JP2008024794A - Polymer blend containing olefin-based block polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition having excellent mechanical characteristics such as impact resistance and tensile strength. <P>SOLUTION: The resin composition (C) comprises 1-98.9 wt.% polyolefin (A), 0.1-50 wt.% olefin-based block polymer (G), and 1-98.9 wt.% vinyl polymer (B) obtained from vinyl monomers comprising one or more kinds selected from an aromatic vinyl compound (m1) and a cyanized vinyl compound (m2) [with the proviso that the total of the components (A), (B) and (C) is 100 wt.%]. The olefin-based block polymer (G) comprises a block (a) of the olefin component, and a block (b) of a polymer residue of a vinyl monomer having a solubility parameter within a range of 18-25 J/m as constituent units, and obtained by mutually binding the block (a) and the block (b) with a covalent bond. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a resin composition containing a polyolefin and a vinyl polymer, and more particularly to a resin composition excellent in mechanical properties such as impact resistance and tensile strength and solvent resistance.

  Polyolefins are excellent in processability, chemical resistance, electrical properties, mechanical properties, etc., so they are processed into extrusion molded products, injection molded products, hollow molded products, films, sheets, etc., and used in various applications. Yes.

  However, since polyolefin is a so-called nonpolar resin that does not have a polar group in the molecule, it has poor affinity with various polar substances including metals, and adhesion with polar substances or blending with polar resins is difficult. It was.

  Methods for improving the physical properties of polyolefins include methods for adjusting the type of monomer, molar ratio, etc., methods for changing the arrangement of monomers such as random and block, and methods for graft copolymerization of polar monomers onto polyolefins. Various methods have been tried.

  When a polar monomer is graft copolymerized with a polyolefin, a method of reacting a polyolefin and a radical polymerizable monomer in the presence of a radical initiator is generally performed. The graft copolymer obtained by such a method is used. Often contains a homopolymer of a radically polymerizable monomer or an unreacted polyolefin, and has a non-uniform graft structure. Furthermore, since the polymer chain is accompanied by a cross-linking reaction or a decomposition reaction of the polymer chain, the physical properties of the polyolefin often change greatly.

  Regarding the method for synthesizing a block polymer of polyolefin and polar polymer without the crosslinking / decomposition reaction as described above, in WO 98/02472, a boron compound is added to a polyolefin having an unsaturated bond at the terminal. A method of forming radical polymerization active species by subsequent oxidation with oxygen and then radical polymerization is described.

As a result of investigations based on such conventional techniques, the present inventors have found that a specific block copolymer containing a polyolefin segment and a polar resin segment can solve the above-described problems.
International Publication WO98 / 02472 Pamphlet

    An object of the present invention is to provide a resin composition excellent in mechanical properties such as impact resistance and tensile strength.

The resin composition (C) according to the present invention is:
1-98.9% by weight of polyolefin (A),
Olefin-based block polymer (G) 0.1 to 50% by weight,
1-98.9% by weight of vinyl polymer (B) obtained from a vinyl monomer comprising at least one selected from an aromatic vinyl compound (m1) and a vinyl cyanide compound (m2)
(Provided that the total amount of (A), (G) and (B) is 100% by weight), wherein the olefin block polymer (G) is a block (a) which is a polyolefin component, and solubility. The block (b), which is a polymer residue of a vinyl monomer having a parameter in the range of 18 to 25 J / m, is used as a structural unit, and the block (a) and the block (b) are covalently linked to each other. It is characterized by.

  In the present invention, the block (b) constituting the olefin block polymer (G) is an aromatic vinyl compound (m1), a vinyl cyanide compound (m2), (meth) acrylic acid and its derivative (m3), ( Consists of one or more structural units derived from a vinyl monomer selected from (meth) acrylamide and its derivatives (m4), maleic acid and its derivatives (m5), maleimide and its derivatives (m6), and vinyl esters (m7). (However, it is also preferred that the structural unit derived from (meth) acrylic acid and its derivative (m3) is less than 50 mol%), and the GPC number average molecular weight of the block (b) constituting the olefin block polymer (G) It is also preferable that (Mn) is in the range of 2,000 to 200,000. It is also preferable that the block (b) constituting the lock polymer (G) has an average of 0.5 to 5 bonds per one molecular chain of the block (a), and the block constituting the olefin block polymer (G) ( It is also preferable that a) is a propylene-based polymer residue (a1) whose propylene-derived structural unit is 50 mol% or more.

  In the present invention, it is also preferable that the polyolefin (A) is a propylene polymer (A1) having a propylene-derived structural unit of 50 mol% or more.

  The resin composition according to the present invention has good compatibility between the polyolefin (A) and the vinyl polymer (B), and is excellent in mechanical properties such as impact resistance, tensile strength, and bending strength.

  The resin composition according to the present invention contains a polyolefin (A), an olefin block polymer (G), and a vinyl polymer (B). Hereinafter, these components will be described sequentially.

[Polyolefin (A)]
The polyolefin (A) used in the present invention is a (co) polymer of at least one olefin selected from α-olefins having 2 to 20 carbon atoms.

Examples of the α-olefin having 2 to 20 carbon atoms include ethylene, propylene, 1-butene, 2-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, Linear or branched α-olefins such as 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene; for example, cyclopentene , Cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl 1,4,5,8-
And cyclic olefins such as dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene.

Polyolefin (A) is a polar monomer such as acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride, bicyclo (2,2,1) -5-heptene-2,3- Α, β-unsaturated carboxylic acids such as dicarboxylic acid anhydrides, and α, β-unsaturated carboxylic acid metal salts such as sodium, potassium, lithium, zinc, magnesium and calcium salts thereof; acrylic acid Methyl, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-methacrylic acid n- Propyl, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate Any α, β-unsaturated carboxylic acid ester; vinyl esters such as vinyl acetate, vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl trifluoroacetate; glycidyl acrylate, methacrylic acid A small amount of unsaturated glycidyl ester such as glycidyl and itaconic acid monoglycidyl ester may be copolymerized.

The polyolefin (A) may be copolymerized with a small amount of vinylcyclohexane, diene or polyene. As the diene or polyene, a cyclic or chain compound having 4 to 30 carbon atoms, preferably 4 to 20 carbon atoms, and having two or more double bonds is used. Specifically, butadiene, isoprene, 4-methyl-1,3-pentadiene, 1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,3-hexadiene, , 3-octadiene, 1,4-octadiene, 1,5-octadiene,
1,6-octadiene, 1,7-octadiene, ethylidene norbornene, vinyl norbornene, dicyclopentadiene; 7-methyl-1,6-octadiene, 4-ethylidene-8
-Methyl-1,7-nonadiene, 5,9-dimethyl-1,4,8-decatriene; further aromatic vinyl compounds such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o, p -Dimethylstyrene, o-ethylstyrene, m-ethylstyrene, p
-Mono- or polyalkyl styrene such as ethyl styrene; containing functional groups such as methoxy styrene, ethoxy styrene, vinyl benzoic acid, methyl vinyl benzoate, vinyl benzyl acetate, hydroxy styrene, o-chlorostyrene, p-chlorostyrene, divinylbenzene Styrene derivatives; 3-phenylpropylene, 4-phenylpropylene, α-methylstyrene and the like.

  The melt flow rate (MFR: ASTM D1238: 230 ° C., load 2.16 kg) of the polyolefin (A) is usually 0.01 to 200 g / 10 minutes, preferably 0.1 to 100 g / 10 minutes.

In the present invention, when the polyolefin (A) has stereoregularity, it may be a syndiotactic polyolefin or an isotactic polyolefin.
Such polyolefin (A) can be produced by a conventionally known method.

In the present invention, it is preferable to use polyethylene or polypropylene as the polyolefin (A).
Preferred polyethylenes include ethylene homopolymers and ethylene / α-olefin copolymers. The ethylene / α-olefin copolymer is, for example, a random copolymer of ethylene and an α-olefin having 4 to 12 carbon atoms.

  Examples of the α-olefin having 4 to 12 carbon atoms include 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, and 1-dodecene. Can be mentioned.

  In such an ethylene / α-olefin copolymer, the structural unit derived from ethylene is present in a proportion of 65 to 99% by weight, preferably 75 to 96% by weight, and the α-olefin having 4 to 12 carbon atoms. Is preferably 1 to 35% by weight, and preferably 4 to 25% by weight.

In this ethylene / α-olefin copolymer, the density is in the range of 0.880 to 0.970 g / cm ³ , preferably 0.890 to 0.955 g / cm ³ .
The ethylene / α-olefin copolymer is melt flow rate (MFR: ASTM).
D1238: 190 ° C., load 2.16 kg) is in the range of 0.01 to 200 g / 10 min, preferably 0.05 to 50 g / 10 min.

  Preferred polypropylenes include, for example, a propylene homopolymer, a propylene / α-olefin copolymer, a copolymer of propylene and an α-olefin and a non-conjugated diene represented by the following formula (1), and the copolymer For example, a hydrogenated product.

Wherein ^{(1), R 1, R} 2, R 3 and R ⁴ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, n is an integer from 1 to 20. ]
The alkyl group having 1 to 6 carbon atoms of R ¹ , R ² , R ³ and R ⁴ may be either linear or branched. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, n-pentyl group, isopentyl group, t-pentyl group, A neopentyl group, n-hexyl group, isohexyl group, etc. are mentioned.

  When polypropylene is a copolymer, it may be either a random copolymer or a block copolymer. Examples of the α-olefin to be copolymerized with propylene include ethylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene and the like. Two or more kinds may be used.

Moreover, in this invention, not only when using one type of polymer independently as a polypropylene, you may use 2 or more types of polymers together.
The method for producing polypropylene is not particularly limited, and can be produced by a known method using a known catalyst such as a Ziegler-Natta catalyst or a metallocene catalyst. In addition, a crystalline polymer can be preferably used, and in the case of a copolymer, it may be a random copolymer or a block copolymer. Furthermore, there are no particular restrictions on the stereoregularity and the molecular weight as long as they satisfy the moldability and have a strength that can be used when formed into a molded body. Commercially available resins can be used as they are.

  The melting point (Tm) of polypropylene is usually 150 to 170 ° C, preferably 155 to 167 ° C. The melt flow rate of polypropylene (MFR: ASTM D1238: 230 ° C., load 2.16 kg) is usually 0.3 to 200 g / 10 minutes, preferably 0.4 to 100 g / 10 minutes, more preferably 0.5 to 70 g. / 10 minutes.

As the polypropylene, a propylene polymer (A1) having a propylene-derived structural unit of 50 mol% or more, preferably 80 mol% or more can be preferably used.
In addition, polypropylene has an isotactic pentad fraction (mmmm fraction) of a propylene homopolymer portion measured by ¹³ C-NMR, preferably 96.0% or more, more preferably 96.5% or more, most Preferably it is 97.0% or more. If the isotactic pentad fraction (mmmm fraction) of the propylene homopolymer portion in polypropylene is lower than 96.0%, the flexural modulus and / or heat resistance may be lowered.

