JP2000281847A - Master batch composition for modifying polypropylene resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a master batch composition for modifying a polypropylene resin, capable of improving rigidity and heat resistance of a polypropylene-based resin by addition of a small amount and greatly bettering the moldability and processability of the polypropylene-based resin. SOLUTION: This master batch composition for modifying a propylene resin comprises (a) 10-70 wt.% of a laminar silicate, (b) 1-45 wt.% of an organic cation, (c) 10-89 wt.% of an unsaturated monomer-modified polypropylene and (d) 0-79 wt.% of a polypropylene resin and >=0.01 wt.% based on the composition of a unit derived from an unsaturated monomer in (c) the unsaturated monomer- modified polypropylene.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a masterbatch composition for modifying a polypropylene resin for improving rigidity and moldability of a polypropylene resin.

[0002]

2. Description of the Related Art Conventionally, in order to improve various properties, particularly rigidity, of a crystalline thermoplastic resin, it has been practiced to mix an inorganic filler such as talc and improve various properties by its reinforcing effect. . For example, talc is known to improve the rigidity of crystalline thermoplastic resins. However, in order to obtain sufficient rigidity, a large amount of talc must be added, and it has not been possible to sufficiently meet the demand for reducing the weight of a molded article. Therefore, there has been a demand for an inorganic filler exhibiting a great effect even when added in a small amount.

In recent years, attempts have been made to use a clay mineral (layered silicate), which is a kind of inorganic layered compound, as an inorganic filler and to disperse it in a thermoplastic resin at a molecular level. It is known that a so-called intercalation compound in which an organic cation such as alkylammonium is inserted between the layers of the clay mineral swells infinitely in the organic solvent, and the layered clay mineral is dispersed almost every layer in the organic solvent. . Similar to dispersing an interlayer compound in an organic solvent at the molecular level, dispersing the interlayer compound in a thermoplastic resin can be achieved by melting and kneading the thermoplastic resin and the interlayer compound, or by heating the interlayer compound swollen with an organic solvent. Attempts have been made by adding it to plastic resins.

[0004] In the case of nylon or polycarbonate systems, it has been reported that the intercalation compound is dispersed at the molecular level by kneading the intercalation compound and the resin, and the physical properties such as rigidity are improved with a small addition (Japanese Unexamined Patent Publication No. Hei 7-1995). 207134). Further, in order to disperse the interlayer compound in the thermoplastic resin, it is reported that the larger the polarity of the resin per unit volume, the more the interlayer compound is dispersed at the molecular level (International Publication WO 97/11998). .

[0005]

However, when the non-polar polypropylene resin and the intercalation compound are mixed and kneaded, the secondary coagulation of the intercalation compound is caused even if the intercalation compound swollen with an organic solvent is used. And uniform dispersion in the polypropylene resin was difficult. Therefore, the effect of improving the physical properties such as rigidity by the clay mineral was not so large. Therefore, JP
Japanese Patent Application Laid-Open No. 3-215775 discloses that polymer is polymerized between layers of clay mineral.
No. 3 and JP-A-6-41346 disclose dispersing a clay mineral in a solvent, dissolving a thermoplastic resin in a solvent, and mixing the two in a solution.

However, even with these methods,
It is difficult to disperse clay minerals evenly in polypropylene resin, and even if possible to some extent, the process for obtaining composite materials is complicated and economical, and firefighting by using organic solvents There was a problem of regulation by laws and deterioration of working environment. JP-A-9-217012
In some cases, such as the method disclosed in Japanese Patent Application Laid-Open Publication No. H10-175, the kneading conditions are specified, the effect of improving physical properties such as rigidity is not satisfactory. Further, Japanese Patent Application Laid-Open No. 10-30
No. 039 and JP-A-10-182892,
It is disclosed that a layered silicate and a polypropylene or propylene oligomer grafted with a functional group are simultaneously added to the polypropylene to disperse the layered silicate in the polypropylene, but the effect of improving the physical properties is not remarkable. This is considered to be because the effect was reduced because the layered silicate and the grafted polypropylene were diffused into the polypropylene before they sufficiently reacted.

[0007] On the other hand, polypropylene-based resin is lightweight and excellent in economical efficiency. Therefore, it is easily molded by melt molding such as extrusion molding, blow molding and injection molding, and is widely used. However, in extrusion molding, blow molding and the like, the melt tension and melt elasticity of the polypropylene resin are insufficient, and a draw-down phenomenon and a neck-in phenomenon of a film or a sheet are often observed. For this reason, attempts have been made to improve the melting properties of polypropylene resins.

For example, a method for achieving the object by improving the catalyst and polymerization prescription at the time of the production of the polypropylene resin to broaden the molecular weight distribution, or the same object by partially cross-linking the polypropylene resin. Attempts have been made to achieve this. However, by expanding the molecular weight distribution of the polypropylene resin, the low-melting point component increases, causing stickiness of the film, and there is almost no effect with a general crosslinking agent such as a peroxide. Had difficulties in designing.

Accordingly, an object of the present invention is to improve the rigidity and heat resistance of a polypropylene resin by adding a small amount thereof.
Another object of the present invention is to provide a polypropylene resin-modifying masterbatch composition that can significantly improve the molding processability of a polypropylene resin.

[0010]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, a modified polypropylene in which a functional group has been introduced into polypropylene to increase the polarity per unit volume has been obtained. It has been found that by laminating and kneading an interlayer compound composed of a silicate and an organic cation, a layered silicate is dispersed in a modified polypropylene at a molecular level. Furthermore, it has been found that the rigidity of the polypropylene resin is greatly improved by adding the resin composition to the polypropylene resin, and the present invention has been achieved.
In addition, it was also found that the polypropylene resin to which the resin composition was added exhibited excellent melting properties, and was able to significantly improve molding processability, such as being able to suppress neck-in during extrusion molding.

That is, the masterbatch composition for modifying a polypropylene resin of the present invention comprises:
70% by weight, (b) 1 to 45% by weight of organic cation,
(C) contains 10 to 89% by weight of an unsaturated monomer-modified polypropylene, and (d) contains 0 to 79% by weight of a polypropylene resin, and is derived from the unsaturated monomer in the (c) unsaturated monomer-modified polypropylene. Unit is 0.01 to the composition.
% By weight or more. Also,
(C) The unsaturated monomer-modified polypropylene preferably has a weight average molecular weight of 80,000 or more.

