JP3279714B2 - Polyolefin-based resin composition, method for producing the same, and molded article made therefrom - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyolefin resin composition, a method for producing the same, and a molded article comprising the same. More specifically, the present invention relates to a polyolefin-based resin composition exhibiting excellent workability, impact resistance, rigidity, surface properties, and the like, a method for producing the same, and a molded article formed therefrom.

[0002]

2. Description of the Related Art Hitherto, polyolefins have been widely used for various molded articles because they are inexpensive and have excellent physical properties.

[0003] However, for example, polypropylene has low viscosity and tension at the time of melting, so that it is inferior in vacuum moldability (hereinafter referred to as thermoformability), calender moldability, blow moldability, foam moldability, etc. Rigidity and impact resistance at low temperatures are low, surface properties (surface gloss),
There are drawbacks in workability such as poor hardness and applicability.

In order to improve the processability of the polypropylene, polyethylene and the like are generally mechanically mixed, but the effect of improving the processability is insufficient.
The disadvantage is that a large amount of polyethylene is required, and the rigidity of the resulting mixture is reduced. Attempts have been made to improve the viscosity and tension during melting by increasing the molecular weight of the polyolefin. However, polyolefins having a large molecular weight are difficult to extrude, which is one of the important processing methods. There is a big problem that there is.

It has been proposed to add an uncrosslinked acrylic polymer to polyethylene to improve its processability (US Pat. No. 4,156,703), but the compatibility of both is insufficient. Also, because the acrylic polymer is uncrosslinked, during calendering, extrusion, etc.
There is a problem that the acrylic polymer separates from the polyolefin and adheres to a roll surface of a calender, a die surface of an extruder (hereinafter, this is referred to as a plate-out), and on the contrary, the processability is reduced.

[0006] Further, in order to improve the rigidity inherent in polyolefin and the decrease in rigidity due to the addition of polyethylene, etc.,
Attempts have been made to add inorganic fillers and the like, however, such inorganic fillers have poor compatibility with polyolefins and cause poor dispersion. There is a disadvantage that it is significantly reduced.

Further, for the purpose of improving impact resistance, mechanical mixing of rubber components such as ethylene-propylene rubber, introduction by block copolymerization and the like are generally performed. However, introduction of the rubber component by mechanical mixing, block copolymerization, or the like is difficult to control the particle size of the dispersion, so that the use efficiency of the rubber component is low, and the effect of improving the impact resistance becomes insufficient. Therefore, a large amount of rubber component is required, and there is a disadvantage that the rigidity of the obtained mixture is reduced. Further, there is a disadvantage that the surface gloss is reduced due to the large particle size of the dispersed rubber component.

Conventionally, a core-shell type modifier widely used as an impact resistance improving agent in a polyvinyl chloride resin or the like efficiently disperses a rubber component (core layer) having a predetermined particle size. Thus, the impact resistance can be improved while suppressing the decrease in rigidity. However, for non-polar polyolefins, the core-shell type modifier is less compatible,
There is a problem that it can hardly be used.

Therefore, it has been proposed to add the above-mentioned core-shell type modifier to polyolefin in the presence of a specific compatibilizer (Japanese Patent Application Laid-Open (JP-A) No. 3-185037, US Pat. No. 4,997,884). ), The process of synthesizing the compatibilizer is complicated, and there are problems such as an increase in cost due to the use of the compatibilizer and a complicated system.

[0010] Thus, excellent workability, impact resistance,
In fact, polyolefin resins satisfying physical properties such as rigidity and surface properties at the same time have not yet been proposed, and the development of polyolefin resins satisfying such properties simultaneously has been awaited.

[0011]

SUMMARY OF THE INVENTION Accordingly, the present inventors
As a result of intensive studies in view of the above prior art, as a result of mixing a polyolefin with a core-shell graft copolymer obtained from a specific crosslinked rubbery polymer and a monomer component, and an inorganic filler, Finally, they have found that a polyolefin-based resin composition exhibiting the excellent physical properties at the same time can be obtained, and have completed the present invention.

[0012]

That is, the present invention provides:
0.5 to 70 parts by weight of a core-shell graft copolymer (B) and 100 parts by weight of a propylene-based polyolefin (A) comprising 50% by weight or more of propylene and 0 parts of an inorganic filler (C) a composition obtained by mixing 400 parts by weight, the core - shell graft copolymer (B) is a diene compound 60 to 100 fold a glass transition temperature of 25 ° C. or less
% And other vinyl copolymerizable with the diene compound
Crosslinked rubbery polymer (a) consisting of 0-40% by weight of compound
70 to 95 parts by weight of an aromatic vinyl compound or the like having a glass transition temperature of 25 ° C. or more when polymerized by itself .
And / or alkyl methacrylate 50 to 10
0% by weight and other vinyl copolymerizable with them
Monomer component (b) 5 to 3 consisting of 0 to 50% by weight of compound
0 are those parts by weight was E by graft copolymerization, the mixing is 0.1 to 70 wt% of the polyolefin (A)
The used, the polyolefin (A) and a core - shell graft copolymer (B) and advance (A) / (B) weight
A polyolefin resin characterized in that a master batch is prepared by mixing at a ratio of 5/95 to 95/5 in a ratio, and the master batch is mixed with the remaining polyolefin (A) and inorganic filler (C). Composition, propylene 50
Propylene-based polyolefin (A) comprising at least% by weight
60 to 100% by weight of a diene compound having a glass transition temperature of 25 ° C. or lower based on 100 parts by weight of the diene compound;
0-40 weight of other vinyl compounds copolymerizable with the base compound
% Of a crosslinked rubbery polymer (a) consisting of 70 % to 95% by weight of
Aromatic vinyl compound and / or meta at 5 ° C. or higher
50-100% by weight of alkyl acrylate and
Other vinyl compounds copolymerizable therewith 0 to 50 times
% To 70% by weight of a core-shell graft copolymer (B) obtained by graft copolymerization of 5 to 30 parts by weight of a monomer component (b) consisting of 0.5% by weight of an inorganic filler (C). ~
When mixing 400 parts by weight, the polyolefin (A)
0.1 to 70% by weight of the polyolefin (A)
And the core-shell graft copolymer (B) at a ratio of (A) / (B) of 5/95 to 95/5 by weight in advance.
In mixture to produce a master batch, the master batch and the rest of the polyolefin (A) and the inorganic filler (C)
And a method for producing a polyolefin-based resin composition characterized by mixing the above, and a film or sheet-like molded article, a thermoformed article comprising the polyolefin-based resin composition,
The present invention relates to an injection molded article, a hollow molded article, and a foam.

