JPH07242773A - Polyolefin resin composition - Google Patents

Abstract

PURPOSE:To provide a polyolefin resin compsn. which is suitable for molding, has an excellent processibility, and gives a molded article excellent in clarity, impact resistance, stiffness, and surface properties. CONSTITUTION:A polyolefin resin compsn. comprises 100 pts.wt. polyolefin (A) and 0.1-100 pts.wt. modified polyolefin (B) obtd. by polymerizing 1-500 pts.wt. vinyl monomer in the presence of 100 pts.wt. nonpolar polyolefin provided the refractive indexes of both polyolefins (A) and (B) are substantially the same.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a polyolefin resin composition. More specifically, it relates to a polyolefin-based resin composition having excellent processability and simultaneously having excellent properties such as transparency, impact resistance, rigidity and surface property when formed into a molded product.

[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, for example, polypropylene has low transparency, and has a low viscosity and a low tension when melted, so that the vacuum moldability (hereinafter referred to as thermoformability), calender moldability, blow moldability, and foam moldability of the sheet. There is a drawback that the workability is poor. Further, compared to polystyrene, polyvinyl chloride, ABS resin, etc., the rigidity and impact resistance at low temperatures are small, and the surface property (surface gloss), hardness,
There are also drawbacks in terms of characteristics such as poor coating properties.

Therefore, in order to improve the transparency of the polypropylene, a nucleating agent has been used, but the effect of improving the transparency is not always sufficient, and at the same time, the workability and the required workability are required. Almost no improvement in properties is seen. In addition, depending on the type of nucleating agent, there is a problem of odor during processing, and in reality, its use in the field of food packaging is limited.

Polyethylene or the like is generally mechanically mixed for the purpose of improving the processability and properties of the polypropylene, but the transparency is impaired or the processability and properties are not sufficiently improved. However, there is a drawback that a large amount of polyethylene is required and the rigidity of the obtained mixture is lowered.

Further, in order to improve the processability of the polypropylene, a method of polymerizing a vinyl monomer in a state in which polypropylene particles are suspended in an aqueous medium and adding the obtained modified polypropylene to the polypropylene. (Japanese Patent Publication No. 49-2346, Japanese Patent Publication No. 58)
-53003, Japanese Patent Publication No. 59-14061,
Japanese Patent Publication No. 63-67484), no attempt has been made to improve transparency by matching the refractive index of the modified polypropylene with that of polypropylene.

Further, in order to improve the transparency and impact resistance of polypropylene, a copolymer having a refractive index substantially matching the refractive index of the propylene polymer trunk can be formed on the propylene polymer trunk. A method of graft-polymerizing a monomer component has been tried (Japanese Patent Laid-Open No. 653/1993).
No. 19), in this case, it is a method of using the modified polypropylene alone, and no attempt has been made to mix the modified polypropylene with the unmodified polypropylene and use it as an agent for improving transparency and processability. Not not.

For the purpose of improving the processability and properties of the polypropylene such as thermoformability, a polyolefin-methacrylate polymer obtained by polymerizing a methacrylate monomer in a hydrocarbon solvent in the presence of a polyolefin and a methacrylate are grafted. Attempts have been made to add a mixture of the above polyolefins to polypropylene (Japanese Patent Laid-Open No. 22316/1990). However, in this case as well as in the case of adding polyethylene, the transparency is lowered by adding the mixture, and in order to sufficiently exert the effect of improving processability and characteristics by this method, It is necessary to add a large amount of the mixture. In addition, since the high temperature solution polymerization method is used, there are problems in manufacturing cost and safety. Further, it is necessary to remove the solvent when the polyolefin is mixed, which causes a problem of poor workability and safety.

Further, for the purpose of improving the impact resistance of polypropylene, generally, a method of mechanically mixing a rubber component such as ethylene-propylene rubber and the like, a method of introducing it by block copolymerization and the like are carried out. However, in the case of a method of mechanically mixing and introducing a rubber component or a method of introducing it by block copolymerization, transparency is remarkably reduced, and at the same time, it is difficult to control the dispersed particle size, Use efficiency is low, and the effect of improving impact resistance is insufficient. Further, as a result, a large amount of rubber component is required, and the rigidity of the obtained mixture is lowered. Further, there is a drawback that the surface gloss decreases due to the large particle size of the dispersed rubber component.

On the other hand, there is a core-shell type modifier which is widely used as an impact resistance improving agent in polyvinyl chloride resins and the like. However, when this is added to polypropylene as it is, the problem that the transparency is lowered. There is.

Therefore, it has been proposed to add the core-shell type modifier to a polyolefin in the presence of a specific compatibilizing agent (Japanese Patent Laid-Open No. 185037/1993).
(US Pat. No. 4,997,884), the process of synthesizing the compatibilizing agent is complicated, and there are problems that the cost is increased by using the compatibilizing agent and the system becomes complicated. further,
As mentioned above, there is a problem that the transparency is lowered.

As described above, the fact is that a polyolefin resin composition which simultaneously satisfies the properties of excellent transparency, processability, impact resistance, rigidity and surface property has not yet been proposed. Further, development of a polyolefin-based resin composition that simultaneously satisfies the above properties is desired.

[0013]

The present invention has the properties of excellent transparency, impact resistance, rigidity and surface property, and excellent processability at the same time, and is suitable for various molded products. An object is to provide a resin composition.

It is another object of the present invention to provide a polyolefin resin composition having the above-mentioned effects and further excellent transparency, rigidity and surface property.

Further, the present invention, in addition to the above effects,
It is another object of the present invention to provide a polyolefin resin composition having excellent impact resistance and processability.

[0016]

[Means for Solving the Problems] That is, the present invention provides a vinyl-based monomer (b) 1 in the presence of 100 parts of polyolefin (A) (parts by weight, the same applies hereinafter) and 100 parts of nonpolar polyolefin (a). A polyolefin resin composition comprising 0.1 to 100 parts of a modified polyolefin (B) obtained by polymerizing 500 parts to 500 parts, and the polyolefin (A) and the modified polyolefin (B) have substantially the same refractive index. A polyolefin resin composition containing 0.01 to 2 parts of a nucleating agent based on 100 parts of the resin composition, and a core-shell graft copolymer having substantially the same refractive index as the polyolefin (A), The present invention relates to a polyolefin resin composition containing 0.01 to 50 parts per 100 parts of the polyolefin (A).

[0017]

Actions and Examples The polyolefin (A) used in the present invention is a component which acts as a base resin in the polyolefin resin composition of the present invention. In order to use polyolefin as the base resin, the composition of the present invention is calendered, extruded, thermoformed, blow molded,
It can be molded by a simple and general method such as an injection molding method, and the obtained molded article has excellent transparency, workability, impact resistance, rigidity and surface property.

The polyolefin (A) is a value obtained by measuring the number of grams of molten polymer falling in 10 minutes under a load of 2.16 kg according to the melt flow index (ASTM D1238). And the value at 190 ° C. in the case of ethylene-based polyolefin) (hereinafter, also referred to as MI) is 10 or less, preferably 5 or less, more preferably 2.5 or less, the processability is improved. It is preferable in that respect.

Specific examples of the polyolefin (A) include polypropylene, high density polyethylene, low density polyethylene, linear low density polyethylene and poly-1.
-Butene, polyisobutylene, polymethylpentene, random or block copolymers in all proportions of propylene and ethylene and / or 1-butene, 10% diene component (wt%, below) in every proportion of ethylene and propylene. The same) ethylene-propylene-diene terpolymer contained below, random with 50% or less of ethylene or propylene and vinyl compounds such as vinyl acetate, methacrylic acid alkyl ester, acrylic acid alkyl ester, aromatic vinyl, etc., Examples thereof include block or graft copolymers. Among the polyolefins (A), a crystallized propylene-based polyolefin obtained by polymerizing a monomer component containing 50% or more, and further 75% or more of propylene, particularly a random copolymer with ethylene is transparent. It is preferable because it is easily available and is inexpensive.

These may be used alone or in admixture of two or more.

The typical refractive index of polyolefin (A) is polypropylene (1.503), high density polyethylene (1.545), low density polyethylene (1.5).
1), linear low density polyethylene (1.52), poly-1
-Butene (1.5125), polymethylpentene (1.
459 to 1.465).

The polyolefin resin composition of the present invention is obtained by polymerizing 1 to 500 parts of the vinyl monomer (b) in the presence of 100 parts of the nonpolar polyolefin (a) together with the above-mentioned polyolefin (A). A modified polyolefin (B) is used.

The modified polyolefin (B) is obtained by modifying the polyolefin (A) to improve the transparency, impact resistance, rigidity and surface property of the molded product obtained from the composition of the present invention. It is a component used to improve properties.

The modified polyolefin (B) has a refractive index substantially equal to the refractive index of the above-mentioned polyolefin (A), and the non-polar polyolefin (a) generally has a vinyl-based monomer component (b). Part thereof is grafted and the refractive index is adjusted to be substantially equal to that of the polyolefin (A). However, from the viewpoint of sufficiently exhibiting the performance of the graft copolymer, a vinyl-based monomer is used. The size of the domains in the modified polyolefin (B) formed by polymerizing the body (b) is preferably 3 μm or less.

