JPH0241341A - Masterbatch composition and production thereof - Google Patents

Abstract

PURPOSE:To obtain a masterbatch composition of a crosslinking agent having excellent workability and dispersibility in a resin by preparing an ethylene.alpha- olefin copolymer by the copolymerization in the presence of a specific catalyst and kneading and extruding the copolymer together with a crosslinking agent at a temperature within a specific range. CONSTITUTION:The objective composition is produced by kneading an extruding a mixture of (A) 50-99.9 pts.wt. of an ethylene.alpha-olefin copolymer having a melt index of 0.01-100g/min, a density of 0.86-0.94g/cm<3>, a maximum peak temperature(Tm) of DSC of >=100 deg.C and a boiling n-hexane-insoluble content of >=10wt.% and produced by the copolymerization of ethylene and a 3-12C, preferably 3-6C alpha-olefin in the presence of a catalyst composed of an organic aluminum compound and a solid component containing Mg and Ti and (B) 50-0.1 pts.wt. of a crosslinking agent (preferably an organic peroxide or a sulfur compound). The extrusion temperature is selected between Tm and Tm-45 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a masterbatch composition of a crosslinking agent used when modifying a thermoplastic resin, and a method for producing the mass-coubatch composition. More specifically, the present invention includes:
The present invention relates to a masterbatch composition comprising an ethylene/α-olefin copolymer with specific properties obtained by copolymerizing ethylene and α-olefin in the presence of a specific catalyst and a crosslinking agent, and a method for producing the composition. The present invention provides mask-batch pellets of a crosslinking agent that have excellent dispersibility in a thermoplastic resin and are useful for improving workability during mixing.

[Prior Art 1] Various molded bodies, sheets, films, etc. are manufactured by molding thermoplastic resins by methods such as injection molding, extrusion molding, blow molding, and inflation molding. In order to improve the mechanical properties, thermal properties, or melt viscoelastic properties of such thermoplastic resins, methods of crosslinking the resins are widely used. Crosslinking technology is used.Crosslinking methods include chemical methods using organic peroxides and sulfur compounds, and physical methods such as irradiation with electron beams.Chemical crosslinking This method generally has the advantage of being more economical than physical methods.

In the case of this chemical crosslinking method, the crosslinking agent is generally added to the thermoplastic resin either directly or after being dissolved or diluted in a solvent, then blended, and further subjected to treatment such as heating.

[Problem to be solved by the invention 1 However, crosslinking agents are often chemically unstable compounds, and sufficient care must be taken when storing and handling them.
It has the disadvantage of requiring complicated operations. Furthermore, further improvement in the dispersibility of the crosslinking agent in the thermoplastic resin has been desired.

An object of the present invention is to provide a composition containing a crosslinking agent that is easy to store and handle, has good work efficiency, and has good dispersibility in a resin, and a method for producing the same.

[Means for Solving the Problem 1 As a result of the inventors' studies to achieve the above object,
This has not been done at all in the conventional field.

We focused on the current formulation, that is, preparing the crosslinking agent as a masterbatch composition in advance and blending the composition with the thermoplastic resin. As a result of further intensive study on this point, we found that by combining an ethylene/α-olefin copolymer with a specific manufacturing method and specific properties with a crosslinking agent,
We have discovered a new masterbatch composition in which the crosslinking agent hardly decomposes, contains a high concentration of the crosslinking agent, and has good dispersibility in thermoplastic resins. In addition, the present inventors have also discovered that the composition can be obtained by extrusion molding an ethylene/α-olefin copolymer and a crosslinking agent at a low temperature that is completely unthinkable in the art, and the present invention has been reached.

That is, the present invention provides (A) a small amount of ethylene and a catalyst having 3 to 12 carbon atoms in the presence of a catalyst consisting of a solid component containing both magnesium and titanium and an organoaluminum compound.
The following (I) obtained by copolymerizing α-olefin with
~(IV) (1) Melt index 0. Old ~ l00g/min
.

