WO2007052804A1 - Polyolefin copolymer, method for producing same and thermoplastic resin composition - Google Patents

Abstract

The present invention aims to provide a polyolefin copolymer which is obtained by radically polymerizing a vinyl monomer in the presence of a polyolefin latex produced by emulsion-polymerizing or suspension-polymerizing an olefin monomer by using a coordination polymerization catalyst. The present invention also aims to produce a polyolefin copolymer while maintaining high polymerization activity in both polyolefin polymerization using a coordination polymerization catalyst and radical polymerization of a vinyl monomer. Such aims are achieved by radically polymerizing a vinyl monomer in the presence of a polyolefin latex produced by emulsion polymerization or microsuspension polymerization of an olefin monomer using a coordination polymerization catalyst.

Description

 Polyolefin copolymer, process for producing the same, and thermoplastic resin composition

 [0001] The present invention relates to a polyolefin-based copolymer obtained by radical polymerization of a vinyl monomer in the presence of a polyolefin-based latex produced by emulsion polymerization or microsuspension polymerization of an olefin-based monomer using a coordination polymerization catalyst. The present invention relates to a polymer, a production method thereof, a thermoplastic resin composition with thermoplastic resin, and a molded article.

 Background art

 [0002] Graft copolymers are characterized by their structural features, such as polymer function-imparting agents, surface function-imparting agents, polymer blend compatibilizers, polymer / filler-based composite surface active agents, and the like. It is effectively used as a functional polymer.

 For example, a technique is known in which a graft copolymer is produced by a polymerization reaction of olefin with an acrylate polymer in the presence of a transition metal catalyst (Patent Document 1).

 [0003] Further, as a graft copolymer obtained by utilizing emulsion polymerization, a core-shell polymer is well known, and particularly, Gen-based rubber particles, acrylic rubber particles, acrylic Z silicone-based composite rubber particles, and the like were used. Core shell polymers such as ABS resin, MBS resin, ASA resin, etc. are commercially available as highly impact resistant resin or resin compositions. However, these resins have a problem that they are difficult to apply to low polarity resins such as polyethylene and polypropylene because of their low dispersibility.

[0004] In addition, in the method of copolymerizing emulsified acrylic monomers in the presence of polyolefin latex, the monomer conversion rate may be poor for acrylic monomers having a relatively low boiling point, particularly acrylonitrile. The cause of this problem is that the boiling point of the acrylic monomer emulsion is low due to heating during polymerization, the reaction heat of the monomer, etc., and the monomer vaporizes, making it difficult to stay in the reaction liquid. Further, in a method in which an acrylic monomer is emulsified and then mixed with a polyethylene latex for polymerization, the emulsified acrylic monomer is absorbed by the polyethylene latex, so that the polymerization proceeds with the water-soluble initiator. Sometimes it was difficult. Patent Document 1: JP 2003-335828

 Disclosure of the invention

 Problems to be solved by the invention

[0005] An object of the present invention is to subject a polyolefin monomer to radical polymerization by polymerization of a olefin monomer in the presence of a polyolefin latex produced by emulsion polymerization or microsuspension polymerization of an olefin monomer using a coordination polymerization catalyst. The object of the present invention is to provide a production method capable of maintaining high polymerization activity in both olefin polymerization using a coordination polymerization catalyst and radical polymerization of a bull monomer.

 Means for solving the problem

[0006] In order to solve the above problems, the present inventors have intensively studied, and as a result, the present invention has been completed.

 That is, the present invention

 A polyolefin copolymer produced by radical polymerization of a butyl monomer in the presence of a polyolefin latex obtained using a coordination polymerization catalyst (Claim 1).

 [0007] The coordination polymerization catalyst is any one of the following general formulas (1) to (5), which is one kind of late transition metal complex-based coordination polymerization catalyst. The polyolefin-based copolymer according to claim 2.

 [0008] [Chemical 1]

(In the formula, M is palladium or nickel. R 1 and R 2 each independently represent 1 to 4 carbon atoms.