The modified polyolefin (B) is the non-polar polyolefin (a) 100 described below, as described above.
1 to 500 vinyl-based monomer (b) described below in the presence of parts
A part of the polymer chains is non-polar, as described below, in which the non-polar polyolefin (a) and the polymer chain in which the vinyl-based monomer (b) is polymerized exist. It exists in a state of being grafted to the polyolein (a), and a part thereof is present in a state of being dispersed in the non-polar polyolefin (a). Only the monomer (b) exists in a polymerized state.

The non-polar polyolefin (a) also exists in a state where a part of the vinyl-based monomer (b) is grafted, and a part of the polymer of the vinyl-based monomer (b) is dispersed inside. Exist in the form of a non-polar polyolefin (a)
And a part of the vinyl-based monomer (b) is grafted and also exists as a polymer dispersed inside.

Among the modified polyolefins (B) existing in the above-mentioned state, the graft copolymer in which the vinyl monomer (b) is grafted to the nonpolar polyolefin (a) is excellent in processability and the like. Show the effect. Particularly, from the viewpoint of sufficiently exhibiting the effect of improving the processability of the graft copolymer, it is preferable that the gel content is as small as possible and the dispersibility is improved (paragraph 24 of Japanese Patent Application No. 6-4698). , 49-55, 232-234).

The non-polar polyolefin (a) used in the production of the modified polyolefin (B) has the transparency, processability, impact resistance, and other properties required for the modified polyolefin (B).
In order to exert the effect of improving rigidity and surface property, it is a main component for facilitating dispersion in the polyolefin (A), and those having excellent compatibility with the polyolefin (A) are preferable.

The non-polar polyolefin (a) is generally a polyolefin having a poor compatibility with a more polar polymer and has an MI of 10 or less, preferably 5 or less, more preferably 2.5 or less for improving processability. It is preferable in that respect.

Examples of the non-polar polyolefin (a) include homopolymers obtained by polymerizing ethylene, propylene, butylene or 4-methylpentene and copolymers obtained by polymerizing two or more kinds of those monomers. At least one selected from a polymer and each copolymer obtained by polymerizing one or more kinds of ethylene, propylene, butylene and 4-methylpentene and another monomer copolymerizable therewith.
The seed is mentioned as a preferable one.

Specific examples of the non-polar polyolefin (a) include homopolymers such as polypropylene, high density polyethylene, low density polyethylene, linear low density polyethylene, poly-1-butene, polyisobutylene and polymethylpentene. , Ethylene-propylene random copolymers, ethylene-propylene block copolymers, etc. random or block copolymers in any proportion of propylene and ethylene and / or 1-butene, diene in any proportion of ethylene and propylene. Ethylene-propylene-diene terpolymer containing 10% or less of components, ethylene-propylene rubber, ethylene-
50% or less of ethylene or propylene such as vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl methacrylate copolymer and the like, for example, vinyl acetate, methacrylic acid alkyl ester, acrylic acid alkyl ester, aromatic vinyl Random, block or graft copolymers with vinyl compounds such as These may be used alone or in combination of two or more. When a polar polyolefin is used instead of the nonpolar polyolefin (a), the polarity is different from that of the polyolefin (A) and the compatibility is reduced, resulting in poor dispersion.

The shape and the existence of the non-polar polyolefin (a) are not particularly limited. For example, pellets having an average particle size of about 1 to 5 mm and an average particle size of 20.
Powders of about 0 to 1000 μm, and latexes and dispersions in which these are dispersed in an aqueous medium can be used. Of these, pellets having an average particle size of about 1 to 5 mm are preferable in terms of versatility.

On the other hand, the vinyl-based monomer (b) is a component for forming a graft copolymer that exerts the effect of improving the processability of the modified polyolefin (B). And those having a large copolymerizability with the crystalline polyolefin (a) are preferable.

The vinyl-based monomer (b) is also a modified polyolefin (B) composed of the crystalline polyolefin (a) and the vinyl-based monomer (b) from the viewpoint of improving the transparency. It is selected so that the refractive index and the refractive index of the polyolefin (A) are substantially equal.

The term "substantially the same refractive index" means that the difference in refractive index is 0.02 or less, preferably 0.01 or less, and more preferably 0.005 or less.

The term "refractive index" as used herein is described in, for example, Polymer Handbook 3rd Edition (John Wiley & Sons. Inc. 1989) and the like. As the ratio, a value calculated proportionally by the weight fraction of each monomer is used.

The vinyl-based monomer (b) includes vinyl monomers (CH ₂ ═CH-group-containing monomers) and vinylidene monomers.

[0038]

[Chemical 1]

Specific examples thereof include styrene,
Aromatic vinyl compounds such as α-methylstyrene; for example, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, etc. The number of carbon atoms in the alkyl group is 1 to
A methacrylic acid alkyl ester which is 22; for example, methyl acrylate, ethyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate,
2-Ethylhexyl acrylate, stearyl acrylate, and other alkyl acrylates in which the alkyl group has 1 to 22 carbon atoms; unsaturated nitrile compounds, such as acrylonitrile and methacrylonitrile; Monomers (for example, acid anhydride groups such as maleic anhydride, methacrylic acid, acrylic acid, methacrylamide, acrylamide, dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate, carboxyl groups, amino groups Vinyl monomers having reactive functional groups such as groups and hydroxy groups, and other vinyl monomers such as phenol group-containing methacrylic acid esters for the purpose of improving the thermal stability of the modified polyolefin (B) )etc It is below. These alone or 2
A mixture of two or more species can be used.

As the vinyl-based monomer (b) to be polymerized in the presence of the nonpolar polyolefin (a), the aromatic vinyl-based compound, the methacrylic acid alkyl ester in which the alkyl group has 1 to 22 carbon atoms, From 80% or more of at least one selected from an alkyl acrylate having an alkyl group having 1 to 22 carbon atoms and the unsaturated nitrile compound, and 20% or less of another vinyl-based monomer copolymerizable therewith It is preferable to use any of the following, from the viewpoints that the effect of improving the processability and transparency of the modified polyolefin (B) can be more sufficiently exhibited, and the versatility and cost of the monomer to be used. Further, when the aromatic vinyl compound is styrene and / or its derivative, the modified polyolefin (B) has a relatively high refractive index in its homopolymer.
It is preferable in that it is useful when the refractive index of is highly adjusted.

The alkyl group has 1 to 22 carbon atoms.
When the methacrylic acid alkyl ester is one or more of methyl methacrylate, n-butyl methacrylate and cyclohexyl methacrylate, it is because the refractive index of the homopolymer is generally relatively low. It is particularly preferable because it is useful for adjusting the refractive index of the modified polyolefin (B) to a low level. In addition, when the alkyl acrylate having 1 to 22 carbon atoms in the alkyl group is one or more of methyl acrylate, ethyl acrylate, n-butyl acrylate and 2-ethylhexyl acrylate. Is particularly preferable because it is useful for adjusting the refractive index of the modified polyolefin (B) to a low value because the homopolymer generally has a relatively low refractive index.

As the vinyl monomer (b), the aromatic vinyl compound is 1 to 50%, preferably 10 to 4%.
0%, methacrylic acid alkyl ester in which the alkyl group has 1 to 22 carbon atoms and / or acrylic acid alkyl ester in which the alkyl group has 1 to 22 carbon atoms 99 to 50%, preferably 90 to 60 When% is used, the refractive index can be arbitrarily adjusted, and the effect of improving the workability is large, which is preferable. Further, when the aromatic vinyl compound is styrene and / or a derivative thereof, it is preferable because the effect of improving the transparency and improving the processability are large.

The alkyl group has 1 to 22 carbon atoms.
It is particularly preferable that the methacrylic acid alkyl ester is one or more of methyl methacrylate, n-butyl methacrylate, and cyclohexyl methacrylate, because the transparency is manifested and the processability is improved. In addition, when the alkyl acrylate having 1 to 22 carbon atoms in the alkyl group is one or more of methyl acrylate, ethyl acrylate, n-butyl acrylate and 2-ethylhexyl acrylate. Is particularly preferable because it has a large effect of improving transparency and processability. In particular, the vinyl-based monomer (b) is styrene 1 to 50%, preferably 10 to 40%, methyl methacrylate and / or n-butyl acrylate 99 to 5
When it is 0%, preferably 90 to 60%, it is preferable because the refractive index can be further adjusted and the workability improving effect is large.

As the vinyl-based monomer (b), the methacrylic acid alkyl ester having an alkyl group having 1 to 22 carbon atoms and / or the acrylic acid having an alkyl group having 1 to 22 carbon atoms When an alkyl ester is used, it is preferable because the effect of adjusting the refractive index and improving the workability is great. Furthermore, the number of carbon atoms in the alkyl group is 1
When the methacrylic acid alkyl ester of ~ 22 is one or more of methyl methacrylate, n-butyl methacrylate and cyclohexyl methacrylate, it is particularly preferable because the effect of adjusting the refractive index and improving the processability is large. preferable. The alkyl group has 1 to 22 carbon atoms.
When the alkyl acrylate is one or more of methyl acrylate, ethyl acrylate, n-butyl acrylate and 2-ethylhexyl acrylate, the effect of adjusting the refractive index and improving the processability is It is particularly preferable because it is larger.

