JP5430244B2 - Compatibilizer for thermoplastic resin and resin composition containing the same - Google Patents

Description

  The present invention relates to a compatibilizer for thermoplastic resins, a resin composition containing the compatibilizer, and a molded article comprising the resin composition. More specifically, the present invention relates to a copolymer of an α-olefin monomer and a compound having a norbornene skeleton. A compatibilizing agent comprising a polymer and having a thermoplastic resin having different characteristics, which gives a resin composition excellent in mechanical strength, organic solvent resistance and appearance, the compatibilizing agent, a polyolefin resin and a polar group. The present invention relates to a resin composition containing a thermoplastic resin, and a molded body made of the resin composition.

  Olefin-based resins are widely used in the manufacture of molded products because of their excellent processability, organic solvent resistance, water absorption resistance, etc., and low specific gravity and low cost. It is an obstacle to the use. Polycarbonate resin, on the other hand, is known as a resin excellent in heat resistance, weather resistance and dimensional stability, but is difficult to injection and extrusion due to poor fluidity, and also has difficulty in solvent resistance. However, the molded product has a strong dependency on the thickness of the impact strength, and there is a drawback that the impact strength is greatly reduced in a thick region.

  Thus, as one of the trials when a single resin material cannot sufficiently satisfy the desired properties, a technique of complementing the insufficient properties by mixing other resin materials is often used. Has been done. Accordingly, if a composition having the good properties of both the polycarbonate resin and the polyolefin resin and complementing undesirable points can be obtained, it is possible to provide an excellent resin material in a wide range of applications. However, since the polycarbonate resin and the polyolefin resin are incompatible with each other and have no affinity, when the two components are simply mixed, the adhesiveness at the interface of the two-phase structure is not good. Therefore, the phase interface of the obtained molded product becomes a defective part, and the mechanical strength decreases. In addition, the two phases are unlikely to be in a uniform and fine dispersion form, and are liable to cause delamination when subjected to shearing stress during molding such as injection molding.

  In order to improve the compatibility between the polycarbonate resin and the polyolefin resin, a method of blending a compatibilizer such as a modified polyolefin is known. For example, Patent Document 1 discloses a method using a hydroxyl group-modified polypropylene as a compatibilizing agent, but a large amount of compatibilizing agent is required in order to obtain the characteristics of the resin material. That is, the effect of improving the compatibility of the hydroxyl group-modified polypropylene is small, and the effect of improving the mechanical properties is also small, which is not satisfactory in practical use. Further, Patent Document 2 discloses a method using a functional group-containing olefin block polymer as a compatibilizing agent, but the manufacturing process of the compatibilizing agent is complicated, so that it is not practical and simpler manufacturing technology. Was desired.

JP-A-6-271718 JP 2007-262325 A

  The present invention has been made to solve the above-mentioned problems of the prior art, and improves the compatibility of a polyolefin resin and a thermoplastic resin having a polar group, for example, a polycarbonate resin, which cannot be achieved by the prior art. Another object of the present invention is to provide a resin composition having a stable domain dispersion structure and excellent mechanical strength and appearance, and a polyolefin compatibilizer suitable as a compatibilizer.

As a result of intensive studies to achieve the above object, the present inventors have found that a copolymer of a specific compound having a norbornene skeleton and an α-olefin monomer is effective for compatibilization of a polyolefin resin and a polycarbonate resin. The present inventors have found that a resin composition that can have a stable domain dispersion structure and is melt-kneaded using the copolymer as a compatibilizing agent is particularly excellent in mechanical strength, organic solvent resistance, and appearance. The present invention has been accomplished based on these findings.
That is, the gist of the present invention resides in the following [1] to [14].

[1] α-olefin monomer and the following general formula (1):
(In the formula, X represents a functional group capable of transesterification or amide exchange reaction with the linking group of the polycondensation resin, n represents an integer of 0 to 10, m represents an integer of 0 to 10, and o represents Represents an integer of 1 to 4.)
A compatibilizer for a thermoplastic resin, comprising a copolymer with a compound represented by the formula:
[2] The compatibilizer according to [1], wherein the polyolefin resin and the thermoplastic resin having a polar group are compatible.
[3] The compatibilizer according to [2], wherein the thermoplastic resin having a polar group is a polycarbonate resin.
[4] The copolymer is a random copolymer of an α-olefin monomer and a compound represented by the general formula (1), and its weight average molecular weight (Mw) is 500 to 1,000,000. The compatibilizer according to any one of 1] to [3].
[5] The copolymer is a block copolymer of an α-olefin monomer, a random copolymer of the compound represented by the general formula (1), and a homopolymer of the α-olefin monomer, and its weight average The compatibilizer according to any one of [1] to [3], which has a molecular weight (Mw) of 500 to 1,000,000.
[6] While the copolymer of the α-olefin monomer and the compound represented by the general formula (1) is continuously supplying the α-olefin monomer to the reaction system containing the compound represented by the general formula (1) The compatibilizing agent according to any one of [1] to [5], which is obtained by polymerization.
[7] Any of [1] to [6], wherein the proportion of the structural unit derived from the compound represented by the general formula (1) in the copolymer is in the range of 0.01 to 10 mol%. The compatibilizer described in 1.
[8] A unit derived from at least three components of the compatibilizer according to any one of [1] to [6], a polyolefin resin (A), and a thermoplastic resin (B) having a polar group. A resin composition characterized by the above.
[9] The resin composition according to [8], wherein the thermoplastic resin (B) having a polar group is a polycarbonate resin.
[10] The proportion of units derived from the compatibilizer is in the range of 0.01 to 30 parts by weight with respect to the total amount of units derived from the polyolefin resin (A) and the thermoplastic resin (B) having a polar group. The resin composition as described in [8] or [9].
[11] The ratio of the structural unit derived from the polyolefin resin (A) to the structural unit derived from the thermoplastic resin (B) having a polar group is 1/99 to 99 / as a weight ratio (A) / (B). The resin composition according to any one of [8] to [10], which is within a range of 1.
[12] The resin composition according to any one of [8] to [11], which is obtained by melt-kneading the three components.
[13] Any one of [8] to [12] obtained by melt-kneading the compatibilizer and the thermoplastic resin (B) having a polar group, and then melt-kneading the remaining components. The resin composition as described.
[14] A molded article comprising the resin composition according to any one of [8] to [13].

  According to the present invention, a copolymer of a compound having a norbornene skeleton represented by the general formula (1) and an α-olefin monomer acts as a reactive compatibilizing agent, and heats a polyolefin resin and a polar group. Since a plastic resin such as a polycarbonate resin is compatibilized, a stable domain dispersion structure is obtained by blending with a composition of a polyolefin resin and a thermoplastic resin having a polar group, such as a polycarbonate resin, and mechanical strength and resistance. A resin composition excellent in organic solvent property and appearance, and a molded product comprising the composition can be provided.

It is a scanning electron micrograph (1000-times multiplication factor) which shows the dispersion form of the resin composition manufactured in Example 1,2. It is a scanning electron micrograph (500-times multiplication factor) which shows the dispersion | distribution form of the resin composition manufactured by Comparative Examples 1-4. It is a transmission electron micrograph (1000-times multiplication factor) which shows the dispersion | distribution form of the resin composition manufactured in Example 1 and Comparative Examples 1-4. 2 is a transmission electron micrograph (magnification 1000 times) showing the dispersion form of the resin compositions produced in Examples 3 and 4 and Comparative Example 5. FIG.

  DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail. However, the description of the constituent elements described below is an example (representative example) of an embodiment of the present invention, and the present invention is limited to these contents. is not.

[1] Compatibilizer for thermoplastic resin The compatibilizer of the present invention comprises an α-olefin monomer and the following general formula (1):
[In formula (1), X represents a functional group capable of transesterification or amide exchange reaction with a linking group of a polycondensation resin, n represents an integer of 0 to 10, and m represents an integer of 0 to 10. , O represents an integer of 1 to 4. ]
It consists of a copolymer with the compound represented by these. Hereinafter, the compatibilizer of the present invention may be simply referred to as “compatibilizer (C)” or “(C) component”.
First, each component which comprises the said copolymer [compatibilizer (C)], the manufacturing method, physical property, etc. of a copolymer are demonstrated.

[1-1] α-Olefin Monomer The monomer α-olefin (α-olefin monomer) constituting the copolymer of the present invention [Compatibilizer (C)] is an olefin having 2 to 12 carbon atoms, Although it is not particularly limited as long as it is a diolefin, cyclic olefin, alkenyl aromatic hydrocarbon or the like and can be copolymerized with the compound represented by the above formula (1), a polyolefin resin ( It is preferably the same as the structural unit of A), and ethylene is particularly preferably used.

  These α-olefins may be used alone or in combination of two or more. When two or more kinds of α-olefins are used, each α-olefin may be distributed randomly or block-wise in the copolymer.

[1-2] Compound Represented by General Formula (1) Compound Represented by General Formula (1) Containing the Copolymer [Compatibilizer (C)] of the Present Invention (Functional Group Having Norbornene Skeleton) In the monomer containing), X is a functional group capable of transesterification or amide exchange reaction with the linking group of the polycondensation resin. X is not particularly limited as long as it has such reactivity, and any functional group can be used. Specific examples include a hydroxyl group, an amino group, an amide group, an imide group, an isocyanate group, a carbodiimide group, an oxazoline group, an epoxy group, a carboxyl group, a carboxylic acid group, an acid anhydride group, and an ester group. Among these, a hydroxyl group is particularly preferable.

n is an integer of 0 to 10, preferably 0 to 8, more preferably an integer of 0 to 3. When n is larger than 8, the copolymerizability deteriorates, the content of X in the component (C) tends to decrease, and the compatibility tends to decrease.
m is an integer of 0 to 10, preferably 0 to 8, and more preferably an integer of 0 to 3. When m is larger than 8, the copolymerizability deteriorates, the content of X in the component (C) tends to decrease, and the compatibility tends to decrease.
o is an integer of 1 to 4, preferably 1 to 2, more preferably an integer of 1. When o is larger than 2, the dispersibility is lowered, and the compatibilizer tends to be dispersed in a lump in the resin composition.