[0013]

Action and Examples As described above, the polyolefin resin composition of the present invention contains 50% by weight or more of propylene.
Of the propylene-based polyolefin (A) (parts by weight, hereinafter the same), 0.5 to 70 parts of the core-shell graft copolymer (B) and 0 to 70 parts of the inorganic filler (C).
400 to 400 % by weight of a diene compound having a glass transition temperature of 25 ° C. or lower, wherein the core-shell graft copolymer (B) has a glass transition temperature of 25 ° C. or less.
0 to 40% by weight of another vinyl compound copolymerizable with the compound
An aromatic vinyl compound and / or methacrylic acid having a glass transition temperature of 25 ° C. or more when polymerized with 70 to 95 parts of a crosslinked rubbery polymer (a) consisting of
50 to 100% by weight of alkyl ester and these
It is obtained by graft copolymerization of 5 to 30 parts of a monomer component (b) composed of 0 to 50% by weight of another copolymerizable vinyl compound . 1 to 70% by weight of the polyolefin
(A) a core - shell graft copolymer (B) and the advance (A) / (B) is in a weight ratio of 5/95 to 95/5
A masterbatch is prepared by mixing at a ratio, and the masterbatch is mixed with the remaining polyolefin (A) and the inorganic filler (C).

The reasons why the polyolefin-based resin composition of the present invention exhibits excellent properties such as excellent processability, impact resistance, rigidity and surface properties at the same time are considered as follows.

By mixing the core-shell graft copolymer (B) with the polyolefin (A), die swell is reduced, and in particular, the polyolefin (A) and the core-shell graft copolymer (B) are mixed. At the time of mixing, a part of the polyolefin (A) and the core-shell graft copolymer (B) are mixed in advance to prepare a master batch, and the master batch, the remaining polyolefin (A) and the inorganic filler (C) , The dispersibility of the core-shell graft copolymer (B) in the polyolefin (A) is further improved and the tension at the time of melting is increased,
Since the drawdown of the molten resin is improved, it is considered that the processability, impact resistance, and surface properties exhibited by the obtained polyolefin-based resin composition are improved.

Further, in the present invention, a core-shell type graft copolymer which could not be compatible with a polyolefin unless a compatibilizing agent is present is used in the present invention. In the conventional core-shell type graft copolymer, the shell layer is mixed to act as an agent for improving the processability and impact resistance of the polyolefin and to improve the dispersibility of the inorganic filler. In the present invention, the rubber component having a specific glass transition temperature, which is the core layer in the core-shell graft copolymer (B), is completely different from the one having exhibited compatibility with the matrix resin. , Polyolefin (A)
This is considered to be based on the fact that it exhibits compatibility with

When the resin composition obtained by mixing the core-shell graft copolymer (B) with the polyolefin (A) is processed, the core-shell graft copolymer (B) is For example, the reason why the rubber component does not plate out to a calender roll surface, a die surface of an extruder, or the like is because the rubber component does not stick to a high-temperature metal surface. Is not only a crosslinked product, but also the fact that a hard component having a glass transition temperature of 25 ° C. or more is graft-copolymerized as a shell layer in the crosslinked product.

The polyolefin (A) used in the present invention
As it is, such as, for example, polypropylene

[0019] a mixture of polyethylene 0-100 parts per flop propylene 50 wt% or more containing the propylene-based polyolefin and the propylene-based polyolefin 100 parts by polymerizing a monomer that is readily available, that it is cheaper It is preferred in that respect. The polyolefin (A)
Has a melt flow index of 4 at 230 ° C.
g / 10 min or less, especially 0.1 to 3 g / 10 min, has good kneadability and dispersibility with the core-shell graft copolymer (B), the inorganic filler (C), etc. It is preferable because effects such as a large tension are sufficiently exhibited.

In the present invention, the core-shell graft copolymer (B) is used for improving the impact resistance, workability, etc. of the polyolefin (A), and has a glass transition temperature of 25 ° C. or lower. A core-shell type graft copolymer having a hard layer made of a vinyl-based compound having a glass transition temperature of 25 ° C. or more as a shell layer when the crosslinked rubber-like polymer is used as a core layer and polymerized by itself. It is. Further, the core-shell graft copolymer referred to in the present specification is a concept including a graft copolymer of a hard shell component in the presence of a crosslinked rubbery polymer forming a core layer.

The core-shell graft copolymer (B) used in the present invention is a crosslinked rubbery polymer (a) having a glass transition temperature of 25 ° C. or lower (hereinafter referred to as a crosslinked rubbery polymer (a)). A monomer component (b) comprising a copolymerizable vinyl compound having a glass transition temperature of 25 ° C. or higher when polymerized by itself (hereinafter referred to as monomer component (b))
) Is obtained by graft copolymerization.

In the present invention, the crosslinked rubbery polymer (a)
Has a glass transition temperature of 25 ° C. or lower as described above, but when the glass transition temperature exceeds 25 ° C., the processability exhibited by the obtained core-shell graft copolymer (B) is obtained. And the effect of improving impact resistance and the like is reduced. As described above, the glass transition temperature when polymerizing with the monomer component (b) alone is 2%.
If the glass transition temperature is 5 ° C. or higher, but the glass transition temperature is lower than 25 ° C., the core-shell graft copolymer (B) becomes agglomerated.

The glass transition temperature and the method for measuring the glass transition temperature are described in, for example, Polymer Handbook, 2nd edition (197).
5) and the like, and in the present invention, a value determined based on the following equation is adopted as the glass transition temperature of the polymer.

1 / Tg = Wa / Tga + Wb / Tgb Tg: Glass transition temperature of copolymer composed of component a and component b (° C.) Tga: Glass transition temperature of component a (° C.) Tgb: Glass transition temperature of component b (° C.) Wa: weight fraction of component a Wb: the weight fraction of component b the crosslinked rubber-like polymer (a), but di ene systems rubber is used <br/>, if this is easily subjected to emulsion polymerization, it is easy to design the grain structure, and either inexpensive der Ru point
It has better RaYoshimi.

Typical examples of the diene rubber include a diene rubber composed of 60 to 100% by weight of a diene compound and 0 to 40% by weight of another vinyl compound copolymerizable with the diene compound. .

As the diene compound used in the diene rubber, for example, butadiene, isoprene, chloroprene and the like can be mentioned, and these can be used alone or as a mixture of two or more kinds. Butadiene is preferred because the resulting core-shell graft copolymer (B) has excellent compatibility with the polyolefin (A), and has excellent effects of improving processability and impact resistance, and is inexpensive.