Here, the isotactic pentad fraction (mmmm fraction) is a method described by A. Zambelli et al. In Macromolecules, Vol. 6,925 (1973), that is, a ¹³ C-NMR method (
It is an isotactic fraction of pentad units in a polypropylene molecular chain, measured by a nuclear magnetic resonance method), and is a fraction of propylene monomer units in which five propylene units are isotactically bonded.

The assignment of peaks in the ¹³ C-NMR spectrum is Macromolecules, Vol. 8,687 (1975
¹³ C-NMR is carried out based on the description of) by using a Fourier transform NMR [500 MHz (at the time of hydrogen nucleus measurement)] apparatus, and by making a cumulative measurement of 20,000 times at a frequency of 125 MHZ, the signal detection limit Can be measured up to 0.001.

  In the present invention, the polyolefin (A) may be used in combination of two or more, and examples of the combination at this time include a combination of a crystalline polyolefin and an amorphous or low-crystalline polyolefin.

[Olefin block polymer (G)]
The olefin block polymer (G) used in the present invention comprises a block (a) which is a polyolefin component and a block (b) which is a polymer residue of a vinyl monomer having a solubility parameter in the range of 18 to 25 J / m. And the block (a) and the block (b) have a structure in which they are bonded by a covalent bond. In the olefin block polymer (G), an average of 0.5 to 5 blocks (b) are bonded per molecular chain of the block (a). The olefin block polymer (G) may have a plurality of blocks (a) and blocks (b) having different compositions and molecular weights.

  The olefin block polymer (G) has a block (a) of 20 to 99.9 parts by weight, preferably 30 to 90 parts by weight, and a block (b) of 0.1 to 70 parts by weight, preferably 10 to 70 parts by weight. It is contained in the amount. When the contents of the blocks (a) and (b) are within the above range, the performance as a compatibilizer for the olefin block polymer (G) is improved, the dispersed particle size of the island phase is refined, and the mechanical strength is increased. Will improve.

The olefin block polymer (G) preferably has an MFR (230 ° C., 2.16 kg load) in the range of 0.01 to 50 g / 10 min.
Here, the block (a) can be a segment derived from a halogen-modified polyolefin (a ′) obtained by halogenating a polyolefin selected from the group consisting of the following (a1) to (a5), for example, b) is a homopolymer or copolymer of one or more monomers selected from radically polymerizable monomers.

<Block (a)>
As the block (a) constituting the olefin block polymer (G), those having a structure similar to that of the polyolefin (A) can be used. Preferably, it is a crystalline polyolefin residue having a melting point of 70 ° C. or higher, particularly preferably 80 to 180 ° C. When the melting point is within the above range, a resin composition having high heat resistance can be obtained.

The melting point (Tm) is measured, for example, as follows. About 5 mg of sample is packed in a special aluminum pan, and it is used from 30 ° C. to 20 ° C. using DSCPyris 1 or DSC 7 manufactured by PerkinElmer.
The temperature was raised to 0 ° C. at 320 ° C./min, held at 200 ° C. for 5 minutes, then cooled from 200 ° C. to 30 ° C. at 10 ° C./min, held at 30 ° C. for another 5 minutes, and then 10 ° C. It is obtained from an endothermic curve when the temperature is increased at / min.

The olefin block polymer (G) has a number average molecular weight of 5,000 in the block (a).
˜1,000,000, preferably 10,000 to 500,000, and the number average molecular weight of the block (b) is 2,000 to 200,000, preferably 5,000 to 150,000. Some polymers are preferred. When the molecular weight of the block (a) is higher than 1,000,000, the olefin block polymer (G) is difficult to be distributed at the interface between the polyolefin (A) and the vinyl polymer (B), and therefore the interface is easy to peel off. As a result, the mechanical strength decreases. When the molecular weight is lower than 5,000, the molecular chain becomes less entangled between the polyolefin (A) or vinyl polymer (B) and the olefin block polymer (G), and the mechanical strength is lowered. .

  The block (a) constituting the olefin-based block polymer (G) is a halogen-modified polyolefin (a ′) obtained by halogenating a polyolefin (a ″) selected from the group consisting of the following (a1) to (a5). It can be a segment derived from.

  The block (a) constituting the olefin block polymer (G) is derived from a polar group-containing olefin copolymer having a radical polymerization initiating group as disclosed in JP-A No. 2002-131620. It may be a segment, or may be a segment derived from a polyolefin having a group 13 element bonded to the terminal as disclosed in the pamphlet of WO01 / 053369.

Here, the number average molecular weight of the polyolefin (a ″) is preferably in the range of 5,000 to 1,000,000, and more preferably 10,000 to 500,000.
The polyolefin (a ″) has a molecular weight distribution (Mw / Mn) of 1.5 or more.

Here, the halogen-modified polyolefin (a ′) obtained by halogenating the polyolefin (a ″) will be described.
(A1) is an α-olefin homopolymer or copolymer (hereinafter referred to as “(co) polymer (a1)” represented by CH ₂ ═CH—C _x H _{2x + 1} (x is 0 or a positive integer). It is also called)
(A2) is a copolymer of an α-olefin represented by CH ₂ ═CH—C _x H _{2x + 1} (x is 0 or a positive integer) and a monoolefin compound having an aromatic ring (hereinafter referred to as “copolymer ( a2) "), and
(A3) is a copolymer of an α-olefin represented by CH ₂ ═CH—C _x H _{2x + 1} (x is 0 or a positive integer) and a cyclic monoolefin compound represented by the following general formula (2) (Hereinafter also referred to as “copolymer (a3)”),
(A4) is a random copolymer (hereinafter referred to as “copolymer”) of an α-olefin represented by CH ₂ ═CH—C _x H _{2x + 1} (x is 0 or a positive integer) and an unsaturated carboxylic acid or derivative thereof. (Also referred to as (a4)).
(A5) is a polyolefin (hereinafter also referred to as “modified polyolefin (a5)”) obtained by modifying the polymer represented by the above (a1) to (a4) with an unsaturated carboxylic acid or a derivative thereof.

In the general formula (2), n is 0 or 1, m is 0 or a positive integer, q
Is 0 or 1. When q is 1, R ^a and R ^b each independently represent the following atom or hydrocarbon group, and when q is 0, each bond is bonded to form a 5-membered ring. Form.

In the general formula (2), R ^{1 to} R ¹⁸ and R ^a and R ^b each independently represent an atom or group selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group.
Here, the halogen atom is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Moreover, as a hydrocarbon group, a C1-C20 alkyl group, a C1-C20 halogenated alkyl group, or a C3-C15 cycloalkyl group is mentioned normally each independently. More specifically, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an amyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, an octadecyl group, and the like. A group in which at least a part of the hydrogen atoms forming such an alkyl group is substituted with a fluorine atom, a chlorine atom, a bromine atom or an iodine atom is exemplified. Examples of the cycloalkyl group include a cyclohexyl group.

These groups may contain a lower alkyl group. Further, in the above general formula (2), R ¹⁵ and R ¹⁶ are R ¹⁷ and R ¹⁸ , R ¹⁵ and R ¹⁷ are R ¹⁶ and R ¹⁸ , R ¹⁵ and R ¹⁸ are R ¹⁶ and R ¹⁷ may be bonded to each other (in cooperation with each other) to form a monocyclic or polycyclic ring. Specific examples of the monocyclic or polycyclic ring formed here include the following.

In the above examples, the carbon atoms assigned numbers 1 and 2 represent carbon atoms to which R ¹⁵ (R ¹⁶ ) or R ¹⁷ (R ¹⁸ ) are bonded in the general formula (2).
Specific examples of the cyclic olefin represented by the general formula (2) include bicyclo [2.2.1
] Hept-2-ene derivatives, tricyclo [4.3.0.1 ^{2, 5]-3-decene} derivatives, tricyclo [4.3.0.1 ^{2, 5]-3-undecene} derivative, tetracyclo [4.4.0.1 ^2,5 .1 ^{7, 10]} -3-dodecene derivatives, pentacyclo ^{[7.4.0.1 2,5 .1 9,12 .0 8,13]} -3- pentadecene derivatives, pentacyclo [6.5.1.1 ^3,6 .0 ^2,7 .0 ^{9, 13]} -4-pentadecene derivatives, pentacyclo ^{[8.4.0.1 2,3 .1 9,12 .0 8,13]} -3- hexadecene derivative, pentacyclo [6.6.1.1 ^3,6 .0 ^2,7 .0 ^{9, 14]} -4-hexadecene derivatives, penta cyclopentadiene decadiene derivative, hexacyclo ^{[6.6.1.1 3,6 .1 10,13 .0 2,7 .0} 9,14] -4- heptadecene derivatives, heptacyclo [8.7.0.1 ^3,6 .1 ^10,17 .1 ^12,15 .0 ^2,7 .0 ^11,16] -4-eicosene derivatives, heptacyclo-5-eicosene derivatives, heptacyclo [8.8.0.1 ^4,7 .1 ^11,18 .1 ^13,16 .0 ^3,8 .0 ^12,17] -5-heneicosene derivatives, octacyclo [8.8.0.1 ^2,9 .1 ^4,7 .1 ^11,18 .1 ^13,16 .0 ^3,8 .0 ^12,17] -5-docosene derivatives, Nonashikuro [10.9.1.1 ^4,7 .1 ^{13, 20} .1 ^{15 and 18} .0 ^3,8 .0 ^2,10 .0 ^12,21 .0 ^14,19] -5-pentacosene derivatives, Nonashikuro ^{[10.10.1.1 5,8 .1 14,21 .1 16,19 .0} 2,11 such .0 ^4,9 .0 ^{13, 22} .0 ^15,20] -5-hexacosenoic derivatives.

The cyclic monoolefin compound represented by the general formula (2) as described above can be produced by subjecting cyclopentadiene and an olefin having a corresponding structure to Diels-Alder reaction. These cyclic olefins can be used alone or in combination of two or more.

≪ (Co) polymer (a1) ≫
In the (co) polymer (a1), as the α-olefin represented by CH ₂ ═CH—C _x H _{2x + 1} (x is 0 or a positive integer), specifically, ethylene, propylene, 1- Butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, Examples thereof include linear or branched α-olefins having 2 to 20 carbon atoms such as 1-hexadecene, 1-octadecene and 1-eicocene. Among these exemplified olefins, it is preferable to use at least one olefin selected from ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene.

  The (co) polymer (a1) is not particularly limited as long as it is obtained by homopolymerization or copolymerization of the above α-olefin, but low density polyethylene, medium density polyethylene, high density polyethylene, linear chain -Like low density polyethylene, ethylene polymers such as ultrahigh molecular weight polyethylene, propylene polymers such as propylene homopolymer, propylene random copolymer, propylene block copolymer, polybutene, poly (4-methyl-1-pentene), poly (1 -Hexene), ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-hexene copolymer, ethylene-octene copolymer, ethylene- (4-methyl-1-pentene) copolymer, propylene-butene Copolymer, propylene- (4-methyl-1-pentene) copolymer, propylene Down - hexene copolymer, propylene - octene copolymer and the like are preferably mentioned, especially structural units derived from propylene 50 mol% or more, preferably a propylene-based polymer is preferably 80 mol% or more.