The proportion of the vinyl-based monomer (b) used relative to 100 parts of the nonpolar polyolefin (a) is 1 to 500 parts from the viewpoint that a graft copolymer capable of exhibiting an improvement effect such as processability can be formed. There is a minimum quantity of 5 or more,
Further, it is preferably 10 parts or more from the viewpoint of easy formation of a graft copolymer capable of exhibiting the effect of improving processability. Further, the maximum amount is preferably 200 parts or less, more preferably 100 parts or less from the viewpoint of good stability during polymerization (no excessive aggregation, fusion, or agglomeration).

The method for producing the modified polyolefin (B) is not particularly limited, and it may be produced by, for example, a suspension polymerization method or a solution polymerization method.

For example, when the suspension polymerization method is used, 1 to 500 parts of the vinyl-based monomer (b) and 1 part of the vinyl monomer (b) are added to 100 parts of the nonpolar polyolefin (a).
Radical polymerization initiator (c) 0.01 to 1 to 100 parts
An aqueous suspension containing 0 part of the vinyl monomer (b) is heated as it is or under a condition that the decomposition of the radical polymerization initiator (c) does not substantially occur, so that the non-polar polyolefin ( The method of impregnating a) and further raising the temperature of the aqueous suspension to complete the polymerization of the vinyl monomer (b) is preferable from the viewpoint of manufacturing cost and safety, and the vinyl monomer is also preferable. The amount of the polymerized (b) present as domains in the modified polyolefin (B) increases,
It is preferable in that the amount of non-domains present is reduced.

When the polyolefin resin composition is prepared by using the modified polyolefin (B) produced by the above-mentioned method, the effect of improving transparency, workability, impact resistance, rigidity, surface property, etc. is further improved. It is possible to obtain a polyolefin resin composition having the characteristic that

The radical polymerization initiator (c) is not particularly limited, but a radical initiation point is generated in the non-polar polyolefin (a) which is substantially in a molten state, and the radical type initiator (c) of the vinyl monomer (b) is generated. From the viewpoint that polymerization and grafting can proceed efficiently, the half-life at about 50 to 200 ° C. is preferably about 1 hour. Further, in order to obtain a modified polyolefin capable of more sufficiently exhibiting the effect of improving the processability when mixed with the above-mentioned polyolefin (A), an oil-soluble one having a high hydrogen abstraction property is preferable.

Specific preferred examples of the radical polymerization initiator (c) include acetyl peroxide, succinic acid peroxide, t-butyl peroctoate, benzoyl peroxide (72 ° C.), t-butyl peroxymaleic acid, 1-hydroxy-1-hydroperoxydicyclohexyl peroxide, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane (87 ° C.), t-butylperoxycrotonate,
2,2-bis (t-butylperoxybutane) (103
C.), t-butyl peroxyisopropyl carbonate (99.degree. C.), t-butyl peroxy vivarate (55).
° C), lauroyl peroxide (62 ° C), t-butylperoxyisobutyrate (77 ° C), di-t-butylperoxide (124 ° C), 1,1,3,3-tetramethylbutylperoxy- 2-ethylhexanoate (6
5 ° C.), 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexane (66 ° C.), 2,5
-Dimethyl-2,5-bis (benzoylperoxy) hexane (100 ° C), t-butylperoxyacetate (103 ° C), 2,5-dimethyl-di (hydroperoxy) hexane, t-butylhydroperoxide (167
℃), t-butyl cumyl peroxide (121 ℃), p
-Menthane hydroperoxide (128 ° C), methyl ethyl ketone peroxide (105 ° C), di-t-butylperoxyphthalate, t-butylperoxybenzoate (104 ° C), dicumyl peroxide (117)
C.), 2,5-dimethyl-2,5-di (t-butylperoxy) hexane (118.degree. C.), 2,4-pentanedione peroxide, azobisisobutyronitrile and the like. Among them, di-t-butyl peroxide, t-
Butyl peroxybenzoate benzoyl peroxide and the like are particularly preferable. These may be used alone or in combination of two or more. The 10-hour half-life temperature is shown in parentheses () after the specific example.

The radical polymerization initiator (c) is used in an amount of 0.01 to 10 with respect to 100 parts of the vinyl monomer (b).
Parts, preferably 1 to 10 parts, more preferably 1 to 5 parts. When the amount of the radical polymerization initiator (c) is less than 0.01 part, the polymerization of the vinyl monomer (b) and the generation of radical initiation points for the nonpolar polyolefin (a) are insufficient. Therefore, it tends to be difficult to obtain a modified polyolefin (B) having a sufficient effect of improving the processability, and when it exceeds 10 parts, the radical polymerization initiator (c) is excessive. Therefore, when the obtained polyolefin-based resin composition prepared by using the modified polyolefin (B) is subjected to thermoforming, for example, decomposition and deterioration easily occur.

The heating under the condition that the radical polymerization initiator (c) is not substantially decomposed means T-50 to T-.
It means heating to a temperature represented by 10 ° C, preferably T-40 to T-10 ° C (T represents a 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 easily impregnated in the non-polar polyolefin (a), and the vinyl-based monomer (b) becomes the non-polar polyolefin (a). This is preferable because it becomes difficult to form independent dispersed particles other than the above.

The heating time cannot be unconditionally determined because it depends on the types of the nonpolar polyolefin (a) and vinyl monomer (b) used, but the above aqueous suspension is kept constant. From the viewpoint that the vinyl-based monomer (b) is impregnated in the crystalline polyolefin (a) by almost 100% by heating at such a temperature, it is usually about 5 hours or less, and further 0.5 to 2 hours. It is preferably about the same.

The temperature at which the temperature of the aqueous suspension is raised to complete the polymerization of the vinyl monomer (b) is
The temperature is equal to or higher than the temperature at which the radical polymerization initiator (c) is substantially decomposed, and preferably 50 to 180.
C., more preferably 70 to 160.degree.

The non-polar polyolefin (a) can be impregnated with the vinyl monomer (b) by heating the aqueous suspension to such a temperature to complete the polymerization.
When the temperature of the aqueous suspension is increased to raise the temperature above the temperature at which the crystalline portion of the nonpolar polyolefin (a) substantially starts melting to complete the polymerization, the nonpolar polyolefin (a) The proportion of non-crystalline parts increases,
At the same time as the polymerization of the vinyl-based monomers (b), the vinyl-based monomer (b) is sufficiently grafted onto the amorphous portion of the non-polar polyolefin (a), and the vinyl-based monomer (b) Modified polyolefin (B) formed by polymerization of
It is preferable because the size of the domain in the inside becomes fine and it becomes easy to obtain the modified polyolefin (B) capable of sufficiently exhibiting the effect of improving processability and transparency.

The temperature at which the crystalline part of the non-polar polyolefin (a) substantially starts melting means that the proportion of the non-crystalline part in the non-polar polyolefin (a) is increased so that the vinyl-based monomer ( The melting point of ± 20 from the viewpoint of promoting the grafting of b) and not excessively cutting the polyolefin chain or gelling due to excessive heating.
℃, especially melting point ± 10 ℃. The melting point of a typical non-polar polyolefin (a) is about 160 to 170 ° C. for polypropylene, about 135 to 150 ° C. for propylene-based polyolefin, and about 138 ° C. for polyethylene.

The temperature at which the crystalline portion of the nonpolar polyolefin (a) substantially starts melting means that the nonpolar polyolefin (a) is heated by a DSC measurement method at a heating rate of 10 ° C./min in a nitrogen stream. (40 ml / min), the temperature is raised from room temperature to a temperature at which it completely melts, and a temperature higher than the middle 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. Say that.

The heating time cannot be unconditionally specified because it depends on the types of the non-polar polyolefin (a) and the vinyl-based monomer component (b) used, but the aqueous suspension is kept at such a temperature for a certain period of time. From the viewpoint that the polymerization of the vinyl-based monomer component (b) is sufficiently completed by heating to 1, it is usually preferably about 0.5 to 10 hours.

As described above, the polyolefin-based resin composition of the present invention is characterized in that it contains the modified polyolefin (B) grafted with the vinyl-based monomer (b). The polymer of the vinyl monomer (b) can be dispersed uniformly and finely when mixed with A), but the uniform fine dispersion of the polymer of the vinyl monomer (b) is an effect of improving the processability. The effect of the polyolefin grafted with the vinyl-based monomer (b) on the expression of the processability-improving effect is greater than the effect on the expression. The effect of improving the transparency is basically the weight of the nonpolar polyolefin (a) and the vinyl monomer (b) used and the vinyl monomer (b) contained in the reaction product thereof. It depends on the amount and particle size of coalescence.

The specific production method by the above-mentioned aqueous suspension polymerization method is the same as the usual aqueous suspension polymerization method except that the nonpolar polyolefin (a) is present in the system. For example water,
The non-polar polyolefin (a) may be suspended and polymerized by appropriately using a suspending agent, an emulsifying agent, a dispersing agent, etc. These types and amounts include various conditions such as temperature, pressure and stirring in the manufacturing process. Under these conditions, there is no particular limitation as long as the aqueous suspension polymer comprising the reaction mixture of each component is kept in a stable state to the extent that it does not excessively aggregate or fuse.

Specific preferred examples of these types and amounts are: about 100 parts of the nonpolar polyolefin (a), about 1.5 parts of calcium phosphate as a dispersant, and Latemur PS (manufactured by Kao Corporation) as an emulsifier. An example of using about 05 parts is given.

Further, in order to optimize the molecular weight of the branches of the graft copolymer, a chain transfer agent such as n-dodecyl mercaptan which is usually used, p-benzoquinone, 1,1-diphenyl-2-picrylhydrazyl, etc. Polymerization inhibitor,
A proper amount of a polymerization inhibitor or the like can also be used.

