JPH09183873A - Production of polypropylene resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a polypropylene resin composition excellent in elasticity modulus and heat resistance. SOLUTION: This resin composition consists of (A) 40-99 pts.wt. of polypropylene resin, (B) 1-60 pts.wt. of talc and (C) 0.001-5 pts.wt. of a crystallization promoter per 100 pts.wt. of (A)+(B). In this case, the polypropylene resin (A) is a highly stereo regular polypropylene resin satisfying ΔHm>=24.50+1.583(log MFR) where (MFR) is the melt flow rate of the polypropylene resin observed according to ASTM D1238 and the (ΔHm) is the heat of fusion(cal/g) observed as the melting peak obtained as follows; heating to 230 deg.C, cooling to 50 deg.C and heating again to 230 deg.C at the rate 10 deg.C/min in differential scanning calorimetry. The polypropylene resin (A) and crystallization promoter (C) are melt-blended and further melt-blended wit talc(B).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a polypropylene resin composition, and more particularly to a method for producing a polypropylene resin composition which can be used for industrial materials, general sundries and the like.

[0002]

SUMMARY OF THE INVENTION Polypropylene resins are widely used for industrial materials such as automobiles and home appliances, and for general goods such as various containers and daily necessities. It is common practice to add talc as a means for improving its elastic modulus and heat resistance. On the other hand, as a means for improving the elastic modulus, there is a method of adding a crystal nucleating agent. Therefore, both are used together (Japanese Patent Publication No. 59-174)
No. 1).

Further, a composition in which a propylene-ethylene block copolymer is used as a polypropylene resin and a crystal nucleating agent and talc are added thereto has improved transparency and good rigidity and low-temperature impact resistance. One is disclosed in Japanese Examined Patent Publication No. 3-74264.

To produce the resin composition as described above,
Usually, each component is kneaded together. Then, talc easily adsorbs the crystal nucleating agent, and the adsorbed crystal nucleating agent cannot sufficiently exhibit its function. Therefore, it becomes necessary to add more crystal nucleating agent than necessary. However, in some cases, when a large amount of a crystal nucleating agent is added, the impact resistance of the resin may be reduced. In addition, the blending amount of talc disclosed in Japanese Examined Patent Publication No. 3-74264 is propylene-
0.01 to 100 parts by weight of ethylene block copolymer
3.0 parts by weight. Although such a small amount of talc is suitable for film use, high rigidity cannot be expected when used as an injection molded product.

According to the present invention, in a polypropylene resin composition containing talc and a crystal nucleating agent, the function of the added crystal nucleating agent is sufficiently exerted to produce a polypropylene resin composition excellent in elastic modulus and heat resistance. The purpose is to provide a method.

[0006]

The present invention relates to (A) 40 to 99 parts by weight of polypropylene resin, (B) 1 to 60 parts by weight, and (A) and (B) in total of 100 parts by weight. (C) A method for producing a resin composition containing 0.001 to 5 parts by weight of a crystal nucleating agent, wherein (A) a polypropylene resin, a melt flow rate (MFR) measured according to ASTM D1238, and a differential scanning calorimetry , 230
After the temperature was raised to ℃, the temperature was lowered to 50 ℃, and the heat of fusion (ΔHm) (unit cal / g) was calculated as the peak when the temperature was raised again to 230 ℃ at a rate of 10 ℃ / min. , The following equation (I):

[0007]

[Formula 2] ΔHm ≧ 24.50 +1.583 (log MFR) (I) The high stereoregular polypropylene resin is used, and (A) polypropylene resin and (C) crystal nucleating agent are melt-blended. Then, the melt-blended product and (B) talc are melt-blended.

Preferred embodiments of the present invention are shown below. (A) The resin composition is (A) polypropylene resin 70-
95 parts by weight, (B) talc 5 to 30 parts by weight, and (A)
And 0.005 to 3 parts by weight of the crystal nucleating agent (C) per 100 parts by weight of the total of (B) and (B). (B) The resin composition is (A) polypropylene resin 70-
95 parts by weight, (B) talc 5 to 30 parts by weight, and (A)
And 0.01 to 2 parts by weight of the crystal nucleating agent (C) per 100 parts by weight of the total of (B) and (B). (C) The polypropylene resin has a melt flow rate (MFR) of 0.01 to 1000. (D) In polypropylene resin, MFR and ΔHm
And the following equation (II):

[0009]

## EQU00003 ## Any one of the above methods satisfying the relationship of .DELTA.Hm.gtoreq.24.55 +1.583 (log MFR) (II). (E) The method as described above, wherein the crystal nucleating agent is a phosphoric acid-based crystal nucleating agent. (F) The method according to any one of the above, wherein the crystal nucleating agent is p- (t-butyl) benzoic acid aluminum salt. (G) The melt blended product containing the components (A) and (C) and the melt blended product containing the components (A) and (B) are further melt blended.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a specific polypropylene resin is used as the (A) polypropylene resin. Such polypropylene resin is AS
The melt flow rate (MFR) measured according to TM D1238 and the heat of fusion (ΔHm) measured by differential scanning calorimetry (DSC) are represented by the following formula (I):

[0011]

## EQU4 ## A highly stereoregular polypropylene resin that satisfies the relationship of ΔHm ≧ 24.50 + 1.583 (log MFR) (I). Preferably, the following formula (II):