(n) Density 0.860-0.940g/cm", (I
I+) Ethylene/α-olefin copolymer 50 to 9 having the following properties: Maximum temperature (Tm) measured by differential scanning calorimetry fDscl is 100°C or higher; 4) Boiling n-hexane insoluble content is 10% by weight or higher.
The present invention relates to a masterbatch composition containing 9.9 parts by weight and 50 to 0.1 parts by weight of a crosslinking agent.

In addition, the present invention provides a method for preparing ethylene and α having 3 to 12 carbon atoms in the presence of (A) a solid component containing at least magnesium and titanium and a catalyst consisting of an organoaluminum compound.
-The following (I) to (obtained by copolymerizing with olefin)
IV) (I) Melt index 0. Old ~ 100g/win
, (II) Density 0.860-0.940g/cm3,
(III) Maximum peak (Tm) temperature measured by differential scanning calorimetry (OSC) is 100°C or higher; (IV) boiling n-hexane insoluble content is 10% by weight or higher;
Ethylene/α-olefin copolymer 50 having the properties of
The maximum peak (Te
The present invention relates to a method for producing a masterbatch composition characterized by kneading and extruding at a temperature ranging from a) to lTr@-45'C.

Forming the composition of the invention into a master patch pellet,
If this is mixed with thermoplastic resin and molded,
No scattering of crosslinking agent during blending or molding process,
From a safety and work perspective.

Furthermore, crosslinking can be carried out very conveniently from the viewpoint of the dispersibility of the crosslinking agent.

The present invention will be explained in detail below.

(1) Ethylene/α-olefin copolymer + A): The ethylene-〇-olefin copolymer used in the present invention is prepared in the presence of a catalyst consisting of a solid component containing at least magnesium and titanium and an organoaluminum compound. Obtained by copolymerizing 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, and the like. Particularly preferred among these are propylene, butene-1,4-methylpentene-1, and hexene-1, each having 3 to 6 carbon atoms. Furthermore, dienes may be used as comonomers without departing from the purpose of the present invention.

For example, butadiene, 1,4-hexadiene, etc. can also be used in combination. The a-olefin content in the ethylene-a-olefin copolymer is preferably 2 to 40 mol%.

The catalyst system used is a combination of a solid catalyst component containing a small amount of magnesium and titanium with an organic aluminum compound. Examples of the solid catalyst component include magnesium metal, magnesium hydroxide, magnesium oxide, carbonate, etc. A double salt containing a magnesium atom and a metal selected from magnesium, magnesium salts such as magnesium chloride, silicon, aluminum, and calcium.

Magnesium such as double oxides, carbonates, chlorides, hydroxides, etc., and those obtained by treating or reacting these inorganic solid compounds with oxygen-containing compounds, sulfur-containing compounds, aromatic hydrocarbons, halogen-containing substances, etc. Examples include those in which a titanium compound is supported on an inorganic solid compound by a known method.

Examples of the above oxygen-containing compounds include water, alcohol,
Examples 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 halogen-containing substances include compounds such as chlorine, hydrogen chloride, metal chlorides, and organic halides.

On the other hand, examples of the titanium compound supported on the 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 suitable, and as a tetravalent titanium compound, specifically, the general formula Ti (ORI. 20 alkyl, aryl, or aralkyl groups, X represents a halogen atom, and n is 0≦
(n is an integer of 4) is preferable, and specifically titanium tetrachloride, titanium tetrabromide, titanium tetraiodide,
Monomethoxytrichlorotitanium, dimethoxydichlorotitanium, trimethoxymonochlorotitanium, tetramethoxytitanium.

Monoethoxytrichlorotitanium, jetoxydichlorotitanium, triethoxymonochlorotitanium, tetraethoxytitanium, monoisopropoxytrichlorotitanium, diisopropoxydichlorotitanium, triisopropoxymonochlorotitanium, tetraisopropoxytitanium, monobutoxytrichlorotitanium, dibutoxydichlorotitanium Titanium, monopentoxytrichlorotitanium, monophenoxytrichlorotitanium, diphenoxydichlorotitanium, triphenoxymonochlorotitanium, tetraphenoxytitanium and the like can be mentioned. As the trivalent titanium compound, titanium trihalides such as titanium trichloride are preferred.

