JPH07138444A - Modified polyolefin-based resin composition, its production and polyolefin-based resin composition containing the same - Google Patents

Abstract

PURPOSE:To provide a method for production of a modified polyolefin-based resin composition, a modified polyolefin-based resin composition produced according to this method excellent in improving effect of workability, and a polyolefin- based resin composition excellent in workability, impact resistance, stiffness, surface properties, etc. CONSTITUTION:This method for production of a modified polyolefin-based resin composition is carried out by heating an aqueous suspension containing (b) a vinyl monomer component in an amount of 1 to 500 pts.wt. based on 100 pts.wt. crystalline polyolefin having <=10g/10min melt flow index and a radical polymerization initiator in an amount of 0.01 to 10 pts.wt. based on 100 pts.wt. (b) component under a condition in which the component (b) is not polymerized by itself in some cases and subsequently polymerizing the component (b). According to this production method, a modified polyolefin-based resin composition is obtained and a polyolefin-based resin composition can be obtained by blending this modified polyolefin-based resin composition, a core-shell graft copolymer and/or an inorganic filler with a polyolefin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a modified polyolefin resin composition, a modified polyolefin resin composition obtained therefrom, and a polyolefin resin composition containing the same. More specifically, a method for producing a modified polyolefin resin composition having improved melting properties and exhibiting an excellent effect of improving processability, a modified polyolefin resin composition obtained by the method, and the modified polyolefin resin composition The present invention relates to a polyolefin resin composition containing a resin composition, which simultaneously exhibits excellent processability, impact resistance, rigidity, surface properties and the like and can be suitably used for various molded articles and the like.

[0002]

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

However, polypropylene, for example, has a low viscosity and a low tension when melted, and therefore is inferior in vacuum formability (hereinafter referred to as thermoformability), calender moldability, blow moldability, foam moldability, etc. to a sheet, Rigidity and impact resistance at low temperature are small compared to polystyrene, polyvinyl chloride, ABS resin, etc., and surface property (surface gloss),
There are drawbacks in terms of workability such as poor hardness and applicability.

Therefore, polyethylene or the like is generally mechanically mixed for the purpose of improving the workability of the polypropylene, but since the effect of improving the workability is insufficient,
The disadvantage is that a large amount of polyethylene is required and the rigidity of the resulting mixture is reduced. Attempts have also been made to improve the viscosity and tension of the polyolefin when it is melted by increasing the molecular weight of the polyolefin. However, polyolefin having a large molecular weight is difficult to extrude, which is one of the important processing methods. There is a big problem that there is.

Further, 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 between the two is insufficient. Also, since the acrylic polymer is not cross-linked, during calendar molding, extrusion molding, etc.
There is a problem that the acrylic polymer separates from the polyolefin and adheres to the roll surface of the calender, the die surface of the extruder (hereinafter, this is referred to as plate-out), and the workability deteriorates.

Further, for the purpose of improving processability such as thermoformability of the polypropylene, a polyolefin, a methacrylate polymer and a methacrylate obtained by polymerizing a methacrylate monomer in the presence of a polyolefin in a hydrocarbon solvent are used. Attempts have been made to add a mixture of grafted polyolefins to polypropylene (Japanese Patent Laid-Open No. 22216/1990), but a large amount of the mixture is necessary in order to sufficiently bring out the effect of improving such processability. Moreover, since the high temperature solution polymerization method is used, there are problems in terms of manufacturing cost and safety. Furthermore, it is necessary to remove the solvent when mixing the polyolefin,
There is a problem of poor workability and safety.

Further, vinyl monomers are polymerized in an aqueous suspension in the presence of polypropylene particles at a temperature at which polypropylene does not substantially melt (Japanese Patent No. 1219793).
It was attempted to improve the processability such as thermoformability of polypropylene by adding particles of the obtained vinyl polymer to polypropylene (Japanese Patent No. 1241800). The particles of the vinyl polymer are characterized in that, when added to polypropylene, the fine dispersion units are uniformly dispersed in the mixture without agglomeration, but the compatibility with polypropylene is insufficient, There is a problem that the effect of improving the processability of polypropylene is substantially insufficient only by uniformly dispersing the vinyl polymer in polypropylene.

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

Conventionally, a core-shell type modifier which has been widely used as an impact resistance improver in polyvinyl chloride resins and the like efficiently disperses a rubber component (core layer) having a preset particle diameter. It is possible to suppress the decrease in rigidity and improve the impact resistance. However, for polyolefins that are non-polar, the core-shell modifier has a low compatibility,
The problem is 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 compatibilizing agent (JP-A-3-185037 and US Pat. No. 4,997,884). However, there is a problem that the process of synthesizing the compatibilizing agent is complicated, the cost is increased by using the compatibilizing agent, and the system becomes complicated.

Thus, excellent workability, impact resistance,
The reality is that a polyolefin resin that simultaneously satisfies physical properties such as rigidity and surface properties has not been proposed, and the development of a polyolefin resin that simultaneously satisfies these physical properties has been awaited.

[0012]

Therefore, the present inventors have found that
As a result of repeated intensive studies in view of the above-mentioned prior art, when an aqueous suspension containing a specific crystalline polyolefin and a vinyl-based monomer is heated at a specific temperature, a molded product such as a sheet is formed. A modified polyolefin-based resin composition excellent in the effect of improving moldability (hereinafter referred to as processability) is obtained, and the modified polyolefin-based resin composition is further added to the polyolefin, and further the core-shell graft copolymer and / or the inorganic filler is filled. Excellent workability when mixed with agents
The inventors finally found that a polyolefin-based resin composition exhibiting physical properties such as impact resistance, rigidity, and surface property can be obtained, and completed the present invention.

[0013]

That is, the present invention is
1 to 500 parts by weight of the vinyl-based monomer component (b) and 100 parts by weight of the vinyl-based monomer component (b) based on 100 parts by weight of the crystalline polyolefin (a) having a melt flow index of 10 g / 10 minutes or less. On the other hand, an aqueous suspension containing 0.01 to 10 parts by weight of the radical polymerization initiator (c) is sometimes used under the condition that the vinyl monomer component (b) does not polymerize by itself. After heating, the vinyl-based monomer component (b) is polymerized, a method for producing a modified polyolefin-based resin composition, the modified polyolefin-based resin composition obtained by the above-described method, and polyolefin (A) 100. Polyolefin resin composition obtained by mixing 0.01 to 100 parts by weight of the modified polyolefin resin composition (B) with 100 parts by weight of polyolefin (A), based on parts by weight. On the other hand, 0.01 to 100 parts by weight of the modified polyolefin resin composition (B) and 40 to 95 parts by weight of the crosslinked rubbery polymer (d) are added to the monomer component (e) 5 consisting of a vinyl compound. A mixture of 0.01 to 100 parts by weight of a core-shell graft copolymer (C) obtained by graft copolymerizing 60 parts by weight and / or 0.1 to 1000 parts by weight of an inorganic filler (D). The present invention relates to a polyolefin resin composition.