<< Copolymer (a2) >>
In the copolymer (a2), the α-olefin represented by CH ₂ ═CH—C _x H _{2x + 1} (x is 0 or a positive integer) is described in the section of the (co) polymer (a1). As the monoolefin compound having an aromatic ring, specifically, styrene-based compounds such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid and salts thereof Examples thereof include compounds and vinyl pyridine. The copolymer (a2) is not particularly limited as long as it is obtained by copolymerizing the above α-olefin and a monoolefin compound having an aromatic ring.

≪Copolymer (a3) ≫
In the copolymer (a3), the α-olefin represented by CH ₂ ═CH—C _x H _{2x + 1} (x is 0 or a positive integer) is described in the section of the (co) polymer (a1). The same alpha olefin as what was done is mentioned, and the structural unit derived from the cyclic monoolefin compound denoted by the above-mentioned general formula (2) is shown by the following general formula (3).

In the formula (3), n, m, q, R ^{1 to} R ¹⁸ and R ^a and R ^b have the same meaning as in the formula (2).
≪Copolymer (a4) ≫
In the copolymer (a4), the α-olefin represented by CH ₂ ═CH—C _x H _{2x + 1} (x is 0 or a positive integer) is described in the section of the (co) polymer (a1). Α-olefins similar to those described above, and unsaturated carboxylic acids or derivatives thereof include, for example, unsaturated monocarboxylic acids and derivatives thereof, unsaturated dicarboxylic acids and derivatives thereof, and vinyl esters. (Meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylic acid halide, (meth) acrylic acid amide, maleic acid, maleic anhydride, maleic acid ester, maleic acid halide, maleic acid amide, Examples thereof include aliphatic vinyl esters such as maleic imide, vinyl acetate and vinyl butyrate. The copolymer (a4) is not particularly limited as long as it is a random copolymer of the above α-olefin and an unsaturated carboxylic acid or a derivative thereof, but 50 mol of the structural unit derived from the α-olefin is used. % Or more is preferable.

≪Modified polyolefin (a5) ≫
Specific examples of the unsaturated carboxylic acid or derivative thereof in the modified polyolefin (a5) include maleic acid, maleic anhydride, maleic ester, maleic halide, maleic amide, maleic imide and the like. Examples of the method for modifying the polymer represented by (a1) to (a4) with an unsaturated carboxylic acid or a derivative thereof include, for example, the presence of a radical generator such as an organic peroxide, or the presence of ultraviolet rays or radiation. Below, the method etc. with which unsaturated carboxylic acid or its derivative (s) are made to react with the (co) polymer represented by said (a1)-(a4) are mentioned.

  The conditions and method for producing the polyolefin (a ″) selected from the group consisting of (a1) to (a5) are not particularly limited, but known transition metals such as Ziegler-Natta catalysts, metallocene catalysts, post-metallocene catalysts, etc. Coordination anionic polymerization using a catalyst, radical polymerization under high pressure or irradiation, etc. can also be used, and polyolefins produced by the above method can also be decomposed with heat or radicals. .

  The block (a) must be composed of a monoolefin compound having only one carbon-carbon double bond or a monoolefin compound having an aromatic ring as described above. A compound having a plurality of heavy bonds, for example, a linear diene compound such as hexadiene or octadiene, a styrene diene compound such as divinylbenzene, a cyclic diolefin compound such as vinyl norbornene or ethylidene norbornene, and the like are copolymerized with the α-olefin. When the obtained polymer is used, unsaturated bonds derived from the diene compound are cross-linked and gelled at the halogenation stage described later, which is not preferable. Therefore, polyolefin selected from the group consisting of (a1) to (a5) as described above is used as polyolefin (a ″) to be halogenated, and these may be used in combination of two or more.

≪Halogen-modified polyolefin (a ') ≫
The halogen-modified polyolefin (a ′) can be produced by halogenating the polyolefin (a ″) as described above. The halogen content of the halogen-modified polyolefin (a ′) thus obtained is 0.01 to 70% by weight, preferably 0.02 to 50% by weight, more preferably 0.05 to 30% by weight, wherein such halogen is selected from fluorine, chlorine, bromine or iodine, It may be a combination.

The halogen-modified polyolefin (a ′) has the following general formula (I) to
A structure in which at least one structural unit selected from the structural units represented by (III) is connected;
And / or a structure in which at least one structural unit selected from structural units represented by the following general formulas (IV) to (VII) is inserted in the polymer main chain.

In the above general formulas (I) to (VII), X represents a halogen atom, and R ^1a , R ^1b , R ^2a ,
R ^2b , R ^3a , R ^3b , R ^3c , R ^4a , R ^5a , R ^5b , R ^6a , R ^6b , R ^7a , R ^7b are substituted with a hydrogen atom, a halogen atom, or one or more halogen atoms. Represents a hydrocarbon group, oxygen-containing group or nitrogen-containing group, which may be the same or different.
Examples of the halogen atom include fluorine, chlorine, bromine and iodine, preferably chlorine or bromine.

Specific examples of the hydrocarbon group include 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, neopentyl, and n-hexyl, preferably 1 -20 linear or branched alkyl groups, 2 to 30 carbon atoms such as vinyl, allyl, isopropenyl, etc., preferably 2-20 carbon atoms such as ethynyl, propargyl, etc. 2-30, preferably 2-20 linear or branched alkynyl groups, phenyl, benzyl, naphthyl, biphenyl, terphenyl, phenanthryl, anthracenyl, etc. 6-30, preferably 6-20 carbon atoms Aryl, tolyl, iso-propylphenyl, t-butylphenyl, dimethylphenyl, di-t-butylphenyl, etc. Etc. Kill substituted aryl group. In the above hydrocarbon group, a hydrogen atom may be substituted with a halogen. For example, a halogenated hydrocarbon group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms such as trifluoromethyl, pentafluorophenyl, chlorophenyl and the like. Can be mentioned. Moreover, the said hydrocarbon group may be substituted by other hydrocarbon groups, for example, aryl group substituted alkyl groups, such as benzyl and cumyl, etc. are mentioned. Moreover, the said hydrocarbon group may be substituted by other hydrocarbon groups, for example, aryl group substituted alkyl groups, such as benzyl and cumyl, etc. are mentioned.

  Furthermore, the hydrocarbon group includes a heterocyclic compound residue, an alkoxy group, an aryloxy group, an ester group, an ether group, an acyl group, a carboxyl group, a carbonate group, a hydroxy group, a peroxy group, a carboxylic acid anhydride group, and the like. Oxygen-containing groups, amino groups, imino groups, amide groups, imide groups, hydrazino groups, hydrazono groups, nitro groups, nitroso groups, cyano groups, isocyano groups, cyanate ester groups, amidino groups, diazo groups, amino groups are ammonium salts It may be substituted with a nitrogen-containing group or the like.

  Of these, the number of carbon atoms is 1-30, preferably 1-20, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, neopentyl, n-hexyl, etc. Linear or branched alkyl groups, phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, anthracenyl, etc. aryl groups having 6-30 carbon atoms, preferably 6-20 carbon atoms, halogen atoms and carbon atoms in these aryl groups A substituted aryl group substituted with 1 to 5 substituents such as an alkyl group or an alkoxy group having 1 to 30, preferably 1 to 20 carbon atoms, an aryl group or an aryloxy group having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, etc. Is preferred.

The oxygen-containing group is a group containing 1 to 5 oxygen atoms in the group. Specifically, for example, an alkoxy group, an aryloxy group, an ester group, an ether group, an acyl group, a carboxyl group, a carbonate group, a hydroxyl group Peroxy group, carboxylic acid anhydride group and the like, and alkoxy group, aryloxy group, acetoxy group, carbonyl group, hydroxyl group and the like are preferable. In addition, when an oxygen containing group contains a carbon atom, it is desirable that it exists in the range of 1-30, preferably 1-20 carbon atoms. Among these oxygen-containing groups, alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-
Butoxy and the like are aryloxy groups such as phenoxy, 2,6-dimethylphenoxy,
2,4,6-trimethylphenoxy and the like are acyl groups such as formyl, acetyl, benzoyl, p-chlorobenzoyl and p-methoxybenzoyl, and ester groups are acetyloxy, benzoyloxy, methoxycarbonyl and phenoxy. Preferred examples include carbonyl and p-chlorophenoxycarbonyl.

  The nitrogen-containing group is a group containing 1 to 5 nitrogen atoms in the group. Specifically, for example, an amino group, imino group, amide group, imide group, hydrazino group, hydrazono group, nitro group, nitroso group , A cyano group, an isocyano group, a cyanate ester group, an amidino group, a diazo group, an amino group converted to an ammonium salt, and the like. An amino group, an imino group, an amide group, an imide group, a nitro group, and a cyano group preferable. In addition, when a nitrogen-containing group contains a carbon atom, it is desirable that it exists in the range of 1-30, preferably 1-20 carbon atoms. Among these nitrogen-containing groups, as amide groups, acetamido, N-methylacetamide, N-methylbenzamide, etc., and as amino groups, methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, dicyclohexylamino, etc. An alkylamino group such as phenylamino, diphenylamino, ditolylamino, dinaphthylamino, methylphenylamino, and the like, an imide group such as acetimide and benzimide, and an imino group such as methylimino. , Ethylimino, propylimino, butylimino, phenylimino and the like are preferred.

Hereinafter, preferred structural units represented by the general formulas (I) to (VII) are exemplified by structural formulas.

In the halogen-modified polyolefin (a ′), two hydrogen atoms are added to the carbon-carbon double bond in the structural unit represented by the general formulas (I) to (III) at the end of the polymer main chain. A structure in which at least one structural unit selected from structural units represented as a structure having a carbon-carbon single bond is connected, and / or a polymer main chain represented by the following general formulas (IV) to (VII): A structure in which at least one constituent unit selected from constituent units represented by a structure in which two hydrogen atoms are added to a carbon-carbon double bond in the constituent unit to form a carbon-carbon single bond is inserted. May have. A preferable form of such a structural unit is shown below by a structural formula.