 14

It is a hydrocarbon group. R 1 and R 2 are each independently a hydrogen atom or a methyl group. R is A hydrogen atom, a hydrogen atom, or an organic group having 1 to 20 carbon atoms. X is an organic group having a heteroatom that can be coordinated to M, and may be connected to R, or X does not exist

 Five

 May be. L— is an arbitrary anion. )

[0010] [Chemical 2]

[Wherein, M is palladium or nickel. R 1 and R 2 each independently represent 1 to 4 carbon atoms.

 14

 It is a hydrocarbon group. R is a halogen atom, a hydrogen atom, or an organic group having 1 to 20 carbon atoms

 Five

 It is. X is an organic group with a heteroatom that can coordinate to M,

 Five

 X or X may not be present. L is an arbitrary key. )

[0012] [Chemical 3]

[In the formula, M is nickel, palladium, or platinum. E is oxygen or sulfur. X is phosphorus, arsenic, or antimony. R 1, R 2, R are each independently hydrogen or carbon number. 1 ~ 20 hydrocarbon groups. R is a fluorine atom or a fluorinated hydrocarbon having 1 to 20 carbon atoms fl

 It is a basic group. R is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a hydroxyl group, an ether group that also has a hydrocarbon group having 1 to 20 carbon atoms, a carbon number of 1 to 20 These are ester groups, sulfonates, and sulfonic acid ester groups that also have a hydrocarbon group having 1 to 20 carbon atoms. )

[0014] [Chemical 4]

 [In the formula, M is nickel, palladium, or platinum. E is oxygen or sulfur. X is phosphorus, arsenic, or antimony. R 1, R 2, R are each independently hydrogen or carbon number. 1

 6 7 8

 ~ 20 hydrocarbon groups. Y is a halogen atom. m is 1-3. ) o

[0017] The bullet monomer is a (meth) acrylic monomer. The polyolefin copolymer according to claim 1, wherein the polyolefin is a copolymer (Claim 3).

[0018] The polyolefin copolymer according to claim 3, which is a (meth) acrylic monomer power tert-butyl (meth) acrylic acid ester (claim 4).

[0019] The monomer having a -tolyl group is used as the bull monomer.

The polyolefin copolymer according to any one of -4 to (Claim 5).

 Monomers having a nitrile group are 5% to 100% by weight of 100% by weight

The polyolefin copolymer according to claim 5, which is% (claim 6).

[0020] The polyolefin copolymer according to [1] or [2] above, wherein the bur monomer is a gen monomer (Claim 7).

[0021] The polyolefin copolymer according to claim 7, wherein the gen-based monomer is isoprene or butadiene (claim 8).

 The polyolefin copolymer according to any one of claims 1 to 8, wherein the polyolefin and the bull polymer are grafted (claim 9).

[0022] The polyolefin copolymer according to any one of claims 1 to 9, wherein the vinyl monomer is radically polymerized in the presence of a polyolefin latex obtained using a coordination polymerization catalyst. Manufacturing method (Claim 10).

[0023] The vinyl monomer is pre-emulsified in the radical polymerization of the butyl monomer in the presence of the polyolefin latex obtained using the coordination polymerization catalyst.

10. A process for producing a polyolefin copolymer according to 10, (claim 11).

[0024] The polyolefin copolymer obtained according to any one of claims 10 to 12, wherein the polyolefin latex obtained using a coordination polymerization catalyst and a butyl monomer are preliminarily mixed and then radical polymerization is performed. Manufacturing method (Claim 12).

[0025] The polyolefin co-polymer according to any one of claims 10 and 11, wherein a butyl monomer is added dropwise to the polyolefin latex obtained using the coordination polymerization catalyst without emulsification, and polymerization is performed. A method for producing a polymer (Claim 13).

[0026] The water-soluble initiator is used when the vinyl monomer is radically polymerized in the presence of the polyolefin latex obtained using the coordination polymerization catalyst.

The method for producing a polyolefin-based copolymer according to claim 1 (4). [0027] The method for producing a polyolefin copolymer according to any one of claims 10 to 13, wherein the polyolefin copolymer obtained by radical polymerization is further hydrolyzed (claim 15).