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

Another example of a catalyst system is a catalyst system in which a reaction product of an organomagnesium compound such as a so-called Grignard compound with a titanium compound is used as a solid catalyst component, and this is combined with an organoaluminium compound. Examples of organomagnesium compounds include organomagnesium compounds such as RMgX, Rd4g, and RMgfORl (where R is carbon ffi
0 organic residue, X represents a halogen atom) and their ether complexes, and these organomagnesium compounds can be further combined with other organometallic compounds such as organosodium, organolithium, organopotassium, organoboron, organocalium, Those modified by adding various compounds such as organic zinc can be used.

Examples of other catalyst systems include S as a solid catalyst component.
An example is a solid material obtained by contacting an inorganic oxide such as iO□, Al2O3, etc. with the solid catalyst component containing at least magnesium and titanium, which is combined with an organic aluminum compound. Examples of inorganic oxides include 5i02, AlzOz, Can, B2O3, Sno□, etc., and double oxides of these oxides can also be used without any problem. Any known method can be used to bring these various inorganic oxides into contact with the solid catalyst component containing magnesium and titanium. That is, in the presence or absence of an inert solvent, at a temperature of 20 to 400°C.
The reaction may be carried out by a method of reacting, preferably at 50 to 300° C. for usually 5 minutes to 20 hours, a method of co-pulverization, or a suitable combination of these methods.

In these catalyst systems, a titanium compound can be used as an adduct with an organic carboxylic acid ester, or the above-described magnesium-containing inorganic solid compound can be used after being brought into contact with an organic carboxylic acid ester. Moreover, there is no problem in using an organoaluminum compound as an adduct with an organic carboxylic acid ester or an organosilicon compound.

Specific examples of organoaluminum compounds to be combined with the solid catalyst component described above include one type R, AI,
R2AIX, RAIX, , R, AlOR, RA
Organoaluminum compound of I (ORIX, R, A1. Preferable compounds are triethylaluminum, triisobutylaluminum, trihexylaluminum, thonooctylaluminium, diethylaluminum chloride, diethylaluminium ethoxide, ethylaluminum sesquiglolide, and mixtures thereof.

The use of organoaluminum compound 1 is not particularly limited, but it can usually be used in an amount of 0.1 to 1000 times the mole of the titanium compound.

In addition, by bringing the catalyst system into contact with an α-olefin and then using it in a polymerization reaction, the polymerization activity can be greatly improved and the system can be operated more stably than in the case without treatment.

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

The polymerization conditions for olefin are a temperature of 20 to 300°C, preferably 40 to 200"C, and a pressure of normal pressure to 70 kg.
/cm"G, preferably 2 kg/cm".G to 6
Although the molecular weight, which is 0 kg/Cm''·G, can be adjusted to some extent by changing polymerization conditions such as polymerization temperature and catalyst molar ratio, it is effectively carried out by adding hydrogen to the polymerization system. Of course, a two-step or more multi-step polymerization reaction with different polymerization conditions such as hydrogen concentration and polymerization concentration can also be carried out without any problem.

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

That is, the melt index + MI) (J
IS K6760 compliant, 190'C12, 16kg
load) is 0.01-100g/10m1n, preferably 0.1-50g710min, more preferably 0.1
~20g710IIin. Density (JIS K67
60) is 0.860 to 0.940 g/am'', and in terms of stickiness and bleeding of the pellet, A is preferably 0.870 to 0.935 g/cm3, more preferably 0.880 to 0.920 g. /cm3.Also, in terms of increasing the amount of crosslinking agent accepted, the density is 0.910g.
less than 0.860g/c+a', preferably 0.870 to 0.91)5g7cm3, more preferably 0.880 to 0.900g/cm''. Maximum by differential scanning calorimetry (SC) Peak temperature (Tml is 100°C or higher, preferably 110°C to 130°C, more preferably 115°C to 125°C, 6 boiling LJ! n-
The hexane-insoluble content is 10% by weight or more, preferably 20% by weight or more, and more preferably 40 to 98% by weight.

