JPH0745603B2 - Resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a resin composition containing 4-methyl-1-pentene as a main component, which is excellent in heat resistance, heat sealability, impact resistance, transparency and the like.

[Conventional technology]

Poly 4-methyl-1-pentene has its transparency, heat resistance,
Taking advantage of chemical resistance, beakers, measuring instruments such as graduated cylinders, syringes for syringes, optical measurement cells,
It is used for baking cartons by coating it on a microwave tray or paper. However, while poly-4-methyl-1-pentene has a high melting point and good heat resistance, it has the drawback of being poor in heat sealability.
As a method of improving impact resistance, heat sealability, etc. of the polyolefin, a method of adding a low crystalline or amorphous ethylene / α-olefin copolymer to the polyolefin (for example, Japanese Patent Publication No. 36-15042). It is best known that when it is added to a copolymer of poly-4-methyl-1-pentene, the transparency, which is a characteristic of poly-4-methyl-1-pentene, is significantly lowered and the heat resistance is also lowered. There was a drawback that the original properties of 4-methyl-1-pentene were impaired.

[Problems to be solved by the invention]

In view of such a situation, the present inventor intends to improve impact resistance and heat sealability without impairing the transparency, heat resistance, electrical characteristics, releasability, etc., which are the original characteristics of poly-4-methyl-1-pentene. As a result of various studies aimed at, by adding a random copolymer of specific 4-methyl-1-pentene and α-olefin having 4 to 6 carbon atoms to poly 4-methyl-1-pentene, It was found that the object could be achieved, and the present invention was completed.

[Means for solving problems]

That is, the present invention is (a) 95% to 20% by weight of poly-4-methyl-1-pentene
And (b) 4-methyl-1-pentene content of 40 to 80 mol%, melting point of 140 to 220 ° C, softening point of 90 to 190 ° C.
And crystallinity by X-ray is in the range of 15 to 35% 4
-Methyl-1-pentene and carbon number 4 to 6 (however, 4
-Excluding methyl-1-pentene) and 5 to 80% by weight of a random copolymer (B) with α-olefin, transparency, heat resistance, chemical resistance, electrical characteristics, mold release The present invention provides a resin composition having excellent properties, impact resistance, and heat sealability.

[Action]

The poly-4-methyl-1-pentene (A) used in the present invention is a 4-methyl-1-pentene homopolymer or 4-methyl-1-pentene.
Methyl-1-pentene and other α-olefins such as ethylene, propylene, 1-butene, 1-hexene, 1-
A copolymer of octene, 1-decene, 1-tetradecene, 1-octadecene and the like with α-olefin having 2 to 20 carbon atoms, usually 4-methyl-1-pentene containing 85 mol% or more of 4-methyl-1-pentene. It is a polymer mainly composed of pentene. The melt flow rate (MFR, load: 5 kg, temperature: 260 ° C.) of poly-4-methyl-1-pentene (A) is preferably 0.
It is in the range of 5 to 200g / 10min. MFR is 0.5g / 10m
If it is less than in, the melt viscosity is high and the moldability is poor, and the MFR is 200.
If it exceeds g / 10 min, the melt viscosity is low and the moldability is poor,
It also has low mechanical strength.

The 4-methyl-1-pentene / α-olefin random copolymer (B) (hereinafter sometimes abbreviated as random copolymer (B)) used in the present invention means that the content of 4-methyl-1-pentene is 40 to 80 mol%, preferably 50 to 75
Mol%, melting point 140-220 ° C, preferably 160-2
10 ° C, softening point 90-190 ° C, preferably 110-18
4-Methyl-1-pentene having a crystallinity of 15 to 35%, preferably 20 to 30% at 0 ° C. and X-rays and 4 to 6 carbon atoms (excluding 4-methyl-1-pentene) ) Is a random copolymer with α-olefin and usually has an intrinsic viscosity [η] in decalin solvent of 135 ° C of 0.5 to
It is in the range of 6 dl / g, preferably 1 to 5 dl / g.