Further, the bending elastic modulus S (kgf / cm) of the composite material obtained by adding the polypropylene resin-modifying masterbatch composition of the present invention to (e) a polypropylene resin is added.
² ), (e) Flexural modulus S ₀ of polypropylene resin
(Kgf / cm ² ) and the ash content m (% by weight) of the composite material, the increase rate T of the flexural modulus per 1% by weight of the ash content determined by the following (Equation 1) is desirably 16 or more. (Equation 1) T = (S−S ₀ ) / S ₀ × 100 / m

The ash content m (% by weight) of a composite material obtained by adding the masterbatch composition for modifying polypropylene resin of the present invention to (e) a polypropylene-based resin is calculated by the least square method from the following (Equation 2). The calculated yield parameter k ₀
Preferably satisfies the relationship of the following (Equation 3). (Equation 2) G ^1/2 = k ₀ + k ₁ (ω · η ₀ ^* (ω) / η ₀ ^* (0.01)) ^1/2 (Equation 3) When m ≧ 1, k ₀ ≧ 1. 75 × m−1.65 m <1 k ₀ ≧ 0.1 (In the above (Equation 2), G is the angular frequency ω (radian / second) in the dynamic viscoelasticity measurement at 180 ° C. of the composite material. Is the absolute value (Pa) of the complex elastic modulus at the time of η ₀ ^* (0.
01) and η ₀ ^* (ω) are the angular frequency 0.01 radian / sec and the angular frequency ω in the dynamic viscoelasticity measurement at 180 ° C. of the (e) polypropylene-based resin, respectively.
(Radian / second), the absolute value of the complex viscosity (Pa ·
s). )

A diffraction peak of a (040) crystal plane of a polypropylene crystal, measured by an X-ray diffraction method, of a composite material molded article obtained by adding the masterbatch composition for modifying a polypropylene resin of the present invention to (e) a polypropylene resin. And the orientation parameter I (040) / I (110), which is the ratio of the integral intensity I (040) of the above and the integral intensity I (110) of the diffraction peak of the polypropylene crystal (110) plane, is desirably 4 or more.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. <(A) Layered silicate> The (a) layered silicate in the present invention has, for example, a charge density of 40 to 150Å ² / charg.
e, swellable clay compounds having a bottom-to-bottom distance d (001) of 7 to 15 ° and a cation exchange capacity (CEC) of 25 to 200 meq / 100 g. Such swellable clay compounds include layered phyllosilicate minerals composed of magnesium silicate or aluminum silicate. Specific examples thereof include smectite-based clay minerals such as montmorillonite, saponite, beidellite, hectorite, nontronite, and stevensite; vermiculites such as trioctahedral vermiculite and dioctahedral vermiculite; Examples include mica such as biotite, lepidrite, baragonite, teniolite, and tetrasilicic mica. Further, a compound synthesized into swellable mica by subjecting talc to a fluorine treatment, or a compound obtained by hydrothermal synthesis to obtain the above structure is exemplified. further,
Various compounds in which the cation carried between the layers is replaced with ions such as sodium, potassium, and lithium can be used.

(A) The charge density of the layered silicate is 40 to 15
Preferably 0Å a ² / charge, 40-100
More preferably, it is ² / charge. Charge density 40Å
^If it is less than ² / charge, the above silicate compound does not exist. On the other hand, if it exceeds 150 ² / charge, the dispersibility in the polypropylene-based resin may decrease, which is not preferable. In other words, the charge density is converted into the cation exchange capacity of the layered silicate. (A) The cation exchange capacity (CEC) of the layered silicate is 25 to 200 meq / 100.
g is preferable, and 50 to 150 meq / 100 g
Is more preferable. When the cation exchange capacity is less than 25 meq / 100 g, the content of the organic cation (b) in the lipophilic intercalation compound is reduced, so that when the cation exchange capacity is dispersed in a polypropylene resin, good dispersibility is not exhibited. Insufficient improvement in material stiffness. If the cation exchange capacity exceeds 200 meq / 100 g, the content of the organic cation (b), which is a low-melting organic substance, increases, so that heat resistance is undesirably reduced.

<(B) Organic Cation> The (b) organic cation used in the present invention is a positively charged organic compound having a structure represented by the following chemical formula.

Embedded image In the formula, R ¹ , R ² , R ³ and R ⁴ are an alkyl group having 1 or more carbon atoms or a hydrogen atom, at least one of which is an alkyl group having a main chain length of 4 or more carbon atoms. Is preferred. More preferably, the alkyl group having 4 or more carbon atoms is 2 or more per molecule. When the longest carbon number of these alkyl groups is less than 4, the interlayer cannot be sufficiently widened until the bonding force between the layers of the layered silicate (a) is weakened. In addition, since the lipophilicity of the (a) layered silicate cannot be improved, the (a) layered silicate is not uniformly dispersed in the polypropylene resin, and the effects of the present invention cannot be achieved.

(B) Specific examples of the organic cation include tetrabutylammonium ion, tetrahexylammonium ion, dihexyldimethylammonium ion, dioctyldimethylammonium ion, hexatrimethylammonium ion, octatrimethylammonium ion, dodecyltrimethylammonium ion, Decyl trimethyl ammonium ion, octadecyl trimethyl ammonium ion, dioctadecyl dimethyl ammonium ion, docosenyl trimethyl ammonium ion, hexadecyl ammonium ion, tetradecyl dimethyl benzyl ammonium ion, octadecyl dimethyl benzyl ammonium ion, dioleyl dimethyl ammonium ion, polyoxyethylene Dodecyl monomethi And an ammonium ion.

Further, (b) organic cations are represented by R ¹ , R
^It may have a functional group at the terminal of ² , R ³ and R ⁴ . Examples of the functional group include a carboxylic acid, a hydroxyl group, and an amino group. As tetraalkylammonium compounds having these functional groups at the terminals,
N-alkylaminocarboxylic acids, N-alkylaminoalcohols, N-alkylamines and the like can be mentioned. Counter anion X ^- is but may organic cation salt anything as long as it helps the ionized when dissolved in water, chloride ions are preferred.