Here, the polymer main chain represents the longest part of the monomer chain structure having the largest number of repeating units derived from the α-olefin present in the polymer single molecular chain and the comonomer copolymerized therewith. There are two terminal positions in such a polymer backbone. Therefore, two hydrogen atoms are added to the structural unit represented by the above general formulas (I) to (III) and the carbon-carbon double bond contained in the structural unit at the end of the polymer main chain to form a carbon-carbon. When at least one structural unit selected from structural units represented as a single bond structure is connected, the maximum number of the structural units contained in one polymer molecular chain is two. Further, carbon-carbon is obtained by adding two hydrogen atoms to the structural unit represented by the following general formulas (IV) to (VII) and the carbon-carbon double bond contained in the structural unit in the polymer main chain. When at least one structural unit selected from structural units represented as a single bond structure is inserted, there is no particular limitation on the number of the structural units present per molecular chain of the polymer, If the number is too large, the properties as a polyolefin may not be sufficiently exhibited. Therefore, two hydrogen atoms are present in the carbon-carbon double bond contained in the structural units represented by the general formulas (I) to (VII) and the structural units represented by the general formulas (I) to (VII). Is preferably 0.01 to 70% by weight in terms of the halogen atom content, as the total number of all the structural units represented by the structure represented by the addition of a carbon-carbon single bond. 0.05 to 50% by weight is more preferable. Moreover, several types of these structural units may be contained in one polymer molecular chain. Among these structural units, halogen-modified products containing structural units represented by the above general formulas (I) to (VII) having a structure in which a carbon-carbon double bond is present and a halogen atom is added to the allylic position. Polyolefin (a ′) can be used as a halogenated polyolefin for adhesives and coating resins, as well as conventionally known chlorinated polyethylene and chlorinated polypropylene, as well as carbon-carbon double bonds present in the molecule. It is possible to introduce a functional group other than halogen by utilizing the reactivity of the above, or to use it as a macromonomer for producing a graft polymer.

  The halogen atom content present in the halogen-modified polyolefin (a ′) can be measured, for example, by a method such as elemental analysis or ion chromatography, and the measured value is usually expressed in units of% by weight. The carbon-carbon double bond content present in the halogen-modified polyolefin (a ′) can be measured by a method such as infrared spectroscopy or nuclear magnetic resonance (NMR), and the measured value is usually , Expressed in units of weight percent or mole percent. Furthermore, the halogen atom present at the allylic position of the carbon-carbon double bond can be confirmed and quantified by, for example, NMR. As a specific example of confirmation of the halogen atom existing at the allylic position, for example, in proton NMR using deuterated orthodichlorobenzene of brominated polypropylene obtained by the above method as a solvent, the signal based on the carbon-carbon double bond is Usually, it is observed in the range of δ4.5 to 6.0 ppm, and the allylic methylene group and methine group to which the bromine atom is bonded are usually observed in δ3.5 to 4.5 ppm. Since the signal position when a bromine atom is introduced into a methylene group and a methine group other than the allylic position is usually δ 3.0 to 3.5 ppm, it is easy to determine whether the bromine atom is present at the allylic position or not. Be identifiable. In addition, for example, by using proton-proton two-dimensional NMR (HH-COSY), the correlation between the signal based on the carbon-carbon double bond and the signals of the methylene group and methine group to which a bromine atom is bonded has been confirmed. It is also possible to do. On the other hand, the molecular weight of the halogen-modified polyolefin (a ′) can be measured, for example, by gel permeation chromatography (GPC). The value of the number average molecular weight (Mn) thus measured and the halogen-modified polyolefin (a ') From the composition ratio (molar fraction) of each unit (unit derived from each olefin monomer, unit bonded with halogen, carbon-carbon double bond unit, etc.) contained in the content of carbon-carbon double bond The amount can be calculated as an average value per molecular chain.

  The average value per molecular chain of the unit to which the halogen is bonded is the number of bonds per molecular chain of the block (b) bonded to the block (a) in the olefin block polymer (G). In the present invention, in the olefin block polymer (G), the block (b) has an average of 0.5 to 5 bonds, preferably 0.5 to 3.5 bonds per block (a). More preferably, 0.5 to 3 are bonded. If the number of bonds per molecular chain of the block (b) bonded to the block (a) is out of this range, the olefin block polymer (G) is difficult to be distributed at the interface between the polyolefin (A) and the vinyl polymer (B). Therefore, the interface is easily peeled off and the mechanical strength is lowered.

≪Method for producing halogen-modified polyolefin (a ′) ≫
The halogen-modified polyolefin (a ′) is produced by reacting the aforementioned polyolefin (a ″) with a halogenating agent.

The halogenating agent is not particularly limited as long as it can produce the halogen-modified polyolefin (A ′) by halogenating the polyolefin (a ″). Specifically, chlorine, bromine, iodine, phosphorus trichloride, Phosphorus tribromide, phosphorus triiodide, phosphorus pentachloride, phosphorus pentabromide, phosphorus pentaiodide, thionyl chloride, sulfuryl chloride, thionyl bromide, N-chlorosuccinimide, N-bromosuccinimide, N-bromocaprolactam, N -Bromophthalimide, 1,3-
Dibromo-5,5-dimethylhydantoin, N-chloroglutarimide, N-bromoglutarimide, N, N′-dibromoisocyanuric acid, N-bromoacetamide, N-bromocarbamic acid ester, dioxane dibromide, phenyltrimethylammonium tri Bromide, pyridinium hydrobromide perbromide, pyrrolidone hydrotribromide, t-butyl hypochlorite, t-butyl hypobromite, copper (II) chloride, copper (II) bromide, iron chloride (III
), Oxalyl chloride, IBr and the like. Of these, chlorine, bromine, N-chlorosuccinimide, N-bromosuccinimide, N-bromocaprolactam, N-bromophthalimide, 1,3-dibromo-5,5-dimethylhydantoin, N-chloroglutarimide, N -Bromoglutarimide, N, N'-dibromoisocyanuric acid, more preferably bromine, N-bromosuccinimide, N-bromocaprolactam, N-bromophthalimide, 1,3-dibromo-5,5-dimethylhydantoin, N -A compound having an N-Br bond such as bromoglutarimide and N, N'-dibromoisocyanuric acid.

The reaction between the polyolefin (a ″) and the halogenating agent is preferably performed in an inert gas atmosphere. Examples of the inert gas include inert gases such as nitrogen, argon, and helium. A solvent can be used for the reaction as needed, and any solvent can be used as long as it does not inhibit the reaction, but specific examples include benzene, toluene, xylene and the like. Aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, nonane and decane, alicyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane and decahydronaphthalene, chlorobenzene, dichlorobenzene , Trichlorobenzene, methylene chloride, chloroform, carbon tetrachloride and tetrac Chlorinated hydrocarbon solvents such as ethylene and tetrachloroethane, alcohol solvents such as methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol and tert-butanol, acetone, methyl ethyl ketone and methyl isobutyl ketone Ketone solvents; ester solvents such as ethyl acetate and dimethyl phthalate, ether solvents such as dimethyl ether, diethyl ether, di-n-amyl ether, tetrahydrofuran and dioxyanisole, etc., preferably pentane. Aliphatic hydrocarbon solvents such as hexane, heptane, octane, nonane and decane, alicyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane and decahydronaphthalene, chlorobenze Chlorinated hydrocarbon solvents such as dichlorobenzene, trichlorobenzene, methylene chloride, chloroform, carbon tetrachloride and tetrachloroethylene, tetrachloroethane, etc. These solvents may be used alone or in combination of two or more. In addition, it is preferable that the reaction solution becomes a homogeneous phase by using these solvents, but a plurality of non-uniform phases may be used.

In the reaction with the halogenating agent, a radical initiator may be added as necessary to accelerate the reaction. Examples of the radical initiator include azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, azobis-2-amidinopropane hydrochloride, azobisisobutyric acid dimethyl, azobisisobutylamidine hydrochloride Or an azo initiator such as 4,4′-azobis-4-cyanovaleric acid, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, di-tert-butyl peroxide, lauroyl peroxide, acetyl peroxide, Diisopropyl dicarbonate oxide, cumene hydroperoxide, tert-butyl hydroperoxide, dicumyl peroxide, p-menthane hydroperoxide, pinane hydroperoxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, diisopropyl peroxydicarbo Peroxide, tert-butylperoxylaurate, di-tert-butylperoxyphthalate, peroxide initiators such as dibenzyl oxide or 2,5-dimethylhexane-2,5-dihydroperoxide, or benzoyl peroxide-N , N-dimethylaniline or redox initiator such as peroxodisulfuric acid-sodium hydrogen sulfite. Of these, azo initiators or peroxide initiators are preferred, and more preferred are benzoyl peroxide, di-tert-butyl peroxide, lauroyl peroxide, acetyl peroxide, diisopropyl dicarbonate, cumene hydro Peroxide, tert-butyl hydroperoxide, dicumyl peroxide, azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, dimethyl azobisisobutyrate. These radical initiators can be used alone or in combination of two or more simultaneously or sequentially.

As the method of reacting the polyolefin (a ″) with the halogenating agent, various conventionally known methods can be employed. For example, the polyolefin (a ″) is usually suspended or dissolved in a solvent, and usually − A method in which a halogenating agent and a radical initiator, if necessary, are mixed and reacted at a temperature of 80 ° C. to 250 ° C., preferably at a temperature of room temperature to the boiling point of the solvent, or polyolefin (a ″) has its melting point As described above, for example, a method in which a halogenating agent and, if necessary, a radical initiator are brought into contact with each other at a temperature of 180 to 300 ° C. under melt kneading.
The halogen-modified polyolefin (a ′) is produced by the above method.

<Block (b)>
The number average molecular weight of the block (b) constituting the olefin block polymer (G) is 2,
The range is from 000 to 200,000, preferably from 5,000 to 150,000. When the number average molecular weight is higher than 200,000, the olefin block polymer (G) is difficult to be distributed at the interface between the polyolefin (A) and the vinyl polymer (B), and therefore the interface is easily peeled off and the mechanical strength is increased. descend. If the number average molecular weight is lower than 2,000, the molecular chain becomes less entangled between the polyolefin (A) or vinyl polymer (B) and the olefin block polymer (G), and the mechanical strength is reduced. descend.
The block (b) is a homopolymer or copolymer of one or more monomers selected from radically polymerizable monomers. Specific examples of the radical polymerizable monomer include aromatic vinyl compounds (m1) such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid and salts thereof.
Vinyl cyanide compounds such as acrylonitrile and methacrylonitrile (m2)
(Meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid-n-propyl, (meth) acrylic acid isopropyl, (meth) acrylic acid-n-butyl, (meth) Isobutyl acrylate, (meth) acrylic acid-tert-butyl, (meth) acrylic acid-n-pentyl, (meth) acrylic acid-n-hexyl, (meth) acrylic acid cyclohexyl, (meth) acrylic acid-n-heptyl , (Meth) acrylic acid-n-octyl, (meth) acrylic acid-2-ethylhexyl, (meth) acrylic acid nonyl, (meth) acrylic acid decyl, (meth) acrylic acid dodecyl, (meth) acrylic acid phenyl, ( Toluyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, (meth) acrylic acid 3-methoxybutyl, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, 2-aminoethyl (meth) acrylate , 2- (dimethylamino) ethyl (meth) acrylate, γ- (methacryloyloxypropyl) trimethoxysilane, ethylene oxide adduct of (meth) acrylic acid, trifluoromethylmethyl (meth) acrylate, (meth) acrylic 2-trifluoromethylethyl acid, 2-perfluoroethylethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, 2-perfluoroethyl (meth) acrylate, ( (Meth) acrylic acid perfluoromethyl, (meth) acrylic acid dipa Fluoromethylmethyl, 2-perfluoromethyl-2-perfluoroethylmethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, (meth) acrylic (Meth) acrylic acid such as 2-perfluorohexadecylethyl acid and its derivatives (m3)
(Meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, N, N-dimethyl (Meth) acrylamide and its derivatives (m4) such as (meth) acrylamide
Maleic anhydride, maleic acid, maleic acid such as monoalkyl ester and dialkyl ester of maleic acid and derivatives thereof (m5)
Maleimides such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide and their derivatives (m6)
Vinyl esters such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, vinyl cinnamate (m7)
Fumaric acid, monoalkyl and dialkyl esters of fumaric acid,
Fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene, vinylidene fluoride,
Silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane;
Olefinic monomers such as ethylene, propylene, butene,
Diene monomers such as butadiene and isoprene,
Examples include vinyl chloride, vinylidene chloride, allyl chloride, and allyl alcohol.
These organic compounds may be used alone or in combination of two or more.