[0014]

Functions and Examples As described above, the method for producing the modified polyolefin resin composition of the present invention comprises 100 parts by weight of a crystalline polyolefin (a) having a melt flow index of 10 g / 10 minutes or less (parts by weight, the same applies hereinafter). With respect to 1 to 500 parts of the vinyl-based monomer component (b) and 100 parts of the vinyl-based monomer component (b), a radical polymerization initiator (c)
An aqueous suspension containing 0.01 to 10 parts is heated under conditions where the vinyl-based monomer component (b) does not substantially polymerize by itself, and then the vinyl-based monomer component ( b) is polymerized.

The crystalline polyolefin (a) used in the present invention has a melt flow index of 10 g / 10 minutes or less. When the melt flow index exceeds 10 g / 10 min, the modified polyolefin resin composition obtained has a polyolefin backbone grafted with a vinyl polymer comprising the vinyl monomer component (b). The average molecular weight becomes small, and the effect of improving the workability cannot be sufficiently exhibited. The melt flow index of the crystalline polyolefin (a) is preferably 5 g / 10 minutes or less, more preferably 1 g / 10 minutes or less. The melt flow index is measured according to ASTM D1238 under a load of 2.16 kg, and is, for example, a value at 230 ° C for propylene-based polyolefin and a value at 190 ° C for ethylene-based polyolefin.

The crystalline polyolefin (a) has crystallinity, for example, propylene homopolymer,
Examples thereof include ethylene homopolymers, α-olefin homopolymers, and propylene-based copolymers with, for example, one or more kinds of ethylene, α-olefins, ethylenically unsaturated monomers, and the like. Examples include, for example, isotactic polypropylene, syndiotactic polypropylene, propylene-ethylene random copolymer, propylene-ethylene block copolymer, high density polyethylene, low density polyethylene, linear low density polyethylene, poly-1-butene. , Polyisobutylene, polymethylpentene and the like, and these may be used alone or in admixture of two or more.

In the present invention, the crystalline polyolefin (a) is a modified polyolefin resin obtained by polymerizing a propylene-based polyolefin obtained by polymerizing a monomer component containing 75% by weight or more of propylene. The composition is preferred because it has excellent compatibility with the polyolefin (A), particularly polypropylene-based polyolefin, and can sufficiently exhibit the effect of improving processability.

The crystalline polyolefin (a) has a melting point of 150 ° C. or less, particularly 150 ° C.
The following propylene-based polyolefin, as will be described later, when the aqueous suspension is heated to a temperature higher than the temperature at which its crystalline portion substantially starts melting, the temperature at which the melting starts and the heat or oxidation causes The temperature at which the main chain of the polyolefin is not broken (170 to 180 in the present invention)
(A temperature of about 0 ° C.) is wide, which is preferable in that the vinyl-based monomer component (b) is easily polymerized.

The shape of the crystalline polyolefin (a) is not particularly limited, and examples thereof include pellets, powder, latex, dispersion and the like.

As the vinyl-based monomer component (b),
For example, aromatic vinyl compounds such as styrene and α-methylstyrene; methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, etc. For example, a methacrylic acid alkyl ester whose alkyl group has 1 to 22 carbon atoms; methyl acrylate, ethyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, For example, stearyl acrylate and the like, for example, an alkyl group having 1 to
Acrylic acid alkyl ester of 22; unsaturated nitrile compounds such as acrylonitrile and methacrylonitrile, and copolymerizable with them, maleic anhydride, methacrylic acid, acrylic acid, methacrylamide, acrylamide, dimethylaminoethyl methacrylate, acrylic Acid anhydride groups such as acid dimethylaminoethyl, hydroxyethyl methacrylate, hydroxyethyl acrylate,
Other vinyl-based monomers having a reactive functional group such as a carboxyl group, an amino group and a hydroxyl group can be given.
These may be used alone or in combination of two or more.

In the present invention, since a modified polyolefin resin composition capable of exhibiting the effect of improving the processability more sufficiently when mixed with the polyolefin (A) described later is obtained, the monomer component used Considering versatility and cost, as the vinyl-based monomer component (b), an aromatic vinyl compound, an alkyl group having 1 to 22 carbon atoms,
Especially 1 to 4 methacrylic acid alkyl esters, 1 to 22 carbon atoms of the alkyl group, especially 1 to 8
Of 80% by weight or more of at least one selected from alkyl acrylates and unsaturated nitrile compounds and 20% by weight or less of other vinyl monomers copolymerizable therewith are preferable. Styrene and methacrylic acid More preferably 80% by weight or more of at least one selected from methyl and n-butyl acrylate and 20% by weight or less of other vinyl monomers copolymerizable therewith, more preferably styrene, methyl methacrylate and acrylic. Particularly preferred is n-butyl acid.

As the radical polymerization initiator (c),
A radical initiation point is generated in the crystalline polyolefin (a), and the polymerization and grafting of the vinyl-based monomer component (b) can be efficiently progressed, so that about 5
A modified polyolefin-based resin composition having a half-life at 0 to 200 ° C. of preferably about 1 hour and capable of exhibiting a sufficient effect of improving processability when mixed with a polyolefin (A) described later is provided. For this purpose, those which are oil-soluble and have a high hydrogen abstraction property are preferable.

Specific examples of the radical polymerization initiator (c) include acetyl peroxide, succinic acid peroxide, t-butyl peroctoate, benzyl peroxide, t-butyl peroxymaleic acid, 1-hydroxy-1. -Hydroperoxydicyclohexyl peroxide, 1,1-bis (t-butylperoxy) -3,
3,5-Trimethylcyclohexane, t-butylperoxycrotonate, 2,2-bis (t-butylperoxybutane), t-butylperoxyisopropyl carbonate, t-butylperoxybivalate, lauroyl peroxide, t -Butyl peroxyisobutyrate,
Di-t-butyl peroxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate,
2,5-Dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexane, 2,5-dimethyl-2,5
-Bis (benzoylperoxy) hexane, t-butylperacetate, 2,5-dimethyl-di (hydroperoxy) hexane, t-butylhydroperoxide, t-
Butyl cumyl peroxide, p-menthane hydroperoxide, methyl ethyl ketone peroxide, di-t-butyl peroxyphthalate, t-butyl perbenzoate, dicumyl peroxide, 2,5-dimethyl-2,5
-Di (t-butylperoxy) hexane, 2,4-pentanedione peroxide, azobisisobutyronitrile and the like can be mentioned, and these can be used alone or in admixture of two or more.

The modified polyolefin resin composition of the present invention comprises a crystalline polyolefin (a) having a melt flow index of 10 g / 10 minutes or less, a vinyl monomer component (b) and a radical polymerization initiator (c). After heating the aqueous suspension containing the vinyl monomer component (b) under conditions where the vinyl monomer component (b) does not polymerize by itself, the vinyl monomer component (b) is polymerized. available.

