JPH0699530B2 - Method for producing rubber-modified thermoplastic resin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION a. Field of Industrial Application The present invention relates to an ethylene-α-olefin copolymer having 4 to 8 carbon atoms or a copolymer of ethylene and α-olefin having 4 to 8 carbon atoms and a non-conjugated diene. A polymer, which is obtained by graft-copolymerizing a vinyl monomer such as styrene or acrylonitrile in the presence of a copolymer mainly containing butene-1 as an α-olefin component, chemical resistance and weather resistance , A method for producing a rubber-modified thermoplastic resin which is excellent in impact resistance, molding appearance and low temperature characteristics.

b. Conventional Technology Conventionally, as an ethylene-α-olefin copolymer, an ethylene-propylene copolymer (EPM) and / or an ethylene-propylene-non-conjugated diene copolymer (EPDM) was used as a rubber component. Graft copolymers (AES resin) with styrene, acrylonitrile, etc., are more UV-rays than ABS resins that use diene rubber as the rubber component.
It is known that it has a large resistance to oxygen and ozone, and that it has remarkably good weather resistance.

However, conventional AES resins have poor molding appearance and are unsatisfactory in low-temperature properties, so various improvements have been made.However, ethylene-α-olefin copolymer or ethylene-α-olefin as a rubber component has been made. -Α in non-conjugated dienes
-Since propylene is used as the olefin, it has been considered difficult to improve these physical properties more than conventional ones. In addition, AES, which has better impact resistance than conventional ones
Resin is always desired, and to improve impact resistance,
It is necessary to increase the amount of the rubber component or the molecular weight of the hard resin component, but in each case, the rigidity of the resin is lowered and the workability is lowered, and the impact resistance and the rigidity and the workability are simultaneously improved. Was difficult.

On the other hand, in Japanese Examined Patent Publication No. 60-22016, as an example,
A thermoplastic elastomer composition obtained by mixing an ethylene-propylene copolymer rubber with an ethylene-butene copolymer as a resinous polyolefin and grafting a styrene compound, shows that the tensile properties, processability and hardness are good. ing. However, the composition is characterized in that it is a thermoplastic elastomer and is grafted with one kind of styrene compound, and is significantly inferior in chemical resistance to conventional AES resins.

c. Problems to be Solved by the Invention As a result of intensive studies to solve the above problems, ethylene-α having a specific composition, molecular weight distribution and DSC melting point was found.
-Olefin copolymer or ethylene-α-olefin-non-conjugated diene copolymer (wherein α-olefin has 4 to 8 carbon atoms) is used as a rubber component to provide a good balance between impact resistance and rigidity. It was also found that a novel rubber-modified thermoplastic resin composition excellent in molding appearance and low temperature characteristics can be obtained.

d. Means for Solving Problems That is, the present invention comprises ethylene and an α-olefin having 4 to 8 carbon atoms, and (a) the weight ratio of ethylene / α-olefin is 95/5 to 60/4.
And (b) the ratio Mw / Mn of weight average molecular weight to number average molecular weight measured by GPC (Gel Permeation Chromatograph) is 2 to 5, (c) Differential scanning calorimeter (DSC) at 40 to 130 ° C. In the presence of ethylene-α-olefin copolymer rubber and / or ethylene-α-olefin-non-conjugated diene copolymer rubber having a melting point (DSC melting point) measured, an aromatic vinyl compound and other copolymerizable with it The present invention provides a method for producing a rubber-modified thermoplastic resin obtained by copolymerizing the above monomer.

That is, conventionally, ethylene-α-olefin copolymer or ethylene-α-olefin-α-olefin of non-conjugated diene copolymer as a rubber component that has been used in AES resin, from propylene satisfy the conditions shown above. A
-By changing to olefin, the crystallinity and the randomness of the texture in the Goss component can be well balanced. Therefore, the rubber-modified thermoplastic resin obtained by the production method of the present invention using this rubber component is
We found that compared with AES resin, it can have sufficient impact resistance even if the amount of rubber component is low, and that increasing the amount of rubber component can improve impact resistance without lowering rigidity. It was Further, since the ethylene-α-olefin copolymer in the present invention has a refractive index closer to that of a hard resin component than that of a conventional ethylene-propylene copolymer, the resin molding appearance could be improved.
Furthermore, since the copolymer has a glass transition temperature (Tg) lower than that of the conventional ethylene-propylene copolymer, the low temperature characteristics of the resin could be improved.

