JPH07133398A - Modified polyolefin resin composition, polyolefin resin composition containing it, and molded article made therefrom - Google Patents

Abstract

PURPOSE:To obtain a modified polyolefin resin composition excellent in processability and the effect of improving the compatibility of a nonpolar polymer with a polar polymer, a polyolefin resin composition excellent in processability, impact resistance, rigidity and surface properties, and a molding made therefrom. CONSTITUTION:An aqueous suspension containing 100 pts.wt. crystalline polyolefin (a), 1-500 pts.wt. vinyl monomer component (b), and a radical polymerization initiator (c) in an amount of 0.01-10 pts.wt. based on 100 pts.wt. component (b) is heated under conditions under which the component (b) does not polymerize alone in some cases, the component (b) is allowed to infiltrate into the component (a), and the suspension is then heated above a temperature at which the crystalline part of the component (a) begins to melt to thereby polymerize the component (b), thus giving a resin composition (d). 100 pts.wt. composition (d) is mixed with 0.01-20 pts.wt. stabilizing agent (e) to give a modified polyolefin resin composition. The title polyolefin resin composition contains this composition. Molded articles are made from these compositions.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a modified polyolefin resin composition, a polyolefin resin composition containing the same, and a molded product made from them. More specifically, a modified polyolefin resin composition having improved melting properties, which exhibits an excellent effect of improving processability and an effect of improving compatibility with a nonpolar polymer and a polar polymer,
A polyolefin-based resin composition comprising the modified polyolefin-based resin composition, which simultaneously exhibits excellent processability, impact resistance, rigidity, surface properties and other physical properties, and which can be suitably used for various molded articles, The modified polyolefin-based resin composition, a molded product made of the polyolefin-based resin composition having excellent surface properties, and the modified polyolefin-based resin composition are blended to provide excellent dispersibility between the nonpolar polymer and the polar polymer. It relates to a resin composition.

[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 grafted. Attempts have been made to add a mixture of the above-mentioned polyolefins to polypropylene (Japanese Patent Laid-Open No. 22316/1990), but a large amount of the mixture is necessary in order to sufficiently bring out the effect of improving such processability, In addition, 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 intensive studies in view of the above-mentioned prior art, a stabilizer was added to a resin composition obtained by heating an aqueous suspension containing a crystalline polyolefin and a vinyl monomer at a specific temperature. The modified polyolefin resin composition thus obtained is excellent in the effect of improving the moldability (hereinafter referred to as processability) of a molded article such as a sheet and the effect of improving the compatibility between a nonpolar polymer and a polar polymer. When the modified polyolefin-based resin composition is further mixed with a stabilizer and / or an inorganic filler, a polyolefin-based resin exhibiting excellent physical properties such as processability, impact resistance, rigidity and surface property at the same time. The present invention finally finds that a composition is obtained, and that a molded article excellent in surface properties and the like can be obtained from the modified polyolefin resin composition and the polyolefin resin composition. It has led to the completion.

[0013]

That is, the present invention is
1 to 500 parts by weight of the vinyl-based monomer component (b) with respect to 100 parts by weight of the crystalline polyolefin (a) and 100 parts by weight of the vinyl-based monomer component (b) with a radical polymerization initiator (c). An aqueous suspension containing 0.01 to 10 parts by weight of the vinyl-based monomer component (b) may be added depending on the case.
Is heated under such a condition that it does not polymerize alone, the crystalline polyolefin (a) is impregnated with the vinyl-based monomer component (b), and the aqueous suspension is further mixed with the crystalline polyolefin (a). The stabilizer (e) is added to 100 parts by weight of the resin composition (d) obtained by polymerizing the vinyl-based monomer component (b) by heating to a temperature higher than the temperature at which the crystalline portion substantially starts melting. 0.01 to 20 parts by weight of the modified polyolefin resin composition,
A 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 the polyolefin (A), and 100 parts by weight of the polyolefin (A). 0.01 to 100 parts by weight of the modified polyolefin resin composition (B) and 0.01 to 20 parts by weight of the stabilizer (e) and / or 0.1 to 1000 parts by weight of the inorganic filler (C). A polyolefin-based resin composition obtained by mixing, a modified polyolefin-based resin composition (B) or a film- or sheet-shaped molded product made of the polyolefin-based resin composition,
The modified polyolefin resin composition 0.1 to 1 with respect to 100 parts by weight of a mixture of a hollow molded article, an injection molded article and a foam, a nonpolar polymer and a polar polymer.
The present invention relates to a resin composition containing 0 part by weight.

[0014]

FUNCTION AND EXAMPLE As described above, the modified polyolefin resin composition of the present invention contains 100 parts by weight of the crystalline polyolefin (a) (parts by weight, the same applies hereinafter) to the vinyl monomer component (b). Radical polymerization initiator (c) based on 1 to 500 parts and 100 parts of the vinyl-based monomer component (b)
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 is added. The crystalline polyolefin (a) is impregnated with (b), and the aqueous suspension is further heated to a temperature higher than the temperature at which the crystalline portion of the crystalline polyolefin (a) substantially starts to melt, and a vinyl-based resin is added. 0.01 to 2 of the stabilizer (e) is added to 100 parts of the resin composition (d) obtained by polymerizing the monomer component (b).
It can be contained at a ratio of 0 part.

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 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 monomers having reactive functional groups such as carboxyl group, amino group, hydroxyl group, methylthiomethyl (meth) acrylate, ethylthiomethyl (meth)
Alkylthioalkyl (meth) acrylates such as acrylate, methylthioethyl (meth) acrylate, ethylthioethyl (meth) acrylate; 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl)- Phenol such as 4-methylphenyl (meth) acrylate, 2- {1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl} -4,6-di-t-pentylphenyl (meth) acrylate Examples thereof include group-containing (meth) acrylates, which may be used alone or in admixture 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,
Considering the versatility and cost of the monomer component used, the vinyl-based monomer component (b) has an aromatic vinyl compound, an alkyl group having 1 to 22 carbon atoms, and particularly 1 to 4 carbon atoms. 80% by weight or more of at least one selected from a certain methacrylic acid alkyl ester, an alkyl acrylate having an alkyl group having 1 to 22 carbon atoms, particularly 1 to 8 carbon atoms and an unsaturated nitrile compound, and other copolymerizable with these 20% by weight or less of the vinyl monomer, and 80% by weight or more of at least one selected from styrene, methyl methacrylate and n-butyl acrylate, and other vinyl monomers copolymerizable therewith. It is more preferable that the amount of the monomer is 20% by weight or less, and styrene, methyl methacrylate and n-butyl acrylate are Preferred. Further, from the viewpoint that the thermal stability of the obtained resin composition (d) can be improved, the vinyl-based monomer component (b) includes alkylthioalkyl (meth) acrylate in an amount of 0.01 to 10% by weight and And / or those containing 0.01 to 10% by weight of a phenol group-containing (meth) acrylate.

Among the vinyl-based monomer components (b), the alkylthioalkyl (meth) acrylate and the phenol group-containing (meth) acrylate also have a function as a stabilizer (e) described later. Therefore, in the present invention, these compounds may be used as the vinyl-based monomer component (b), or may be contained as the stabilizer (e) in the resin composition (d) in the blending ratio described below. Good.