A copolymer having a 4-methyl-1-pentene content of less than 40 mol% lowers the heat resistance and mechanical strength of the composition, while a copolymer having a content of more than 80 mol% has impact resistance and heat sealability. There is no improvement effect of. 4-methyl-1- in the present invention
The pentene content is a value measured by ¹³ C-NMR method.

A copolymer having a melting point of less than 140 ° C. lowers the heat resistance and mechanical strength of the composition, while a copolymer having a melting point of more than 220 ° C. has no effect of improving the heat-sealing property. The melting point in the present invention, the differential scanning calorimeter (DSC), using a 10mmg sample from the press sheet with a thickness of 0.1mm 20 hours after molding, 10 ℃
The heating curve was measured from 0 to 250 ° C. at a heating rate of / min, and the maximum endothermic peak was taken as the melting point (Tm).

A copolymer having a softening point of less than 90 ° C lowers the heat resistance of the composition, while a copolymer having a softening point of more than 190 ° C does not have the effect of improving the heat-sealing property. The softening point in the present invention, using a thermal mechanical analyzer (TMA), a 1 cm square sample is taken from a 1 mm-thick press sheet after 20 hours from molding, and a 0.025 inch diameter needle is placed on one side of the sample. A load of 49 g of pad was applied and heating was performed at a temperature rising rate of 10 ° C./min, and the temperature when the needle penetrated to a depth of 0.1 mm was read and used as the softening point.

A copolymer having a crystallinity of less than 15% by X-ray deteriorates the rigidity and mechanical strength of the composition, while a copolymer having a crystallinity of more than 35% has no effect of improving impact resistance. The crystallinity in the present invention is 2 from the press sheet having a thickness of 1.0 mm 20 hours after the forming.
A sample of x4 cm was sampled, an X-ray diffraction curve was measured by an X-ray diffraction method, and a reflection angle 2θ: 4 to 30 degrees was used as a baseline.
After separating the crystal part and the amorphous component and measuring the area, the crystal part was determined as the weight%.

In each press sheet, the random copolymer (B) was put into a mold having a thickness of 0.1 and 1.0 mm, respectively, in a predetermined amount, preheated for 5 minutes and then pressed for 5 minutes in a hydraulic press molding machine heated to 240 ° C. The mold was immediately transferred to a cooling press molding machine cooled with water at 20 ° C., and cooling was performed for 5 minutes.

The α-olefin having 4 to 6 carbon atoms which is copolymerized with 4-methyl-1-pentene in the random copolymer (B) used in the present invention is specifically 1-butene or 1-butene.
Examples thereof include pentene, 1-hexene and 1-heptene. Among these α-olefins, 1-butene and 1-hexene are preferable, and 1-hexene is particularly preferable because it has the highest transparency. Α- with 3 or less carbon atoms
Copolymers with olefins, i.e. ethylene or propylene, reduce transparency, while having 8 or more carbon atoms, for example 1
-Copolymers with decene, 1-hexadecene and the like also reduce transparency and mechanical strength, and neither of them can achieve the object of the present invention.

In addition to the above characteristics, the random copolymer (B) used in the present invention has a solubility in acetone / n-decane mixed solvent (volume ratio 1/1) at 10 ° C. of 4 × [η] ^−0.8 % by weight. Less than,
Furthermore, 0.2 x [η] ^{-0.8 to} 3.8 x [η] ^-0.8 wt%
([Η] is a numerical value of the intrinsic viscosity of the random copolymer (B), which is a value excluding the unit), is a bleeding of a low molecular weight polymerized component on the surface when processed into a film or the like. It is preferable because it does not cause stickiness due to out and is excellent in anti-blocking property and heat sealing property. The soluble content of the copolymer in the mixed solvent in the present invention is measured and determined by the following method. That is, in a 150 ml flask equipped with a stirring blade, 1 g of the copolymer sample, 0.05 g of 2,6-di-tert-butyl-4-methylphenol, and 50 ml of n-decane were placed, and the mixture was placed on an oil bath at 120 ° C. Dissolve. After dissolution, let it cool naturally at room temperature for 30 minutes, then add 50 ml of acetone in 30 seconds,
Allow to cool for 60 minutes on a 10 ° C water bath. The precipitated copolymer and the solution of the low-molecular weight polymer component were dissolved by filtration with a glass filter, the solution was dried at 10 mmHg at 150 ° C. until a constant weight was obtained, and its weight was measured. The soluble content of the polymer was calculated and determined as a percentage with respect to the weight of the sample copolymer. In the measuring method, stirring was continuously performed from the time of dissolution until immediately before filtration.

