JP2007321025A - Polymer blend containing olefin-based block polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition excellent in mechanical characteristics such as impact resistance, tensile strength, etc. <P>SOLUTION: This resin composition (C) consists of (A1) 1 to 98.9 wt.% polyolefin, (A2) 0.1 to 50 wt.% olefin-based block polymer and (B) 1 to 98.9 wt.% acrylic resin (provided that the total amount of the (A1), (A2) and (B) is made as 100 wt.%). The olefin-based block polymer (A2) is provided by using (a) a block of the polyolefin component and (b) a block which is a residual group of the polymer of a vinyl monomer having 18 to 25 J/m solubility parameter as constituting unit, and the blocks (a) and (b) are joined by a covalent bond with each other. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a resin composition containing a polyolefin and an acrylic resin, 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 pamphlet, 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

The resin composition (C) according to the present invention is:
1-98.9% by weight of polyolefin (A1),
0.1 to 50% by weight of an olefin block polymer (A2),
Acrylic resin (B) 1-98.9 wt% (provided that the total amount of (A1), (A2) and (B) is 100 wt%),
The olefin block polymer (A2) is composed of 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, The block (a) and the block (b) are covalently bonded to each other.

  In this invention, it is preferable that the content in this (A2) of the block (b) which comprises the said olefin type block polymer (A2) is 0.1 to 70 weight%. Moreover, it is preferable that the block (a) which comprises the said olefin type block polymer (A2) is a crystalline polyolefin residue which has melting | fusing point of 70 degreeC or more.

  In the present invention, the block (b) constituting the olefin block polymer (A2) is composed of (meth) acrylic acid and derivatives thereof, (meth) acrylonitrile, styrene and derivatives thereof, (meth) acrylamide and derivatives thereof, maleic acid And a chain of at least one structural unit derived from a vinyl monomer selected from maleimides and derivatives thereof, maleimides and derivatives thereof, and vinyl esters. Further, the block (b) constituting the olefin block polymer (A2) radically (co) polymerizes one or more vinyl monomers selected from styrene, acrylonitrile, 2-hydroxyethyl methacrylate, glycidyl methacrylate and methyl methacrylate. It is preferable that it is a polymer residue obtained. Furthermore, the block (b) constituting the olefin block polymer (A2) preferably has a number average molecular weight in the range of 2,000 to 200,000. In the olefin block polymer (A2), it is preferable that 0.5 to 5 blocks (b) are bonded to one molecular chain of the block (a).

  The resin composition (C) according to the present invention is a composition containing at least a polyolefin and an acrylic resin, and has a solubility parameter in a room temperature chloroform insoluble component of the composition in the range of 18 to 25 J / m. The content of the monomer polymer is in the range of 0.1 to 50% by weight.

  The resin composition according to the present invention has good compatibility between the polyolefin (A1) and the acrylic resin (B), and is excellent in mechanical properties such as impact resistance, tensile strength, and bending strength.

  The resin composition according to the present invention includes a polyolefin (A1), an olefin block polymer (A2), and an acrylic resin (B). Hereinafter, these components will be described sequentially.

[Polyolefin (A1)]
The polyolefin (A1) 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-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene And cyclic olefins.

Polyolefin (A1) 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 Α, β-unsaturated carboxylic acid esters such as vinyl acetate, vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl trifluoroacetate, etc .; glycidyl acrylate, methacrylic acid A small amount of unsaturated glycidyl ester such as acid glycidyl and itaconic acid monoglycidyl ester may be copolymerized.

The polyolefin (A1) 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, 1,3-octadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, ethylidenenorbornene, vinylnorbornene, 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,
Mono- or polyalkyl styrene such as p-ethylstyrene; functional groups such as methoxystyrene, ethoxystyrene, vinyl benzoic acid, methyl vinyl benzoate, vinyl benzyl acetate, hydroxystyrene, o-chlorostyrene, p-chlorostyrene, divinylbenzene Containing 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 (A1) is usually 0.01 to 200 g / 10 minutes, preferably 0.1 to 100 g / 10 minutes.

Such polyolefin (A1) can be produced by a conventionally known method.
In the present invention, when the polyolefin (A1) has stereoregularity, it may be either a syndiotactic polyolefin or an isotactic polyolefin.

