JPH06306212A - Polyolefinic resin composition - Google Patents

Abstract

PURPOSE:To obtain a polyolefinic resin composition excellent in processability. CONSTITUTION:The polyolefinic resin composition comprises (A) 100 pts.wt. polyolefin, (B) 0.001-10 pts.wt. fibrous polytetrafluoroethylene, as necessary, (C) 0.1-100 pts.wt. core-shell graft copolymer obtained by carrying out the graft copolymerization of (b) 60-5 pts.wt. monomeric component composed of a copolymerizable vinyl compound capable of providing >=25 deg.C glass transition temperature when polymerized in itself with (a) 40-95 pts.wt. cross-linked rubber- like polymer having <=25 deg.C glass transition temperature and/or (D) 0.1-400 pts.wt. inorganic filler.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a polyolefin resin composition comprising polyolefin, fibrous polytetrafluoroethylene, and optionally a core-shell graft copolymer and an inorganic filler, which has improved processability. Regarding

[0002]

2. Description of the Related Art Polyolefins are widely used because they are inexpensive and have excellent physical properties. However, for example, polypropylene has (1) a low viscosity and a low tension when melted,
Therefore, the thermoformability such as the vacuum formability of the sheet, the calender formability, the blow moldability, and the foam moldability are not good,
(2) Rigidity is inferior to polystyrene, polyvinyl chloride, ABS resin, etc., (3) Poor impact resistance at low temperature, (4) Surface property, that is, surface gloss, hardness, paintability, etc. are not good. It has drawbacks such as.

In order to improve the processability of the polypropylene, it is widely practiced to physically mix polyethylene and the like, but the effect of improving the processability by adding polyethylene is insufficient and therefore many polyethylene components are required. Therefore, the rigidity is lowered. Further, the viscosity and tension at the time of melting have been improved by increasing the molecular weight of polypropylene, but this is not preferable because it makes extrusion molding, which is an important processing method of polypropylene, difficult.

Attempts have been made to improve processability by adding an uncrosslinked acrylic polymer to polyethylene (US Pat. No. 4,156,703), but the compatibility of the acrylic polymer is insufficient. In calendering or extrusion, the acrylic polymer is separated from polyethylene because it is not crosslinked, and adheres to the roll surface of the calender and the die surface of the extruder (plate out). Therefore, the actual situation is that the workability is rather reduced.

To improve the inherent low rigidity of polyolefin,
In addition, an inorganic filler or the like is added for the purpose of preventing a decrease in rigidity due to the addition of polyethylene or the like, but the compatibility with the polyolefin is low, and the improvement in dispersion significantly reduces the surface property of the molded product, for example, an extruded sheet. It has the drawback.

In order to improve impact resistance, a physical mixture of rubber components such as ethylene-propylene rubber, or
The introduction of rubber components by polymerization such as block copolymerization is widely performed. However, physical mixing or introduction of a rubber component by polymerization is insufficient in controlling the dispersed particle size, so that the use effect of the rubber component is low and the impact resistance improving effect is insufficient. Therefore, a large amount of rubber component is required, leading to a decrease in rigidity. Further, since the particle diameter of the dispersed rubber component is large, the surface gloss is reduced.

A core-shell type modifier which has been widely used as an impact resistance improver in polyvinyl chloride resins and the like has been capable of efficiently dispersing a rubber component (core layer) having a preset particle diameter. This is an excellent method for improving impact resistance by suppressing deterioration of rigidity. However, in non-polar polyolefins,
The core-shell type modifier has low compatibility and its use is limited.

Although it has been proposed to add a core-shell type modifier to a polyolefin in the presence of a specific compatibilizing agent (Japanese Patent Laid-Open No. 3-185037, US Pat. No. 4,997,884), It is not preferable because the synthesis of the compatibilizing agent is complicated, there are problems that the cost is increased by using the compatibilizing agent, and the system becomes complicated.

As described above, the fact is that a polyolefin resin having excellent workability, impact resistance, rigidity and surface property has not yet been obtained.

[0010]

An object of the present invention is to provide a polyolefin resin composition having excellent processability.

[0011]

The present invention provides a polyolefin resin composition comprising (A) 100 parts of polyolefin (parts by weight; the same applies hereinafter) and (B) 0.001 to 10 parts of fibrous polytetrafluoroethylene. Regarding things.

