JP2777436B2 - Modified soft polypropylene composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a modified flexible polypropylene composition, and more particularly to a modified flexible polypropylene composition having excellent adhesiveness, heat resistance, low-temperature impact resistance and moldability. .

[Prior Art] Generally, polyolefin resins such as polypropylene are widely used because they are excellent in mechanical strength and moldability and chemically stable, but have a drawback of poor adhesion.

As a method for improving the adhesiveness of a polyolein resin, a method of adding an unsaturated carboxylic acid and an organic peroxide to a polyolefin resin and melt-kneading the polyolefin resin has been conventionally known. It was enough and not satisfactory. In addition, there was a problem that the low-temperature impact resistance was inferior.

Further, a method of adding a rubber substance has also been proposed (Japanese Patent Publication No. 54-40112 or Japanese Patent Publication No. 55-5766). However, when a rubber substance is added, there is a new problem that heat resistance and moldability decrease.

[Problems to be Solved by the Invention] The present inventor has conducted various studies to solve the above-mentioned problems. As a result, when a specific soft polypropylene is modified, it has excellent heat resistance, low-temperature impact resistance and moldability, as well as adhesion. It has been found that a modified flexible polypropylene composition having significantly improved properties can be obtained. The present invention is based on this finding.

[Means for Solving the Problems] Accordingly, the present invention provides (A) 100 parts by weight of soft polypropylene, (B) 0.2 to 15 parts by weight of an unsaturated carboxylic acid or a derivative thereof, and (C) 0.01% of an organic peroxide. To 0.5 parts by weight.

In the present specification, “soft polypropylene” means any of the following homopolymers or copolymers described in (1) to (4), and further, a composition containing such a polymer.

(1) (i) 10 to 90% by weight of a boiling heptane-soluble polypropylene having an intrinsic viscosity of 1.2 dl / g or more, and (ii) 90 to 10% by weight of a boiling heptane-insoluble polypropylene having an intrinsic viscosity of 0.5 to 9.0 dl / g. (2) (i) a boiling hexane-soluble component having an α-olefin unit content of 0.1 to 5 mol% and an intrinsic viscosity of 1.2 dl / g or more; 20-99.9% by weight, and (iii)
(B) a random copolymer of propylene and an α-olefin having 4 to 30 carbon atoms having a tensile modulus of 5000 kg / cm ² or less; (3) (i) the polypropylene-based polymer (a) 10 to 95;
Weight percent, and (ii) ethylene unit content is 10 to 60 mol%
And an ethylene-propylene copolymer (c) having an intrinsic viscosity of 0.5 to 7.0 dl / g and / or (ii) an ethylene unit content of 10 to 60 mol% and a polyene unit content of 1 to 10 mol% With a changing viscosity of 0.5 to 7.0 dl / g
A propylene-based composition (d) comprising 90 to 5% by weight of an ethylene-propylene-polyene copolymer (c '), and (4) (i) 10 to 95% by weight of the random copolymer (b).
And (ii) 90 to 5% by weight of the ethylene-propylene copolymer (c) and / or the ethylene-propylene-polyene copolymer (c ') (e).

Incidentally, the polypropylene polymer (a) preferably has the following properties (i) to (iv).

(I) In the pentad fraction by ¹³ C-NMR, rrrr / 1
-Mmmm 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 10
0 J / g or less.

(Iv) In observation with a transmission electron microscope, a domain structure is observed.

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

Gas-phase one-stage polymerization method The catalyst system used in the gas-phase one-stage polymerization method includes, for example, (I) (i) a crystalline polyolefin and (ii) a solid catalyst component comprising magnesium, titanium, a halogen atom and an electron donating compound. A solid component consisting of (II) an organoaluminum compound, (III) an alkoxy group-containing aromatic compound, and (IV) an electron donating compound.

The solid component (I) is prepared by adding the solid catalyst component (ii) to 0.005 to 3 parts by weight based on 1 part by weight of the crystalline polyolefin (i).
0 parts by weight (preferably 0.02 to 10 parts by weight).