The mixing ratio of the crystalline polyolefin (a), the vinyl monomer component (b) and the radical polymerization initiator (c) in the aqueous suspension is 100 parts by weight of the crystalline polyolefin (a). The vinyl monomer component (b) is 1 to 500 parts, preferably 5 to 200 parts, and more preferably 10 to 100 parts. When the blending amount of the vinyl-based monomer component (b) is less than 1 part, the modified polyolefin-based resin composition is a polyolefin grafted with a vinyl-based polymer including the vinyl-based monomer component. When the polymerization amount is small, the effect of improving the processability becomes insufficient, and when it exceeds 500 parts, the polymerization of the vinyl-based monomer components (b) becomes the main component. Excessive aggregation, fusion, agglomeration and the like will occur in the aqueous suspension of.

The vinyl-based monomer component (b) 100
0.01 parts by weight of the radical polymerization initiator (c)
-10 parts, preferably 1-10 parts, more preferably 1 part
~ 5 parts. When the amount of the radical polymerization initiator (c) blended is less than 0.01 part, the polymerization of the vinyl-based monomer component (b) and the generation of a radical initiation point for the crystalline polyolefin (a) are unsuccessful. Since it becomes sufficient, it becomes difficult to obtain a modified polyolefin resin composition exhibiting a sufficient effect of improving the processability, and when it exceeds 10 parts, the radical polymerization initiator (c) is Since it is excessive, the polyolefin-based resin composition obtained by using the modified polyolefin-based resin composition becomes a cause of decomposition and deterioration during thermoforming, for example.

The heating under the condition that the vinyl monomer component (b) does not polymerize by itself means T-50.
To T-5 (° C), preferably a temperature represented by T-40 to T-5 (° C) (T is 10 of the radical polymerization initiator (c)).
Time half-life temperature (° C) is shown).
By heating the aqueous suspension to such a temperature, the vinyl-based monomer component (b) becomes a crystalline polyolefin (a).
It is preferable that the vinyl-based monomer component (b) forms another independent dispersed particle with respect to the crystalline polyolefin (a) and the polymerization is suppressed from proceeding as it is.

The heating time cannot be unconditionally determined because it depends on the types of the crystalline polyolefin (a) and the vinyl-based monomer component (b) used, but it is usually about 5 hours or less. Preferably there is.

Further, in the present invention, when the vinyl-based monomer component (b) is polymerized, the aqueous suspension has a temperature not lower than a temperature at which the crystalline portion of the crystalline polyolefin (a) substantially starts melting. Heating to a high temperature is preferable because the effect of improving the processability of the obtained modified polyolefin-based resin composition is more sufficiently exhibited.

Heating the crystalline part of the crystalline polyolefin (a) to a temperature higher than the temperature at which it substantially starts melting means that the crystalline polyolefin (a) is heated at a heating rate of 10 ° C./min by the DSC measurement method. Under nitrogen flow (40
(ml / min), the temperature is raised from room temperature to complete melting, and the temperature is higher than the temperature between the melting start temperature and the melting point (the temperature corresponding to the apex of the peak in the melting curve) obtained as a result of the measurement. The melting point of ± 20 ° C., especially the melting point of ± 10 ° C. from the viewpoint of increasing the proportion of non-crystalline portion in the crystalline polyolefin (a) and not excessively cutting the polyolefin chain or gelling due to excessive heating. Heating to temperature is preferred.

The time for heating to such a high temperature cannot be unconditionally determined because it depends on the types of the crystalline polyolefin (a) and the vinyl-based monomer component (b) used, but it is usually 0.5. It is preferably about 10 hours.

As described above, when the crystalline part of the crystalline polyolefin (a) is heated to a temperature higher than the temperature at which the crystalline part of the crystalline polyolefin (a) substantially starts melting, the proportion of the non-crystalline part in the crystalline polyolefin (a) becomes large. At the same time as the polymerization of the vinyl-based monomer components (b), the grafting of the vinyl-based polymer comprising the vinyl-based monomer component (b) to the amorphous portion of the crystalline polyolefin (a) is promoted at the same time. It is possible to obtain a modified polyolefin resin composition that is more excellent in the expression of the effect of improving the processability.

When the crystalline part of the crystalline polyolefin (a) is heated to a temperature higher than the temperature at which the crystalline part of the crystalline polyolefin (a) substantially starts melting, as described above, the crystalline polyolefin (a) is heated.
When the melting point of the crystalline polyolefin (a) is 150 ° C. or less, the temperature at which the crystalline portion of the crystalline polyolefin (a) substantially starts melting and the crystalline polyolefin (a) that is mainly melted by heat or oxidation are used. The temperature range where the chain is not broken, that is, the temperature of about 170 to 180 ° C. in the present invention is wide, and the vinyl monomer component (b) is easily polymerized.

As described above, the modified polyolefin resin composition obtained by the production method of the present invention is characterized in that it contains a polyolefin grafted with a vinyl polymer, and when mixed with the polyolefin, it is a vinyl resin. Although it is possible to disperse the polymer uniformly and finely, the polyolefin on which the vinyl polymer is grafted has an effect of improving the processability rather than the effect of the uniform fine dispersion of the vinyl polymer on the expression of the effect of improving the processability. Has a greater effect on the expression of.

When the modified polyolefin resin composition of the present invention is obtained, for example, water, a suspending agent, an emulsifier, a dispersant, etc. may be appropriately used. Under the conditions such as temperature, pressure, stirring, etc. in the manufacturing process of the polyolefin resin composition, the aqueous suspension consisting of the reaction mixture of each component is kept in a stable state to the extent that it does not excessively aggregate or fuse. There is no particular limitation as long as it is drunk.

The polyolefin resin composition of the present invention is
Polyolefin (A) and the modified polyolefin resin composition (hereinafter, modified polyolefin resin composition (B)
That is) and can be obtained by mixing.

Polyolefin (A) used in the present invention
Examples include polypropylene, high density polyethylene, low density polyethylene, linear low density polyethylene, poly-1-butene, polyisobutylene, random or block copolymers of propylene with ethylene and / or 1-butene in any ratio. , Ethylene-propylene-diene terpolymer having a diene component of 10% by weight or less in any ratio of ethylene and propylene, polymethylpentene, ethylene or propylene and 50% by weight or less of vinyl acetate, methacrylic acid alkyl ester Random, block or graft copolymers with vinyl compounds such as alkyl acrylates and aromatic vinyl can be used, and these can be used alone or in admixture of two or more.

In the present invention, as the polyolefin (A), a propylene-based polyolefin obtained by polymerizing a monomer component containing 50% by weight or more of propylene, and 100 parts by weight of the propylene-based polyolefin. , An ethylene-based polyolefin obtained by polymerizing a monomer component containing 50% by weight or more of polyethylene.
A mixture of 1 to 100 parts is preferable because it is easily available and inexpensive.