The reaction product obtained by the aqueous suspension polymerization method is usually a graft copolymer, a non-polar polyolefin which has not been grafted, or a polymer obtained by polymerizing a vinyl monomer (b) which has not been grafted ( Hereinafter, it is also referred to as a vinyl polymer) as a component. The primary structure of the graft copolymer in these components can be estimated by performing fractionation and analysis of the composition in the reaction product.

For example, the reaction product is heated and dissolved in a hydrocarbon solvent such as xylene, and if necessary, a good solvent for vinyl polymer such as methyl ethyl ketone is added, and then the solution is cooled to obtain a graft. The mixture of the copolymer and the ungrafted polyolefin and the ungrafted vinyl-based polymer can be separated as a precipitate and a solution in a solution, respectively.

By purifying the fractionated ungrafted vinyl polymer and weighing it, or
The graft ratio and the content of vinyl polymer branches in the graft copolymer can be measured by purifying the mixture of the fractionated graft copolymer and the ungrafted polyolefin and performing elemental analysis and IR analysis. .

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, (molecular weight of branch of graft copolymer) = (molecular weight of non-grafted vinyl polymer)
And

Usually, the molecular weight of the branch of the graft copolymer obtained in the aqueous suspension polymerization method is about 1000 to 2,000,000 as the weight average molecular weight in terms of polystyrene in GPC measurement, the catalyst species, the amount and the polymerization temperature. ,
It can be adjusted by adjusting various conditions relating to the polymerization such as the kind of the monomer, the concentration, the chain transfer agent, the combined use of a minute amount of the polymerization inhibitor or the polymerization inhibitor, but in the present invention,
The weight average molecular weight of the branch of the graft copolymer that particularly effectively exhibits the processability improving effect of the polyolefin is preferably 10,000 to 1,000,000.

Further, usually, the content of the branch polymerized with the vinyl monomer (b) in the graft copolymer in the reaction product obtained by the aqueous suspension polymerization method is determined by the weight relative to the whole reaction product. The ratio is about 0.1 to 30%.

When the reaction product obtained in the aqueous suspension polymerization method is observed by an electron microscope, the domain having an average dispersed particle size of about 0.01 to 10 μm is contained in the modified polyolefin (B), although it depends on the polymerization recipe. In the case of a small one, it is possible to confirm a vinyl polymer which is homogeneously and finely dispersed in a domain of about 0.01 to 0.08 μm.

The domain is considered to be a vinyl polymer which is not mainly grafted. This is supported by the fact that this domain was not observed even when the product obtained by removing the ungrafted vinyl polymer by the above-mentioned fractionation was observed.

It is preferable that the content of the polymer other than the graft chain, such as a vinyl polymer forming a domain, is small, but when it is contained, it is contained in the form of a domain to express the transparency of the polyolefin. From the point of, it is preferable. The size of the domain is preferably small from the viewpoint that it does not serve as a light-scattering source for manifesting transparency of the polyolefin, and is preferably 3 μm or less, further preferably 1 μm or less.

The polyolefin resin composition of the present invention is
It is obtained by mixing the polyolefin (A) and the modified polyolefin (B) having substantially the same refractive index.

The blending ratio of the polyolefin (A) and the modified polyolefin (B) constituting the polyolefin resin composition of the present invention is such that the modified polyolefin (B) is 0.1 parts with respect to 100 parts of the polyolefin (A). ~ 100 copies. When the blending ratio of the modified polyolefin (B) is less than 0.1 part, it becomes difficult to sufficiently exert the effect of improving the workability, and when it exceeds 100 parts, the cost is low. The general versatility of the resin composition is deteriorated, and the physical properties and mechanical properties of the resulting resin composition such as mechanical strength are deteriorated.

The preferred minimum amount of the modified polyolefin (B) component is 0.5 part or more, more preferably 1 part or more. In this case, the processability improving effect is sufficiently exhibited and the transparency is sufficiently high. The effect of expressing sex is obtained. In addition, the preferable maximum amount of the compounding ratio is 20 parts or less, and further 10 parts or less. In this case, the physical properties such as mechanical strength and the surface property are not deteriorated, and the excellent processability is exhibited. available. From the above viewpoint, the blending ratio of the component (B) is, for example, preferably 0.1 to 20 parts, more preferably 0.1 to 10 parts.

The polyolefin resin composition of the present invention may further contain a nucleating agent for improving transparency, surface property, rigidity and the like, and for improving impact resistance, processability and the like. A core-shell graft copolymer or the like having a refractive index substantially the same as that of the polyolefin (A) may be blended with.

Specific examples of the nucleating agent include sodium benzoate, bisbenzylidene sorbitol,
Examples thereof include bis (p-methylbenzylidene) sorbitol, bis (p-ethylbenzylidene) sorbitol, sodium 2,2-methylenebis (4.6-di-tert-butylphenyl) phosphite and the like. These may be used alone or in combination of two or more. Among these, bisbenzylidene sorbitol, bis (p-methylbenzylidene) sorbitol, sodium 2,2-methylenebis (4,6-di-tertiarybutylphenyl) phosphite from the viewpoint of the balance of transparency, surface property and rigidity. Is preferred.

The blending amount of the nucleating agent is preferably 0.01 to 2 parts with respect to 100 parts of the polyolefin resin composition. The amount of the nucleating agent blended is 0.01
If it is less than 1 part, the transparency or surface property tends to be insufficient, and if it exceeds 2 parts, the effect is saturated, and if more is added, the effect of further improving the physical properties is small.

The core-shell graft copolymer can be obtained by a usual method such as a suspension polymerization method and an emulsion polymerization method (for example, Japanese Patent Application No. 5-83567). In the present invention, those having a refractive index substantially equal to that of the polyolefin (A) are used. Therefore, the cross-linked rubber-like polymer as the core and the graft monomer as the shell are selected and synthesized so that the refractive index of the core-shell graft copolymer is substantially equal to that of the polyolefin (A).

The above-mentioned "substantially equal" means that the difference in refractive index is 0.02 or less, but 0.01 or less, and further 0.0 or less.
It is preferably not more than 05 from the viewpoint of suppressing the decrease in transparency of the polyolefin.

For example, a core-shell graft copolymer having a refractive index substantially equal to that of polypropylene is obtained by graft-copolymerizing 50 parts of cross-linked polybutadiene rubber obtained by emulsion polymerization with 50 parts of methyl methacrylate or acrylic acid. 70% n-butyl and 30% styrene
To 70 parts of a crosslinked acrylic rubber obtained by emulsion-polymerizing a monomer to which 1% of allyl methacrylate was added, a monomer component consisting of 27 parts of methyl methacrylate and 3 parts of styrene was graft-copolymerized. There are things such as things.

The amount of the core-shell graft copolymer mixed is 100 parts by weight of the polyolefin (A).
It is preferably 0.01 to 50 parts, and more preferably 0.1 to 20 parts. If the blending amount is less than 0.01 part, workability,
The effect of improving surface properties, impact resistance, etc. is not sufficient, and when it exceeds 50 parts, the inherent heat resistance and rigidity of the polyolefin tend to be impaired.

The method for producing the polyolefin resin composition of the present invention is not particularly limited, and the above-mentioned polyolefin (A) and modified polyolefin (B) can be prepared by a conventional method such as an extrusion mixing method or a roll mixing method. Can be produced by mixing a nucleating agent, a core-shell graft copolymer and the like.

When a nucleating agent is used, the mixing method is not particularly limited as long as the nucleating agent is finally uniformly contained in the composition comprising the polyolefin (A) and the modified polyolefin (B). , Modified polyolefin (B)
Alternatively, it may be blended with the nonpolar polyolefin (a) and used as a master pellet. In this case, it is preferable to mix the nonpolar polyolefin (a) and the nucleating agent into pellets first, from the viewpoint of dispersion of the nucleating agent, and the modified polyolefin (B) and the nucleating agent. From the viewpoint of dispersion of the nucleating agent, it is preferable to mix them into pellets first.

When the core-shell graft copolymer is used, the core-shell graft copolymer may be mixed particularly in the composition as long as it is finally uniformly contained in the composition comprising the polyolefin (A) and the modified polyolefin (B). Although not limited, the modified polyolefin (B) may be blended and used as a master pellet.

If desired, the polyolefin resin composition of the present invention may further contain, for example, stabilizers and lubricants.

The stabilizer is a component used for suppressing oxidative deterioration and improving thermal stability. When the stabilizer is used, it is possible to sufficiently suppress deterioration of physical properties such as processability during molding of the polyolefin resin composition, impact resistance of the molded article, rigidity, and surface property. Stabilizers include
Examples include phenol-based stabilizers, phosphorus-based stabilizers, and sulfur-based stabilizers.

Specific examples of the phenolic stabilizer include tetrakis {methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate} methane and 2,6-di-t-butyl- 4-methylphenol,
Octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, triethylene glycol 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} -1,1-
Specific examples of hindered phenol compounds such as dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane and phosphorus stabilizers include triphenylphosphite and tris (monononylphenyl). Specific examples of phosphite compounds such as phosphite, tris (2,4-di-t-butylphenyl) phosphite, bis (nonylphenyl) -dinonylphenylphosphite, and sulfur stabilizers include dilauryl 3, Examples thereof include sulfur-containing organic esters such as 3'-thiodipropionate, distearyl 3,3'-thiodipropionate, pentaerythrityl tetrakis (3-lauryl thiopropionate), and di-t-dodecyl disulfide. . These may be used alone or in combination of two or more.