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

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

As the magnesium compound, for example, magnesium dihalide such as magnesium dichloride, magnesium oxide, magnesium hydroxide, hydrotalcite, carboxylate of magnesium, alkoxymagnesium such as diethoxymagnesium, allyloxymagnesium,
Alkoxymagnesium such as alkoxymagnesium halide, allyloxymagnesium halide, ethylbutylmagnesium, etc.Alkylmagnesium halides, or organomagnesium compounds and electron donors, and reactants such as halosilanes, alkoxysilanes, silanols and aluminum compounds can be mentioned. Of these, magnesium halide, alkoxymagnesium, alkylmagnesium, and alkylmagnesium halide are preferred. These magnesium compounds may be used alone or in combination of two or more.

Examples of the titanium compound include tetramethoxytitanium, tetraethoxytitanium, tetra-n-propoxytitanium, tetraisopropoxytitanium, and tetra-n-titanium.
Butoxytitanium, tetraisobutoxytitanium, tetracyclohexyloxytitanium, tetraalkoxytitanium such as tetraphenoxytitanium, titanium tetrachloride, titanium tetrabromide, titanium tetraiodide and other titanium tetrahalides, methoxy titanium trichloride, ethoxy titanium trioxide Chloride, propoxytitanium trichloride, n-
Butoxytitanium trichloride, trihalogenated alkoxytitanium such as ethoxytitanium tribromide,
Halogenated dialkoxytitanium such as dimethoxytitanium dichloride, diethoxytitanium dichloride, dipropoxytitanium dichloride, di-n-propoxytitanium dichloride, diethoxytitanium dibromide, trimethoxytitanium chloride, triethoxytitanium chloride, tripropoxytitanium chloride Monohalogenated trialkoxy titanium such as tri-n-butoxytitanium chloride and the like,
Among them, a titanium compound having a high halogen content, particularly titanium tetrachloride is preferred. Each of these titanium compounds may be used alone, or two or more of them may be used in combination.

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.

Such electron donating compounds include, for example, esters, theoesters, amines, ketones, nitriles, phosphines, ethers, thioethers, acid anhydrides, acid halides, acid amides, aldehydes, Organic acids and the like can be mentioned. Further, for example, diphenyldimethoxysilane, diphenyldiethoxysilane, dibenzyldimethoxysilane, tetramethoxysilane, tetraethoxysilane, tetraphenoxysilane,
Organosilicon compounds such as methyltrimethoxysilane, methyltriethoxysilane, methyltriphenoxysilane, phenyltrimethoxysilane and benzyltrimethoxysilane; aromatic dicarboxylic esters such as n-butyl phthalate and diisobutyl phthalate; benzoic acid , P-
C1-C4 alkyl esters of aromatic monocarboxylic acids 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-amylmethyl ether and t-amylethyl 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, azo compounds such as 2-phenylazo-2,4-dimethyl-4-tricypentanenitrile having a sterically hindered substituent bonded to an azo bond. They may be used, or two or more kinds may be used in combination.

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, ethyl propyl Isobutyl terephthalate,
Aromatics such as dimethyl isophthalate, diethyl isophthalate, dipropyl isophthalate, diisobutyl isophthalate, methyl ethyl isophthalate, methyl propyl isophthalate, methyl isobutyl isophthalate, ethyl propyl isophthalate, ethyl isobutyl isophthalate and propyl isobutyl isophthalate 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, methyl 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;
C2-C18 esters such as γ-valerolactone, coumarin, phthalide, ethylene carbonate, benzoic acid, organic acids such as p-oxybenzoic acid, succinic anhydride, benzoic anhydride, p-toluic anhydride and the like. C3 to C15 ketones such as acid anhydrides, acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone and benzoquinone; and C2 to C15 aldehydes such as acetaldehyde, octyl aldehyde, benzaldehyde, tolualdehyde and naphthyl aldehyde , Acetyl chloride, benzyl chloride, toluic acid chloride, anisic acid chloride and other acid halides having 2 to 15 carbon atoms, methyl ether, ethyl ether, isopropyl ether, n-butyl ether, amyl ether, tetrahydrofuran, anisole C2-C20 ethers such as diphenyl ether and ethylene glycol butyl ether, acid amides such as acetate amide, benzoic acid amide and toluic acid amide, tributylamine, N, N'-dimethylpiperazine, tribenzylamine, aniline, Examples thereof include amines such as pyridine, picoline and tetramethylethylenediamine, and nitriles such as acetonitrile, benzonitrile and tolunitrile.