[0012]

The polyolefin used in the present invention includes polypropylene, high density, low density or linear low density polyethylene, poly-1-butene, polyisobutylene, propylene and ethylene and / or 1-butene. Random or block copolymer in the ratio of, ethylene and propylene in an arbitrary ratio, the diene component is 50% (wt%; hereinafter the same) less than terpolymer ethylene-propylene-diene, polymethylpentene Random with ethylene or propylene and vinyl compounds such as 50% or less of vinyl acetate, methacrylic acid alkyl ester, acrylic acid alkyl ester, and aromatic vinyl.
Block or graft copolymers and the like are included. Preferred polyolefins include propylene-based polyolefin containing 50% or more of propylene, and propylene of 5
A mixture of 100 parts of a propylene-based polyolefin containing 0% or more and 0.1 to 100 parts of an ethylene-based polyolefin containing 50% or more of ethylene can be mentioned.
Those having a melt flow index according to STM D1238 of 10 g / 10 minutes or less, preferably 5 g / 10 minutes or less, more preferably 2.5 g / 10 minutes or less have high melt tension and excellent processability. According to ASTM D1238, the melt flow index is 230 ° C. for a propylene-based polyolefin at 2.16 Kg load and 190 ° C. for an ethylene-based polyolefin at 2.1.
Measured with a 6 Kg load.

The fibrous polytetrafluoroethylene used in the present invention is typically a high molecular weight polytetrafluoroethylene obtained by emulsion polymerization or the like,
It is made into a fiber by applying a shearing force. Even polytetrafluoroethylene, which does not become fibrous due to a difference in synthesis method, is not used in the present invention.

[0014] Polytetrafluoroethylene powder may be kneaded and processed into a polyolefin obtained by previously applying a shearing force to the fiber, or may be kneaded with the polyolefin while applying a shearing force to form a fiber. The one that is fibrous in the polyolefin-based resin composition,
All are included in the present invention.

The fibrous polytetrafluoroethylene has a diameter of about 2 μm or less, preferably about 1 μm when formed into a fiber.
m or less, and more preferably about 0.5 μm or less. The length cannot be generally specified because it takes a network structure, but it is about 3 μm or more, preferably about 5 μm or more, more preferably about 10 μm or more.

Commercially available raw materials for obtaining fibrous polytetrafluoroethylene include Polyflon TFE-F103 and F104 manufactured by Daikin Industries, Ltd. and Teflon TFE-6J, 6C-J and 62-J manufactured by Mitsui Jupon. As a representative example.

In the present invention, by mixing a small amount of fibrous polytetrafluoroethylene with polyolefin, the tension at the time of melting is increased in the processing of the polyolefin-based resin composition, the removability at the time of calendering, the heat-forming at the time of thermoforming or Drawdown of molten resin during blow molding,
Cell open cell formation during foam molding is improved, and processability such as calendering, thermoforming, blow molding and foam molding is improved. Further, the discharge amount at the time of extrusion molding and the surface condition of the extrusion molded product such as a sheet and a film are improved, and the extrusion processability is improved.

In the present invention, the fibrous polytetrafluoroethylene is 0.005 parts based on 100 parts of the polyolefin.
1 to 10 parts are included. If it is less than 0.001 part, the workability improving effect is not sufficient, and if it is more than 10 parts, versatility such as low cost is impaired, which is not preferable. This range is preferably 0.005 to 5 parts, more preferably 0.005 to
3 parts.

The present invention relates to (A) polyolefin 100
Part, (B) fibrous polytetrafluoroethylene 0.00
1-10 parts and (C) (a) glass transition temperature of 25 ° C.
40 to 95 parts by weight of the following crosslinked rubbery polymer,
(B) If it is polymerized by itself, the glass transition temperature is 25 ° C.
Polyolefin resin composition containing 0.1 to 100 parts of core-shell graft copolymer obtained by graft-copolymerizing 60 to 5 parts by weight of a monomer component composed of the above-described copolymerizable vinyl compound Also related to things.

In the present invention, a polyolefin resin composition having excellent impact resistance can be obtained by mixing the core-shell graft copolymer. Improving impact resistance is
Calender molding, extrusion molding related to polyolefin,
It is expressed in all processing methods such as thermoforming, blow molding, injection molding and foam molding. Further, the die swell is reduced, and the dispersibility of the inorganic filler is improved when the inorganic filler is mixed as described later, thereby improving the surface state of the sheet and the film during calendar processing or extrusion processing. To be done. Further, the tension at the time of melting is increased, and the workability of thermoforming, blow molding, foam molding and the like is improved. In addition, shrinkage and warpage during injection molding are improved, and injection moldability is improved.