  A specific example of the compound represented by the general formula (1) (functional group-containing monomer having a norbornene skeleton) is as follows.

5-norbornene-2-ol, 5-norbornene-2-methanol, 5-norbornene-2-ethanol, 5-norbornene-2-propanol, 5-norbornene-2-butanol, 5-norbornene-2-pentanol, 5 -Monoalcohols such as norbornene-2-hexanol, 5-norbornene-2-heptanol, 5-norbornene-2-octanol, 5-norbornene-2-nonanol, 5-norbornene-2-decanol;

5-norbornene-2,2-diol, 5-norbornene-2,2-dimethanol, 5-norbornene-2,2-diethanol, 5-norbornene-2,2-dipropanol, 5-norbornene-2,2- Dibutanol, 5-norbornene-2,2-dipentanol, 5-norbornene-2,2-dihexanol, 5-norbornene-2,2-diheptanol, 5-norbornene-2,2-dioctanol, 5-norbornene-2 , 2-dinonanol, 5-norbornene-2,2-didecanol, 5-norbornene-2,3-diol, 5-norbornene-2,3-dimethanol, 5-norbornene-2,3-dipropanol, 5-norbornene -2,3-dibutanol, 5-norbornene-2,3-dipentanol, 5-norbornene-2 3- Jihekisanoru, 5-norbornene-2,3-Jiheputanoru, 5-norbornene-2,3-octanol, 5-norbornene-2,3-Jinonanoru, diols such as 5-norbornene-2,3-Jidekanoru;

5-norbornene-2,2,3-triol, 5-norbornene-2,2,3-trimethanol, 5-norbornene-2,2,3-triethanol, 5-norbornene-2,2,3-tripropanol 5-norbornene-2,2,3-tributanol, 5-norbornene-2,2,3-tripentanol, 5-norbornene-2,2,3-trihexanol, 5-norbornene-2,2,3 -Triols such as triheptanol, 5-norbornene-2,2,3-trioctanol, 5-norbornene-2,2,3-trinonanol, 5-norbornene-2,2,3-tridecanol;

2,2,3,3-tetrahydroxy-5-norbornene, 5-norbornene-2,2,3,3-tetramethanol, 5-norbornene-2,2,3,3-tetraethanol, 5-norbornene-2 , 2,3,3-tetrabutanol, 5-norbornene-2,2,3,3-tetrapentanol, 5-norbornene-2,2,3,3-tetrahexanol, 5-norbornene-2,2,3 , 3-tetraheptanol, 5-norbornene-2,2,3,3-tetraoctanol, 5-norbornene-2,2,3,3-tetranonanol, 5-norbornene-2,2,3,3- Tetraols such as tetradecanol;

Amino compounds such as 2-amino-5-norbornene, 2-aminomethyl-5-norbornene, 2,3-diamino-5-norbornene;
N-alkyl-5-norbornene-2,3-dicarboximide (N-methyl-5-norbornene-2,3-dicarboximide, etc.), N-hydroxy-5-norbornene-2,3-dicarboximide, etc. Imides of

Carboxylic acids such as 5-norbornene-2-carboxylic acid and 5-norbornene-2,3-dicarboxylic acid; Acid anhydrides such as 5-norbornene-2,3-dicarboxylic acid anhydride; 5-norbornene-2-carboxylic acid Esters such as methyl and dimethyl 5-norbornene-2,3-dicarboxylate.

  Among these, 5-norbornen-2-ol, 5-norbornene-2-methanol, and 5-norbornene-2,3-dimethanol are preferable, and 5-norbornen-2-ol is more preferable.

[1-3] Production Method of Copolymer [Compatibilizer (C)] The copolymer is represented by the α-olefin monomer and the general formula (1) in the presence of a nickel metal complex catalyst described later. It can be produced by polymerizing the compound. Here, the nickel metal complex catalyst production and polymerization method are described in J. Am. Cham. Soc. 2001, 123, 5352-5353, Organometallics 2007, 26, 5339-5345, Organometallics 2008, 27, 2273-2280, JP This can be carried out according to the methods described in JP-A-2006-519300 and JP-A-2006-519914. The outline will be described below.

[1-3-1] Nickel metal complex catalyst and preparation method thereof In the present invention, a nickel metal complex catalyst represented by the following general formula (2) is preferably used.

LNiX _p Y _q (2)
[In formula (2), Ni represents a nickel atom, and L is chelate-coordinated to Ni with any atom selected from the group consisting of an oxygen atom, a nitrogen atom, a phosphorus atom, an arsenic atom, a sulfur atom and a carbon atom. Represents a ligand, X represents a ligand that forms a σ bond with Ni, m represents an integer of 1 to 4, Y represents a Lewis base, and coordinates with Ni by a lone pair of electrons. Child is shown, n shows the integer of 1-4. ]

Here, in said formula (2), Ni is a nickel atom. The valence of the nickel atom is zero, monovalent or divalent, preferably zero or divalent.
L is an atom selected from the group consisting of an oxygen atom, a nitrogen atom, a phosphorus atom, an arsenic atom, a sulfur atom, and a carbon atom, and is a ligand that chelates with Ni as a central metal. This ligand L is preferably a bidentate ligand.

  As an atom coordinated to Ni, nitrogen, oxygen, phosphorus, and sulfur are preferable, and nitrogen, oxygen, and phosphorus are particularly preferable.

  X is a ligand that forms a σ bond with Ni. The ligand X is not particularly limited as long as it can form a σ bond with Ni. For example, a hydrogen atom, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a silicon-containing hydrocarbon group, an oxygen-containing group Examples include a hydrocarbon group, an amino group, a substituted amino group, or a nitrogen-containing hydrocarbon group.

  In the present invention, during the polymerization reaction, a monomer is inserted between the Ni-X bonds of the ligand X and reacts. Therefore, if the Ni-X bond is too strong, the reactivity is lowered and a reaction aid such as a promoter is required. It may be. On the other hand, if the Ni-X bond is too weak, the catalyst may become unstable and may not be suitable for polymerization reaction applications. Therefore, it is preferable that the ligand X has an appropriate binding property.

  Examples of the ligand X include a hydrogen atom, a halogen atom, an optionally substituted hydrocarbon group, a substituted amino group, or a nitrogen-containing hydrocarbon group. Among them, in terms of reactivity, a hydrogen atom, a chlorine atom, a methyl group, an i-butyl group, a phenyl group which may have a substituent, a benzyl group which may have a substituent, a dimethylamino group A diethylamino group, a hydrogen atom, a methyl group, an optionally substituted phenyl group, and an optionally substituted benzyl group, more preferably a methyl group and an optionally substituted group. Particularly preferred are a good phenyl group and an optionally substituted benzyl group. Here, preferred as a substituent are a C1-C4 alkyl group, a C1-C4 alkoxy group, a chlorine atom, and a substituted amino group.

  p is the number of ligands X, and is usually an integer of 1 to 4. The number (p) of the ligand X is preferably 1 or 2, and more preferably 1.

  Y is a Lewis base and is a ligand that coordinates to Ni by a lone pair (σ coordination). The ligand Y is not particularly limited as long as it can be a Lewis base and can form a σ coordination with Ni. For example, an oxygen-containing hydrocarbon compound; an amino compound, a substituted amino compound, nitrogen-containing Examples include hydrocarbon compounds.

  Among them, the ligand Y is specifically preferably diethyl ether, furan, 2-methylfuran, tetrahydrofuran, aniline, diphenylaniline, pyridine, 2,6-lutidine, pyrazolyl, indolyl, and diethyl ether. , Tetrahydrofuran, aniline, pyridine, and 2,6-lutidine are more preferable, and pyridine and 2,6-lutidine are particularly preferable.

  q is the number of ligands Y, and is usually an integer of 1 to 4. The number (q) of the ligand Y is preferably 1 or 2, and more preferably 1.

  Furthermore, as the nickel metal complex represented by the formula (2), the ligand L is preferably represented by the following general formula (a).

[In Formula (a), A ^{1 to} A ⁵ may each independently form a ring with adjacent substituents A ^{1 to} A ⁵ (provided that A ² and A ^{3 form} a ring). A hydrocarbon group, a silicon-containing hydrocarbon group, a halogenated hydrocarbon group, an oxygen-containing hydrocarbon group or a nitrogen-containing hydrocarbon group, D represents a carbon atom or a silicon atom, and j represents 0 to 0 2 represents an integer, T represents a carbon atom, a nitrogen atom or a phosphorus atom, and G represents any atom selected from the group consisting of an oxygen atom, a nitrogen atom having a substituent and a phosphorus atom having a substituent. And an atom that is Ni or σ-bonded or σ-coordinated. ]

Here, in formula (a), A ^{1 to} A ⁵ are each independently any of a hydrocarbon group, a silicon-containing hydrocarbon group, a halogenated hydrocarbon group, an oxygen-containing hydrocarbon group, or a nitrogen-containing hydrocarbon group. It is. Preferably it is a hydrocarbon group, and the carbon number is 1-20 normally. Among them, as A ^{1 to} A ⁵ , a methyl group, i-propyl group, i-butyl group, t-butyl group, cyclohexyl group, phenyl group, methylphenyl group, and methoxyphenyl group are preferable, a methyl group, More preferred are i-propyl, i-butyl, cyclohexyl and phenyl.

In A ^{1 to} A ⁵ , two groups may be bonded to each other to form a ring, but A ² and A ³ do not form a ring.

D is a carbon atom or a silicon atom, preferably a carbon atom.
j is an integer of 0 to 2, and 0 or 1 is preferable.
T is a carbon atom, a nitrogen atom or a phosphorus atom, preferably a nitrogen atom or a phosphorus atom.