In the present invention, it is preferable to use polyethylene or polypropylene as the polyolefin (A1).
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 0.880 to 0.970 g.
/ Cm ³ , preferably in the range of 0.890 to 0.955 g / cm ³ .
The ethylene / α-olefin copolymer has a melt flow rate (MFR: ASTM D1238: 190 ° C., load 2.16 kg) of 0.01 to 200 g / 10 min, preferably 0.05 to 50 g / 10 min. Is in range.

  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.

  Among such polypropylene resins, a propylene homopolymer and a propylene / ethylene block copolymer can be preferably used from the viewpoint of injection moldability of the resin and heat-resistant rigidity.

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. Isotactic pentad fraction (mmmm fraction) of propylene homopolymerization part in polypropylene
If it is lower than 96.0%, the flexural modulus and / or heat resistance may decrease.

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 (A1) 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 (A2)]
The olefin block polymer (A2) 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 (A2), 0.5 to 5 blocks (b) are bonded per one molecular chain of the block (a). The olefin block polymer (A2) may have a plurality of blocks (a) and blocks (b) having different compositions and molecular weights.

  In the olefin block polymer (A2), the block (a) is 20 to 99.9 parts by weight, preferably 30 to 90 parts by weight, and the block (b) is 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 of the olefin block polymer (A2) is improved, the dispersed particle size of the island phase is refined, and the mechanical strength is increased. Will improve.

The olefin block polymer (A2) 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 (A2), those having a structure similar to that of the polyolefin (A1) 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.

In the olefin block polymer (A2), the number average molecular weight of the block (a) is 5,000.
0 to 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. A polymer is preferred. When the molecular weight of the block (a) is higher than 1,000,000, the olefin block polymer (A2) is difficult to be distributed at the interface between the polyolefin (A1) and the acrylic resin (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, polyolefin (A1) or acrylic resin (
The entanglement of the molecular chains between B) and the olefin block polymer (A2) is reduced, and the mechanical strength is lowered.

  The block (a) constituting the olefin block polymer (A2) 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 (A2) 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, and 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 derivative, 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 - docosenoic derivatives, Nonashikuro ^{[10.9.1.1 4,7 .1 13,20 .1 15,18 .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 .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 copolymers and the like are preferably mentioned.

<< 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 a structure in which at least one structural unit selected from structural units represented by the following general formulas (I) to (III) is connected to the terminal of the polymer main chain,
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, and an amino group converted to an ammonium salt. The amino group, imino group, amide group, imide group, nitro group, 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, or the like, an imide group such as acetimide or 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 (A2). In the present invention, in the olefin block polymer (A2), the block (b) has 0.5 to 5 bonds, preferably 0.5 to 3.5 bonds, per block (a) in one molecular chain. More preferably, 0.5 to 3 are bonded. When the number of bonds per one molecular chain of the block (b) bonded to the block (a) is out of this range, the olefin block polymer (A2) is bonded to the interface between the polyolefin (A1) and the acrylic resin (B). The polymer (A2) becomes difficult to be distributed, and 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 oxide dicarbonate, 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 (A2) is in the range of 2,000 to 200,000, preferably 5,000 to 150,000. When the number average molecular weight is higher than 200,000, the olefin block polymer (A2) is difficult to be distributed at the interface between the polyolefin (A1) and the acrylic resin (B), and therefore the interface is easy to peel 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 (A1) or acrylic resin (B) and the olefin block polymer (A2), 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 (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid-n-propyl, and isopropyl (meth) acrylate. , (Meth) acrylic acid-n-butyl, (meth) acrylic acid isobutyl, (meth) acrylic acid-tert-butyl, (meth) acrylic acid-n-pentyl, (meth) acrylic acid-n-hexyl, (meta ) Cyclohexyl acrylate, (meth) acrylic acid-n-heptyl, (meth) acrylic acid-n-octyl, (meth) acrylic acid-2-ethylhexyl, (meth) acrylic acid nonyl, (meth) acrylic acid decyl, ( (Meth) dodecyl acrylate, phenyl (meth) acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate, (meth) acrylic acid 2-methoxyethyl, 3-methoxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate, (meth) acrylic Glycidyl acid, 2-aminoethyl (meth) acrylate, 2- (dimethylamino) ethyl (meth) acrylate, γ- (methacryloyloxypropyl) trimethoxysilane, ethylene oxide adduct of (meth) acrylic acid, (meta ) Trifluoromethylmethyl acrylate, 2-trifluoromethylethyl (meth) acrylate, 2-perfluoroethylethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, (Meth) acrylic acid 2-perfluoroethyl, (meth) acrylic acid -Fluoromethyl, diperfluoromethyl methyl (meth) acrylate, 2-perfluoromethyl-2-perfluoroethyl methyl (meth) acrylate, 2-perfluorohexyl ethyl (meth) acrylate, 2- (meth) acrylic acid 2- (Meth) acrylic monomers such as perfluorodecylethyl, 2-perfluorohexadecylethyl (meth) acrylate, styrenes such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid and their salts Monomers such as monomers, fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene and vinylidene fluoride, silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane, maleic anhydride, maleic acid and maleic acid monoalkyl ester And dialkyl esters, fumaric acid, monoalkyl and dialkyl esters of fumaric acid, maleimide, methyl maleimide, ethyl maleimide, propyl maleimide, butyl maleimide, hexyl maleimide, octyl maleimide, dodecyl maleimide, stearyl maleimide, phenyl maleimide, cyclohexyl maleimide, etc. Maleimide monomers, nitrile group-containing vinyl monomers such as acrylonitrile and methacrylonitrile, (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl Amide group-containing vinyl polymers such as (meth) acrylamide, N-butyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, etc. Monomers, vinyl acetate monomers such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, vinyl cinnamate, olefin monomers such as ethylene, propylene and butene, diene monomers such as butadiene and isoprene, vinyl chloride, Examples include vinylidene chloride, allyl chloride, and allyl alcohol. These organic compounds may be used alone or in combination of two or more.