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

The solid catalyst component (ii) is prepared by a known method (JP-A-53-43094, JP-A-55-135102, JP-A-55-135103, JP-A-56-18606). Gazette). For example, (1) a method in which a magnesium compound or a complex compound of a magnesium compound and an electron donor is pulverized in the presence of an electron donor and a pulverization aid used as required, and reacted with a titanium compound; )
A method in which a liquid substance of a magnesium compound having no reducing ability and a liquid titanium compound are reacted in the presence of an electron donor to precipitate a solid titanium composite, (3) the method of (1) or (2). (4) a method of reacting the compound obtained in (1) or (2) with an electron donor and a titanium compound, (5) a magnesium compound or magnesium (6) a method of pulverizing a complex compound of a compound and an electron donor in the presence of an electron donor, a titanium compound, and a pulverization aid used as required, and treating with a halogen or a halogen compound; It can be prepared by a method of treating the compounds obtained in 1) to (4) with a halogen or a halogen compound.

Further, methods other than these methods (JP-A-56-166205)
JP-A-57-63309, JP-A-57-190004, JP-A-57-300407, and JP-A-58-47003). Can be prepared.

Also, an oxide of an element belonging to Group II to IV of the periodic table, for example, an oxide such as silicon oxide, magnesium oxide, or aluminum oxide or a composite oxide containing at least one oxide of an element belonging to Group II to IV of the periodic table Product, for example, a solid in which the magnesium compound is supported on silica alumina or the like, an electron donor and a titanium compound in a solvent, from 0 to 200
° C, preferably from 2 minutes to 24 hours at a temperature in the range of 10 to 150 ° C.
The solid catalyst component (ii) can be prepared by contacting for a period of time.

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

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

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

Examples of the organoaluminum compound used here include a general formula 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 3) 3) can be mentioned. Such aluminum compounds include, for example, trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum monochloride, diisopropylaluminum monochloride, diisobutylaluminum monochloride, dioctylaluminum Dialkylaluminum monohalides such as monochloride and alkylaluminum sesquihalides such as ethylaluminum sesquichloride can be suitably used. One of these aluminum compounds may be used, or two or more thereof may be used in combination.

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

In the method for preparing the solid component (I), an α-olefin having 2 to 10 carbon atoms such as ethylene, propylene, butene-1, or 4-methylpentene-1 is used as the olefin, usually at 30 to 80 ° C., preferably at 30 to 80 ° C. Preliminary polymerization is carried out at a temperature in the range of 55 to 70 ° C., preferably with a melting point of 100 ° C.
The above-mentioned crystalline polyolefin is formed. 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 selected in the range of 0 to 50, preferably 0.1 to 2. It is.

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

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

As described above, the catalyst system used in the gas-phase one-stage polymerization method includes the solid component (I), the organoaluminum compound (II), the alkoxy group-containing aromatic compound (III), and the electron donating compound (I
V), and the compounds described above can be used as the organoaluminum compound (II) and the electron donating compound (IV).