The amount of the stabilizer blended is about 0.01 to 3 parts with respect to 100 parts of polyolefin.
About 5 to 2 parts is preferable.

Typical examples of the above-mentioned lubricant include sodium salts, calcium salts, magnesium salts of saturated or unsaturated fatty acids such as lauric acid, palmitic acid, oleic acid and stearic acid. These may be used alone or in combination of two or more. Also,
The blending amount of such a lubricant is usually about 0.1 to 3 parts, especially 0.1 to 2 parts, relative to 100 parts of the polyolefin (A).
From the viewpoint of cost reduction, it is preferable that it is about a part.

The polyolefin resin composition of the present invention comprises
Greatly improved excellent transparency, processability, impact resistance,
Since it has rigidity, surface properties, etc., various molding methods including the molding method, which is difficult when the conventional polyolefin resin composition is used, from the polyolefin resin composition of the present invention. Thus, a useful molded body can be manufactured.

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 extrusion-molding 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, injection molding or blow molding can be obtained by injection molding or blow molding the pellets obtained by subjecting the resin 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.

Although the polyolefin resin composition of the present invention has been described above centering on the compositions described in claims 1 and 2, the main compositions among the compositions which have not yet been sufficiently explained. The combination of each constituent element and the effect thereof will be described below together with the composition already explained.

Invention 1 Vinyl monomer (b) 1 in the presence of 100 parts of polyolefin (A) and 100 parts of non-polar polyolefin (a).
Modified polyolefin (B) obtained by polymerizing ~ 500 parts
A polyolefin-based resin composition comprising 0.1 to 100 parts and having substantially the same refractive index as the polyolefin (A) and the modified polyolefin (B).

Invention 2 The modified polyolefin (B) contains 1 to 50 parts of the vinyl monomer (b) per 100 parts of the nonpolar polyolefin (a).
An aqueous suspension containing 0.01 to 10 parts of the radical polymerization initiator (c) per 0 part and 100 parts of the vinyl-based monomer (b) is used as it is, or the radical suspension of the radical polymerization initiator (c) is added. Heat under conditions that do not cause substantial decomposition,
The vinyl monomer (b) is impregnated into the non-polar polyolefin (a), and the temperature of the aqueous suspension is further raised to complete the polymerization of the vinyl monomer (b). A polyolefin-based resin composition according to Invention 1.

Invention 3-1 The modified polyolefin (B) is the polyolefin (A) 1
The polyolefin-based resin composition of Invention 1, which is 0.1 to 20 parts with respect to 00 parts.

Invention 3-2 The modified polyolefin (B) is the polyolefin (A) 1
The polyolefin-based resin composition of Invention 2, which is 0.1 to 20 parts with respect to 00 parts.

Invention 4-1 The modified polyolefin (B) is the polyolefin (A) 1
The polyolefin-based resin composition of Invention 1 which is 0.1 to 10 parts with respect to 00 parts.

Invention 4-2 The modified polyolefin (B) is the polyolefin (A) 1
The polyolefin resin composition according to Invention 2, wherein the amount is 0.1 to 10 parts with respect to 00 parts.

Invention 5-1 The polyolefin resin composition according to Invention 1, wherein the polyolefin (A) is a crystalline propylene-based polyolefin obtained by polymerizing a monomer component containing 75% or more of propylene.

Invention 5-2 The polyolefin resin composition according to Invention 2, wherein the polyolefin (A) is a crystalline propylene-based polyolefin obtained by polymerizing a monomer component containing 75% or more of propylene.

Invention 6-1 The non-polar polyolefin (a) is obtained by polymerizing each homopolymer obtained by polymerizing ethylene, propylene, butylene or 4-methylpentene and two or more kinds of those monomers. Each copolymer and each copolymer obtained by polymerizing one or more of ethylene, propylene, butylene, and 4-methylpentene with another monomer copolymerizable therewith (ethylene-vinyl acetate copolymer, etc.) The polyolefin resin composition of Invention 1, which is at least one selected from the group consisting of:

Invention 6-2 The non-polar polyolefin (a) is obtained by polymerizing ethylene, propylene, butylene or 4-methylpentene, each homopolymer and two or more kinds of those monomers. Each copolymer and each copolymer obtained by polymerizing one or more of ethylene, propylene, butylene, and 4-methylpentene with another monomer copolymerizable therewith (ethylene-vinyl acetate copolymer, etc.) The polyolefin resin composition of Invention 2, which is at least one selected from the group consisting of:

Invention 7: The polyolefin resin composition according to Invention 2, wherein the temperature of the aqueous suspension is raised to a temperature at which the crystalline portion of the nonpolar polyolefin (a) substantially starts melting. .

Invention 8-1 The vinyl monomer (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. The polyolefin-based resin composition according to Invention 1, which comprises 80% or more of at least one selected from alkyl acrylates and unsaturated nitrile compounds and 20% or less of other vinyl-based monomers copolymerizable therewith.

Invention 8-2 The vinyl monomer (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. The polyolefin resin composition of Invention 2, which comprises at least one selected from an alkyl acrylate and an unsaturated nitrile compound in an amount of 80% or more, and 20% or less of another vinyl monomer copolymerizable therewith.

Invention 9-1 The vinyl monomer (b) is an aromatic vinyl compound 1-5.
0%, methacrylic acid alkyl ester whose alkyl group has 1 to 22 carbon atoms and / or acrylic acid alkyl ester 99 whose alkyl group has 1 to 22 carbon atoms
The polyolefin-based resin composition of Invention 1, which comprises 50%.

Invention 9-2 The vinyl monomer (b) is an aromatic vinyl compound 1-5.
0%, methacrylic acid alkyl ester whose alkyl group has 1 to 22 carbon atoms and / or acrylic acid alkyl ester 99 whose alkyl group has 1 to 22 carbon atoms
The polyolefin-based resin composition of Invention 2, which comprises 50%.

Invention 10-1 The vinyl-based monomer (b) has an alkyl group having 1 to 2 carbon atoms.
The polyolefin resin composition according to Invention 1, which is composed of a methacrylic acid alkyl ester which is 2 and / or an acrylic acid alkyl ester whose alkyl group has 1 to 22 carbon atoms.

Invention 10-2 The vinyl-based monomer (b) has an alkyl group having 1 to 2 carbon atoms.
The polyolefin resin composition of Invention 2, which is composed of a methacrylic acid alkyl ester of 2 and / or an acrylic acid alkyl ester of which the alkyl group has 1 to 22 carbon atoms.

Invention 11-1 The polyolefin resin composition according to Invention 8-1, wherein the aromatic vinyl compound is styrene and / or a derivative thereof.

Invention 11-2 The polyolefin resin composition according to Invention 8-2, wherein the aromatic vinyl compound is styrene and / or a derivative thereof.

Invention 11-3 The polyolefin resin composition according to Invention 9-1, wherein the aromatic vinyl compound is styrene and / or its derivative.

Invention 11-4 The polyolefin resin composition according to Invention 9-2, wherein the aromatic vinyl compound is styrene and / or its derivative.

Invention 12-1 The polyolefin system according to Invention 8-1 wherein the alkyl methacrylate having an alkyl group having 1 to 22 carbon atoms is methyl methacrylate, ethyl methacrylate, n-butyl methacrylate or cyclohexyl methacrylate. Resin composition.

Invention 12-2 The polyolefin system according to Invention 8-2, wherein the alkyl methacrylate having an alkyl group having 1 to 22 carbon atoms is methyl methacrylate, ethyl methacrylate, n-butyl methacrylate or cyclohexyl methacrylate. Resin composition.

Invention 12-3 The polyolefin system according to Invention 9-1, wherein the alkyl methacrylate having an alkyl group having 1 to 22 carbon atoms is methyl methacrylate, ethyl methacrylate, n-butyl methacrylate or cyclohexyl methacrylate. Resin composition.

Invention 12-4 The polyolefin system according to Invention 9-2, wherein the alkyl methacrylate having an alkyl group having 1 to 22 carbon atoms is methyl methacrylate, ethyl methacrylate, n-butyl methacrylate or cyclohexyl methacrylate. Resin composition.

Invention 12-5 The polyolefin system according to Invention 10-1, wherein the alkyl methacrylate having an alkyl group having 1 to 22 carbon atoms is methyl methacrylate, ethyl methacrylate, n-butyl methacrylate or cyclohexyl methacrylate. Resin composition.

Invention 12-6 The polyolefin system according to Invention 10-2, wherein the alkyl methacrylate having an alkyl group having 1 to 22 carbon atoms is methyl methacrylate, ethyl methacrylate, n-butyl methacrylate or cyclohexyl methacrylate. Resin composition.

Invention 13-1 An alkyl acrylate having an alkyl group having 1 to 22 carbon atoms is methyl acrylate, ethyl acrylate,
The polyolefin-based resin composition of Invention 8-1, which is n-butyl acrylate or 2-ethylhexyl acrylate.

Invention 13-2 An acrylic acid alkyl ester having an alkyl group having 1 to 22 carbon atoms is methyl acrylate, ethyl acrylate,
The polyolefin resin composition of Invention 8-2, which is n-butyl acrylate or 2-ethylhexyl acrylate.