G is an atom selected from the group consisting of an oxygen atom, a nitrogen atom having a substituent, and a phosphorus atom having a substituent, and is an atom that is σ-bonded or σ-coordinated with Ni. Specifically, an oxygen atom, PR ² R ³ , NR ² , NR ² R ³ (wherein R ² and R ³ represent an alkyl group which may have a C1-C8 substituent). Either. Among these, NR ² , NR ² R ³ and oxygen atoms are preferable, and oxygen atoms are more preferable. In the case of an oxygen atom or NR ² , Ni and σ bond, and in the case of PR ² R ³ and NR ² R ³ , Ni and σ are coordinated.

  Furthermore, as the nickel metal complex represented by the above formula (2), one represented by the following general formula (3) is more preferable.

[In the formula (3), R ¹ represents a hydrocarbon group, a silicon-containing hydrocarbon group, a halogenated hydrocarbon group, an oxygen-containing hydrocarbon group or a nitrogen-containing hydrocarbon group, and Ar ¹ and Ar ² are each independently An aromatic hydrocarbon group which may have a substituent, X represents a ligand which forms a σ bond with Ni, m represents an integer of 1 to 4, Y represents a Lewis base, , Ni represents a ligand coordinated by a lone electron pair, and n represents an integer of 1 to 4. ]

That is, in the metal complex represented by the formula (3), in the formula (2), L is a nitrogen-oxygen combination of coordinating atoms, a coordination form is a σ coordination-σ bond, and R ¹ , Ar ¹ and Ar ² are bidentate ligands having a specific structure, and X and Y are synonymous with the formula (1), and m and n are 1 compounds.

Here, in the formula (3), R ¹ represents a hydrocarbon group, a silicon-containing hydrocarbon group, a halogenated hydrocarbon group, an oxygen-containing hydrocarbon group or a nitrogen-containing hydrocarbon group, preferably a hydrocarbon group, The carbon number is 1-12 normally, Preferably it is 1-10, More preferably, it is 1-8.

  Among them, a methyl group, i-propyl group, i-butyl group, t-butyl group, cyclohexyl group, phenyl group, methylphenyl group, and methoxyphenyl group are preferable, and a methyl group, i-propyl group, i-butyl group are preferable. More preferably a group, a cyclohexyl group, or a phenyl group.

Ar ¹ and Ar ² are each independently an aromatic hydrocarbon group which may have a substituent, and usually an aromatic hydrocarbon group which affects the ligand field of Ni. It is. (Here, the substituent that may have is preferably a substituent having a halogen atom or an oxygen atom.)

Among them, particularly preferred groups as Ar ¹ and Ar ^{2 are} as follows.
Phenyl group, pentafluorophenyl group, 2-methylphenyl group, 2-i-propylphenyl group, 2-i-butylphenyl group, 2-t-butylphenyl group, 2-cyclohexylphenyl group, 2-benzylphenyl group, 2-diphenyl group, 2- (1-naphthyl) phenyl group, 2- (2-naphthyl) phenyl group, 2-methoxyphenyl group, 2-phenoxyphenyl group, 2- (methoxyphenyl) phenyl group, 2- (furyl) ) Phenyl group, 2,6-dimethylphenyl group, 2,6-di-i-propylphenyl group, 2,6-di-i-butylphenyl group, 2,6-dicyclohexylphenyl group, 2,6-triphenyl Group, 2,6-dimethoxyphenyl group, 2,6-bis (phenoxy) phenyl group, 2,6-bis (methoxyphenyl) phenyl group, 2,6- Scan (furyl) phenyl group.

Among these compounds, the following complex 2 in which R is a methyl group, Ar ¹ and Ar ² are 2,6-diisopropylphenyl groups, X is a benzyl group, and Y is 2,6-lutidine is particularly preferable.

The metal complex represented by the formula (2) detailed above is a compound known per se. For example, the metal complex represented by the formula (3) can be produced, for example, according to the method described in Organometallics, 2007, 26, pp. 5329.
Hereinafter, the manufacturing method of the metal complex represented by Formula (3) is demonstrated as a specific example of the manufacturing method of the metal complex represented by Formula (2).

The metal complex represented by the formula (3) is a metal salt formed by the reaction of an iminoamide ligand represented by the following general formula (6) and a metal hydride compound (potassium hydride and sodium hydride). It can manufacture by making it react with the precursor of the nickel metal complex made into.
Wherein (6), R ^1, Ar ^1, and Ar ² is as defined in the above formula (3). ]

  Here, the precursor of the nickel metal complex (hereinafter sometimes simply referred to as “precursor”) can be synthesized from a raw material of a general organic or inorganic salt of nickel or a complex.

  As these raw materials, for example, nickel chloride, nickel bromide, di (π-allyl) dinickel dibromide, bis (π-allyl) nickel, bis (cyclooctadienyl) nickel are preferable, and di (π More preferred are -allyl) dinickel, bis (π-allyl) nickel, and bis (cyclooctadienyl) nickel.

The precursor is usually obtained by mixing the Ni compound, the compound X—R ″, and Y. Here, X and Y have the same meaning as in the above formula (2).
The X—R ″ compound is a compound that oxidatively adds to a nickel compound, and R ″ is a chlorine atom, a bromine atom, an iodine atom, a triflate, or the like.

  X—R ″ is preferably, for example, methyl iodide, methyl bromide, phenyl iodide, phenyl bromide, phenyl triflate, benzyl iodide, benzyl bromide, benzyl chloride, methyl iodide, methyl bromide, iodide. Phenyl, phenyl bromide, benzyl iodide, benzyl bromide and benzyl chloride are more preferred, and benzyl iodide, benzyl bromide and benzyl chloride are particularly preferred.

  The mixing method of the Ni compound and the compounds XR "and Y is not particularly limited. Usually, a solution of the mixture of XR" and Y (may be solvent-free) is changed to a solution of Ni compound (may be solvent-free). What is necessary is just to add. The ratio (mol / mol) of X—R ″ and Ni compound is usually 1 equivalent or more, preferably 1.01 equivalent or more, more preferably 1.1 equivalent or more, and usually 5 equivalents or less, preferably 3 equivalents or less. More preferably, it is 2 equivalents or less.

  The ratio of Y to Ni compound (mol / mol) is usually 2 equivalents or more, preferably 3 equivalents or more, more preferably 4 equivalents or more, and usually 50 equivalents or less, preferably 40 equivalents or less, more preferably 30 equivalents or less. It is.

  Although the solvent to be used is not particularly limited, for example, aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as chloroform, methylene chloride, carbon tetrachloride, tetrachloroethane, chlorobenzene and o-dichlorobenzene; n -Polar solvents such as butyl acetate, methyl isobutyl ketone, tetrahydrofuran, and cyclohexanone.

  The concentration of the precursor raw material compound is not particularly limited, but is usually 100 g or less, preferably 50 g or less, more preferably 25 g or less, and usually 0.0001 g or more, preferably 0.01 g or more, with respect to 1 L of the reaction solution. More preferably, it is 1 g or more.

  There is no particular limitation on the reaction method of the metal salt and the precursor, but the metal salt may be added to the reaction solution in which the precursor was manufactured, or the reaction is performed by mixing all the raw materials for manufacturing the precursor and the metal salt. However, it is preferable to add a metal salt to the reaction solution in which the precursor has been produced.

There are no particular restrictions on the reaction temperature, reaction pressure, and reaction time during the production of the precursor and the metal complex (when the metal salt and the precursor are reacted). The optimum setting may be made in consideration of the ability.
That is, the reaction temperature is usually −80 ° C. or higher, preferably −10 ° C. or higher, more preferably 0 ° C. or higher, and usually 100 ° C. or lower, preferably 90 ° C. or lower. The reaction pressure is usually normal pressure, and may be slightly pressurized or slightly reduced pressure. The reaction time is usually 1 minute or more, preferably 2 minutes or more, more preferably 3 minutes or more, and is usually 100 hours or less, preferably 70 hours or less, more preferably 50 hours or less.

  The metal complex thus produced can be added to the polymerization reaction system and used as a reaction catalyst.

[1-3-2] Polymerization Reaction Method In the production of the copolymer [Compatibilizer (C)], there is no particular limitation on the polymerization reaction mode, and a polymerization method known per se, for example, batch (batch) polymerization. The polymerization can be carried out by any method of continuous polymerization.

  The polymerization reaction may or may not use a solvent. Specific examples of the solvent include hydrocarbons such as n-pentane, n-hexane, n-heptane, n-octane, n-decane, benzene, toluene, xylene, cyclohexane, methylcyclohexane, dimethylcyclohexane, chloroform, Halogenated hydrocarbons such as methylene chloride, carbon tetrachloride, tetrachloroethane, chlorobenzene and o-dichlorobenzene; polar solvents such as n-butyl acetate, methyl isobutyl ketone, tetrahydrofuran, cyclohexanone and dimethyl sulfoxide. Of these, hydrocarbons are preferred. Moreover, you may use these mixtures as a solvent.

  The nickel metal complex catalyst is applied not only to solution (suspension) polymerization using a solvent, but also to liquid-phase solventless polymerization and gas phase polymerization that do not substantially use a solvent.

  Mixing of each of the above catalyst components is carried out in the reactor used for copolymerization of the α-olefin monomer and the compound represented by the general formula (1) (functional group-containing monomer having a norbornene skeleton). The reaction may be performed under or in the absence of the reaction, or may be performed in a container separate from the reactor.

  There are no particular restrictions on the supply of catalyst and monomer to the polymerization reactor, and various supply methods can be used depending on the purpose. For example, in the case of batch polymerization, it is possible to take a technique in which a predetermined amount of monomer is supplied to a polymerization reactor in advance and a catalyst is supplied thereto. In this case, an additional monomer or an additional catalyst may be supplied to the polymerization reactor. In the case of continuous polymerization, a method can be used in which a predetermined amount of monomer and catalyst are continuously or intermittently supplied to the polymerization reactor to continuously carry out the polymerization reaction.