Other vinyl compounds copolymerizable with the diene compound include, for example, aromatic vinyl compounds such as styrene and α-methylstyrene; methyl methacrylate, ethyl methacrylate, n-butyl methacrylate;
Alkyl methacrylate having an alkyl group having 1 to 22 carbon atoms such as i-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate; methyl acrylate, ethyl acrylate, acrylic acid n-butyl, acrylic acid i
-Butyl, t-butyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, etc .; alkyl acrylates having an alkyl group having 1 to 22 carbon atoms; unsaturated nitrile compounds such as acrylonitrile, methacrylonitrile; anhydrous Maleic acid, methacrylic acid, acrylic acid, methacrylamide, acrylamide,
Examples thereof include vinyl compounds having a reactive functional group such as an acid anhydride group such as dimethylaminoethyl methacrylate, hydroxyethyl methacrylate, and hydroxyethyl acrylate, and a carboxyl group, an amino group, and a hydroxyl group. Among these, the core-shell graft copolymer (B) obtained is excellent in the compatibility with the polyolefin (A), and the effect of improving the processability and impact resistance is excellent. Styrene and n-butyl acrylate are preferred because they are inexpensive.

The amount of the diene compound and the other vinyl compound copolymerizable with the diene compound in the diene rubber is 60 to 100% by weight of the diene compound and 0 to 40% by weight of the other vinyl compound. Preferably, the diene compound is 70 to 100% by weight and the other vinyl compound is 0 to 30% by weight, and the blending amount of the diene compound is less than 60% by weight, that is, the blending amount of the other vinyl compound is 40% by weight. If it exceeds%,
There is a tendency that the resulting core-shell graft copolymer (B) has a reduced compatibility with the polyolefin (A), and an improved effect on processability and impact resistance.

[0029]

[0030]

[0031]

[0032]

[0033]

[0034] can sell crosslinked rubber-like polymer (a) by crosslinking the diene rubber.

The method of crosslinking is not particularly limited. For example, a method of self-crosslinking with butadiene, a method using a polyfunctional crosslinking agent such as divinylbenzene, 1,3-butanediol dimethacrylate, allyl methacrylate,
The method can be appropriately selected and employed from ordinary methods such as a method using a grafting agent such as allyl acrylate and diallyl phthalate and a method using a peroxide depending on the type of the rubbery polymer to be used. In the case of acrylic rubber, the method of using a polyfunctional crosslinking agent and a grafting agent in combination or the method of using a grafting agent can be employed when crosslinking and graft copolymerization at the same time as graft copolymerization. Is preferred in that

The obtained crosslinked rubbery polymer (a) is preferably adjusted so that the crosslinked gel content is at least 50% by weight, especially at least 60% by weight. When the crosslinked gel content is less than 50% by weight, when the obtained polyolefin-based resin composition is subjected to, for example, calendering, the polyolefin-based resin composition is plate-out on the roll surface and processed. There is a tendency that the effect of improving the properties is not sufficiently exhibited.

The term "crosslinked gel component" refers to the ratio of insoluble components separated by an ultracentrifuge after a crosslinked rubbery polymer is immersed in a good solvent of a rubber component such as toluene or methyl ethyl ketone for 48 hours. Show.

Examples of the monomer component (b) include aromatic vinyl compounds exemplified as other vinyl compounds copolymerizable with a diene compound in the crosslinked rubbery polymer (a); 1 to 22 carbon atoms
Methacrylic acid alkyl ester; for example, alkyl acrylate having 1 to 22 carbon atoms in an alkyl group; unsaturated nitrile compound; having a reactive functional group such as an acid anhydride group, a carboxyl group, an amino group, or a hydroxyl group. vinyl compounds and the like,

[0039] Before SL aromatic vinyl compound and / or methacrylic acid alkyl esters 50-100 wt% and these and other copolymerizable vinyl compounds 0-50
It is preferable that the content is in the range of wt.

Styrene and α-methylstyrene are particularly preferred as the aromatic vinyl compound from the viewpoint of good polymerizability and low cost, and the alkyl methacrylate is preferably an alkyl group having a carbon number of an alkyl group. Is preferably 1 to 8.

The core-shell graft copolymer (B)
Is obtained by graft copolymerizing the monomer component (b) with the crosslinked rubbery polymer (a).

The proportion of the crosslinked rubbery polymer (a) and the monomer component (b) used is 70%.
The monomer component (b) is 5 to 30 parts per 95 to 95 parts, preferably the monomer component (b) 10 to 30 parts per 70 to 90 parts of the crosslinked rubbery polymer (a).

If the amount of the crosslinked rubbery polymer (a) is less than 70 parts, that is, if the amount of the monomer component (b) exceeds 30 parts, the resulting core-shell graft copolymer ( The effect of improving processability and impact resistance exhibited by B) is reduced, and the blending amount of the crosslinked rubbery polymer (a) exceeds 95 parts, that is, the blending of the monomer component (b) When the amount is less than 5 parts, the core-shell graft copolymer (B) becomes agglomerated.

The core-shell graft copolymer (B)
Can be polymerized by ordinary radical polymerization,
For example, a polymerization method such as a suspension polymerization method or an emulsion polymerization method can be employed. Among them, the emulsion polymerization method is preferable from the viewpoint of controlling the particle diameter, the particle structure, and the like. In the present invention, the particles of the obtained core-shell graft copolymer (B) can be enlarged by adding an acid, a salt, a coagulant or the like during the polymerization.

The core-shell graft copolymer (B) thus obtained has an average particle diameter of 3 μm or less, preferably 2.5 μm or less, in order to improve the surface properties of the obtained polyolefin resin composition. preferable.

The inorganic filler (c) used in the present invention comprises:
It has an effect of improving the rigidity, paintability, printability, and the like of the obtained polyolefin-based resin composition. Representative examples of such an inorganic filler (C) include, for example, heavy calcium carbonate, light calcium carbonate, talc,
Glass fiber, magnesium carbonate, mica, kaolin, calcium sulfate, barium sulfate, titanium white, white carbon, carbon black, aluminum hydroxide,
Examples thereof include magnesium hydroxide, and these can be used alone or in combination of two or more. Among them, heavy calcium carbonate, light calcium carbonate, and talc are preferable from the viewpoint of easy availability. The average particle diameter of the inorganic filler (C) is about 10 μm or less,
In particular, it is preferably about 5 μm or less. When the average particle diameter of the inorganic filler (C) exceeds the above range, the surface property of the obtained polyolefin-based resin composition tends to decrease.

The polyolefin resin composition of the present invention comprises
It is obtained by mixing the core-shell graft copolymer (B) and the inorganic filler (C) with the polyolefin (A).