Invention 13-3 An alkyl acrylate whose alkyl group has 1 to 22 carbon atoms is methyl acrylate, ethyl acrylate,
The polyolefin-based resin composition of Invention 9-1, which is n-butyl acrylate or 2-ethylhexyl acrylate.

Invention 13-4 An alkyl acrylate whose alkyl group has 1 to 22 carbon atoms is methyl acrylate, ethyl acrylate,
The polyolefin-based resin composition of Invention 9-2, which is n-butyl acrylate or 2-ethylhexyl acrylate.

Invention 13-5 An acrylic acid alkyl ester having an alkyl group having 1 to 22 carbon atoms is methyl acrylate, ethyl acrylate,
The polyolefin-based resin composition of Invention 10-1, which is n-butyl acrylate or 2-ethylhexyl acrylate.

Invention 13-6 An alkyl acrylate whose alkyl group has 1 to 22 carbon atoms is methyl acrylate, ethyl acrylate,
The polyolefin-based resin composition of Invention 10-2, which is n-butyl acrylate or 2-ethylhexyl acrylate.

Invention 14-1 The invention 9-1 according to Invention 9-1, wherein the vinyl-based monomer (b) comprises 1 to 50% of styrene, methyl methacrylate and / or 99 to 50% of n-butyl acrylate. Polyolefin resin composition.

Invention 14-2 According to Invention 9-2, the vinyl-based monomer (b) is composed of 1 to 50% styrene, methyl methacrylate and / or 99 to 50% n-butyl acrylate. Polyolefin resin composition.

Invention 15-1 The polyolefin resin composition of Invention 1 wherein the size of the domain in the modified polyolefin (B) formed by polymerization of the vinyl monomer (b) is 3 μm or less.

Invention 15-2 The polyolefin resin composition according to Invention 2, wherein the size of the domain in the modified polyolefin (B) formed by polymerization of the vinyl monomer (b) is 3 μm or less.

Invention 16-1 The polyolefin resin composition according to Invention 1, wherein the size of the domain in the modified polyolefin (B) formed by polymerization of the vinyl monomer (b) is 1 μm or less.

Invention 16-2 The polyolefin resin composition according to Invention 2, wherein the size of the domain in the modified polyolefin (B) formed by polymerization of the vinyl monomer (b) is 1 μm or less.

Invention 17 Inventions 1, 2, 3-1, 3 containing 0.01 to 2 parts of a nucleating agent to 100 parts of a polyolefin resin composition.
-2, 4-1, 4-2, 5-1, 5-2, 6-1, 6-
2, 7, 8-1, 8-2, 9-1, 9-2, 10-1,
10-2, 11-1, 11-2, 11-3, 11-4,
12-1, 12-2, 12-3, 12-4, 12-5,
12-6, 13-1, 13-2, 13-3, 13-4,
13-5, 13-6, 14-1, 14-2, 15-1,
The polyolefin resin composition of 15-2, 16-1 or 16-2.

Invention 18 A non-polar polyolefin (a) and / or a nucleating agent is used.
Inventions 1, 2, 3-1, 3 in which 0.01 to 2 parts of a nucleating agent is contained with respect to 100 parts of the polyolefin resin composition characterized by being blended with the modified polyolefin (B).
-2, 4-1, 4-2, 5-1, 5-2, 6-1, 6-
2, 7, 8-1, 8-2, 9-1, 9-2, 10-1,
10-2, 11-1, 11-2, 11-3, 11-4,
12-1, 12-2, 12-3, 12-4, 12-5,
12-6, 13-1, 13-2, 13-3, 13-4,
13-5, 13-6, 14-1, 14-2, 15-1,
The polyolefin resin composition of 15-2, 16-1 or 16-2.

Invention 19 A core-shell graft copolymer having substantially the same refractive index as that of the polyolefin (A) is prepared by using the polyolefin (A) 10
Inventions 1, 2, 3-1, 3-2, 4-1, 4-2, 5-characterized by containing 0.01 to 50 parts with respect to 0 part
1, 5-2, 6-1, 6-2, 7, 8-1, 8-2, 9
-1, 9-2, 10-1, 10-2, 11-1, 11-
2, 11-3, 11-4, 12-1, 12-2, 12-
3, 12-4, 12-5, 12-6, 13-1, 13-
2, 13-3, 13-4, 13-5, 13-6, 14-
1, 14-2, 15-1, 15-2, 16-1, 16-
The polyolefin resin composition of 2, 17 or 18.

The composition of the invention 1 has excellent processability and excellent properties such as transparency, impact resistance, rigidity and surface property when formed into a molded product. However, a polyolefin-based resin composition that can be suitably used for various molded articles is obtained, and the modified polyolefin (B) in Invention 1 is limited as in Invention 2 to produce by a simplified polymerization method. The effect of lowering the cost and increasing the amount of the vinyl-based monomer (b) polymerized as a domain in the modified polyolefin (B) and decreasing the amount of the domain without being a domain. The effects of cost reduction and versatility are achieved by limiting the blending amount of the modified polyolefin (B) in Inventions 1 and 2 as in Invention 3 or 4, and the effect of reducing the polyolefin (A) in Invention 5 is obtained. 1 to 5-2, the effects of being transparent, general-purpose and easily available, and inexpensive can be obtained, and the non-polar polyolefin (a) in Inventions 1 to 2 is used in Invention 6-1 to By limiting as 6-2, the improving effect in Inventions 1 and 2 is more likely to be exhibited, and by limiting the polyolefin (a) to an ethylene-vinyl acetate copolymer, impact resistance is exhibited. By controlling the temperature of the aqueous suspension in the invention 2 as in the invention 7, the vinyl-based monomer (b) is particularly sufficient for the non-crystalline portion of the nonpolar polyolefin (a). Modified polyolefin (B) grafted onto
The size of the domain in the inside becomes fine, and improvement effects such as transparency and processability can be sufficiently expressed, and the invention 1 to
The vinyl-based monomer component (b) in 2 is the invention 8-1 to 1
By restricting as 0-2, it is possible to more sufficiently express the effects of improving the processability, transparency, surface property and rigidity in Inventions 1 and 2, and the invention 8
-1 to 10-2 by limiting the vinyl-based monomer component (b) as in Inventions 11-1 to 14-2,
Inventive 8-1 to 10-2 are made more versatile by reducing the production cost by simplifying the polymerization method, and the vinyl-based monomer () in the modified polyolefin (B) of Inventives 1 and 2 ( By limiting the size of the domain formed by polymerization of b) as in Inventions 15-1 to 16-2, transparency and surface property are improved, and each polyolefin resin composition of Inventions 1 to 16-2 is improved. In the case of the invention 17 in which a predetermined amount of the nucleating agent is blended with the product, transparency, surface property, and rigidity are sufficiently exhibited, and when the nucleating agent is blended as in the invention 18, dispersion of the nucleating agent. Is good, especially transparency,
When a predetermined amount of a core-shell graft copolymer having improved surface properties and rigidity and having a refractive index substantially equal to that of the polyolefin (A) is added to each of the polyolefin resin compositions of Inventions 1 to 18, impact resistance is improved. It can be further improved.

The composition of the present invention will be described in more detail based on the following examples, but the present invention is not limited thereto.

Production Example 1 Production of Modified Polyolefin (B-1) 5000 parts of pure water was charged into a pressure-resistant closed reaction vessel, and then nonpolar random polypropylene particles (ethylene content 3%,
DSC melting start temperature 80 ° C, DSC melting point 146.7 ° C,
Average particle size 3 mm, MI6) 700 parts, methyl methacrylate 132 parts, n-butyl acrylate 100 parts, styrene 68 parts, calcium phosphate 15 parts, Latemur PS (manufactured by Kao Corporation) 6 parts and di-t- 3.6 parts of butyl peroxide (10-hour half-life temperature of 124 ° C.) were added and mixed with stirring to obtain an aqueous suspension. 1 of the aqueous suspension
After stirring at 00 ° C for 1 hour, the mixture was further heated at 140 ° C for 5 hours with stirring to complete the polymerization.

The obtained particles were washed with water to remove residual monomer, catalyst, calcium phosphate and emulsifier, and then dried to obtain modified polyolefin (B-1). The obtained modified polyolefin (B-1) is white granular (average particle size 3 m
m), and the conversion rate was 90%.

The conversion rate means the rate of conversion into a polymer in the total weight of the vinyl monomer (b). This conversion rate was measured by the modified polyolefin (B-
Calculated by measuring the total weight of 1), subtracting the weight of the nonpolar random polypropylene particles used from this, and using the obtained value as the weight of the vinyl-based monomer (b) converted into a polymer. Is.

Modified polyolefin obtained from 132 parts of methyl methacrylate, 100 parts of n-butyl acrylate, 68 parts of styrene and 700 parts of random polypropylene (B
The calculated refractive index of -1) is 1.504, and the calculated glass transition temperature of the graft chain is 30 ° C.

A part of the obtained modified polyolefin (B-1) was dissolved in 17 times the amount of xylene at 120 ° C., and allowed to cool at room temperature for 2 hours. The polymer and the mixture of the graft copolymer and the ungrafted polypropylene, which are insoluble in xylene, were separated by filtration and analyzed by IR measurement of the mixture of the graft copolymer and the ungrafted polypropylene after drying. However, the vinyl polymer branch content in the modified polyolefin (B-1) was about 10%.