The 4-methyl-1-pentene / α-olefin random copolymer (B) having various properties as described above is, for example, (a) a magnesium compound, a titanium compound, a diester, and optionally a halogen compound (magnesium compound). Or a highly active titanium catalyst component containing magnesium, titanium, a halogen and a diester as essential components, which are formed by reacting each other with each other when the titanium compound contains a halogen atom). 4-methyl-1-pentene at a temperature of about 20 to about 200 ° C. in the presence of a catalyst formed from an aluminum compound catalyst component and (c) an organosilicon compound catalyst component having a Si—O—C bond. It can be obtained by copolymerizing with α-olefin having 4 to 6 carbon atoms such as 1-butene and 1-hexene. Regarding the copolymerization conditions and the like for producing the random copolymer (B) suitable for use in the present invention as described above, Japanese Patent Application No. 60-2162 by the applicant of the present invention can be referred to.
58.

The resin composition of the present invention comprises 95 to 20% by weight, preferably 80 to 30% by weight, of the poly-4-methyl-1-pentene (A) and the 4-methyl-1-pentene / α-olefin random copolymer. (B) 5 to 80% by weight, preferably
It is composed of 20 to 70% by weight. If the amount of the random copolymer (B) is less than 5% by weight, the impact resistance and heat sealability of the poly-4-methyl-1-pentene (A) are not improved, while if it exceeds 80% by weight, the heat resistance becomes high. Properties, rigidity, mechanical strength, scratch resistance, etc. are reduced.

To produce the resin composition of the present invention, poly-4-methyl-1
-Pentene (A) and random copolymer (B) are mixed by various known methods within the above range, for example, V-blender, ribbon blender, Henschel mixer, tumbler blender, or extrusion after mixing with the blender. Granulation method, single-screw extruder, multi-screw extruder, kneader, Banbury mixer, etc., melt kneading, granulation or pulverization, or in one polymerization reaction system poly-4-methyl-1 By so-called block polymerization, in which after a predetermined amount of pentene (A) or random copolymer (B) is polymerized, a predetermined amount of random copolymer (B) or poly-4-methyl-1-pentene (A) is subsequently polymerized. It may be produced by polymerization as a non-polymer blend type composition.

In addition to the above components, the resin composition of the present invention includes a weather resistance stabilizer, a heat resistance stabilizer, an antistatic agent, an anti-blocking agent, a slip agent, a lubricant, a hydrochloric acid absorbent, a pigment, a dye, a drip agent, a nucleating agent, etc. Various compounding agents usually used by adding to the polyolefin may be added within a range not impairing the object of the present invention.

The resin composition of the present invention can be injection-molded, compression-molded, extrusion-molded, T-die film-molded, inflation film-molded, blow-molded, thermo-molded, like other conventional polyolefins such as poly-4-methyl-1-pentene. Films, sheets, containers, pipes, rods and the like can be molded by various known methods such as molding. In addition, its heat sealability, transparency,
Taking advantage of heat resistance, impact resistance, etc., polyester such as poly-4-methyl-1-pentene, polyethylene terephthalate, polyethylene terephthalate / isophthalate copolymer, polyamide, ethylene vinyl alcohol copolymer,
With polyvinylidene chloride, vinyl chloride / vinylidene chloride copolymer, etc., or transparency is impaired, but paper, aluminum foil, etc. are laminated by utilizing heat resistance, heat sealability, releasability, flexibility, etc. It can also be formed into a film, sheet, tray, container or the like.

〔The invention's effect〕

The resin composition of the present invention has transparency, heat resistance, chemical resistance, electrical characteristics, which are the original characteristics of poly-4-methyl-1-pentene,
Impact resistance, heat sealability, flexibility, etc. have been improved without deteriorating mold releasability, boiling water resistance, etc., making use of such characteristics, as a single film, packaging material for retort food, vegetables, meats, Packaging materials such as pharmaceuticals, hollow molding,
It is suitable for use in injection-molded chemicals and food containers. In addition, a laminated film laminated with polyamide, polyester, paper, and aluminum foil to provide gas permeation resistance and the like is also suitably used for applications such as packaging materials for retort foods.