The mixing ratio of the polyolefin (A), the core-shell graft copolymer (B) and the inorganic filler (C) is such that the core-shell graft copolymer (B) is added to 100 parts of the polyolefin (A). 0.5 to 70 parts and 0 to 400 parts of inorganic filler (C), preferably 0.5 to 70 parts of core-shell graft copolymer (B) and 0 to 300 parts of inorganic filler (C). . When the amount of the core-shell graft copolymer (B) is less than 0.5 part, the effect of improving the processability and surface properties exhibited by the core-shell graft copolymer (B) is obtained. Is insufficient, and when it exceeds 70 parts, the original characteristics of the polyolefin (A) are deteriorated. When the amount of the inorganic filler (C) exceeds 400 parts,
The surface property of the obtained polyolefin resin composition is reduced.

In the present invention, when the polyolefin (A), the core-shell graft copolymer (B) and the inorganic filler (C) are mixed, a part of the polyolefin (A) and the core Preparing a masterbatch by pre-mixing the shell graft copolymer (B),
It is preferable to mix the masterbatch, the remaining polyolefin (A) and the inorganic filler (C) in that the dispersibility of the core-shell graft copolymer (B) is further improved.

The amount of the polyolefin (A) to be preliminarily mixed with the core-shell graft copolymer (B) is 0.1 to 70% by weight of the total amount of the polyolefin (A). Is preferred.

Polyolefin (A) and core-shell graft copolymer (B) in the preparation of the master batch
Is 5 to 95% by weight of polyolefin (A).
And 5 to 95% by weight of the core-shell graft copolymer (B), especially 5 to 80% by weight of the polyolefin (A)
And core-shell graft copolymer (B) 20 to 95
% By weight. When the compounding amount of the polyolefin (A) is less than 5% by weight, that is, when the compounding amount of the core-shell graft copolymer (B) exceeds 95% by weight, the viscosity is improved and mixing tends to be difficult. And the blending amount of the polyolefin (A) exceeds 95% by weight, that is, the core-shell graft copolymer (B)
Is less than 5% by weight, the effect of improving dispersibility tends to decrease.

The method for preparing a master batch by previously mixing a part of the polyolefin (A) and the core-shell graft copolymer (B) is not particularly limited. However, among these, the extrusion mixing method is preferable from the viewpoint of productivity and the like.

The method of mixing the masterbatch thus obtained with the remaining polyolefin (A) and the inorganic filler (C) is not particularly limited. Examples of the method include extrusion mixing and roll mixing. It is preferable to select appropriately according to the application.

[0054] Incidentally, after the partially inorganic filler of the polyolefin (A) and (C) were mixed For example other, remaining polyolefin (A) and core to - shell graft copolymer (B) was added Although the polyolefin resin composition can be produced by a multi-stage mixing method such as a mixing method, the composition of the present invention is prepared by a master batch method.
Limited to

The polyolefin resin composition of the present invention comprises:
Although produced as described above, the polyolefin-based resin composition may further include, if necessary, a stabilizer, a lubricant, and a core-shell type processability conventionally used in a polyvinyl chloride-based resin and the like. Agents and the like can be added.

Examples of the stabilizer include pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and triethylene glycol-bis [3- (3-t- Butyl-5-
Methyl-4-hydroxyphenyl) propionate], phosphorus stabilizers such as tris (monononylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, dilaurylthio Examples thereof include sulfur-based stabilizers such as dipropionate, and these can be used alone or in combination of two or more. The amount of the stabilizer is usually about 0.01 to 3 parts, preferably about 0.05 to 2 parts, per 100 parts of the polyolefin (A).

Representative examples of the lubricant include sodium and calcium saturated or unsaturated fatty acids such as lauric acid, palmitic acid, oleic acid and stearic acid.
Examples thereof include magnesium salts, and these can be used alone or in combination of two or more. The amount of such a lubricant is usually about 0.1 to 3 parts, preferably about 0.1 to 2 parts, per 100 parts of the polyolefin (A).

The addition of the stabilizers, lubricants, processability improvers, etc. can be carried out during the preparation of the masterbatch by mixing the masterbatch with the remaining polyolefin (A) and the inorganic filler (C). It may be very special, and there is no particular limitation.

The polyolefin resin composition of the present invention comprises:
Because it exhibits excellent workability, impact resistance, rigidity, surface properties, etc., greatly improved from the polyolefin resin composition of the present invention, when using a conventional polyolefin resin composition, A useful molded article can be produced by various molding methods including the difficult molding method.

Examples of the molding method used in the present invention include a calender molding method, an extrusion molding method, a thermoforming method, an injection molding method, a blow molding method and a foam molding method.

For example, by calendering or extruding the polyolefin resin composition of the present invention,
A film or sheet-like molded product can be obtained. Further, a thermoformed article can be obtained by subjecting the film or sheet shaped article to thermoforming at a temperature suitable for the polyolefin resin composition used. In addition, for example, an injection molded article or a hollow molded article can be obtained by injection molding or blow molding a pellet obtained by subjecting the composition to extrusion processing.

Further, a foam can be obtained by adding a foaming agent to the polyolefin-based resin composition of the present invention and subjecting it to foam molding using, for example, an extruder.

Examples of the blowing agent include trichloromonofluoromethane, methylene chloride, methyl chloride, dichlorodifluoromethane, dichloromonofluoromethane,
Monochlorodifluoromethane, dichlorotetrafluoroethane, halogenated hydrocarbons such as trichlorotrifluoroethane, aliphatic hydrocarbons such as propane, butane, pentane, hexane, alcohols, esters,
Chemical blowing agents such as ketones, ethers, sodium hydrogencarbonate, azodicarbonamide, N, N-dinitrosopentamethylenetetramine, p-toluenesulfonylsemicarbazide, etc., and these may be used alone or in combination of two or more. Among them, among these, for example, the boiling point under normal pressure such as trichloromonofluoromethane and dichlorotetrafluoroethane is -40 to 40
It is preferable to use an organic volatile foaming agent at about 60 ° C. alone or as a mixture of two or more. The amount of the foaming agent is not particularly limited, but it is usually preferably about 3 to 50 parts with respect to 100 parts of the polyolefin resin composition.

Next, the polyolefin-based resin composition of the present invention, the method for producing the same, and the molded article comprising the same will be described in more detail with reference to Examples. However, the present invention is not limited to only these Examples. Absent.

REFERENCE EXAMPLE 1 Crosslinked polybutadiene rubber was obtained by emulsion polymerization of butadiene. The glass transition temperature of the obtained crosslinked polybutadiene rubber was -85 ° C, and the average particle size was 0.2.
5 μm, the crosslinked gel content was 85% by weight.