Further, the weight average molecular weight of the branches of the graft copolymer (hereinafter,

[0144]

[Outer 1]

(Also referred to as)),
It was 0-400000.

Further, the obtained modified polyolefin (B
When the size of the domain was measured by microscopic observation of (-1), it was 0.05 to 0.1 μm.

Production Example 2 Production of Modified Polyolefin (B-2) 5000 parts of pure water was charged into a pressure-resistant closed reaction tank, and then nonpolar low-density polyethylene particles (trade name: Nisseki Lexron F102, Nippon Petrochemical Co., Ltd.) Made, DSC melting start temperature 60 ° C, DSC melting point 102 ° C, MI0.25, average particle size 3 mm (hereinafter, also referred to as LDPE) 700 parts, n-butyl acrylate 261 parts, styrene 39 parts, calcium phosphate 15 parts, emulsifier As Latemur PS (Kao Corporation)
6 parts) and 3.6 parts of di-t-butyl peroxide were added and mixed with stirring to obtain an aqueous suspension. The aqueous suspension was stirred at 80 ° C. for 1 hour and then heated at 105 ° C. for 5 hours with stirring to complete the polymerization.

The obtained particles were washed with water to remove residual monomer, catalyst, calcium phosphate and emulsifier, and then dried to obtain modified polyolefin (B-2). The modified polyolefin (B-2) obtained was white granular (average particle size 3 m.
m), and the conversion rate was 90%.

A part of the obtained modified polyolefin (B-2) was dissolved in 17 times the amount of xylene at 120 ° C., and allowed to cool at room temperature for 2 hours. The polymer and the mixture of the graft copolymer and the ungrafted LDPE, which are insoluble in xylene, were filtered off, and the weight of each was measured after drying, and the total amount of the graft copolymer and the ungrafted LDPE was measured. The weight ratio of the vinyl polymer and the non-grafted vinyl polymer was about 77:23, and the content of the vinyl polymer branch in the modified polyolefin (B-2) was about 77:23. It was 10%. In addition, the branch of the graft copolymer

[0150]

[Outside 2]

Was 50,000 to 150,000.

The modified polyolefin (B-2) obtained from 261 parts of n-butyl acrylate, 39 parts of styrene, and 700 parts of low-density polyethylene has a calculated refractive index of 1.50.
It is 3. The domain size is 0.05-0.1.
was μm.

Production Example 3 Production of Modified Polyolefin (B-3) 5000 parts of pure water was charged in a pressure-resistant closed reaction tank, and ethylene-propylene rubber (trade name: EP07P, manufactured by Nippon Synthetic Rubber Co., Ltd., MI0.7). , Average particle diameter 3 mm) (hereinafter EP
R) 700 parts, n-butyl acrylate 90 parts,
210 parts of styrene, 15 parts of calcium phosphate, 6 parts of Latemul PS (manufactured by Kao Corporation) as an emulsifier and di-t-
3.6 parts of butyl peroxide was mixed and mixed with stirring to obtain an aqueous suspension. The aqueous suspension was stirred at 60 ° C for 1 hour and then at 80 ° C for 5 hours to complete the polymerization.

The obtained particles were washed with water to remove residual monomer, catalyst, calcium phosphate and emulsifier, and then dried to obtain modified polyolefin (B-3). The modified polyolefin (B-3) was white granular (average particle size 3 mm), and its conversion rate was 90%.

90 parts of n-butyl acrylate, 2 of styrene
The calculated refractive index of the modified polyolefin (B-3) obtained from 10 parts and 700 parts of ethylene-propylene rubber is 1.503. The domain size is 0.1
It was 0.2 μm.

For the obtained modified polyolefin (B-3), the total amount of the graft copolymer and the ungrafted EPR and the abundance ratio of the ungrafted vinyl polymer were measured in the same manner as in Production Example 2. As a result, the weight ratio was about 77:23, and based on this value, the content of the vinyl polymer branch in the modified polyolefin (B-3) was about 1
It was 0%. In addition, the branch of the graft copolymer

[0157]

[Outside 3]

Was 50,000 to 100,000.

Production Example 4 Production of Modified Polyolefin (B-4) 5000 parts of pure water was charged in a pressure-resistant closed reaction tank, and an ethylene-vinyl acetate copolymer (trade name: Evaflex 260 was used.
Mitsui DuPont Polychemical Co., Ltd., MI6, average particle size 3 mm (hereinafter also referred to as EVA) 700 parts, n-butyl acrylate 195 parts, styrene 105 parts, calcium phosphate 15 parts, Latemur PS (Kao (stock) 6) and di-t-butyl peroxide 3.
6 parts were mixed and mixed with stirring to obtain an aqueous suspension. The aqueous suspension was heated with stirring at 60 ° C. for 1 hour and then further stirred at 80 ° C.
Polymerization was completed by heating and stirring at 5 ° C for 5 hours. The obtained particles are washed with water to remove residual monomer, catalyst, calcium phosphate,
After removing the emulsifier, the modified polyolefin (B
-4) was obtained. The modified polyolefin (B-4) was white granular (average particle size 3 mm), and its conversion rate was 90%.

The calculated refractive index of the modified polyolefin (B-4) obtained from 195 parts of n-butyl acrylate, 105 parts of styrene and 700 parts of ethylene-vinyl acetate copolymer is 1.503. The domain size is 0.
It was 05 to 0.1 μm.

For the obtained modified polyolefin (B-4), the total amount of the graft copolymer and the ungrafted EVA and the abundance ratio of the ungrafted vinyl polymer were measured in the same manner as in Production Example 2. As a result, the weight ratio was about 77:23, and based on this value, the content of vinyl polymer branches in the modified polyolefin (B-4) was about 1
It was 0%. In addition, the branch of the graft copolymer

[0162]

[Outside 4]

Was 100,000 to 150,000.

Comparative Production Example 1 Production of Modified Polyolefin (B′-1) 5000 parts of pure water was charged into a pressure-resistant closed reaction vessel, and 700 parts of non-polar random polypropylene particles (the same as those used in Production Example 1), Styrene 300 parts, calcium phosphate 1
5 parts, 6 parts of Latemul PS (manufactured by Kao Corporation) as an emulsifier and 3.6 parts of di-t-butyl peroxide were mixed,
The mixture was stirred and mixed to obtain an aqueous suspension. 100 of the aqueous suspension
After heating and stirring at 1 ° C for 1 hour, the mixture was further heated and stirred at 140 ° C for 5 hours to complete the polymerization. The obtained particles were washed with water to remove residual monomer, catalyst, calcium phosphate and emulsifier, and then dried to obtain modified polyolefin (B'-1). The modified polyolefin (B'-1) was white and had a conversion rate of 90%.

Modified polyolefin (B'-) obtained from 300 parts of styrene and 700 parts of random polypropylene.
The calculated refractive index of 1) is 1.530. The size of the domain was 0.05 to 0.1 μm.

Obtained modified polyolefin (B'-1)
Was measured by IR in the same manner as in Production Example 1 to find that the content of vinyl polymer branches in the modified polyolefin (B′-1) was about 12%. In addition, the technique of graft copolymer

[0167]

[Outside 5]

It was 150000 to 250,000.

Production Example 5 Production of Core-Shell Graft Copolymer 100 parts of a monomer component consisting of 70 parts of n-butyl acrylate, 30 parts of styrene and 1 part of allyl methacrylate was emulsion polymerized to obtain a crosslinked acrylic rubber. Allyl methacrylate was used as a crosslinking agent and a grafting agent. The average particle size of the obtained crosslinked acrylic rubber is 0.2.
μm, crosslinked gel content was 85%.

30 parts of a monomer component consisting of 27 parts of methyl methacrylate and 3 parts of styrene was added to 70 parts (solid content) of the crosslinked acrylic rubber latex, and graft copolymerization was carried out by emulsion polymerization. A polymer (hereinafter, referred to as a graft copolymer (D)) was obtained. The final conversion was 98%, the particle size was 0.22 μm, and the refractive index was 1.503 (calculated value).

The latex of this graft copolymer (D) is salt-folded, dehydrated and dried to obtain the graft copolymer (D).
Powder (average particle size 180 μm) was obtained.

Examples 1 to 12 and Comparative Examples 1 to 6 100 parts of the polyolefin (A) listed in Table 1 was added to the modified polyolefin described in Table 1 and a nucleating agent (Gelol DH (manufactured by Shin Nippon Rika Co., Ltd., Bis (p-methylbenzylidene) sorbitol) and the graft copolymer (D) obtained in Production Example 5 were blended in the proportions shown in Table 1, and a twin-screw extruder (screw diameter 44 mm, L / D: 30) was blended. Using 200
Extruded and kneaded at 100 ° C. at 100 ° C. to obtain a pelletized polyolefin resin composition (hereinafter, also referred to as PO composition).

Using the PO composition thus obtained, workability, impact resistance, flexural modulus, transparency, melt tension and surface gloss were evaluated by the following methods. The results are shown in Table 2.

When blending the nucleating agent, the polyolefin (A), the modified polyolefin and the nucleating agent were mixed and then kneaded by a twin-screw extruder to obtain a pelletized PO composition.