Ml of the ethylene/α-olefin copolymer (A) is 0.
If it is less than 0.01 g/10 m1n, the MI will be too small and the fluidity will be poor. Furthermore, if the MI exceeds 100 g/l On+in, the master patch pellet becomes too soft and the surface becomes sticky.

If the density is less than 0.860 g/cm3, the surface will become sticky, and if the density exceeds 0.940 g/cm3, bleeding will occur during long-term storage, resulting in instability.

When the maximum peak temperature due to O20 is less than 100°C, the master patch pellet becomes sticky.

If the boiling n-hexane insoluble content is less than 10% by weight,
As expected, the surface of the master patch pellet is sticky, which is not desirable.

In addition, these ethylene-α-olefin copolymers (A
) is preferably in powder or granule form.

(2) Crosslinking agent (B): The crosslinking agent used in the present invention is not particularly limited, and examples thereof include those called crosslinking agents based on a free radical mechanism or crosslinking agents based on an ionic mechanism. . Among these, organic peroxides, sulfur compounds, selenium,
Tellurium and its compounds, aromatic nitro compounds, and the like are used, and among these, organic peroxides and sulfur-based compounds are particularly preferred in order to exhibit the effects of the present invention.

The organic peroxide is usually one with a half-life of 1 minute at a temperature of 100°C or higher, preferably 120°C or higher, and includes dialkyl peroxide, diacyl peroxide, peroxy ester, hydroperoxide,
Examples include ketone peroxide. Specific examples of these include 2,5-dimethyl-2,5-di(butylperoxy)hexane, di-butylperoxide, di(t-butylperoxy)diisopropylbenzene, and di(t-butylperoxy). butylperoxy) diisobutylbenzene, dicumyl peroxide, t-butylcumyl peroxide, t-butylperoxybenzoate, 1.1-
Examples include bis(dobutylperoxy)-3,3,5-trimethyl peroxide, benzoyl peroxide, and p-chlorobenzoyl peroxide.

In addition, as the sulfur-based compound, sulfur, thiurams such as tetramethylthiuram disulfide, thiazoles such as mercaptobenzothiazole, and the like are preferably used.

These crosslinking agents may be used alone or in combination, or may be combined with crosslinking aids such as liquid polybutadiene, divinylbenzene, ethylene dimethacrylate, diallyl phthalate, and the like.

(3) Composition ratio: The crosslinking agent masterbatch composition of the present invention contains the above-mentioned ethylene/α-olefin copolymer (A) and crosslinking agent (B).

The composition ratio of the ethylene/α-olefin copolymer (A) and the crosslinking agent (B) in the crosslinking agent masterbatch pellet of the present invention is 50 to 50% of the ethylene/α-olefin (A).
99.9 parts by weight, preferably 50 to 97 parts by weight, more preferably 60 to 95 parts by weight, and the crosslinking agent (B) is 50 to 0.
．． The amount is 1 part by weight, preferably 50 to 3 parts by weight, and more preferably 40 to 5 parts by weight. If the crosslinking agent content is less than 0.1 parts by weight, the amount of masterbatch used will be too large and the efficiency will be poor. Moreover, if the crosslinking agent content is more than 50 parts by weight, it is difficult to form strands even by extrusion molding, and it is difficult to form pellets. Furthermore, the crosslinking agent bleeds onto the surface of the obtained pellet, resulting in stickiness, which is undesirable.