[0012]

(5) ΔHm ≧ 24.55 +1.583 (log MFR) (II) is satisfied. More preferably, the following formula (III):

[0013]

[Equation 6] ΔHm ≧ 24.60 +1.583 (log MFR) (III) is satisfied. If the above relationship is not satisfied, a molded product having insufficient rigidity and heat resistance can be obtained. As long as the above relationship is satisfied, homopolypropylene, copolymers of propylene and α-olefin (including block copolymers and random copolymers) and the like can be mentioned, and preferably impact-resistant propylene copolymer Examples of the compound (ICP) include propylene-ethylene block copolymer. In the case of the copolymer, the amount of the copolymerization component with propylene is preferably 50% by weight or less of the whole copolymer so as not to significantly reduce the elastic modulus.

Here, the heat of fusion (ΔHm) measured by differential scanning calorimetry (DSC) means that the sample is enclosed in an aluminum pan, heated to 230 ° C., then cooled to 50 ° C., and again.
It means a value (unit cal / g) calculated by dividing the peak when the temperature is raised to 230 ° C at a rate of 10 ° C / min to the melting peak and dividing the corresponding heat quantity by the sample quantity. The melt flow rate (MFR) is 23 in accordance with ASTM D1238.
The values are measured under conditions of 0 ° C and a load of 2.16 kg. The MFR of the polypropylene resin is preferably 0.01 to 1000. If it is less than 0.01, the moldability tends to be poor, and if it exceeds 1,000, impact resistance and ductility tend to be reduced.

The production method of such a polypropylene resin is not particularly limited, but in the case of a polypropylene homopolymer, for example, the method described in detail in JP-A-7-206921, that is, a magnesium chloride-supported solid Those produced by using a regular catalyst and combining them with appropriate silane-added prepolymerization and silane-added main polymerization are preferred. This method is specifically (a) magnesium,
Obtained by contacting (preliminary polymerization) a solid component containing titanium, a halogen and an electron donating compound as essential components with (d) an olefin in the presence of (b) an organoaluminum compound and (c) an organosilicon compound. This is carried out by polymerizing or copolymerizing propylene or, if desired, other olefin with the catalyst component (main polymerization).

The solid component (a) is prepared, for example, by bringing a magnesium compound, a titanium compound and an electron donating compound into contact with each other. When none of the above compounds contains a halogen atom, a halogen compound is added to the compound to bring them into contact. Examples of the magnesium compound include dialkyl magnesium such as Mg (CH ₃ ) ₂ ; Mg
Diarylmagnesium such as (C ₆ H ₅ ) ₂ ; Mg (O
Dialkoxy magnesium such as C ₄ H ₉ ) ₂ ; Mg (O
C ₆ H ₅ ) ₂ etc. diaryloxymagnesium; C ₂
Alkyl magnesium halides such as H ₅ MgBr; C
Aryl magnesium halide such as ₆ H ₅ MgCl;
Examples thereof include alkoxy magnesium halides such as (C ₄ H ₉ O) MgBr; aryloxy magnesium halides such as (C ₆ H ₅ O) MgCl; magnesium halides such as MgCl ₂ . The magnesium compound is
(A) When preparing the solid component, it may be prepared from metallic magnesium. As the titanium compound, a divalent, trivalent or tetravalent titanium compound can be used, and preferred specific examples thereof include titanium tetrachloride, trichloroethoxy titanium, dichlorodibutoxy titanium and dichlorodiphenoxy titanium. Examples of electron-donating compounds include carboxylic acids and their derivatives (anhydrides, esters, halides, etc.), alcohols, phenols, ethers, ketones, amines, amides, nitriles, aldehydes, alcoholates. Etc. Examples of the halogen compound include halogenated hydrocarbons such as methyl chloride; halogenated alcohols such as chloroethanol; halogenated phenols such as bromophenol; HSiCl ₃
And halogenated silicon compounds; metal halides and the like. The contact of the above compounds is carried out by mixing and stirring or mechanically co-milling in the presence or absence of an inert medium (e.g., hexane, heptane, cyclohexane, benzene, toluene, etc.), and 40 to It can be carried out under heating at 150 ° C. For the preparation of the solid component (a), it is preferable to use the methods disclosed in detail in JP-A-63-264607, JP-A-58-198503 and JP-A-62-146904. Illustrating one preferable method among them, (a) magnesium metal, (b) halogenated hydrocarbon, (c) general formula X _n M (OR) _mn (where,
X is a hydrogen atom, a halogen atom or a C _{1 to} C ₂₀ hydrocarbon; M is B, C, Al, Si or P; R is a C _{1 to} C ₂₀ hydrocarbon; m is a valence of M And m
A magnesium-containing solid obtained by contacting a compound represented by the formula (> n ≧ 0) with (d) a halogen-containing alcohol, and then with (e) an electron-donating compound and (f) a titanium compound ( JP 63-2
64607).