As the radical polymerization initiator (c),
A radical initiation point is generated in the crystalline polyolefin (a) which is substantially in a molten state, and the polymerization and grafting of the vinyl-based monomer component (b) can be efficiently progressed, so that it is about 50. It is preferable that the half-life at about 200 ° C. is about 1 hour, and a modified polyolefin resin composition capable of exhibiting a sufficient effect of improving processability when mixed with the polyolefin (A) described later is obtained. 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.

As the stabilizer (e), the main chain cleavage due to the oxidative deterioration of the crystalline polyolefin (a) is suppressed,
Further, those having a function as a stabilizer that suppresses the oxidative deterioration of the polyolefin (A) when mixed with the polyolefin (A) described later are preferable, and the processability during molding is
Those capable of sufficiently suppressing deterioration of physical properties such as impact resistance, rigidity and surface property are preferable.

Specific examples of the stabilizer (e) include tetrakis {methylene-3- (3,5-di-t-).
Butyl-4-hydroxyphenyl) propionate} methane, 2,6-di-t-butyl-4-methylphenol, octadecyl-3- (3,5-di-t-butyl-4)
-Hydroxyphenyl) propionate, triethyleneglycol-bis {3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate}, pentaerythrityl-tetrakis {3- (3,5-di-t-) Butyl-4-hydroxyphenyl) propionate},
3,9-bis [2- {3- (3-t-butyl-4-hydroxy-5-methylphenyl) -propionyloxy}-
Phenolic antioxidants such as hindered phenolic compounds such as 1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane; triphenylphosphite, trisnonylphenylphosphite , Tris (2,4-di-t-butylphenyl) phosphite, bis (nonylphenyl) -dinonylphenylphosphite and other phosphite compounds, and other phosphorus-based antioxidants; dilauryl-3,3'-thio Sulfur-based antioxidants such as sulfur-containing organic esters such as dipropionate, distearyl-3,3'-thiodipropionate, pentaerythrityl tetrakis (3-lauryl thiopropionate) and di-t-dodecyl disulfide. ;
Examples include light stabilizers such as benzotriazole,
These may be used alone or in combination of two or more.

Among the above stabilizers (e), hindered phenol compounds, phosphite compounds and sulfur-containing organic esters are preferable from the viewpoint of versatility, and triethylene glycol is low in cost and easy to handle. -Bis {3- (3-t-butyl-5-methyl-
A mixture of 4-hydroxyphenyl) propionate} and dilauryl-3,3'-thiodipropionate is particularly preferred.

The alkylthioalkyl (meth) acrylate and the phenol group-containing (meth) acrylate exemplified as the vinyl monomer component (b) act as the stabilizer (e) as described above. In the present invention, these compounds may be used as the vinyl-based monomer component (b) or the stabilizer (e).

The modified polyolefin resin composition of the present invention comprises an aqueous suspension containing the crystalline polyolefin (a), the vinyl monomer component (b) and the radical polymerization initiator (c). By heating, the vinyl-based monomer component (b) is heated under the condition that the vinyl-based monomer component (b) does not polymerize by itself, and then the vinyl-based monomer component (b) is impregnated into the crystalline polyolefin (a). A resin composition obtained by heating the aqueous suspension to a temperature higher than the temperature at which the crystalline portion of the crystalline polyolefin (a) substantially starts melting to polymerize the vinyl-based monomer component (b). It is obtained by containing the stabilizer (e) in (d).

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 production amount of the polyolefin grafted with the vinyl-based monomer component in the modified polyolefin-based resin composition is small,
The improvement effect of workability becomes insufficient, and 50
If it exceeds 0 parts, the polymerization of the vinyl-based monomer components (b) becomes the main component, so that excessive aggregation, fusion, agglomeration, etc. may occur in the aqueous suspension during the polymerization. Become.

The vinyl-based monomer component (b) 10
With respect to 0 part, the radical polymerization initiator (c) is 0.0
It is 1 to 10 parts, preferably 1 to 10 parts, and more preferably 1 to 5 parts. When the amount of the radical polymerization initiator (c) is less than 0.01 part, polymerization of the vinyl-based monomer component (b) and crystalline polyolefin (a)
As a result, the radical initiation point is insufficiently generated, and it becomes difficult to obtain a modified polyolefin resin composition exhibiting a sufficient processability-improving effect.
If it exceeds the range, the radical polymerization initiator (c) is in excess, so that the polyolefin-based resin composition obtained by using the modified polyolefin-based resin composition causes decomposition and deterioration during thermoforming, for example. Will be

Further, the compounding amount of the stabilizer (e) is
0.01 to 20 parts per 100 parts of the resin composition (d),
Preferably 0.05 to 10 parts, more preferably 0.1.
~ 5 parts. The amount of the stabilizer (e) compounded is 0.0
When it is less than 1 part, the stabilizing effect by using such a stabilizer is small, and it becomes difficult to obtain a modified polyolefin resin composition exhibiting sufficient thermal stability. If it exceeds, physical properties such as mechanical strength and surface properties of the modified polyolefin resin composition are deteriorated.

The heating under the condition that the vinyl-based monomer component (b) does not polymerize by itself means T-50.
To T-10 (° C), preferably T-40 to T-10
Heating at a temperature represented by (° C.) (T represents the 10-hour half-life temperature (° C.) of the radical polymerization initiator (c)). By heating the aqueous suspension to such a temperature, the vinyl-based monomer component (b) is impregnated into the crystalline polyolefin (a), and the vinyl-based monomer component (b) becomes the crystalline polyolefin (a). On the other hand, another independent dispersed particle is formed, and the progress of polymerization is suppressed as it is, which is preferable.

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.

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 begins to melt, D
According to the SC measurement method, the temperature was raised from room temperature to complete melting under a nitrogen stream (40 ml / min) at a heating rate of 10 ° C./min, and the melting start temperature and melting point (peak of melting curve Heating to a temperature higher than the intermediate temperature of (the temperature corresponding to the apex), and increasing the proportion of the amorphous portion in the crystalline polyolefin (a),
In addition, it is preferable to heat to a temperature of melting point ± 20 ° C, particularly melting point ± 10 ° C from the viewpoint that the polyolefin chain is not excessively cut or gelated due to excessive heating.

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.

When the crystalline part of the crystalline polyolefin (a) is heated to a temperature below the temperature at which the crystalline part of the crystalline polyolefin (a) substantially begins to melt, the polymerization of the vinyl-based monomer components (b) proceeds, but the crystalline The progress of the grafting of the vinyl-based monomer component (b) to the polymerizable polyolefin (a) is insufficient and the vinyl-based polymer can be finely dispersed in the polyolefin, but the processability is sufficiently improved. It is difficult to obtain a modified polyolefin resin composition that can be developed.

On the other hand, 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 amorphous part of the crystalline polyolefin (a) becomes The ratio increases, and at the same time as the polymerization of the vinyl-based monomer component (b), the grafting of the vinyl-based monomer component (b) to the amorphous portion of the crystalline polyolefin (a) is promoted.

As described above, the modified polyolefin resin composition of the present invention is characterized by containing a polyolefin grafted with a vinyl polymer comprising the vinyl monomer component (b). Although it is possible to disperse the vinyl polymer uniformly and finely when mixed with the polyolefin,
The effect of the polyolefin grafted with the vinyl polymer on the expression of the processability improving effect is larger than the effect of the uniform fine dispersion of the vinyl polymer on the expression of the processability improving effect.