The ethylene-α-olefin copolymer and the ethylene-α-olefin-non-conjugated diene copolymer used in the present invention are composed of ethylene and an α-olefin having 4 to 8 carbon atoms and have a weight ratio of ethylene / α-olefin. But from 95/5
60/40, preferably 95/5 to 70/30, more preferably 93/7
It is in the range of ~ 80/20. If the elenium content exceeds 95% by weight, the random properties of the copolymer will be significantly impaired.
The impact resistance of the obtained rubber-modified thermoplastic resin is reduced.
On the other hand, if it is less than 60% by weight, the crystallinity in the copolymer is remarkably lost, so that the rigidity of the obtained rubber-modified thermoplastic resin is remarkably lowered.

Furthermore, regarding the copolymer using a non-conjugated diene,
The unsaturated group amount is preferably 4 to 40 in terms of iodine value. If the amount of unsaturated groups exceeds 40 in terms of iodine value, a three-dimensional gel will be generated in the copolymer, the reactivity with vinyl compounds will decrease, and the randomness of the copolymer will be impaired. The impact resistance of is not sufficient. Non-conjugated dienes used include alkenyl norbornenes,
There are cyclic dienes and aliphatic dienes, preferably 5-
5-ethylidene-2 with ethylidene-2-norbornene
-By using norbornene, the impact resistance is further improved.

Further, in the rubber-modified thermoplastic resin composition obtained by the production method of the present invention, compared with the conventional ethylene-propylene copolymer and / or ethylene-propylene-non-conjugated diene copolymer as an AES resin using as a rubber component. In order to have the above-mentioned improved properties, the following conditions must be satisfied in addition to the above.

The ethylene-α-olefin copolymer used in the present invention and the α-olefin component unit of the ethylene-α-olefin-non-conjugated diene copolymer include α-olefins having 4 to 8 carbon atoms, particularly butene-1. preferable. A mixed component of butene-1 and an α-olefin other than butene-1 may be used. Specifically, propylene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-
Examples include heptene and 1-octene. In this case, the α-olefin content other than butene-1 is preferably 0 to 10% by weight based on the total α-olefin component.

GPC (Gel Permeation Chromatograph) of the above copolymer
The molecular weight distribution (Mw / Mn) represented by the ratio of the weight average molecular weight and the number average molecular weight measured by
Must be in the range 2.5-3.5. A copolymer having an Mw / Mn of less than 2 is difficult to produce, and a copolymer having an Mw / Mn of more than 5 causes the balance of the randomness and the crystallinity of the copolymer of the present invention to collapse, resulting in a rigidity higher than that of a conventional AES resin. A resin having a good balance of impact resistance cannot be obtained.

Furthermore, the melting point measured by a differential scanning calorimeter (hereinafter,
DSC melting point) is 40 ~ 130 ℃, preferably 40 ~ 90 ℃,
More preferably, it is in the range of 50 to 80 ° C. This DSC melting point is a measure showing the balance between the randomness and crystallinity of the copolymer, and when the DSC melting point is less than 40 ° C., the crystallinity in the copolymer is extremely low, so the resin composition of the present invention Rigidity is significantly reduced. When the DSC melting point exceeds 130 ° C,
Since the copolymer itself has a resinous property, the impact resistance of the resin composition cannot be sufficiently improved.

If there are two or more DSC melting points, the low temperature side DSC
In addition to the melting point satisfying the above conditions, the difference between the low temperature side DSC melting point and the high temperature side DSC melting point is preferably 20 ° C. or higher, more preferably 30 ° C. or higher. When the difference in DSC melting point is 20 ° C. or less, the crystallinity of the copolymer itself is high and the impact resistance is lowered.