As a mode of action of (a) the layered silicate and (b) the organic cation, a wet method is generally used.
After (a) the layered silicate is sufficiently solvated with water, alcohol, or the like, (b) an organic cation is added and stirred, and (a) the metal ion between the layers of the layered silicate is replaced with the organic cation. Thereafter, the unsubstituted (b) organic cation is sufficiently washed, filtered and dried. In addition, (a) layered silicate and (b) organic cation are directly reacted in an organic solvent, or (a) layered silicate and (b) organic cation are heated and kneaded in an extruder in the presence of a resin or the like. It is also possible to react.

<(C) Unsaturated Monomer-Modified Polypropylene> The (c) unsaturated monomer-modified polypropylene (hereinafter referred to as (c) modified polypropylene) in the present invention is obtained by grafting an unsaturated monomer onto polypropylene. Modified polypropylene copolymerized or block copolymerized. Examples of the unsaturated monomer include mono- or dicarboxylic acids such as acrylic acid, methacrylic acid, maleic acid, and itaconic acid, and unsaturated carboxylic acid derivatives which are anhydrides thereof; (meth)
(Meth) acrylates such as hydroxyethyl acrylate, glycidyl (meth) acrylate, aminoethyl (meth) acrylate; alkoxy having a vinyl group such as vinyltrimethoxysilane and γ-propyltrimethoxysilane And silane. Among these, maleic anhydride and glycidyl methacrylate are particularly preferred because of excellent dispersibility of the layered silicate.

The weight average molecular weight of the modified polypropylene (c) is not particularly limited, but may be 80,000.
Or more, more preferably 100,0
00 or more. It is considered that the modified polypropylene (c) exists at the interface between the layered silicate and the polypropylene resin as the matrix resin, and enhances their adhesiveness. When the weight average molecular weight is 80,000 or more, the adhesiveness is further improved, rigidity and rheological properties are sufficiently improved, and heat resistance is also improved by increasing the molecular weight. Generally, the weight average molecular weight can be determined by gel permeation chromatography (GPC).

Examples of the polypropylene used for the modified polypropylene (c) include, for example, homopolypropylene, propylene / ethylene block copolymer, propylene / ethylene random copolymer, propylene / α-olefin block copolymer, and propylene / propylene copolymer. α-olefin random copolymer and the like. These may be used alone or in combination of two or more.

Examples of a method for modifying polypropylene include a method in which a mixture of polypropylene and an unsaturated monomer is heated and kneaded in an extruder in the presence of an organic peroxide or the like. It is also possible to obtain a mixture of polypropylene and an unsaturated monomer by heating and dissolving the mixture in an organic solvent such as xylene, adding an organic peroxide and reacting the mixture, and adding a poor solvent such as acetone to crystallize the mixture. is there. Also, a method of irradiating the polypropylene with ultraviolet light or radiation in the presence of an unsaturated monomer, a method of contact-mixing the unsaturated monomer after irradiating the polypropylene with ionizing radiation, Examples of the method include bringing the mixture into contact with oxygen or ozone.

<(D) polypropylene resin and (e)
Polypropylene Resin> The (d) polypropylene resin and (e) polypropylene resin used in the present invention may be of different types or the same type, for example, homopolypropylene, propylene / ethylene block copolymer, propylene / ethylene random copolymer. Coalesce, propylene-α-olefin block copolymer, propylene
α-olefin random copolymer and the like. These may be used alone or in combination of two or more. The weight average molecular weights of the (d) polypropylene resin and the (e) polypropylene resin are not particularly limited and are selected according to the purpose of the molding material. However, from the viewpoint of heat resistance, rigidity and the like, 80,000. Or more, more preferably 100,000
It is desirable that this is the case. By adding the polypropylene resin (d) to the polypropylene resin-modifying masterbatch composition of the present invention, there are advantages such as easy kneading in an extruder and stabilization of strands.

(E) In order to improve the impact strength of the polypropylene resin, an elastomer component or the like is generally added. However, in the present invention, the elastomer component may be added as long as the effects of the present invention are not impaired. There is no problem adding it. In the present invention, such a polypropylene resin to which such an elastomer component is added is referred to as a polypropylene resin.

<Composition Ratio of Constituent Components> The amount of the layered silicate (a) in the masterbatch composition for modifying a polypropylene resin of the present invention is 10 to 70% by weight, preferably 20 to 50% by weight.
% By weight. (A) When the content of the layered silicate is less than 10% by weight, the amount of the inorganic substance is too low, so that it must be added in a large amount to the target polypropylene-based resin as a reforming master batch composition, which increases the cost of the composite material. . Also,
If it exceeds 70% by weight, the dispersion of the layered silicate (a) becomes poor, and it becomes difficult to knead the polypropylene resin-modified master batch composition.

The amount of the organic cation (b) in the masterbatch composition for modifying a polypropylene resin of the present invention is from 1 to 4
It is 5% by weight, preferably 5 to 25% by weight. If (b) the organic cation is less than 1% by weight, the dispersion of the (a) layered silicate becomes poor. If the content exceeds 45% by weight, rigidity and heat resistance decrease. Also, (b) the amount of the organic cation is
(A) More preferably, it is determined by measuring the cation exchange capacity (CEC) of the layered silicate. For example, a column permeation method (see “Clay Handbook”, pp. 576-577,
Nichido Publishing) and a method for measuring the amount of adsorbed methylene blue (Standard Test Method of Japan Bentonite Industry Association, JBAS-107-9)
It can be determined by a method such as 1). In other words, the amount of the (b) organic cation added to (a) the layered silicate is desirably in the range of 0.3 to 5 equivalents to the CEC. If it is less than 0.3 equivalent, the dispersion of the (a) layered silicate is reduced, and if it is more than 5 equivalents, the rigidity and heat resistance of the polypropylene-based composite material decrease.

