage polymerization In a stainless steel pressure-resistant autoclave 5 containing 20 g of polypropylene powder, AlEt ₃ 3 mmol, 1-
Allyl-3,4-dimethoxybenzene (ADMB) 0.
15 mmol, diphenyldimethoxysilane (DPDM
20 ml of a heptane solution containing 0.23 mmol of S) and 100 mg of the solid component (I) of (2) (0.06 mmol in terms of Ti atom) was added. After evacuating the system for 5 minutes, gas phase polymerization was carried out at 70 ° C. for 1.7 hours while supplying propylene gas until the total pressure reached 28 kg / cm ² . 640 g of soft polypropylene having a melt index (MI) of 0.5 g / 10 min was obtained. The boiling polypropylene-soluble content (HSP content) of this soft polypropylene was 49.5% by weight, and the intrinsic viscosity was 1.99 dl / g. In addition, boiling heptane insoluble matter (HIP content) is 50.5% by weight.
And the intrinsic viscosity was 4.13 dl / g. further
Pentad fraction by ¹³ C-NMR rrrr /
1-mmmm is 34.5%, melting peak temperature (Tm) measured by DSC is 158 ° C, melting enthalpy (ΔH) measured by DSC is 58.2 J / g,
And the domain structure was observed in the observation with the transmission electron microscope.

Production Example 2: Block Soft Polypropylene In the same manner as the homo-soft polypropylene, the solid catalyst component and the solid component A were prepared, and then the following was performed.

(1) Gas-phase first-stage polymerization In a stainless steel pressure-resistant autoclave 5 containing 20 g of polypropylene powder, AlEt ₃ 3 mmol, 1-
Allyl-3,4-dimethoxybenzene (ADMB) 0.
15 mmol, diphenyldimethoxysilane (DPDM
S) 0.23 mmol, and a heptane solution 2 containing 100 mg (0.06 mmol in terms of Ti atom) of the solid component (I) prepared in the above Production Example 1 (1) and (2).
0 ml was added. After evacuating the system for 5 minutes, hydrogen gas was added to 0.
Introduced to 6 kg / cm ^2, further total pressure was carried out for 1.7 hours gas phase polymerization at 70 ° C. while supplying propylene gas until 28Kg / cm ^2.

(2) Gas-Phase Second Stage Polymerization After the reaction of (1) above was completed, the system was depressurized and evacuated, then hydrogen gas 0.5 kg / cm ² and ethylene-propylene mixed gas (molar ratio 1/4 ) Up to 10 Kg / cm ² and 50
Gas phase polymerization was performed at 1.4 ° C. for 1.4 hours.

550 g of soft polypropylene having a melt index (MI) of 3.9 g / 10 min was obtained. This soft polypropylene was composed of 72% by weight of polypropylene homopolymer and 28% by weight of ethylene-propylene copolymer, and the homopolymer had a boiling heptane-soluble content (HSP content) of 48 with an intrinsic viscosity of 1.18 dl / g. 0.2% by weight and an intrinsic viscosity of 1.8
4 dl / g boiling heptane insoluble matter (HIP content) 51.8
% By weight, rrrr / 1-mmmm is 34.5% in the pentad fraction by ¹³ C-NMR, DSC
Melting temperature (Tm) measured at 158 ° C, DS
Melting enthalpy (ΔH) measured at C is 62.6J
/ G, and the domain structure was observed in the observation with the transmission electron microscope. On the other hand, the ethylene unit content of the copolymer is 30 mol% and the intrinsic viscosity is 1.77 dl / g.
Met.

(1) The organic fillers shown in Tables 1 and 2 below were vacuum dried (120 ° C., 3 hours) and dry blended with soft polypropylene.

(2) The resin temperature is 180 ℃ ~ 20 in Banbury mixer
The rotation speed and pressure were adjusted so that the temperature became 0 ° C., the resin temperature was adjusted to 180 ° C. to 200 ° C., and then kneading was performed for 5 minutes.