The amount of core-shell graft copolymer is 0.
If it is less than 1 part, the workability and impact resistance improving effects are not sufficient, and if it is more than 100 parts, the heat resistance inherent to the polyolefin,
It is not preferable because it impairs properties such as rigidity. This range is preferably 0.5 to 70 parts, more preferably 0.5 to 5 parts.
It is 0.

The core-shell graft copolymer used in the present invention has a glass transition temperature of 25 ° C or higher when a crosslinked rubbery polymer having a glass transition temperature of 25 ° C or lower is polymerized in the core layer alone. It is a core-shell type graft copolymer having a hard layer made of a vinyl compound in a shell layer. The core-shell graft copolymer referred to in the present invention can be obtained by graft copolymerizing (a) a crosslinked rubbery polymer with (b) a monomer component composed of a copolymerizable vinyl compound.

The cross-linked rubber-like polymer is, for example, a polymer having a glass transition temperature of 25 ° C. or lower, which is composed of 60 to 100% of a diene compound and 40 to 0% of a vinyl compound copolymerizable therewith. Rubber, an alkyl acrylate 60 having an alkyl group with 2 to 22 carbon atoms
~ 100% and vinyl compound 40 copolymerizable therewith
Acrylic rubber consisting of ˜0% is mentioned, and acrylic rubber is particularly preferable. Other typical examples are crosslinked rubber-like polymers such as olefin rubber and silicone rubber.

As the diene compound used for the diene rubber, butadiene, isoprene, chloroprene, etc., and as the vinyl compound copolymerizable therewith,
Typical examples are aromatic vinyl compounds, methacrylic acid alkyl esters having an alkyl group having 1 to 22 carbon atoms, acrylic acid alkyl esters having an alkyl group having 1 to 22 carbon atoms, and unsaturated nitrile compounds.

As the aromatic vinyl compound, styrene,
α-methylstyrene, etc., whose alkyl group has 1 to 2 carbon atoms
Examples of the alkyl methacrylate of 2 include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, etc. Examples of the alkyl acrylate having 1 to 22 include ethyl acrylate,
Typical examples of the unsaturated nitrile compound include n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, and acrylonitrile and methacrylonitrile. . Further, as a copolymerizable vinyl compound, an acid anhydride group, a carboxylic acid group,
It is also possible to use vinyl compounds having reactive functional groups such as amino groups and hydroxy groups, such as maleic anhydride, methacrylic acid, acrylic acid, methacrylamide, acrylamide, dimethylaminoethyl methacrylate, hydroxyethyl methacrylate, and hydroxyethyl acrylate. Is. These copolymerizable vinyl compounds may be used in a mixture of one or more, if necessary.

The alkyl acrylate having 2 to 22 carbon atoms in the alkyl group used for the acrylic rubber is ethyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, acrylic acid. 2-ethylhexyl, stearyl acrylate, etc.
Other examples of the vinyl compound copolymerizable therewith include the above-mentioned aromatic vinyl compound, methyl acrylate, the above-mentioned methacrylic acid alkyl ester having an alkyl group having 1 to 22 carbon atoms, and the above-mentioned unsaturated nitrile compound. Take as an example.

As a cross-linking method for obtaining a cross-linked rubbery polymer, a method generally used in this field can be used. For example, self-crosslinking with butadiene, crosslinking with the use of polyfunctional crosslinking agents such as divinylbenzene, 1,3-butanediol dimethacrylate, crosslinking with the use of grafting agents such as allyl methacrylate, allyl acrylate, diallyl phthalate, peroxidation. For example, material bridge. These can be used together. The crosslinked rubbery polymer is prepared so that the crosslinked gel content is 50% or more, preferably 60% or more. 5
When the content is 0% or less, for example, in calendering, the resin plate-outs on the roll surface, and the workability improving effect is not always sufficient.

The crosslinked gel component is immersed in a good solvent for the rubber component, such as toluene or methyl ethyl ketone for 48 hours,
It is measured as insoluble matter separated by an ultracentrifuge.