In the prepolymerization, the above solid component (a) is added to
In the presence of (b) an organoaluminum compound and (c) an organosilicon compound, (d) an olefin (eg, α-olefin such as ethylene, propylene, butene) is contacted. Examples of the organic aluminum compound include trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, trihexyl aluminum and the like. Examples of the organosilicon compound include bis (oxacyclopent-3-yl) dimethoxysilane, dimethoxymethyl-2-oxacyclohexylsilane, and 2,3,4-trimethyl-3-azacyclopentyltrimethoxysilane. . Further, if necessary, it is preferable to add an electron-donating compound during the prepolymerization. As such an electron donating compound, for example, an organosilicon compound such as tetramethoxysilane, tetraphenoxysilane, vinyltriethoxysilane or the like is preferable.

The prepolymerization is preferably carried out in the presence of an inert medium, usually at a temperature of 100 ° C. or lower. The polymerization system may be a batch system or a continuous system, and may be carried out in one stage or in multiple stages of two or more stages. Preferably, the concentration of the (b) organoaluminum compound in the prepolymerization system is 10
Used to give ~ 500 mmol / l,
(A) Used so as to be 1 to 50,000 mol per 1 g atom of titanium in the solid component. The organosilicon compound (c) is used so that the concentration in the prepolymerization system is 5 to 1000 mmol / liter. The olefin polymer is incorporated into the solid component (a) by prepolymerization, and the amount of the polymer is preferably 0.1 to 200 g per 1 g of the solid component (a).

The catalyst component thus prepared can be diluted or washed with an inert medium. After washing, it may be dried.

The catalyst component thus obtained is used in combination with an organometallic compound and, if necessary, an electron donating compound to carry out main polymerization such as homopolymerization of propylene or copolymerization with other monoolefin. To do. As the organometallic compound, an organic compound of Li, Mg, Ca, Zn, or Al can be used. Among them, organoaluminum compounds are particularly preferable, for example, trialkylaluminums such as trimethylaluminum, triethylaluminum, and triisobutylaluminum; dialkylaluminum monohalides such as diethylaluminum chloride; monoalkylaluminum dihalides such as ethylaluminum dibromide; methylaluminum sesqui. Examples thereof include alkylaluminum sesquihalides such as chlorides; dialkylaluminum monoalkoxides such as dimethylaluminum methoxide; and dialkylaluminum hydrides such as diisobutylaluminum hydride. Examples of the electron-donating compound include organic silicon compounds such as di (1-methylbutyl) dimethoxysilane, dineopentyldimethoxysilane, and neopentyltriethoxysilane.

The main polymerization reaction is carried out in a gas phase or a liquid phase (for example, in an inert hydrocarbon such as butane, isobutane, cyclohexane, benzene and toluene and in a liquid monomer).
The polymerization can be carried out at a polymerization temperature of -80 to + 150 ° C and a polymerization pressure of 1 to 60 atm. The molecular weight of the resulting polymer can be controlled by the presence of hydrogen or other known molecular weight regulator. The polymerization reaction may be carried out batchwise or continuously, and may be carried out in one stage or in multiple stages of two or more stages.

When the polymerization reaction is carried out using the catalyst component obtained as described above, the heat of fusion (ΔHm) and the melt flow rate (M) determined by differential scanning calorimetry (DSC).
It is possible to obtain a highly crystalline polypropylene resin having a relationship with FR) represented by the above formula (I).

A preferred method for producing the polypropylene block copolymer used in the present invention is described in JP-A-7-62047.
The method comprises a step of polymerizing propylene to give a highly crystalline polypropylene (step a) shown below and a step of copolymerizing propylene and ethylene (step b) shown below. (1) Step a Step a consists of polymerizing propylene in the presence of the catalyst component described above in the method for producing a polypropylene homopolymer. The polymerization reaction may be carried out in either a gas phase or a liquid phase, and in the case of polymerizing in a liquid phase, n-butane, isobutane, n-pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene, toluene,
It can be carried out in an inert hydrocarbon such as xylene and in a liquid monomer. Polymerization temperature is usually -80 ℃ to +150
C., preferably 40 to 120.degree. The polymerization pressure is, for example, 1 to 60 atmospheres. Further, the molecular weight of the obtained polymer is controlled by the presence of hydrogen or other known molecular weight regulator.

In step a, it is desirable that the polypropylene obtained there accounts for 50 to 98% by weight, especially 70 to 95% by weight of the block copolymer. (2) Step b Copolymerization of propylene and ethylene is carried out in the presence of the catalyst component described above in the method for producing a polypropylene homopolymer. The copolymerization is carried out by contacting and reacting propylene with ethylene so that the ethylene content in the copolymer obtained there becomes 30 to 95% by weight, preferably 40 to 80% by weight. The copolymerization reaction is step a
It can be appropriately selected from the range of the polymerization conditions carried out in step 1. The use of a molecular weight modifier such as hydrogen is also the same as in step a.

The amount of the copolymer obtained in step b is preferably 2 to 50% by weight, particularly 5 to 30% by weight of the block copolymer.

The steps a and b are in that order,
Alternatively, in addition to the serial method performed in reverse, a method of performing step a and step b in parallel and combining the polymers obtained in each step may be employed. Among them, the serial method in which the steps a and b are performed in that order is advantageous and desirable in terms of the apparatus.

The (B) talc used in the present invention is
The particle size and the like are not particularly limited. Also, talc is
Surface treatment may be performed.

When surface treatment is carried out, organosilane or titanium coupling agents, various surfactants, silicone oils, various silane compounds, metal soaps, higher alcohols, polymerizable monomers, polyolefins, unsaturated carboxylic acid modification Polyolefin or the like can be used.
In particular, various silane compounds, such as a silane coupling agent and silicone oil, which have a high effect of suppressing the aggregation of talc and improving the dispersion in the composition, are preferable.