Further, the ethylene-α-olefin copolymer rubber and / or the ethylene-α-olefin-non-conjugated diene copolymer is obtained by a differential scanning calorimeter, and is a total crystal of a heat of fusion of crystals (Hh) at a temperature of 110 ° C. or higher. The ratio Hh / Ht to the heat of fusion (Ht) is preferably in the range of 0 ≦ Hh / Ht ≦ 0.15, more preferably 0 ≦ Hh / Ht ≦ 0.1.
When Hh / Ht> 0.15, regardless of the presence or absence of the DSC melting point on the high temperature side, the crystallinity of the copolymer itself is high, and sufficient impact resistance cannot be obtained.

The relationship between the DSC melting point and the α-olefin content preferably satisfies the following formula: 95 ≦ [DSC melting point (° C.)] + 3.15 × [C ₄ content (wt%)] ≦ 140. This is a scale showing the chain distribution of the copolymer, and a copolymer not satisfying this condition is
It is difficult to manufacture, or there is a chain distribution, and it is difficult to obtain the molding appearance aimed at by the present invention.

As the ethylene-α-olefin copolymer, for example, a combination of a vanadium compound and an organic aluminum compound is used as a polymerization catalyst, and ethylene and a carbon number of 4 to 8 are used.
It can be produced by copolymerizing the α-olefin. At this time, an activity improver can be added if necessary.

Examples of the vanadium compound include vanadium oxyhalide compounds, vanadium tetrachloride, alkyl vanadate, vanadium oxychloride and alcohol reaction mixture, electron donors other than vanadium oxychloride and alcohol (amines, ketones, ethers, etc.) And a reaction mixture with Preferably, vanadium oxychloride, vanadium tetrachloride, alkyl vanadate (ethyl vanadate, n-propyl vanadate, isopropyl vanadate, n-butyl vanadate, sec-butyl vanadate, 2-ethylhexyl vanadate, etc.), oxy Reaction mixture of vanadium chloride and alcohol (alcohol: ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, 2-ethylhexyl alcohol, etc.), vanadium oxychloride (V The composition ratio of the reaction mixture of (abbreviated as) and alcohol (abbreviated as R—OH) is ROH / V = 1/1 to 3/1 (molar ratio).

The organoaluminum compound has the general formula RnAlX _3- n
A halogenated organoaluminum compound represented by (R: alkyl residue, X: halogen). As a concrete example,
It is possible to use ethylaluminum dichloride, diethylaluminum chloride, ethylsesquialuminum chloride, isobutylsesquialuminum chloride, or a mixture of two or more kinds thereof. Ethyl sesquialuminum chloride is preferably used.

The composition ratio of the vanadium compound and the organoaluminum compound in the above polymerization catalyst is Al / V = 10/1 to 200/1 (molar ratio), preferably 10/1 to 150/1 (molar ratio). The ethylene-α-olefin copolymer in the present invention can be produced using a polymerization catalyst having a wide composition range of Al / V (molar ratio), but when Al / V <(molar ratio), The molecular weight distribution (indicated by Mw / Mn in GPC measurement) becomes broad, and the surface stickiness of the molded product deteriorates. Further, since the catalytic activity is lowered, it is necessary to use a large amount of vanadium compound, and a large amount of vanadium metal oxide remains in the copolymer, which causes the hue of the final product to pass through. Further, in the case of Al / V> 200 (molar ratio), the reduction of the vanadium compound proceeds too much, so that the polymerization activity is reduced and the copolymerizability of the α-olefin is also reduced. No copolymer is obtained.

Furthermore, an activity improver can be added if necessary,
Examples of the activity improver include polyhalogen compounds, specifically, trichloroacetic acid ester, 2,3,4,4-tetrachlorobutenoic acid ester and the like. Besides, electron donors such as alcohols, ketones and amines may be added in advance or simultaneously with the vanadium compound or the aluminum compound.