As the copolymerizable vinyl compound used in the graft polymerization for obtaining the core-shell graft copolymer, the above-mentioned aromatic vinyl compound and the above-mentioned methacrylic acid having an alkyl group having 1 to 22 carbon atoms can be used. Typical examples thereof include alkyl esters, alkyl acrylates having 1 to 22 carbon atoms in the alkyl group, and unsaturated nitrile compounds described above.

As the aromatic vinyl compound, styrene and α-methylstyrene, which have good polymerizability and are low in cost, and the methacrylic acid alkyl ester has 1 to 1 carbon atoms.
A methacrylic acid alkyl ester of 4 is preferred.

The core-shell graft copolymer has, for example, (a) 40 to 95 parts by weight of a crosslinked rubbery polymer having a glass transition temperature of 25 ° C. or lower, and (b) a polymer having a glass transition temperature when polymerized by itself. It can be obtained by graft-copolymerizing 60 to 5 parts by weight of a monomer component composed of a copolymerizable vinyl compound having a temperature of 25 ° C or higher.

Preferably, (a) 40 to 95 parts of the crosslinked rubber-like polymer, and (b) another vinyl copolymerizable with 100 to 50% of at least one of an aromatic vinyl compound and alkyl methacrylate. It is obtained by graft-copolymerizing 60 to 5 parts of a monomer component consisting of 0 to 50% of the compound.
When the amount of the crosslinked rubber-like polymer (a) is 40 parts or less, the processability and impact resistance improving effects are lowered, and when it is 95 parts or more, the graft copolymer is lumped, which is not preferable.

The glass transition temperature of the crosslinked rubbery polymer is 25.
When the temperature is higher than ℃, the workability and the impact resistance improving effect tend to decrease. In addition, the glass transition temperature of the polymerized only with the monomer component used in the graft copolymerization is 25
If the temperature is lower than 0 ° C, the graft copolymer tends to agglomerate.

The glass transition temperature as referred to herein and its measurement are well known in this field, as is apparent from, for example, Polymer Handbook 2nd Edition (1975). Further, in the present invention, the glass transition temperature of the copolymer is a value calculated by the following formula.

1 / Tg = Wa / Tga + Wb / Tgb Tg: glass transition temperature of copolymer comprising components (a) and (b) Tga: component (a) glass transition temperature of homopolymer Tgb: component (b) Glass transition temperature of homopolymer Wa: Weight fraction of component (a) Wb: Weight fraction of component (b) The core-shell graft copolymer can be polymerized by ordinary radical polymerization, suspension polymerization, emulsion polymerization. Although a polymerization method such as that described above is used, emulsion polymerization is preferable from the viewpoint of controlling the particle size and particle structure. Further, the particles can be enlarged by adding an acid, a salt, a coagulant or the like. The particle size is
It is preferably 3 microns or less in terms of surface property.

The present invention relates to (A) polyolefin 100
Part, (B) fibrous polytetrafluoroethylene 0.00
It also relates to a polyolefin resin composition comprising 1 to 10 parts and (D) an inorganic filler of 0.1 to 400 parts.

The present invention particularly relates to (A) 100 parts of a polyolefin having a melt index of 2.5 g / 10 minutes or less,
(B) Fibrous polytetrafluoroethylene 0.001-
A polyolefin resin composition comprising 10 parts and (D) 0.1 to 400 parts of an inorganic filler is preferable, and
(A) 100 parts of at least one kind selected from the group consisting of polyethylene-based polyolefins consisting of at least 50% by weight of ethylene, polypropylene and ethylene-propylene random copolymer, (B) fibrous polytetrafluoroethylene 0.001-10 And a (D) inorganic filler of 0.1 to 400 parts are preferred.

In these inventions, the inclusion of 0.1 to 400 parts of the inorganic filler improves rigidity and heat resistance and improves workability such as adhesion prevention to the roll surface in calendering. Cost reduction can be achieved. If it is less than 0.1 part, the effect of improving rigidity is not sufficient,
When it is more than 400 parts, the surface property is deteriorated, which is not preferable. This range is preferably 1-350 parts, more preferably 1-3.
It is 00 copies. A polyolefin having a melt index of 2.5 g / 10 min or less was used because it has good dispersibility in fibrous polytetrafluoroethylene, core-shell graft copolymer, inorganic filler, etc. This is because the effect such as high is achieved. Further, at least one selected from the group consisting of polyethylene-based polyolefins consisting of at least 50% by weight of ethylene, polypropylene and ethylene-propylene random copolymer is used as the polyolefin because it is versatile and inexpensive.