The polyolefin (A) has a melt flow index of 10 g / 10 minutes or less, preferably 5 g / 10 minutes or less, more preferably 2.5 g / 10.
Those having an amount of less than or equal to minutes have good kneadability and dispersibility with the core-shell graft copolymer (C), the inorganic filler (D), etc., which will be described later, a large tension at the time of melting, and excellent workability. Is desirable because it is sufficiently expressed. The melt flow index is measured according to ASTM D1238 under a load of 2.16 kg. For example, the propylene-based polyolefin has a value at 230 ° C and the ethylene-based polyolefin has a value at 190 ° C.

The mixing ratio of the polyolefin (A) and the modified polyolefin resin composition (B) is 0.01 to 100 for the modified polyolefin resin composition (B) based on 100 parts of the polyolefin (A). Part, preferably 0.0
It is 1 to 20 parts, more preferably 0.01 to 10 parts. When the compounding amount of the modified polyolefin resin composition (B) is less than 0.01 part, it is difficult to sufficiently exert the effect of improving the processability, and when it exceeds 100 parts. Will be less versatile, such as low cost.

The polyolefin resin composition of the present invention is
As described above, it is obtained by mixing the polyolefin (A) and the modified polyolefin resin composition (B), each of which has an adjusted blending amount. In addition to these, the core-shell graft copolymer A coalescence (C), an inorganic filler (D), etc. can be blended.

The core-shell graft copolymer (C)
Is used to further improve the impact resistance, processability, surface property, etc. of the polyolefin (A), wherein the crosslinked rubber-like polymer is used as the core layer, and the hard layer made of the vinyl compound is used as the shell layer. Is a core-shell type graft copolymer. 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 rubber-like polymer forming a core layer.

The core-shell graft copolymer (C) used in the present invention comprises a monomer component (e) (hereinafter referred to as a monomer component (e) composed of a vinyl compound in the crosslinked rubbery polymer (d). A)) is obtained by graft copolymerization.

In the present invention, the crosslinked rubbery polymer (d)
It is preferable that the glass transition temperature is 25 ° C. or lower. When the glass transition temperature of the crosslinked rubber-like polymer (d) exceeds 25 ° C., the resulting core-shell graft copolymer (C) exerts an improving effect such as processability and impact resistance. Tends to fall. The monomer component (e) preferably has a glass transition temperature of 25 ° C. or higher when polymerized by itself.
When the glass transition temperature when the monomer component (e) is polymerized by itself is less than 25 ° C., the core-shell graft copolymer (C) tends to be agglomerated. is there.

The glass transition temperature and its measuring method are described, for example, in Polymer Handbook (INTERSC).
IENCE PUBLISHERS, 2nd Edition, 197
5) and the like, and in the present invention, as the glass transition temperature of the polymer, a value obtained based on the following formula is adopted.

1 / Tg = Wa / Tga + Wb / Tgb Tg: glass transition temperature of copolymer 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: Weight fraction of component b The crosslinked rubbery polymer (d) includes, for example, diene rubber, acrylic rubber, olefin rubber, silicone rubber, etc. Alternatively, the core-shell graft copolymer (C) obtained may be used as a mixture of two or more kinds, but it is excellent in compatibility with the polyolefin (A) and the modified polyolefin resin composition (B). A crosslinked rubber-like polymer (d) containing 50% by weight or more of a diene rubber and / or an acrylic rubber is preferable, and the acrylic polymer is superior in heat stability. The rubber 50
Particularly preferred is the crosslinked rubbery polymer (d), which is contained in an amount of not less than wt%.

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

Examples of the diene compound used in the diene rubber include butadiene, isoprene, chloroprene and the like. These can be used alone or in combination of two or more. The core-shell graft copolymer (C) is excellent in compatibility with the polyolefin (A) and the modified polyolefin resin composition (B), and has an excellent effect of improving processability, impact resistance and surface property, and is inexpensive. From this point, butadiene is preferable.

Other vinyl compounds copolymerizable with the diene compound include aromatic vinyl compounds such as styrene and α-methylstyrene; methyl methacrylate, ethyl methacrylate, n-butyl methacrylate,
For example, methacrylic acid alkyl ester 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., for example, alkyl acrylates whose alkyl group has 1 to 22 carbon atoms; unsaturated nitrile compounds such as acrylonitrile and methacrylonitrile; anhydrous Maleic acid, methacrylic acid, acrylic acid, methacrylamide, acrylamide,
Examples thereof include vinyl compounds having an acid anhydride group such as dimethylaminoethyl methacrylate, hydroxyethyl methacrylate, and hydroxyethyl acrylate, and a reactive functional group such as a carboxyl group, an amino group, and a hydroxyl group, which may be used alone or in combination. Although the above can be mixed and used, among these, the compatibility and processing of the obtained core-shell graft copolymer (C) with the polyolefin (A) and the modified polyolefin resin composition (B) Styrene and n-butyl acrylate are preferred from the viewpoints of excellent properties, impact resistance and surface property improving effects and being inexpensive.

The compounding 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. It is preferable that the amount of the diene compound is 70 to 100% by weight and the amount of the other vinyl compound is 0 to 30% by weight, and the amount of the diene compound is less than 60% by weight, that is, the amount of the other vinyl compound is 40% by weight. If it exceeds%,
Compatibility of the obtained core-shell graft copolymer (C) with the polyolefin (A) and the modified polyolefin-based resin composition (B) and the effects of improving processability, impact resistance and surface property tend to decrease. is there.

As a typical example of the acrylic rubber, for example, 60 to 100% by weight of an alkyl acrylate whose alkyl group has 2 to 22 carbon atoms and another vinyl compound which can be copolymerized with the acrylic acid alkyl ester are used.
An acrylic rubber or the like made up of -40% by weight may be used.

Examples of the alkyl acrylate having an alkyl group of 2 to 22 carbon atoms used in the acrylic rubber include, for example, ethyl acrylate and acrylic acid n.
-Butyl, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate and the like can be used, and these can be used alone or in admixture of two or more. Then, the obtained core-shell graft copolymer (C) is excellent in compatibility with the polyolefin (A) and the modified polyolefin resin composition (B), and is excellent in processability and impact resistance, and is inexpensive. Therefore, acrylic acid n-
Butyl and 2-ethylhexyl acrylate are preferred.

The other vinyl compound copolymerizable with the alkyl acrylate ester is, for example, an aromatic vinyl compound exemplified as the other vinyl compound copolymerizable with the diene compound; for example, the number of carbon atoms of the alkyl group. Is a methacrylic acid alkyl ester having 1 to 22;
Methyl acrylate; unsaturated nitrile compounds; vinyl compounds having a reactive functional group such as an acid anhydride group, a carboxyl group, an amino group and a hydroxyl group, and the like. These are used alone or in combination of two or more. However, among these, styrene and methyl methacrylate are preferable because they have an excellent effect of improving the processability of the core-shell graft copolymer (C) and are inexpensive.