The above-mentioned crosslinked polybutadiene rubber latex 7
0 parts (solid content), 30 parts of a monomer component consisting of 15 parts of methyl methacrylate and 15 parts of styrene (glass transition temperature of the polymer: 100 ° C.) were added, and graft copolymerization was carried out by emulsion polymerization. A core-shell graft copolymer (hereinafter, referred to as graft copolymer (B) -1) was obtained. The final conversion was 98%, and the graft copolymer (B)-
1 had an average particle size of 0.26 μm.

The latex of the graft copolymer (B) -1 was salted out, dehydrated and dried, and 20 parts of the obtained powder of the graft copolymer (B) -1 was mixed with polypropylene (trade name: Hypol-B). -200, manufactured by Mitsui Petrochemical Co., Ltd.
Melt flow index at 230 ° C: 0.5 g / 1
(0 min) (hereinafter referred to as PP), and extruded and kneaded at 200 ° C. and 100 rpm using a twin-screw extruder (screw diameter: 44 mm, L / D: 30) to form pellets.

The melt tension of the obtained pellets and 230
The melt flow index at 0 ° C was measured according to the following method. Table 1 shows the results.

(A) Melt tension Using a Capillograph (manufactured by Toyo Seiki Co., Ltd.), 200
° C, die 2mm × 10mm, extrusion speed 20mm /
And the melt tension (g) at a take-up speed of 1 m / min.

(B) Melt Flow Index (230 ° C.) The melt flow index (g / 10 minutes) at 230 ° C. was measured according to ASTM-D1238.

Next, the obtained pellets were roll-kneaded at 200 ° C. to prepare a roll sheet, and press-molded to obtain test pieces according to the following ASTM tests.

The appearance of the roll sheet during the kneading of the rolls was visually observed for the surface condition, the presence or absence of thermal coloring, and the presence or absence of plate-out on the roll surface.
The evaluation was made based on the following evaluation criteria. Table 1 shows the results.

(Evaluation Criteria) (A) Surface Condition of Roll Sheet A: The surface has no irregularities and excellent gloss. B: The surface is slightly uneven and the gloss is slightly inferior. C: The surface unevenness is remarkable, and the gloss is inferior.

(B) Thermal coloring of the roll sheet A: No thermal coloring. B: Thermal coloring is slightly observed. C: Thermal coloring is remarkable.

(C) Plate out to roll surface A: Not at all. B: Slightly recognized. C: It's amazing.

Using the obtained test piece, ASTM-D25
6 and ASTM-D790, an Izod impact resistance test and a bending elasticity test were performed. Table 1 shows the results.
Shown in

In the same manner as described above, 10
A sheet having a thickness of 0 mm x 100 mm and a thickness of 1.5 mm is formed, and the opening is fixed with a clamp of 76 mm x 76 mm.
The sheet drawdown (mm) for 30 minutes in an oven at 190 ° C. was measured. Table 1 shows the results.

Reference Example 2 A cross-linked diene rubber was obtained by emulsion polymerization of a monomer component comprising 70 parts of butadiene and 30 parts of styrene. The glass transition temperature of the obtained crosslinked diene rubber was −50 ° C., the average particle size was 0.1 μm, and the crosslinked gel content was 80% by weight.

Next, the core in Example 1, except for using the above way E was crosslinked diene rubber latex 70 parts in place of the crosslinked polybutadiene rubber latex (solid content) in the same manner as in Reference Example 1 -Shell graft copolymer (hereinafter, referred to as graft copolymer (B) -2)
I got The final conversion was 98%, and the average particle size of the graft copolymer (B) -2 was 0.12 μm.

[0080] Further, in Reference Example 1, except that the graft copolymer (B) -1 was changed to the graft copolymer (B) -2 were pelleted in the same manner as in Reference Example 1, using the pellets Roll sheets, test pieces and sheets were prepared.

The physical properties of the obtained pellet, roll sheet, test piece and sheet were examined in the same manner as in Reference Example 1.
Table 1 shows the results.

Reference Examples 3 and 4 In Reference Example 1, the blending amount of graft copolymer (B) -1 was changed to 50 parts ( Reference Example 3), or the blending amount of graft copolymer (B) -1 was changed to 70 parts. A pellet was formed in the same manner as in Reference Example 1 except that the part was changed ( Reference Example 4), and a roll sheet, a test piece, and a sheet were produced using the pellet.

The physical properties of the obtained pellet, roll sheet, test piece and sheet were examined in the same manner as in Reference Example 1.
Table 1 shows the results.

Reference Example 5 A monomer component comprising 100 parts of n-butyl acrylate and 1 part of allyl methacrylate was emulsion-polymerized to obtain a crosslinked polybutyl acrylate rubber. The glass transition temperature of the obtained crosslinked polybutyl acrylate rubber was -55 ° C, the average particle size was 0.2 µm, and the crosslinked gel content was 85% by weight.

A monomer component comprising 27 parts of methyl methacrylate and 3 parts of n-butyl methacrylate (glass transition temperature of the polymer: 95 ° C.) is added to 70 parts (solid content) of the crosslinked polybutyl acrylate rubber latex. Part was added, and graft copolymerization was performed by emulsion polymerization.
A shell graft copolymer (hereinafter, referred to as graft copolymer (B) -3) was obtained. The final conversion was 98%, and the average particle size of the graft copolymer (B) -3 was 0.22 μm.
Met. The obtained latex of the graft copolymer (B) -3 was salted out, dehydrated and dried to obtain a powder of the graft copolymer (B) -3.

[0086] Next, in Example 1, except that the graft copolymer (B) -1 was changed to the graft copolymer (B) -3 are in the same manner as in Reference Example 1 was pelletized, using the pellets Thus, a roll sheet, a test piece and a sheet were prepared.

The physical properties of the obtained pellet, roll sheet, test piece and sheet were examined in the same manner as in Reference Example 1.
Table 1 shows the results.

[0088] In Reference Comparative Examples 1 to 3 Example 1, except that changing the composition as shown in Table 1 in the same manner as in Reference Example 1 was pelletized, prepared roll sheet, test specimen and sheet using the pellets did.

The physical properties of the obtained pellet, roll sheet, test piece and sheet were examined in the same manner as in Reference Example 1.
Table 1 shows the results.

Reference Comparative Example 4 An uncrosslinked polybutyl acrylate rubber was obtained by emulsion polymerization of a monomer component consisting of 100 parts of butyl acrylate. The average particle size of the obtained uncrosslinked polybutyl acrylate rubber is 0.1.
2 μm, the crosslinked gel content was 0% by weight.