  Regarding the control of the copolymer composition, a method of controlling a copolymer by supplying a plurality of monomers to a reactor and changing the supply ratio thereof can be generally used. Other methods include controlling the copolymer composition using the difference in monomer reactivity ratio due to the difference in catalyst structure, and controlling the copolymer composition using the polymerization temperature dependence of the monomer reactivity ratio. .

  In the method of supplying two types of monomers to the polymerization reactor in advance and supplying the catalyst thereto, a copolymer in which the two types of monomers are randomly introduced (random copolymer) is produced. On the other hand, first, one type of monomer and catalyst are supplied to the reactor and homopolymerization is performed for a predetermined time, and then another type of monomer is additionally supplied and copolymerization is performed for a predetermined time. An AB block copolymer having segments of the polymer (A) and the random polymer (B) can be produced.

  A conventionally known method can be used for controlling the molecular weight of the polymer. That is, a method for controlling the molecular weight by controlling the polymerization temperature, a method for controlling the molecular weight by controlling the monomer concentration, a method for controlling the molecular weight by using a chain transfer agent, and a molecular weight by controlling the ligand structure in the transition metal complex. The method etc. which control are mentioned. When a chain transfer agent is used, a conventionally known chain transfer agent can be used. For example, hydrogen, metal alkyl, etc. can be used.

The polymerization temperature, polymerization pressure, and polymerization time are not particularly limited, but usually, optimum settings can be made in consideration of productivity and process capability from the following ranges.
That is, the polymerization temperature is usually 0 ° C. or higher, preferably 10 ° C. or higher, more preferably 20 ° C. or higher, and is usually 150 ° C. or lower, preferably 120 ° C. or lower. The polymerization pressure is usually 0.01 MPa or more, preferably 0.05 MPa or more, particularly preferably 0.1 MPa or more, and is usually 100 MPa or less, preferably 20 MPa or less, particularly preferably 7 MPa or less. The polymerization time is usually 0.1 hours or more, preferably 0.2 hours or more, particularly preferably 0.3 hours or more, usually 30 hours or less, preferably 25 hours or less, more preferably 20 hours or less, particularly preferably. Is 15 hours or less.

The post-treatment method after the completion of the polymerization reaction is not particularly limited, but usually the solvent when unreacted monomer or solvent is used is separated from the produced copolymer. The separated unreacted monomer and solvent may be recycled and used, and at the time of recycling, these monomers and solvent may be purified and reused, or may be reused without purification. . A conventionally known method can be used to separate the produced copolymer from the unreacted monomer and the solvent. For example, methods such as filtration, centrifugation, solvent extraction, and reprecipitation using a poor solvent can be used. A method by filtration is preferred.
The copolymer thus obtained can be suitably used as a compatibilizing agent (C) for a thermoplastic resin, as will be described later.

[1-4] Properties and Reactivity of Copolymer [Compatibilizer (C)] The molecular weight of the copolymer is not particularly limited, but when used as a compatibilizer (C) for a thermoplastic resin. In consideration of reactivity, moldability, etc., it is necessary to use those having an appropriate molecular weight according to the physical properties of the thermoplastic resin used as the composition. For this reason, the preferable range of molecular weight is 500-1,000,000 normally as a weight average molecular weight (Mw), Preferably it is 1,000-500,000, More preferably, it is 10,000-300,000. If it is less than 500, physical properties such as impact resistance and heat resistance tend to be lowered, and if it exceeds 1,000,000, compatibility tends to be poor.
The preferred range of molecular weight is the same for both random copolymers and block copolymers.

  There is no particular limitation on the molecular weight distribution, but when used as a compatibilizer (C) for thermoplastic resins, it is appropriate depending on the properties of the thermoplastic resin used as the composition in consideration of reactivity and moldability. It is necessary to use one having a molecular weight distribution. For this reason, the preferable range of molecular weight distribution is the ratio (Mw / Mn) of a weight average molecular weight (Mw) and a number average molecular weight (Mn), and is 1-10 normally, More preferably, it is 1-5. If the molecular weight distribution is too small, the melt viscosity according to the molecular weight is high, so that the moldability tends to be poor. If it is too large, the reactivity of the copolymer can be uneven and the compatibility tends to be poor.

  In the copolymer, the content of the structural unit derived from the compound represented by the general formula (1) (functional group-containing monomer having a norbornene skeleton) is preferably 0.01 to 10 mol%, more preferably 0.8. 1 to 5 mol%. When the content is less than 0.01 mol%, when used as a compatibilizing agent for thermoplastic resins, the transesterification or amide exchange reactivity is poor. When the content exceeds 10 mol%, the dispersibility decreases, and the resin composition contains There is a tendency that the copolymer [compatibilizer (C)] is dispersed as a lump.

  The copolymer [compatibilizer (C)] and a thermoplastic resin (B) having a polar group used in the resin composition of the present invention described later (hereinafter sometimes referred to as “component (B)”). By melting and mixing at a high temperature, the functional group (for example, hydroxyl group) in the compatibilizing agent (C) reacts with the linking group (for example, carbonate bond) in the component (B) even under solvent-free conditions, and nucleophilic substitution reaction It is considered that (C) component and (B) component form a chemical bond. That is, the compatibilizer (C) is a reactive compatibilizer for the polyolefin resin (A) used in the resin composition of the present invention (hereinafter sometimes referred to as “component (A)”) and component (B). It is considered that it can function and thereby exhibit excellent compatibility.

[1-5] Method for Quantifying Functional Group-Containing Monomer Having Norbornene Skeleton The measurement of the structural unit derived from the compound represented by the general formula (1) (functional group-containing monomer having a norbornene skeleton) in the copolymer is as follows. It can carry out by a method known per se using NMR or IR. For example, taking 5-norbornen-2-ol as an example, the quantitative method is as follows.

  The structure and assignment number are shown in [Chemical Formula 7], and the range of chemical shift derived from each hydrogen is shown in Table 1. The chemical shift of the peak derived from each structure varies somewhat depending on the NMR measurement conditions, and the peak is not necessarily a single peak, but a complex split pattern based on a fine structure (split pattern). ) Must be noted, and attribution should be made.

  The signal of the 5-norbornen-2-ol unit was detected at 4.1 ppm (H25) for the endo isomer and 3.7 ppm (H15) for the exo isomer, confirming the presence of the comonomer. From the integration ratio, the comonomer content when the total polymer amount was 100 mol% was calculated by the following formula.

exo-NBOH content: X _exo = 4 × I _b / (I _a -8 × (I _b + I _c )) × 100
endo-NBOH content: X _endo = 4 × I _c / (I _a -8 × (I _b + I _c )) × 100
NBOH content: X _NBOH = X _exo + X _endo
(In the above formula, I _a means an integral value of the chemical shift range a.)

[2] Resin Composition The resin composition of the present invention comprises a polyolefin resin (A) [component (A)], a thermoplastic resin having a polar group (B) [component (B)], and a compatibilizer (C ) [Contains units derived from at least three components of component (C)]. Next, the resin composition of the present invention will be described in more detail.

[2-1] Polyolefin resin (A)
The polyolefin resin as the component (A) is an olefin polymer having a monomer having an addition polymerizable double bond as a main structural unit. Examples of the monomer having an addition polymerizable double bond include olefins, diolefins, cyclic olefins, and alkenyl aromatic hydrocarbons. Examples of such monomers include the following compounds.

Ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, vinylcyclohexane Olefins such as;

1,5-hexadiene, 1,4-hexadiene, 1,4-pentadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 4-methyl-1,4-hexadiene, 5-methyl- 1,4-hexadiene, 7-methyl-1,6-octadiene, 5-ethylidene-2-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene, 5-methyl-2-norbornene, norbornadiene, 5-methylene- Diolefins such as 2-norbornene, 1,5-cyclooctadiene, 1,3-butadiene, isoprene, 1,3-hexadiene, 1,3-octadiene, 1,3-cyclooctadiene, 1,3-cyclohexadiene ;

Norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-butylnorbornene, 5-phenylnorbornene, 5-benzylnorbornene, tetracyclododecene, tricyclodecene, tricycloundecene, pentacyclopentadecene, pentacyclohexadecene, Cyclic olefins such as 8-methyltetracyclododecene, 8-ethyltetracyclododecene, 8-methyl-8-tetracyclododecene;

Alkenylbenzene (styrene, 2-phenylpropylene, 2-phenylbutene, 3-phenylpropylene, etc.), alkylstyrene (p-methylstyrene, m-methylstyrene, o-methylstyrene, p-ethylstyrene, m-ethylstyrene, o-ethylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,4-dimethylstyrene, 3,5-dimethylstyrene, 3-methyl-5-ethylstyrene, p-tertiary butylstyrene, alkenyl aromatic hydrocarbons such as p-secondary butyl styrene), bisalkenylbenzene (divinylbenzene, etc.), alkenylnaphthalene (1-vinylnaphthalene, etc.), and the like.

  These monomers may be used in homopolymerization or as copolymerization. Among these, an ethylene homopolymer, a propylene homopolymer, a copolymer of ethylene and an α-olefin other than ethylene, or a mixture thereof is preferably used.

  When applied to industrial parts, generally, an ethylene homopolymer, a propylene homopolymer, an ethylene / propylene block copolymer, and an ethylene / propylene random copolymer are suitably used. Polymer and propylene homopolymer.

  The melt flow rate (MFR) of the olefin polymer is not particularly limited, and a suitable MFR ethylene homopolymer or propylene homopolymer can be used depending on the purpose. However, considering the balance between moldability and physical properties, the MFR is usually 0.01 (g / 10 min) or more, preferably 0.1 (g / 10 min) or more, and usually 1000 (g / 10 min) or less, preferably Is 100 (g / 10 min) or less, more preferably 50 (g / 10 min) or less. If the MFR is less than 0.01 (g / 10 min), the moldability of the resin composition is inferior, and if it exceeds 1000 (g / 10 min), the heat resistance and mechanical properties may be inferior.