The amount of the acrylic acid alkyl ester having an alkyl group of 2 to 22 carbon atoms in the acrylic rubber and the other vinyl compound copolymerizable with the acrylic acid alkyl ester is 60% of the acrylic acid alkyl ester. ~ 100 wt% and other vinyl compounds 0 ~
40% by weight, especially acrylic acid alkyl ester 6
5 to 100% by weight and 0 to 35% by weight of other vinyl compound are preferable, and if the amount of the alkyl acrylate ester is less than 60% by weight, that is, the amount of the other vinyl compound is more than 40% by weight. By the way, the compatibility of the obtained core-shell graft copolymer (C) with the polyolefin (A) and the modified polyolefin resin composition (B), and the effect of improving processability and impact resistance tend to decrease. There is.

Examples of the olefinic rubber include ethylene-propylene-diene rubber and butyl rubber, and examples of the silicone rubber include polydimethylsiloxane rubber.

The crosslinked rubbery polymer (d) can be obtained by crosslinking the rubbery polymer such as the diene rubber, the acrylic rubber, the olefin rubber and the silicone rubber.

The crosslinking method is not particularly limited. For example, a self-crosslinking method with butadiene, a method using a polyfunctional crosslinking agent such as divinylbenzene or 1,3-butanediol dimethacrylate, allyl methacrylate,
It can be appropriately selected and used according to the kind of the rubber-like polymer to be used from the usual methods such as a method using a grafting agent such as allyl acrylate and diallyl phthalate and a method using a peroxide. In the case of acrylic rubber, a method of using a polyfunctional crosslinking agent and a grafting agent in combination or a method of using a grafting agent may be adopted. Is preferable in that

The crosslinked rubbery polymer (d) thus obtained is preferably adjusted so that the crosslinked gel content is 50% by weight or more, especially 60% by weight or more. When the crosslinked gel content is less than 50% by weight, when the obtained polyolefin resin composition is subjected to, for example, calender molding, the polyolefin resin composition is plated out on the roll surface and processed. There is a tendency that the effect of improving the sex is not sufficiently exhibited.

The term "crosslinked gel content" means the proportion of insoluble matter separated by ultracentrifugation after the crosslinked rubbery polymer is immersed in a good solvent for the rubber component such as toluene or methyl ethyl ketone for 48 hours. Show.

The monomer component (e) is, for example, an aromatic vinyl compound exemplified as another vinyl compound copolymerizable with a diene compound in the crosslinked rubbery polymer (d); for example, an alkyl group. Has 1 to 2 carbon atoms
A methacrylic acid alkyl ester having 2; for example, an acrylic acid alkyl ester having an alkyl group having 1 to 22 carbon atoms; an unsaturated nitrile compound; a reactive functional group such as an acid anhydride group, a carboxyl group, an amino group or a hydroxyl group. Examples thereof include vinyl compounds and the like, and these can be used alone or in combination of two or more kinds.

As the monomer component (e), 50 to 100% by weight of the aromatic vinyl compound and / or methacrylic acid alkyl ester and 0 to 50% by weight of other vinyl compound copolymerizable therewith are used. The following are preferable because the decrease in the polymerizability and the increase in cost hardly occur.

From the viewpoint of good polymerizability and low cost, styrene and α-methylstyrene are particularly preferable as the aromatic vinyl compound, and the number of carbon atoms of the alkyl group is as the methacrylic acid alkyl ester. Are particularly preferred.

The core-shell graft copolymer (C)
Can be obtained by graft-copolymerizing the monomer component (e) with the crosslinked rubbery polymer (d).

The mixing ratio of the crosslinked rubbery polymer (d) and the monomer component (e) is 40% by weight of the crosslinked rubbery polymer (d).
To 60 parts by weight of the monomer component (e), preferably 10 to 60 parts of the monomer component (e) with respect to 40 to 90 parts of the crosslinked rubbery polymer (d).

When the content of the crosslinked rubbery polymer (d) is less than 40 parts, that is, when the content of the monomer component (e) exceeds 60 parts, the core-shell graft copolymer ( The effect of improving the processability and impact resistance exhibited by C) is reduced, and the amount of the crosslinked rubbery polymer (d) is more than 95 parts, that is, the amount of the monomer component (e) is mixed. When the amount is less than 5 parts, the core-shell graft copolymer (C) becomes agglomerated.

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

The average particle size of the core-shell graft copolymer (C) thus obtained is 3 μm or less, and particularly 2.5 μm or less in order to improve the surface property of the obtained polyolefin resin composition. preferable.

The core-shell graft copolymer (C)
The compounding ratio of 0.01 to 100 parts, preferably 0.1 to 80 parts, relative to 100 parts of the polyolefin (A),
More preferably, the amount is 0.5 to 70 parts. When the blending amount of the core-shell graft copolymer (C) is less than 0.01 part, the surface property, processability, and impact resistance exhibited by the core-shell graft copolymer (C). The effect of improving properties such as properties tends to be insufficient, and when it exceeds 100 parts, properties such as heat resistance and rigidity inherent to the polyolefin (A) tend to deteriorate.

The inorganic filler (D) has the function of improving the rigidity, coatability, printability, etc. of the obtained polyolefin resin composition and realizing cost reduction. Typical examples of the inorganic filler (D) include 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,
Magnesium hydroxide and the like can be mentioned, and these can be used alone or in admixture of two or more, and 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 (D) is preferably about 10 μm or less, more preferably about 5 μm or less in order to improve the surface property of the obtained polyolefin resin composition.

The blending ratio of the inorganic filler (D) is 0.1 to 100 relative to 100 parts of the polyolefin (A).
0 part, preferably 5 to 300 parts, more preferably 10 parts
It is desirable that the content is -100 parts. When the compounding amount of the inorganic filler (D) is less than 0.1 part, the effect of improving the rigidity exhibited by the inorganic filler (D) tends to be insufficient, and the amount is 1000 parts. If it exceeds, the surface property of the obtained polyolefin resin composition tends to be deteriorated.

The method for producing the polyolefin resin composition of the present invention is not particularly limited, and the polyolefin (A) and the modified polyolefin resin composition can be prepared by a conventional method such as an extrusion mixing method or a roll mixing method. The polyolefin resin composition can be obtained by mixing the substance (B), the core-shell graft copolymer (C), the inorganic filler (D) and the like.

The polyolefin resin composition of the present invention is
Although produced as described above, the polyolefin-based resin composition may have, if necessary, further improved processability of a core-shell type which has been used for stabilizers, lubricants, polyvinyl chloride-based resins 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] and other phenolic stabilizers, tris (monononylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite and other phosphorus stabilizers, and dilaurylthio. Examples thereof include sulfur stabilizers such as dipropionate, and these can be used alone or in admixture of two or more. The amount of the stabilizer to be added is usually about 0.01 to 3 parts, preferably about 0.05 to 2 parts, relative to 100 parts of the polyolefin (A).