(3) Approximately 3 mm at a temperature of 140 ° C with a biaxial roll having a diameter of 25 cm
And the sheet.

(4) The sheet prepared in (3) above is pre-dried at 120 ° C. for 3 hours, cut into a size of 6 × 12 cm, and put into a hollow iron plate frame (thickness 2 mm) with a press molding machine. Further, sandwich both sides with a polyethylene terephthalate (PET) film and an iron plate, preheat at 180 ° C. for 1 minute, and 0 to 50
Perform defoaming operation 5 to 10 times at a pressure of Kg / cm ² to 50 Kg / c
After pressing at a pressure of m ² and further pressure cooling with a cooling press, a sheet (8 cm × 15 cm × 2 mm) was obtained.

The materials used are as follows (the abbreviations in parentheses are those shown in Tables 1 and 2).

Soft homopolypropylene (soft PP (homo)): Soft polypropylene prepared by Production Example 1 Soft block polypropylene (Soft PP (block)): Soft polypropylene polypropylene (PP) prepared by Production Example 2 Idemitsu Petrochemical Co., Ltd. ); Polypropylene J-750H Leather powder (100 μm): Leather powder having an average particle size of 100 μm (described in JP-A-63-152698 and JP-A-63-11311) Leather powder (5 μm): Average particle Leather powder with a diameter of 5 μm (as described in JP-A-63-152698 and JP-A-63-11311) Cellulose powder (400 mesh pass powder): W400 silk powder (Sanyo Kokusaku Pulp Co., Ltd.) 7 μm): Kanebo Silk Kyojin Co., Ltd. P20 gelatin (5 μm): Powder having an average molecular weight of 100,000 (Nitta Gelatin Co., Ltd.) is dried and further ale milled. It was used as pulverizng average particle size of 5 [mu] m.

The evaluation was performed by the following method.

Moisture absorption and desorption property The test sheet was left standing in an atmosphere of 23 ° C and 30% relative humidity for 24 hours and weighed. Then, from the atmosphere of 23 ° C and 30% relative humidity to 23 ° C and 80% relative humidity.
The atmosphere is changed to 24 hours and the weight is measured. This change in weight serves as an index of hygroscopicity. On the other hand, the moisture release is measured by using a test sheet at 23 ° C and a relative humidity of 80%.
After leaving it to stand in the atmosphere for 24 hours and measuring the weight,
It is carried out by allowing the sample to stand for 24 hours in an atmosphere having a temperature of 30 ° C. and a relative humidity of 30%, measuring the weight, and determining the difference.
The following four grades were evaluated from the average value of the hygroscopicity and the hygroscopicity.

◎ ... difference during moisture absorption / desorption = 150 mg / g. 24 Hr or more change 〇 ... difference during moisture absorption / desorption = 150 to 50 mg / g. 24Hr change × ... difference in moisture absorption / release = 20 mg / g. Change of 24Hr or less Dry touch feeling The touch was evaluated by the following four grades.

◎… Very dry and dry ○… Dry and dry △… Not dry enough ×… Not dry, dripping when touched Softness (tensile elastic modulus) ◎… Less than 5,000 Kg / cm ² ◯ ... 5,000 to 8,000 Kg / cm ² Δ ... 8,000 to 12,000 Kg / cm ² × ... 12,000 Kg / cm ² or more Elongation Tested by a plastic tensile test method according to JIS K6871.

[Effects of the Invention] The resin composition of the present invention exhibits a soft and elastic behavior, and has excellent moisture absorption and desorption properties.

The resin composition of the present invention is suitably used, for example, as a material for wall materials, automobile interior parts, sheet materials or grips.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C08L 53/00 LLV 7142-4J 89/00 LSE 7415-4J 97/00 LSW 7415-4J // C08F 4/658 MFG 9053-4J 10/06

Claims (1)

[Claims] 1. Soft polypropylene 95 to 40% by weight,
5 to 60% by weight of one kind of organic filler selected from the group consisting of leather powder, gelatin, casein, silk powder, cellulose powder, bamboo powder and chitin powder,
Resin composition.