The inorganic filler used in the present invention includes:
Typical examples include heavy calcium carbonate, light calcium carbonate, talc, glass fiber, magnesium carbonate, mica, kaolin, calcium sulfate, barium sulfate, titanium white, white carbon, carbon black, ammonium hydroxide, magnesium hydroxide and the like. . Preference is given to heavy calcium carbonate, light calcium carbonate, talc and the like.

The present invention further comprises (A) 100 parts of polyolefin, (B) 0.001 to 10 parts of fibrous polytetrafluoroethylene, (C) 0.1 to 100 parts of the core-shell graft copolymer, and (D) Inorganic filler 0.
It also relates to a polyolefin resin composition comprising 1 to 400 parts.

In the present invention, by containing the four components (A) to (D) in the above proportions, the workability and impact resistance are excellent, and the deterioration of the surface properties of the extruded sheet, which is usually observed when an inorganic filler is added, is reduced. To be prevented.

If necessary, additives such as stabilizers and lubricants may be added to the polyolefin resin compound of the present invention. As a stabilizer, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-]
Hydroxyphenyl) propionate], triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] and other phenolic stabilizers, tris (monononylphenyl) phosphite, tris ( Phosphorus stabilizers such as 2,4-di-t-butylphenyl) phosphite, sulfur stabilizers such as dilaurylthiodipropionate, and lubricants such as lauric acid, palmitic acid, oleic acid, or stearic acid. The sodium, calcium or magnesium salts thereof are typical examples.

The polyolefin resin composition of the present invention is
It is obtained by mixing the polyolefin with the fibrous polytetrafluoroethylene and optionally the core-shell graft copolymer and the inorganic filler.
As the mixing method, conventionally well-known methods such as extrusion kneading and roll kneading are used. Further, it is also possible to mix the emulsified dispersion of polytetrafluoroethylene and the emulsified dispersion of the core-shell graft copolymer and then use the mixture in the form of an agglomerated mixture.

Further, fibrous polytetrafluoroethylene, core-shell graft copolymer, inorganic filler and a part of polyolefin are mixed to prepare a masterbatch, and then the rest of polyolefin and core-shell graft copolymer. It is also possible to perform multi-stage mixing such as further adding and mixing an inorganic filler.

The polyolefin resin composition obtained according to the present invention has greatly improved processability, impact resistance, rigidity and surface property, and is a processing method which cannot be processed by conventional polyolefin resin compositions. Including the above, a molded product can be produced by various processing methods, and a useful molded product can be obtained.

The processing method of the polyolefin resin composition improved by the present invention includes calendering, extrusion,
Typical examples are thermoforming, blow molding, injection molding and foam molding.

Representative examples of useful molded articles obtained in the present invention include sheets, film-shaped molded articles, thermoformed articles, hollow molded articles, injection molded articles and foamed molded articles.

Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited by these.

Example 1 As polytetrafluoroethylene, 0.1 part of powder of Polyflon TFE-F104 manufactured by Daikin Industries, Ltd., 100 parts of powder of polypropylene manufactured by Mitsui Petrochemical and Hypol-B-200 were heated at room temperature at high speed with a Henschel mixer. At the same time as stirring and mixing, shearing was applied to form polytetrafluoroethylene into fibers. Mix the mixture with screw diameter 4
4mm, twin screw extruder with L / D of 30 at 200 ° C,
It was extruded at 100 rpm, kneaded, and pelletized. The mixing ratio is shown in Table 1. Various test pieces were obtained by roll-kneading and pelletizing the obtained pellets at 200 ° C. The appearance of roll sheets during roll kneading was visually compared. The evaluation method was as follows: ◯: the surface was not uneven and the gloss was excellent, Δ: the surface was slightly uneven and the gloss was slightly inferior, and ◯: the surface unevenness was remarkably inferior. ASTM-D
In accordance with 256, ASTM-D790, Izod impact resistance test and flexural elasticity test were performed. Also, in the same way,
A sheet was formed into a 100 mm square and a thickness of 1.5 mm, fixed with a clamp having an opening of 76 mm square, and the drawdown of the sheet was measured in an oven at 190 ° C. for 30 minutes. In addition, the obtained pellets are 200 ° C in a Toyo Seiki Capillograph, die φ2mm × 10mm, extrusion speed 2
The melt tension was measured at 0 mm / min and a take-up speed of 1 m / min. Further, using the pellets obtained in the same manner, the melt flow index at 230 ° C. was measured according to ASTM-D1238. The results obtained are shown in Table 2.
Shown in.

