JPH06104701B2 - Propylene-based random copolymer and impact modifier for thermoplastic resin comprising the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel propylene random copolymer. More specifically, a propylene-based random copolymer having a narrow molecular weight distribution and composition distribution, excellent transparency, surface non-adhesiveness, tensile properties and other properties, for example, excellent packaging properties such as transparency and blocking resistance. Excellent effect of improving heat sealability and impact resistance by compounding with thermoplastic resin such as propylene random copolymer and olefin polymer suitable for forming film, sheet, and other melt-molded products. The present invention relates to a modifier for thermoplastic resin.

[Conventional technology]

Conventionally, the use of vinyl chloride resin has been predominantly used in the application field of soft or semi-rigid resin molding, but problems such as the generation of corrosive gas during waste incineration and safety concerns regarding residual monomer and plasticizer There has been a growing demand for conversion from olefin-based soft or semi-rigid resins. Therefore, the demand for the α-olefin soft copolymer is increasing more and more in the field of molding or applications such as various resin modifiers.

As the α-olefin soft copolymer, two or more α
-Olefin copolymers are generally known, and the production method thereof is two or more in the presence of a titanium catalyst composed of a titanium compound and an organoaluminum compound or a vanadium catalyst composed of a vanadium compound and an organoaluminum compound. A method for copolymerizing the above α-olefin is known. The α-olefin soft copolymer obtained by the titanium catalyst is generally inferior in random copolymerizability, has a broad molecular weight distribution and composition distribution, and is inferior in transparency, surface non-adhesiveness and mechanical properties. Further, the α-olefin soft copolymer obtained with the vanadium catalyst generally has an ethylene content of 50 mol% or more, and they have improved randomness as compared with those obtained with the titanium catalyst, and have a molecular weight distribution and Although the composition distribution is narrowed and transparency, surface non-adhesiveness, and mechanical properties are considerably improved, they are still insufficient for applications where these performances are severely required. Olefin based soft copolymers are required.

Recently, as the olefin resin used in the field of molding application of such soft or semi-hard resin,
There are olefin-based copolymers such as ethylene-based copolymers, propylene-based copolymers and 1-butene-based copolymers. Of these olefin soft or semi-hard resins, 1-
Many proposals have been made for a soft 1-butene random copolymer composed mainly of butene and 1-butene and propylene. Among them, U.S. Pat.No. 3,278,504, U.S. Pat.No. 3,332,921, U.S. Pat.No. 4,168,3
No. 61 and British Patent No. 1,018,341 disclose 1-butene random copolymers produced using titanium trichloride or titanium tetrachloride catalysts. However, what these 1-butene random copolymers have in common is that low molecular weight polymer components such as boiling methyl acetate soluble and acetone / n-decane mixed solvent (volume ratio 1/1) soluble components. Since the content of the 1-butene random copolymer is large, and the composition distribution and the molecular weight distribution are wide, the surface adhesiveness of the molded article, especially the film and the sheet is large,
Blocking is remarkable. Further, most of them have low randomness, have a large amount of boiling methyl acetate-soluble components, and have poor transparency, and it has been impossible to obtain a molded product having a high commercial value.

U.S. Pat. No. 3,278,504 proposes a propylene / 1-butene copolymer having a 1-butene content of 30 to 70 mol%. It is described that the 1-butene-based copolymer is produced by using titanium tetrachloride or titanium trichloride. However, the copolymer produced by such a catalyst system has a boiling methyl acetate-soluble content. It is a soft resin having a content of more than 2% by weight, a large amount of acetone / n-decane mixed solvent (volume ratio 1/1) soluble content, surface tackiness, and poor transparency.

U.S. Pat.No. 3,332,921 and British Patent No. 1,08
No. 4,953 also produced using titanium trichloride catalyst 1
-Various 1-butene-based copolymers having different butene contents have been proposed. Among these copolymers, the 1-butene-based copolymer having a 1-butene content of 60 to 99 mol% is It has the same properties as the 1-butene-based copolymer proposed in US Pat. No. 3,278,504.

Further, according to the above-mentioned British Patent No. 1018341, a transition metal halide such as titanium trichloride and a derivative of phosphoric acid are used in combination to obtain a copolymer having a 1-butene content of 25 to 90 mol%. There is. Among the copolymers specifically disclosed in this proposal, the content of 1-butene is 50 to 90 mol%.
As for the 1-butene-based copolymer, only those having an acetone-soluble content of 1.5% by weight or more are disclosed. According to the studies by the present inventors, these copolymers have a higher content of boiling methyl acetate-soluble components exceeding 2% by weight, and a soluble content of acetone / n-decane mixed solvent (volume ratio 1/1). It was also found that the content of γ was more than 5 × [η] ^-1.2 % by weight, and that the 1-butene copolymer had a large surface tackiness and that only a molded product having poor transparency could be obtained. .

Further, the above-mentioned U.S. Pat.No. 4,168,361 discloses a propylene / 1-butene copolymer having a propylene content in the range of 40 to 90 mol%, but among these copolymers, 1-butene As for the copolymer having a butene content of 50 to 60 mol%, similarly to the above, according to the study by the present inventors, the content of the acetone / n-decane mixed solvent-soluble component is high, and the 1-butene system From the copolymer, it is possible to obtain only a molded product having high surface tackiness and poor transparency.

On the other hand, a method for obtaining an amorphous random copolymer by carrying out polymerization at a high temperature using a titanium trichloride-based catalyst has been proposed in JP-A-50-38787.

According to the studies made by the present inventors, this method has a large amount of methyl acetate-soluble components and is inferior in tensile properties and cannot be used for resinous purposes.