(4) Production of crosslinking agent masterbatch composition 2. The masterbatch composition for thermoplastic resin modification of the present invention is produced by uniformly kneading the above-mentioned ethylene/α-olefin copolymer and polybutene to a predetermined composition ratio. It is then extruded and usually pelletized. These kneading,
Any known technique can be used for extrusion. Typical examples include cross-wire and extrusion methods using a -screw extruder or twin-screw extruder. The kneading and extrusion temperature at this time is within the range of the maximum peak temperature of the ethylene/α-olefin copolymer determined by DSC from Trs to Tm-45)°C, preferably from (Tm-5)°C to Tm-40°C.
) t:, more preferably (Tm-10)°C to Tm-30)°C. If the extrusion temperature exceeds Tm, the crosslinking agent will be more or less decomposed and the efficiency as a masterbatch will decrease, which is not preferable. In addition, the extrusion temperature exceeds TII+ (To++30)
In the temperature range of °C, the melt viscosity of the ethylene/α-olefin copolymer is high, and a portion of the crosslinking agent decomposes, resulting in crosslinking of the ethylene/α-olefin copolymer, resulting in a higher melting temperature. This makes extrusion molding difficult. When the extrusion temperature is (Tm◆30)t: or more, the decomposition of the crosslinking agent further progresses, the melt viscosity of the ethylene/α-olefin increases significantly, and extrusion molding becomes more difficult. Also, the extrusion temperature (
If the temperature is lower than Tm - 45)°C, the extrudate will turn into powder and the strat
It is difficult to form pellets into pellets.

In the present invention, the ethylene/α-olefin copolymer and the crosslinking agent may be mechanically mixed in advance before kneading, or may be added simultaneously or separately during kneading.

Note that the crosslinking agent may be kneaded as is with the ethylene/α-olefin copolymer, or it may be dissolved and diluted in a solvent and then kneaded, but when using an organic peroxide as the crosslinking agent, it must be dissolved in the solvent in advance. Alternatively, it is preferable to dilute it and knead it with the ethylene/α-olefin copolymer.

Any known technique can also be used for the pelletizing step in the present invention. Typical examples include 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 with a beletizer, a hot cut method, etc. can be mentioned.

Note that there is no problem in adding conventionally known plasticizers, fillers, pigments, lubricants, antioxidants, etc. together with the crosslinking agent.

The crosslinking agent masterbatch composition of the present invention hardly causes gelation other than when crosslinking is performed to such a degree that gelation of the thermoplastic resin occurs in a hot solvent, such as in electric wire coatings, foamed molded products, etc. It can be used in a wide range of crosslinking technical fields, such as when crosslinking is performed to a mild degree to change melt viscoelasticity.

〔Effect of the invention〕

The crosslinking agent masterbatch composition obtained in the present invention has the following characteristics.

■ Crosslinking agents are unstable compounds due to their chemical structure, but
By making it into a masterbatch, storage and handling become easier, and it is advantageous in terms of safety.

■ Work efficiency can be improved when blending a crosslinking agent.

- The dispersibility of the crosslinking agent is better than when the crosslinking agent is directly triblended with the thermoplastic resin and molded.

(Examples) Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.

Measuring method of physical properties: (1) Differential scanning calorimetry (DSC) A hot press-molded film with a thickness of 100 μm was used as a sample, heated to 170°C, held at that temperature for 15ml, and then cooled at a cooling rate of 25°C/sin. Cool to 0°C.

Next, from this state, increase the temperature to 170°C at a temperature increase rate of 10°C/sin.
Measurement is performed by raising the temperature to . The maximum peak temperature (Tm) is defined as the position of the highest peak that appears during the temperature increase from 0°C to 170°C.

(2) Method for measuring insoluble content in boiling n-hexane A sheet with a thickness of 200 μm was formed using a hot press, and three sheets of 20 mm x 30 m1 in length and width were cut from it.
Extraction is carried out with boiling 11n-hexane for 5 hours using a double-tube Soxhlet extractor. After taking out the n-hexane insoluble matter and vacuum drying (7 hours under vacuum, 50° C.), the boiling n-hexane insoluble matter (C6 insoluble matter) is calculated using the following formula.

(3) Method for measuring gel fraction Using a heat press (200°C x 5 minutes),
Three sheets of 40 mm x 20 m+m were cut out, each of which was placed in a 120-mesh all-mesh bag, and extracted with boiling xylene for 5 hours using a double-tube Soxhlet extractor.