In the present invention, the method for incorporating the stabilizer (e) into the resin composition (d) is not particularly limited, and the stabilizer (e) may be used, for example, as a vinyl monomer. The component (b) may be mixed with the aqueous suspension before impregnating the crystalline polyolefin (a), or may be mixed with the aqueous suspension when the vinyl-based monomer component (b) is polymerized. Of course, the vinyl-based monomer component (b) may be polymerized and then mixed with the aqueous suspension, or may be mixed with the isolated resin composition (d). Further, the stabilizer (e) may be in a state of being copolymerized with the vinyl-based monomer component (b).

Further, when the modified polyolefin resin composition of the present invention is obtained, an ordinary aqueous suspension polymerization method can be used. For example, water, a suspending agent, an emulsifying agent, a dispersing agent and the like can be appropriately used. Well, these types and amounts include the temperature in the manufacturing process of the modified polyolefin resin composition,
There is no particular limitation as long as the aqueous suspension comprising the reaction mixture of each component is maintained in a stable state under the conditions of pressure, stirring, etc., to the extent that it does not excessively aggregate or fuse.

The composition of the reaction product obtained by the above aqueous suspension polymerization method is usually a graft copolymer which is a polyolefin grafted with a vinyl polymer, a non-grafted polyolefin and a non-grafted vinyl polymer. The primary structure of such a graft copolymer can be estimated by fractionating and analyzing the composition of the reaction product.

For example, the reaction product is heated and dissolved in a hydrocarbon solvent such as xylene, a good solvent for vinyl polymer such as methyl ethyl ketone is added if necessary, and then the solution is cooled to obtain a graft. Mixtures of copolymers and ungrafted polyolefins and ungrafted vinyl polymers can be fractionated as precipitates and melts in solution, respectively.

Elemental analysis and the like are carried out by purifying the fractionated non-grafted vinyl polymer and weighing it, or purifying the mixture of the fractionated graft copolymer and the non-grafted polyolefin. Thus, the graft ratio and the content of the vinyl polymer branch in the graft copolymer can be estimated.

Further, the molecular weight of the branches of the graft copolymer can be estimated by purifying the fractionated non-grafted vinyl polymer and measuring its molecular weight.

In the present invention, the molecular weight of the branches of the graft copolymer is the same as the molecular weight of the ungrafted vinyl polymer.

In the present invention, the molecular weight of the branch of the graft copolymer is the weight average molecular weight in terms of polystyrene in GPC measurement, such as catalyst type, usage amount, polymerization temperature, monomer type, reaction solution. Various conditions, such as the amount of a chain transfer agent such as n-dodecyl mercaptan, a polymerization inhibitor such as p-benzoquinone or 1,1-diphenyl-2-picrylhydrazyl, or the amount of a polymerization inhibitor used. By this, about 1000-2
It is possible to adjust within the range of 000000,
In the present invention, the weight average molecular weight of the branches of the graft copolymer is 10,000 to 100,000 in order to particularly effectively exhibit the processability improving effect of the polyolefin.
It is preferably adjusted to about 0.

The content of the vinyl polymer branch in the graft copolymer is preferably about 0.1 to 30% by weight based on the total composition of the reaction product.

In the above-mentioned reaction product, the domain of the average dispersed particle diameter is about 0.01 to 10 μm in the polyolefin, and in the smaller one, the average dispersed particle diameter is about 0.01 to 0.08 μm, depending on, for example, the polymerization formulation. It is possible to confirm a vinyl-based polymer in which the domains of are homogeneously finely dispersed. It is presumed that this is a vinyl-based monomer that is not mainly grafted, and it is difficult to confirm the dispersed state of the graft copolymer. Is considered to be.

In the present invention, a foaming agent may be added to the modified polyolefin resin composition for the purpose of obtaining a foam, for example, as described later.

Examples of the foaming agent include tocryloromonofluoromethane, methylene chloride, methyl chloride, dichlorodifluoromethane, dichloromonofluoromethane,
Monochlorodifluoromethane, dichlorotetrafluoroethane, trichlorotrifluoroethane and other halogenated hydrocarbons, propane, butane, pentane, hexane and other aliphatic hydrocarbons, alcohols and esters,
Chemical blowing agents such as ketones, ethers, sodium hydrocarbons, azodicarbonamide, N, N-dinitrosopentamethylenetetramine, p-toluenesulfonyl semicarbazide, etc. may be mentioned alone or in admixture of two or more. Can be used.

The blending amount of the foaming agent is 1 to 20% by weight of the modified polyolefin resin composition, especially 5 to 15%.
It is preferable from the viewpoint that the foaming ratio of the molded product that can be obtained by weight% is suitable, the stability of the foam is good, and the surface property of the molded product is excellent.

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, the polyolefin (A) is a propylene-based polyolefin obtained by polymerizing a monomer component containing 50% by weight or more of propylene, and 100 parts 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.
If the amount is less than or equal to the amount, sufficient effect such as good kneadability and dispersibility with the stabilizer (e), the inorganic filler (C) described later, etc., a large tension at the time of melting, and excellent processability is obtained. It is desirable because it is expressed. The melt flow index is 2.16 in accordance with ASTM D1238.
Measured in kg, for example, the value at 230 ° C. for propylene-based polyolefin and the value at 190 ° C. for ethylene-based polyolefin.

The blending ratio of the polyolefin (A) and the modified polyolefin resin composition (B) is 0.01 to 100 parts of the modified polyolefin resin composition, preferably 100 parts of the polyolefin (A). 0.01-20
Parts, more preferably 0.01 to 10 parts. The amount of the modified polyolefin resin composition (B) blended is 0.
When it is less than 01 part, it becomes difficult to sufficiently exert the effect of improving the workability, and when it exceeds 100 parts, the versatility such as low cost is deteriorated.

The modified polyolefin resin composition (B) of the present invention is characterized by containing a graft copolymer, which is a polyolefin grafted with a vinyl polymer, as described above. In addition to the above, the modified polyolefin resin composition (B) and the matrix polyolefin (A), which necessarily contains a non-grafted vinyl-based monomer and a non-grafted polyolefin, Even when the graft copolymer and the non-grafted polyolefin are blended as they are without mixing when mixed with, the processability-improving effect of the modified polyolefin resin composition (B) is exhibited. Is not particularly affected. Of course, even if the mixture of the graft copolymer and the ungrafted polyolefin is purified and added to the polyolefin (A), the modified polyolefin resin composition (B) is processed. The effect of improving the sex is sufficiently exhibited.

The polyolefin resin composition of the present invention comprises
As described above, it can be obtained by mixing the polyolefin (A) and the modified polyolefin-based resin composition (B), each of which has a blended amount adjusted. In addition to these, the stabilizer (e) is further added. , An inorganic filler (C) and the like can be added.

Examples of the stabilizer (e) include compounds used in obtaining the modified polyolefin resin composition (B), and these may be used alone or in admixture of two or more. Among these, triethylene glycol-bis {3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate} and dilauryl are versatile, inexpensive and easy to handle. Mixtures with -3,3'-thiodipropionate are preferred.