As the polymerization solvent used in the polymerization reaction, a hydrocarbon compound having 3 to 10 carbon atoms and / or a halogenated hydrocarbon compound having 1 to 5 carbon atoms is used. Specifically, propane, butane, pentane, hexane, heptane, octane, decane, propylene, 1-butene, hexene, methyl chloride,
It is ethyl chloride, methylene chloride, ethylene chloride, etc., and preferably n-hexane or n-heptane is used.

The polymerization temperature may be in the range of -50 ° C to 120 ° C, but is preferably in the range of -20 ° C to 40 ° C. When the polymerization temperature is lower than -50 ° C, a large amount of energy is required for cooling the reaction system, which is economically disadvantageous. On the other hand, the polymerization temperature is 120 ℃
When it is higher, the copolymerization in the present invention cannot be obtained because the polymerization activity is lowered and the copolymerizability of the α-olefin is lowered.

The polymerization form in the production of the ethylene-α-olefin copolymer does not essentially differ in either slurry polymerization or homogeneous solution polymerization, but slurry polymerization is preferable.
In homogeneous solution polymerization, the above copolymer has polyethylene crystals, and therefore the polymerization temperature must be raised considerably, which is not preferable.

Further, the reaction operation of the polymerization may be either batch type or continuous type. The reactor used is a single or a plurality of reactors in series,
Alternatively, they are connected in parallel, and the respective raw material olefins are introduced separately or in advance by mixing. The reaction temperature in the reaction system is maintained by an external cooling method or by utilizing latent heat of vaporization of the solvent monomer. The pressure is reduced (1.00mHg)
Therefore, it can be carried out under pressure (about 150 atm).

The molecular weight of the ethylene-α-olefin copolymer can be controlled only by appropriately selecting the above-mentioned catalyst composition ratio, catalyst amount, catalyst species, and polymerization temperature, but a molecular weight regulator such as hydrogen is further used. Can be done.

Separation of the produced copolymer from the reaction medium and unreacted monomers, deactivation of the used catalyst, removal of catalyst residue, drying and granulation of the copolymer, etc. are performed by general methods well known in the art. Can be done at.

Next, as the method for producing the rubber-modified thermoplastic resin of the present invention, various methods of radically polymerizing a vinyl monomer in the presence of a rubber component, for example, an emulsion polymerization method, a bulk polymerization method, a suspension polymerization method, a solution There are polymerization methods.

As the vinyl monomer, another copolymerizable monomer such as an aromatic vinyl compound and a vinyl cyanide compound is used in combination.

As the vinyl monomer, a rubber-modified thermoplastic resin composition obtained by using a monomer containing an aromatic vinyl compound and a vinyl cyanide compound as a main component is prepared by using a vinyl cyanide compound-free one. In comparison, it is preferable because it has excellent chemical resistance, and in coating the molded product, it has excellent properties such as uneven coating, cracks, and poor adhesion, and the like.

Aromatic vinyl compounds include styrene, α-methylstyrene, methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, fluorostyrene, p-tert-butylstyrene, ethylstyrene, vinylnaphthalene. Etc., and these are used by 1 type (s) or 2 or more types. A preferred aromatic vinyl compound is one containing 50% by weight or more of styrene.

Examples of vinyl cyanide compounds include acrylonitrile and methacrylonitrile, and these are used alone or in combination of two or more. Especially preferred is acrylonitrile.

Other copolymerizable monomers include methyl acrylate, ethylene acrylate, propylene acrylate,
Butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, dodecyl acrylate, octadecyl acrylate, phenyl acrylate, alkyl esters of acrylic acid such as benzyl acrylate, methyl methacrylate, ethyl methacrylate, propylene methacrylate, butyl methacrylate. , Amyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, phenyl methacrylate, methacrylic acid alkyl esters such as benzyl methacrylate, maleic anhydride, itaconic anhydride, anhydrous cytosine Examples thereof include unsaturated acid anhydrides such as conic acid, and unsaturated acids such as acrylic acid and methacrylic acid. These are one or more kinds within a range that does not hinder the rubber-modified thermoplastic resin intended by the present invention. Used in.