  Block (b) includes aromatic vinyl compound (m1), vinyl cyanide compound (m2), (meth) acrylic acid and its derivative (m3), (meth) acrylamide and its derivative (m4), maleic acid and its A polymer obtained by (co) polymerizing one or two or more monomers selected from a derivative (m5), a maleimide and a derivative thereof (m6), and a vinyl ester (m7) is preferable, and styrene, acrylonitrile, Polymer obtained by (co) polymerizing one or more monomers selected from acrylic acid-n-butyl, glycidyl methacrylate and methyl methacrylate (however, (meth) acrylic acid and its derivatives (m3)) Is more preferable, and styrene is particularly preferable.

  The solubility parameter of the copolymer constituting the block (b) can be calculated from the composition of the copolymer constituting the block (b). The solubility parameter of the block (b) is in the range of 18-25, preferably in the range of 18.2-22, more preferably in the range of 18.5-20. When the value of the solubility parameter is out of this range, the compatibility between the block (b) and the vinyl polymer is lowered, the effect as a compatibilizer is lowered, and the mechanical strength is lowered.

  The solubility parameter of the copolymer was determined by changing the composition of block (b) from Million Zillion software, Inc. Manufactured by CHEOPS Ver. 4.0 was entered and calculated.

In the resin composition (C), the composition of the block (b) can be calculated by analyzing a room temperature chloroform-insoluble component by ¹ H-NMR.
The content of the component derived from the block (b) contained in the room temperature chloroform insoluble component is 0.1 to 70% by weight, preferably 0.5 to 50% by weight, more preferably 1 to 40% by weight. The component derived from the block (b) contained in the room temperature chloroform insoluble component is detected because the block (a) and the block (b) are covalently bonded to each other in the resin composition (C). Indicates that When the content of the component derived from the block (b) contained in the chloroform-insoluble component at room temperature is within the above range, the performance as a compatibilizer of the olefin block polymer (G) is improved, and the dispersed particles of the island phase The diameter becomes finer and the mechanical strength is improved.

The room temperature chloroform insoluble component is measured as follows. 5 g of the resin composition (C) is dissolved in 100 ml of xylene reflux. Pour the solution obtained while stirring 1 L of chloroform with a homogenizer. The solution in which the polymer is precipitated and becomes a slurry is filtered and separated into a filtrate and a filtrate. The filtrate becomes a chloroform-insoluble component (the filtrate is a chloroform-soluble component). The composition analysis in the chloroform insoluble component is performed by ¹ H-NMR, and the weight percentage of the content of the component derived from the block (b) contained in the room temperature chloroform insoluble component is measured.

≪Olefin block polymer (G) ≫
The olefin-based block polymer (G) has a low content of impurities such as catalyst residue components and good resin properties. The transition metal content incorporated during polymerization is 100 ppm or less, and the white and transition metal content is low. More preferably, it is 50 ppm or less. When the olefin block polymer (G) is in the form of powder, the average particle size is 1 to 1,000.
μm and a bulk density measured by a method defined in JIS K6891 is 0.10 to 0.90.
It is preferably in the range of g / cm ³ . The olefin block polymer (G) can be used in any form of pellets, powders, and veils.

<Method for producing olefin block polymer (G)>
The olefin block polymer (G) can be produced, for example, by atom transfer radical polymerization of one or more monomers selected from radically polymerizable monomers using the halogen-modified polyolefin (a ′) as a macroinitiator. it can. The macroinitiator is a polymer having the ability of initiating atom transfer radical polymerization, and represents a polymer having a site that can be the starting point of atom transfer radical polymerization in the molecular chain.

Atom transfer radical polymerization is one of living radical polymerizations, in which radical polymerizable monomers are radically polymerized using an organic halide or sulfonyl halide compound as an initiator and a metal complex having a transition metal as a central metal as a catalyst. Is the method. Specifically, for example, Matyjaszewski et al., Chem. Rev., 101, 2921 (2001), WO96 / 30421 pamphlet, WO97 / 18247 pamphlet, WO98 / 01480 pamphlet, WO98 / 40415 pamphlet, WO00 / 156795 Pamphlet, or Sawamoto et al., Chem. Rev., 101, 3689 (2001), JP-A-8-41117, JP-A-9-208616, JP-A-2000-264914, JP-A-2001-316410, JP-A-2002-80523, JP-A-2004-307872, and the like can be mentioned. As the initiator used,
Examples thereof include organic halides and sulfonyl halide compounds. In particular, a carbon-halogen bond present at the α-position of a carbon-carbon double bond or a carbon-oxygen double bond, or a plurality of halogen atoms on one carbon atom. The added structure is suitable as the initiator structure. In the halogen-modified polyolefin (a ′), a carbon-halogen bond existing at the α-position of a carbon-carbon double bond, or a structure in which a plurality of halogens are added on one carbon atom can be used as an initiator structure. it can.

The production method of the olefin block polymer (G) by using the halogen-modified polyolefin (a ′) as a macroinitiator is basically the above modified polyolefin (a ′).
In the presence of (), a radically polymerizable monomer is atom transfer radical polymerized using a metal complex having a transition metal as a central metal as a catalyst.

Although it does not specifically limit as a transition metal complex used as a polymerization catalyst, Preferably it is a metal complex which uses a periodic table 7th group, 8th group, 9th group, 10th group, or 11th group element as a central metal. More preferable examples include a complex of zero-valent copper, monovalent copper, divalent ruthenium, divalent iron, or divalent nickel. Of these, a copper complex is preferable. Specific examples of monovalent copper compounds include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, cuprous perchlorate, etc. is there. When using a copper compound, 2,2′-bipyridyl or a derivative thereof, 1,10-phenanthroline or a derivative thereof, or tetramethylethylenediamine, pentamethyldiethylenetriamine or hexamethyltris (2-aminoethyl) amine is used to increase the catalytic activity. Polyamines such as are added as ligands. A tristriphenylphosphine complex of divalent ruthenium chloride (RuCl ₂ (PPh ₃ ) ₃ ) is also suitable as a catalyst. When a ruthenium compound is used as a catalyst, an aluminum alkoxide is added as an activator. Further, a divalent iron bistriphenylphosphine complex (FeCl ₂ (PPh ₃ ) ₂ ), a divalent nickel bistriphenylphosphine complex (NiCl ₂ (PPh ₃ ) ₂ ), and a divalent nickel bistributylphosphine Complex (NiBr ₂ (PBu _3
2 ) is also suitable as a catalyst.

Examples of the one or more monomers selected from radically polymerizable monomers include the same compounds as those exemplified in the above-mentioned block (b).
In the method for producing the olefin block polymer (G), the polymerization method is not particularly limited, and bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, bulk / suspension polymerization, and the like can be applied. As the solvent that can be used in radical polymerization, any solvent that does not inhibit the reaction can be used. For example, as specific examples, aromatic hydrocarbon solvents such as benzene, toluene, and xylene, pentane, hexane, Aliphatic hydrocarbon solvents such as heptane, octane, nonane and decane, alicyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane and decahydronaphthalene, chlorobenzene, dichlorobenzene, trichlorobenzene, methylene chloride, chloroform, tetrachloride Chlorinated hydrocarbon solvents such as carbon and tetrachloroethylene, alcohol solvents such as methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol and tert-butanol, acetone, methyl ethyl ketone, And ketone solvents such as methyl isobutyl ketone; ester solvents such as ethyl acetate and dimethyl phthalate; ether solvents such as dimethyl ether, diethyl ether, di-n-amyl ether, tetrahydrofuran and dioxyanisole. . Further, suspension polymerization and emulsion polymerization can be performed using water as a solvent. These solvents may be used alone or in admixture of two or more. Moreover, it is preferable that the reaction liquid becomes a homogeneous phase by using these solvents, but a plurality of non-uniform phases may be used.

  The reaction temperature may be any temperature as long as the radical polymerization reaction proceeds, and is not uniform depending on the degree of polymerization of the desired polymer, the type and amount of the radical polymerization initiator and solvent used, but is usually -100 ° C. ~ 250 ° C. Preferably it is -50 degreeC-180 degreeC, More preferably, it is 0 degreeC-160 degreeC. In some cases, the reaction can be performed under reduced pressure, normal pressure, or increased pressure. The polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon. The olefin block polymer (G) produced by the above method is isolated by using a known method such as distillation of the solvent used for the polymerization or unreacted monomer or reprecipitation with a non-solvent. Furthermore, by treating the obtained polymer with a polar solvent such as acetone or THF using a Soxhlet extraction apparatus, it is possible to remove the by-product homoradical polymer.

≪Method for producing powdery olefin block polymer (G) ≫
Examples of the method for producing the olefin block polymer (G) include a method in which the olefin block polymer (G) produced by the above-described production method is uniformly dissolved in an appropriate solvent and then crystallized, or the olefin block polymer (G) ), A radical polymerization using a powdery halogen-modified polyolefin (A ′) having an average particle diameter of 1 to 1,000 μm and a bulk density of 0.10 to 0.50 g / cm ³ as a macroinitiator. And a method of producing one or more monomers selected from the polymerizable monomers by atom transfer radical polymerization of the powdery halogen-modified polyolefin (A ′) in a non-molten state. The average particle size of the powdery halogen-modified polyolefin (A ′) is more preferably 1 to 500 μm.