In addition, the applicant of the present invention has disclosed in JP-A No. 54-85293 that 1-butene / propylene random copolymer containing 1-butene as a main component has a narrow composition distribution, a small amount of boiling methyl acetate-soluble components, and a small surface tackiness. A polymer was proposed. However, the content of the low molecular weight component of the 1-butene / propylene copolymer provided by this proposal, especially the content of the low molecular weight polymer represented by the boiling methyl acetate-soluble component, and a molded article composed of the copolymer It is clear that the surface tackiness of the 1-butene random copolymer is significantly improved as compared with the conventional one, but the molecular weight distribution (w / n) of the 1-butene random copolymer is 3.6, which is not sufficiently narrow. , A low molecular weight polymer component in the copolymer, especially an acetone / n-decane mixed solvent (volume ratio 1 /
1) A molded article of a resin composition in which the content of a low molecular weight polymer component represented by a soluble component is still high, and a polypropylene resin is blended with the 1-butene / propylene random copolymer to improve impact resistance. For example, it is difficult to say that the film is still sufficient for applications in fields in which performance such as surface non-adhesiveness and transparency is highly required, since it has drawbacks such that surface tackiness tends to increase with time. It was Further, the 1-butene-propylene random copolymer according to this proposal has a low crystallinity, is inferior in mechanical properties such as rigidity, and is unsuitable for use in fields where these mechanical properties are highly required. It was enough.

On the other hand, as a new Ziegler type olefin polymerization catalyst different from conventionally known titanium-based catalysts or vanadium-based catalysts, a catalyst composed of a zirconium compound and aluminoxane is disclosed in JP-A-58-19309 and JP-A-59- 95292
5, JP-A-60-35005, JP-A-60-35006, JP-A-60-35007, and JP-A-60-35009, respectively. These prior art documents also exemplify copolymers of two or more kinds of α-olefins, for example, Example 7 in JP-A-58-19309 and JP-A-60-350.
Example 1 to Example 3 of JP-A No. 06, and Example 10 and Example 11 of JP-A-60-35007 are ethylene / α-olefin copolymers having an α-olefin content of 3 to 43 mol%. However, all of these ethylene / α-olefin copolymers have a broad molecular weight distribution and composition distribution, or have performances such as transparency, surface non-adhesiveness and mechanical properties, and thermoplastic resins. The performance as a modifier is often insufficient depending on the application in the field of application, and there is a strong demand for α-olefin soft copolymers having improved performance.

Further, regarding the soft low crystalline propylene-based copolymer containing a propylene component by copolymerizing propylene and α-olefin other than propylene, the applicant of the present invention has disclosed those disclosed in JP-A Nos. 52-19153 and 55-55. -118909, JP 55-118910, JP 53-79984, JP 53-104686, JP 54-85293, JP 6
It is proposed in the publication such as 0-38414. These soft low-crystalline propylene-based copolymers have a reduced content of boiling methyl acetate-soluble components compared to conventionally known soft low-crystalline propylene-based copolymers, and have a surface non-adhesiveness and blocking property. And transparency is improved, but it is difficult to say that this is sufficient for applications in fields where these performances are more severely required. Furthermore, the copolymers obtained by these methods all have a wide molecular weight distribution. In the field of applications where performance is strictly required in terms of mechanical properties as well, there is a strong demand for a soft low-crystalline propylene-based copolymer having further excellent performance.

[Problems to be solved by the invention]

The present inventors have found that the conventional propylene-based random copolymer has a wide molecular weight distribution and composition distribution, has a large content of low-molecular weight polymers, and the molded product obtained from the propylene-based random copolymer has surface non-adhesiveness. Recognizing that it is inferior in mechanical properties such as transparency and rigidity, it is an object to provide a propylene random copolymer having improved physical properties as compared with conventional propylene random copolymers. I have been carrying out development research as.

As a result, the present inventors have shown that a propylene-based random copolymer composed of a propylene component and an ethylene component,
Moreover, it was discovered that a propylene-based random copolymer, which has not been described in the related art and has the characteristic values defined in the following (A) to (J), can exist, and its synthesis was successful.

Further, this novel propylene random copolymer has a narrower molecular weight distribution and compositional distribution than conventionally known propylene random copolymers, and has a low molecular weight polymer component, especially soluble components in acetone methyl acetate and acetone. The content of the low molecular weight polymer component represented by both the soluble components in the n-decane mixed solvent (volume ratio 1/1) is low, and the molded product obtained from the propylene random copolymer has no surface tackiness. It was found that the mechanical properties such as transparency, rigidity and the like are particularly excellent.

Therefore, an object of the present invention is to provide a novel propylene random copolymer comprising a propylene component and an ethylene component.

Further, another object of the present invention is to provide a modifier for a thermoplastic resin having an excellent effect of improving heat sealability or impact resistance by blending it with a thermoplastic resin such as an olefin polymer. is there.

The above as well as many other objects and advantages of the present invention will become more apparent in the following description.

[Means and Actions for Solving Problems]

According to the present invention, there is provided a propylene random copolymer comprising an ethylene component and a propylene component, the composition of which (A) has an ethylene component content of 10 to 70 mol% and a propylene component content of 30 to 90 mol%. , (B) the intrinsic viscosity [η] measured in decalin at 135 ° C
It is in the range of 0.5 to 6 dl / g. (C) Gel permeation chromitography (GP
The molecular weight distribution (Mw / Mn) measured in C) is in the range of 3 or less, and (D) the melting point [Tm] measured by a differential scanning calorimeter is 40.
(E) the crystallinity measured by X-ray diffraction is in the range of 0.5 to 60%, and (F) the soluble amount in boiling methyl acetate [W ₁ % by weight] is 1 (G) the amount of soluble components [W ₂ % by weight] in an acetone / n-decane mixed solvent (volume ratio 1/1) at 10 ° C is 4 x [η] ^-1.2 % or less. And (H) the triad chain of propylene has a microisotacticity in the range of 0.8 or more. (I) In the ¹³ C-NMR spectrum of the copolymer, two adjacent two in the main chain of the copolymer are The signals of αβ and βγ based on the methylene chain between the tertiary carbon atoms are not observed, and (J) the general formula [I] [In the formula, P _O represents the content mole fraction of the propylene component in the copolymer, P _E represents the content mole fraction of the ethylene component, P _E
OE represents the mole fraction of propylene / ethylene chains in the entire dyad chain], and the B value represented by the general formula (II) is within the range of 1.00 ≦ B ≦ 2 [II]. Provided is a thermoplastic resin modification comprising a polymer and the propylene-based random copolymer.

In the propylene random copolymer of the present invention, the composition (A) of the copolymer is such that the ethylene component is in the range of 10 to 70 mol%, preferably 20 to 65 mol%, and the content of the propylene component is 30. To 90 mol%, preferably 35 to 80 mol%. When the content of the propylene component in the copolymer is less than 30 mol% and the content of the ethylene component is more than 70 mol%, the content of the low molecular weight component of the copolymer is increased, and transparency, The blocking property and the slip property are deteriorated. When the content of the propylene component is more than 90 mol% and the content of the ethylene component is less than 10 mol%, the transparency of the copolymer is deteriorated. In addition, the hardness becomes high and it cannot be used for applications requiring elasticity.