The mixing ratio of the stabilizer (e) is 0.01 to 20 with respect to 100 parts of the polyolefin (A).
Parts, preferably 0.05 to 10 parts, more preferably 0.1 to 5 parts. When the compounding amount of the stabilizer (e) is less than 0.01 part, the stabilizing effect by using the stabilizer (e) tends to be small, and when it exceeds 20 parts. In the meantime, physical properties such as mechanical strength and surface properties of the obtained polyolefin resin composition tend to be deteriorated.

The inorganic filler (C) has a function of improving rigidity, coating property, printability and the like of the obtained polyolefin resin composition, and realizing cost reduction. Typical examples of the inorganic filler (C) 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 size of the inorganic filler (C) 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 mixing ratio of the inorganic filler (C) is 0.1 to 100 with respect 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 content of the inorganic filler (C) is less than 0.1 part, the effect of improving the rigidity exhibited by the inorganic filler (C) 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 stabilizer (e), the inorganic filler (C) and the like.

The polyolefin resin composition of the present invention is
Although produced as described above, the polyolefin-based resin composition may further contain, for example, a lubricant, a core-shell type processability improver conventionally used for polyvinyl chloride-based resins and the like, if necessary. It can be added.

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).

Further, in the present invention, as in the modified polyolefin resin composition (B), a foaming agent may be added to the polyolefin resin composition for the purpose of obtaining a foam, for example.

Examples of the foaming agent include compounds that can be added to the modified polyolefin resin composition (B), and these can be used alone or in admixture of two or more.

The blending amount of the foaming agent is 1 to 20% by weight, especially 5 to 15% by weight of the polyolefin resin composition, and it is preferable that the expansion ratio of the molded article is suitable and the stability of the foam. Is preferable and the surface property of the molded article is excellent, which is preferable.

The modified polyolefin resin composition of the present invention exhibits an excellent effect of improving processability.
The polyolefin-based resin composition of the present invention comprising the modified polyolefin-based resin composition exhibits significantly improved excellent processability, impact resistance, rigidity, surface property, and the like. Manufacture of useful molded products from modified polyolefin resin compositions and polyolefin resin compositions by various molding methods, including molding methods that were difficult when conventional polyolefin resin compositions were used can do.

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

By extruding the modified polyolefin resin composition or the polyolefin resin composition of the present invention, for example, a calendering process or an extruding process can be performed to obtain a film or sheet-like molded product. The strength can be improved by uniaxially or biaxially orienting when obtaining such a film or sheet-shaped molded product. Further, a desired molded product can be obtained by performing thermoforming such as vacuum molding and pressure molding at a temperature suitable for the modified polyolefin resin composition or the polyolefin resin composition used. Furthermore, for example, injection molding or blow molding can be obtained by subjecting the pellet obtained by subjecting the composition to extrusion molding or blow molding such as extrusion blow molding or injection blow molding. Further, the modified polyolefin-based resin composition or the polyolefin-based resin composition of the present invention is added with, for example, a foaming agent as described above to obtain a foamable composition, and foam-molded by using, for example, an extruder, thereby foaming. You can get your body.

Further, the modified polyolefin resin composition (B) of the present invention exhibits the effect of improving the compatibility between polymers exhibiting low compatibility, in addition to the effect of improving the processability. Therefore, for example, a resin composition in which the modified polyolefin resin composition (B) is blended with a mixture of a non-polar polymer and a polar polymer that normally exhibit low compatibility has improved compatibility,
It has excellent dispersibility.

Examples of the non-polar polymer used in the present invention include the polyolefins exemplified as the polyolefin (A), and these may be used alone or in admixture of two or more.

Examples of the polar polymer used in the present invention include acrylonitrile-butadiene-styrene copolymer, acetal polymer, polyarylate,
(Meth) acrylic acid ester-styrene copolymers, acrylonitrile- (meth) acrylic acid ester-styrene copolymers and other (meth) acrylic acid ester polymers,
Acrylonitrile-styrene copolymer modified with ethylene-propylene rubber, cellulose, polyester-polyether block copolymer, for example, polyester such as polybutylene terephthalate, polyethylene terephthalate, liquid crystal polyester, polyetheramide, polyetherketone, polyetherimide , Polyether sulfone, ethylene-vinyl alcohol copolymer, polyvinyl chloride, chlorinated polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, such as polystyrene, high-impact polystyrene, styrene-acrylonitrile copolymer, styrene-butadiene copolymer Styrene such as polymer, styrene-maleic anhydride copolymer, copolymer composed of styrene copolymerizable monomers such as styrene and alkyl-substituted styrene Polymers, polyphenylene ether, polyphenylene sulfide, polysulfone, polyurethane, for example nylon-6, nylon-6,6, nylon-6,9, nylon-6,10, nylon 6,1
2, polyamide such as nylon-11, nylon-12, nylon such as amorphous nylon, polyamide imide, polycaprolactone, polyglutarimide,
Examples thereof include polymethylmethacrylate, for example, a polymer composed of an alkyl (meth) acrylate having 1 to 8 carbon atoms, and polycarbonate. These may be used alone or in combination of two or more. Have good properties and good melt fluidity, polystyrene, (meth) acrylic acid ester polymer, styrene-acrylonitrile copolymer, ethylene-
At least one selected from the group consisting of vinyl alcohol copolymer, polyamide, polyester, polycarbonate, polyphenylene ether, polyvinyl chloride, acrylonitrile-butadiene-styrene copolymer and polyvinylidene chloride is used, and the polyolefin of the nonpolar polymer is used. When the mixture is used as a mixture, the effect of improving the compatibility of the modified polyolefin resin composition (B) of the present invention is more sufficiently exhibited, and the dispersibility of the obtained resin composition is further improved.

The blending ratio of the non-polar polymer to the polar polymer is 95: 5 to 5:95 by weight, especially 8
It is preferably from 0:20 to 20:80. When the blending ratio of the nonpolar polymer and the polar polymer is less than the above range, the effect of improving the physical properties of the obtained resin composition is small, which is exhibited when the polar polymer is blended with the nonpolar polymer. When the amount exceeds the above range, the effect of improving the physical properties of the obtained resin composition, which is exhibited when the polar polymer is mixed with the nonpolar polymer, tends to be small.

The amount of the modified polyolefin resin composition (B) used to obtain the resin composition is 0.1 to 10 parts, preferably 100 parts by weight with respect to 100 parts of the mixture of the nonpolar polymer and the polar polymer. 1 to 5 parts. The amount of the modified polyolefin resin composition (B) blended is 0.1.
When it is less than 10 parts, the effect of improving the compatibility becomes insufficient, and when it exceeds 10 parts, the effect of improving the compatibility by increasing the compounding amount becomes small.

Next, the modified polyolefin-based resin composition of the present invention, the polyolefin-based resin composition containing the same, and the molded article made of them will be described in more detail with reference to Examples. Is not limited to only such examples.

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 part, di-t-butyl peroxide (10-hour half-life temperature 124 ° C.) 3.6 parts, calcium phosphate 100 parts and Latemul PS (manufactured by Kao Corporation) 0.45 as an emulsifier.
Parts were mixed and mixed with stirring to obtain an aqueous suspension. The aqueous suspension was heated and stirred at 100 ° C. for 1 hour, and then further stirred for 14 hours.
Polymerization was completed by heating with stirring at 0 ° C. for 5 hours. Resin composition 10 obtained by washing the obtained particles with water and then drying
Irganox 245 (manufactured by Japan Ciba-Geigy Co., Ltd., triethylene glycol-bis (3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate) 2 parts and dilauryl-
Two parts of 3,3'-thiodipropionate (hereinafter referred to as DLTP) were mixed and allowed to stand at room temperature to obtain a modified polypropylene resin composition (B) -1.