The above-mentioned (A) polypropylene resin and (B) talc are based on 40 to 99 parts by weight of (A),
(B) 1 to 60 parts by weight are blended. More preferably,
(A) 70 to 95 parts by weight, (B) 5 to 30 parts by weight. If the amount of talc is too small, the flexural modulus and heat resistance of the polypropylene resin cannot be improved, and if it is too large, the impact resistance decreases.

The crystal nucleating agent (C) used in the present invention is preferably a phosphoric acid type crystal nucleating agent, a sorbitol type crystal nucleating agent, a p- (t-butyl) benzoic acid aluminum salt crystal nucleating agent and a β crystal crystal. It is a compound selected from the group consisting of nucleating agents. Examples of the phosphoric acid type crystal nucleating agent include bis (4-
t-Butylphenyl) phosphoric acid, bis (4-t-amylphenyl) phosphoric acid, bis (4-t-octylphenyl) phosphoric acid, bis (2,4-dibutylphenyl) phosphoric acid, bis (2,4- Dioctylphenyl) phosphoric acid, bis (2-t-butyl-4-methylphenyl) phosphoric acid, bis (2-t-butyl-4-ethylphenyl) phosphoric acid, bis (2-t-butyl-4,6-) Dimethylphenyl) phosphoric acid, bis (2-cyclohexyl-4-methylphenyl) phosphoric acid, bis (2-α-methylcyclohexyl-4-methylphenyl) phosphoric acid, bis (4-phenylphenyl) phosphoric acid, bis (4 -Cumylphenyl) phosphoric acid, 2,2'-methylenebis (4,6-di-t-butylphenyl) phosphoric acid, 2,2'-methylenebis (4-methyl-6-t-butylphenyl) phosphoric acid,
2,2'-methylenebis (4-ethyl-6-t-butylphenyl)
Phosphoric acid, 2,2'-methylenebis (4,6-dimethylphenyl)
Phosphoric acid, 2,2'-methylenebis (4-methyl-6-α-methylcyclohexylphenyl) phosphoric acid, 2,2'-ethylidenebis (4,6-di-t-butylphenyl) phosphoric acid, 2,2 '-Ethylidenebis (4-sec-butyl-6-t-butylphenyl) phosphoric acid, 2,2'-thiobis (4-methyl-6-t-butylphenyl)
Phosphoric acid, 2,2'-thiobis (4-t-octylphenyl) phosphoric acid, 2,2'-bis (4-methyl-6-t-butylphenyl) phosphoric acid, 2,2'-bis (4, 6-di-t-butylphenyl) phosphoric acid,
And salts thereof such as sodium salt. These may be used alone or in combination of two or more. Among them, 2,2'-methylenebis (4,6-di-t-
Sodium butylphenyl) phosphate is under the trademark ADEKA STAB NA-11, and sodium bis (4-t-butylphenyl) phosphate is under the trademark ADEKA STAB NA-10.
Both are commercially available from Asahi Denka Co., Ltd.

Examples of the sorbitol type crystal nucleating agent include dibenzylidene sorbitol, bis (p-methylbenzylidene) sorbitol, bis (p-ethylbenzylidene) sorbitol, bis (p-chlorobenzylidene) sorbitol and the like. Bis (p-methylbenzylidene) sorbitol is commercially available under the trademark Gelol MD from Shin Nippon Rika Co., Ltd., and bis (p-ethylbenzylidene) sorbitol is commercially available under the trademark NC-4 from Mitsui Toatsu Chemicals, Inc. There is.

The p- (t-butyl) benzoic acid aluminum salt crystal nucleating agent is commercially available as Shell crystal nucleating agent from Shell Chemical Co., Ltd.

Examples of the β-crystal nucleating agent include alkali metal or alkaline earth metal salts of carboxylic acids (eg sodium benzoate, potassium 1,2-hydroxystearate, magnesium succinate, magnesium phthalate, etc.), dibasic bases. Alternatively, di- or triesters of tribasic carboxylic acids, aromatic sulfonic acid compounds (for example, sodium benzenesulfonate), phthalocyanine compounds (for example, phthalocyanine blue), and pigments such as quinacridone can be used. Of these, quinacridone is preferable.

In the present invention, the above-mentioned crystal nucleating agents can be used alone or in combination of two or more kinds.

The crystal nucleating agent (C) is 0.001 parts by weight or more, preferably 0.005 parts by weight or more, more preferably 0.01 parts by weight or more, and 5 parts by weight per 100 parts by weight of the total of (A) and (B). The amount is not more than 3 parts by weight, preferably not more than 3 parts by weight, more preferably not more than 2 parts by weight. If the amount of the crystal nucleating agent is too small, the effect as the crystal nucleating agent is low, and if it is too large, the impact resistance of the resin is lowered.

In the method of the present invention, the above-mentioned (A) polypropylene resin and (C) crystal nucleating agent are previously melt-blended (melt-blending at the first stage), and (B) talc is added to the obtained melt-blended product. It is characterized in that it is added and melt blended again (second stage melt blending). This is the first-stage melt blending, in which at least a part of the component (A) and the component (C) are melt-blended, and the second stage comprises the component (B) or the rest of the component (A). Means melt blending.