The amount of the modified polypropylene (c) in the masterbatch composition for modifying a polypropylene resin of the present invention is as follows:
It is 10 to 89% by weight, preferably 35 to 85% by weight. (C) When the content of the modified polypropylene is less than 10% by weight,
(A) Dispersion of the layered silicate becomes poor and rigidity and heat resistance decrease. When the content exceeds 89% by weight, (a)
Since the amount of the layered silicate is reduced, it must be added to the target resin in a large amount as a reforming master batch composition, which increases the cost as a composite material. (C) The unit derived from the unsaturated monomer in the modified polypropylene is contained in an amount of 0.01% by weight or more, preferably 0.1% by weight or more, based on the masterbatch composition for modifying a polypropylene resin. is necessary. If the amount is less than this, the polarity per unit volume of the resin in the composition becomes small, and the dispersion of the interlayer compound may be poor.

Here, the unit derived from the unsaturated monomer in the composition is measured by a general method such as infrared spectroscopy and nuclear magnetic resonance. Infrared spectrophotometry is generally used because of its simplicity and high accuracy. Before measurement, unreacted unsaturated monomers contained in the modified polypropylene (c) in the composition must be removed. When the polypropylene is modified with an unsaturated monomer, unreacted unsaturated monomer often remains, and the unsaturated monomer remains (c).
When the modified polypropylene is directly used for the production of a masterbatch composition and the concentration of the unsaturated monomer in the masterbatch composition is measured, the modified polypropylene may be overestimated than the effective amount.

As a method for removing unreacted unsaturated monomers, the composition is heated and dissolved in an organic solvent capable of dissolving the (c) modified polypropylene such as toluene and xylene, cooled, and then cooled with the above organic solvent. It is effective to add a poor solvent such as acetone or alcohol in an amount larger than the amount to precipitate the composition, filter off, wash with the above poor solvent, and dry to re-precipitate. A pressed sheet having a thickness of about 0.1 mm was prepared from the treated sample, and the absorbance at an absorption peak specific to the unsaturated monomer used was measured by infrared spectrophotometry. Determine the amount of saturated monomer. As an absorption peak peculiar to the unsaturated monomer in the infrared spectrophotometry, as for an unsaturated acid anhydride such as maleic anhydride or a (meth) acrylic acid derivative such as glycidyl methacrylate, 1795-1.
Stretching vibration of carbonyl around 710 cm ^-1 (ν (C =
The peak resulting from O)) is employed.

The amount of the polypropylene (d) in the masterbatch composition for modifying a polypropylene resin of the present invention is at most 79% by weight, preferably at most 50% by weight.
When (d) the polypropylene exceeds 79% by weight, the amount of the (a) layered silicate is relatively reduced, and it must be added to the target resin in a large amount as a reforming master batch composition. Increase costs.

<Flexural Modulus S> The flexural modulus S (kg) of a composite material obtained by adding the polypropylene resin-modified masterbatch composition of the present invention to (e) a polypropylene resin is used.
f / cm ² ), (e) the flexural modulus S ₀ (kgf / cm ² ) of the polypropylene resin, and the ash m of the composite material
(Ash content 1) determined from the following (formula 1) from (weight%)
The increase rate T of the flexural modulus per weight% is desirably 16 or more. (Equation 1) T = (S−S ₀ ) / S ₀ × 100 / m

The relationship between the flexural modulus S and the ash content m represents the rate of improvement of the rigidity of the composite material obtained by adding the masterbatch composition to the polypropylene resin with respect to the amount of the inorganic filler added. The rigidity of the resin is improved. The elastic modulus S and the ash m are calculated by the above (Equation 1)
The polypropylene resin-modified masterbatch composition that does not satisfy the relationship of (1) cannot sufficiently improve rigidity when added to (e) a polypropylene resin. Here, the flexural modulus S was measured in accordance with ASTM D in a dry state at 23 ° C.
It is measured according to 790.

<Yield Parameter> The angular frequency ω in the dynamic viscoelasticity measurement at 180 ° C. of the composite material obtained by adding the polypropylene resin-modified masterbatch composition of the present invention to the polypropylene resin (e) was measured. (Radian / second)
The absolute value of the complex elastic modulus at the time of is defined as G (Pa), and the angular frequency 0.01 radian / sec and the angular frequency ω (radian / The absolute value of the complex viscosity at (sec) is η ₀ ^* (0.01) (Pa · s) and η, respectively.
₀ ^* (ω) (Pa · s), the square root G ^1/2 of the absolute value of the complex elastic modulus of the composite material is (ω · η ₀ ^* (ω) / η ₀ ^*
(0.01)) ^{1/2 is} proportional to the following (Equation 2). (Equation 2) G ^1/2 = k ₀ + k ₁ (ω · η ₀ ^* (ω) / η ₀ ^* (0.01)) ^1/2

The above (Equation 2) uses the modified Casson's equation (Shigeharu Onoki, “Rheology for Chemists”, p.206, Kagaku Doujin) to calculate the complex viscosity η instead of the shear viscosity.
The absolute value of ^* can be derived by using the angular velocity ω instead of the shear rate. Here, k ₀ is a yield parameter, and k ₁ is a constant corresponding to the square root of viscosity at a very high angular velocity (shear rate) ω.

The yield parameter k ₀ obtained by the least square method from the above (Equation 2) and the ash m of the composite material
(% By weight) desirably satisfies the relationship of the following (Equation 3). (Equation 3) When m ≧ 1, k ₀ ≧ 1.75 × m−1.65 When m <1, k ₀ ≧ 0.1 The larger this yield parameter k ₀ , the higher the melt viscosity at a low shear rate. It means high, and the moldability such as drawdown and neck-in during extrusion is improved.

<Orientation Parameter> The orientation parameter I (040), which is the X-ray crystal diffraction peak intensity ratio of the composite material molded article obtained by adding the polypropylene resin-modified masterbatch composition of the present invention to the polypropylene resin (e). ) / I
(110) is desirably 4 or more, preferably 6 or more. This peak intensity ratio indicates the degree of orientation of the lamella composed of polypropylene crystals, and the larger the numerical value, the higher the rigidity can be improved. When the orientation parameter I (040) / I (110) is less than 4, the crystal orientation is insufficient, and the effect of improving rigidity is not exhibited.