Remove the insoluble matter from boiling xylene and vacuum dry (7 hours,
80°C), and the boiling xylene insoluble content is determined as the gel fraction.

Production of ethylene/α-olefin copolymer sample: Ethylene/α-olefin copolymer components (components (^-1), (A-2)) used in Examples and Comparative Examples.

(A-3)) is described below.

(1) Production of components (A-1) and (A-3) Using a solid catalyst component obtained from substantially anhydrous magnesium chloride, 1,2-dichloroethane and titanium tetrachloride, and a catalyst consisting of triethylaluminum. ethylene and butene
1 to form an ethylene-butene-1 copolymer (A
-1) and (^-3) were obtained.

(2) Production of component (A-2) Ethylene and propylene are copolymerized using a solid catalyst component obtained from substantially anhydrous magnesium chloride, anthracene, and titanium tetrachloride, and a catalyst consisting of triethylaluminum. Propylene copolymer (A-2)
I got it.

The properties of these ethylene/α-olefin copolymer components are shown in Table 1.

Examples 1 to 3 Granular ethylene butene was prepared to have the composition shown in Table 2.
1 copolymer (A-1) and 2.5 dimethyl-2,5-di(butylperoxy)hexane as a crosslinking agent.
A 0% hexane solution was triblended in a tumbler. Next, after volatilizing the hexane, the mixture was transferred to a single screw extruder (screw diameter 20 mmφ, L/D=20, die 2
mn+φ), kneaded at a temperature of 105° C. and a screw rotation speed of 70 rpm, extruded a strand, and after cooling with water, formed into a pellet to obtain a crosslinking agent masterbatch.

Example 4 In Example 1, granular ethylene-propylene copolymer (A-2) was used as the component A, and powdered α, α°-di-1-butylbaroxydi-p-isopropylbenzene was used as the crosslinking agent. A crosslinking agent masterbatch was obtained in the same manner as in Example 1 except that the mixture was dissolved in 5 times the amount (weight ratio) of acetone and the extrusion temperature was 90°C.

Examples 5 to 6 In Example 1, granular ethylene-butene-1 copolymer (A-3) was used as the A component, and 2,5-dimethyl-2,5-di(t-butylperoxy)hexine was used as the crosslinking agent. 1
A crosslinking agent masterbatch was obtained in the same manner as in Example 1 except that a 0% hexane solution was used and the extrusion temperature was 120°C.

In all of Examples 1 to 6, it was possible to extrude continuously into a strand, and it was possible to form pellets using a pelletizer without any problems. Furthermore, a product with extremely little stickiness was obtained. The physical property evaluation results for these Examples are also listed in Table 2.

Comparative Example 1 Example 1 was carried out in the same manner as in Example 1 except that the extrusion temperature was 150° C. However, the extrudate was powdered and no strands were obtained, and it was not possible to form it into a pellet.

Comparative Example 2 Commercially available high-density polyethylene (IDPE) was used instead of the granular ethylene-butene-1 copolymer in Example 1.
(Manufactured by Nippon Petrochemical ■, Stacrene E-807F (Ml-
The same procedure as in Example 1 was carried out except that 0,6)) was used. Although the extruder motor was under considerable stress, it was possible to extrude the strands. However, the surface of the strands was rough and they were frequently cut, making it impossible to stably form them into belet.

Comparative Example 3 In Example 1, commercially available low density polyethylene (LDPE) was used instead of the granular ethylene-butene-1 copolymer.
The same procedure as in Example 1 was carried out except that Xuron F22 (Ml-1) manufactured by Nippon Petrochemical Co., Ltd. was used. However, the extruder motor was under high load and could not extrude the strands.

Comparative Example 4 The same procedure as in Example 4 was carried out except that the extrusion temperature in Example 3 was 130°C. The surface of the strands is very rough;
In addition, the strands were easy to break and had poor molding stability.

