JPH0717755B2 - Method for producing masterbatch composition for modifying thermoplastic resin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of use] The present invention relates to a method for producing a masterbatch composition for modifying a thermoplastic resin which is less sticky and has good workability.

More specifically, it relates to a method for producing a masterbatch composition consisting of an ethylene / α-olefin copolymer having a specific property and polybutene obtained by copolymerizing ethylene and α-olefin, and in particular, less sticky, The present invention provides a masterbatch composition for modifying a thermoplastic resin, which does not cause bleeding even during long-term storage, has no defects such as blocking and bridging, and has good workability.

[Conventional technology]

Various molded articles, sheets, films, etc. are manufactured by molding a thermoplastic resin by methods such as injection molding, extrusion molding, blow molding, and inflation molding. In general, such a thermoplastic resin is provided with various modifiers such as a liquid or solid powder in order to impart characteristics required for each application, such as a plasticizer, a filler, a dye,
Contains pigments, lubricants and antioxidants. These modifiers are used by blending them with a thermoplastic resin in advance and pelletizing them, or by preparing masterbatch pellets with a high content of the modifier in advance and dry blending with the base resin at the time of molding. It In particular, when the modifier is in a liquid state, a method in which master batch pellets are manufactured in advance and dry blended for use is widely adopted.

[Problems to be Solved by the Invention]

When polybutene is used as the modifier, it is necessary to produce masterbatch pellets having a high polybutene content. However, since polybutene has poor compatibility with other iriolefin resins, it has the following problems.

In other words, immediately after production or after a few days, polybutene bleeds on the surface of the pellet and stickiness increases, bridging occurs in the hopper during blocking of the pellets and dry blending, and a predetermined amount cannot be blended, or it is uneven. It is a problem that workability becomes extremely difficult, such as when it becomes.

As a result of intensive studies for solving these problems, the present inventors found that a masterbatch composition containing a specific ethylene / α-olefin copolymer and polybutene had a stickiness due to bleeding of polybutene. It has been found to have excellent physical properties such as a small amount, and ethylene / α in a specific temperature range below the maximum peak temperature (Tm) by the differential scanning calorimetry (DSC) of the above specific ethylene / α-olefin copolymer. It was found that the masterbatch composition can be produced by kneading and extruding an olefin copolymer and polybutene, and has already filed a patent application (Japanese Patent Application No. 63-23843).

[Means for Solving the Problems]

Further, as a result of further intensive studies by the present inventors, as a temperature at the time of kneading and extruding an ethylene / α-olefin copolymer having a specific property and polybutene, a temperature higher than Tm is specified. Within the temperature range (150 to 250 ° C), there is little stickiness due to bleeding of polybutene,
Workability such as blocking during dry blending and bridging in the hopper is remarkably improved, almost no bleeding phenomenon is observed even during long-term storage, and a masterbatch composition having excellent surface smoothness can be produced. Heading, arrived at the present invention.

That is, the present invention provides (1) (A) copolymerizing ethylene with an α-olefin having 3 to 12 carbon atoms in the presence of a catalyst composed of a solid component containing at least magnesium and titanium and an organoaluminum compound. The following (I) to (IV) (I) melt index 0.01 to 100 g / 10 min, (II) density 0.860 to 0.910 g / cm ³ , (III) maximum peak temperature by differential scanning calorimetry (DSC) Ethylene / α-olefin copolymer 30 to 100 ° C or higher, (IV) boiling n-hexane insoluble content of 10% by weight or more
Thermoplastic resin modification characterized by melt-kneading and extruding 95 parts by weight and (B) 5 to 70 parts by weight of polybutene having a number average molecular weight of 300 to 4000 at a temperature range of 150 to 250 ° C. The present invention relates to a method for producing a masterbatch composition for a car.

Hereinafter, the present invention will be described in detail.

(1) Ethylene / α-olefin copolymer (A) The ethylene-α-olefin copolymer used in the present invention is in the presence of a solid component containing at least magnesium and titanium and a catalyst composed of an organoaluminum compound, It is obtained by copolymerizing ethylene and α-olefin. As the α-olefin, those having 3 to 12 carbon atoms can be used. Specific examples include propylene, butene-1,4-methylpentene-1, hexene-1, octene-1, decene-1, dodecene-1. Of these, particularly preferred are propylene, butene-1, 4-methylpentene-1 and sexen-1 having 3 to 6 carbon atoms. Further, as a comonomer, dienes such as butadiene, 1, may be used without departing from the object of the present invention.
4-hexadiene and the like can be used together. The α-olefin content in the ethylene / α-olefin copolymer is preferably 5 to 40 mol%.