Here, the orientation parameter I (040) / I (110) of the molded article made of the composite material is determined by a test piece (JIS2) prepared from the composite material under a constant injection molding condition.
No. dumbbell test piece, thickness 2 mm), wide angle X-ray diffraction measurement was performed, and from the obtained X-ray profile, 2θ = 1
Integral value of intensity in the range of 2.5 ° to 15.0 ° (I (11
0)) and the integrated value (I (040)) of the intensity in the range of 2θ = 15.5 ° to 17.5 ° can be calculated using these values.

<Additional Components> Other additional components may be added to the polypropylene resin-modified masterbatch composition of the present invention as long as the effects of the present invention are not impaired. For example, well-known antioxidants, weather resistance improvers, other nucleating agents, flame retardants, impact resistance improvers, plasticizers, flow improvers,
(A) An organic filler other than the layered silicate, an inorganic filler such as talc, a reinforcing agent, and the like may be added. For practical use, well-known substances such as various colorants and their dispersants can be used.

<Production Method of Masterbatch Composition for Modifying Polypropylene Resin> In the present invention, a polypropylene resin containing (a) a layered silicate, (b) an organic cation, (c) a modified polypropylene and (d) a polypropylene resin In order to obtain a reforming master batch composition, a method of melt-kneading them, a method of mixing them in a solution, and the like can be used, but if similar performance is obtained,
Melt kneading using a kneader is preferred from the viewpoint of process and cost. As the melt kneader, a kneader generally used for thermoplastic resins can be used. For example, a single-screw or multi-screw kneading extruder, a roll, a Banbury mixer, or the like may be used.

[0042]

The present invention will be described below in detail with reference to examples. [I] Raw material [inorganic filler] (a-1): synthetic mica (ion exchange capacity: 107 me)
q / 100g, manufactured by Corp Chemical Co., Ltd., trade name: MAE,
Swelling agent treatment ((b) organic cation: use dioctadecyl dimethyl ammonium salt), inorganic content ((a) layered silicate) 62% by weight) (a-2): synthetic mica (ion exchange capacity: 107 me)
q / 100g, manufactured by Corp Chemical, trade name: ME10
0, no swelling agent treatment) (a-3): Talc (manufactured by Hayashi Chemicals, trade name: Micron White 5000SA)

[(C) Unsaturated monomer-modified polypropylene] (c-1): Maleic anhydride-modified polypropylene (manufactured by Nippon Polyolefin Co., Ltd., trade name: Adtex P9001M, maleic anhydride group: 2.1% by weight, (C-2): maleic anhydride-modified polypropylene (manufactured by Japan Polyolefin, trade name: Adtex P9000M, maleic anhydride group: 1.4% by weight, Mw = 70,000)
(C-3): Unmodified polypropylene wax (manufactured by Sanyo Chemical Industries, trade name: Viscol 330P, Mw = 30,00)
0)

(C-4): Maleic anhydride-modified polypropylene (manufactured by Nippon Polyolefin Co., Ltd., maleic anhydride group:
0.6% by weight, Mw = 130,000) (c-5): Maleic anhydride-modified polypropylene (manufactured by Nippon Polyolefin Co., Ltd., maleic anhydride group: 0.1% by weight, Mw = 200,000) (c-6) ): Maleic anhydride-modified polypropylene wax (manufactured by Sanyo Chemical Industries, trade name: Umex 1001, maleic anhydride group: 2.1% by weight, Mw = 30,000) (c-7): Unmodified polypropylene (Nippon Polyolefin Co., Ltd.) Mw = 130,000)

[(D) polypropylene resin and (e)
Polypropylene resin] (d-1) Homopolypropylene: MFR = 30 g / 10
min, manufactured by Nippon Polyolefin Co., Ltd. (d-2) Homopolypropylene: MFR = 60 g / 10
min, manufactured by Japan Polyolefin Co., Ltd. (e-1) Homopolypropylene: MFR = 30 g / 10
min, manufactured by Nippon Polyolefin Co., Ltd.

[II] Evaluation method For evaluation, each physical property value and various properties were measured by the following methods. [Flexural modulus] ASTM D790 (dry state, 23
° C). [Ash content] Take 3 to 5 g of a sample in a crucible and heat it at 600 ° C. for 3 hours in air using an electric furnace to burn and evaporate organic substances. Then, cool to room temperature in a desiccator and measure the remaining amount. did.

[Amount of unsaturated monomer in composition] Composition 3
g and 250 ml of xylene are placed in a separable flask having a volume of 500 ml, and stirred under a nitrogen atmosphere.
While maintaining the temperature at 0 ° C., the composition was dissolved and dispersed. Stop heating,
The mixture was allowed to cool to 60 ° C., 250 ml of acetone was added, and the mixture was allowed to stand at room temperature for 12 hours. The precipitate was separated by filtration, washed with acetone, and dried under vacuum at 80 ° C. for 2 hours. A 0.1 mm-thick press sheet was prepared from the obtained sample, and the amount of unsaturated monomer was determined by infrared spectrophotometry.

The infrared absorption spectrum was measured by JASCO Corporation.
The measurement was performed using a VALOR-III type infrared spectrophotometer manufactured by the company. From the infrared absorption spectrum of the sample, the absorbance of a peak at 1790 cm ^-1 due to carbonyl stretching vibration of maleic anhydride was determined. Maleic anhydride is partially hydrolyzed to maleic acid, which may appear as a separate peak near 1720 cm ^-1 . The absorbance was also added to the absorbance of the maleic anhydride peak. Similarly, a 0.1 mm-thick press sheet was prepared from maleic anhydride-modified polypropylene known to contain maleic anhydride at 0.2, 0.6 and 1.1% by weight, and the infrared absorption spectrum was measured. Then, a calibration curve was prepared by determining the absorbance of the carbonyl stretching vibration, and the amount of maleic anhydride contained in the sample was determined from the absorbance of the sample.