When an aromatic vinyl compound and a vinyl cyanide compound are used as the monomer component, the preferred ratio is aromatic vinyl compound / vinyl cyanide compound = 30/70 to 98/2, more preferably 60/40 to 95/5. (Weight ratio).

The rubber component content in the rubber-modified thermoplastic resin obtained by the production method of the present invention can be arbitrarily selected according to the purpose, but in order not to impair the impact resistance of the resin composition, it is 5 to 45% by weight. , Preferably in the range of 10-40% by weight.

Specific examples of preferable combinations of monomers other than the rubber component in the present invention are shown below.

Styrene-methylmethacrylate Styrene-acrylonitrile Styrene-acrylonitrile-methylmethacrylate By substituting α-methylstyrene for part or all of the above styrene, it is possible to impart heat resistance to the rubber-modified thermoplastic resin composition of the present invention. it can. Further, flame retardancy can be imparted by replacing part or all of styrene with halogenated styrene.

Further, when methyl methacrylate is used in combination with the above-mentioned monomer combination, the transparency of the rubber-modified thermoplastic resin composition is improved and the rubber-modified thermoplastic resin composition has excellent colorability.

The rubber-modified thermoplastic resin obtained by the production method of the present invention can be blended with other polymers depending on the purpose. For example, polyvinyl chloride, polyphenylene ether polycarbonate, polyethylene terephthalate,
Polybutylene terephthalate, polyacetal, polyamide, polyvinylidene fluoride, polystyrene, high-impact polystyrene, styrene-acrylonitrile copolymer, ABS resin, MBS resin, AES resin, AAS resin, styrene-methyl methacrylate copolymer, styrene-maleic anhydride Acid copolymer, conventional ABS resin, chlorinated polyethylene, E
PR, EPDM, 1,2-polybutadiene, etc. may be mentioned. These can be used alone or in combination of two or more.

Among these, the rubber-modified thermoplastic resin (A) of the present invention
And a resin composition (B) comprising an aromatic vinyl compound, a vinyl cyanide compound and, if necessary, a methacrylic acid ester compound, (A) / (B) = 20 / 80-80 / 20 (parts by weight ratio) It is particularly preferable to mix them in a ratio of (4). Here, by making the rubber-modified thermoplastic resin component (A) 20 parts by weight or more, the impact resistance of the resin composition is improved,
On the contrary, when the amount is 80 parts by weight or less, the rigidity of the resin composition can be improved. In this case, the aromatic vinyl compound and the vinyl cyanide compound in the resin (B) are
5/95 to 95/5 (% by weight) is preferable, and 20 is more preferable.
It is / 80-80 / 20. By satisfying the above range, sufficient rigidity can be obtained.

e. Examples Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples as long as the gist thereof is not exceeded.

The test methods and measurement methods for each physical property shown in the following examples and comparative examples are as follows.

<Iodine value (I ₂ -No)> By measuring the infrared absorption value of a standard sample whose iodine value has been obtained beforehand by the titration method, the relationship between the iodine value and the infrared absorption measurement value is shown based on this value. An infrared spectral calibration curve was prepared, and the iodine value was calculated from the infrared absorption measurement value of the copolymer obtained in the example using this calibration curve.

<Ethylene content> ethylene-α-olefin copolymer, ¹ H-NMR, ¹³ C-NM
Using R, determine the ethylene / α-olefin composition ratio,
A calibration curve indicating the relationship between this and the result of infrared analysis, which was obtained in advance, was created. The composition of the copolymer obtained in each example was determined based on this calibration curve.

<Mw / Mn> According to Takeuchi, Gel Permeation Chromatograph, published by Maruzen Co., Ltd., the following measurements were performed.

[1] A standard polystyrene having a known molecular weight (manufactured by Toyo Soda Co., Ltd., monodisperse polystyrene) is used to obtain a molecular weight M
And its GPC (Gel Permeation Chromatograph) count are measured to plot a correlation curve between the molecular weight M and EV (Elution Volume). The concentration at this time is 0.02% by weight. The standard polystyrene calibration curve is corrected to the EBM calibration curve by the universal method.