The melt blending of the first stage (including the polypropylene resin and the crystal nucleating agent) and the melt blending of the second stage (including the melt blended product of the first stage and talc) can be carried out by a melt kneading method. It is possible to use a conventional melt-kneading device such as a single-screw kneader, a twin-screw kneader, or a Banbury mixer. The melt kneading in the first stage is preferably carried out at 120 to 300 ° C, more preferably
180 to 250 ° C. The melt kneading in the second stage is 120
~ 300 ℃ is preferable, more preferably 180 ~ 25
0 ° C. After the first stage melt blending, the melt blend can be pelletized and the pellets and talc melt blended again, or the first melt blending can be followed by continuous talc blending (eg, side feed). In-line blending). It is also possible to melt-blend the components (A) and (C), add a melt-blended product containing the components (A) and (B) to the mixture, and further melt-blend.

In the method of the present invention, various conventional additives such as heat stabilizers, antioxidants and antistatic agents can be added alone or in combination. Additive is the first
It may be carried out in either the stage or the second stage melt blending, but is preferably carried out in the first stage melt blending. Further, after the addition in the first stage, the heat stabilizer, the antioxidant and the like may be added again in order to suppress the deterioration of the resin also in the second stage.

Further, ethylene-propylene rubber (EP
R), styrene-ethylene-butadiene rubber (SEB
It is also possible to add rubbers such as S). The rubbers may be added in either the first stage or the second stage melt blending, but are preferably added in the second stage melt blending.

[0040]

When a talc and a crystal nucleating agent are added to a polypropylene resin to produce a resin composition, conventionally, all the components have been melt-blended together. However,
If the crystal nucleating agent is melt-blended with the polypropylene resin in advance, even if talc is added later, the adsorption of the crystal nucleating agent to talc is suppressed, so that the function of the added crystal nucleating agent is fully exerted. It has been found in the present invention that it is possible to effectively improve the elastic modulus and heat resistance of the composition. Further, in the present invention, by using the highly stereoregular polypropylene resin, a resin composition having particularly excellent flexural modulus and heat resistance can be obtained.

[0041]

The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto.

In the examples and comparative examples, the heat of fusion (ΔHm) by differential scanning calorimetry (DSC) was measured using DSC220C manufactured by Seiko Denshi Kogyo Co., Ltd. as follows. Sample preparation From a 0.5 mm thick sheet pressed at 210 ° C for 1 minute,
10 mg was punched out and enclosed in an aluminum pan. Measurement conditions After holding at 230 ° C for 5 minutes, the temperature was lowered to 50 ° C at 10 ° C / minute, held at 50 ° C for 5 minutes, and then raised to 230 ° C at 10 ° C / minute. The peak of 85 ° C to 175 ° C at the time of this temperature rise was taken as the melting peak, and the corresponding heat quantity (cal) was divided by the sample quantity (g) to calculate the heat of fusion (ΔHm).

The flexural modulus is ASTM D790.
Izod impact strength is measured according to ASTM D25
6, the notched Izod impact strength was measured at 23 ° C., and the heat distortion temperature was measured according to ASTM D648.

Example 1 (1) Preparation of highly stereoregular homopolypropylene Preparation of component (a) In a 1 liter reaction vessel equipped with a reflux condenser, under a nitrogen gas atmosphere, chip-shaped metallic magnesium (purity: 99.5% ) was prepared. ,
8.3 g of an average particle diameter of 1.6 mm and 250 ml of n-hexane were added, the mixture was stirred at 68 ° C. for 1 hour, metallic magnesium was taken out, and dried under reduced pressure at 65 ° C. to obtain pre-activated metallic magnesium.

Next, 140 ml of n-butyl ether and n-butyl ether solution (1.75 mol / liter) of n-butyl magnesium chloride were added to 0.5 g of this metallic magnesium.
The suspension added with ml was kept at 55 ° C., and a solution in which 38.5 ml of n-butyl chloride was dissolved in 50 ml of n-butyl ether was added dropwise over 50 minutes. After the reaction was carried out at 70 ° C for 4 hours under stirring, the reaction solution was kept at 25 ° C.

Then, HC (OC
It was added dropwise ₂ H _{5) 3 55.7ml} over one hour. After the completion of the dropping, the reaction was carried out at 60 ° C for 15 minutes, the reaction product solid was washed 6 times with 300 ml of n-hexane each time and dried under reduced pressure at room temperature for 1 hour to obtain 31.6 g of magnesium-containing solid containing 19.0% magnesium and 28.9% chlorine. Was recovered.

In a 300 ml reaction vessel equipped with a reflux condenser, a stirrer and a dropping funnel, 6.3 g of a magnesium-containing solid and 50 ml of n-heptane were placed under a nitrogen gas atmosphere to prepare a suspension, which was stirred at room temperature. , 2,2,2-Trichloroethanol 20ml (0.02mmol) and n-heptane 11m
The mixed solution (1) was added dropwise from the dropping funnel over 30 minutes, and the mixture was further stirred at 80 ° C. for 1 hour. The solid obtained was filtered off, washed with 100 ml of n-hexane at room temperature four times, and further washed twice with 100 ml of toluene each time to obtain a solid component.