Further, the alkoxy group-containing aromatic compound (III) has, for example, the general formula Wherein R ¹ is an alkyl group having 1 to 20 carbon atoms, and R ² is an alkyl group having 1 carbon atom.
Hydrocarbon group, hydroxyl group or nitro group, m is an integer of 1 to 6, n is an integer of 0 to (6-m)], 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-hydroxy-3-methoxybenzyl alcohol, methoxy Benzyl alcohol, nitroanisole, monoalkoxy compounds such as nitrophenetole, o-dimethoxybenzene, m-dimethoxybenzene, p-dimethoxybenzene, 3,4-dimethoxytoluene, 2,6-dimethoxyphenol, 1-allyl-3, Dialkoxy compounds such as 4-dimethoxybenzene and 1,3,5-trimethoxybenzene, 5-allyl-1,2,3-trimethoxybenzene,
Allyl-1,2,4-trimethoxybenzene, 1,2,3-trimethoxy-5- (1-propenyl) benzene, 1,2,4-trimethoxy-5- (1-propenyl) benzene, 1,2, Three
Examples include trialkoxy compounds such as -trimethoxybenzene and 1,2,4-trimethoxybenzene. Of these, dialkoxy compounds and trialkoxy compounds are preferred. 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 reaction volume in terms of titanium atom. The amount of the alkoxy group-containing aromatic compound (III) to be used is 0.01 to 500 mol, preferably 1 to 300 mol, per 1 mol of titanium atoms in the solid component (I). If this amount is less than 0.01 mol, the physical properties of the produced polymer decrease, 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: 1 to 3000 (preferably Is 1: 40-800). If the atomic ratio is out of the range, sufficient catalytic activity cannot be obtained. Further, an aromatic compound containing an alkoxy group (III)
And the molar ratio of 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 above-mentioned polypropylene-based polymer (a) is obtained by performing propylene homopolymerization, and the above-described random copolymer is obtained by performing copolymerization of propylene with an α-olefin having 4 to 30 carbon atoms. The polymer (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 20-30 kg / cm ² ), and the polymerization time is 5 minutes to 10 hours.

Slurry one-stage polymerization method In the slurry one-stage polymerization method, for example, any 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. Or (2) (A) a solid catalyst obtained by reacting (A) the above-mentioned solid component with (b) an alkoxy group-containing aromatic compound in the presence or absence of (c) an organoaluminum compound. And (B) a combination of organoaluminum compounds.

First, the catalyst system of the above (1) will be described. The solid component (a) contains magnesium, titanium, a halogen atom and an electron donor as essential components, and contacts a magnesium compound, a titanium compound and an electron donor. 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, for example, an aliphatic hydrocarbon (hexane, heptane, etc.), an aromatic hydrocarbon ( Benzene, toluene, etc.) or halogenated hydrocarbons (mono- and poly-halogen compounds of saturated or unsaturated aliphatic, alicyclic and aromatic hydrocarbons having 1 to 12 carbon atoms) alone or in combination of two or more. They can be used in combination.

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

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

Regarding the amount of each component constituting the catalyst system (1),
The solid component (a) is usually used in an amount of 0.0005 to 1 mol per 1 reaction volume in terms of titanium atom, and the alkoxy group-containing aromatic compound (b) has a molar ratio of the solid component (a) to the titanium atom. , Usually 0.01 to 500 (preferably 1 to 30
0). If the molar ratio is less than 0.01, the physical properties of the produced polymer decrease, and if it exceeds 500, the catalytic activity decreases, which is not preferable. The organoaluminum compound (c) is used in an amount such that the aluminum / titanium atomic ratio is usually 1 to 3000 (preferably 40 to 800). If this amount is outside the above range, the catalytic activity becomes insufficient.

Next, the catalyst system (2) will be described. The solid catalyst component (A) in the catalyst system (2) comprises the solid component (a) of the catalyst system (1) and an alkoxy group-containing aromatic compound (B). ) And the aforementioned organoaluminum compound (c)
Can be prepared by reacting in the presence or absence of In this preparation, a hydrocarbon-based solvent (for example, a hydrocarbon-based solvent used for preparing the catalyst system (1)) is generally used.

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

The reaction time varies depending on the reaction temperature.
Minutes 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 /). When this concentration is less than 0.05 mmol /, the organoaluminum compound (c)
The effect of performing the reaction in the presence of
If it exceeds mmol / mol, the reduction of titanium in the solid component (a) proceeds, and the catalytic activity decreases.

On the other hand, in the absence of the organoaluminum compound (c),
Solid component (a) and alkoxy group-containing aromatic compound (b)
When the solid catalyst component (A) is prepared by reacting the compound (A), the molar ratio of the alkoxy group-containing compound (B) to the titanium atom in the solid component (A) is usually 0.1 to 200 (preferably 1 to 50). ), And the concentration of the compound (b) 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 outside the above range, it is difficult to obtain a catalyst having a desired activity. If the concentration is less than 0.01 mmol /, the volumetric efficiency is low and it is not practical.
If the amount exceeds mmol / mol, overreaction tends to occur, and the catalytic activity decreases.