〔Example〕

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples as long as the gist thereof is not exceeded.

Example 1 [Production of 4-methyl-1-pentene / 1-hexene random copolymer] (Preparation of titanium catalyst component (a)) 4.76 g (50 mmol) of anhydrous magnesium chloride, 25 ml of decane and 23.4 ml of 2-ethylhexyl alcohol. (150 mmol)
Was heated at 130 ° C for 2 hours to form a uniform solution, and 1.11 g (7.5 mmol) of phthalic anhydride was added to this solution.
Stirring and mixing are further performed at 0 ° C. for 1 hour to dissolve phthalic anhydride in the homogeneous solution. After cooling the homogeneous solution thus obtained to room temperature, titanium tetrachloride kept at -20 ° C.
The total amount is dropped into 200 ml (1.8 mmol) over 1 hour. After the charging is completed, the temperature of this mixed solution is 110 for 4 hours.
The temperature was raised to ℃, and when it reached 110 ℃, 2.68 ml (12.5 mmol) of diisobutyl phthalate was added, and the mixture was maintained at the same temperature for 2 hours with stirring. After completion of the reaction for 2 hours, a solid portion was collected by hot filtration, and the solid portion was resuspended in 200 ml of TiCl ₄ and then heated at 110 ° C. for 2 hours. After the completion of the reaction, the solid part is again collected by hot filtration and thoroughly washed with decane and hexane at 110 ° C. until no free titanium compound is detected in the washing liquid. The titanium catalyst component (a) prepared by the above production method was stored as a hexane slurry, and a part of this was dried for the purpose of examining the catalyst composition. The titanium catalyst component (a) thus obtained had a composition of 3.1 wt% titanium, 56.0 wt% chlorine, 17.0 wt% magnesium and 20.9 wt% diisobutylphthalate.
It was.

(Polymerization) Into a 200 l SUS reaction kettle, 20 l of 1-hexene per hour,
60 l of 4-methyl-1-pentene (hereinafter abbreviated as 4MP), 80
mmol triethylaluminum, 80 mmol trimethylmethoxysilane, and 1.2 mmol of titanium catalyst component (a) in terms of titanium atoms were continuously charged. The hydrogen partial pressure in the gas phase
The polymerization temperature was kept at 70 ° C. and 1.5 kg / cm ² .

The polymerization liquid was continuously withdrawn so that the liquid volume in the reaction vessel was 100 l, the polymerization was stopped with a small amount of methanol, and unreacted monomers were removed to obtain 7.5 kg of a copolymer per hour. The 4-methyl-1-pentene / 1-hexene random copolymer (hereinafter abbreviated as PMH-I) thus obtained had a 4MP content of 55 mol%, a melting point of 168 ° C. and a softening point of 140 ° C. , Crystallinity 24%, intrinsic viscosity [η] is 2.2dl / g and acetone.
The n-decane-soluble content was 1.7% by weight.

[Manufacturing of film]

Poly 4-methyl-1-pentene [1-hexadecene / 1-
Octadecene (weight ratio 50/50) content 6 mol%, MFR: 26g
/ 10 min, hereinafter abbreviated as PMP-1] 70% by weight, and PMH-I obtained by the above method (however, as a stabilizer, PMH-I: tetrakis [methylene-3 (3,5-di- -Tert-butyl-4-hydroxyphenol) propionate] methane 0.15 parts by weight, dilaurylthiodipropionate 0.25
Parts by weight and zinc stearate 0.03 parts by weight were added. ) 30
% By weight with a Henschel mixer, and then melt-kneaded with a 40 mmφ extruder (setting temperature 260 ° C), and a T-die (setting temperature 2
60 ° C), cool with a cooling roll at 60 ° C, and
A thick film was obtained.

Then, the film was evaluated by the following methods.