The catalyst system used is a combination of an organoaluminum compound with a solid catalyst component containing at least magnesium and titanium. Examples of the solid catalyst component include magnesium salts such as metal magnesium, magnesium hydroxide, magnesium oxide, magnesium carbonate and magnesium chloride, double salts containing a metal selected from silicon, aluminum and calcium, and a magnesium atom,
Double oxides, carbonates, chlorides, hydroxides, etc., as well as magnesium obtained by treating or reacting these inorganic solid compounds with oxygen-containing compounds, sulfur-containing compounds, aromatic hydrocarbons, halogen-containing substances, etc. An inorganic solid compound containing a titanium compound supported by a known method may be used.

Examples of the oxygen-containing compound include water, alcohol,
Examples thereof include organic oxygen-containing compounds such as phenols, ketones, aldehydes, carboxylic acids, esters, alkoxysilanes, polysiloxanes and acid amides, and inorganic oxygen-containing compounds such as metal alkoxides and metal oxychlorides. Examples of the sulfur-containing compound include organic sulfur-containing compounds such as thiol and thioether, and inorganic sulfur compounds such as sulfur dioxide, sulfur trioxide, and sulfur. Examples of aromatic hydrocarbons include various monocyclic and polycyclic aromatic hydrocarbon compounds such as benzene, toluene, xylene, anthracene, and phenanthrene. Examples of the halogen-containing substance include compounds such as chlorine, hydrogen chloride, metal chlorides and organic halides.

On the other hand, examples of the titanium compound supported on the organic solid compound containing magnesium include titanium halides, alkoxy halides, alkoxides and halogenated oxides. As the titanium compound, a tetravalent titanium compound and a trivalent titanium compound are preferable, and the tetravalent titanium compound is specifically represented by the general formula Ti (OR) _n X _4-x.
(Here, R represents an alkyl group having 1 to 20 carbon atoms, an aryl group or an aralkyl group, X represents a halogen atom, and n
Is an integer of 0 ≦ n ≦ 4), and specifically, titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, monomethoxytrichlorotitanium, dimethoxydichlorotitanium, trimethoxymonochlorotitanium, Tetramethoxytitanium, monoethoxytrichlorotitanium, diethoxydichlorotitanium, triethoxymonochlorotitanium, tetraethoxytitanium, monoisopropoxytrichlorotitanium, diisopropoxydichlorotitanium, triisopropoxymonochlorotitanium, tetraisopropoxytitanium, monobutoxytrichlorotitanium. , Dibutoxydichlorotitanium, monopentoxytrichlorotitanium, monophenoxytrichlorotitanium, diphenoxydichlorotitanium, triphenoxymonochlorotitanium, tetraphenoxytitanium, etc. Door can be. The trivalent titanium compound is preferably titanium trihalide such as titanium trichloride.

Among these titanium compounds, tetravalent titanium compounds are preferable, and titanium tetrachloride is particularly preferable.

As another example of the catalyst system, a catalyst system in which an organomagnesium compound such as a so-called Grignard compound and a reaction product of a titanium compound are used as a solid catalyst component and an organoaluminum compound is combined therewith can be exemplified. Examples of the organomagnesium compound include those represented by the general formula
Organomagnesium compounds such as RMgX, R ₂ Mg and RMg (OR) (wherein R represents an organic residue having 1 to 20 carbon atoms, X represents a halogen atom), ether complex thereof, and organomagnesium thereof It is possible to use those obtained by modifying the compound by further adding other organic metal compounds, for example, various compounds such as organic sodium, organic lithium, organic potassium, organic boron, organic calcium, and organic zinc.

As another example of the catalyst system, Si is used as a solid catalyst component.
O ₂ , using a solid substance obtained by contacting an inorganic oxide such as Al ₂ O ₃ and the above-mentioned solid catalyst component containing at least magnesium and titanium, it is possible to exemplify a combination of an organoaluminum compound it can. Examples of inorganic oxides include SiO ₂ , Al ₂ O ₃ , CaO, B ₂ O ₃ , SnO _{2 and the} like, and a complex oxide of these oxides can be used without any trouble. As a method for bringing these various inorganic oxides into contact with the solid catalyst component containing magnesium and titanium, known methods can be adopted. That is, in the presence or absence of an inert solvent,
The reaction may be carried out at a temperature of 20 to 400 ° C., preferably 50 to 300 ° C. for usually 5 minutes to 20 hours, a method of co-milling treatment, or a combination of these methods as appropriate.