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 In a pressure-tight sealed reaction tank, 2000 parts of pure water was used in Example 1.
700 parts of the same crystalline random polypropylene particles as used in above, 300 parts of styrene, 3.6 parts of di-t-butyl peroxide, 20 parts of Irganox 245, DLT.
20 parts of P, 15 parts of calcium phosphate and 0.45 part of Latemur PS as an emulsifier were mixed and mixed with stirring to obtain an aqueous suspension. The aqueous suspension was heated and stirred at 100 ° C. for 1 hour, and then further heated and stirred at 130 ° C. for 5 hours to complete the polymerization. The obtained particles were washed with water and then dried to obtain a modified polypropylene resin composition (B) -4.

Example 5 In a pressure tight sealed reaction tank, 2000 parts of pure water was used in Example 1
700 parts of the same crystalline random polypropylene particles as used in the above, 300 parts of styrene, 3.6 parts of di-t-butyl peroxide, 15 parts of calcium phosphate and 0.45 part of Latemul PS as an emulsifier were mixed and mixed with stirring to obtain an aqueous solution. A suspension was obtained. The aqueous suspension was heated and stirred at 100 ° C. for 1 hour, and then further heated and stirred at 130 ° C. for 2 hours to initiate polymerization. Irgan at 130 ° C. for this aqueous suspension.
20 parts of ox245 and 20 parts of DLTP were added dropwise over 1 hour, and the mixture was heated and stirred at the same temperature for 2 hours to complete the polymerization. The obtained particles were washed with water and then dried to obtain a modified polypropylene resin composition (B) -5.

Example 6 In a pressure-tight reaction vessel, Example 1 was added to 2000 parts of pure water.
700 parts of the same crystalline random polypropylene particles as used in the above, 300 parts of styrene, 3.6 parts of di-t-butyl peroxide, 15 parts of calcium phosphate and 0.45 part of Latemul PS as an emulsifier were mixed and mixed with stirring to obtain an aqueous solution. A suspension was obtained. The aqueous suspension was heated and stirred at 100 ° C. for 1 hour, and further heated and stirred at 140 ° C. for 5 hours to complete the polymerization. After this, Irga was added to this aqueous suspension.
20 parts of nox245 and 20 parts of DLTP were added, and the mixture was further heated with stirring at 140 ° C. for 1 hour. The obtained particles are washed with water, the residual monomers, calcium phosphate, latemul PS and di-t-butyl peroxide are removed, and then dried to obtain modified polypropylene resin composition (B) -6.
I got it.

Example 7 In a pressure tight sealed reaction vessel, 2000 parts of pure water was used in Example 1
700 parts of the same crystalline random polypropylene particles as used in Example 1, 300 parts of styrene, 3 parts of ethylthioethyl acrylate, 3.6 parts of di-t-butyl peroxide, 15 parts of calcium phosphate and Latemur PS as an emulsifier.
0.45 parts was mixed and mixed with stirring to obtain an aqueous suspension.
The aqueous suspension was heated and stirred at 100 ° C. for 1 hour, and then further heated and stirred at 130 ° C. for 5 hours to complete the polymerization.
The obtained particles were washed with water and then dried to obtain a modified polypropylene resin composition (B) -7.

Example 8 In a pressure tight sealed reaction tank, 2000 parts of pure water was used in Example 1
The same crystalline random polypropylene particles as used in Example 700, styrene 300 parts, SumilizerGM
(Sumitomo Chemical Co., Ltd., 2-t-butyl-6- (3-
t-butyl-2-hydroxy-5-methylbenzyl)-
4-Methylphenyl acrylate) (3 parts), di-t-butyl peroxide (3.6 parts), calcium phosphate (15 parts) and Latemur PS (0.45 parts) as an emulsifier were mixed and mixed with stirring to obtain an aqueous suspension. The aqueous suspension was heated and stirred at 100 ° C. for 1 hour, and then further heated and stirred at 130 ° C. for 5 hours to complete the polymerization. The obtained particles are washed with water and dried to give a modified polypropylene resin composition (B) -8.
I got it.

Comparative Example 1 In a pressure tight sealed reaction tank, Example 1 was added to 2000 parts of pure water.
700 parts of the same crystalline random polypropylene particles as used in the above, 300 parts of styrene, 3.6 parts of di-t-butyl peroxide, 15 parts of calcium phosphate and 0.45 part of Latemul PS as an emulsifier were mixed and mixed with stirring to obtain an aqueous solution. A suspension was obtained. The aqueous suspension was heated and stirred at 100 ° C. for 1 hour, and further heated and stirred at 140 ° C. for 5 hours to complete the polymerization. The obtained particles were washed with water and then dried to obtain a polypropylene resin composition (B ').

Example 9 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 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.
× 200 mm at a die with a length of 10 mm, extrusion speed 5
It was measured at mm / min and a take-up speed of 1 m / min. The results are shown in Table 1.

Next, the obtained pellets were roll-kneaded at 200 ° C. to prepare a roll sheet. As the appearance of the roll sheet at the time of this roll kneading, the surface state was visually observed and evaluated based on the following evaluation criteria. The results are shown in Table 1.

(Evaluation Criteria) A: The surface is not uneven and has excellent gloss. B: The surface is slightly uneven, and the gloss is slightly inferior. C: The surface is uneven and the gloss is poor.

The roll sheet was press-molded to prepare test pieces conforming to the following ASTM tests.
Izod impact resistance test and bending elasticity test were performed according to -D256 and ASTM-D790. The results are shown in Table 1.

The pellets were melted and kneaded with a mill roll at 190 ° C., and then high-pressure press-molded in a press at 190 ° C., and after 10 minutes, they were placed in an unheated press at high pressure for 10 minutes to obtain 100 mm × A sheet with a thickness of 100 mm and a thickness of 1.5 mm is molded, and the opening is 76 mm x 7
At 6 mm, the leg was fixed with a clamp having a metal difference for measuring the drawdown, and the drawdown (mm) at the center of the sheet was measured for 30 minutes in an oven at 190 ° C. The results are shown in Table 1.

Examples 10 to 16 and Comparative Examples 2 to 6 Pelletization was performed in the same manner as in Example 9 except that the composition was changed as shown in Table 1, and the pellets were used for roll sheet and test. Pieces and sheets were made.

Physical properties of the obtained pellets, roll sheets, test pieces and sheets were examined in the same manner as in Example 9.
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).

Further, in Table 1, the modified polypropylene resin composition (B) -1 obtained in Example 1 or Comparative Example 1
Using the polypropylene resin composition (B ') obtained in
Physical properties of pellets, roll sheets, test pieces and sheets produced in the same manner as in Example 9 are also shown.

[0096]

[Table 1]

From the results shown in Table 1, the modified polypropylene resin compositions obtained in Example 1 and the modified polypropylene resin obtained in Examples 1 to 3 as in Examples 9 to 16 were obtained. The composition of the composition, while maintaining suitable impact resistance, physical properties such as bending elasticity,
It can be seen that the drawdown, which is an index for thermoforming, blow molding, etc., is small and the workability is significantly improved.