Organoaluminum compound (B) in catalyst system (2)
The organic aluminum exemplified for the catalyst of the above-mentioned one-stage gas phase method can be used.

The modified flexible polypropylene of the present invention is prepared by modifying the above flexible polypropylene (A) with an unsaturated carboxylic acid or its derivative (B) and an organic peroxide (C).

The unsaturated carboxylic acid (B) has 3 carbon atoms in the entire compound.
~ 8 mono or poly (especially di) carboxylic acids of alkenes or alkynes, specifically maleic acid, fumaric acid, citraconic acid, crotonic acid, isocrotonic acid, mesaconic acid, itaconic acid, angelic acid, Sorbic acid, acrylic acid and the like are preferred. Examples of the derivative of the unsaturated carboxylic acid include anhydrides of the unsaturated carboxylic acid (for example, maleic anhydride, nadic acid anhydride, itaconic anhydride, citraconic anhydride), metal salts, amides, imides, esters and the like. Can be. Of these, maleic anhydride is particularly preferred. In the present invention, one or more of the above unsaturated carboxylic acids or derivatives thereof can be used.

The unsaturated carboxylic acid or its derivative (B) is added in an amount of 0.2 to 100 parts by weight of the soft polypropylene (A).
15 parts by weight (preferably 0.5 to 10 parts by weight). If the amount is less than 0.2 parts by weight, the amount of the polar group becomes small, so that the adhesiveness becomes insufficient. If the amount exceeds 15 parts by weight, gelation proceeds and yellowing occurs.

The decomposition temperature of the organic peroxide (C) is preferably
Compounds at 80 to 140 ° C, particularly preferably 90 to 130 ° C, are suitably used, for example, dicumyl peroxide, t-butyl hydroperoxide, 1,3-bis (t-butylperoxyisopropyl) benzene, -T-butyl peroxide, 2,5-di (t-butylperoxy) hexane,
t-butyl peroxybenzoate and the like.

The addition amount of the organic peroxide (C) is 0.01 to 0.5 part by weight (preferably 0.03 to 0.3 part by weight) based on 100 parts by weight of the soft polypropylene (A). If the amount is less than 0.01 part by weight, no improvement in adhesiveness is observed, and if it exceeds 0.5 part by weight, the decomposition of the polypropylene becomes severe and the physical properties deteriorate.

In the production of the modified flexible polypropylene according to the present invention, for example, each component of the above-mentioned flexible polypropylene (A), unsaturated carboxylic acid or its derivative (B), and organic peroxide (C) is heated at 190 to 270 ° C. (Preferably 200-250 ° C)
It can be carried out by melt-kneading for ~ 10 minutes. If the reaction temperature is lower than 190 ° C, the reaction hardly proceeds,
If the temperature exceeds 70 ° C, yellowing tends to progress.

At the time of melt kneading or after melt kneading, if necessary, other thermoplastic resins, rubbers such as ethylene-propylene rubber or ethylene-propylene-diene-polymer, and further adhesiveness such as rosin resin or polyterpene resin. Granting agents, waxes, various fillers, antioxidants, ultraviolet absorbers, antistatic agents, dispersants and other additives can be appropriately compounded within a range that does not impair the object of the present invention.

The production of the modified soft polypropylene according to the present invention further comprises the step of converting the soft polypropylene (A) into hot xylene (preferably about
After dissolving in xylene at 120 to 140 ° C., an unsaturated carboxylic acid or its derivative (B) and an organic peroxide (C) are added to the solution, and after the reaction is completed (generally, immediately after
Minutes), the reaction product is precipitated with a suitable organic solvent (preferably acetone), and the unreacted unsaturated carboxylic acid or its derivative (B) can be removed by filtration.

The modified soft polypropylene thus obtained according to the present invention includes metal materials such as aluminum, iron, tin, tin, and copper, polyolefin, polyester, polystyrene resin, saponified ethylene-vinyl acetate copolymer, and polyamide resin. Adhesion easily and with sufficient strength to other materials such as thermoplastic resin such as polycarbonate resin, thermosetting resin such as epoxy resin and polyurethane resin, cellulosic material such as paper, cloth and wood, and glass. Therefore, it can be suitably used for the production of various laminates.