In the propylene random copolymer of the present invention, 135
The intrinsic viscosity [η] (B) measured in decalin at 0 ° C was 0.
It is in the range of 5 to 6 dt / g, preferably 1 to 5 dl / g. This characteristic value is a measure of the molecular weight of the propylene-based random copolymer of the present invention, and together with other characteristic values, it serves to give the random copolymer the excellent properties described above.

The molecular weight distribution (w / n) (C) of the 1-butene random copolymer of the present invention determined by gel permeation chromatography (GPC) is 3 or less, preferably 2.8 or less,
It is particularly preferably in the range of 2.5 or less. The conventionally proposed 1-butene random copolymer has a w / n value of 3
From the above, the molecular weight distribution cannot be said to be sufficiently narrow, and low molecular weight polymer components are mixed, so that the surface non-tackiness is poor and this is a cause of blocking. Of the present invention
This characteristic value in the 1-butene random copolymer, together with other characteristic values, gives the copolymer the above-mentioned excellent properties. The w / n value was measured according to "Gel Permeation Chromatography," published by Maruzen by Takeuchi, as follows.

(1) Using a standard polystyrene of known molecular weight (Toyo Soda (manufactured by Toyo Soda) monodisperse polystyrene), the molecular weight M and its GPC (Gel Permeation Chromatograph) count are measured, and the correlation diagram calibration between the molecular weight M and EV (Elution Volume) is performed. A curve was created. The concentration at this time was 0.02 wt%.

(2) Take a GPC chromatograph of the sample by GPC measurement,
The number average molecular weight n and the weight average molecular weight w in terms of polystyrene are calculated by the above (1) to obtain the w / n value.
The sample preparation conditions and GPC measurement conditions in that case are as follows.

[Sample preparation]

(B) The sample was dispensed into an Erlenmeyer flask together with the O-dichlorobenzene solvent so that the sample would be 0.1 wt%.

(B) Anti-aging agent 2,6 in Erlenmeyer flask containing sample
-Di-tert-butyl-P-cresol was added at 0.05 wt% with respect to the polymer solution.

(C) The Erlenmeyer flask was heated to 140 ° C. and stirred for about 30 minutes to dissolve it.

(D) The liquid was applied to GPC.

[GPC measurement conditions]

 It carried out on the following conditions.

(B) Equipment Waters (150C-ALC / GPC) (b) Column Toyo Soda (GMH type) (c) Sample volume 400 μl (d) Temperature 140 ° C (v) Flow rate 1 ml / min Propylene random of the present invention The melting point of the copolymer measured by a differential scanning calorimeter [hereinafter, may be abbreviated as DSC melting point] (D) is 40 to 140 ° C., preferably 45.
To 120 ° C. The presence of the DSC melting point is a measure showing that it is a copolymer having crystallinity which is distinguished from the conventional amorphous propylene random copolymer, and it is taken together with other characteristic values. It is useful for giving the above-mentioned excellent properties to the copolymer. The measurement was performed using a differential scanning calorimeter (DSC-II manufactured by PERKIN-ELMER). About 5 mg of the sample was put into a sample case for measurement, weighed, and attached to a measuring instrument. Next, leave it at 200 ℃ for 5 minutes and then at 20 ℃ /
Cooled to 20 ° C at min rate. Using this sample, 10 ℃ / mi
The endothermic spectrum chart was obtained by raising the temperature at a rate of n.

The propylene random copolymer of the present invention has a crystallinity (E) measured by X-ray diffraction of 0.5 to 60%, preferably 0.5 to 50%. This characteristic value is
It is a measure showing that the propylene-based random copolymer of the present invention has excellent tensile properties, and together with other property values, it is useful for giving the random copolymer the above-mentioned excellent properties. The crystallinity was determined by X-ray diffraction measurement of a 1.5 mm pressed sheet.

In the 1-butene random copolymer of the present invention, the soluble amount [W ₁ % by weight] (F) in boiling methyl acetate is 1% by weight or less based on the weight of the copolymer, for example, 0.001 to
It is in the range of 1% by weight, preferably 0.002-0.5% by weight, particularly preferably 0.003-0.2% by weight. This characteristic value is a measure showing the content of the low molecular weight polymer component in the propylene random copolymer of the present invention and showing the breadth of the composition distribution and the molecular weight distribution of the copolymer, and propylene which has been conventionally proposed. The random random copolymer has a large amount of boiling methyl acetate-soluble content, is inferior in surface non-tackiness, and is a cause of large blocking property. This characteristic value in the propylene-based random copolymer of the present invention, together with other characteristic values, serves to give the copolymer the above-mentioned excellent properties. In the present invention, the boiling methyl acetate-soluble content was measured by the following method. That is, a strip sample of about 1 mm x 1 mm x 1 mm is put into a cylindrical glass filter, the refractory frequency is set to about 1/5 minutes, and extracted with a Soxhlet extractor for 7 hours, and the extraction residue is vacuum-dried (vacuum degree 10 mmHg Less than)
Was dried until the weight became constant and the weight was determined, and the boiling methyl acetate-soluble component weight was determined from the weight difference from the original sample. The boiling methyl acetate soluble content [W ₁ ] was determined as a percentage of the boiling methyl acetate soluble content with respect to the original sample weight.