Example 17 Irga was added to 100 parts of the polypropylene resin composition (B ').
nox245 (2 parts) and DLTP (2 parts) are mixed, and a Labo Plastmill (manufactured by Toyo Seiki Co., Ltd.) is used at 240 ° C
The composition was obtained by melt-kneading at 100 rpm for 5 minutes. 5 parts of the obtained composition was mixed with 100 parts of PP, a sheet was prepared in the same manner as in Example 9, and its drawdown was measured. The results are shown in Table 2.

Examples 18 to 30 and Comparative Examples 7 to 9 Sheets were prepared in the same manner as in Example 17 except that the composition was changed as shown in Table 2, and the drawdown thereof was measured. The results are shown in Table 2.

The stabilizer (e) in Table 2 is as follows, and the compounding amount thereof is a value based on 100 parts of the polypropylene resin composition (B ').

IR245: Irganox245 AO60: Asahi Denka Kogyo KK, Tetrakis {methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate} methane AO80: Asahi Denka KK , 3,9-bis [2-
{3- (3-t-Butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.
5] Undecane SUGM: SumilizerGM SUGS: SumilizerGS, manufactured by Sumitomo Chemical Co., Ltd., 2- {1- (2-hydroxy-3,5-di-)
t-pentylphenyl) ethyl} -4,6-di-t-pentylphenyl acrylate TNPP: trisnonylphenyl phosphite MARK: MARK 329K, Asahi Denka Kogyo KK, bisnonylphenyl-dinonylphenyl phosphite When melt kneading with a plastomill was not performed, the drawdown of the sheet was measured in the same manner as above, and as a result, all were 0 mm.

[0102]

[Table 2]

From the results shown in Table 2, Examples 17 to 3
When the one obtained by blending the stabilizer (e) as shown in 0 was used, none of the blends containing the stabilizer (e) of Comparative Examples 7 to 9 was used. It can be seen that the increase in drawdown of the sheet after melt-kneading is significantly suppressed, and the thermal stability is significantly improved, as compared with the case.

Example 31 The modified polypropylene resin composition (B) -4 was melt-kneaded with a Labo Plastomill at 240 ° C. and 100 rpm for 5 minutes to obtain a composition. 5 parts of the obtained composition was added to PP100
The sheet was prepared in the same manner as in Example 9 and the drawdown thereof was measured. The results are shown in Table 3.

Examples 32 to 37 and Comparative Examples 10 to 12 Sheets were prepared in the same manner as in Example 31 except that the composition was changed as shown in Table 3, and the drawdown thereof was measured. The results are shown in Table 3.

The values in parentheses () in the drawdown in Table 3 are the values when melt kneading was not carried out in a Labo Plastomill.

[0107]

[Table 3]

From the results shown in Table 3, stabilizer (e)
Even when using the modified polypropylene resin composition obtained by adding to the aqueous suspension before polymerization, during polymerization and after polymerization, the drawdown of the sheet after melt-kneading is significantly increased. It can be seen that the thermal stability is suppressed and the thermal stability is significantly improved.

Example 38 100 parts of modified polypropylene resin composition (B) -7 was mixed with 2452 parts of Irganox and melt kneaded at 240 ° C. and 100 rpm for 5 minutes using a Labo Plastomill to obtain a composition. The obtained composition was mixed so that the modified polypropylene resin composition (B) -7 was 5 parts with respect to 100 parts of PP, a sheet was prepared in the same manner as in Example 9, and its drawdown was measured. . The results are shown in Table 4.

Examples 39 to 41 and Comparative Examples 13 to 14 Sheets were prepared in the same manner as in Example 38 except that the composition was changed as shown in Table 4, and the drawdown thereof was measured. The results are shown in Table 4.

The blending amount of the modified polypropylene resin composition (B) in Table 4 is the value based on 100 parts of PP, and the blending amount of the stabilizer (e) is the modified polypropylene resin composition (B). It is a value for 100 copies. Moreover, the compositions of Example 40 and Comparative Example 13 were modified polypropylene resin composition (B) -8 or polypropylene resin composition (B, respectively) instead of modified polypropylene resin composition (B) -7 of Example 38. ′), And in Examples 39 and 41 and Comparative Example 14, kneading with a Labo Plastomill was performed without adding the stabilizer (e).

When the melt kneading with the Labo Plastomill was not performed, the drawdown of the sheet was measured in the same manner as above, and as a result, all were 0 mm.

[0113]

[Table 4]

From the results shown in Table 4, comparing Examples 38 and 40 with Comparative Example 13, and comparing Examples 39 and 41 with Comparative Example 14, the stabilizer (e) was It can be seen that when the blended modified polypropylene resin composition is used, the increase in the drawdown of the sheet is suppressed and the thermal stability is improved.

Further, comparing Examples 38 and 39,
Further, comparing Examples 40 and 41, when the modified polypropylene resin composition was further blended with the stabilizer (e), the increase in the drawdown of the sheet was further suppressed, and the thermal stability was further improved. You can see that it will improve.

Examples 42 to 44 and Comparative Example 15 The formulations having the compositions shown in Table 5 were supplied to an extruder which is a pretreatment step of calendering and extrusion kneaded, and the obtained molten resin was inverted L-shaped calender. Is continuously supplied to 0.5m thick
m rolled sheet was obtained.

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

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

HDPE in Table 5 is high-density polyethylene having a melt flow index of 0.25 g / 10 min at 190 ° C., and inorganic filler (C) -1 is light carbonic acid surface-treated with fatty acid. Calcium (average particle size: 1.
8 μm) and CaS represent calcium stearate (the same applies hereinafter).

[0120]

[Table 5]

From the results shown in Table 5, Examples 42 to 4
It can be seen that all of the rolled sheets obtained in No. 4 have excellent surface properties.

Examples 45 to 47 and Comparative Example 16 Using the formulations having the compositions shown in Table 6, kneading was carried out in the same manner as in Example 9 using a twin-screw extruder, and extruded to obtain pellets. From the pellets obtained, a single screw extruder (screw diameter: 50 m
m, L / D: 20) was used to perform T-die extrusion at 230 ° C. to obtain an extruded sheet having a width of 300 mm and a thickness of 0.5 mm.

The surface condition of the extruded sheet thus obtained is shown in Example 4.
It investigated like 2 to 44. The results are shown in Table 6.

[0124]

[Table 6]

From the results shown in Table 6, Examples 45 to 4
It can be seen that the extruded sheets obtained in No. 7 all have excellent surface properties.

Examples 48 to 49 and Comparative Examples 17 to 18 The rolled and extruded sheets obtained in Examples 43 and 46 and Comparative Examples 15 and 16 were cup-shaped at a heater temperature (upper and lower) of 350 ° C. Mold (caliber: 80m
m, depth: 72 mm, aperture ratio: 0.9, taper: about 1
The surface of the sheet was heated to about 170 to 180 ° C. using a single-shot sheet vacuum forming machine (made by Asano Laboratory) having a temperature of 5 degrees) to perform vacuum forming to obtain a cup-shaped thermoformed body.