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

The polyolefin resin composition of the present invention comprises
Since it exhibits greatly improved excellent processability, impact resistance, rigidity, surface property, etc., when a conventional polyolefin resin composition is used from the polyolefin resin composition of the present invention, Useful moldings can be produced by various molding methods including difficult molding methods.

Examples of the molding method used for the polyolefin resin composition of 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,
It is possible to obtain a film-shaped or sheet-shaped molded body. Further, by thermoforming the film or sheet shaped article at a temperature suitable for the polyolefin resin composition used, a thermoformed article can be obtained. Further, for example, an injection molded product or a hollow molded product can be obtained by injection molding or blow molding a pellet obtained by subjecting the composition to extrusion processing. Furthermore, a foaming agent 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.

Next, the method for producing the modified polyolefin resin composition of the present invention, the modified polyolefin resin composition obtained therefrom, and the polyolefin resin composition containing the same are further described based on Examples. Although described in detail, the present invention is not limited to only such embodiments.

EXAMPLE 1 Crystallized random polypropylene particles (DSC melting start temperature 60
℃, DSC melting point 144 ℃, melt flow index at 230 ℃ 0.5g / 10 minutes) 700 parts, styrene 30
0 parts, 3.6 parts of di-t-butyl peroxide (10-hour half-life temperature 124 ° C.), 15 parts of calcium phosphate and 0.45 parts of Latemur PS (manufactured by Kao Corporation) as an emulsifier were mixed and mixed with stirring. To give an aqueous suspension. The aqueous suspension was heated and stirred at 100 ° C. for 1 hour, and then 140
Polymerization was completed by heating and stirring at 5 ° C for 5 hours. The obtained particles are washed with water to remove residual monomers, calcium phosphate, latemur PS and di-t-butyl peroxide, and then dried to obtain modified polypropylene resin composition (B) -1.
I got it.

Example 2 In Example 1, the crystalline random polypropylene particles had a DSC melting start temperature of 80 ° C. and a DSC melting point of 14
4 melt flow index at 7 ° C and 230 ° C
Example 1 except using 700 parts of particles which are g / 10 min
Modified polypropylene resin composition (B) -2
I got it.

Example 3 In Example 1, the crystalline random polypropylene particles had a DSC melting start temperature of 80 ° C. and a DSC melting point of 14
6 melt flow index at 8 ° C and 230 ° C
Example 1 except using 700 parts of particles which are g / 10 min
Modified polypropylene resin composition (B) -3 in the same manner as
I got it.

Example 4 The same as Example 2 except that the polymerization was completed by heating and stirring at 130 ° C. for 5 hours instead of heating and stirring at 140 ° C. for 5 hours. Modified polypropylene resin composition (B) -4 was obtained.

Example 5 The same as Example 2 except that the polymerization was completed by heating and stirring at 120 ° C. for 5 hours instead of heating and stirring at 140 ° C. for 5 hours. Modified polypropylene resin composition (B) -5 was obtained.

Example 6 In Example 1, di-t-butyl peroxide 3.6 was used.
Instead of parts, t-butyl peroxybenzoate (10
Example 3 except that the aqueous suspension was heated and stirred at 90 ° C. for 1 hour and further heated and stirred at 110 ° C. for 5 hours to complete the polymerization. Similarly, a modified polypropylene resin composition (B) -6 was obtained.

Example 7 A modified polypropylene resin composition (B) -7 was obtained in the same manner as in Example 2 except that the compounding amount of di-t-butyl peroxide was changed to 15 parts.

Example 8 In Example 2, 150 parts of n-butyl acrylate and 15 parts of methyl methacrylate were used instead of 300 parts of styrene.
Modified polypropylene resin composition (B) -8 was obtained in the same manner as in Example 2 except that 0 part was used.

Example 9 In Example 1, crystalline homopolypropylene particles (D
SC melting start temperature 80 ° C, DSC melting point 162 ° C, 230
Melt flow index at ℃ 0.5g / 10 minutes) 7
Modified polypropylene resin composition (B) -9 was obtained in the same manner as in Example 1 except that 100 parts was used.

Example 10 In Example 2, the amount of the crystalline random polypropylene particles was changed to 500 parts, the amount of styrene was changed to 500 parts, and the amount of di-t-butyl peroxide was changed to 6 parts. Modified polypropylene resin composition (B) -10 was obtained in the same manner as in Example 2 except for the above.

Example 11 In Example 2, the compounding amount of the crystalline random polypropylene particles was 800 parts, the compounding amount of styrene was 200 parts, and the compounding amount of di-t-butyl peroxide was 2.
Modified polypropylene resin composition (B) -11 was obtained in the same manner as in Example 2 except that the content was changed to 4 parts.

Comparative Example 1 In Example 1, the crystalline random polypropylene particles had a DSC melting start temperature of 80 ° C. and a DSC melting point of 14
A melt flow index of 2 at 9 ° C and 230 ° C
A polypropylene resin composition (B ') was obtained in the same manner as in Example 1 except that 700 parts of particles having a weight of 0 g / 10 minutes were used.

Example 12 Polypropylene (trade name: Hypol-B-200, manufactured by Mitsui Petrochemical Co., Ltd., melt flow index at 230 ° C .: 0.5 g / 10 minutes) (hereinafter referred to as PP) 10
A modified polypropylene resin composition (B) -1 (1 part) was mixed with 0 part, and a twin-screw extruder (screw diameter: 44 mm, L /
D: 30) was extruded and kneaded at 200 ° C. and 100 rpm to form pellets.

The pellets thus obtained are roll-kneaded at 200 ° C. to prepare a roll sheet, which is press-formed to 100 mm.
A sheet with a size of 100 mm and a thickness of 1.5 mm is formed, and the opening is fixed with a clamp with a size of 76 mm × 76 mm, and then 190 ° C
Sheet drawdown (m
m) was measured. The results are shown in Table 1.

Examples 13 to 19 and Comparative Examples 2 to 6 Pelletization was performed in the same manner as in Example 12 except that the composition was changed as shown in Table 1, and a sheet was prepared using the pellets. .

Example 1 was used to draw down the obtained sheet.
It investigated similarly to 2. The results are shown in Table 1.

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

[0096]

[Table 1]

From the results shown in Table 1, Examples 12 to 1
As in 9, the blends of the modified polypropylene resin compositions obtained in Examples 1 to 3 with polyolefin have a small drawdown, which is an index of thermoforming, blow molding, etc., and the workability is remarkably improved. It is understood that it was done. Further, as is clear by comparing Examples 14, 16 and 17, the more the modified polypropylene resin composition obtained from the crystalline polyolefin having a small melt flow index is blended, the smaller the drawdown and the processability. It can be seen that is improved.

Further, it can be seen that the polypropylene resin compositions obtained from crystalline polyolefins having a large melt flow index as in Comparative Examples 5 and 6 have a poor processability improving effect.

Examples 20 to 22 Pelletization was carried out in the same manner as in Example 12 except that the composition was changed as shown in Table 2 to prepare a sheet using the pellets.