For example, when laminating with a saponified ethylene-vinyl acetate copolymer or polyamide resin, the modified soft polypropylene of the present invention is usually 1 to 70% by weight (preferably 2% by weight).
-50% by weight) and low-density polyethylene (preferably linear low-density polyethylene) 99-30% by weight (preferably 98-50
% By weight).

The production of the laminate is performed by selecting from an extrusion laminating method, a thermocompression bonding method, a melt coating method, a powder coating method and the like in consideration of the type and shape of the material of the laminated body.

[Examples] Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

Glass three-neck flask having an inner volume of 500ml was prepared thoroughly purged with nitrogen in Production Example Production Example 1 (1) fixed catalyst component of soft polypropylene, purified heptane 20 ml, Mg (OEt) ₂ 4g and phthalate -n- butyl 1.2 g, keeping the system at 90 ° C., and adding ₄ ml of TiCl ₄ dropwise with stirring, and then further 111 ml of TiCl ₄
Was added, and the temperature was raised to 110 ° C. After reacting at 110 ° C for 2 hours, it was washed with purified heptane at 80 ° C. 115 ml of TiCl ₄ was added to the obtained solid phase and reacted at 110 ° C. for another 2 hours. After the completion of the reaction, the product was washed several times with 100 ml of purified heptane to obtain a solid catalyst component [corresponding to the solid catalyst component (ii) of the gas phase method].

(2) Preparation of solid component A purified heptane 1.7, AlEt ₃ 0.07 mol, diphenyldimethoxysilane (DPDMS) 0.05 mmol and 120 g of the catalyst component (1) were added to a 2.5-volume glass pressure-resistant _three- necked flask sufficiently purged with nitrogen. Was. Keep the system at 30 ° C, continuously supply propylene while stirring,
It was kept at 0.5 kg / cm ² . After continuing this reaction for 1 hour, the solid was washed five times with purified heptane 1 to obtain a solid component [corresponding to the solid component (I) of the gas phase method].

(3) the 5 stainless steel pressure autoclave containing vapor first stage polymerization polypropylene powder 20 g, AlEt ₃ 3 mmol, 1-allyl-3,4-dimethoxybenzene (ADMB) 0.15 mmol of diphenyldimethoxysilane (DPDMS) 0.23 20 ml of a heptane solution containing 100 mmol (0.06 mmol in terms of Ti atom) of the solid component (I) of the above (2) were added. After exhausting the system for 5 minutes, hydrogen gas was introduced up to 0.7 kg / cm ² ,
Further, 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 . Soft polypropylene 640 with melt index (MI) of 8.7g / 10min
g was obtained. This soft polypropylene had a boiling heptane soluble matter (HSP content) of 35% by weight and an intrinsic viscosity of 1.95 dl / g. The boiling heptane-insoluble matter (HIP content) was 65% by weight, and the intrinsic viscosity was 4.78 dl / g. Further ¹³ C-N
Rrrr / 1-mmmm in Petad fraction by MR is 34.5%, melting peak temperature (Tm) measured by DSC is 158 ° C,
The melting enthalpy (ΔH) measured by DSC was 62.6 J / g, and the domain structure was observed by observation with a transmission electron microscope.

5 stainless steel pressure autoclave containing Production Example 2 (1) vapor-phase first-stage polymerization polypropylene powder 20 g, AlEt ₃ 3 mmol, 1-allyl-3,4-dimethoxybenzene (ADMB) 0.15 mmol of diphenyldimethoxysilane ( DPDMS (0.23 mmol) and 20 ml of a heptane solution containing 100 mg (0.06 mmol in terms of Ti atom) of the solid component (I) prepared in Production Examples 1 (1) and (2) were added. After evacuating the system for 5 minutes, supply propylene gas until the total pressure reaches 28 kg / cm ^2.
The gas phase polymerization was carried out at 1.7 ° C. for 1.7 hours.

(2) Gas-phase second-stage polymerization After the reaction of (1) is completed, the system is depressurized and evacuated, and then an ethylene-propylene mixed gas (molar ratio 1/4)
Was supplied to 10 kg / cm ^2, and gas phase polymerization was carried out at 50 ° C. for 1.4 hours.