In the propylene random copolymer of the present invention, 10 ° C
Acetone / n-decane mixed solvent (volume ratio 1/1)
The amount of soluble components [W ₂ % by weight] (G) is 4 × [η] ^−1.2 % by weight or less, preferably 0.1% by weight, based on the weight of the copolymer.
1 × [η] ^{-1.2 to} 3.5 × [η] ^-1.2 % by weight, particularly preferably in the range of 0.3 × [η] ^{-1.2 to} 3 × [η] ^-1.2 (where [η] is The numerical value of the intrinsic viscosity of the polymer excluding the dimension). This characteristic value is a scale showing the content of the low molecular weight polymer component in the propylene random copolymer of the present invention and showing the composition distribution and the range of the molecular weight of the copolymer. The conventionally known propylene random copolymer is
A large amount of n-decane mixed solvent is soluble, which is inferior in surface non-adhesiveness and causes a large blocking property. This characteristic value in the propylene-based random copolymer of the present invention, together with other characteristic values, serves to give the copolymer the above-mentioned excellent properties. In the present invention, the soluble content of the copolymer in the mixed solvent is measured and determined by the following method. That is, in a 150 ml flask with stirring blades, 1 g of the copolymer sample, 0.05 g of 2,6-ditert-butyl-
Add 4-methylphenol and 50 ml of n-decane, and add 120
Dissolve on oil bath at ℃. After dissolution, the mixture is allowed to cool naturally at room temperature for 30 minutes, 50 ml of acetone is added thereto in 30 seconds, and the mixture is cooled on a water bath at 10 ° C for 60 minutes. The precipitated copolymer and the solution of the low-molecular weight polymer component were dissolved in a glass filter, and the solution was dried at 10 mmHg at 150 ° C until a constant weight was obtained.The weight of the solution was measured, and the copolymer was added to the mixed solvent. The soluble content of the polymer was calculated and determined as a percentage with respect to the weight of the sample copolymer. In the above-mentioned measuring method, stirring was continuously performed from the time of dissolution to the time immediately before excess.

In the present invention, "3 propylene chains" of the copolymer
The micro isotacticity (H) seen above is 0.8 or more,
It is preferably 0.9 or more. The value of the microisotacticity is "3 propylene chains" which is the minimum unit of the three-dimensional structure among the propylene chains in the copolymer chain of the propylene random copolymer of the present invention (intervening ethylene units are not necessary. Of the total number of possible combinations (meaning 3 propylene continuous units) x (eg 1,3 propylene continuous units 1,4 propylene continuous units 2,5 propylene continuous units In the case of 3), in the case of 3 types of sequences that the “3 propylene chains” can take, namely, m · m sequence (isotactic sequence), m · r sequence and r · r sequence, The ratio (y / x) of the number y is shown in the "three propylene chains" having the m sequence.

As described above, in the present invention, the micro-isotacticity observed with three propylene chains is focused on three propylene chains by the method of ¹³ C nuclear magnetic resonance spectrum known per se, and the three propylene chains It is a quantification of the fraction in which three propylenes in the propylene chain unit are arranged isotactically.

Those having a numerical value of less than 0.8, for example, those produced using a vanadium-based catalyst are usually 0.6 or less, but such a copolymer is unfavorable because it has a low softening point and a low tensile strength.

Regarding the arrangement state (I) of the ethylene component and the propylene component in the propylene random copolymer of the present invention, the ¹³ C-NMR spectrum of the copolymer shows that two adjacent two in the main chain of the copolymer. .Alpha..beta. And .beta..gamma. Signals based on the methylene chain between the tertiary carbon atoms of .alpha. To explain this more specifically, in the copolymer of ethylene and propylene, the following bond: Is the central three methylene groups from the left side when viewed from the tertiary carbon on the left side derived from propylene, while α, β and γ are from the right side when viewed from the tertiary carbon on the right side.
In the position. Therefore, there is a methylene group giving the signals of αγ and ββ in the above binding unit, but no methylene group giving the signals of αβ and βγ.

Similarly, the following bond in which propylene comrades are bonded head-to-tail Exists only in methylene groups that give αα signals, and there is no methylene group that gives αβ and βγ signals.

On the other hand, the following combination Each have a methylene group that provides a βγ signal and an αβ signal.

As is clear from the above description, the propylene random copolymer of the present invention has a regular bonding direction of ethylene and propylene. This specification in the propylene random copolymer of the present invention shows the arrangement state of the ethylene component and the propylene component constituting the copolymer, and together with other characteristic values, the excellent properties as described above are obtained. It is useful to give to the copolymer.

The propylene-based copolymer of the present invention has the following formula (I): [In the formula, P _E represents the content mole fraction of the ethylene component in the copolymer, P _O represents the content mole fraction of the propylene component, P _O
OE represents the mole fraction of propylene / ethylene chains in the entire dyad chain], and the B value (I) is in a range satisfying the following formula (II) 1.00 ≦ B ≦ 2 (II). Further, the B value of the propylene-based random copolymer of the present invention is preferably in the following relationship with the content mole fraction (P _E ) of the ethylene component in the copolymer.

When the ethylene content of the copolymer is 50 mol% or less; 1.0 + 0.3 × P _E ≦ B ≦ 1 / (1-P _E ), more preferably the general formula 1.0 + 0.4 × P _E ≦ B ≦ 1 / (1-P _E ), particularly preferably 1.0 + 0.5 × P _E ≦ B ≦ 1 / (1-P _E ), when the ethylene content of the copolymer is 50 mol% or more; 1.3-0.3 × P _E ≦ B ≦ 1 / P _E , more preferably the general formula 1.4−0.4 × P _E ≦ B ≦ 1 / P _E , and most preferably the general formula 1.5−0.5 × P _E ≦ B ≦ 1 / P _E , Is within the range of satisfying.

In the propylene random copolymer of the present invention, the characteristic value consisting of this B value is an index showing the distribution state of each monomer component in the copolymer chain. The larger the B value, the less the number of blocky chains and the less ethylene. It shows that the distribution of the component and the propylene component is uniform, it is excellent in randomness, and that it is a copolymer with a narrow composition distribution. Together with other characteristic values, the copolymer has the above excellent properties. It's helpful to give to.

The B value is reported by GJ Ray et al. (Macromolecu-les 10 , 773
Calculated from P _E , P _O and P _OE according to (1977). P _E , P
_O and P _OE were determined from ¹³ C-NMR spectrum measurement of the copolymer sample. That is, a ¹³ C-NMR spectrum of a sample obtained by uniformly dissolving about 200 mg of a copolymer in 1 ml of hexachlorobutadiene in a 10 mmφ sample tube was measured at a measurement temperature of 120.
℃, measurement frequency 25.05MHz, spectrum width 1500Hz, filter width 1500Hz, pulse repetition time 4.2sec, pulse width 7
The measurement was performed under the measurement conditions of μsec and the number of integration of 2000 to 5000 times, and P _E , P _O , and P _OE were obtained from this spectrum.