  The structure of the olefin polymer, for example, stereoregularity, molecular weight, molecular weight distribution, etc. is not particularly limited, and those having a necessary structure can be used according to the purpose.

[2-2] Thermoplastic resin having a polar group (B)
As the thermoplastic resin having a polar group (B), it can undergo transesterification or transamidation with the substituent X in the compatibilizer (C) derived from the compound represented by the general formula (1). A polycondensation resin having at least one bond such as an amide bond, a carbonate bond or an ester bond as a linking group is preferred. Specific examples include polyester resins, polyamide resins, polyether resins, polycarbonate resins, and block copolymers thereof. Of these, polycarbonate resins are particularly preferred.

  More specifically, examples of the polyester resin in the component (B) include aromatic ring-containing polyesters and aliphatic polyesters. Here, examples of the aromatic ring-containing polyester include polyalkylene (C2-24) terephthalate such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT); polyalkylene such as polyethylene isophthalate and polybutylene isophthalate (C2 24) Isophthalate: poly-p-phenylene malonate, poly-p-phenylene adipate, poly-p-phenylene ester such as poly-p-phenylene terephthalate, and the like. Examples of the aliphatic polyester include polybutylene adipate and polyethylene. Examples include adipate, poly-ε-caprolactone, and polylactic acid.

  Examples of polyamide resins include polycapramide (6-nylon), polyhexamethylene adipamide (6,6-nylon), polyhexamethylene sebacamide (6,10-nylon), polyundecanamide (11-nylon), poly -Ω-aminoheptanoic acid (7-nylon), poly-ω-aminononanoic acid (9-nylon), and the like.

  Examples of the polyether resin include polyoxymethylene, polyoxyethylene, polyoxyphenylene (PPO), and poly-1,3-dioxolane.

  These resins are generally known per se and can be purchased and used as necessary.

  In the resin composition of the present invention, the polycarbonate resin preferably used as the component (B) is a phosgene method in which various dihydroxydiaryl compounds and phosgene are reacted, or an ester in which a dihydroxydiaryl compound is reacted with a carbonate such as diphenyl carbonate. A polymer or copolymer obtained by an exchange method or the like. Among these, a representative example is an aromatic polycarbonate resin produced from 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) and phosgene.

  Examples of the dihydroxydiaryl compound as the raw material include, in addition to bisphenol A, the following compounds.

Bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, bis ( 4-hydroxyphenyl) phenylmethane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxy-3-tert-butylphenyl) propane, 2,2-bis ( Bis such as 4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane (Hydroxyaryl) alkanes;

Bis (hydroxyaryl) cycloalkanes such as 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane;
Dihydroxy diaryl ethers such as 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3′-dimethyldiphenyl ether;

Dihydroxyaryl sulfides such as 4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfide;
Dihydroxydiaryl sulfoxides such as 4,4′-dihydroxydiphenyl sulfoxide, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfoxide;
Dihydroxydiaryl sulfones such as 4,4′-dihydroxydiphenylsulfone, 4,4′-dihydroxy-3,3′-dimethyldiphenylsulfone, and the like;

  These compounds are used alone or in combination of two or more in the production of polycarbonate resin. In addition to these, piperazine, dipiperidyl hydroquinone, resorcin, and 4,4′-dihydroxydiphenyls are used in combination. May be.

  The molecular weight of the polycarbonate resin used in the present invention is usually 10,000 to 50,000 from the viewpoint of mechanical strength and fluidity (ease of moldability) as a viscosity average molecular weight (Mv) converted from the solution viscosity. Preferably it is 12,000-40,000, More preferably, it is 14,000-35,000, Most preferably, it is 16,000-32,000. Two or more types of polycarbonate resins having different viscosity average molecular weights may be mixed to adjust the viscosity average molecular weight. Moreover, you may mix and use the polycarbonate resin whose viscosity average molecular weight is outside said suitable range as needed.

[2-3] Compatibilizer (C)
Component (C) is the above-described copolymer. The compatibilizer preferable as the component (C) is the same as the preferable copolymer described above.

[2-4] Other components In addition to the above-described components, other components may be blended in the resin composition of the present invention as necessary within a range not impairing the effects of the present invention. Examples of such components include compatibilizers other than the compatibilizer (C), pigments for coloring, phenol-based, sulfur-based, phosphorous-based antioxidants; anti-static agents, hindered amines, and other light-stabilizing agents. Agents, ultraviolet absorbers, various nucleating agents such as organic aluminum and talc, dispersants, neutralizing agents, foaming agents, copper damage prevention agents, lubricants, flame retardants and the like.

[2-5] Blending ratio of each component, content in the resin composition There is no particular limitation on the blending ratio of the component (A) and the component (B), and the preferred range varies depending on the use of the resulting resin composition. The blending ratio of the component (A) and the component (B) is usually 1/99 to 99/1, preferably 5/95 to 90/10, more preferably (A) / (B) (weight ratio). Is 10/90 to 70/30.

  Moreover, there is no restriction | limiting in particular also in the compounding quantity of (C) component, Preferably it is 0.01-30 weight part with respect to the total amount of (A) component and (B) component, More preferably, it is 0.1-20. Part by weight, particularly preferably 1 to 10 parts by weight. When the blending ratio is less than 0.01 parts by weight, the compatibility tends to be inferior, and when it exceeds 30 parts by weight, physical properties such as impact resistance and heat resistance tend to be lowered.

  The compatibilizer (C) used in the resin composition of the present invention is capable of transesterification or amide exchange reaction with the thermoplastic resin (B) having a polar group, as described above. Then, there exists a possibility that it exists in a chemical bond with the thermoplastic resin (B). In the present specification, the content of units derived from each component means the total amount of the components reacted with the unreacted components present in the resin composition, and the amount of each component is as described above. The same as the blending amount (ratio).

[2-6] Manufacturing method of resin composition There is no restriction | limiting in particular in the manufacturing method of the resin composition of this invention, It can manufacture by a method known per se. That is, it can manufacture by melt-kneading each component mentioned above with a suitable apparatus so that it may become a composition according to the use of a resin composition.

  What is necessary is just to mix | blend each component with arbitrary forms according to the physical property as needed. For example, it may be blended as a solid, as a solution dissolved in a solvent, or as a slurry dispersed in a solvent.

  Examples of the melt kneader include those usually used for producing a resin composition such as a single screw extruder, a twin screw extruder, a Banbury mixer, a roll mixer, a Brabender plastograph, and a kneader.

  In the melt-kneading, it is preferable to select a kneading method capable of improving the dispersion of each component, and it is usually preferable to use a twin screw extruder or a Brabender plastograph. In the kneading using these devices, the blend of each component may be kneaded simultaneously, or each component may be divided and kneaded. By adopting the latter method in particular, the performance of the resin composition is greatly improved. Specifically, it is preferable to first knead a part or all of the compatibilizer (C) and a thermoplastic resin (B) having a polar group, for example, a polycarbonate resin, and then knead the remaining components. It is. The minimum amount of the compatibilizing agent (C) to be first kneaded may be about 0.01 part with respect to the total amount.

  Furthermore, in the present invention, a thermoplastic resin (B) having a polar group, for example, a polyolefin resin (A) is finely dispersed in a polycarbonate resin matrix, and a molded product having both good appearance and high solvent resistance and impact resistance is obtained. Preferable kneading conditions for obtaining differ depending on the physical properties of the thermoplastic resin (B) and polyolefin resin (A) having a polar group to be used, the blending ratio thereof, the presence or absence of other additives, etc. For example, the following conditions may be adopted.

  That is, for example, when producing a polycarbonate / polyethylene composite resin composition (molded article), as described above, the blended and blended composition is kneaded at a cylinder temperature of 200 to 300 ° C. and a screw rotation speed of 80 to 400 rpm. At this time, the polycarbonate, the compatibilizer (C), and the polyolefin may be supplied together and kneaded. However, when kneading is performed in a batch supply, the compatibilizing agent (C) is taken into the polyolefin with high affinity, and the transesterification reaction with the polycarbonate hardly proceeds, so that it is difficult to work as a compatibilizing agent. Therefore, more preferably, by using a multi-stage kneading method or a side feed method, the polycarbonate and the compatibilizing agent (C) are kneaded first, the polyolefin is added after the transesterification reaction proceeds, and further kneading is added. If the method of extruding later is used, the compatibilizing effect will be higher. The extruded strand is cooled, cut and pelletized.

  When kneading, the screw rotation speed and the discharge amount are balanced, the resin pressure in the die is set to about 2 to 40 MPa, and extrusion is performed while applying the resin pressure to a constant value, and the polyolefin component in the polycarbonate resin is effectively applied. The dispersibility of is improved. Even if kneading is performed without filling the cylinder with a resin, sufficient shear stress is not applied, and the dispersibility of the polyolefin component does not increase, so that a large domain is likely to be formed.

[3] Molded Product The resin composition of the present invention can be molded by various methods known per se to obtain molded products for various uses. Examples of the molding method include injection molding (including gas injection molding), injection compression molding (press injection), extrusion molding, hollow molding, calender molding, inflation molding, uniaxially stretched film molding, biaxially stretched film molding, and the like. It is. Of these, injection molding and injection compression molding are more preferable.

  Since the resin composition and the molded product of the present invention are excellent in mechanical strength, organic solvent resistance and appearance, they can be used for various applications. Specific applications include, for example, automobile parts, home appliance parts, packaging materials, building materials, agricultural materials, civil engineering materials, fibers, filter media, fishery materials, sanitary / medical materials, and other industrial materials. Can be mentioned. More specifically, examples include automobile skin parts, automobile interior parts, automobile engine peripheral parts, home appliance casings, electrical equipment parts, trays, bottles, cushioning foams, fish boxes, agricultural materials, medical equipment, and the like. .