40 ml of toluene was added to the above solid component,
Further, titanium tetrachloride was added so that the volume ratio of titanium tetrachloride / toluene was 3/2, and the temperature was raised to 90 ° C. With stirring, a mixed solution of 2 ml of di-n-butyl phthalate and 5 ml of toluene was added dropwise over 5 minutes, and then the mixture was stirred at 120 ° C. for 2 hours.
The solid substance obtained was filtered off at 90 ° C, and 100 m of toluene each
Wash twice with 1 at 90 ° C. Further, titanium tetrachloride was newly added so that the volume ratio of titanium tetrachloride / toluene was 3/2, and the mixture was stirred at 120 ° C for 2 hours, and 100 ml of n
-Washing with hexane seven times gave 5.5 g of component (a). In a 500 ml reactor equipped with a prepolymerization stirrer, under a nitrogen gas atmosphere, 3.5 g of the component (a) obtained above and n-heptane were added.
300 ml was added and cooled to 5 ° C. with stirring. Next, a solution of triethylaluminum (hereinafter abbreviated as TEAL) in n-heptane (2.0 mol / liter) and 2,
The concentration of TEAL and 2,3,4-trimethyl-3-azacyclopentyltrimethoxysilane in the reaction system of 3,4-trimethyl-3-azacyclopentyltrimethoxysilane becomes 100 mmol / liter and 10 mmol / liter, respectively. So added and stirred for 5 minutes. Then
After depressurizing the system, propylene gas was continuously supplied,
Propylene was polymerized for 2.2 hours. After completion of the polymerization, propylene in the gas phase was purged with nitrogen gas, and the solid phase portion was washed with 100 ml of n-hexane three times at room temperature. Further, the solid phase portion was dried under reduced pressure at room temperature for 1 hour to prepare a catalyst component. As a result of measuring the amount of magnesium contained in the catalyst component, the amount of preliminary polymerization was 3.1 g per 1 g of the component (a). In a 5 liter stainless steel autoclave equipped with the main polymerization stirrer, 6 ml of TEAL n-heptane solution (0.1 mol / liter) and di (1-methylbutyl) were added under a nitrogen gas atmosphere.
6 ml of an n-heptane solution of dimethoxysilane (0.01 mol / liter) was mixed, and the mixture which had been kept for 5 minutes was added. Then, 0.1 liters of hydrogen gas as a molecular weight regulator and 3 liters of liquid propylene were injected under pressure, and the reaction system was cooled to 70%.
The temperature was raised to ° C. After charging 64.7 mg of the catalyst component obtained above to the reaction system, propylene was polymerized for 1 hour. After the polymerization was completed, unreacted propylene was purged to obtain 487.6 g of white polypropylene powder. The amount of polypropylene produced (CE) per 1 g of the component (a) was 30.9 kg.

The melt flow rate (MFR) of this homopolypropylene was 0.35 g / 10 minutes (24.50 +1.58).
3 (log MFR) = 23.78), heat of fusion (ΔHm) is 24.63
It was cal / g. The flexural modulus is 18,100 kgf / c.
The m ² and heat distortion temperature were 117 ° C. (2) Production of resin composition The highly stereoregular homopolypropylene (referred to as PP-1) produced in the above (1) and a phosphate-based crystal nucleating agent ADEKA STAB NA-11 (produced by Asahi Denka Co., Ltd., crystals (Referred to as nucleating agent 1) at a ratio shown in Table 1 and then a twin-screw kneader (TEX30 type, manufactured by Japan Steel Works, Ltd., φ30 m)
m, L / D = 42), kneading temperature 200 ° C, rotation speed 300
It was melt-kneaded under the conditions of rpm and pelletized. In addition to this, Talc (LMS100 manufactured by Fuji Talc Industry Co., Ltd.)
(No surface treatment) was added at a ratio shown in Table 1, blended again, and then melt-kneaded under the same conditions using the above-mentioned biaxial kneader to pelletize. Test pieces for measuring physical properties were injection-molded from the pellets, and the physical properties were measured using the test pieces. The results are shown in Table 1.

Example 2 (1) Preparation of highly stereoregular homopolypropylene Preparation of component (a) In the same manner as in Example 1, the component (a) was prepared. Prepolymerization In the prepolymerization in (1) of Example 1, bis (oxacyclopent-3-yl) dimethoxysilane was used in place of 2,3,4-trimethyl-3-azacyclopentyltrimethoxysilane. And instead of TEAL 100 mmol / l, triisobutylaluminum (hereinafter TIBA
Abbreviated as L) 80 mmol / liter, a temperature of 5 ° C. to 0 ° C., a polymerization time of 2.2 hours to 3.0 hours, and a polymerization amount of 3.1 g / g component (a) to 3.0 g / g component (a). Preliminary polymerization was carried out in the same manner except that the above was changed to. Main Polymerization In the main polymerization in Example 1 (1), neopentyltriethoxysilane was used in place of di (1-methylbutyl) dimethoxysilane, TIBAL was used in place of TEAL, and a hydrogen gas amount of 0.1 liter was used. The main polymerization was carried out in the same manner except that the amount was changed to 6.8 liters.