Haze (%): ASTM D 1003 Impact strength (kg ・ cm / cm): ASTM D 3420 Heat seal strength (g / 15mm): 2kg / cm ² at a temperature between 180 ℃ and 240 ℃ Pressure for 1 second: Heat seal with a 10 mm wide seal bar and allow to cool. A test piece with a width of 15 mm was cut from this, and the strength when peeling the heat-sealed portion at a crosshead speed of 200 mm / min was shown.

The results are shown in Table 1.

Example 2 Example 1 was repeated except that PMP-1 was 50% by weight and PMH-I was 50% by weight. The results are shown in Table 1.

Examples 3 and 4 4MP content obtained by polymerizing 70% by mol of 4MP obtained by changing the charging amounts of 1-hexene and 4MP instead of PMH-I and appropriately changing the hydrogen partial pressure. , Melting point 195 ° C, softening point
4-methyl-1-, 165 ° C, crystallinity 26%, intrinsic viscosity [η] 2.5 dl / g and acetone / n-decane soluble content 2.0% by weight
Pentene / 1-hexene random copolymer (hereinafter PMH-I
The same procedure as in Example 1 and Example 2 was performed except that (abbreviated as I) was used. The results are shown in Table 1.

Comparative Example 1 The procedure of Example 1 was repeated except that PMP-1 was used alone in Example 1. The results are shown in Table 1.

Comparative Example 2 Polymerization was carried out by changing the charging amounts of 1-hexene and 4MP instead of PMH-I in Example 1 and appropriately changing the hydrogen partial pressure to obtain 4MP content of 90 mol%. 4-methyl-1 having a melting point of 225 ° C, a softening point of 195 ° C, a crystallinity of 36%, an intrinsic viscosity [η] of 2.4 dl / g and an acetone / n-decane-soluble content of 0.9% by weight.
-Pentene-1-hexene random copolymer (hereinafter PMH
-Abbreviated as -III) was performed in the same manner as in Example 1. The results are shown in Table 1.

Example 5 (Production of injection-molded test piece) Poly 4-methyl-1-pentene [1-hexadecene / 1-
Octadecene (weight ratio 50/50) content 6 mol%, MFR: 26g
/ 10 min, hereinafter abbreviated as PMP-1] 70% by weight, PMH-I obtained in Example 1 (however, as a stabilizer, PMH-I: tetrakis [methylene-3 (3,5- Di-tert-butyl-4-hydroxyphenol) propionate] methane 0.15 parts by weight, dilaurylthiodipropionate 0.25
Parts by weight and zinc stearate 0.03 parts by weight were added. ) 30
% By weight with a Henschel mixer and then melt-kneaded with a 40 mmφ extruder (set temperature 260 ° C.) to obtain a composition-1 pellet.

Using the pellet, a test piece was prepared by an injection molding machine (set temperature 300 ° C.) and evaluated by the following method.

Haze (℃): ASTM D 1003 Flexural modulus (kg / cm ² ): ASTM D 790 Izod impact strength (kg · cm / cm): ASTM D 256 The results are shown in Table 2.

Example 6 Example 6 was repeated except that PMP-1 was 50% by weight and PMH-I was 50% by weight. The results are shown in Table 2.

Example 7 Example 5 was repeated except that PMH-II was used instead of PMH-I in Example 5. The results are shown in Table 2.

Comparative Example 3 The procedure of Example 5 was repeated except that PMP-1 was used alone in Example 5. The results are shown in Table 2.

Comparative Example 4 The procedure of Example 5 was repeated except that PMH-III was used in place of PMH-I in Example 5. The results are shown in Table 2.

Claims (1)

[Claims] 1. (a) Poly-4-methyl-1-pentene (A) 95 to 20% by weight, (b) 4-methyl-1-pentene content of 40 to 80 mol%, and melting point of 140 to 220. ℃, softening point 90 to 190 ℃
And crystallinity by X-ray is in the range of 15 to 35% 4
-Methyl-1-pentene and carbon number 4 to 6 (however, 4
(Except methyl-1-pentene) and a random copolymer (B) of 5 to 80% by weight with an α-olefin, which is excellent in transparency and heat sealability.