 [0028] The method for producing a polyolefin copolymer according to claim 16, wherein a carboxylic acid group is generated by hydrolysis (claim 16).

[0029] A thermoplastic resin composition comprising the polyolefin copolymer according to any one of claims 1 to 9 and a thermoplastic resin (claim 17).

[0030] A thermoplastic resin composition comprising a polyolefin copolymer and a thermoplastic resin obtained by the method according to any one of claims 10 to 17 (claim 18).

[0031] A molded article comprising the thermoplastic resin composition according to any one of claims 18 and 19.

 (Claim 19). It is.

 The invention's effect

 [0032] In the polyolefin copolymer of the present invention, both the polymerization of the olefin monomer and the radical polymerization of the butyl monomer by the coordination polymerization catalyst can be polymerized with high activity, and as a result, the olefin is highly efficient. A copolymer can be produced. In particular, since the olefin monomer can be polymerized with high activity, coloring of the obtained copolymer and the composition by the catalyst residue can be greatly reduced. In addition, since an acrylic monomer having a low boiling point, particularly acrylonitrile, can be efficiently polymerized, the obtained polyolefin copolymer is suitable for imparting polarity, and a thermoplastic resin composition to which this is added has high-frequency sealing properties. Greatly improved.

 BEST MODE FOR CARRYING OUT THE INVENTION

[0033] The present invention is described in detail below.

 The present invention relates to a polyolefin copolymer produced by radical polymerization of a butyl monomer in the presence of a polyolefin latex obtained by polymerizing an olefin monomer in the presence of a coordination polymerization catalyst.

[0034] (Coordination polymerization catalyst)

The coordination polymerization catalyst for producing polyolefin latex is not particularly limited as long as it is a coordination polymerization catalyst having olefin polymerization activity in the presence of water and a polar compound. As a preferred example, Chemical Review, 2000, 100 卷, 116 9–1203, Chemical Review, 2003, 103 卷, 283-3, 15 pp. Journal of Synthetic Organic Chemistry, 2000, 58 卷, 293, Angelevante Chemie International Edition, 2002, 41 卷, 544–561, Angelante 'Chemie International Edition, 2005, 44 卷, Examples include those described on pages 429-432. However, the present invention is not limited to this. From the viewpoint of easy synthesis and high activity, a late transition metal complex-based coordination polymerization catalyst represented by the general formulas (1) to (5) is preferred.

[0035] [Chemical 6]

(Wherein, M is palladium or nickel. R 1 and R 2 each independently represents 1 to 4 carbon atoms)

 14

 It is a hydrocarbon group. R 1 and R 2 are each independently a hydrogen atom or a methyl group. R is

 2 3 5, a rogen atom, a hydrogen atom, or an organic group having 1 to 20 carbon atoms. X is an organic group having a heteroatom that can be coordinated to M, and may be connected to R, or X does not exist

 Five

 May be. L— is an arbitrary anion. )

[0037] [Chemical 7]

[In the formula, M is palladium or nickel. R 1 and R 2 each independently represent 1 to 4 carbon atoms.

 14

 It is a hydrocarbon group. R is a halogen atom, a hydrogen atom, or an organic group having 1 to 20 carbon atoms

 Five

 It is. X is an organic group with a heteroatom that can coordinate to M,

 Five

 X or X may not be present. L is an arbitrary key. )

[0039] [Chemical 8]

 [0040] (wherein M is nickel, palladium, or platinum. E is oxygen or sulfur. X is phosphorus, arsenic, or antimony. R 1, R 2, and R are each independently hydrogen or carbon number. 1

 6 7 8

 ~ 20 hydrocarbon groups. R is a fluorine atom or a fluorinated hydrocarbon having 1 to 20 carbon atoms fl

It is a basic group. R is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a hydroxyl group, an ether group that also has a hydrocarbon group having 1 to 20 carbon atoms, a carbon number of 1 to 20 Ester group, sulfonate, or carbon number of 1-2 It is a sulfonic acid ester group that also has zero hydrocarbon group power. )

[0041] [Chemical 9]

 [0043] (wherein M is nickel, palladium or platinum. E is oxygen or sulfur. X is phosphorus, arsenic or antimony. R 1, R 2 and R 3 are each independently hydrogen or carbon number. 1

 6 7 8

 ~ 20 hydrocarbon groups. Y is a halogen atom. m is 1-3. )

 The late transition metal complex-based coordination polymerization catalyst represented by the general formula (1) or (2) is known as a broo khart catalyst!