When the olefin block polymer (G) is used industrially, it is preferably obtained in a benign state with a small content of impurities such as catalyst components. Specifically, the average particle size is 1 to 1,000.
It is preferably in the form of a powder having a thickness of μm and a bulk density of 0.10 to 0.90 g / cm ³ . The process of controlling the powder properties can be carried out in any process for producing the olefin block polymer (G), but in the process for producing the raw material polyolefin, that is, the process for polymerizing olefins, the catalyst and the polymerization conditions are used. A method of controlling by a method of controlling, a method of controlling by crystallization or the like is preferably used. As a method by crystallization, a raw material polymer, that is, a normal particle-like or pellet-like polymer is previously converted into a benign powder by a crystallization operation, and an olefin-based block polymer (G) is produced while maintaining this morphology. In the process of preparing the macroinitiator, a crystallization operation is performed to convert the powder into a benign powder, and the olefin block polymer (G) is manufactured while maintaining this morphology, or the olefin block polymer (G) is manufactured. Thereafter, a method of converting into a benign powder by a crystallization operation is preferably used. In the crystallization operation, it is possible to control the particle size and bulk density by precipitating polymer particles by dissolving a polymer in a good solvent and then adding a poor solvent or lowering the temperature. The polymer concentration, good solvent species, poor solvent species, stirring speed, temperature drop rate, and the like are important factors for controlling the particle size and bulk density by the crystallization operation. The good solvent in the crystallization operation is not particularly limited as long as it can dissolve or swell the polymer, and one or more solvents can be selected according to the type of polymer to be dissolved. However, an aromatic hydrocarbon solvent or an aliphatic hydrocarbon solvent is preferably used as a solvent having high affinity for polyolefins, and among them, toluene, xylene, chlorobenzene, decane, or a mixed solvent thereof is preferable. Particularly preferably used. Further, when a polyolefin having a melting point above room temperature, such as polyethylene or polypropylene, is difficult to dissolve at room temperature, it can be dissolved by heating in the solvent. The polymer concentration at this time is usually in the range of 5 g / L to 500 g / L, preferably 10 g / L to 300 g / L.

  The poor solvent in the crystallization operation is not particularly limited as long as it is a solvent capable of precipitating a polymer, and one or more solvents can be selected depending on the type of polymer to be dissolved. . When performing the crystallization operation, it is usually possible to reduce the particle size by increasing the stirring speed. Further, when the polymer is precipitated by lowering the temperature, it is generally preferable to slow the temperature lowering rate before and after the temperature at which the polymer is precipitated. The temperature lowering rate at this time is usually 5 ° C./hr to 100 ° C./hr, preferably 5 ° C./hr to 50 ° C./hr.

  Such a method for producing an olefin block polymer (G) having good properties is particularly preferably used when the melting point of the polyolefin portion is 80 ° C. or higher, preferably 100 ° C. or higher.

  In addition, the polymer whose particle properties are well controlled can easily remove not only the solvent but also impurities such as organic residues and catalyst residues generated in the production stage by centrifugation and filtration operations. It is industrially advantageous compared to a polymer having a heterogeneous particle property.

  The production method of the olefin block polymer (G) is such that atom transfer radical polymerization proceeds at the start of atom transfer radical polymerization or while the macroinitiator which is a powdery halogen-modified polyolefin (A ′) is not melted during the polymerization. It is characterized by doing.

In atom transfer radical polymerization, a solvent may or may not be used. Any solvent can be used as long as it does not inhibit the reaction. For example, aromatic hydrocarbon solvents such as benzene, toluene and xylene, pentane, hexane, heptane, and octane can be used as specific examples. , Aliphatic hydrocarbon solvents such as nonane and decane, alicyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane and decahydronaphthalene, chlorobenzene, dichlorobenzene, trichlorobenzene, methylene chloride, chloroform, carbon tetrachloride and tetra Chlorinated hydrocarbon solvents such as chloroethylene, alcohol solvents such as methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol and tert-butanol, acetone, methyl ethyl ketone and methyl isobutyl Examples thereof include ketone solvents such as ketones; ester solvents such as ethyl acetate and dimethyl phthalate; ether solvents such as dimethyl ether, diethyl ether, di-n-amyl ether, tetrahydrofuran, and dioxyanisole. Water can also be used as a solvent. These solvents may be used alone or in admixture of two or more.

  The reaction temperature may be any temperature as long as the powdery halogen-modified polyolefin (A ′), which is a macroinitiator, does not melt or swell, and the radical polymerization reaction proceeds. Although it is not uniform depending on the kind and amount of the radical polymerization initiator and the solvent to be used, it is usually -100 ° C to 250 ° C. Preferably it is -50 degreeC-120 degreeC, More preferably, it is 0 degreeC-100 degreeC. In some cases, the reaction can be performed under reduced pressure, normal pressure, or increased pressure. The polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon.

Specifically, for example, the powdery olefin block polymer (G) can be produced as follows.
A nitrogen-substituted glass reactor is charged with a powdery halogen-modified polyolefin (A ′) containing a halogen atom, an organic solvent such as toluene, and a radical polymerizable monomer such as methyl methacrylate, and heated to 80 ° C. The polymer is dispersed in a slurry by heating and stirring. Copper bromide and N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine (PMDETA) are added to this slurry solution, and polymerization is carried out at 80 ° C. for 1.5 hours. Methanol is added to the reaction solution, the polymer is filtered and washed, and the precipitated polymer is dried under reduced pressure to obtain a powdery olefin block polymer (G).

  The powdery olefin block polymer (G) produced by the above method can remove the catalyst residue, solvent and unreacted monomer used in the polymerization by simple filtration / washing or centrifugation.

[Vinyl polymer (B)]
The vinyl polymer (B) used in the present invention is a polymer obtained from a vinyl monomer containing at least one selected from an aromatic vinyl compound (m1) and a vinyl cyanide compound (m2).

  Examples of the aromatic vinyl compound (m1) include styrene, vinyl toluene, α-methyl styrene, o-, m-, p-methyl styrene, 1,3-dimethyl styrene, 2,4-dimethyl styrene, vinyl naphthalene, and vinyl anthracene. 4-propyl styrene, 4-cyclohexyl styrene, 4-dodecyl styrene, 2-ethyl-4-benzyl styrene, 4- (phenylbutyl) styrene, chlorostyrene, styrene sulfonic acid and salts thereof. Of these, styrene and α-methylstyrene are preferable.

Examples of the vinyl cyanide compound (m2) include acrylonitrile and methacrylonitrile.
In the vinyl polymer (B) used in the present invention, vinyl compounds other than the above, for example, esters of diene, (meth) acrylic acid and alcohol, maleimide compounds, and the like can be used as raw material monomers.

Dienes include butadiene, isoprene, 4-methyl-1,3-pentadiene, 1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene,
Examples include 1,3-hexadiene, 1,3-octadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, and the like.
Examples of the ester of (meth) acrylic acid and an alcohol having a linear or side chain having 1 to 12 carbon atoms include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (meth ) Butyl acrylate, 2-ethylhexyl (meth) acrylate, and the like. Examples of maleimide compounds include phenylmaleimide, cyclohexylmaleimide, butylmaleimide and the like.

  Examples of the vinyl polymer (B) include a homopolymer of an aromatic vinyl compound (m1) (for example, polystyrene) and a copolymer of an aromatic vinyl compound (m1) and a diene (for example, a butadiene / styrene copolymer). A copolymer of an aromatic vinyl compound (m1) and a vinyl cyanide compound (m2) (for example, an acrylonitrile / styrene copolymer), an aromatic vinyl compound (m1), a vinyl cyanide compound (m2) and a diene; (For example, acrylonitrile / butadiene / styrene copolymer, etc.).

The vinyl polymer (B) used in the present invention can be produced by a conventionally known method, and a commercially available vinyl polymer (B) can also be used.
〔Additive〕
In the resin composition of the present invention, various known additives can be blended in accordance with the application within a range that does not greatly impair the purpose and effect. Examples of additives that can be used include modifiers such as dispersants, lubricants, plasticizers, flame retardants, antioxidants, antistatic agents, light stabilizers, ultraviolet absorbers, and crystallization accelerators (nucleating agents). Quality additives, pigments, colorants such as dyes, carbon black, titanium oxide and the like. Moreover, particulate fillers such as talc, clay, mica, silicates and carbonates, fibrous fillers such as glass fiber and wollastonite, and whiskers such as potassium titanate can be blended.

[Composition of resin composition]
The composition ratio of the polyolefin (A), the olefin block polymer (G), and the vinyl polymer (B) constituting the resin composition of the present invention is as follows. A) is usually 1 to 98.9% by weight, preferably 5 to 90% by weight. When the component (A) is less than 1% by weight, the solvent resistance is lowered, and when it is more than 98.9% by weight, the impact strength and the bending strength are lowered. Moreover, a component (G) is 0.1 to 50 weight% normally, Preferably it is 0.5 to 30 weight%. When the component (G) is less than 0.1% by weight, the effect as a compatibilizer is lowered, and when it is more than 50% by weight, the mechanical properties are lowered. Moreover, a component (B) is 1-98.9 weight% normally, Preferably it is 9.5-95.5 weight%. When the component (B) is less than 1% by mass, the mechanical properties are lowered, and when it is more than 98.9% by weight, the solvent resistance is lowered. Further, a resin other than the polyolefin (A), the polyolefin-based block polymer (G), and the vinyl polymer (B) may be included as long as the physical properties of the resin composition are not deteriorated.

  The resin composition (C) according to the present invention contains at least a polyolefin and a vinyl polymer, and the content of the vinyl monomer polymer having a solubility parameter in the room temperature chloroform insoluble component in the range of 18 to 25 J / m. Is in the range of 0.1 to 50% by weight, preferably 0.3 to 30% by weight, more preferably 0.5 to 20% by weight.

In addition, the weight of the polymer of the vinyl monomer whose solubility parameter in the room temperature chloroform insoluble component of the composition is in the range of 18 to 25 J / m is determined as follows.
5 g of the resin composition (C) is dissolved in 100 ml of xylene reflux. Pour the solution obtained while stirring 1 L of chloroform with a homogenizer. The solution in which the polymer is precipitated and becomes a slurry is filtered and separated into a filtrate and a filtrate. The filtrate becomes a chloroform-insoluble component. The composition analysis in the chloroform insoluble component is performed by ¹ H-NMR, and the weight percentage of the content of the component derived from the block (b) contained in the room temperature chloroform insoluble component is measured. The composition analysis in the chloroform-soluble component is conducted by ¹ H-NMR, and the weight% in the resin composition (C) is measured for the same component as the block (b).

[Method for preparing resin composition]
The method for preparing the resin composition of the present invention is not particularly limited, and can be adjusted by a known method such as a melting method or a solution method, and a melt kneading method is practically preferable.

  As a melt-kneading method, a kneading method generally used for thermoplastic resins can be applied as it is. For example, each powdery or granular component, and if necessary, additional components are uniformly dry-mixed with a Henschel mixer, ribbon blender, V-type blender, etc., and then a uniaxial or multiaxial kneading extruder, kneading roll, It can be melt-kneaded with a batch kneader, kneader, Banbury mixer or the like.

  The melt kneading temperature of each component (for example, cylinder temperature in the case of an extruder) is not particularly limited as long as each component is melted, but is usually 160 to 350 ° C, preferably 200 to 300 ° C. The kneading order and method of each component are not particularly limited. It is also possible to remove unreacted components and decomposition products in the polymer by kneading under reduced pressure.