[2] The GPC pattern of the sample is taken by the GPC measurement method, and M is known from the above [1]. The sample preparation conditions and GPC measurement conditions at that time are as follows: -Sample preparation- (a) o-dichlorobenzene solvent as an antioxidant
Add 0.08% 2,6-di-tert-butyl-cresol,
Dissolve.

(B) A sample is collected in an Erlenmeyer flask together with an o-dichlorobenzene solvent so that the sample becomes 0.1%.

(C) The Erlenmeyer flask is heated to 120 ° C. and stirred for about 60 minutes to dissolve the sample.

(D) Apply the solution to GPC. In addition, it is automatically filtered with a 0.5 micron sintered filter in the GPC device.

-GPC measurement conditions- (a) Device: Waters 150C type (b) Column: Toyo Soda Co., Ltd. H type (c) Sample amount: 500μ (d) Temperature: 120 ° C (e) Flow rate: 1 ml / min (F) Total theoretical plate number of column: 1 * 10 2 * 10 (measured value with acetone) (Measurement method of melting point and crystal fusion calorific value with differential scanning calorimeter) Differential scanning calorimeter is 910 type Deupont Sca manufactured by Dupont
An nning Calolimeter (hereinafter abbreviated as DSC) was used, and a recorder used was a Model 990 Thermal Analyzer manufactured by Dupont. The sample amount was 10 ± 0.1 mg, and α-alumina was used as the reference substance. For the measurement, the sample and the standard substance are loaded into the DSC, heated to 180 ° C, and then cooled to -100 ° C at a constant rate of 10 ° C for 1 minute. Then, the endothermic change is measured at a constant temperature rising rate of 20 ° C. for 1 minute. Representative DSC obtained
The pattern is shown in FIG.

In FIG. 1, Tl and Th are referred to as DSC melting points, the high temperature side melting point of the ethylene copolymer of the present invention is Th, and the low temperature side melting point is Tl. These DSC melting points are temperatures at respective points. It is read from the coordinate axis.

(Calculation of Crystal Endotherm) The tangent line a of the low temperature side baselines A to B in FIG. Then, the tangent line b of the endothermic peaks B to C which is considered to be the Tg portion is obtained. Let P be the intersection of the tangents a and b, and draw a perpendicular line c from P. Then, h is calculated according to the following equation (1).

h (mm) = 2.25 x S (mg) (1) (however, h is the distance from the point P in the actual size of the DSC chart (mm), S is the sample amount (mg)) The distance along the perpendicular line c from the point P Draw a horizontal line d at the position of h. The intersection Q between the horizontal line d and the endothermic curve is determined.

A tangent line e from the intersection point Q to the high temperature side base lines D to E is drawn. A contact point R between the tangent line e and the baseline is obtained. Tangent e
And the shaded area surrounded by the endothermic curve is the heat of fusion of all crystals (H
equivalent to t). Subsequently, the endothermic portion was divided at the position of 110 ° C, and the endothermic portion at 110 ° C or higher was taken as the high temperature endotherm (Hh). The total crystal melting heat quantity (Ht) and the high temperature side crystal melting heat quantity (Hh) were calculated based on indium (standard sample for DSC manufactured by Dupont) for each area (hatched portion in FIG. 1).

<Izod impact strength> Measured according to ASTM D256.

Sample: Cross section 1/4 x 1/2 inch, with notch <Gloss> The reflectance at an incident angle of 45 ° was measured according to JIS Z8741.

<Measurement of Appearance> The appearance was visually judged according to the following criteria.

Judgment Good: No defective appearance of pearl-like color separation at all Defect: Obviously defective appearance of pearl-like color separation <Rockwell hardness> Measured according to ASTM D785.

<Graft ratio> The graft ratio is determined by extracting the soluble part of the graft polymer with acetone at room temperature and measuring the weight of the remaining acetone-insoluble part after drying, and measuring this weight and the rubber used in the production of the polymer. The weight difference of the quality polymer was calculated from the following formula as the weight of the monomer chemically bonded to the rubber polymer.