The propylene-based random copolymer of the present invention satisfies the specific values specified in (A) to (J) described above. Further preferred propylene random copolymers of the present invention further satisfy at least one of the following characteristic values (K) to N.

In the propylene random copolymer of the present invention, JIS
The stress at break (K) measured by the method of K6301 is 3
To 1000 kg / cm ² , preferably 5 to 800 kg / cm ² , and the elongation at break (L) measured by the method of JIS K6301 is 300% or more, preferably 500 to 1500%.

In the present invention, the above-mentioned characteristic values of stress at break (K) and elongation at break (L) were measured according to the method of tensile test of JIS K6301. That is, as a sample, a ring-shaped test piece having an inner diameter of 18 mm and an outer diameter of 22 mm punched out from a 1 mm-thick press sheet molded according to JIS K6758 is used, and measurement is performed at a tensile speed of 500 mm / min in an atmosphere of 25 ° C.

In the propylene random copolymer of the present invention, JISK
JIS A hardness (M) measured by a method according to JIS K6301 of a 3 mm sheet molded by 6758 is 30 to 120,
It is preferably in the range of 40 to 110. Further, in the propylene random copolymer of the present invention, a haze (N) measured by JISK6714 of a sheet having a thickness of 1 mm formed by JISK6758 is in the range of 30% or less, preferably 20% or less. .

The propylene random copolymer of the present invention may be copolymerized with a trace amount of other components such as α-olefin, for example, 1-butene, as long as the physical properties described above are not impaired.

The propylene random copolymer of the present invention has a low content of a low molecular weight polymer component as compared with the conventionally known ethylene / propylene random copolymer in the entire range of the propylene component content rate, and has a high transparency. It has excellent characteristics such as excellent surface non-adhesiveness, rigidity and other mechanical properties.

The propylene-based random copolymer of the present invention coordinates a predetermined amount of ethylene and propylene with (A) a group of at least two indenyl groups, a substituted indenyl group or a partial hydride thereof bonded through ethylene. It can be produced by polymerizing in the presence of a zirconium compound as a child and a catalyst composed of (B) aluminoxane.

Examples of the zirconium compound include ethylene bis (indenyl) dimethyl zirconium, ethylene bis (indenyl) diethyl zirconium, ethylene bis (indenyl) diphenyl zirconium, ethylene bis (indenyl) methyl zirconium monochloride, ethylene bis (indenyl) ethyl zirconium mono. Chloride, ethylenebis (indenyl) methylzirconium monobromide, ethylenebis (indenyl) zirconium dichloride, ethylenebis (indenyl) zirconium cybromide, ethylenebis (4,5,6,7-tetrahydro-
1-indenyl) dimethyl zirconium, ethylene bis (4,5,6,7-tetrahydro-1-indenyl) methyl zirconium monochloride, ethylene bis (4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride, ethylene Bis (4,5,6,7-tetrahydro-1-indenyl) zirconium dibromide, ethylene bis (4-
Methyl-1-indenyl) zirconium dichloride, ethylenebis (5-methyl-1-indenyl) zirconium dichloride, ethylenebis (6-methyl-1-indenyl) zirconium dichloride, ethylenebis (7-methyl-1-indenyl) zirconium dichloride Ethylenebis (5-mesoxy-1-indenyl) zirconium dichloride, ethylenebis (2,3-dimethyl-1-indenyl) zirconium dichloride, ethylenebis (4,
Examples thereof include 7-dimethyl-1-indenyl) zirconium dichloride and ethylenebis (1,7-dimethyloxy-1-indenyl) zirconium dichloride.

Specific examples of the aluminoxane (B) as a catalyst constituent used in the method of the present invention include general formula [I] or general formula [II] (In the formula, R represents a hydrocarbon group, m represents a number of 2 or more, preferably 20 or more, and particularly preferably 25 or more). In the aluminoxane, R is a hydrocarbon group such as a methyl group, an ethyl group, a propyl group and a butyl group,
It is preferably a methyl group or an ethyl group, particularly preferably a methyl group, and m is an integer of 2 or more, preferably a number of 20 or more, particularly preferably an integer of 25 to 100. The following method can be exemplified as a method for producing the aluminoxane.

(1) Trialkylaluminum is added to a hydrocarbon medium suspension containing a compound containing adsorbed water, a salt containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, and aluminum sulfate hydrate. To react.

(2) A method in which water is allowed to act directly on a trialkylaluminum in a medium such as benzene, toluene, ethyl ether, or tetrahydrofuran.

Among these methods, the method (1) is preferably adopted. The aluminoxane may contain a small amount of organic metal component. In the present invention, it was found that a copolymer having properties never before proposed can be obtained by producing a copolymer of propylene and ethylene in a specific ratio using the above catalyst system. It is a thing. The copolymerization of propylene and ethylene can be carried out in either the liquid phase or the gas phase, but it is particularly preferably carried out in the liquid phase. When carried out in the liquid phase, it is usually carried out in a hydrocarbon medium. As a hydrocarbon medium,
Specifically, for example, aliphatic hydrocarbons such as pentane, hexane, peptaneofudane, and decane; cyclopentane,
Alicyclic hydrocarbons such as methylcyclopentane, cyclohexane, and cyclooctane; aromatic hydrocarbons such as benzene, toluene, xylene; petroleum fractions such as gasoline, kerosene, and light oil, and other raw materials such as olefin. It can be mentioned as a medium. Of these hydrocarbon media, aromatic hydrocarbons are preferred.

The use ratio of the zirconium compound when carrying out the method of the present invention by the liquid phase polymerization method is usually 10 ⁻⁷ to 10 ⁻² g atom / as the concentration of zirconium metal atom in the polymerization reaction system.
l, preferably in the range of 10 ⁻⁶ to 10 ⁻³ gram atom / l. The aluminoxane content is usually 10 as the concentration of aluminum atoms in the polymerization reaction system.
^-4 to 10 ^-1 gram atom / l, preferably 10 ^-3 to 5 ×
The amount is in the range of 10 ^-2 gram atom / l, and the ratio of aluminum atom to zirconium metal atom in the polymerization reaction system is usually 20 to 10 ⁶ , preferably 50 to 1
It is in the range of 0 ⁵ .