To 50 parts (solid content) of the uncrosslinked polybutyl acrylate rubber latex, 50 parts of methyl methacrylate were added, and graft copolymerization was carried out by emulsion polymerization.
Graft copolymer (hereinafter, graft copolymer (B) -4)
). The final conversion was 98%, and the average particle system of the graft copolymer (B) -4 was 0.24 μm.
The latex of the obtained graft copolymer (B) -4 is salted out, dehydrated and dried to obtain the graft copolymer (B) -4.
Powder was obtained.

[0092] Next, in Example 1, except that the graft copolymer (B) -1 was changed to the graft copolymer (B) -4 in the same manner as in Reference Example 1 was pelletized, using the pellets Thus, a roll sheet, a test piece and a sheet were prepared.

The physical properties of the obtained pellet, roll sheet, test piece and sheet were examined in the same manner as in Reference Example 1.
Table 1 shows the results.

Reference Comparative Example 5 A monomer (hereinafter, referred to as polymer-5) was obtained by emulsion polymerization of a monomer component consisting of 100 parts of methyl methacrylate. The final conversion was 98%, and the average particle size of Polymer-5 was 0.1%.
μm, the crosslinked gel content was 0% by weight. The obtained latex of polymer-5 was salted out, dehydrated and dried to obtain polymer-5 powder.

[0095] Next, in Example 1, except that the graft copolymer (B) -1 was changed to the polymer -5 pelletized in the same manner as in Reference <br/> Example 1, using the pellets Roll sheets, test pieces and sheets were prepared.

The physical properties of the obtained pellet, roll sheet, test piece and sheet were examined in the same manner as in Reference Example 1.
Table 1 shows the results.

[0097]

[Table 1]

The LDPE in Table 1 represents a low-density polyethylene having a melt flow index at 190 ° C. of 0.25 g / 10 min (the same applies hereinafter).

From the results shown in Table 1, the core-shell graft copolymers obtained in Reference Examples 1 to 5 were mixed with polypropylene, all of which were polyolefin only ( Reference Comparative Examples 1 to 3). Compared with this, the melt flow index is small and the melt tension is large, so the draw down of the sheet is small and the workability has been improved.The surface condition of the sheet during roll kneading is good, It can be seen that there is no plate out, and the surface properties are remarkably improved. Reference Example 1
It can be seen that all of the samples obtained in Nos. To 5 have an excellent balance between workability, impact resistance, and rigidity (bending elasticity).

When a graft copolymer comprising an uncrosslinked rubbery polymer ( Reference Comparative Example 4) or an uncrosslinked acrylic polymer ( Reference Comparative Example 5) was used, the plate on the roll surface It can be seen that a practical one cannot be obtained because the roll-out is remarkable and the surface condition of the roll sheet is bad.

Furthermore, it can be seen that the one using the crosslinked acrylic rubbery polymer obtained in Reference Example 5 is particularly excellent in terms of thermal coloring and has high thermal stability.

REFERENCE EXAMPLE 6 In Reference Example 1, light calcium carbonate (average particle diameter: 0.15 μm) treated with a fatty acid together with 20 parts of the graft copolymer (B) -1 powder (hereinafter referred to as (C) −
Example 1 was pelletized in the same manner as in Reference Example 1 except that 50 parts of PP was mixed with 100 parts of PP, and a roll sheet, a test piece and a sheet were prepared using the pellets.

The physical properties of the obtained pellet, roll sheet, test piece and sheet were examined in the same manner as in Reference Example 1.
Table 2 shows the results.

Further, the pellets were subjected to a 230-screw extruder (screw diameter: 50 mm, L / D: 20) using a single screw extruder.
Extrude T-die at ℃, width 300mm, thickness 0.5
mm extruded sheet was obtained.

The surface condition of the obtained extruded sheet was visually observed, and evaluated based on the same evaluation criteria as the surface condition of the roll sheet. Table 2 shows the results.

[0106] Reference Example 7-9 and Reference Comparative Examples 6-7 Reference Example 6, except that the composition was changed as shown in Table 2 were pelleted in the same manner as in Reference Example 6, the roll sheet using the pellets, Test pieces, sheets and extruded sheets were prepared.

The physical properties of the obtained pellet, roll sheet, test piece, sheet and extruded sheet were examined in the same manner as in Reference Example 6. Table 2 shows the results.

[0108]

[Table 2]

From the results shown in Table 2, the results obtained by mixing the core-shell graft copolymer and the inorganic filler obtained in Reference Examples 6 to 9 with polypropylene were all obtained by mixing the inorganic filler with only the polyolefin. Compared with Comparative Examples ( Reference Comparative Examples 6 and 7), the melt flow index was small and the melt tension was large, indicating that the sheet had low drawdown and improved workability. In addition, all of those obtained in Reference Examples 6 to 9 have remarkably improved surface properties of the roll sheet and the extruded sheet, and have an excellent balance between workability, impact resistance, and rigidity (bending elasticity). It turns out that it is a thing.

Example 1 60% by weight of a powder of the graft copolymer (B) -1 and P
P40% by weight and a twin screw extruder (screw diameter: 4
4 mm, L / D: 30), 200 ° C., 100 rpm
The mixture was extruded and kneaded at m to prepare a master batch.

50 parts of master batch obtained, PP80
Part, heavy calcium carbonate surface-treated with fatty acid (average particle size: 1.8 μm) (hereinafter referred to as (C) -2) 5
0 part and 0.5 part of calcium stearate (hereinafter referred to as CaS) were mixed, and a twin screw extruder (screw diameter: 4
4 mm, L / D: 30), 200 ° C., 100 rpm
m, and extruded and kneaded, and pelletized.

[0112] From the obtained pellets, rolled sheet in the same manner as in Reference Example 1, test pieces and to produce a sheet, it was examined in the same manner for each of the properties as in Reference Example 1. Table 4 shows the results. The melt tension of the pellet was measured by using a
× 10 mm, and the extrusion speed was changed to 5 mm / min.

The physical properties of the roll sheet were determined by subjecting the obtained roll sheet to osmium staining, observing the dispersibility of the core-shell graft copolymer using a transmission electron microscope, and evaluating the properties based on the following evaluation criteria. Was evaluated.

(Evaluation Criteria) A: Dispersibility is very good . B: Dispersibility is good. C: Dispersibility is not good.

Reference Example 10 The procedure of Example 1 was repeated except that the graft copolymer (B) -1 30
Parts, 100 parts of PP, 50 parts of (C) -2 and CaS
O. Pellets were formed in the same manner as in Example 1 except that 5 parts were mixed at a time, and a roll sheet, a test piece and a sheet were prepared using the pellets.

The physical properties of the obtained pellet, roll sheet, test piece and sheet were examined in the same manner as in Reference Example 8.
Table 4 shows the results.