  The block (b) is selected from (meth) acrylic acid and derivatives thereof, (meth) acrylonitrile, styrene and derivatives thereof, (meth) acrylamide and derivatives thereof, maleic acid and derivatives thereof, maleimide and derivatives thereof, and vinyl esters. Preferred is a polymer obtained by (co) polymerizing one or two or more monomers selected from the group consisting of styrene, acrylonitrile, 2-hydroxyethyl methacrylate, glycidyl methacrylate and methyl methacrylate. A polymer obtained by (co) polymerizing a monomer is more preferred, and a polymer obtained by polymerizing methyl methacrylate is particularly preferred.

  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 to 25, preferably in the range of 18.2 to 22, and more preferably in the range of 18.5 to 20. If the value of the solubility parameter is out of this range, the compatibility between the block (b) and the acrylic resin 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 (A2) 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 (A2) ≫
The olefin-based block polymer (A2) has a low content of impurities such as catalyst residue components and a good resin property, the transition metal content incorporated during polymerization is 100 ppm or less, the white and transition metal content is More preferably, it is 50 ppm or less. Further, when the olefin block polymer (A2) is in the form of powder, the average particle size is 1 to 1.0.
The bulk density measured by the method defined in 00 μm and JIS K6891 is 0.10-0.
It is preferably in the range of 90 g / cm ³ . Also, olefin block polymer (A
2) can be used in any form of pellets, powders, and veils.

<Method for Producing Olefin Block Polymer (A2)>
The olefin block polymer (A2) 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 to initiate atom transfer radical polymerization, and represents a polymer having a site that can serve as an initiation point for 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 (A2) by using the halogen-modified polyolefin (a ′) as a macroinitiator basically uses a transition metal as a central metal in the presence of the modified polyolefin (a ′). A radical polymerizable monomer is atom transfer radical polymerized using a metal complex 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 A 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 item of the polar polymer segment (B).
In the method for producing the olefin block polymer (A2), 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 (A2) produced by the above method is isolated by using a known method such as distillation of the solvent used in 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 (A2) ≫
Examples of the method for producing the olefin block polymer (A2) include a method in which the olefin block polymer (A2) produced by the production method described above is uniformly dissolved in an appropriate solvent and then crystallized, or the olefin block polymer (A2). ), 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 (A2) 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 1.00.
It is preferably in the form of a powder having a thickness of 0 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 (A2). However, in the process for producing the raw material polyolefin, that is, the process for polymerizing olefins, the catalyst and the polymerization conditions 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 the olefin-based block polymer (A2) 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 (A2) is manufactured while maintaining this morphology, or the olefin block polymer (A2) 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 (A2) 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 (A2) 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 combination 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 (A2) 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 (A2).