Example 1 was used to draw down the obtained sheet.
It investigated similarly to 2. The results are shown in Table 2.

[0101]

[Table 2]

From the results shown in Table 2, Examples 20-2
2, the modified polypropylene resin composition (B) -4, obtained by heating the aqueous suspension to a temperature higher than the temperature at which the crystalline portion of the crystalline polyolefin substantially starts melting.
It can be seen that when (B) -6 is used, drawdown is further reduced and workability is further improved. In addition,
This is also clear from the results of Example 16 (using the modified polypropylene resin composition (B) -2) shown in Table 1 above.

Examples 23 to 29 Pelletization was carried out in the same manner as in Example 12 except that the composition was changed as shown in Table 3 to prepare a sheet.

Example 1 was used to draw down the obtained sheet.
It investigated similarly to 2. The results are shown in Table 3.

[0105]

[Table 3]

From the results shown in Table 3, Examples 23 to 2
9, the modified polypropylene resin compositions (B) -7 to (B) -11 obtained in Examples 7 to 11 are the same as Comparative Examples 2 to 4 shown in Table 1. It can be seen that the drawdown, which is an index for thermoforming, blow molding, etc., is small and the workability is remarkably improved as compared with the case where the modified polypropylene resin composition is not used.

Examples 30 to 31 and Comparative Examples 7 to 8 Emulsion polymerization of butadiene was carried out to obtain crosslinked polybutadiene rubber. The obtained crosslinked polybutadiene rubber had a glass transition temperature of −85 ° C., an average particle size of 0.25 μm and a crosslinked gel content of 85% by weight.

The crosslinked polybutadiene rubber latex 7
To 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.) was added, and graft copolymerization was carried out by emulsion polymerization. A core-shell graft copolymer (hereinafter referred to as a graft copolymer (C)) was obtained.
The final conversion was 98%, and the average particle size of the graft copolymer (C) was 0.26 μm.

This graft copolymer (C) latex was salted out, dehydrated and dried to obtain a powder of the graft copolymer (C), and the composition was changed as shown in Table 4. Pelletization was carried out in the same manner as in Example 12.

The melt tension (g) of the obtained pellets was measured with a Capillograph (manufactured by Toyo Seiki Co., Ltd.) to have a diameter of 1 mm ×
With a 10 mm long die, 200 ° C, extrusion speed 5 m
It was measured at m / min and a take-up speed of 1 m / min. The results are shown in Table 4.

Next, the obtained pellets were roll-kneaded at 200 ° C. to prepare a roll sheet, which was press-molded to obtain a test piece according to each ASTM test shown below.

Using the obtained test piece, ASTM D25
6 and Izod impact test and flexural elasticity test according to ASTM D790. The results are shown in Table 4.

In addition, 10 pellets were prepared in the same manner as described above.
A sheet of 0 mm x 100 mm and a thickness of 1.5 mm is formed and fixed with a clamp having an opening of 76 mm x 76 mm,
Sheet drawdown (mm) for 30 minutes was measured in an oven at 190 ° C. The results are shown in Table 4.

Further, the appearance of the roll sheet during roll kneading was visually observed and the surface condition was evaluated based on the following evaluation criteria. The results are shown in Table 4.

(Evaluation Criteria) A: There is no unevenness on the surface and the gloss is excellent. B: The surface is slightly uneven, and the gloss is slightly inferior. C: The unevenness of the surface is remarkable and the gloss is inferior.

[0116]

[Table 4]

From the results shown in Table 4, Examples 30 to 3
All of the products obtained in No. 1 had a small drawdown, which is an index of thermoforming, blow molding, etc., and the workability was significantly improved, and at the same time, the surface property of the sheet during roll kneading was significantly improved. Also, it can be seen that the impact resistance is remarkably improved.

Further, those obtained in Examples 30 to 31 are
It can be seen that it has an excellent balance of impact resistance and rigidity (flexural elasticity).

Examples 32 to 33 and Comparative Examples 9 to 10 In Examples 30 to 31, light calcium carbonate (average particle size: 0.15 μm) surface-treated with fatty acid without using the graft copolymer (C) was used. ) Was used and pelletized in the same manner as in Examples 30 to 31 except that the composition was changed as shown in Table 5, and roll sheets, test pieces, and sheets were produced using the pellets.

Physical properties of the obtained pellets, roll sheets, test pieces and sheets were examined in the same manner as in Examples 30 to 31. The results are shown in Table 5.

[0121]

[Table 5]

From the results shown in Table 5, Examples 32 to 3
The products obtained in No. 3 have a small drawdown, which is an index for thermoforming, blow molding, etc., and have significantly improved workability, and at the same time, have a good balance of impact resistance and rigidity (flexural elasticity). It turns out that it is excellent.

Examples 34 to 35 and Comparative Examples 11 to 12 In Examples 30 to 31, the graft copolymer (C) and the same light calcium carbonate as those used in Examples 32 to 33 were used, and the compositions were shown in Table 6. Pelletization was performed in the same manner as in Examples 30 to 31 except that the pellets were used, and roll sheets, test pieces, and sheets were produced using the pellets.

Physical properties of the obtained pellets, roll sheets, test pieces and sheets were examined in the same manner as in Examples 30 to 31. The results are shown in Table 6.

[0125]

[Table 6]

From the results shown in Table 6, Examples 34 to 3
The products obtained in No. 5 had a small drawdown, which is an index of thermoforming, blow molding, etc., and the workability was significantly improved, and at the same time, the surface property of the sheet during roll kneading was significantly improved. It can be seen that it has a good balance of impact resistance and rigidity (flexural elasticity).

[0127]

The modified polyolefin resin composition obtained by the production method of the present invention has an excellent effect of improving the processability, and the modified polyolefin resin composition and core-shell graft The polyolefin resin composition of the present invention obtained by mixing a polymer and / or an inorganic filler simultaneously exhibits excellent processability, impact resistance, rigidity, surface properties and the like. A useful molded product can be produced from the resin composition by various molding methods.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] April 19, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0071

[Correction method] Change

[Correction content]

[0071] The method for producing the polyolefin resin composition of the present invention is not particularly limited, and for example, extrusion mixing method, the by conventional methods Poriore <br/> off fin (A) and modified, such as roll mixing method The polyolefin resin composition (B), the core-shell graft copolymer (C), the inorganic filler (D) and the like can be mixed to obtain a polyolefin resin composition.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0121

[Correction method] Change

[Correction content]

[0121]

[Table 5]

[Procedure 3]

[Document name to be amended] Statement

[Name of item to be corrected] 0125

[Correction method] Change

[Correction content]

[0125]

[Table 6]

Claims (26)