The melt flow rate of this homopolypropylene was 39.8 g / 10 minutes (24.50 +1.583 (log MF
R) = 27.03) and the heat of fusion (ΔHm) was 27.44 cal / g. (2) Production of resin composition Two-step melt-kneading was performed in the same manner as in (2) of Example 1 except that the highly stereoregular homopolypropylene (referred to as PP-2) produced in (1) above was used. Then, the test piece was prepared by pelletizing the test piece, and the test piece was subjected to the same physical property test as in Example 1. The results are shown in Table 1.

Example 3 (1) Preparation of highly stereoregular propylene-ethylene block copolymer (referred to as ICP ) Preparation of component (a) Component (a) was prepared in the same manner as in Example 1. Prepolymerization In the same manner as in Example 1, a catalyst component was prepared. In a 5 liter stainless steel autoclave equipped with the main polymerization stirrer, under nitrogen gas atmosphere, 4 ml of TEAL n-heptane solution (0.3 mol / liter) and n-heptane solution of diisopropoxydimethoxysilane (0.08 mol / liter) were added.
It was mixed with 3 ml and kept for 5 minutes.

Then, as a molecular weight regulator, hydrogen gas 8.
After press-fitting 8 liters and 3.0 liters of liquid propylene, the reaction system was heated to 70 ° C. After charging 120 mg of the prepolymerization catalyst component obtained above to the reaction system, propylene was polymerized for 1 hour (step a). After the polymerization was completed, unreacted propylene and hydrogen gas were purged until the pressure inside the container reached 0.2 kg / cm ² · G.

After collecting a small amount of the polymer obtained in step a, hydrogen gas was introduced into the container. Then, a mixed gas having a molar ratio of propylene and ethylene of 1.59 was supplied to maintain the internal pressure of the container at 6.05 kg / cm ² · G and perform propylene-ethylene copolymerization at 75 ° C for 1.2 hours (step b). . After the completion of the polymerization, the unreacted gas was purged to obtain 462 g of a powdery white propylene-ethylene block copolymer.

The melt flow rate (MFR _H ) of the homopolypropylene portion in this propylene-ethylene block copolymer (ICP) was 90 g / 10 minutes (24.5
0 +1.583 (log MFR) = 27.59), heat of fusion (ΔHm)
Was 28.03 cal / g. Further, melt flow rate (MFR) of ICP = 30 g / 10 min, ratio of ethylene-propylene copolymer portion in ICP (C _v ) = 18% by weight, ethylene content in ethylene-propylene copolymer portion (G _v ) = 35% by weight, ethylene in ICP-
The intrinsic viscosity [η] _CXS = 3 of the propylene copolymer part (cold xylene solubles) was 3. (2) Production of resin composition of Example 1 except that the highly stereoregular propylene-ethylene block copolymer (ICP) produced in (1) above was used.
In the same manner as in (2), two-step melt-kneading was performed and pelletized, and then a test piece was prepared and subjected to the same physical property test as in Example 1. The results are shown in Table 1.

Example 4 In (2) of Example 2, surface-treated talc (prepared by treating 1 part by weight of silazane-modified polysiloxane with respect to 100 parts by weight of talc used in Example 1) was used. Otherwise in the same manner as in Example 2, melt kneading was performed in two steps, pelletized, and a test piece was prepared from the pellet, and the same physical property test as in Example 1 was performed. The results are shown in Table 1.

Example 5 In the production of a resin composition, a crystal nucleating agent 2 (p- (t-butyl) benzoic acid aluminum salt, manufactured by Shell Chemical Co., Ltd.) was used in place of the crystal nucleating agent 1, and PP- Example 2 Except that 20 parts by weight of talc (no surface treatment) was used for 80 parts by weight, two-step melt-kneading was carried out in the same manner as in Example 1, pelletization was carried out, and a test piece was prepared from this. The same physical property test was performed. The results are shown in Table 1.

Example 6 In (2) of Example 2, the amount of PP-2 was changed to 80 parts by weight, and during the second stage of melt kneading, ethylene-propylene rubber (EPR) (Japan Synthetic Rubber EP961S manufactured by Co., Ltd.
A resin composition was prepared and pelletized in the same manner as in Example 2 except that 10 parts by weight of P) was further added. Then, a test piece was prepared from this pellet and subjected to the same physical property test as in Example 1. The results are shown in Table 1.

Example 7 Except that the ethylene-propylene rubber (EPR) of Example 6 was changed to styrene-ethylene-butadiene rubber (SEBS) (G1652 manufactured by Shell Chemical Co., PS content = 29% by weight). In the same manner as in Example 6, a resin composition was produced by two-step melt kneading and pelletized. Then, a test piece was prepared from this pellet and subjected to the same physical property test as in Example 1. The results are shown in Table 1.

[0060]

[Table 1] Comparative Example 1 When a resin composition was produced, melt kneading was not performed in two steps,
Pellets were prepared in the same manner as in Example 1 except that all the components were melt-kneaded together, and test pieces were prepared therefrom, and subjected to the same physical property tests as in Example 1. Table 2 shows the results.

Comparative Example 2 Melt kneading and pelletizing were carried out in the same manner as in Comparative Example 1 except that the amount of the crystal nucleating agent was changed to the ratio shown in Table 2 during the production of the resin composition. Pieces were prepared and subjected to the same physical property tests as in Example 1. Table 2 shows the results.