The copolymerization of the present invention can be carried out in the same manner as the polymerization of olefin using a conventional Ziegler type catalyst. The temperature of the copolymerization is usually selected in the range of -80 to 50, preferably -60 to 30, and the polymerization is preferably carried out under pressure, usually atmospheric pressure to 30 kg, preferably 2 to 20 kg
It is preferably performed under a pressure of about / cm ² . The raw material supplied to the polymerization reaction system is a mixture of propylene and ethylene. The content of propylene in the polymerization raw material olefin is usually 40 to 98 mol%, preferably 50 to 95 mol%, and the content of ethylene is usually 2 to 60 mol%, preferably 5 to 50 mol%. is there. The molecular weight of the copolymer can be controlled by adjusting the hydrogen and / or the polymerization temperature, and further by the proportion of the catalyst component used.

The propylene-based random copolymer of the present invention is different from the conventionally proposed ones in that it is not sticky and has various other properties as described above. This propylene-based random copolymer, by any molding method such as extrusion molding, hollow molding, injection molding, press molding, vacuum molding,
It can be formed into films, sheets, hollow containers, and other various products, and can be used for various purposes. In particular, it is suitable as a packaging film because it has good blocking resistance and heat sealability. Due to the above properties, it can be suitably used as a protective film made of metal or the like.

When molding, various stabilizers, antioxidants, UV absorbers,
Antistatic agents, lubricants, plasticizers, pigments, inorganic or organic fillers can be added. Examples of these are 2,6
-Di-tert-butyl-p-cresol, tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, 4,4'-butylidene bis (6-tert-butyl) -M-cresol), tocopherols, ascorbic acid, dilaurylthiodipropionate, phosphoric acid stabilizer, fatty acid monoglyceride, N, N- (bis-2-hydroxyethyl) alkylamine, 2- (2'-hydroxy) -3 ', 5'-di-tert-
(Butylphenyl) -5-chlorobenzotriazole, calcium stearate, magnesium oxide, magnesium hydroxide, alumina, aluminum hydroxide, silica, hydrotalcite, talc, clay, gypsum, glass fiber, titania, calcium carbonate, carbon black, petroleum resin , Bolybdenum, wax, synthetic or natural rubber and the like.

The propylene random copolymer of the present invention can improve impact resistance, low temperature impact resistance, flex resistance and low temperature heat sealability by being mixed with various thermoplastic resins as a modifier. Examples of the thermoplastic resin include other ethylene-based polymers containing ethylene as a main component, crystalline olefin polymers other than the ethylene-based polymers, engineering resins and the like.

By blending the propylene random copolymer of the present invention with another ethylene polymer containing ethylene as a main component such as polyethylene, impact resistance and low temperature impact resistance of a molded product of the other ethylene polymer The flex resistance and the low temperature heat sealability can be improved. Examples of the other ethylene-based polymers include high-density polyethylene, medium-density polyethylene, low-density polyethylene, ethylene and propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1 -Dodecene, 1
-Tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, etc. α having 3 to 20 carbon atoms
Examples thereof include ethylene-based copolymers containing olefin as a main component, which are copolymers with olefin. Intrinsic viscosity [η] measured in decalin at 135 ℃
Is usually in the range of 0.5 to 20 dl / g.

When the propylene random copolymer of the present invention is blended with the other ethylene polymer, the blending ratio is usually 1 to 100 parts by weight, preferably 2 to 60 parts by weight based on 100 parts by weight of the ethylene polymer. It is a range of parts. The resulting ethylene-based polymer composition, if necessary, an antioxidant, a hydrochloric acid absorbent, an anticoagulant, a heat stabilizer, an ultraviolet absorber, a lubricant, a weather resistance stabilizer, an antistatic agent, a nucleating agent, a pigment, Various additives such as a filler can also be blended. The mixing ratio is appropriate. The ethylene polymer composition can be prepared according to a conventionally known method.

Further, by incorporating the propylene random copolymer of the present invention into a crystalline olefin polymer other than the other ethylene polymer, the impact resistance of a molded article made of the crystalline olefin polymer, particularly The low temperature impact resistance can be improved. Specific examples of the crystalline olefin polymer other than the ethylene polymer include polypropylene, poly-1-butene, poly-4-methyl-1-pentene, and the like, and a propylene / 1-butene copolymer. , 1-butene / ethylene copolymers, 1-butene / propylene copolymers, and the like, α-olefin (a ₁ ) such as propylene, 1-butene, 1-hexene and ethylene, propylene,
1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1
Α-olefins having 2 to 20 carbon atoms, such as eicosene, which are different from the α-olefins (a ₁ ).
Examples thereof include crystalline α-olefin copolymers containing olefin (a ₂ ). The intrinsic viscosity [η] of the crystalline olefin polymer measured in decalin at 135 ° C. is usually in the range of 0.5 to 10 dl / g, and the crystallinity is 5% or more, preferably 20% or more.

When the propylene random copolymer of the present invention is blended with the crystalline α-olefin polymer, the compounding ratio is usually 1 to 100 parts by weight with respect to 100 parts by weight of the crystalline α-olefin polymer. And preferably in the range of 2 to 60 parts by weight. In the crystalline α-olefin polymer composition, if necessary, an antioxidant, a hydrochloric acid absorbent, an anticoagulant, a heat stabilizer, an ultraviolet absorber, a lubricant, a weather stabilizer, an antistatic agent, a nucleating agent, Various additives such as pigments and fillers can also be blended. The crystalline α-olefin polymer composition can be prepared by a conventionally known method.

Furthermore, by blending the propylene random copolymer of the present invention with various engineering resins, the physical properties of the engineering resin, such as impact resistance and sliding characteristics, can be improved. When the engineering resin is an engineering resin having a polar group, in order to improve the affinity or dispersibility to the engineering resin, the propylene random copolymer of the present invention, maleic acid, citraconic acid, Uses a modified propylene random copolymer graft-copolymerized with unsaturated carboxylic acids such as itaconic acid, maleic anhydride, citraconic anhydride, itaconic anhydride, dimethyl maleate, dimethyl citraconate and dimethyl itaconic acid Preferably. The graft ratio of the unsaturated dicarboxylic acid or its derivative component is usually in the range of 0.02 to 50 parts by weight with respect to 100 parts by weight of the propylene random copolymer. Specifically as the engineering resin, polyethylene terephthalate, polyester such as polybutylene terephthalate, hexamethylene adipamide, octamethylene adipamide, decamethylene adipamide, dodecamethylene adipamide, polycaprolactone,
Examples thereof include polyamides, polyarylene oxides such as polyphenylene oxide, polyacetames, ABS, AES, polycarbonates, and the like. The blending ratio of the propylene random copolymer or a modified product thereof is usually 0.2 to 100 parts by weight of the engineering resin.
It is in the range of 20 parts by weight. The engineering resin composition may include an antioxidant, a hydrochloric acid absorbent, an anticoagulant, a heat resistance stabilizer, an ultraviolet absorber, a lubricant, a weather resistance stabilizer, an antistatic agent, a nucleating agent, a pigment, a filler, etc., if necessary. Various additives can be blended. The engineering resin composition can also be prepared according to a conventionally known method.