In these catalyst systems, the titanium compound can be used as an adduct with the organic carboxylic acid ester, or the inorganic solid compound containing magnesium described above can be used after being contact-treated with the organic carboxylic acid ester. Further, there is no problem even if the organic aluminum compound is used as an adduct with the organic carboxylic acid ester or the organic silicon compound.

Specific examples of the organoaluminum compound to be combined with the above-mentioned solid catalyst component include general formulas R ₃ Al, R ₂ AlX, R
Organoaluminum compounds of AlX ₂ , R ₂ AlOR, RAl (OR) X and R ₃ Al ₂ X ₃ (wherein R represents an alkyl group having 1 to 20 carbon atoms, an aryl group or an aralkyl group, and X represents a halogen atom,
R may be the same or different) are preferable, and triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum chloride, diethylaluminum ethoxide, ethylaluminum sesquiglolide, and these A mixture etc. are mentioned.

The amount of the organoaluminum compound used is not particularly limited, but usually it can be used in an amount of 0.1 to 1000 mol times that of the titanium compound.

Further, by using the above catalyst system in the polymerization reaction after contacting it with the α-olefin, the polymerization activity can be greatly improved and the operation can be performed more stably than in the untreated case.

The polymerization reaction is carried out in the same manner as the polymerization reaction of olefins using a conventional Ziegler type catalyst. That is, all the reactions are carried out in the state of substantially eliminating oxygen, water, etc. in the gas phase or in the presence of an inert catalyst, or using the monomer itself as a solvent.

Olefin polymerization conditions are temperature 20 ~ 300 ℃, preferably 40
˜200 ° C., and the pressure is normal pressure to 70 kg / cm ² · G, preferably 2 kg / cm ² · G to 60 kg / cm ² · G. The molecular weight can be adjusted to some extent by changing the polymerization conditions such as the polymerization temperature and the molar ratio of the catalyst, but it is effectively performed by adding hydrogen to the polymerization system. of course,
It is possible to carry out a two-step or multi-step multi-step polymerization reaction with different polymerization conditions such as hydrogen concentration and polymerization concentration without any trouble.

By the above method, the ethylene / α-olefin copolymer (A) having the specific properties of the present invention is produced.

That is, the melt index (MI) of the ethylene / α-olefin copolymer (A) used in the present invention (JIS K6
760 compliant, 190 ℃, 2.16kg load) is 0.01-100g / 10mi
n, preferably 0.1 to 50 g / 10 min, more preferably 0.1 to 20
It is g / 10min. Density (according to JIS K6760) is 0.860 ~
It is 0.910 g / cm ³ , preferably 0.870 to 0.905 g / cm ³ , and more preferably 0.870 to 0.900 g / cm ³ . Maximum peak temperature (Tm) by differential scanning calorimetry (DSC) is 100 ° C or higher, preferably 110 ° C to 130 ° C, more preferably 115 ° C to 125 ° C.
Is. The boiling n-hexane insoluble content is 10% by weight or more, preferably 20 to 95% by weight, more preferably 20 to 90% by weight.

MI of ethylene / α-olefin copolymer (A) is 0.01 g /
If it is less than 10 min, the MI is too small and the fluidity deteriorates. If the MI exceeds 100 g / 10 min, the masterbatch composition becomes too soft and the surface becomes sticky.

Further, if the density is less than 0.860 g / cm ³ , the surface becomes sticky as well, and if the density exceeds 0.910 g / cm ³ , bleeding is likely to occur during long-term storage and the product tends to be unstable.

If the maximum peak temperature by DSC is less than 100 ° C, the masterbatch composition becomes sticky.

When the boiling n-hexane insoluble content is less than 10% by weight, the surface of the masterbatch composition is still sticky, which is not preferable.

Further, these ethylene-α-olefin copolymers (A) are preferably powdery or granular.

(2) Polybutene (B) The polybutene (B) used in the present invention can be selected from a wide range depending on its application. For example, butadiene can be obtained from the C ₄ fraction obtained during naphtha cracking, which is usually obtained industrially. A viscous polymer obtained by polymerizing the removed butane-butene fraction in the presence of an acidic catalyst such as aluminum chloride, silica-alumina or a cation exchange resin, particularly a Friedel-Crafts type catalyst, can be mentioned. These polybutenes usually have a number average molecular weight of 300 to 4000, preferably 400.
~ 3000 are used. If the number average molecular weight is less than this range, the flash point becomes low, which is not preferable, and when stored for a long period of time, there is a possibility of volatilization. If the number average molecular weight is larger than this range, the viscosity is too high and handling becomes difficult.