  The powdery olefin block polymer (A2) produced by the above method can remove the catalyst residue, solvent and unreacted monomer used in the polymerization by simple filtration / washing or centrifugation.

[Acrylic resin (B)]
Examples of the acrylic resin (B) used in the present invention include acrylic ester polymer (polyacrylate), methacrylic ester polymer (polymethacrylate), and copolymer resins thereof.

  Specifically, polymethyl acrylate, polyethyl acrylate, polybutyl acrylate, poly 2-ethylhexyl acrylate, polyisobutyl acrylate, poly n-hexyl acrylate, poly n-octyl acrylate, polylauryl acrylate, polystearyl acrylate, etc. Is mentioned.

  Specific examples of the polymethacrylate include polymethyl methacrylate, polyethyl methacrylate, polybutyl methacrylate, polylauryl methacrylate, polystearyl methacrylate, polyisobutyl methacrylate, poly n-hexyl methacrylate, poly n-octyl methacrylate and the like. The acrylic resins (B) as described above can be used alone or in combination of two or more.

The molecular weight of the acrylic resin (B) is preferably in the range of 500 to 10,000 in terms of number average molecular weight, and more preferably in the range of 1,000 to 5,000. In addition, the number average molecular weight here is obtained by using polystyrene as a standard using GPC.
Such an acrylic resin (B) can be produced by a known polymerization method such as a solution polymerization method, a suspension polymerization method, or a bulk polymerization method.

〔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 (A1), the olefin block polymer (A2), and the acrylic resin (B) constituting the resin composition of the present invention is as follows. A1) is usually 1 to 98.9% by weight, preferably 5 to 90% by weight. When the component (A1) 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 (A2) is 0.1 to 50 weight% normally, Preferably it is 0.5 to 30 weight%. When the component (A2) 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. In addition, a resin other than the polyolefin (A1), the polyolefin block polymer (A2), and the acrylic resin (B) may be included as long as the physical properties of the resin composition are not deteriorated.

[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 comprising the resin composition according to the present invention, the gasoline tank has rigidity, impact resistance,
Excellent oil 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
The MFR was measured according to ASTM D 1238 (230 ° C., load 2.16 kg). (2) Tensile test In accordance with ASTM D638, the tensile test was performed by testing a dumbbell-shaped test piece punched from a press sheet having a thickness of 1 mm at 23 ° C, a span interval of 30 mm, and a pulling speed of 30 mm / min.
(3) 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
Test piece thickness: 1/8 inch (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 notches were made by machining. The following resins were used as polyolefins and acrylic resins.

Polyolefin (A1-1):
Crystalline polypropylene homopolymer manufactured by Prime Polymer Co., Ltd., MFR = 13 g / 10 min, melting point = 165 ° C.
Polyolefin (A1-2):
Tuffmer A4050 (trade name) manufactured by Mitsui Chemicals, Inc. Ethylene / 1-butene random copolymer, MFR = 6 g / 10 min.
Acrylic resin (B-1)
Sumipex MHF (trade name) manufactured by Sumitomo Chemical Co., Ltd.

[Production Example 1] Synthesis of halogenated polypropylene Propylene / 10-undecen-1-ol copolymer (Mw = 106,000, Mn = 56,000, synthesized according to the method described in JP-A-2002-145944) 170 g of comonomer content (0.12 mol%) was placed in a 2 L glass reactor purged with degassed nitrogen, 1700 ml of hexane and 9.2 ml of 2-bromoisobutyric acid bromide were added, and the mixture was heated and stirred at 60 ° C. for 2 hours. After the reaction, the resulting slurry was filtered and dried under reduced pressure to obtain 169.5 g of a white solid polymer. ^{From 1} H-NMR analysis, it was found that 94% of OH groups were polypropylene modified with 2-bromoisobutyric acid groups.
The number of 2-bromoisobutyric acid groups per polypropylene molecular chain calculated from the number average molecular weight of polypropylene, the comonomer content, and the modification ratio of 2-bromoisobutyric acid groups was 1.5 units.