  EXAMPLES Next, although an Example demonstrates this invention further more concretely, this invention will not be restrict | limited by these Examples, unless it deviates from the summary.

Various physical properties in the following examples were measured according to the following procedures.
(1) NMR measurement Using an Inova 500 spectrometer manufactured by Varian, measurement was performed by the following method.
Samples 10 to 100 mg are completely dissolved at 130 ° C. using 0.55 ml of orthodichlorobenzene in a 5 mm diameter NMR sample tube. Next, 0.1 ml of deuterated benzene is added as a lock solvent and homogenized, and then measured at 130 ° C.

(2) Differential scanning calorimetry (DSC)
Measurement was carried out by the following method using a thermal analysis system TA2000 manufactured by DuPont.
A sample (about 5 to 10 mg) is melted at 200 ° C. for 5 minutes, cooled to 20 ° C. at a rate of 10 ° C./min, held at the same temperature for 5 minutes, and then heated to 200 ° C. at 10 ° C./min. Thus, a melting curve was obtained, and the peak top temperature of the main endothermic peak in the final temperature rising stage was determined as the melting point. The amount of heat of fusion was determined from the area of the region surrounded by this main endothermic peak and the baseline. By the way, when the amount of heat of fusion is small, it may be difficult to distinguish between baseline fluctuations and true endothermic peaks. In this case, it is confirmed whether or not there is an exothermic peak due to crystallization in the temperature lowering process described above, and this corresponds to the endothermic peak. If there is a corresponding exothermic peak, it is determined that there is a true endothermic peak based on crystal melting, and if not, it is determined that there is a baseline variation.

(3) Melt flow rate (MFR)
Polyethylene was performed in accordance with JIS K6922-2 at 190 ° C. and a load of 2.16 kg.
The polycarbonate was formed according to ISO 1133 at 300 ° C. and 1.2 kg load.

(4) Gel filtration chromatography (GPC)
Measurement was performed under the following conditions.
Apparatus: GPCV 2000 manufactured by Waters
Column temperature: 135 ° C
Solvent: o-dichlorobenzene Flow rate: 1.0 ml / min
Column: TSKgel GMH-HT (30 cm × 4, column diameter 7.8 mm) manufactured by Tosoh Corporation
Injection volume: 0.5 ml (after filtration)
Solution concentration: 0.1 wt%
Sample preparation: The sample was dissolved in ODCB added with BHT (0.5 g / L) in a high-temperature GPC pretreatment device PL-SP 260VS (dissolution temperature 135 ° C.) and measured after filtration with a glass filter (hole diameter 1 μm).
Calibration curve: A polystyrene standard sample (trade name: TSK standard polystyrene, Mw (weight average molecular weight) / Mn (number average molecular weight) <1.2) manufactured by Tosoh Corporation is used.
Calibration curve order: 3rd order

(5) Appearance evaluation (5-1) Without additive (coloring material) Appearance of tensile test specimens (thickness 0.2 mm) is evaluated in the following three stages centering on delamination did.
○: Smooth and uniform overall.
Δ: Some unevenness.
X: Unevenness is severe, and in some cases, streaks and cracks are observed.

(5-2) When additive (coloring material) is present The appearance of the test piece was visually observed, and the blackness was evaluated in the following three stages.
○: Almost good overall black.
Δ: Overall whitening slightly.
X: Significant whitening is observed as a whole.

(6) Dispersion particle diameter In order to quantitatively analyze the dispersion state of the matrix and the domain, the domain dispersion particle diameter was measured by image analysis based on the dispersion form photograph image of the cross section of the molded product.
The image stored in the electronic file was input and used as the original image. Binarization (automatic threshold or manual) was performed with Image-Pro Plus to extract particles having a diameter of 0.01 μm or more, and then the overlapping particles were separated by manual processing. Area, size (length), and size (width) were measured and saved in an Excel file. The size (length) represents the maximum length projected in the major axis direction of the approximate ellipse, and the size (width) represents the maximum length projected in the minor axis direction of the approximate ellipse. The equivalent area circle diameter was calculated from the area measured with Excel, and the average value was output. The range of the minimum value and the maximum value of the equal area circle diameter is described.

(7) Matrix components Based on the photographic image of the dispersed form of the cross-section of the molded product, the resin phase surrounding the domain was judged as a matrix.

(8) Tensile test Based on JIS-K7113, it carried out as follows.
Measurement is performed at 23 ° C. and a relative humidity of 55% using Tensilon STA-1225 manufactured by A & D. The test speed is 50 mm / min, and the test piece is compliant with JIS-K7113 type 2 test piece having a thickness of 0.2 mm.
The method for preparing the test piece is as follows.
Using a test press (manufactured by Ueshima Seisakusho) and a metal spacer (thickness 0.2 mm), 3.2 g of the resin composition was preheated at 220 ° C. for 3 minutes, degassed for 1 minute, and pressurized (50 kg / cm ² ). Perform for 1 minute to create a 0.2 mm thick sheet. From the obtained sheet, a test piece conforming to JIS-K7113, No. 2 type test piece is prepared using a dumbbell punching machine.

<Preparation of complex>
Complex 1, Complex 2, and Ni (COD) ₂ (COD: cyclooctadiene) used in the following production examples have the structure shown in [Chemical Formula 8].

  The above complex 1 and complex 2 were synthesized as follows according to the methods described in the literature listed in the section of the method for producing a copolymer [compatibilizer (C)]. The synthesis process was carried out under a purified nitrogen atmosphere using a standard glove box and Schlenk technology, and THF dried with Na-benzophenone was used. Toluene and n-hexane were dehydrated solvents purchased from Kanto Chemical.

Synthesis Example 1: N- (2,6-diisopropylphenyl) -2- (2,6-diisopropylphenylimino) propaneamidate-κ ² N, O) (η ¹ -benzyl) (trimethylphosphine) nickel (complex Synthesis of 1) (1) Synthesis of sodium salt of ligand N- (2,6-diisopropylphenyl) -2- (2,6-diisopropylphenylimino) propanamide (1.5 g, 3.69 mmol) and hydrogen A suspension of sodium chloride (0.13 g, 5.45 mmol) in THF (40 mL) was stirred at 40 ° C. for 1 hour, and then stirred at room temperature for 3 hours. Then, the solvent of the filtrate obtained by filtration was distilled off to obtain a sodium salt of the ligand (1.58 g, 100% yield).

(2) Synthesis of complex The sodium salt of the ligand obtained in (1) was dissolved in toluene (40 mL). A solution of nickel (η ³ -benzyl) chloro (trimethylphosphine) (1.25 g, 3.69 mmol) in toluene (10 mL) was added dropwise at room temperature, stirred for 2.5 hours, and filtered to remove the by-product salt. It was. The solvent was distilled off until the liquid volume of the filtrate reached 5 mL, 20 mL of hexane was added, and recrystallization was performed at −30 ° C. The resulting complex was washed with hexane (4 mL × 2) to obtain the title complex (0.93 g, 40% yield) as a red powder.

Synthesis Example 2: N- (2,6-diisopropylphenyl) -2- (2,6-diisopropylphenylimino) propaneamidate-κ ² N, O) (η ¹ -benzyl) (2,6-lutidine) nickel Synthesis of (complex 2) (1) Synthesis of sodium salt of ligand N- (2,6-diisopropylphenyl) -2- (2,6-diisopropylphenylimino) propanamide (7.18 g, 17.8 mmol) And a suspension of sodium hydride (0.63 g, 26.3 mmol) in THF (86 mL) was stirred at 40 ° C. for 1 hour, and then stirred at room temperature for 3 hours.

(2) Synthesis of complex Ni (COD) ₂ (4.87 g, 17.7 mmol) in THF (220 mL) was added to benzyl chloride (2.2 mL, 19.1 mmol) and 2,6-lutidine (7.0 mL, A solution of 53.1 mmol) in THF (20 mL) was added at room temperature. After stirring at room temperature for 5 minutes, a THF solution of the sodium salt of the ligand synthesized in (1) (the filtrate of (1)) was added dropwise to the mixture at room temperature, and the mixture was stirred overnight at the same temperature. After THF was completely distilled off, the target complex was extracted with toluene to remove by-produced salts, the solvent was distilled off, and the crude complex was washed with hexane (20 mL × 3). The purification process shown below was repeated three times to give the title complex (3.83 g, 32% yield) as an orange powder. Purification step: Toluene / hexane (30/30 mL) extraction twice, solvent distillation, hexane washing (30 mL × 3).

<Production of Copolymer [Compatibilizer (C)]>
Using the complexes 1 and 2 prepared in Synthesis Examples 1 and 2 as catalysts, the compatibilizer (C) was produced as follows. All of the polymerization steps were performed under a purified nitrogen atmosphere, and the solvent was dehydrated with molecular sieve (MS-4A) and then degassed by bubbling with purified nitrogen. 5-norbornen-2-ol was used after sublimation purification or recrystallization purification of a commercial product which was an endo / exo isomer mixture.

Production Example 1: Production of ethylene / 5-norbornen-2-ol copolymer (Copolymer 1) To a 1 L-autoclave that had been dried and purged with nitrogen, a toluene solution of Complex 1 (40 μmol; 25.3 mg of Complex 1) and 5mL solution dissolved in toluene), Ni; with a solution (COD) ₂ in toluene (100 [mu] mol Ni (COD of 27.5 mg) ₂ was dissolved in toluene 10 mL), 5-norbornene-2-ol Toluene solution (9 mmol; 991 mg of 5-norbornen-2-ol dissolved in 5 mL of toluene) and an amount of toluene in which the total volume of the toluene solution was 60 mL were added.