The propylene random copolymer of the present invention can improve the physical properties of the rubber-like polymer such as chemical resistance and rigidity by blending various rubber-like polymers.
Specific examples of the rubber-like polymer include ethylene.
Examples thereof include propylene / non-conjugated diene copolymer, ethylene / 1-butene / non-conjugated diene copolymer, polybutadiene rubber, polyisoprene rubber, styrene / butadiene / styrene block copolymer and the like. The mixing ratio of the propylene random copolymer is the rubber-like polymer.
It is usually in the range of 1 to 100 parts by weight with respect to 100 parts by weight. The rubber-like polymer composition may optionally contain a filler, a cross-linking agent,
Various fillers such as a crosslinking aid, a pigment and a stabilizer can be blended. The rubbery polymer composition can be prepared according to a conventionally known method.

〔Example〕

Next, the method of the present invention will be specifically described with reference to examples.

Example-1 Preparation of ethylene bis (indenyl) zirconium dichloride (a) A 400 ml glass flask thoroughly purged with nitrogen was charged with 100 ml of tetrahydrofuran and cooled to -195 ° C. 8.2 g of zirconium tetrachloride was added thereto, and the temperature was gradually raised to room temperature to form a suspension. Subsequently, a lithium salt of bis (indenyl) ethane dissolved in 80 ml of tetrahydrofuran (ref. J. Organometal. Chem., 232 , 233 (198
2)) 35 mmol was added and the mixture was stirred at 20 ° C. for 2 hours. Then, hydrogen chloride gas was blown in for a few seconds, and immediately tetrahydrofuran and hydrogen chloride gas were removed under reduced pressure to obtain a solid. The solid was washed with 10% hydrochloric acid, water, ethanol and diethyl ether and dried under reduced pressure. 4.9 g of ethylenebis (indenyl) zirconium dichloride was obtained.

Preparation of ethylenebis (4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride (b) 4.5 g of ethylenebis (indenyl) zirconium dichloride synthesized above in the stainless steel autoclave of 1), platinum (IV) oxide 300 mg And dichloromethane 100
After charging ml, hydrogen was introduced to make 100 kg / cm ² G. The hydrogenation reaction was carried out at 20 ° C for 1 hour. After the reaction mixture was transferred into dichloromethane 1 and platinum (IV) oxide was separated and dichloromethane was removed, a solid was obtained. The solid was washed with petroleum ether and recrystallized with hot toluene to obtain 2.9 g of ethylenebis (4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride.

(C) Preparation of Methylaluminoxane MgCl 2 was added to a 2 L glass flask sufficiently purged with argon.
Was charged with ₂ · 6H ₂ O70g and toluene 625 ml, was added dropwise trimethylaluminum 1.25 mole diluted with cooled toluene 625 ml to 0 ° C.. After completion of the dropping, the temperature was raised to 60 ° C. and the reaction was performed at that temperature for 96 hours. After the reaction, solid-liquid separation was performed by filtration, and the separated liquid was used as an aluminoxane solution for polymerization. Toluene was partially removed from the separated liquid to prepare a sample for molecular weight measurement. The molecular weight determined by freezing point depression in benzene is 1570.
And the m value of the aluminoxane was 25.

(D) Polymerization 20 liters of purified toluene and 10 kg (238 moles) of propylene were placed in a stainless steel autoclave with an internal volume of 100 liters that had been sufficiently replaced with nitrogen.
Then, 2.9 kg (104 mol) of ethylene was charged at -15 ° C, and subsequently methylaluminoxane corresponding to 0.4 g atom in terms of aluminum atom, and 0 in terms of zirconium atom.
Ethylenebis (4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride corresponding to 4 milligram atoms was charged, and polymerization was carried out at -15 ° C for 5 hours. Polymerization was stopped by adding a small amount of methanol and unreacted propylene and ethylene were purged. Furthermore, after removing the catalyst residue with warm water containing a small amount of hydrochloric acid and methanol,
The polymer was deposited by pouring the polymerization liquid into a large amount of methanol. After further washing the precipitated polymer with methanol, 10
It was dried under reduced pressure overnight at 0 ° C. In this way, 1230 g of copolymer was obtained. The propylene content of the copolymer measured by ¹³ C-NMR was 58.2 mol%, and the intrinsic viscosity [η] was 2.80.
dl / g, w / n calculated from GPC is 2.42, DSC melting point is 64 ° C,
Crystallinity 0.9% which have been conducted under the measured X-ray diffraction method, the boiling methyl acetate-soluble content of 0.04 wt%, 0.22 wt% acetone · n-decane mixed solvent-soluble content, micro determined from ¹³ C-NMR The isotacticity was 0.95 and the B value was 1.26. The stress at break is 10 kg / cm ² , and the elongation at break is 1100%.
JIS A hardness was 45, and haze was 9%. In addition, the ¹³ C-NMR spectrum of the obtained copolymer shows α
No signals based on β and βγ were observed.

Examples 2 to 4 Polymerization was carried out in the same manner as in Example 1 except that the proportions of propylene and ethylene supplied in the polymerization of Example 1 and the polymerization temperature were changed. In addition, no signals based on αβ and βγ were observed in the ¹³ C-NMR spectrum of the obtained copolymer. The results are shown in Table 1.

Example 5 Ethylenebis (indenyl) zirconium dichloride synthesized in the same manner as in Example 1 was converted into zirconium atom.
Polymerization was performed in the same manner as in Example 1 except that 0.45 mg of atom was used and the polymerization time was 10 hours. In addition, no signals based on αβ and βγ were observed in the ¹³ C-NMR spectrum of the obtained copolymer. The results are shown in Table 1.