(Use)
The resin composition according to the present invention can be used in various applications, for example, in the following applications.
(1) Film and Sheet The film and sheet made of the resin composition according to the present invention are excellent in any one of flexibility, transparency, adhesiveness, antifogging property, heat resistance and separability.
(2) Laminate comprising at least one layer comprising the resin composition according to the present invention Separation of, for example, agricultural film, wrapping film, shrink film, protective film, plasma component separation membrane, water selective pervaporation membrane, etc. Examples of membranes, selective separation membranes such as ion exchange membranes, battery separators, and optical separation membranes.
(3) Microcapsules, PTP packaging, chemical valves, drug delivery systems. (4) Building materials and civil engineering materials For example, floor materials, floor tiles, floor sheets, sound insulation sheets, heat insulation panels, vibration insulation materials, decorative sheets, baseboards, asphalt modifiers, gaskets / sealing materials, roofing sheets, waterstops Building materials such as sheets, resin for civil engineering, and moldings for building materials and civil engineering.
(5) Automotive interior / exterior material and gasoline tank Automotive interior / exterior material and gasoline tank made of the resin composition according to the present invention are excellent in rigidity, impact resistance, oil resistance, and heat resistance.
(6) Electricity, electronic parts, etc. Electrical insulating materials; Electronic parts processing equipment; Magnetic recording media, binders for magnetic recording media, sealing materials for electrical circuits, materials for household appliances, containers for containers such as microwave oven containers, electronic Film for range, polymer electrolyte substrate, conductive alloy substrate, etc. Connector, socket, resistor, relay case, switch, coil bobbin, condenser, variable capacitor case, optical pickup, optical connector, oscillator, various terminal boards, transformer, plug, printed wiring board, tuner, speaker, microphone, headphones, small size Electric and electronic parts such as motors, magnetic head bases, power modules, housings, semiconductors, liquid crystal display parts, FDD carriages, FDD chassis, HDD parts, motor brush holders, parabolic antennas, computer-related parts; VTR parts, televisions Parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, audio equipment parts such as audio / laser discs (registered trademark) / compact discs, lighting parts, refrigerator parts, Houses represented by computer parts, typewriter parts, word processor parts, etc., office electrical product parts, office computer related parts, telephone related parts, facsimile related parts, copying machine related parts, electromagnetic shielding materials, speaker cone materials, speaker vibrations Elements, etc.
(7) Aqueous Emulsion An aqueous emulsion containing the resin composition according to the present invention can be an adhesive for polyolefins excellent in heat sealability.
(8) Paint base The solvent dispersion containing the resin composition according to the present invention has excellent dispersion stability with respect to a solvent, and exhibits good adhesion when bonding a metal or polar resin to a polyolefin.
(9) Medical and hygiene materials Non-woven fabrics, non-woven fabric laminates, electrets, medical tubes, medical containers, infusion bags, prefilled syringes, syringes and other medical supplies, medical materials, artificial organs, artificial muscles, filtration membranes, Food hygiene / health goods; retort bags, freshness keeping films, etc.
(10) Miscellaneous Goods Stationery such as desk mats, cutting mats, rulers, pen barrels, grips and caps, grips such as scissors and cutters, magnet sheets, pen cases, paper folders, binders, label seals, tapes, whiteboards, etc. : Clothing, curtains, sheets, carpets, doormats, bath mats, buckets, hoses, bags, planters, air conditioner and exhaust fan filters, dishes, trays, cups, lunch boxes, coffee siphon funnels, glasses frames, containers, storage cases Daily goods such as shoes, hangers, ropes, laundry nets: Sporting goods such as shoes, goggles, skis, rackets, balls, tents, underwater glasses, fins, fishing rods, cooler boxes, leisure seats, sports nets: Block, card, etc Toys: Kerosene cans, drums, bottles for detergents and shampoos, etc .; signs, pylons, plastic chains: etc.
[Example]
EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples.

In the following examples, each physical property was measured and evaluated as follows.
In the examples and comparative examples, the test methods used for various evaluations are shown below.
(1) MFR
MFR was measured according to ASTM D 1238. However, MFR ₁₉₀ has a temperature of 190
The MFR was measured under the conditions of ° C and a load of 2.16 kg, and MFR ₂₃₀ was the MFR measured under the conditions of a temperature of 230 ° C and a load of 2.16 kg.
(2) Bending strength The bending strength was measured under the following conditions in accordance with ASTM D790.

<Measurement conditions>
Test piece: 12.7 mm (width) x 3.2 mm (thickness) x 127 mm (length)
Bending speed: 5 mm / min Bending span: 100 mm
Specimen thickness: 1/8 inch (3) Tensile test The tensile test was measured according to ASTM D638 under the following conditions.

<Measurement conditions>
Test piece: ASTM-IV dumbbell test piece Tensile speed: 5 mm / min (4) Izod impact strength (IZ)
The Izod impact strength (IZ) was measured under the following conditions in accordance with ASTM D256.

<Test conditions>
Temperature: 23 ° C
Test piece: 12.7 mm (width) x 3.2 mm (thickness) x 64 mm (length)
The notch was created by machining.
(6) Peeling The layer peeling state of the molded product was evaluated by a cello tape (registered trademark) peeling test (three times) in the vicinity of the gate part of the ASTM-I test piece.

Judgment criteria:
○… No peeling △… Partial peeling ×… Full surface peeling Also, the following resins were used as polyolefins and vinyl polymers.
Polyolefin (A-1):
Crystalline polypropylene homopolymer manufactured by Prime Polymer Co., Ltd., MFR ₂₃₀ = 13
g / 10 min, melting point = 165 ° C.
Polyolefin (A-2):
Tuffmer A0550 (trade name) manufactured by Mitsui Chemicals, Inc. Ethylene / 1-butene random copolymer, density 860 kg / m ³ , MFR ₁₉₀ = 1.0 g / 10 minutes,
Vinyl polymer (B-1):
Acrylonitrile butadiene styrene copolymer (trade name) manufactured by Nippon A & L Co., Ltd. (trade name) Santac GA101, melt volume rate (ISO 1133, 220 ° C., 10 kg load) = 26, flexural modulus (ISO 178, 23 ° C.) = 2600 MPa
Vinyl polymer (B-2):
Acrylonitrile / butadiene / styrene copolymer (trade name) Santac SXD220, melt volume rate (ISO 1133, 220 ° C., 10 kg load) = 90, flexural modulus (ISO 178, 23 ° C.) = 2650 MPa, manufactured by Nippon A & L Co., Ltd.
Vinyl polymer (B-3):
General-purpose polystyrene (trade name) Nippon Polystyrene G430, manufactured by Nippon Polystyrene Co., Ltd.
Vinyl polymer (B-4):
Acrylonitrile styrene copolymer (trade name) LIGHTAC 100PCF, melt volume rate (ISO 1133, 220 ° C., 10 kg load) = 18, flexural modulus (ISO 178, 23 ° C.) = 3600 MPa, manufactured by Nippon A & L Co., Ltd.
Copolymer P-1:
Asahi Kasei Chemicals Corporation Tuftec H1043 (trade name) Polystyrene-poly (ethylene butene) -polystyrene block copolymer copolymer P-2:
MODIPER A3400 (trade name) manufactured by Nippon Oil & Fat Co., Ltd. Polypropylene-poly (styrene / acrylonitrile) block copolymer copolymer P-3:
MODIPER A3100 (trade name) manufactured by Nippon Oil & Fat Co., Ltd. Polypropylene-polystyrene block copolymer [Production Example 1]
A propylene / 10-undecen-1-ol copolymer produced according to the method described in Example 1 of JP-A-2002-145944 is placed in a glass reactor so that the polymer concentration becomes 100 g / L. Hexane was added to form a slurry. 5-fold equivalent of 2-bromoisobutyric acid bromide was added to the amount of hydroxyl groups present in the polymer, heated to 60 ° C., and heated and stirred for 3 hours. The reaction solution was cooled to 20 ° C. at a cooling rate of 20 ° C./h, and the polymer was filtered off. The polymer was again placed in acetone and stirred for 10 minutes for solid-liquid washing, and then filtered again. The obtained white polymer was dried at 50 ° C. under a reduced pressure of 10 Torr for 10 hours. As a result of the high-temperature GPC analysis, the weight average molecular weight in terms of polypropylene Mw = 106,000
0, polypropylene-equivalent number average molecular weight Mn = 56,400, melting point is 154 ° C. from DSC measurement result, ¹ H-NMR analysis shows that the end introduced bromine derived from 2-bromoisobutyric acid bromide is the average introduction The number was 1.9 / chain. As a result of ¹ H-NMR, 94% of the hydroxyl groups were halogenated polypropylene modified with 2-bromoisobutyric acid groups.

Put the halogenated polypropylene in a glass polymerizer and add the toluene solution prepared so that styrene (St) and acrylonitrile (AN) are 4.9M and 2.1M, respectively, so that the polymer concentration becomes 93 g / L. Then, deoxygenation operation was performed by nitrogen bubbling. Then, copper bromide (I): N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine (PM
A 1: 2 (mol ratio) toluene solution of DETA) was added to the halogen content of the halogenated polypropylene so as to be 2 equivalents of copper (I) bromide, and heated and stirred. When the polymerization was carried out at 105 ° C. for 2.5 hours, the mixture was cooled in an ice bath, the polymer mixture was filtered, and the polymer on the filter paper was washed with methanol. The obtained polymer was dried at 80 ° C. under reduced pressure to obtain a white polymer (hereinafter referred to as block polymer (G-1)). Table 1 summarizes the composition of the polymer, the solubility parameter of the radical polymerization segment, and the segment molecular weight determined from ¹ H-NMR.
[Production Example 2]
A propylene / 10-undecen-1-ol copolymer produced according to the method described in Example 1 of JP-A-2002-145944 is placed in a glass reactor so that the polymer concentration becomes 100 g / L. Hexane was added to form a slurry. 5-fold equivalent of 2-bromoisobutyric acid bromide was added to the amount of hydroxyl groups present in the polymer, heated to 60 ° C., and heated and stirred for 3 hours. The reaction solution was cooled to 20 ° C. at a cooling rate of 20 ° C./h, and the polymer was filtered off. The polymer was again placed in acetone and stirred for 10 minutes for solid-liquid washing, and then filtered again. The obtained white polymer was dried at 50 ° C. under a reduced pressure of 10 Torr for 10 hours. As a result of the high-temperature GPC analysis, the polypropylene-converted weight average molecular weight Mw = 82,800, the polypropylene-converted number average molecular weight Mn = 41,300, the melting point is 154 ° C. from the DSC measurement result, and from ¹ H-NMR analysis, 2 -The average number of introduced bromine introduced bromine derived from bromisobutyric acid bromide was 1.3 / chain. As a result of ¹ H-NMR, 97% of the hydroxyl groups were halogenated polypropylene modified with 2-bromoisobutyric acid groups.