[Claims] 1. The melt flow index is 10 g / 1.
Initiation of radical polymerization of 1 to 500 parts by weight of the vinyl-based monomer component (b) and 100 parts by weight of the vinyl-based monomer component (b) per 100 parts by weight of the crystalline polyolefin (a) of 0 minutes or less An aqueous suspension containing 0.01 to 10 parts by weight of the agent (c) is heated under conditions where the vinyl-based monomer component (b) does not substantially polymerize by itself, and then the vinyl-based suspension is added. A process for producing a modified polyolefin resin composition, which comprises polymerizing a monomer component (b). 2. The aqueous suspension is heated under conditions where the vinyl-based monomer component (b) does not substantially polymerize by itself in some cases, and then the crystalline portion of the crystalline polyolefin (a) is substantially present. The method for producing a modified polyolefin-based resin composition according to claim 1, wherein the vinyl-based monomer component (b) is polymerized by heating at a temperature higher than the temperature at which melting is started. 3. The method for producing a modified polyolefin resin composition according to claim 1, wherein the crystalline polyolefin (a) has a melt flow index of 5 g / 10 minutes or less. 4. The method for producing a modified polyolefin resin composition according to claim 1, wherein the crystalline polyolefin (a) has a melt flow index of 1 g / 10 minutes or less. 5. The modified polyolefin-based resin according to claim 1, wherein the crystalline polyolefin (a) is a propylene-based polyolefin obtained by polymerizing a monomer component containing 75% by weight or more of propylene. Method of making the composition. 6. The crystalline polyolefin (a) has a melting point of 1
The method for producing a modified polyolefin resin composition according to claim 1, which is a propylene-based polyolefin at 50 ° C or lower. 7. The vinyl monomer component (b) is an aromatic vinyl compound, a methacrylic acid alkyl ester having an alkyl group having 1 to 22 carbon atoms, and an alkyl group having 1 to 22 carbon atoms.
80% by weight or more of at least one selected from an alkyl acrylate ester and an unsaturated nitrile compound of 22 and another vinyl-based monomer copolymerizable therewith 2
3. The composition according to claim 1, 2, 3 or
A method for producing the modified polyolefin resin composition according to 4, 5, or 6. 8. The vinyl monomer component (b) is styrene,
The composition comprises at least 80% by weight of at least one selected from methyl methacrylate and n-butyl acrylate, and 20% by weight or less of other vinyl monomers copolymerizable therewith. The method for producing the modified polyolefin resin composition according to 4, 5, or 6. 9. The method for producing a modified polyolefin resin composition according to claim 1, wherein the vinyl monomer component (b) is styrene. 10. The method for producing a modified polyolefin resin composition according to claim 1, wherein the vinyl monomer component (b) is methyl methacrylate. 11. The vinyl-based monomer component (b) is n-butyl acrylate, 1, 2, 3, 4, 5 or 6.
A method for producing the modified polyolefin resin composition described. 12. A radical polymerization initiator (c) is used as an aqueous suspension based on 100 parts by weight of a vinyl-based monomer component (b).
1 to 10 parts by weight are contained,
A method for producing the modified polyolefin resin composition according to 3, 4, 5, 6, 7, 8, 9, 10 or 11. 13. The method according to claim 1, 2, 3, 4, 5, 6, 7,
A modified polyolefin resin composition obtained by the method described in 8, 9, 10, 11 or 12. 14. A polyolefin resin composition obtained by mixing 0.01 to 100 parts by weight of the modified polyolefin resin composition (B) according to claim 13 with 100 parts by weight of the polyolefin (A). 15. The polyolefin resin composition according to claim 14, wherein the amount of the modified polyolefin resin composition (B) compounded is 0.01 to 20 parts by weight based on 100 parts by weight of the polyolefin (A). 16. The polyolefin (A) is propylene 5
15. A propylene-based polyolefin obtained by polymerizing a monomer component containing 0% by weight or more.
5. The polyolefin resin composition according to item 5. 17. The polyolefin (A) is propylene 5
Ethylene-based polyolefin obtained by polymerizing a monomer component containing 50% by weight or more of ethylene with respect to 100 parts by weight of a propylene-based polyolefin obtained by polymerizing a monomer component containing 0% by weight or more. The polyolefin resin composition according to claim 14 or 15, which is a mixture of 0.1 to 100 parts by weight. 18. 0.01 to 100 parts by weight of the modified polyolefin resin composition (B) according to claim 13 and 40 to 95 parts of a crosslinked rubbery polymer (d) per 100 parts by weight of the polyolefin (A). Core-shell graft copolymer (C) 0.01 obtained by graft-copolymerizing 5 to 60 parts by weight of a monomer component (e) composed of a vinyl compound in parts by weight.
A polyolefin resin composition obtained by mixing up to 100 parts by weight. 19. The polyolefin (A) is propylene 5
The polyolefin resin composition according to claim 18, which is a propylene-based polyolefin obtained by polymerizing a monomer component containing 0% by weight or more. 20. The polyolefin (A) is propylene 5
Ethylene-based polyolefin obtained by polymerizing a monomer component containing 50% by weight or more of ethylene with respect to 100 parts by weight of a propylene-based polyolefin obtained by polymerizing a monomer component containing 0% by weight or more. The polyolefin resin composition according to claim 18, which is a mixture of 0.1 to 100 parts by weight. 21. To 100 parts by weight of the polyolefin (A), 0.01 to 100 parts by weight of the modified polyolefin resin composition (B) according to claim 13 and 0.1 to 1000 parts of the inorganic filler (D). A polyolefin resin composition obtained by mixing parts by weight. 22. The polyolefin (A) is propylene 5
22. The polyolefin resin composition according to claim 21, which is a propylene-based polyolefin obtained by polymerizing a monomer component containing 0% by weight or more. 23. The polyolefin (A) is propylene 5
Ethylene-based polyolefin obtained by polymerizing a monomer component containing 50% by weight or more of ethylene with respect to 100 parts by weight of a propylene-based polyolefin obtained by polymerizing a monomer component containing 0% by weight or more. 22. The polyolefin resin composition according to claim 21, which is a mixture of 0.1 to 100 parts by weight. 24. 0.01 to 100 parts by weight of the modified polyolefin resin composition (B) according to claim 13, and 40 to 95 parts of the crosslinked rubbery polymer (d) per 100 parts by weight of the polyolefin (A). 0.01 to 1 of a core-shell graft copolymer (C) obtained by graft-copolymerizing 5 to 60 parts by weight of a monomer component (e) composed of a vinyl compound in parts by weight.
A polyolefin resin composition obtained by mixing 00 parts by weight and 0.1 to 1000 parts by weight of the inorganic filler (D). 25. The polyolefin (A) is propylene 5
The polyolefin resin composition according to claim 24, which is a propylene-based polyolefin obtained by polymerizing a monomer component containing 0% by weight or more. 26. The polyolefin (A) is propylene 5
Ethylene-based polyolefin obtained by polymerizing a monomer component containing 50% by weight or more of ethylene with respect to 100 parts by weight of a propylene-based polyolefin obtained by polymerizing a monomer component containing 0% by weight or more. 25. The polyolefin resin composition according to claim 24, which is a mixture of 0.1 to 100 parts by weight.