550 g of a soft polypropylene having a melt index (MI) of 0.1 g / 10 min was obtained. This soft polypropylene is
It consists of 65% by weight of a polypropylene homopolymer and 35% by weight of an ethylene-propylene copolymer. The homopolymer has an intrinsic viscosity of 35% by weight of a soluble heptane (HSP) having an intrinsic viscosity of 1.95 dl / g and an intrinsic viscosity of 35% by weight. 4.78dl / g boiling heptane insolubles (HIP
Min) 65% by weight, rrrr / 1-mmmm is 34.5% in pentad fraction by ¹³ C-NMR, melting peak temperature (Tm) measured by DSC is 158 ° C., melting enthalpy measured by DSC ( ΔH) was 62.6 J / g, and a domain structure was observed in a transmission electron microscope. On the other hand, the ethylene unit content of the copolymer was 31 mol%, and the intrinsic viscosity was 4.81 dl / g.

5 stainless steel pressure autoclave containing Production Example 3 (1) vapor-phase first-stage polymerization polypropylene powder 20 g, AlEt ₃ 3 mmol, 1-allyl-3,4-dimethoxybenzene (ADMB) 0.15 mmol of diphenyldimethoxysilane ( DPDMS (0.23 mmol) and 20 ml of a heptane solution containing 100 mg (0.06 mmol in terms of Ti atom) of the solid component (I) prepared in Production Examples 1 (1) and (2) were added. After exhausting the system for 5 minutes, hydrogen gas was introduced up to 0.7 kg / cm ² , and the total pressure was increased to 28 kg / cm ^2.
The gas-phase polymerization was carried out at 70 ° C. for 1.7 hours while supplying propylene gas until the temperature became.

(2) Gas-phase second-stage polymerization After the reaction of the above (1) is completed, the inside of the system is depressurized and evacuated, and then hydrogen gas 0.75 kg / cm ² and ethylene-propylene mixed gas (molar ratio 1/4) To 15 kg / cm ² at 50 ° C.
Gas phase polymerization was performed for hours.

830 g of a propylene elastomer having a melt index (MI) of 4.4 g / 10 minutes was obtained. This elastomer is composed of 55% by weight of a polypropylene homopolymer and 45% by weight of an ethylene-propylene copolymer. The homopolymer has an intrinsic viscosity of 1.95 dl / g and a boiling heptane-soluble component (HSP content) of 35% by weight.
And a boiling heptane insoluble component (HIP content) with an intrinsic viscosity of 4.78 dl / g 6
Consists of a 5 wt%, rrrr / 1-mmmm 34.5% in the pentad fraction by ¹³ C-NMR, the melting peak temperature measured in DCS (Tm) is 158 ° C., enthalpy of fusion was measured by DSC ([Delta] H) is 62.6 J / g, and a domain structure was observed by observation with a transmission electron microscope. On the other hand, the copolymer has an ethylene unit content of 30 mol% and an intrinsic viscosity of 1.
It was 76 dl / g.

5 stainless steel pressure autoclave containing Production Example 4 (1) vapor-phase first-stage polymerization polypropylene powder 20 g, AlEt ₃ 2 mmol, diphenyldimethoxysilane (DPDMS) 0.5 mmol, and Preparation Example (1) and (2) Component (I) 17mg
Heptane solution containing (0.01 mmol in terms of Ti atom)
20 ml was added. After exhausting the system for 5 minutes, the hydrogen gas was
cm ² , and gas-phase polymerization was performed at 75 ° C. for 1.7 hours while supplying propylene gas until the total pressure reached 31 kg / cm ² . 530 g of polypropylene having a melt index (MI) of 4.0 / 10 minutes was obtained. The boiling heptane soluble matter (HSP content) of this polypropylene is 2% by weight, and the intrinsic viscosity is 0.8dl.
/ g. The boiling heptane insoluble matter (HIP content) is 98
% By weight, and the intrinsic viscosity was 1.85 dl / g.