[0117] In Example 2 Example 1, (C) addition was not used -2 pelletized in the same manner as in Example 1, was prepared roll sheet, test specimen and sheet using the pellets.

The physical properties of the obtained pellet, roll sheet, test piece and sheet were examined in the same manner as in Example 1 .
Table 4 shows the results.

Reference Example 11 A pellet was prepared in the same manner as in Example 1 except that (C) -2 was not used in Reference Example 10 , and a roll sheet, a test piece and a sheet were produced using the pellet.

The physical properties of the obtained pellet, roll sheet, test piece and sheet were examined in the same manner as in Example 1 .
Table 4 shows the results.

[0121] In addition, Examples 1 and 2 and Reference Example 1:10
Table 3 summarizes the kneading methods and compositions in No. 1 .

[0122]

[Table 3]

[0123]

[Table 4]

From the results shown in Table 4, Examples 1 and
A master batch was prepared by previously mixing the core-shell graft copolymer obtained in Part 2 with a part of polyolefin, and the master batch was mixed with the remaining polyolefin, inorganic filler and other components as a reference. Example 1
Compared to a mixture of all the components obtained in 0 and 11 , the dispersibility of the core-shell graft copolymer in the polyolefin is further excellent, the melt flow index is small, and the melt tension is large. Shows that the drawdown is small, the workability is further improved, and the impact resistance is more excellent.

Reference Examples 12 to 14 and Reference Comparative Example 8 Compounds having the compositions shown in Table 5 were supplied to an extruder, which is a pre-treatment step of calendering, and were extruded and kneaded, and the obtained molten resin was inverted L-shaped. 0.5m thick by continuously supplying to the calendar
m rolled sheet was obtained.

The surface condition of the obtained rolled sheet was visually observed and evaluated based on the following evaluation criteria. Table 5 shows the results.

(Evaluation Criteria) A: Surface gloss is excellent. B: Surface gloss is slightly inferior. C: Surface gloss is poor.

[0128]

[Table 5]

HDPE in Table 5 represents high-density polyethylene having a melt flow index at 190 ° C. of 0.25 g / 10 minutes (the same applies hereinafter).

From the results shown in Table 5, reference examples 12 to 1 were obtained.
It can be seen that all of the rolled sheets obtained in No. 4 have excellent surface properties.

Reference Examples 15 to 18 and Reference Comparative Examples 9 to 10 Using the compounds having the compositions shown in Table 6, the mixture was kneaded with a twin-screw extruder in the same manner as in Example 1 and extruded to obtain pellets. From the obtained pellets, a single screw extruder (screw diameter: 50 m
m, L / D: 20), and T-die extrusion was performed at 230 ° C. to obtain an extruded sheet having a width of 300 mm and a thickness of 0.5 mm.

Reference Example 1 shows the surface condition of the obtained extruded sheet.
They were examined in the same manner as 2 to 14. Table 6 shows the results.

[0133]

[Table 6]

The EPR in Table 6 represents an ethylene-propylene rubber having a melt flow index at 190 ° C. of 0.4 g / 10 minutes (the same applies hereinafter).

The results shown in Table 6 indicate that Examples 17 to 2
It can be seen that all of the extruded sheets obtained in No. 0 have extremely good surface properties.

Reference Examples 19 to 20 and Reference Comparative Examples 11 to 12 The rolled sheets and extruded sheets obtained in Reference Examples 14 and 18 and Reference Comparative Examples 8 and 9 were cupped at a heater temperature (upper and lower) of 350 ° C. Die mold (diameter: 80m)
m, depth: 72 mm, draw ratio: 0.9, taper: about 1
The surface of the sheet was heated to about 170 to 180 ° C. using a single-sheet vacuum forming machine (manufactured by Asano Lab.) Having a temperature of 5 ° C., and vacuum forming was performed to obtain a cup-shaped thermoformed body.

The drawdown state of the sheet during heating was visually observed and evaluated based on the following evaluation criteria. Table 7 shows the results.

(Evaluation Criteria) A: Drawdown is small. B: Drawdown is slightly large. C: Drawdown is large.

Further, the thickness variation of the obtained cup-shaped thermoformed body was examined by determining the ratio of the thickness to the original sheet thickness (0.5 mm), and evaluated based on the following evaluation criteria. Table 7 shows the results.

(Evaluation Criteria) A: The thickness deviation is small. B: The thickness unevenness is slightly large. C: The thickness unevenness is large.

[0141]

[Table 7]

From the results shown in Table 7, in Reference Examples 19 and 20 , even when the rolled sheet or the extruded sheet was heated and vacuum formed, It can be seen that the drawdown of the sheet is small and the obtained thermoformed body has a small thickness unevenness.

Reference Examples 21 to 23 and Reference Comparative Examples 13 to 14 Using the compounds having the compositions shown in Table 8, the mixture was kneaded with a twin-screw extruder in the same manner as in Reference Example 1, and extruded to obtain pellets. Using the pellets obtained, injection molding at 230 ° C
A test piece according to the TM test was obtained.

Using the obtained test pieces, an Izod impact resistance test and a bending elasticity test were performed in the same manner as in Reference Example 1. Table 8 shows the results.

Further, the pellets were subjected to injection molding at 230 ° C. to obtain 100 mm × 150 mm and a thickness of 3 mm.
Was produced. The presence or absence of warpage of the obtained flat plate was visually observed, and evaluated based on the following evaluation criteria. Table 8 shows the results.

(Evaluation Criteria) A: Warpage is small. B: The warpage is slightly large. C: The warpage is large.

[0147]

[Table 8]

From the results shown in Table 8, reference examples 21 to 2 were obtained.
The sheet obtained in 3 is impact resistant and rigid (bending elasticity)
It can be seen that the flatness of the flat plate is small and the dimensional stability is improved.

Reference Examples 24 to 25 and Reference Comparative Example 15 A mixture having the composition shown in Table 9 was kneaded with a twin-screw extruder in the same manner as in Reference Example 1, and extruded to obtain pellets. Using the obtained pellets, blow molding was performed at 230 ° C. to obtain a bottle having a thickness of 0.5 mm.

The draw-down state of the parison during blow molding was visually observed, and evaluated based on the same evaluation criteria as those used in Reference Examples 19 and 20 . Table 9 shows the results.
Shown in

Further, the thickness deviation of the obtained bottle was measured by measuring the thickness of each part of the bottle, and the difference between the maximum value and the minimum value was obtained and examined. The difference was the same as that used in Reference Examples 19 to 20 . The evaluation was based on the evaluation criteria. Table 9 shows the results.