[Production Example 2] Synthesis of PP-PMMA hybrid polymer Into a 2 L glass reactor sufficiently purged with nitrogen, 100 g of the halogenated polypropylene obtained above, 800 ml of methyl methacrylate (MMA), and 200 ml of toluene were placed at 25 ° C. And stirred. To this slurry, 98 mg of copper (I) bromide, PMDETA 0.29
ml was added and polymerization was carried out at 80 ° C. for 30 minutes. The reaction solution was filtered, and the solid on the filter was washed with methanol and dried under reduced pressure to obtain 158.7 g of a solid polymer. 4.98 g of the obtained polymer was taken and Soxhlet extraction was performed for 9 hours under reflux using 150 ml of acetone. The extraction residue was dried under reduced pressure to obtain 4.95 g of a polymer. From the ¹ H-NMR analysis of the sample after extraction, the composition ratio of PP / PMMA was 64/36 (wt%).

  The solubility parameter of PMMA constituting the block (b) of the block polymer (A2-1) calculated from the composition ratio was 19.1. The molecular weight of the block (b) calculated from the composition ratio, the number average molecular weight of polypropylene, and the number of 2-bromoisobutyric acid groups per polypropylene molecular chain was 21,000.

[Example 1]
210 parts by weight of polypropylene (A1-1), 45 parts by weight of polypropylene (A1-2), 15 parts by weight of the block polymer (A2-1) produced in Production Example 2, 90 parts by weight of acrylic resin (B-1), The mixture was melt-kneaded with a twin-screw extruder to prepare a pellet-shaped polyolefin resin composition. Room temperature chloroform insoluble component amount was measured using the obtained polyolefin resin composition. Moreover, the ASTM test piece was shape | molded with the injection molding machine (IS55, Toshiba Machine Co., Ltd. make). The melt kneading conditions and injection molding conditions are shown below. The contents of components derived from the block (b) contained in the chloroform-insoluble components at room temperature (hereinafter referred to as block (b) contents) and the physical properties of the molded products are shown in Table 1. Shown in

<Melting and kneading conditions>
Same-direction twin-screw kneader: Product number KZW15-30HG, manufactured by Technobel Co., Ltd.
Kneading temperature: 240 ° 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: 60 ℃

[Comparative Example 1]
An ASTM test piece was molded in the same manner as in Example 1 except that the block polymer (A2-1) was not used. Table 1 shows the content of the block (b) and the physical properties of the molded product.

Claims (8)

1-98.9% by weight of polyolefin (A1),
0.1 to 50% by weight of an olefin block polymer (A2),
Acrylic resin (B) 1-98.9 wt% (provided that the total amount of (A1), (A2) and (B) is 100 wt%),
The olefin block polymer (A2) is composed of 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, The resin composition (C), wherein the block (a) and the block (b) are covalently bonded to each other.   The resin composition (C) according to claim 1, wherein the content of the block (b) constituting the olefin block polymer (A2) in the (A2) is 0.1 to 70% by weight. .   The block (b) constituting the olefin block polymer (A2) is (meth) acrylic acid and derivatives thereof, (meth) acrylonitrile, styrene and derivatives thereof, (meth) acrylamide and derivatives thereof, maleic acid and derivatives thereof, The resin composition (C) according to claim 1 or 2, comprising a chain of one or more structural units derived from a vinyl monomer selected from maleimide and derivatives thereof, and vinyl esters.   The block (b) constituting the olefin block polymer (A2) is obtained by radical (co) polymerizing one or more vinyl monomers selected from styrene, acrylonitrile, 2-hydroxyethyl methacrylate, glycidyl methacrylate and methyl methacrylate. The resin composition (C) according to claim 3, which is a residue of a polymer obtained.   The resin composition according to any one of claims 1 to 4, wherein the block (a) constituting the olefin block polymer (A2) is a crystalline polyolefin residue having a melting point of 70 ° C or higher. (C).   The resin composition according to any one of claims 1 to 5, wherein the block (b) constituting the olefin block polymer (A2) has a number average molecular weight in the range of 2,000 to 200,000. Product (C).   Resin according to any one of claims 1 to 6, wherein the olefin block polymer (A2) has 0.5 to 5 blocks (b) bonded to one molecular chain of the block (a). Composition (C).   A composition comprising at least a polyolefin and an acrylic resin, wherein the content of the vinyl monomer polymer having a solubility parameter in the room temperature chloroform insoluble component of the composition in the range of 18 to 25 J / m is 0.1 to A resin composition (C) characterized by being in the range of 50% by weight.