5 stainless steel pressure autoclave containing Production Example 5 (1) vapor-phase first-stage polymerization polypropylene powder 20 g, AlEt ₃ 2 mmol, diphenyldimethoxysilane (DPDMS) 0.5 mmol, and Preparation Example 1 (1) and (2 ) The solid component (I) 17 prepared in
20 ml of a heptane solution containing mg (0.01 mmol in terms of Ti atom) was added. After exhausting the inside of the system for 5 minutes, the hydrogen gas is
g / cm ² , and gas-phase polymerization was performed at 70 ° C. for 1.7 hours while supplying propylene gas until the total pressure reached 31 kg / cm ² .

(2) Gas phase second stage polymerization After the reaction of the above (1) is completed, the system is depressurized and evacuated, and then a hydrogen gas of 0.2 kg / cm ² and an ethylene-propylene mixed gas (molar ratio of 2/3) Up to 10 kg / cm ² at 50 ° C.
Gas phase polymerization was performed for hours.

620 g of polypropylene having a melt index (MI) of 1.8 g / 10 min was obtained. This polypropylene is composed of 81% by weight of a polypropylene homopolymer and 19% by weight of an ethylene-propylene copolymer, and the homopolymer has an intrinsic viscosity of 0.1%.
It consists of 3 dl / g of boiling heptan soluble (HSP content) of 8 dl / g and 97 pt of boiling heptan insoluble (HIP content) of 1.9 dl / g intrinsic viscosity. The copolymer has an ethylene unit content of 33%. Mol%, and the intrinsic viscosity was 3.0 dl / g.

Examples 1 to 8 Based on 100 parts by weight of the soft polypropylene obtained in Production Examples 1 to 3, the amounts of maleic anhydride and 1,3
After dry-blending -bis (t-butylperoxyisopropyl) benzene, the mixture was melt-kneaded. 220 ° C for kneading
For 5 minutes.

Comparative Examples 1 and 2 Examples 1 to 2 were repeated except that the polypropylene obtained in Production Examples 4 and 5 was used instead of the soft polypropylene.
The same operation as in Example 8 was performed.

Comparative example 3 It carried out similarly to Example 1 except having decreased the addition amount of maleic anhydride.

Comparative Example 4 Using the flexible polypropylene of the present invention (Production Example 3), the required amount of maleic anhydride was added, but the reaction was performed without adding an organic peroxide.

Evaluation method (1) Evaluation of adhesiveness 30 parts by weight of the modified flexible polypropylene composition and isotactic polypropylene (density = 0.900 g / cm ³ , MI = 3 g / 10
And 70 parts by weight of the resin composition were dry-blended and melt-kneaded to obtain a pelletized resin composition. The resulting resin composition was extruded from an extruder A, and a saponified ethylene-vinyl acetate copolymer (EVA) or nylon 6 (PA6) was extruded from an extruder B, and the thickness was 200 μm using a two-layer T die. A / 200 μm two-layer sheet was formed. A test piece having a width of 25 mm was cut out from the two-layer sheet, and the delamination strength was measured using a tensile tester.

(2) Evaluation of heat resistance A kneaded product of 30 parts by weight of the modified soft polypropylene composition and 70 parts by weight of isotactic polypropylene (trade name: J-400M, manufactured by Idemitsu Petrochemical Co., Ltd.) was used to obtain a 3 mm-thick square plate. Molded. A test piece having a length of 120 mm, a width of 20 mm and a thickness of 3 mm was cut out from the molded product, and a heat sag test was performed at 120 ° C. for 1 hour to measure the amount of droop before and after heating.

(3) Evaluation of low-temperature impact resistance A falling weight impact test at −20 ° C. was performed using the square plate molded product of (2).

[Effect of the Invention] The modified flexible polypropylene composition of the present invention has heat resistance,
Not only are the low-temperature impact properties and moldability excellent, but also the adhesion is significantly improved. Therefore, this modified soft polypropylene composition has excellent adhesiveness to materials such as saponified ethylene-vinyl acetate copolymer, polyamide resin or polyester resin, and is suitably used for producing a laminate with these materials. The target value is great.

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Claims (1)

(57) [Claims] 1. A modified soft polypropylene comprising (A) 100 parts by weight of a soft polypropylene, (B) 0.2 to 15 parts by weight of an unsaturated carboxylic acid or a derivative thereof, and (C) 0.01 to 0.5 part by weight of an organic peroxide. Composition.