[0152]

[Table 9]

From the results shown in Table 9, in Reference Examples 24 and 25 , the drawdown of the parison during blow molding was small, and the obtained bottle had a small thickness unevenness. You can see that.

[0154] After a mixture of formulations having the composition shown in Reference Examples 26-27 and Comparative Reference Example 16 Table 10 as the resin composition, the foam for the manufacture of a diameter 65mm having a circular die with a diameter 10mm at the tip of this It was fed to an extruder. Next,
Trichloromonofluoromethane and dichlorotetrafluoroethane compressed to 100 to 200 kg / cm ² as a foaming agent were supplied from a blowing agent pressure inlet provided in the middle of the extruder for foam production to 100 parts of the resin composition. About 13 parts each. While sufficiently kneading the resin composition and the foaming agent, the mixture was cooled to a temperature suitable for foaming, and extruded from a circular die into the air to obtain a round rod-shaped foam.

The expansion ratio of the obtained foam was determined as a ratio of a volume change to a constant weight. Table 10 shows the results.

The surface condition of the obtained foam was visually observed and evaluated based on the following evaluation criteria. Table 10 shows the results.

(Evaluation Criteria) A: The surface is smooth and the cell structure is uniform. B: Slight irregularities were observed on the surface, and the cells became slightly open cells, resulting in an uneven cell structure. C: The unevenness of the surface is remarkable, the bubbles are connected to each other, and the bubble structure is not uniform.

[0158]

[Table 10]

In Table 10, PPEB represents polypropylene (trade name: Noblen EB, manufactured by Mitsui Toatsu Co., Ltd.) having a melt flow index at 230 ° C. of 0.5 g / 10 min.

From the results shown in Table 10, the foams obtained in Reference Examples 26 and 27 had a high expansion ratio, had a smooth surface, and did not form bubbles. It can be seen that the bubble structure is uniform.

[0161]

The polyolefin resin composition used in the present invention exhibits excellent workability, impact resistance, rigidity and surface properties at the same time even when mixed together. A molded article can be manufactured, and the obtained molded article has an effect that it has excellent impact resistance, rigidity, and surface properties.

The polyolefin resin composition of the present invention comprises :
For producing the two-stage process incorporating all ingredients after first prepared Ma <br/> masterbatch with some components of the polyolefin-based resin composition, without preparing a master batch
Even better workability compared to batch mixing ,
The effect of exhibiting impact resistance and the like is exhibited.

────────────────────────────────────────────────── (5) References JP-A-5-78525 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08J 3/22 C08L 23/00-23 / 36

Claims (15)

(57) [Claims] 1. A process comprising at least 50% by weight of propylene.
For 100 parts by weight of pyrene-based polyolefin (A),
A composition comprising a mixture of 0.5 to 70 parts by weight of a core-shell graft copolymer (B) and 0 to 400 parts by weight of an inorganic filler (C), wherein the core-shell graft copolymer (B)
Is a diene compound 6 having a glass transition temperature of 25 ° C. or lower.
0-100% by weight and copolymerizable with the diene compound
An aromatic vinyl polymer having a glass transition temperature of 25 ° C. or more when polymerized with 70 to 95 parts by weight of a crosslinked rubbery polymer (a) composed of 0 to 40% by weight of another vinyl compound alone.
Compound and / or alkyl methacrylate
50 to 100% by weight and copolymerizable with them
Obtained by graft copolymerizing 5 to 30 parts by weight of a monomer component (b) comprising 0 to 50% by weight of another vinyl compound , wherein the mixture is 0.1 % of polyolefin (A).
To 70% by weight of the polyolefin (A) and the core
The shell graft copolymer (B) and (A) /
(B) is mixed at a weight ratio of 5/95 to 95/5 to prepare a master batch, and the master batch is mixed with the remaining polyolefin (A) and the inorganic filler (C). Polyolefin-based resin composition. Wherein the polyolefin (A) is poly propylene emissions
Polyolefin resin composition of claim 1 wherein is. Wherein the polyolefin (A) a melt flow index of the polyolefin resin composition according to claim 1 or 2, wherein less 4g / 10 min at 230 ° C. for. 4. The method according to claim 1, wherein the aromatic vinyl compound is styrene and / or
Or polyolefin resin composition of claim 1 wherein the α- methyl styrene. 5. A method according to claim 1 or 4 polyolefin resin composition according alkyl methacrylate ester having a carbon number of the alkyl group is of 1 to 8. 6. The method according to claim 1, wherein the core-shell graft copolymer (B) is obtained by emulsion polymerization.
3, 4 or 5 polyolefin resin composition. 7. The method according to claim 1, wherein the core-shell graft copolymer (B) has an average particle size of 3 μm or less.
5 or the polyolefin resin composition of 6, wherein. 8. The method of claim 1, 2, 3, 4 Inorganic filler (C) is calcium carbonate and / or talc, 6
Polyolefin resin composition or 7 wherein. 9. A process comprising 50% by weight or more of propylene.
For 100 parts by weight of pyrene-based polyolefin (A),
Diene compound 60 having a glass transition temperature of 25 ° C. or lower
To 100% by weight and copolymerizable with the diene compound
Other vinyl compounds consisting of 0-40 wt% crosslinked rubber-like polymer (a) 70 to 95 parts by weight, the aromatic vinyl glass transition temperature of 25 ° C. or more when allowed it only polymerization
Compound and / or alkyl methacrylate
50 to 100% by weight and copolymerizable therewith
0.5 to 70 parts by weight of a core-shell graft copolymer (B) obtained by graft copolymerizing 5 to 30 parts by weight of a monomer component (b) comprising 0 to 50% by weight of another vinyl compound ; When mixing 0 to 400 parts by weight of the inorganic filler (C), 0.1 to 70% by weight of the polyolefin (A) is used.
There, the polyolefin (A) and the core - shell graft copolymer (B) and advance (A) / (B) weight ratio
A masterbatch is prepared by mixing at a ratio of 5/95 to 95/5 with a master batch, and the remaining masterbatch is mixed with the remaining polyolefin (A) and inorganic filler (C). Manufacturing method of goods. 10. A film or sheet-like molded product obtained by subjecting the polyolefin resin composition according to claim 1 to calendering. 11. A film or sheet-like molded product obtained by extruding the polyolefin-based resin composition according to claim 1. 12. A thermoformed article obtained by subjecting a film or sheet-shaped molded article comprising the polyolefin resin composition according to claim 1 to thermoforming. 13. An injection molded article obtained by injection molding the polyolefin resin composition according to claim 1. 14. A hollow molded article obtained by blow molding the polyolefin resin composition according to claim 1. 15. A foam obtained by foam-forming the polyolefin-based resin composition according to claim 1, further comprising a foaming agent.