  After replacing the autoclave with ethylene (0.2 MPaG x 2 times), when ethylene was introduced and the reactor pressure reached 3.45 MPa, the polymerization start time was taken, and ethylene was continuously supplied to keep the pressure constant. The pressurized reaction mixture was stirred at about 20 ° C. for 60 minutes. After about 60 minutes, about 5 mL of acetone was added to stop the polymerization, and after purging ethylene, the inside of the reactor was replaced with nitrogen.

  Thereafter, the autoclave was opened, and the produced polymer was recovered together with the solvent, and then acetone was added in the same amount as the solvent while stirring to form a polymer swollen in toluene. Stirring was continued for about 30 minutes, and then the polymer was removed by suction filtration. Further, washing with acetone and filtration were repeated three times. By this operation, the color of the complex disappeared from the cleaning liquid and became colorless and transparent.

The obtained polymer particles were dried at 80 ° C. for 3 hours in a vacuum dryer to obtain 2.89 g of an ethylene / 5-norbornen-2-ol copolymer (Copolymer 1). The physical properties of this copolymer 1 were as follows.
GPC analysis: M _w = 1.87 × 10 ⁵ , M _w / M _n = 1.7.
DSC analysis: T _m (1) = 95.9 ° C. (wide peak), T _m (2) = 120.5 ° C. (small peak).
¹ H-NMR analysis: hydroxyl group content is 5.0 mol%.

Production Example 2: Production of ethylene / 5-norbornen-2-ol copolymer (block copolymer) (Copolymer 2) Dry, nitrogen-substituted 1 L-autoclave body side with combustor feeder with rupturable plate to a toluene solution of complex 1; and (40 [mu] mol solution of complex 1 were dissolved in toluene 5mL of 25.3mg), Ni (COD) ₂ in toluene (100 [mu] mol; the 27.5mg of Ni (COD) 2 10mL Of toluene) and an amount of toluene so that the total volume of the toluene solution is 60 mL. Further, a toluene solution of 5-norbornen-2-ol (9 mmol; 991 mg of 5-norbornen-2-ol dissolved in 5 mL of toluene) was added to the comonomer feeder under a nitrogen stream. The autoclave charged with the raw material was cooled to near the polymerization temperature (4 ° C.), and the reactor internal temperature was stabilized at a set temperature of −1 to 2 ° C.

  After replacing the autoclave with ethylene (0.2 MPaG x 2 times), when ethylene was introduced and the reactor pressure reached 0.69 MPa, the polymerization start time was set, and ethylene was continuously supplied so that the pressure was constant. The pressurized reaction mixture was stirred at about 4 ° C. for 20 minutes. Thereafter, the catalyst feeder side was pressurized with ethylene, the rupturable plate was broken, and the comonomer was charged into the autoclave. Subsequently, the ethylene pressure was 0.69 MPa and the reactor internal temperature was about 4 ° C. for 20 minutes. After about 40 minutes from the polymerization start time, about 5 mL of acetone was added to stop the polymerization, and after purging ethylene, the inside of the reactor was replaced with nitrogen.

  Thereafter, the autoclave was opened, and the produced polymer was recovered together with the solvent, and then acetone was added in the same amount as the solvent while stirring to form a polymer swollen in toluene. Stirring was continued for about 30 minutes, and then the polymer was removed by suction filtration. Further, washing with acetone and filtration were repeated three times. By this operation, the color of the complex disappeared from the cleaning liquid and became colorless and transparent.

The obtained polymer particles were air-dried with a draft, and then dried at 80 ° C. for 3 hours in a vacuum dryer to obtain 1.6 g of an ethylene / 5-norbornen-2-ol copolymer (Copolymer 2). . The physical properties of this copolymer 2 were as follows.
GPC analysis: M _w = 5.48 × 10 ⁴ , M _w / M _n = 1.5.
DSC analysis: T _m = 127.1 ° C.
¹ H-NMR analysis: hydroxyl group content is 1.4 mol%.

Production Example 3 Production of Ethylene / 5-Norbornen-2-ol Copolymer (Copolymer 3) To a 1 L-autoclave that was dried and purged with nitrogen was added a toluene solution of complex 1 (200 μmol; 126 mg of complex 1 in 5 mL). a solution) which was dissolved in toluene, Ni; with a solution (COD) ₂ in toluene (500 [mu] mol Ni (COD of 138 mg) of ₂ were dissolved in toluene 30 mL), 5-norbornene-2-ol in toluene ( 9 mmol; 991 mg of 5-norbornen-2-ol dissolved in 5 mL of toluene) and an amount of toluene in which the total volume of the toluene solution was 300 mL was added.

  After replacing the autoclave with ethylene (0.2 MPaG x 2 times), when ethylene was introduced and the reactor pressure reached 3.45 MPa, the polymerization start time was taken, and ethylene was continuously supplied to keep the pressure constant. The pressurized reaction mixture was stirred at about 20 ° C. for 10 minutes. Ten minutes later, about 10 mL of acetone was added to stop the polymerization, and after purging ethylene, the inside of the reactor was replaced with nitrogen.

  Thereafter, the autoclave was opened, and the produced polymer was recovered together with the solvent, and then acetone was added in the same amount as the solvent while stirring to form a polymer swollen in toluene. Stirring was continued for about 30 minutes, and then the polymer was removed by suction filtration. Further, washing with acetone and filtration were repeated three times. By this operation, the color of the complex disappeared from the cleaning liquid and became colorless and transparent.

The obtained polymer particles were air-dried with a draft, and then dried at 80 ° C. for 3 hours in a vacuum dryer to obtain 12.7 g of an ethylene / 5-norbornen-2-ol copolymer (copolymer 3). . The physical properties of this copolymer 3 were as follows.
GPC analysis: M _w = 1.13 × 10 ⁵ , M _w / M _n = 1.5.
DSC analysis: T _m = 122.6 ° C.
¹ H-NMR analysis: hydroxyl group content is 0.5 mol%

Production Example 4: Production of ethylene / 5-norbornen-2-ol copolymer (copolymer 4) To a 1 L-autoclave that had been dried and purged with nitrogen, a toluene solution of complex 1 (200 μmol; 126 mg of complex 1 was added to 5 mL a solution) which was dissolved in toluene, Ni; with a solution (COD) _two of a toluene solution (500 [mu] mol Ni (COD of 138 mg) of ₂ were dissolved in toluene 30 mL), 5-norbornene 2-ol in toluene ( 9 mmol; 991 mg of 5-norbornen-2-ol dissolved in 5 mL of toluene) and an amount of toluene in which the total volume of the toluene solution was 300 mL was added.

  After replacing the autoclave with ethylene (0.2 MPaG x 2 times), when ethylene was introduced and the reactor pressure reached 3.45 MPa, the polymerization start time was taken, and ethylene was continuously supplied to keep the pressure constant. The pressurized reaction mixture was stirred at about 20 ° C. for 60 minutes. After about 60 minutes, about 10 mL of acetone was added to stop the polymerization, and after purging ethylene, the inside of the reactor was replaced with nitrogen.

  Thereafter, the autoclave was opened, and the produced polymer was recovered together with the solvent, and then acetone was added in the same amount as the solvent while stirring to form a polymer swollen in toluene. Stirring was continued for about 30 minutes, and then the polymer was removed by suction filtration. Further, washing with acetone and filtration were repeated three times. By this operation, the color of the complex disappeared from the cleaning liquid and became colorless and transparent.

The obtained polymer particles were air-dried with a draft and then dried at 80 ° C. for 3 hours in a vacuum dryer to obtain 36.2 g of an ethylene / 5-norbornen-2-ol copolymer. The physical properties of this copolymer 4 were as follows.
GPC analysis: M _w = 2.72 × 10 ⁵ , M _w / M _n = 1.6.
DSC analysis: T _m = 124.6 ° C.
¹ H-NMR analysis: hydroxyl group content is 0.3 mol%

Production Example 5 Production of Ethylene / 5-norbornen-2-ol Copolymer (Copolymer 5) Toluene was added to the barrel side of a 2L-autoclave equipped with a catalyst feeder with a rupturable plate which had been dried and purged with nitrogen. 200 mL was added. Thereafter, a toluene solution of Complex 2 (453 μmol; a solution in which 300 mg of Complex 2 was dissolved in 7 mL of toluene) was added to the catalyst feeder under a nitrogen stream, and then a toluene solution of 5-norbornen-2-ol ( 40.7 mmol; 4.49 g of 5-norbornen-2-ol dissolved in 10 mL of toluene) was added. After the autoclave cylinder side was substituted with ethylene (0.2 MPaG × 10 times), the temperature was raised to near the polymerization temperature (50 ° C.), and the reactor internal temperature was stabilized at a set temperature of −1 to 2 ° C.

  Thereafter, the catalyst feeder side was pressurized with ethylene, and immediately after the bursting plate was broken and the catalyst was put into the autoclave, ethylene was introduced through the catalyst feeder, and the inside of the reactor was pressurized to 0.5 MPaG. While maintaining the set temperature (50 ° C.) while introducing ethylene so that the pressure becomes constant and continuing stirring for 5 minutes, the amount of ethylene introduced is increased and the reactor is maintained while maintaining the polymerization temperature over 5 minutes. Was increased to 1.8 MPaG. After the reactor pressure reached 1.8 MPaG, ethylene was continuously supplied so that the pressure was constant, and the pressurized reaction mixture was stirred at 50 ° C. for 60 minutes. After 60 minutes, about 30 ml of acetone was added to stop the reaction, and after purging of unreacted monomers, the inside of the reactor was replaced with nitrogen.

  Thereafter, the autoclave was opened, and the produced polymer was recovered together with the solvent, and then acetone was added in the same amount as the solvent while stirring to form a polymer swollen in toluene. Stirring was continued for about 30 minutes, and then the polymer was removed by suction filtration. Further, washing with acetone and filtration were repeated three times. By this operation, the color of the complex disappeared from the cleaning liquid and became colorless and transparent.