[Yield Parameter] Paar Physi
The dynamic viscoelasticity of the composite material and the dynamic viscoelasticity of the (e) polypropylene resin used for the composite material were measured by using a UDS-200 type rheometer manufactured by CA, and the measurement results and the above (Equation 2) were used. , The yield parameter k by the least squares method
₀ calculated. After using a parallel disk type jig having a diameter of 25 mm as a measurement jig and performing preheating at 180 ° C. for 2 hours or more, all measurement temperatures = 180 ° C., strain = 10%, angular frequency ω = 0.01 to It was measured in the range of 100 radians / second. The test piece was prepared by preparing a sheet having a thickness of 2 mm from a composite material by press molding, and cutting out the sheet from the sheet into a predetermined size.

[Orientation Parameter] An X-ray diffractometer RAD manufactured by Rigaku Denki Co., Ltd. was used for a test piece obtained by injection molding.
It measured using -3R. Here, the measurement conditions are tube voltage;
40 kV, tube current: 40 mA, slit diameter DS = 0.
05 mm, RS = 0.15 mm, SS = 0.5 deg. From the obtained X-ray profile, 2θ = 12.5
Integral value of intensity in the range of ° to 15.0 ° (I (110))
And 2θ = 15.5 ° to 17.5 °, the integral value of the intensity (I (040)) was determined, and the orientation parameter was calculated using these values.

[Heat deformation temperature] Measured according to ASTM D648. 18.56 kg / cm ² (264 ps
A load was applied to the center of the test piece for 5 minutes so that the fiber stress of i) acts, and the temperature was increased at a rate of 2 ± 0.2 ° C./min for measurement. [Neck-in value] According to the T-die method, a die width of 300 mm
Under conditions of a lip gap of 1 mm, an extrusion temperature of 230 ° C., and a chill roll temperature of 37 ° C., a 30 μm thick film is formed.
At this time, the difference between the die width and the extruded film width (neck-in value, unit: mm) was measured.

[Example 1] (B) 28.7 parts by weight of a layered silicate (a-1) treated with an organic cation and 71.3 parts by weight of maleic anhydride-modified polypropylene (c-1) were treated with Henschel. The mixture was sufficiently mixed and stirred by a mixer. Then
Using a KTX30 twin screw extruder manufactured by Kobe Steel,
Under a kneading condition of a set temperature of 200 ° C. and a screw rotation number of 360 rpm, the mixture was melt-kneaded and pelletized. This is designated as master batch MB-1. Table 1 shows the compositions and their contents.

17 parts by weight of MB-1 and 83 parts by weight of homopolypropylene (e-1) were mixed with a Henschel mixer, and this was mixed with a Kobe Steel KTX30 twin screw extruder at a set temperature of 200 ° C. Screw rotation speed 360rpm
The mixture was melt-kneaded under kneading conditions of m and pelletized. The pellets were subjected to injection molding using an injection molding machine (Model 100 manufactured by FANUC) at a cylinder temperature of 200 ° C. and a mold cooling temperature of 40 ° C. to produce test pieces. The injection-molded test piece was allowed to stand at room temperature of 23 ° C. and a humidity of 80% for 2 to 4 days.
The ash content m and the dynamic viscoelasticity were measured. Table 2 shows the results.

Example 2 A masterbatch MB-2 was prepared in the same manner as in Example 1 except that (c-2) was used as the modified polypropylene (c). Table 1 shows the compositions and their contents. A composite material was prepared and evaluated in the same manner as in Example 1 except that MB-2 was used. Table 2 shows the results.

Example 3 (a-1) 38.3 parts by weight
Master batch MB-3 was produced in the same manner as in Example 1, except that 36.8 parts by weight of (c-1) and 25 parts by weight of (d-1) were used. Table 1 shows the compositions and their contents. A composite material was prepared and evaluated in the same manner as in Example 1, except that 12.5 parts by weight of MB-3 and 87.5 parts by weight of homopolypropylene (e-1) were used. Table 2 shows the results.

Example 4 (a-1) 55.6 parts by weight,
Master batch MB-4 was produced in the same manner as in Example 1, except that 19.4 parts by weight of (c-1) and 25 parts by weight of (d-2) were used. Table 1 shows the compositions and their contents. A composite material was prepared and evaluated in the same manner as in Example 3, except that 12.6 parts by weight of MB-4 was used. Table 2 shows the results.

[Comparative Example 1] (b) 17.8 parts by weight of synthetic mica (a-2) and (c-1) 8 not treated with an organic cation
Performed in the same manner as in Example 1 except that 2.2 parts by weight was used.
A master batch MB-5 was prepared and evaluated. Pellets could not be formed because the viscosity did not reach kneading.

[Comparative Example 2] (a-2) 23.8 parts by weight,
A master batch MB-6 was produced in the same manner as in Example 1, except that 51.3 parts by weight of (c-1) and 25 parts by weight of (d-1) were used. Table 1 shows the compositions and their contents. A composite material was prepared and evaluated in the same manner as in Example 1, except that 12.5 parts by weight of MB-6 and 87.5 parts by weight of homopolypropylene (e-1) were used. Table 2 shows the results. The flexural modulus S of the obtained composite material was low, and the yield parameter k ₀ did not satisfy the relationship of the above (Equation 3).

Comparative Example 3 A master batch MB-7 was prepared in the same manner as in Comparative Example 2, except that talc (a-3) was used instead of the layered silicate. Table 1 shows the compositions and their contents. A composite material was prepared and evaluated in the same manner as in Comparative Example 2 except that MB-7 was used. Table 2 shows the results. The flexural modulus S of the obtained composite material was low, and the yield parameter k ₀ did not satisfy the relationship of the above (Equation 3).

[Comparative Example 4] Unmodified polypropylene wax (c-
A master batch MB-8 was produced in the same manner as in Example 3, except that 3) was used. Table 1 shows the compositions and their contents. A composite material was prepared and evaluated in the same manner as in Comparative Example 2 except that MB-8 was used. Table 2 shows the results.
The flexural modulus S of the obtained composite material was low, and the yield parameter k ₀ did not satisfy the relationship of the above (Equation 3).

Comparative Example 5 A homopolypropylene was prepared without adding a masterbatch composition for modifying polypropylene resin.
Evaluation was performed in the same manner as in Example 5 except that only (e-1) was used. Table 2 shows the results. The flexural modulus S was low.