<MFR> Measured according to ASTM D1238 (190 ° C, load 2.16 kg).

A rubbery polymer was prepared by the following method.

<Rubber polymer No. 1> Copolymerization was carried out using a continuous polymerization device having an internal volume of 10.
In a polymerization vessel sufficiently replaced with N ₂ gas, ethyl sesquialuminum chloride 6.5 g / Hr, oxyvanadium trichloride 0.15 g / Hr, n-hexane 7.2 / Hr butene-1 615 g / H
It is continuously supplied at a flow rate of r and the temperature is maintained at 20 ° C.
Ethylene was continuously supplied at a flow rate of r and a pressure of 3.0 kgG / cm ² , and polymerization was carried out under the condition of a residence time of 1 Hr. The analysis and physical properties of the obtained copolymer are shown in Table 1.

<Rubber Copolymer No. 2, 3, 4> Polymerization was carried out in the same manner as in Rubber Copolymer No. 1 by further continuously supplying 5-ethylidene-2-norbornene (ENB) at 30 g / Hr. It was

<Rubber Copolymer No. 5 and 6> In the same manner as in Rubber Copolymer No. 1, the pressure is 1.5 to 8.0 kg.
Polymerization was carried out by continuously supplying ethylene while changing the range of G / cm ² .

<Rubber Copolymer No. 7> In the same manner as in Rubber Polymer No. 6, 5-ethylidene-2-norbornene (ENB) was further continuously supplied at 30 g / Hr for polymerization.

<Rubber Copolymer No. 8> In the same manner as in Rubber Copolymer No. 1, propylene was continuously supplied instead of butene-1, and polymerization was carried out.

<Rubber Copolymer No. 9> In the same manner as in Rubber Copolymer No. 8, 5-ethylidene-2-norbornene ENB) was further continuously supplied at 25 g / Hr for polymerization.

<Rubber Copolymer No. 10> In the same manner as in Rubber Copolymer No. 1, hexene-1 was continuously fed instead of butene-1 to carry out polymerization.

<Rubber Copolymer No. 11> Polymerization was performed in the same manner as in Rubber Copolymer No. 1 using diethyl aluminum chloride and titanium tetrachloride supported on magnesium chloride.

<Production of Rubber-Modified Thermoplastic Resin> Example 1 10 autoclave reactor was charged with 20 parts by weight of rubbery polymer (No. 1), 56 parts by weight of styrene, 24 parts by weight of acrylonitrile, 100 parts by weight of toluene, and the rubber was heated at 50 ° C. Was stirred until completely dissolved, and 0.3 part by weight of tert-dodecyl mercaptan and 0.5 part by weight of tert-butyl peroxybenzoate were added, and then a polymerization reaction was carried out at 100 ° C. for 10 hours. After desolvation and drying by a conventional method, 0.4 part by weight of 2,2-methylenebis (4-ethyl-6-tert-butylphenol) was added to pelletize through a 40 mmφ extruder (200 ° C), and then 50z injection molding machine ( The test product was molded at 230 ° C and the physical properties were measured.

Examples 2 to 5 and Comparative Examples 1 to 5 Polymers were obtained in the same manner as in Example 1 except that the type of rubbery polymer was changed (Comparative Example 6 was rubbery polymer No. 1).
Was used in the same manner as in Example 1 to carry out graft polymerization with styrene alone to obtain a polymer. ). The physical properties of the rubbery polymers and resins used in Examples and Comparative Examples are shown in Table 1.

From these results, by changing the α-olefin component from propylene to butene-1 or hexane-1,
It has been found that it is possible to obtain a resin composition that has a good balance between the rigidity and impact resistance of the resin, and that has improved molding appearance and low temperature properties.

Further, by using a non-conjugated diene-containing ethylene-butene-1 copolymer or ethylene-hexene-1 copolymer, the hardness and MFR of the resin are slightly lowered, but the impact resistance could be further improved. .