Examples 2 to 6 and Comparative Examples 1 to 3 Tests were conducted in the same manner as in Example 1 except that the mixing ratio was changed as shown in Table 1. The results are shown in Table 2.

The one containing fibrous polytetrafluoroethylene has a significantly higher melt tension than the one not containing it, and the drawdown, which is an index of thermoformability, blow moldability, etc., is remarkably improved. You can see that Further, when the fibrous polytetrafluoroethylene in the roll sheet of Example 3 was dyed with ruthenium and observed with a transmission microscope, the fibrous polytetrafluoroethylene had a diameter of 0.05 to 0.3 μm and a length of 5 .About.20 .mu.m or more.

[0052]

[Table 1]

[0053]

[Table 2]

Examples 7 to 9 and Comparative Examples 4 to 6 Formulation Examples Containing Core-Shell Graft Copolymer [Production of Core-Shell Graft Copolymer A] Polymerization was carried out by ordinary emulsion polymerization to obtain crosslinked polybutadiene rubber. . No cross-linking agent was used. The particle size was 2500 Å, and the crosslinked gel content was 85%. In the presence of 70 parts (solid content) of the obtained polybutadiene rubber latex,
30 parts of a monomer component consisting of 15 parts of methyl methacrylate and 15 parts of styrene was graft-copolymerized by ordinary emulsion polymerization. The final conversion was 98% and the particle size was 2600 angstroms. The obtained polymer latex was salted out by a usual method, dehydrated and dried to obtain a graft copolymer A.

[Production of Core-Shell Graft Copolymer B] A cross-linked polybutyl acrylate rubber was obtained by polymerizing a monomer component consisting of 100 parts of n-butyl acrylate and 1 part of allyl methacrylate by ordinary emulsion polymerization. . Particle size is 2
000 Å, crosslinked gel content was 85%. In the presence of 70 parts (solid content) of the obtained crosslinked polybutyl acrylate rubber latex, methyl methacrylate 27
And 3 parts of n-butyl methacrylate monomer component 3
0 part was graft-copolymerized by ordinary emulsion polymerization. The final conversion was 98% and the particle size was 2200 angstroms. The obtained polymer latex was salted out by a usual method, dehydrated and dried to obtain a graft copolymer B.

Kneading and molding were carried out in the same manner as in Example 1 except that polypropylene, fibrous polytetrafluoroethylene and the core-shell graft copolymer were blended as shown in Table 3, and the results were evaluated by testing. I did. The results are shown in Table 4.

A mixture of fibrous polytetrafluoroethylene and a graft copolymer in polypropylene was a mixture of only the graft copolymer (Comparative Example 4).
The impact resistance is improved as compared with the above (6). Further, it is understood that the melt tension is increased and the drawdown of the sheet is remarkably improved. Further, it is understood that the combined use of both improves the surface property of the roll sheet at the same time as drawdown.

[0058]

[Table 3]

[0059]

[Table 4]

Examples 10 to 15 and Comparative Examples 7 to 12 Compounding examples containing an inorganic filler Polypropylene, polyethylene, fibrous polytetrafluoroethylene, core-shell graft copolymer, fatty acid surface-treated particle size 0.15 μm Kneading and molding were carried out and tested in the same manner as in Example 1 except that the light calcium carbonate of was blended as shown in Table 5 and evaluated. The results are shown in Table 6.

A mixture of fibrous polytetrafluoroethylene, an inorganic filler and, if necessary, a graft copolymer in polypropylene was compared with one containing no fibrous polytetrafluoroethylene (Comparative Examples 7 to 12). hand,
It can be seen that the melt tension is increased and the workability, especially the drawdown of the sheet, is improved. Also, shock resistance,
It can be seen that the balance of rigidity is also excellent.