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

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

Further, the thickness deviation of the obtained cup-shaped thermoformed article was examined by obtaining the ratio with the original sheet thickness (0.5 mm), and evaluated based on the following evaluation criteria. The results are shown in Table 7.

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

[0131]

[Table 7]

From the results shown in Table 7, in Examples 48 and 49, the drawdown of the sheet during heating was small even when the rolled sheet or the extruded sheet was heated and vacuum formed. It can be seen that the obtained thermoformed product has a small thickness deviation.

Examples 50 to 51 and Comparative Example 19 Using the formulations having the compositions shown in Table 8, they were kneaded in a twin-screw extruder in the same manner as in Example 9 and extruded to obtain pellets. Using the obtained pellets, blow molding was performed at 230 ° C. to obtain a bottle having a wall thickness of 0.5 mm.

The state of drawdown of the parison during blow molding was visually observed and evaluated based on the same evaluation criteria as those used in Examples 48 to 49. The results are shown in Table 8
Shown in.

Further, the thickness unevenness of the obtained bottle was examined by measuring the thickness of each part of the bottle and obtaining the difference between the maximum value and the minimum value thereof, the same as that used in Examples 48 to 49. It evaluated based on the evaluation criteria. The results are shown in Table 8.

[0136]

[Table 8]

From the results shown in Table 8, it can be seen that in Examples 50 and 51, the drawdown of the parison at the time of blow molding was small, and the obtained bottles had a small thickness deviation.

Examples 52 to 53 and Comparative Example 20 A mixture having the composition shown in Table 9 was mixed into a resin composition, which was then extruded for producing a foam having a diameter of 65 mm and having a circular die having a diameter of 10 mm at its tip. Supplied to the machine.

Next, from the foaming agent pressure inlet provided in the middle of the foam-producing extruder, 100 to 2 as a foaming agent is introduced.
About 13 parts of trichloromonofluoromethane and dichlorotetrafluoroethane compressed to 00 kg / cm ² were pressed into 100 parts of the resin composition. While sufficiently kneading the resin composition and the foaming agent, the resin composition was cooled to a temperature suitable for foaming, and extruded into the air through a circular die to obtain a round rod-shaped foamed body.

The expansion ratio of the obtained foam was determined as the ratio of the volume change to a constant weight. The results are shown in Table 9.

Further, the surface condition of the obtained foam was visually observed and evaluated according to the following evaluation criteria. The results are shown in Table 9.

(Evaluation Criteria) A: The surface is smooth and the cell structure is uniform. B: Some irregularities are recognized on the surface, and a small number of bubbles are formed into open cells, resulting in a non-uniform cell structure. C: The unevenness of the surface is remarkably large, and bubbles are formed as continuous bubbles, resulting in a non-uniform cell structure.

PPEB in Table 9 represents polypropylene having a melt flow index at 230 ° C. of 0.5 g / 10 minutes (trade name: Noblen EB, manufactured by Mitsui Toatsu Co., Ltd.), and sodium hydrogencarbonate. And citric acid is a cell nucleating agent.

[0144]

[Table 9]

From the results shown in Table 9, the foams obtained in Examples 52 and 53 have a high expansion ratio and a smooth surface, and the cells do not form continuous cells and the cell structure is uniform. It turns out to be a thing.

Examples 54 to 59 and Comparative Examples 21 to 26 Using the formulations having the compositions shown in Table 10, the mixture was kneaded in a twin-screw extruder in the same manner as in Example 9 and extruded to obtain resin composition pellets.

The obtained pellets were freeze-fractured, and the cross section thereof was observed by SEM (manufactured by Hitachi, Ltd.) to examine the dispersibility of polar polymer particles in nonpolar polymer particles.
It evaluated based on the following evaluation criteria. The results are shown in Table 10.
Shown in.

(Evaluation Criteria) A: Particles are uniformly dispersed. B: The dispersion of particles is slightly non-uniform. C: The dispersion of particles is remarkably non-uniform.

The polar polymers in Table 10 are as follows.

PS: polystyrene, styrene G14,
Nippon Steel Chemical Co., Ltd., Specific gravity: 1.07, Melt flow index at 200 ° C .: 9.5 g / 10 minutes PVC: Polyvinyl chloride, S1007, P700, Kanemuchi Chemical Co., Ltd. PMMA: Poly Methyl methacrylate, parapet G1
000, manufactured by Kuraray Co., Ltd., specific gravity: 1.19, melt flow index at 230 ° C .: 8 g / 10 minutes PC: polycarbonate, Panlite L1250, manufactured by Teijin Limited, specific gravity: 1.2 PET: polyethylene terephthalate, Crappet 10
30, manufactured by Kuraray Co., Ltd., specific gravity: 1.56 Ny6: nylon-6, UBE nylon 1013B, manufactured by Ube Industries, Ltd., specific gravity: 1.14

[0151]

[Table 10]

From the results shown in Table 10, Examples 54 to
It can be seen that the resin composition obtained by blending the modified polypropylene resin composition of No. 59 has excellent compatibility with the non-polar polymer and the polar polymer and has excellent dispersibility.

[0153]

EFFECT OF THE INVENTION The modified polyolefin resin composition of the present invention has an excellent effect of improving the processability, and the modified polyolefin resin composition and the stabilizer and / or the inorganic filler are added to the polyolefin. The polyolefin-based resin composition of the present invention obtained by mixing the same exhibits physical properties such as excellent processability, impact resistance, rigidity and surface property, and therefore, the polyolefin-based resin composition and modified polyolefin Various molded products obtained from the resin composition by various molding methods are useful and have excellent surface properties, for example.

Further, since the modified polyolefin resin composition of the present invention is excellent in the effect of improving the compatibility between the nonpolar polymer and the polar polymer, the modified polyolefin resin composition is a mixture of the nonpolar polymer and the polar polymer. The resin composition obtained by blending the quality polyolefin resin composition has excellent dispersibility.

Claims (44)