However, elastomers (EBM, EBDM) that do not satisfy the conditions specified in the present invention, regardless of the presence or absence of non-conjugated dienes,
It was found that no remarkable improvement in physical properties could be obtained compared to conventional AES resins.

Example 6 In the same manner as in Example 1, except that the rubbery polymer No. 1 was used, α-methylstyrene was used in place of styrene for graft polymerization to obtain a copolymer. The results are shown in Table-1.

Even when α-methylstyrene is used, the molding appearance and low temperature properties are improved.

Comparative Example 7 In the same manner as in Example 1, the rubbery polymer No. 11 was used for graft polymerization.

As a result, the composition obtained in Comparative Example 7 has high crystallinity and poor impact resistance as shown in Table 1.

Example 7 Resin composition (A) obtained in Example 1 and styrene-acrylonitrile copolymer resin (containing 60% by weight of styrene)
(B) and (A) :( B) = 60: 40 (parts by weight) were mixed to obtain a resin composition. The characteristics of this resin composition were measured, and the results are shown in Table 1.

Example 8 A resin composition was prepared in the same manner as in Example 7 except that a styrene-acrylonitrile-methylmethacrylate copolymer resin (21% by weight of styrene, 29% by weight of acrylonitrile, 50% by weight of methylmethacrylate) was used as the resin (B). Obtained. The characteristics of this resin composition were measured, and the results are shown in Table-1.
It was shown to.

Comparative Example 8 In the same manner as in Example 7, a resin composition was obtained by mixing (A) :( B) = 10: 90. The results are shown in Table-1.

As a result, the obtained resin composition had too many resin components and sufficient impact resistance could not be obtained.

f. Effects of the Invention The rubber-modified thermoplastic resin obtained by the production method of the present invention has a good balance of rigidity and impact resistance, and also has a good molding appearance and low-temperature characteristics, and thus is suitable for use in automobile exterior parts and the like. can do.

[Brief description of drawings]

FIG. 1 is a diagram showing an example of measurement of a melting point, a total crystal melting heat quantity and a high temperature side crystal melting heat quantity of a rubber component in the present invention by a differential scanning calorimeter.

Claims (5)

[Claims] 1. A composition comprising ethylene and an α-olefin having 4 to 8 carbon atoms, and (a) the weight ratio of ethylene / α-olefin is 95/5 to 60/4.
And (b) the ratio Mw / Mn of weight average molecular weight to number average molecular weight measured by GPC (Gel Permeation Chromatograph) is 2 to 5, (c) Differential scanning calorimeter (DSC) at 40 to 130 ° C. A melting point (DSC melting point) by measurement exists. Aromatic vinyl compound and other copolymerizable with ethylene-α-olefin copolymer rubber and / or ethylene-α-olefin-non-conjugated diene copolymer rubber A method for producing a rubber-modified thermoplastic resin, which is obtained by copolymerizing the above monomer. 2. A process for producing a rubber-modified thermoplastic resin according to claim 1, wherein the copolymerizable monomer contains an aromatic vinyl compound and a vinyl cyanide compound as main components. Method. 3. The ethylene-α- wherein the ratio of the heat of fusion of crystal (Hh) to the total heat of fusion of crystal (Ht) at a temperature of 110 ° C. or higher determined by a differential scanning calorimeter is 0 ≦ Hh / Ht ≦ 0.15. An olefin copolymer rubber and / or ethylene-α-olefin-non-conjugated diene copolymer rubber is used, and the method for producing a rubber-modified thermoplastic resin according to claim (1). 4. An ethylene-α-olefin-non-conjugated diene copolymer rubber, wherein the non-conjugated diene is 5-ethylidene-
Ethylene-α-olefin using 2-norbornene
The method for producing a rubber-modified thermoplastic resin according to claim (1), which is a non-conjugated diene copolymer rubber. 5. A copolymer rubber having a melting point measured by a differential scanning calorimeter at 40 to 90 ° C. is used.
A method for producing the rubber-modified thermoplastic resin according to the item.