Comparative Example 1 Preparation of Titanium Catalyst Commercially available anhydrous magnesium chloride 20 g, ethyl benzoate 4.5 ml
In a nitrogen atmosphere, 3.0 ml of methyl polysiloxane was placed in a stainless steel pot with an internal volume of 800 ml containing 2.8 kg of stainless steel balls (diameter 15 mm) and crushed and contacted for 12 hours at an impact acceleration of 7 G. Next, 10 g of the obtained solid treated product was suspended in 100 ml of titanium tetrachloride and reacted at 80 ° C. for 2 hours. After the reaction was completed, it was separated and the solid part obtained was thoroughly washed with hexane. Thus, a titanium catalyst containing 2.0% by weight of titanium and 6.5% by weight of ethyl benzoate was obtained.

Polymerization 30 liters of purified decane were charged into a stainless steel autoclave with an internal volume of 100 liters that had been sufficiently replaced with nitrogen, and a propylene-ethylene mixed gas (propylene / ethylene molar ratio of 75/25) was added.
19 kg / hr and hydrogen at a flow rate of 80 l / hr, and after elevating to 60 ° C., triethylaluminum is 25 mg atom in terms of aluminum atom, methyl p-toluate is 8.5 mmol, and the titanium catalyst is 0.5 mg in terms of titanium atom. Polymerization was started by charging the atom, and the polymerization was carried out for 15 minutes.
The subsequent operation was performed in the same manner as in Example 1. The results are shown in Table 1.
Shown in.

Application Example 1 Propylene-based random copolymer obtained in Example 1 [PE
R] and crystalline polypropylene (MFR (230 ℃) 24.7g / 10mi
n, isotactic index 98%) [PP] and 20 /
After melt-mixing in a ratio of 80, this composition was molded at a molding temperature of 185
Injection molding was carried out at a mold temperature of 60 ° C to obtain a specimene. The tensile properties, bending properties, low temperature impact properties and brittle temperature of the molded product were evaluated according to the following methods.

(1) Tensile property ASTM D638 (2) Bending property ASTM D790 (3) Low temperature impact property ASTM D256 (with notch) (4) Brittle temperature ASTM D746 Table 2 shows the evaluation results.

Application Example 2 The procedure of Application Example 1 was repeated except that the blend ratio of [PP] and [PER] was changed to 70/30. The results are shown in Table 2.

Application 3 MFR (230 ℃) 23.6g / as crystalline polypropylene [PP]
The procedure was the same as in Application Example 1 except that a 96-minute 10 min isotactic index was used. The results are shown in Table 2.

Comparative Application Examples 1 and 2 The crystalline polypropylene used in Application Examples 1 to 3 was evaluated in the same manner as in Application Example 1. The results are shown in Table 2.

Comparative Application Example 3 The procedure of Application Example 1 was repeated except that the propylene-based random copolymer obtained in Comparative Example 1 was used. The results are shown in Table 2.

[Effects of the Invention] As described above, the propylene-based random copolymer of the present invention has a narrow molecular weight distribution and composition distribution, is excellent in transparency, is non-tacky on the surface, and has low crystallinity.

The above copolymer of the present invention is incorporated into a thermoplastic resin to improve various properties of the resin.

Claims (2)

[Claims] 1. A propylene random copolymer comprising an ethylene component and a propylene component, wherein (A) the composition is such that the ethylene component is in the range of 10 to 70 mol% and the propylene component is in the range of 30 to 90 mol%. , (B) the intrinsic viscosity [η] measured in decalin at 135 ° C
It is in the range of 0.5 to 6 dl / g. (C) Gel permeation chromitography (GP
The molecular weight distribution (w / n) measured in C) is in the range of 3 or less, and (D) the melting point [Tm] measured by a differential scanning calorimeter is 40.
To 140 ° C, (E) the crystallinity measured by X-ray diffraction is in the range of 0.5 to 60%, and (F) the soluble amount [W ₁ % by weight] in boiling methyl acetate is 1 (G) Soluble amount [W ₂ wt%] in acetone / n-decane mixed solvent (volume ratio 1/1) at 10 ° C is 4 x [η] ^-1.2 wt% or less. The (H) propylene triad chain has a microisotacticity of 0.8 or more, and (I) in the ¹³ C-NMR spectrum of the copolymer, two adjacent two in the main chain of the copolymer No signals of αβ and βγ based on a methylene chain between the tertiary carbon atoms of (J) [In the formula, P _O represents the content mole fraction of the propylene component in the copolymer, P _E represents the content mole fraction of the ethylene component, P _E
OE represents the mole fraction of propylene / ethylene chains in the entire dyad chain], and the B value represented by the general formula (II) is within the range of 1.00 ≦ B ≦ 2 [II]. Polymer. 2. A propylene random copolymer comprising an ethylene component and a propylene component, wherein (A) the composition is such that the ethylene component is in the range of 10 to 70 mol% and the propylene component is in the range of 30 to 90 mol%. (B) The intrinsic viscosity [η] measured at 135 ° C in decalin is
It is in the range of 0.5 to 6 dl / g. (C) Gel permeation chromitography (GP
The molecular weight distribution (w / n) measured in C) is in the range of 3 or less, and (D) the melting point [Tm] measured by a differential scanning calorimeter is 40.
(E) the crystallinity measured by X-ray diffraction is in the range of 0.5 to 60%, and (F) the soluble amount in boiling methyl acetate [W ₁ % by weight] is 1 (G) Soluble amount [W ₂ wt%] in acetone / n-decane mixed solvent (volume ratio 1/1) at 10 ° C is 4 x [η] ^-1.2 wt% or less. The (H) propylene triad chain has a microisotacticity of 0.8 or more, and (I) in the ¹³ C-NMR spectrum of the copolymer, two adjacent two in the main chain of the copolymer No signals of αβ and βγ based on a methylene chain between the tertiary carbon atoms of (J) [In the formula, P _O represents the content mole fraction of the propylene component in the copolymer, P _E represents the content mole fraction of the ethylene component, P _E
OE represents the mole fraction of propylene / ethylene chains in the entire dyad chain], and the B value represented by the general formula (II) is within the range of 1.00 ≦ B ≦ 2 [II]. An impact resistance improver for a thermoplastic resin comprising a polymer.