[Claims] 1. Radical polymerization with respect to 100 parts by weight of the crystalline polyolefin (a), 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). An aqueous suspension containing 0.01 to 10 parts by weight of the initiator (c) is heated under conditions where the vinyl-based monomer component (b) does not polymerize by itself, and then, A vinyl monomer component (b) is impregnated in the crystalline polyolefin (a), and the aqueous suspension is further heated to a temperature higher than the temperature at which the crystalline portion of the crystalline polyolefin (a) substantially starts melting. 100 parts by weight of the resin composition (d) obtained by polymerizing the vinyl-based monomer component (b) and 0.01 to 20 parts by weight of the stabilizer (e) were added. A characteristic modified polyolefin resin composition. 2. 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 12 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
The modified polyolefin resin composition according to claim 1, which comprises 0% by weight or less. 3. The vinyl-based monomer component (b) is styrene,
The modification according to claim 1, which comprises 80% by weight or more of at least one selected from methyl methacrylate and n-butyl acrylate and 20% by weight or less of another vinyl-based monomer copolymerizable therewith. Polyolefin resin composition. 4. The vinyl monomer component (b) is an alkylthioalkyl (meth) acrylate in an amount of 0.01 to 10% by weight.
The modified polyolefin resin composition according to claim 1, which contains 0.01 to 10% by weight of a phenol group-containing (meth) acrylate. 5. The vinyl-based monomer component (b) is used as the aqueous suspension.
Radical polymerization initiator (c) 1-1 for 100 parts by weight
The modified polyolefin-based resin composition according to claim 1, which contains 0 part by weight. 6. The crystalline polyolefin (a) is a propylene-based polyolefin obtained by polymerizing a monomer component containing 75% by weight or more of propylene.
4. The modified polyolefin resin composition according to 4 or 5. 7. The stabilizer (e) is at least one selected from phenolic antioxidants, phosphorus antioxidants and sulfur antioxidants.
Alternatively, the modified polyolefin resin composition according to the item 6. 8. The modified polyolefin resin composition according to claim 7, wherein the phenolic antioxidant is a hindered phenolic compound. 9. The modified polyolefin resin composition according to claim 7, wherein the phosphorus antioxidant is a phosphite compound. 10. The modified polyolefin resin composition according to claim 7, wherein the sulfur-based antioxidant is a sulfur-containing organic ester. 11. The stabilizer (e) is triethylene glycol-bis {3- (3-t-butyl-5-methyl-4-).
Hydroxyphenyl) propionate} and dilauryl-
The modified polyolefin resin composition according to claim 1, 2, 3, 4, 5, or 6, which is a mixture with 3,3'-thiodipropionate. 12. A stabilizer (e) before impregnating the crystalline polyolefin (a) with the vinyl monomer component (b).
Is mixed with an aqueous suspension.
The modified polyolefin resin composition according to 5, 6, 7, 8, 9, 10 or 11. 13. The method according to any one of claims 1, 2, 3, 4, 5, 6, wherein the stabilizer (e) is mixed with the aqueous suspension when the vinyl-based monomer component (b) is polymerized. The modified polyolefin resin composition described in 7, 8, 9, 10 or 11. 14. The method according to claim 1, wherein the vinyl monomer component (b) is polymerized and then the stabilizer (e) is mixed with the aqueous suspension. The modified polyolefin resin composition described in 7, 8, 9, 10 or 11. 15. The isolated resin composition (d), which is mixed with the stabilizer (e), 1, 2, 3, 4, 5,
The modified polyolefin-based resin composition according to 6, 7, 8, 9, 10 or 11. 16. A foaming agent in an amount of 1 to 20% by weight, which is included in 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 1.
The modified polyolefin-based resin composition according to 1, 12, 13, 14 or 15. 17. The method according to claim 1, 2, 3, 4, 5, 6, 7,
8, 9, 10, 11, 12, 13, 14, 15 or 1
A film or sheet-shaped molded product comprising the modified polyolefin-based resin composition according to item 6. 18. The film- or sheet-shaped molded product according to claim 17, which is uniaxially or biaxially oriented. 19. The film or sheet-shaped molded product according to claim 17, which is subjected to calendering or extrusion. 20. A molded product obtained by vacuum molding or pressure molding of the film or sheet-shaped molded product according to claim 17 or 18. 21. Claims 1, 2, 3, 4, 5, 6, 7,
8, 9, 10, 11, 12, 13, 14, 15 or 1
A hollow molded article comprising the modified polyolefin resin composition according to item 6. 22. The hollow molded article according to claim 21, which is formed by extrusion blow molding or injection blow molding. 23. Claims 1, 2, 3, 4, 5, 6, 7,
8, 9, 10, 11, 12, 13, 14, 15 or 1
An injection-molded article comprising the modified polyolefin-based resin composition according to item 6. 24. Claims 1, 2, 3, 4, 5, 6, 7,
8, 9, 10, 11, 12, 13, 14, 15 or 1
A foam comprising a foamable composition containing the modified polyolefin-based resin composition according to item 6. 25. The composition according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9, based on 100 parts by weight of the polyolefin (A).
Modified polyolefin resin composition (B) 0.01 to 10 according to 10, 11, 12, 13, 14, 15 or 16
A polyolefin resin composition obtained by mixing 0 parts by weight. 26. The polyolefin resin composition according to claim 25, wherein the amount of the modified polyolefin resin composition (B) compounded is 0.01 to 20 parts by weight with respect to 100 parts by weight of the polyolefin (A). 27. The polyolefin (A) is propylene 5
A propylene-based polyolefin obtained by polymerizing a monomer component containing 0% by weight or more.
6. The polyolefin resin composition according to item 6. 28. 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 25 or 26, which is a mixture of 0.1 to 100 parts by weight. 29. The composition according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9, based on 100 parts by weight of the polyolefin (A).
Modified polyolefin resin composition (B) 0.01 to 10 according to 10, 11, 12, 13, 14, 15 or 16
A polyolefin resin composition obtained by mixing 0 part by weight and 0.01 to 20 parts by weight of a stabilizer (e). 30. The composition according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9, based on 100 parts by weight of the polyolefin (A).
Modified polyolefin resin composition (B) 0.01 to 10 according to 10, 11, 12, 13, 14, 15 or 16
A polyolefin resin composition obtained by mixing 0 part by weight and 0.1 to 1000 parts by weight of an inorganic filler (C). 31. The composition according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9, with respect to 100 parts by weight of the polyolefin (A).
Modified polyolefin resin composition (B) 0.01 to 10 according to 10, 11, 12, 13, 14, 15 or 16
A polyolefin resin composition obtained by mixing 0 part by weight, 0.01 to 20 parts by weight of a stabilizer (e) and 0.1 to 1000 parts by weight of an inorganic filler (C). 32. 25 to 26, 27, 28, 29, 30 or 31 containing 1 to 20% by weight of a foaming agent.
The polyolefin resin composition described. 33. Claims 25, 26, 27, 28, 2
A film or sheet-shaped molded product comprising the polyolefin resin composition described in 9, 30, 31 or 32. 34. The film or sheet-shaped molded product according to claim 33, which is uniaxially or biaxially oriented. 35. The film or sheet-shaped molded product according to claim 33, which is calendered or extruded. 36. A molded product obtained by vacuum molding or pressure molding of the film or sheet-shaped molded product according to claim 33 or 34. 37. Claims 25, 26, 27, 28, 2
A hollow molded article comprising the polyolefin-based resin composition according to 9, 30, 31, or 32. 38. The hollow molded article according to claim 37, which is formed by extrusion blow molding or injection blow molding. 39. Claims 25, 26, 27, 28, 2
An injection-molded article comprising the polyolefin-based resin composition according to 9, 30, 31, or 32. 40. 25, 26, 27, 28, 2
A foam comprising a foamable composition containing the polyolefin resin composition described in 9, 30, 31 or 32. 41. A method according to claim 1, wherein 100 parts by weight of a mixture of a non-polar polymer and a polar polymer are used.
3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 1
A resin composition comprising 0.1 to 10 parts by weight of the modified polyolefin resin composition described in 3, 14, 15 or 16. 42. The blending ratio of the nonpolar polymer and the polar polymer is 95: 5 to 5:95 by weight.
The resin composition described. 43. The resin composition according to claim 41 or 42, wherein the non-polar polymer is a polyolefin. 44. The polar polymer is polystyrene, (meth) acrylic acid ester polymer, styrene-acrylonitrile copolymer, ethylene-vinyl alcohol copolymer, polyamide, polyester, polycarbonate, polyphenylene ether, polyvinyl chloride, acrylonitrile-butadiene- The resin composition according to claim 41, 42 or 43, which is at least one selected from the group consisting of a styrene copolymer and polyvinylidene chloride.