Comparative Example 3 When a resin composition was produced, melt kneading was not carried out in two steps,
Pellets were prepared in the same manner as in Example 2 except that all the components were melt-kneaded together, and test pieces were prepared therefrom, and subjected to the same physical property tests as in Example 1. Table 2 shows the results.

Comparative Example 4 Melt kneading and pelletizing were carried out in the same manner as in Comparative Example 3 except that the amount of the crystal nucleating agent was changed to the ratio shown in Table 2 during the production of the resin composition. Pieces were prepared and subjected to the same physical property tests as in Example 1. Table 2 shows the results.

Comparative Example 5 In the production of the resin composition, melt kneading and pelletization were carried out in the same manner as in Comparative Example 3 except that the amount of the crystal nucleating agent was further increased as shown in Table 2. Test pieces were prepared and subjected to the same physical property tests as in Example 1. Table 2 shows the results
Shown in

Comparative Example 6 When a resin composition was produced, melt kneading was not carried out in two steps,
Pellets were prepared in the same manner as in Example 3 except that all the components were melt-kneaded together, and test pieces were prepared therefrom, and subjected to the same physical property tests as in Example 1. Table 2 shows the results.

[0066]

[Table 2] Comparative Example 7 In the production of the resin composition, melt kneading was not performed in two steps,
Pellets were prepared in the same manner as in Example 4 except that all the components were melt-kneaded together, and test pieces were prepared therefrom, and subjected to the same physical property tests as in Example 1. The results are shown in Table 3.

Comparative Example 8 In the production of a resin composition, as a polypropylene resin,
Instead of PP-1, commercially available homopolypropylene (PP
-3) (manufactured by Tonen Chemical Co., Ltd., J209, MFR
= 9 g / 10 min, ΔHm = 25.4 cal / g, 24.50 −1.583
(log MFR) = 26.04) was used, and two-step melt-kneading was performed in the same manner as in Example 1 to form pellets, from which test pieces were prepared and subjected to the same physical property tests as in Example 1. The results are shown in Table 3.

Comparative Example 9 When a resin composition was produced, melt kneading was not performed in two steps,
Pellets were prepared in the same manner as in Example 5 except that all the components were melt-kneaded together, and test pieces were prepared therefrom, and subjected to the same physical property tests as in Example 1. The results are shown in Table 3.

Comparative Example 10 When a resin composition was produced, melt kneading was not performed in two steps,
Pellets were prepared in the same manner as in Example 6 except that all the components were melt-kneaded together, and test pieces were prepared therefrom, and subjected to the same physical property tests as in Example 1. The results are shown in Table 3.

Comparative Example 11 When a resin composition was produced, melt kneading was not performed in two steps,
Pellets were prepared in the same manner as in Example 7 except that all the components were melt-kneaded together, and test pieces were prepared therefrom, and subjected to the same physical property tests as in Example 1. The results are shown in Table 3.

[0071]

[Table 3] From Tables 1 to 3, the method of the present invention (two-stage melt blending)
Comparing the resin composition produced by the method with the resin composition produced by the conventional method (collective melt blending), the Izod impact strength is about the same, but the resin composition produced by the method of the present invention is more flexible. It can be seen that the elastic modulus and heat resistance are high (Example 1 and Comparative Example 1, Example 2 and Comparative Example 3, Example 3 and Comparative Example 6, Example 4 and Comparative Example 7, and Example 5 and Comparative Example 9). ).

Further, it is found that the amount of the crystal nucleating agent is tripled in order to obtain the flexural modulus comparable to that of Example 1 by the method of collective melt-kneading (Comparative Example 2). The same can be said for Example 2 and Comparative Example 5, but in this case, a quadruple amount of the crystal nucleating agent is required.

It can be seen that a resin composition having high flexural modulus and heat resistance can be obtained by using a polypropylene resin having a relationship between ΔHm and MFR satisfying the formula (I) (compared with Examples 1 and 2). Example 8).

[0074]

INDUSTRIAL APPLICABILITY According to the present invention, in a polypropylene resin composition containing talc and a crystal nucleating agent, the amount of the crystal nucleating agent adsorbed on talc can be reduced, and therefore a small amount of the crystal nucleating agent can be added. The effect of improving the flexural modulus and heat resistance of the composition can be achieved. Furthermore, since a highly stereoregular polypropylene resin whose relationship between ΔHm and MFR satisfies the formula (I) is used, a polypropylene resin composition having extremely excellent flexural modulus and heat resistance can be obtained.

Claims (1)

[Claims] 1. A crystalline nucleating agent (C) of 0.001 to 40 parts by weight of (A) polypropylene resin, 1 to 60 parts by weight of (B) talc, and 100 parts by weight of (A) and (B) in total.
A method for producing a resin composition containing 5 to 5 parts by weight,
(A) As polypropylene resin, ASTM D12
Melt flow rate (MFR) measured according to No. 38,
In differential scanning calorimetry, after heating to 230 ℃, 50 ℃
The heat of fusion (ΔH) was calculated as the peak when the temperature was lowered to 230 ° C at a rate of 10 ° C / min.
Hm) (unit cal / g) is a high stereoregular polypropylene resin that satisfies the following formula (I): [Formula 1] ΔHm ≧ 24.50 +1.583 (log MFR) (I), and (A) A polypropylene resin and (C) a crystal nucleating agent are melt-blended, and then the melt-blended product and (B) talc are melt-blended.