[0062]

[Table 5]

[0063]

[Table 6]

[0064]

EFFECT OF THE INVENTION The polyolefin resin composition of the present invention has a large tension when melted during processing, retrievability during calendering, drawdown of molten resin during thermoforming or blow molding, and foaming during foam molding. It has good open cell properties and excellent workability in calendering, thermoforming, blow molding, foam molding, etc. Further, when the composition of the present invention is used, the surface condition of an extruded product such as a sheet and a film is improved, and the extrusion processability is good. Further, a mixture of the core-shell graft copolymer has excellent impact resistance, a small die swell,
Further, the mixture of the inorganic additives further improves the surface condition of the sheet and film during calendering or extrusion.

Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI Technical display location C08L 51/04 LKX 7308-4J LKY 7308-4J 53/00 LLV 7308-4J LLY 7308-4J // (C08L 23 / 00 27:18)

Claims (12)

[Claims] 1. (A) 100 parts by weight of polyolefin and (B) 0.001 of fibrous polytetrafluoroethylene.
A polyolefin resin composition comprising 10 to 10 parts by weight. 2. (A) 100 parts by weight of polyolefin,
(B) Fibrous polytetrafluoroethylene 0.001-
10 parts by weight and (C) (a) glass transition temperature of 25 ° C.
40 to 95 parts by weight of the following crosslinked rubbery polymer,
(B) If it is polymerized by itself, the glass transition temperature is 25 ° C.
A polyolefin resin containing 0.1 to 100 parts by weight of a core-shell graft copolymer obtained by graft-copolymerizing 60 to 5 parts by weight of the above-mentioned copolymerizable vinyl compound monomer component. Composition. 3. (A) 100 parts by weight of polyolefin,
(B) Fibrous polytetrafluoroethylene 0.001-
10 parts by weight, (C) (a) 40 to 95 parts by weight of a crosslinked rubbery polymer having a glass transition temperature of 25 ° C or lower, and (b) a polymer having a glass transition temperature of 25 ° C or higher when polymerized by itself. Monomer component 60 composed of a polymerizable vinyl compound
A polyolefin resin composition comprising 0.1 to 100 parts by weight of a core-shell graft copolymer obtained by graft-copolymerizing 5 parts by weight, and 0.1 to 400 parts by weight of (D) an inorganic filler. 4. The melt flow index of the polyolefin is 10 g / 10 minutes or less, 1, 2, or 3.
The polyolefin resin composition described. 5. The polyolefin resin composition according to claim 1, 2 or 3, wherein the melt flow index of the polyolefin is 2.5 g / 10 minutes or less. 6. (A) The melt flow index is 2.
100 parts by weight of polyolefin of 5 g / 10 minutes or less,
(B) Fibrous polytetrafluoroethylene 0.001-
A polyolefin resin composition comprising 10 parts by weight and 0.1 to 400 parts by weight of (D) an inorganic filler. 7. The polyolefin-based resin composition according to claim 1, wherein the polyolefin is a propylene-based polyolefin containing at least 50% by weight of a propylene unit. 8. A propylene-based polyolefin 1 in which the polyolefin contains at least 50% by weight of propylene units.
The polyolefin resin composition according to claim 1, 2, 3, 4, 5, or 6, which comprises a mixture of 00 parts by weight and 0.1 to 100 parts by weight of an ethylene-based polyolefin containing at least 50% by weight of an ethylene unit. 9. The method according to claim 1, wherein the polyolefin comprises at least one selected from the group consisting of polypropylene, ethylene propylene random copolymer and ethylene propylene block copolymer. Polyolefin resin composition. 10. The polyolefin is polypropylene,
Propylene-based polyolefin 100 comprising at least one selected from the group consisting of ethylene-propylene random copolymers and ethylene-propylene block copolymers
0.1 parts by weight of ethylene-based polyolefin comprising at least one selected from the group consisting of low density polyethylene, linear low density polyethylene and high density polyethylene.
To 100 parts by weight of a mixture.
The polyolefin resin composition according to 4, 5, or 6. 11. (A) 100 parts by weight of at least one kind selected from the group consisting of ethylene-based polyolefins consisting of at least 50% by weight of ethylene, polypropylene and ethylene propylene random copolymer, (B) fibrous polytetrafluoro A polyolefin resin composition comprising 0.001 to 10 parts by weight of ethylene and 0.1 to 400 parts by weight of (D) an inorganic filler. 12. The polyolefin resin composition according to claim 3, 6 or 11, wherein the inorganic filler is calcium carbonate and / or talc.