[Comparative Example 6] (a-1) 4.9 parts by weight,
(C-1) 12.1 parts by weight of homopolypropylene (e-1) and 83 parts by weight of homopolypropylene (e-1) were simultaneously mixed in a Henschel mixer, pelletized in the same manner as in Example 5, injection molded, and a test piece was prepared. Was evaluated. Table 2 shows the results
Shown in The flexural modulus S of the obtained composite material was low, and the yield parameter k ₀ did not satisfy the relationship of the above (Equation 3).

[0063]

[Table 1]

[0064]

[Table 2]

From the results shown in Tables 1 and 2, the intercalation compound consisting of (a) a layered silicate and (b) an organic cation,
(C) A composite material obtained by diluting and kneading a composition obtained by kneading an unsaturated monomer-modified polypropylene with a polypropylene-based resin greatly improves the elastic modulus by adding a small amount, and is an index of moldability. The yield parameter k ₀ was increased as compared with the polypropylene resin to which no layered silicate was added as shown in Comparative Example 5, indicating that the melting properties were significantly improved.

Example 5 (b) 40.3 parts by weight of a layered silicate (a-1) treated with an organic cation and 59.7 parts by weight of maleic anhydride-modified polypropylene (c-4) The mixture was sufficiently mixed and stirred with a Henschel mixer. Then, using a KTX30 twin-screw extruder manufactured by Kobe Steel Ltd., the temperature was set at 250 ° C. and the screw rotation speed was 300 rpm
Under the kneading conditions described above, the mixture was melt-kneaded and formed into pellets. This is designated as MB-9. Table 3 shows the compositions and their contents.

4 parts by weight of MB-9 and 96 parts by weight of homopolypropylene (e-1) were mixed with a Henschel mixer, and the mixture was set at a preset temperature of 200 using the twin-screw extruder.
The mixture was melt-kneaded under kneading conditions at 360 ° C. and a screw rotation speed of 360 rpm to form pellets. The pellets were subjected to injection molding using an injection molding machine (Model 100 manufactured by FANUC) at a cylinder temperature of 200 ° C. and a mold cooling temperature of 40 ° C. to produce test pieces. The injection-molded test piece was allowed to stand at room temperature of 23 ° C. and a humidity of 80% for 2 to 4 days, and then subjected to flexural modulus S, ash m, orientation parameter, dynamic viscoelasticity, heat deformation temperature and The neck-in value was measured. Homopolypropylene (e-1) but also to measure the elastic modulus and the dynamic viscoelasticity bent similarly for to determine the elastic modulus increase T and yield parameters k ₀ targeting this. Table 4 shows the results.

Example 6 A masterbatch MB-10 was prepared in the same manner as in Example 5, except that (c-5) was used as the modified polypropylene (c). Table 3 shows the compositions and their contents. A composite material was prepared and evaluated in the same manner as in Example 5 except that MB-10 was used. Table 4 shows the results.

Example 7 (a-1) 32.3 parts by weight
Master batch MB-11 was produced in the same manner as in Example 5, except that 47.7 parts by weight of (c-4) and 20 parts by weight of (d-1) were used. Table 3 about composition and contents
Shown in A composite material was prepared and evaluated in the same manner as in Example 5, except that 5 parts by weight of MB-11 and 95 parts by weight of (e-1) were used. Table 4 shows the results.

Reference Example 1 Example 5 was repeated except that the maleic anhydride-modified polypropylene wax (c-6) was used instead of the maleic anhydride-modified polypropylene (c-4).
Was performed in the same manner as in the above to prepare a master batch MB-12.
Table 3 shows the compositions and their contents. A composite material was prepared and evaluated in the same manner as in Example 5, except that MB-12 was used. Table 4 shows the results. (C) When a modified polypropylene having a low molecular weight was used, heat resistance was lowered and rigidity was also slightly lowered.

[Comparative Example 7] Instead of maleic anhydride-modified polypropylene (c-4), unmodified polypropylene (c
Master batch MB-13 was produced in the same manner as in Example 5, except that -7) was used. Table 3 shows the compositions and their contents. A composite material was prepared and evaluated in the same manner as in Example 5, except that MB-13 was used. Table 4 shows the results. When polypropylene not modified with the unsaturated monomer was used, the rigidity did not increase, and no increase in the yield parameter as an index of the moldability was observed.

Comparative Example 8 Instead of (a-1), (b)
Masterbatch MB-14 was produced in the same manner as in Example 5, except that 25 parts by weight of synthetic mica (a-2) not treated with an organic cation and 75 parts by weight of (c-4) were used. Table 3 shows the compositions and their contents. A composite material was prepared and evaluated in the same manner as in Example 5, except that MB-14 was used. Table 4 shows the results. (B) When a master batch composition was prepared without using an organic cation, neither the rigidity nor the yield parameter was improved.

Comparative Example 9 A master batch MB-15 was produced in the same manner as in Comparative Example 8, except that talc (a-3) was used instead of (a-1). Table 3 shows the compositions and their contents. Example 5 except that MB-15 was used
A composite material was prepared and evaluated in the same manner as described above. Table 4 shows the results
Shown in When talc, which is generally used as a reinforcing material, was used, the addition of a small amount did not increase the rigidity and did not increase the yield parameter.

[0074]

[Table 3]

[0075]

[Table 4]

From the results shown in Table 4, it was found that (a) a layered silicate and (b) an intercalation compound comprising an organic cation,
(C) A composite material obtained by diluting and kneading a masterbatch composition obtained by kneading an unsaturated monomer-modified polypropylene having a weight-average molecular weight of 80,000 or more with a polypropylene resin has a large orientation parameter by adding a small amount. As a result, the elastic modulus and the heat resistance are improved. Further, the yield parameter, which is an index of the formability, was increased as compared with the polypropylene resin to which no layered silicate was added as shown in the comparative example, indicating that the melting property was significantly improved.