The obtained halogenated polypropylene was put into a glass polymerization vessel, styrene monomer was added so that the polymer concentration was 189 g / L, and deoxygenation operation was performed by nitrogen bubbling. Then, copper bromide (I): N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine (
PMDETA) in a 1: 2 (molar ratio) toluene solution was added to the halogen content of the halogenated polypropylene so as to be 1.5 equivalents of copper (I) bromide, and heated and stirred. When polymerized at 100 ° C. for 5 hours, the mixture was cooled in an ice bath to precipitate a polymer, and then filtered and washed with methanol. The obtained polymer was dried at 80 ° C. under reduced pressure (10 Torr) to obtain a white polymer (hereinafter referred to as block polymer (G-2)). Table 1 summarizes the composition of the polymer, the solubility parameter of the radical polymerization segment, and the segment molecular weight determined from ¹ H-NMR.
[Production Example 3]
The halogenated polypropylene synthesized by the method described in Production Example 1 is put into a glass polymerization vessel so that acrylic acid-n-butyl (nBA) and methyl methacrylate (MMA) are 1.1 M and 0.1 M, respectively. The toluene solution prepared above was added so that the polymer concentration was 30 g / L, and deoxygenation operation was performed by nitrogen bubbling. Thereafter, a 1: 2 (molar ratio) toluene solution of copper (I) bromide: N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine (PMDETA) was added to the halogen content of the halogenated polypropylene. On the other hand, it was added to 3.5 equivalents of copper (I) bromide, and heated and stirred. When polymerization was performed at 105 ° C. for 9 hours, the mixture was cooled in an ice bath, the polymer mixture was filtered, and the polymer on the filter paper was washed with methanol. The obtained polymer was dried at 80 ° C. under reduced pressure to obtain a white block copolymer (hereinafter referred to as block polymer (G-3)). The composition of various monomers, the solubility parameter of the radical polymerization segment, and the segment molecular weight are summarized in Table 1.
[Production Example 4]
The halogenated polypropylene synthesized by the method described in Example 1 was placed in a glass polymerizer, and styrene (St), acrylonitrile (AN), and glycidyl methacrylate (GMA) were 4.6 M, 2.0 M, and 0.005, respectively. A toluene solution prepared to 7 M was added so that the polymer concentration became 86 g / L, and deoxygenation operation was performed by nitrogen bubbling. Thereafter, copper (I) bromide: N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine (PMD
A 1: 2 (mol ratio) toluene solution of ETA) was added to the halogen content of the halogenated polypropylene so as to be 1.5 equivalents of copper (I) bromide, and heated and stirred. After polymerization at 80 ° C. for 1.5 hours, the mixture was cooled in an ice bath, the polymer mixture was filtered, and the polymer on the filter paper was washed with methanol. The obtained polymer was dried at 80 ° C. under reduced pressure to obtain a white polymer (hereinafter referred to as block polymer (G-4)). The composition of various monomers, the solubility parameter of the radical polymerization segment, and the segment molecular weight are summarized in Table 1.
[Production Example 5]
The halogenated polypropylene synthesized by the method described in Production Example 1 is placed in a glass polymerization vessel so that acrylic acid-n-butyl (nBA) and glycidyl methacrylate (GMA) are 3.0 M and 0.30 M, respectively. The toluene solution prepared above was added so that the polymer concentration became 93 g / L, and deoxygenation operation was performed by nitrogen bubbling. Then, copper bromide (I): N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine (PMDETA) 1: 2 (m
ol ratio) of toluene solution was added to the halogen content of the halogenated polypropylene so as to be 2 equivalents of copper (I) bromide, and heated and stirred. After polymerization at 75 ° C. for 1 hour, the mixture was cooled in an ice bath, the polymer mixture was filtered, and the polymer on the filter paper was washed with methanol. The obtained polymer was dried at 80 ° C. under reduced pressure to obtain a white polymer (hereinafter referred to as block polymer (G-5)). The composition of various monomers, the solubility parameter of the radical polymerization segment, and the segment molecular weight are summarized in Table 1.
[Production Example 6]
A toluene solution prepared by putting the halogenated polypropylene synthesized by the method described in Production Example 1 into a glass polymerization vessel so that styrene (St) and methyl methacrylate (MMA) are 5.9 M and 0.6 M, respectively. Was added so that the polymer concentration became 87 g / L, and deoxygenation operation was performed by nitrogen bubbling. Then, copper bromide (I): N, N, N ′, N ″, N ″ −
A 1: 2 (molar ratio) toluene solution of pentamethyldiethylenetriamine (PMDETA) was added to the halogen content of the halogenated polypropylene to 2.0 equivalents of copper (I) bromide, and the mixture was heated and stirred. . After polymerization at 80 ° C. for 6.0 hours, the mixture was cooled in an ice bath, the polymer mixture was filtered, and the polymer on the filter paper was washed with methanol. The obtained polymer was dried at 80 ° C. under reduced pressure to obtain a white polymer (hereinafter referred to as block polymer (G-6)). The composition of various monomers, the solubility parameter of the radical polymerization segment, and the segment molecular weight are summarized in Table 1.
[Production Example 7]
A toluene solution prepared by putting the halogenated polypropylene synthesized by the method described in Production Example 1 into a glass polymerization vessel so that styrene (St) and methyl methacrylate (MMA) are 5.9 M and 1.2 M, respectively. Was added so that the polymer concentration became 87 g / L, and deoxygenation operation was performed by nitrogen bubbling. Then, copper bromide (I): N, N, N ′, N ″, N ″ −
A 1: 2 (molar ratio) toluene solution of pentamethyldiethylenetriamine (PMDETA) was added to the halogen content of the halogenated polypropylene to 2.0 equivalents of copper (I) bromide, and the mixture was heated and stirred. . After polymerization at 80 ° C. for 4.5 hours, the mixture was cooled in an ice bath, the polymer mixture was filtered, and the polymer on the filter paper was washed with methanol. The obtained polymer was dried at 80 ° C. under reduced pressure to obtain a white polymer (hereinafter referred to as block polymer (G-7)). The composition of various monomers, the solubility parameter of the radical polymerization segment, and the segment molecular weight are summarized in Table 1.
[Production Example 8]
A toluene solution prepared by putting the halogenated polypropylene synthesized by the method described in Production Example 1 into a glass polymerization vessel so that styrene (St) and methyl methacrylate (MMA) are 5.9 M and 1.8 M, respectively. Was added so that the polymer concentration became 87 g / L, and deoxygenation operation was performed by nitrogen bubbling. Then, copper bromide (I): N, N, N ′, N ″, N ″ −
A 1: 2 (mol ratio) toluene solution of pentamethyldiethylenetriamine (PMDETA) was added to 2.0 halogen equivalents of copper bromide to the halogen content of the halogenated polypropylene, and the mixture was heated and stirred. . When polymerization was performed at 80 ° C. for 3.0 hours, the mixture was cooled in an ice bath, the polymer mixture was filtered, and the polymer on the filter paper was washed with methanol. The obtained polymer was dried at 80 ° C. under reduced pressure to obtain a white polymer (hereinafter referred to as block polymer (G-8)). The composition of various monomers, the solubility parameter of the radical polymerization segment, and the segment molecular weight are summarized in Table 1.

[Example 1]
A twin screw extruder comprising 66.7 parts by weight of polypropylene (A-1), 4.8 parts by weight of the block polymer (G-1) produced in Production Example 1, and 28.5 parts by weight of the vinyl polymer (B-1). And kneaded to prepare a pellet-shaped polyolefin resin composition. Room temperature chloroform insoluble component amount was measured using the obtained polyolefin resin composition. Furthermore, the obtained polyolefin resin composition was dried overnight with a vacuum dryer at 80 ° C., and an ASTM test piece was molded with an injection molding machine. The melt-kneading conditions and injection molding conditions are shown below, and the physical properties of the molded products are shown in Table 2.

<Melting and kneading conditions>
Same-direction twin-screw kneader: Product number KZW15-30HG, manufactured by Technobel Co., Ltd.
Kneading temperature: 200 ° C
Screw rotation speed: 200rpm
<Injection molding conditions>
Injection molding machine: Part number IS55, manufactured by Toshiba Machine Co., Ltd. Cylinder temperature: 200 ° C
Mold temperature: 30 ℃
[Examples 2 to 12]
ASTM test specimens were molded in the same manner as in Example 1 except that the types and amounts of the polyolefin, block polymer and vinyl polymer were changed. The physical properties of the molded products are shown in Tables 2 and 3.
[Comparative Examples 1 to 9]
ASTM test pieces were molded in the same manner as in Example 1 except that the types and amounts of the polyolefin and the vinyl polymer were changed, the copolymers P-1 to P-3 were used, and the block polymer was not used. . The physical properties of the molded products are shown in Tables 2 and 3.

As is apparent from Table 2, it can be seen that by adding the block polymer, impact strength and tensile elongation are improved without lowering the rigidity of the resin composition. When the copolymer P-1 is added, the impact strength and the tensile elongation are improved, but the rigidity is lowered.
Further, as can be seen from Table 3, it can be seen that the addition of the block polymer improves the tensile elongation without reducing the rigidity of the resin composition.

Claims (6)

1-98.9% by weight of polyolefin (A),
Olefin-based block polymer (G) 0.1 to 50% by weight,
1-98.9% by weight of vinyl polymer (B) obtained from a vinyl monomer comprising at least one selected from an aromatic vinyl compound (m1) and a vinyl cyanide compound (m2)
(Provided that the total amount of (A), (G) and (B) is 100% by weight), wherein the olefin block polymer (G) is a block (a) which is a polyolefin component, and solubility. The block (b), which is a polymer residue of a vinyl monomer having a parameter in the range of 18 to 25 J / m, is used as a structural unit, and the block (a) and the block (b) are covalently linked to each other. The resin composition (C) characterized by these.   The block (b) constituting the olefin block polymer (G) is an aromatic vinyl compound (m1), a vinyl cyanide compound (m2), (meth) acrylic acid and its derivative (m3), (meth) acrylamide and It consists of one or more structural units derived from a vinyl monomer selected from its derivative (m4), maleic acid and its derivative (m5), maleimide and its derivative (m6), and vinyl esters (m7). The structural unit derived from (meth) acrylic acid and its derivative (m3) is less than 50 mol%). The resin composition (C) according to claim 1, wherein   The resin composition according to claim 1 or 2, wherein the GPC number average molecular weight (Mn) of the block (b) constituting the olefin block polymer (G) is in the range of 2,000 to 200,000. Product (C).   The block (b) constituting the olefin-based block polymer (G) has an average of 0.5 to 5 bonds per one molecular chain of the block (a). The resin composition (C) described.   The block (a) constituting the olefin-based block polymer (G) is a propylene-based polymer residue (a1) having a propylene-derived structural unit of 50 mol% or more. Any resin composition. The resin composition according to claim 1, wherein the polyolefin (A) is a propylene-based polymer (A1) having a propylene-derived structural unit of 50 mol% or more.