(3) Composition Ratio The composition ratio of the ethylene / α-olefin copolymer (A) and the polybutene (B) in the thermoplastic resin modifying masterbatch composition of the present invention is the ethylene / α-olefin (A). Is 30 to 95 parts by weight, preferably 40 to 90 parts by weight, more preferably 45 to 90 parts by weight, and polybutene (B) is 5 to 5 parts by weight.
70 parts by weight, preferably 10 to 60 parts by weight, more preferably
10 to 55 parts by weight.

If the polybutene content is less than 5 parts by weight, the amount of masterbatch used will be too large and the efficiency will be poor. If the polybutene content is more than 70 parts by weight, the resulting masterbatch composition becomes sticky, which is not preferable.

(4) Production of Masterbatch Composition for Modifying Thermoplastic Resin The masterbatch composition for modifying thermoplastic resin of the present invention comprises:
The above-mentioned ethylene / α-olefin copolymer and polybutene are uniformly melt-kneaded so as to have a predetermined composition ratio and then extruded. Any known technique can be used for these melt-kneading and extrusion. Typical examples include melt-kneading and extrusion methods using a single-screw extruder or a twin-screw extruder. At this time, the melt-kneading and extrusion temperatures are 150 to 250 ° C, preferably 160 to 230 ° C, more preferably 170 to 220 ° C. Melt kneading
When the extrusion temperature is higher than Tm and lower than 150 ° C., the moldability is poor, bleeding occurs on the surface of the obtained pellet, and stickiness increases, which is not preferable. Further, if the temperature exceeds 250 ° C., the ethylene / α-olefin copolymer and polybutene cause thermal deterioration, which is not preferable. The ethylene / α-olefin copolymer and polybutene may be mechanically mixed in advance before melt-kneading, or may be added simultaneously or separately during melt-kneading.

The composition in the present invention is usually used by pelletizing. The pelletizing step can also use any known technique. As a typical example, the cold cut method,
That is, a method in which the resin extruded under the above conditions is cooled by water cooling or air cooling, and then cut by a pelletizer, or a hot cut method is used.

In addition to conventionally known plasticizers, fillers, dyes, pigments, lubricants, antioxidants, etc., aliphatic, aromatic petroleum resins, alicyclic petroleum resins, terpene resins, rosins and derivatives thereof, etc. You may mix | blend a tackifying resin with these compositions beforehand.

Since the masterbatch composition for modifying a thermoplastic resin obtained by the above-mentioned production method of the present invention has the above-mentioned excellent characteristics, its application range is extremely wide. Examples of applications of the masterbatch composition of the present invention include (a) various packaging films (wrap films, stretch films, agricultural films) (b) various sheets (c) coating materials (d) sound insulation materials , Damping materials, sealing materials, waterproof materials (e) Footwear (f) Hoses, packing materials, and other thermoplastic resin modifiers used in various fields.

〔The invention's effect〕

The masterbatch composition for modifying a thermoplastic resin obtained in the present invention has the following characteristics.

(A) When the composition of the present invention is pelletized, there is little stickiness on the pellet surface, so there is less blocking between pellets, and good uniform dispersibility during dry blending.
Bridging in the hopper can be prevented and a stable amount can be supplied.

(B) Since the polybutene content as a modifier can be increased, the efficiency of the masterbatch can be increased.

(C) The surface smoothness of the pellet is good.

〔Example〕

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

Measuring method of physical properties: (1) Differential scanning calorimetry (DSC) A film of 100 μm thick that was hot press molded was used as a sample, and 1
After raising the temperature to 70 ℃ and holding it at that temperature for 15 minutes, the rate of temperature decrease 2
Cool to 0 ° C at 5 ° C / min. Next, from this state, the temperature is raised to 170 ° C. at a heating rate of 10 ° C./min, and measurement is performed. The maximum peak temperature (Tm) is defined as the position of the apex of the maximum peak that appears while the temperature rises from 0 ° C to 170 ° C.

(2) Method for measuring boiling n-hexane insolubles A heat press was used to form a sheet with a thickness of 200 µm, and three 20 mm x 30 mm sheets were cut from each length and width, and a double tube Soxhlet extractor was used. Then, extraction is carried out with boiling n-hexane for 5 hours. The n-hexane insoluble matter is taken out, dried under vacuum (7 hours, under vacuum, 50 ° C.), and the boiling n-hexane insoluble matter (C ₆ insoluble matter) is calculated by the following formula.