When the graft copolymer (D) is blended, the polyolefin composition (A), the modified polyolefin and the graft copolymer (D) are mixed and then kneaded by a twin-screw extruder to form a pelletized PO composition. I got a thing.

PP in Table 1 is polypropylene (trade name: Hypol-B-2) in which ethylene is copolymerized by 3%.
30, manufactured by Mitsui Petrochemical Co., Ltd., refractive index 1,500
(Measured value) MI 0.5) (hereinafter, also referred to as PP) is L
DPE is Nisseki Lexron F102, ERP is EPO7
P represents EVA and Evaflex 260 represents.

(Processability) The PO composition was roll-kneaded at 200 ° C. for 3 minutes to prepare a roll sheet having a thickness of 1 mm.
Two obtained roll sheets are piled up and 200 ℃ × 3
It was press-molded under the condition of 0 kg / cm ² × 10 minutes and then cooled at room temperature under the condition of 50 kg / cm ² × 10 minutes to obtain a sheet having a thickness of 1.5 mm. A 100 mm square test piece was cut out from this sheet.

The obtained test piece was fixed with a frame having openings of 76 mm square, a metal object difference for hanging measurement was attached to the legs of the frame, and the frame with the sheet was set in an oven set at 190 ° C. The sheet was placed on a sheet, and the sag (also referred to as drawdown) (mm) of the central portion of the sheet was measured for 30 minutes.

(Transparency) A test piece having a thickness of 1.0 mm and 30 mm square was prepared in the same manner as described in the above (workability).
It was measured according to ASTM-D-1003. Table 1
In the table, T represents the total light transmittance, and HAZE represents the turbidity.

(Impact resistance) 1/4 inch thick test pieces were prepared in the same manner as described in the above (workability), and ASTM-D
The Izod impact strength with notch was measured according to 256.

(Flexural Modulus) A 1/4 inch thick test piece was prepared in the same manner as described in the above (workability), and ASTM
-Measured according to D790.

(Melt tension) Using a PO composition, a capillograph having a diameter of 1 mm and a length of 10 mm manufactured by Toyo Seiki Co., Ltd., 200 ° C., an extrusion speed of 5 mm / min,
The melt tension at a take-up speed of 1 m / min was measured.

(Surface gloss) The PO composition was T-die extruded at 230 ° C. using a single-screw T-die extruder (screw diameter: 50 mm, L / D: 30) to obtain a sheet having a width of 300 mm and a thickness of 0.5 mm. Was produced.

The surface gloss of the obtained sheet was visually observed and evaluated based on the following evaluation criteria.

(Evaluation Criteria) A: Very high gloss B: High gloss C: Low gloss

[0186]

[Table 1]

[0187]

[Table 2]

From the results shown in Table 2, the modified polyolefin (B-
The mixture of 1) to (B-4) with the non-polar polyolefin (a) has improved transparency and, at the same time, has significantly improved drawdown which is a problem in processing such as thermoforming and blow molding. I understand. Also, it can be seen that the gloss is superior to that of polypropylene alone. Furthermore, it can be seen that impact resistance is also improved in (B-3) and (B-4).

When the difference in the refractive index between the polyolefin (A) and the modified polyolefin (B) is not substantially equal to 0.030 as in Comparative Example 2, the transparency is higher than that of the present invention. Take

Further, LDPE, EPR or EVA may be replaced with PP instead of the modified polyolefin (B) used in the present invention.
Comparative Examples 3 to 6 mixed with each other are more transparent than the present invention.
It can be seen that workability and surface gloss are excellent.

From the results shown in Table 2, when the nucleating agent is further added as in Examples 8 to 11, the processability is not only markedly improved, but the transparency is also markedly improved. It turns out that it will be improved.

Further, when a core-shell graft copolymer having a refractive index substantially equal to that of the polyolefin is blended as in Example 12, the impact resistance is further improved. .

[0193]

EFFECT OF THE INVENTION The polyolefin resin composition of the present invention has excellent processability and at the same time has excellent properties such as transparency, impact resistance, rigidity and surface property when formed into a molded product. Therefore, a useful molded article can be produced from the polyolefin resin composition by various molding methods.

Claims (19)

[Claims] 1. A modified polyolefin (B) obtained by polymerizing 1 to 500 parts by weight of a vinyl monomer (b) in the presence of 100 parts by weight of the polyolefin (A) and 100 parts by weight of the non-polar polyolefin (a). A polyolefin-based resin composition comprising 0.1 to 100 parts by weight and having substantially the same refractive index as the polyolefin (A) and the modified polyolefin (B). 2. The modified polyolefin (B) comprises 1 to 500 parts by weight of a vinyl-based monomer (b) and 100 parts by weight of the vinyl-based monomer (b) with respect to 100 parts by weight of a nonpolar polyolefin (a). Radical polymerization initiator (c)
An aqueous suspension containing 0.01 to 10 parts by weight is heated as it is or under a condition that the decomposition of the radical polymerization initiator (c) does not substantially occur, to thereby obtain the vinyl-based monomer (b). The polyolefin resin composition according to claim 1, wherein the non-polar polyolefin (a) is impregnated with the aqueous solution, and the temperature of the aqueous suspension is further raised to complete the polymerization of the vinyl monomer (b). object. 3. The polyolefin resin composition according to claim 1 or 2, wherein the modified polyolefin (B) is 0.1 to 20 parts by weight with respect to 100 parts by weight of the polyolefin (A). 4. The polyolefin-based resin composition according to claim 1, wherein the modified polyolefin (B) is 0.1 to 10 parts by weight with respect to 100 parts by weight of the polyolefin (A). 5. The polyolefin (A) is propylene 7
A crystalline propylene-based polyolefin obtained by polymerizing a monomer component containing 5% by weight or more.
The polyolefin resin composition described. 6. A homopolymer obtained by polymerizing ethylene, propylene, butylene or 4-methylpentene as the non-polar polyolefin (a) and two of those monomers.
Selected from copolymers obtained by polymerizing one or more kinds, and copolymers obtained by polymerizing one or more kinds of ethylene, propylene, butylene and 4-methylpentene and another monomer copolymerizable therewith The polyolefin resin composition according to claim 1, which is at least one selected from the group consisting of: 7. The polyolefin resin according to claim 2, wherein the temperature at which the temperature of the aqueous suspension is raised is equal to or higher than the temperature at which the crystalline portion of the nonpolar polyolefin (a) substantially starts melting. Composition. 8. The vinyl monomer (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 2 carbon atoms.
80% by weight or more of at least one selected from alkyl acrylates and unsaturated nitrile compounds which are 2, and other vinyl monomers 20 copolymerizable therewith
The polyolefin-based resin composition according to claim 1 or 2, wherein the polyolefin-based resin composition comprises not more than wt%. 9. The vinyl monomer (b) comprises 1 to 50% by weight of an aromatic vinyl compound and an alkyl group having 1 to 2 carbon atoms.
The polyolefin resin composition according to claim 1 or 2, which comprises 99% to 50% by weight of a methacrylic acid alkyl ester of 2 and / or an acrylic acid alkyl ester having an alkyl group of 1 to 22 carbon atoms. 10. The vinyl monomer (b) comprises an alkyl methacrylate having an alkyl group having 1 to 22 carbon atoms and / or an acrylic acid alkyl ester having an alkyl group having 1 to 22 carbon atoms. The polyolefin resin composition according to claim 1 or 2, wherein 11. The polyolefin resin composition according to claim 8 or 9, wherein the aromatic vinyl compound is styrene and / or its derivative. 12. The alkyl methacrylate having an alkyl group having 1 to 22 carbon atoms is methyl methacrylate, ethyl methacrylate, n-butyl methacrylate or cyclohexyl methacrylate, 8.
The polyolefin resin composition according to 0. 13. An alkyl acrylate whose alkyl group has 1 to 22 carbon atoms is methyl acrylate, ethyl acrylate, n-butyl acrylate, acrylic acid 2
-The polyolefin resin composition according to claim 8, which is ethylhexyl. 14. The vinyl monomer (b) is styrene 1
~ 50% by weight, methyl methacrylate and / or
The polyolefin resin composition according to claim 9, which comprises 99 to 50% by weight of n-butyl acrylate. 15. The polyolefin resin composition according to claim 1 or 2, wherein the size of the domain in the modified polyolefin (B) formed by polymerizing the vinyl monomer (b) is 3 μm or less. . 16. The polyolefin resin composition according to claim 1, wherein the size of the domain in the modified polyolefin (B) formed by polymerizing the vinyl monomer (b) is 1 μm or less. . 17. The nucleating agent is contained in an amount of 0.01 to 2 parts by weight based on 100 parts by weight of the polyolefin-based resin composition. , 9, 1
The polyolefin resin composition according to 0, 11, 12, 13, 14, 15 or 16. 18. The non-polar polyolefin (a) and / or modified polyolefin (wherein the nucleating agent is contained in an amount of 0.01 to 2 parts by weight based on 100 parts by weight of the polyolefin resin composition). B) is mixed with claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 1
The polyolefin resin composition according to 2, 13, 14, 15 or 16. 19. A core-shell graft copolymer having a refractive index substantially equal to that of the polyolefin (A) is contained in an amount of 0.01 to 50 parts by weight based on 100 parts by weight of the polyolefin (A). Items 1, 2, 3, 4,
5, 6, 7, 8, 9, 10, 11, 12, 13, 14,
The polyolefin resin composition according to 15, 16, 17 or 18.