Reference Example 1 Bullet-shaped ethylene-butene-1 copolymer (A-1)
97.5% by weight and 2.5% by weight of the pellet-shaped crosslinking agent masterbatch obtained in Example 3 were triblended using a tumbler, and then a single-screw extruder (screw diameter 20I!1ll1φ, L/D= 20, dice (0,5
mm
II11, a sheet with a wall thickness of 200 μm was molded. The Ml of the obtained composition was 0.3], and the number of gels (Fisher's eyes with a size of 0.5 mm or more) per 0.1 rn' was visually counted to be 2 to 5.

Reference Comparative Example 1 In Reference Example 1, without using the crosslinking agent masterbatch, 2,
A 10% solution of 5-dimethyl-2,5-di(t-butylperoxy)hexane was directly added to the ethylene-butene-1 copolymer (A-1) so that the concentration of the crosslinking agent was 0.025ffi%. and sheet molding was performed in the same manner as in Reference Example 1. The MI of the obtained composition was 0.28, and the sheet was 0.1r.
The number of gels per n'' was 12 to 16.

Reference Comparative Example 2 Sheet molding was carried out in the same manner as in Example 1, except that the crosslinking agent master patch obtained in Comparative Example 4 was used in Reference Example 1. The composition obtained had a former of 0.6 and a sheet of 0. lrn”
The number of gels per gel was over 100.

Reference Example 2 Bullet-shaped ethylene/propylene copolymer (A-2)
45% by weight, ethylene-propylene-diene copolymer rubber (manufactured by Japan Synthetic Rubber Co., Ltd., EP579) 45% by weight,
10% by weight of the crosslinking agent masterbatch obtained in Example 4 was charged into a Banbury mixer preheated to 200°C and kneaded at a rotational speed of 40 rpm for 10 minutes to obtain a thermoplastic elastomer composition. This composition had an MI of 0.2 and a gel fraction of 35%.

Reference example 3 Low density polyethylene (LDPE) (Japan Petrochemical Co., Ltd.
After tri-blending 85% by weight of Rexron W3000 (MI-2) and 15% by weight of the crosslinking agent masterbatch obtained in Example 5 in a tumbler, a -screw extruder (screw diameter 20mmφ, L/D = 20, Dice 2mm
φ), and was kneaded and extruded at a temperature of 160°C to obtain a crosslinking agent-containing pellet. Pressure this pellet at 100kg/cm
2. Press molding was carried out under conditions of a temperature of 210° C. and a pressing time of 10 minutes to obtain a crosslinked sheet with a thickness of 2Iffl. The gel fraction of this was 99.5%, 7.

Claims (1)

[Claims] (1) (A) Copolymerizing ethylene and an α-olefin having 3 to 12 carbon atoms in the presence of a solid component containing at least magnesium and titanium and a catalyst consisting of an organoaluminum compound. (I) Melt index 0.01-100 g/min, (II) Density 0.860-0.940 g/cm^3, (III) Differential scanning calorimetry (DSC) ) maximum peak (Tm) temperature of 100°C or higher, (IV) boiling n-hexane insoluble content of 10% by weight or higher, ethylene/α-olefin copolymer 50
99.9 parts by weight, and (B) a crosslinking agent 50 to 0.1 parts by weight. (2) (A) The following (I ) ~ (IV) (I) Melt index 0.01 ~ 100 g/min, (II) Density 0.860 ~ 0.940 g/cm^3, (III) Maximum peak (Tm) determined by differential scanning calorimetry (DSC) ) A temperature of 100°C or higher; (IV) A boiling n-hexane insoluble content of 10% by weight or higher. Ethylene/α-olefin copolymer 50
~99.9 parts by weight, and (B) 50 to 0.1 parts by weight of the crosslinking agent, the maximum peak (Tm) temperature measured by differential scanning calorimetry (DSC) of the above ethylene/α-olefin copolymer A method for producing a masterbatch composition, which comprises kneading and extruding at a temperature range of from (Tm-45)°C.