(3) Stickiness of pellets Strands with a length of about 50 mm are sandwiched between two transparent polyester films (38 μm) and gently pressed with your fingertips.
After the strands remaining on the polyester film were judged according to the following criteria.

◎: No stickiness (no traces remain) ○: Almost no (slight traces remain) △: Somewhat good (significant traces remain) ×: Yes (remains on the entire surface) Ethylene / α-olefin copolymer Production: The ethylene / α-olefin copolymer components (components (A-1), (A-2), (A-3) and (A-4)) used in Examples and Comparative Examples are described below.

(1) Production of Component (A-1) Ethylene and butene-1 were produced using a solid catalyst component obtained from substantially anhydrous magnesium chloride, 1,2-dichloroethane and titanium tetrachloride and a catalyst consisting of triethylaluminum. Were copolymerized to obtain an ethylene-butene-1 copolymer (A-1).

(2) Preparation of components (A-2) and (A-3) A reaction product of substantially anhydrous magnesium chloride and aluminum triethoxide is brought into contact with silica, and titanium tetrachloride and ethyl silicate are further added thereto. Ethylene and butene-1 were copolymerized in the gas phase using a solid catalyst component obtained by the reaction and a catalyst composed of triethylaluminum to form an ethylene / butene-1 copolymer (A-2) and (A-
3) got.

(3) Production of Component (A-4) Obtained by contacting a reaction product of substantially anhydrous magnesium chloride and aluminum triethoxide with silica, and further reacting this with titanium tetrachloride and silicon tetrachloride. Ethylene and propylene were copolymerized in the gas phase using a catalyst composed of the above catalyst component and triethylaluminum to obtain an ethylene / propylene copolymer (A-4).

Examples 1 to 6 Polybutene (trade name: Nisseki Potabten, manufactured by Nippon Petrochemical Co., Ltd.), which was prepared by heating a granular ethylene / α-olefin copolymer to 80 ° C so as to have the composition shown in Table 2. ) Were preheated by pumps from the hopper ports to the extrusion temperatures shown in Table 2 (screw diameter 20 mmφ, L
/ D = 20, die 2 mmφ), a melt-kneaded extruded strand was obtained at a rotation speed of 70 rpm. Then, the obtained strand was cooled with water and pelletized by a pelletizer.

In Examples 1 to 6, it was possible to continuously extrude into a strand shape and to pelletize with a pelletizer. Moreover, the thing with little stickiness was obtained. The results of evaluation of physical properties in these examples are also shown in Table 2.

Comparative Example 1 Instead of using the granular ethylene / α-olefin copolymer in Example 1, a commercially available low-density polyethylene (trade name: Nisseki Lexron F41, manufactured by Nippon Petrochemical Co., Ltd., T
m = 109 ° C.) (LDPE) was used to prepare pellets in the same manner as in Example 1. The obtained masterbatch pellets were extremely sticky, and the pellets adhered to each other to form blocks.

Comparative Example 2 In Example 1, instead of using the granular ethylene / α-olefin copolymer, a commercially available high-density polyethylene (trade name: Nisseki Stafren E807 (F), manufactured by Nippon Petrochemical Co., Ltd., Tm = 129) was used. C.) (HDPE) was used, and pellets were prepared in the same manner as in Example 1. The obtained masterbatch pellets were extremely sticky, and the pellets adhered to each other to form blocks.

Comparative Examples 3 and 4 Pellets were prepared in the same manner as in Example 1 except that the melt-kneading and extrusion temperatures shown in Table 2 were used. In Comparative Example 3, the strand had a large stickiness and the physical properties were poor. Further, in Comparative Example 4, only the polymer-modified and colored strands were obtained, and the stickiness of the strands was large and the physical properties were poor.

Claims (1)

[Claims] (A) The following obtained by copolymerizing ethylene and an α-olefin having 3 to 12 carbon atoms in the presence of (A) a catalyst comprising a solid component containing at least magnesium and titanium and an organoaluminum compound. (I) to (IV) (I) Melt index 0.01 to 100 g / 10 min, (II) Density 0.860 to 0.910 g / cm ³ , (III) Maximum peak temperature by differential scanning calorimetry (DSC) is 100 ° C. or higher, (IV) Boiling n-hexane insoluble content of 10% by weight or more, ethylene / α-olefin copolymer 30 to 30
Thermoplastic resin modification characterized by melt-kneading and extruding 95 parts by weight and (B) 5 to 70 parts by weight of polybutene having a number average molecular weight of 300 to 4000 at a temperature range of 150 to 250 ° C. For producing a masterbatch composition for use.