The obtained polymer particles (or agglomerates) were air-dried with a draft and then dried at 80 ° C. for 3 hours in a vacuum dryer to obtain an ethylene / 5-norbornen-2-ol copolymer (copolymer 5). 145 g was obtained. The physical properties of this copolymer 5 were as follows.
GPC analysis: M _w = 1.28 × 10 ⁵ , M _w / M _n = 2.2.
DSC analysis: T _m = 110.2 ° C.
¹ H-NMR analysis: hydroxyl group content is 0.58 mol%.

<Manufacture of resin composition>
(A) Polyethylene resin (commercial product) as component (B), polycarbonate resin (commercial product) as component (B), copolymer 1-5 as component (C), and commercially available compatibilizer (comparative example), Resin compositions were produced as in Examples 1 to 5 and Comparative Examples 1 to 5, and their physical properties were evaluated.
The (A) component, (B) component used in each example, and the compatibilizer of the comparative example are as follows.

Component (A) Polyethylene (A1) [manufactured by Nippon Polyethylene Co., Ltd., trade name: HE492, MFR = 24 (g / 10 min]]
Polyethylene (A2) [manufactured by Nippon Polyethylene Co., Ltd., trade name: HY420, MFR = 0.37 (g / min)]
Polyethylene (A3) [manufactured by Nippon Polyethylene Co., Ltd., trade name: HF310, MFR = 0.06 (g / min)]

Component (B): Polycarbonate resin [Mitsubishi Engineering Plastics, trade name: Iupilon S2000, Mv = 24000, MFR = 12 (g / min)]

(Compatibilizer of comparative example)
・ Ethylene / GMA (glycidyl methacrylate) copolymer (manufactured by Sumitomo Chemical Co., Ltd., trade name: Bond First-E)
・ Ethylene / vinyl acetate copolymer (Made by Mitsubishi Chemical Co., Ltd., trade name: EVA-A543)
・ Ethylene / methacrylic acid copolymer (Mitsui DuPont Polychemical Co., Ltd., trade name: Nucrel-N0903HC)

Examples 1-2 and Comparative Examples 1-4: Production of resin composition and evaluation of physical properties (1)
(1) Kneading and evaluation of physical properties By blending composition shown in Table 2, polyolefin resin (A), polycarbonate resin (B) and compatibilizer are blended, and phenolic antioxidant (Ciba Specialty Chemicals, trade name) : IRGANOX 1076) 0.5 parts by weight, phosphorus antioxidant (Ciba Specialty Chemicals, trade name: Irgafos 168) 0.5 parts by weight and dry blended, then using Brabender (Toyo Seiki 30C150) The mixture was melt-kneaded for 5 minutes under the conditions of a mixer rotation speed of 150 rpm and a mixer temperature of 220 (C) to obtain a resin composition.
Using the obtained resin composition, a test piece was prepared by the method described above, and various physical properties were evaluated. The evaluation results are shown in Table 2. In the table below, “PE” means polyethylene and “PC” means polycarbonate.

(2) Dispersion form A part of the molded product was cut out, and a magnification of 500 times and 1000 times using a Hitachi scanning electron microscope S-4500 (manufactured by Hitachi High-Technologies) or Hitachi transmission electron microscope H-9000UHR (manufactured by Hitachi High-Technologies) The dispersion form of the dispersed phase was observed at a magnification of 1000 times. A dispersion form photograph is shown in FIGS.

Examples 3 to 4, Comparative Example 5: Production of resin composition and evaluation of physical properties (2)
(1) Kneading and evaluation of physical properties Polyolefin resin (A), polycarbonate resin (B), and compatibilizing agent (C) were blended according to the blending composition shown in Table 3. First, polycarbonate resin (B) and compatibilizer (C), phenolic antioxidant (Ciba Specialty Chemicals, trade name: IRGANOX 1076) 0.5 parts by weight, phosphorus antioxidant (Ciba Specialty Chemicals) Product name: Irgafos 168) After dry blending with 0.5 parts by weight, it is introduced into a micro-type high shear molding machine (manufactured by Imoto Seisakusho, HSE3000mini) under conditions of a mixer rotation speed of 1200 rpm and a mixer temperature of 280 ° C. Melt kneaded for 2 minutes. Subsequently, the polyolefin resin (A) was introduced and melt kneaded for 2 minutes to obtain a resin composition. Using the obtained resin composition, a test piece was prepared by the method described above, and various physical properties were evaluated. The evaluation results are shown in Table 3.

(2) Dispersed form A part of the molded product was cut out, and the dispersed form of the dispersed phase was observed at a magnification of 1000 times using a Hitachi transmission electron microscope H-9000UHR (manufactured by Hitachi High-Technologies Corporation). A dispersion form photograph is shown in FIG.

Example 5: Production of resin composition and evaluation of physical properties (3)
The resin pellets used for the molding were set to L / D = 52.5, cylinder diameter = 32 mm, cylinder temperature = 280 ° C. with a twin screw extruder (manufactured by Nippon Steel Co., Ltd., TEX30α). Compounding component [(A) component [PE (F310)] / (B) component [PC (S2000)] / (C) component (copolymer 5) / additive (Royal Black 904) = 5/93/1 / 1] was melt-kneaded.

Of each compounding component, polyethylene resin (component (A): PE (F310) other than blended) is added from the first inlet, passed through the kneading site, and then added from the second inlet. After kneading, the extruded strand was extruded as a resin pressure of 10 to 15 MPa and a discharge rate of 30 kg / h at this time.The extruded strand was cooled by applying cooling water using a cooling belt conveyor. And the resin pellet was obtained by cutting to a length of 3-6 mm and pelletizing.
As a result of evaluating the physical properties of the obtained resin composition by the above-described method, the appearance was “◯” and the matrix component was “PC (polycarbonate)”.

  As shown in Examples 1 to 5 above, by using a compatibilizing agent (copolymers 1 to 5) having a norbornene skeleton, Comparative Examples 1 and 5 in which these compatibilizing agents were not used, other phases Compared with Comparative Examples 2 to 4 using a solubilizer, the compatibility between the polyethylene resin and the polycarbonate resin has been greatly improved (dispersion refinement), and the mechanical strength and resistance to resistance possessed by the properties of the polyethylene resin and the polycarbonate resin are combined. A resin composition having good chemical properties and excellent appearance was obtained.

  As described above, by using the compatibilizing agent of the present invention, for example, heat having excellent organic solvent resistance of polyolefin resin and excellent mechanical properties of polycarbonate resin, and excellent appearance of the molded product. A plastic resin composition can be provided. Thus, as a so-called engineering plastic, it is a composition in which a polycarbonate resin having excellent mechanical strength and a polyolefin resin excellent in solvent resistance are mixed, and one of the resins forming the dispersed phase is as fine as several microns. The composition which shows dispersion | distribution and has the physical property which could not be achieved by the conventional mixing method can be provided.

  The compatibilizing agent of the present invention is a resin composition excellent in mechanical strength, organic solvent resistance and appearance by compatibilizing a thermoplastic resin having a polyolefin resin and a polar group so as to have a stable domain dispersion structure. A molded article comprising the composition can be provided. The resin composition of the present invention containing the compatibilizing agent of the present invention, a polyolefin resin and a thermoplastic resin having a polar group, and a molded product thereof are excellent in mechanical strength, organic solvent resistance, and appearance, and are used for automobile parts, It can be used for various applications such as home appliance parts, packaging materials, building materials, agricultural materials, civil engineering materials, fibers, filter materials, fishery materials, sanitary / medical materials and other industrial materials.

Claims (10)

Polyolefin resin (A), thermoplastic resin (B) having a polar group, α-olefin monomer and the following general formula (1):
(In the formula, X represents a hydroxyl group, an amino group, an amide group, an imide group, an isocyanate group, a carbodiimide group, an oxazoline group, an epoxy group, a carboxyl group, a carboxylic acid group, an acid anhydride group, or an ester group; An integer of 0 to 10, m represents an integer of 0 to 10, and o represents an integer of 1 to 4). a resin composition characterized by containing units derived from at least three components of the compatibilizer (C), characterized in that the thermoplastic resin for compatibilization agent (C) satisfies the following requirements A resin composition.
1) The weight average molecular weight (Mw) is 10,000 to 300,000.
2) The ratio of the structural unit derived from the compound represented by General formula (1) in a copolymer is 0.1-5 mol%.   The resin composition according to claim 1, wherein the thermoplastic resin (B) having a polar group is a polycarbonate resin.   The resin composition according to claim 1 or 2, wherein the compatibilizer (C) for the thermoplastic resin is a random copolymer of the α-olefin monomer and the compound represented by the general formula (1).   The compatibilizer for thermoplastic resin (C) is a block copolymer of a random copolymer of the compound represented by the α-olefin monomer and the general formula (1) and a homopolymer of the α-olefin monomer. The resin composition according to any one of claims 1 to 3.   The thermoplastic resin compatibilizer (C) is obtained by polymerizing a reaction system containing a compound represented by the general formula (1) while continuously supplying an α-olefin monomer. The resin composition of any one of -4.   The proportion of units derived from the thermoplastic resin compatibilizer (C) is 0.01 to 30 based on the total amount of units derived from the polyolefin resin (A) and the thermoplastic resin (B) having a polar group. The resin composition according to any one of claims 1 to 5, which is in the range of parts by weight.   The ratio of the structural unit derived from the polyolefin resin (A) and the structural unit derived from the thermoplastic resin (B) having a polar group is in the range of 1/99 to 99/1 as the weight ratio (A) / (B). The resin composition of any one of Claims 1-6 which is inside.   The resin composition according to any one of claims 1 to 7, which is obtained by melt-kneading three components. Was melted and kneaded with a thermoplastic resin (B) a thermoplastic resin for compatibilizer and (C) having a polar group, is obtained by melt-kneading the remaining ingredients of claims 1 to 8 The resin composition according to any one of the above.   A molded body comprising the resin composition according to any one of claims 1 to 9.