[0077]

As described above, the masterbatch composition for modifying a polypropylene resin of the present invention comprises (a) 10 to 70% by weight of a layered silicate and (b) 1 to 45% of an organic cation.
% By weight, (c) unsaturated monomer-modified polypropylene 10
89% by weight, and (d) polypropylene resin 0 to 79
(C) The unit derived from the unsaturated monomer in the unsaturated monomer-modified polypropylene is contained in an amount of 0.01% by weight or more based on the master batch composition. Thereby, the rigidity and heat resistance of the polypropylene resin can be improved. Further, by adding a small amount, the melting properties such as melt tension and melt elasticity of the polypropylene resin are improved, and the moldability of the polypropylene resin can be greatly improved. Further, when the weight average molecular weight of the unsaturated monomer-modified polypropylene (c) is 80,000 or more, the rigidity, heat resistance and moldability of the polypropylene resin can be further improved.

Further, the master batch composition for modifying a polypropylene resin of the present invention is a composite material obtained by adding the master batch composition to a polypropylene resin (e), wherein the polypropylene resin has a flexural modulus S ₀ , a layered silicate When the increase rate T of the flexural modulus per 1% by weight of the ash content determined by the above (Equation 1) from the flexural modulus S of the composite material and the ash content m of the layered silicate composite material is 16 or more, talc or the like was added. The rigidity of the polypropylene-based resin can be further increased at the same specific gravity as the system, and as a result, the weight can be reduced.

The masterbatch composition for modifying a polypropylene resin of the present invention is characterized in that, in a composite material obtained by adding the masterbatch composition to a polypropylene resin (e), the yield determined by the least square method from the above (Equation 2) Parameter k
_{When 0} and the ash content m of the composite material satisfy the relationship of the above-described (formula 3), it is possible to improve the moldability such as drawdown and neck-in during extrusion molding of the polyolefin-based resin to which the polyolefin resin is added. .

The master batch composition for modifying polypropylene resin of the present invention is obtained by adding the above-mentioned orientation parameter I (040) / I (110 In the case where (4) is 4 or more, the orientation of the lamella composed of the polypropylene crystal becomes large, and the rigidity of the polyolefin-based resin to which this is added can be further improved.

Continued on the front page (72) Inventor Kazuhiro Hara 2-3-2, Yakko, Kawasaki-ku, Kawasaki-city, Kanagawa Prefecture Inside the Japan Polyolefin Co., Ltd. Kawasaki Research Laboratories (72) Inventor Reiji Higuchi 2--3, Yakko, Kawasaki-ku, Kawasaki-ku, Kanagawa Prefecture No. 2 Japan Polyolefin Co., Ltd., Kawasaki Research Laboratory (72) Inventor Hideo Watanabe 2-3-2 Night Light, Kawasaki-ku, Kawasaki City, Kanagawa Prefecture Japan Polyolefin Co., Ltd. Kawasaki Research Laboratory (72) Inventor Yoshihiro Mogi, Kawasaki City, Kanagawa Prefecture 2-3-2, Yakko, Kawasaki-ku Japan Polyolefin Co., Ltd.Kawasaki Research Laboratory (72) Inventor Hirofumi Inoue 3-2 Chidoricho, Kawasaki-ku, Kawasaki City, Kanagawa Prefecture Showa Denko KK (72) Inventor Kenshi Tamura 3-2, Chidoricho, Kawasaki-ku, Kawasaki-ku, Kanagawa Prefecture F-term (reference) 4J002 BB12X BB14X BB15X BN03W BN04W BN05W BN06W BN21W BP02X BP03W CH05Y DJ006 DJ046 DJ056 EN137 FA016 FB076 FB086 FB086 FB086

Claims (5)

[Claims] (1) 10 to 70% by weight of a layered silicate,
(B) 1 to 45% by weight of an organic cation, (c) 10 to 89% by weight of an unsaturated monomer-modified polypropylene, and (d)
It contains 0 to 79% by weight of a polypropylene resin, and (c) 0.01% by weight or more of the unit derived from the unsaturated monomer in the unsaturated monomer-modified polypropylene is contained in the composition. A masterbatch composition for modifying a polypropylene resin, comprising: 2. The masterbatch composition for modifying a polypropylene resin according to claim 1, wherein the weight average molecular weight of the unsaturated monomer-modified polypropylene (c) is 80,000 or more. 3. A flexural modulus S (kgf / cm ² ) of a composite material obtained by adding a polypropylene resin-modified masterbatch composition to (e) a polypropylene resin, and (e) a flexural modulus of the polypropylene resin. S ₀ (kgf / cm
² ) and an increase rate T of flexural modulus per 1% by weight of ash content determined by the following (Equation 1) from the ash content m (% by weight) of the composite material is 16 or more. Or the masterbatch composition for polypropylene resin modification according to claim 2. (Equation 1) T = (S−S ₀ ) / S ₀ × 100 / m 4. An ash content m (% by weight) of a composite material obtained by adding a masterbatch composition for modifying a polypropylene resin to (e) a polypropylene resin, and a yield determined by the least square method from the following (Formula 2). The master batch composition for modifying a polypropylene resin according to any one of claims 1 to 3, wherein the parameter k ₀ satisfies the following relationship (formula 3). (Equation 2) G ^1/2 = k ₀ + k ₁ (ω · η ₀ ^* (ω) / η ₀ ^* (0.01)) ^1/2 (Equation 3) When m ≧ 1, k ₀ ≧ 1. K ₀ ≧ 0.1 in the case of 75 × m−1.65 m <1 (wherein G is the angular frequency ω (radian / radian / Sec), the absolute value (Pa) of the complex elastic modulus at η ₀ ^* (0.
01) and η ₀ ^* (ω) are, respectively, the angular frequency 0.01 radian / sec and the angular frequency ω in the dynamic viscoelasticity measurement at 180 ° C. of the (e) polypropylene-based resin.
(Radian / second), the absolute value of the complex viscosity (Pa ·
s). ) 5. The integrated intensity of a diffraction peak of a (040) plane of a polypropylene crystal measured by an X-ray diffraction method of a composite material molded article obtained by adding a masterbatch composition for modifying a polypropylene resin to (e) a polypropylene resin. I (040)
And the orientation parameter I (0) consisting of the ratio of the integrated intensity I (110) of the diffraction peak on the (110) plane of the polypropylene crystal.
The master batch composition for modifying a polypropylene resin according to any one of claims 1 to 4, wherein 40) / I (110) is 4 or more.