[0044] The ability to be stable in water, in particular, M is preferably palladium. Carbon number represented by R and R

 14

As the hydrocarbon group of 1 to 4, a methyl group, an ethyl group, an isopropyl group, a t-butyl group, an n-butyl group and the like are preferable, and a methyl group and an isopropyl group are more preferable. [0045] Molecules capable of coordinating to M represented by X include jetyl ether, acetone, methyl ethyl ketone, acetonitrile, acetic acid, ethyl acetate, water, ethanol, acetonitrile, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide. In addition, there is no need to be able to exemplify polar compounds such as propylene carbonate. R is a heteroatom, especially

 Five

 In the case where it has a carbonyl oxygen such as a sulfur bond, it may be coordinated as this carbon oxygen force. Further, it is known that the olefin is coordinated during polymerization with olefin.

 [0046] The counter-one represented by L- is produced together with a cation (M +) by the reaction of a catalyst comprising an a-dimine type ligand and a transition metal and a cocatalyst. Anything that can form a non-coordinating ionic pair is acceptable!

 [0047] An a-dimine type ligand having an aromatic group on both imine nitrogens, specifically, ArN

 = C (R) — The compound represented by C (R) = NAr is easy to synthesize and has high activity.

twenty three

 preferable. R and R are preferably hydrocarbon groups, particularly hydrogen atoms, methyl groups, and

 twenty three

 And those having a acenaphthene skeleton represented by the general formula (2) are preferred because they are easy to synthesize and have high activity. Furthermore, it is preferable to use an α-dimine type ligand having a substituted aromatic group at both imine nitrogens because it is effective in terms of steric factors and tends to increase the molecular weight of the polymer. Therefore, it is preferable that Ar is an aromatic group having a substituent, for example, 2, 6 dimethyl file, 2, 6 diisopropyl file and the like.

[0048] As the auxiliary ligand (R) in the active species obtained from the late transition metal complex of the present invention,

 5 A hydrocarbon group, a halogen group or a hydrogen group is preferred. Cocatalyst cation (Q +), which will be described later, has a metal-halogen bond, is a metal-hydrogen bond, is a metal-hydrogen bond, and a halogen is extracted from the hydrogen-carbon bond to form a salt, while the catalyst is active Cation (M +) possessing a metal carbon bond, metal halogen bond or metal monohydrogen bond is generated, and it is necessary to form a non-coordinating ion pair with the promoter cation (L—). Because there is.

[0049] Specific examples of R include a methyl group, a black mouth group, a bromo group, and a hydrogen group.

 Five

In particular, a methyl group or a black mouth basic force synthesis is preferable because it is simple. Note that the insertion of olefins into M + halogen bonds leads to the addition of M + carbon bonds (or hydrogen bonds). Ref is particularly preferred as an auxiliary ligand for the catalyst because it is easier to insert refin.

 5 Methyl group.

 [0050] Further, R has an ester bond having a carboxylic oxygen capable of coordinating to M.

 Five

 For example, a group from which methyl butyrate can also be obtained may be mentioned.

[0051] The cocatalyst can be expressed as Q + L-. Examples of Q include Ag, Li, Na, Κ, and Η, and Ag is preferable because the halogen extraction reaction is easily completed. Na and K are preferable because they are inexpensive. L includes BF, B (C F), B (C H (CF)), PF, AsF, SbF, (

 4 6 5 4 6 3 3 2 4 6 6 6

RfSO) CH, (RfSO) C, (RfSO) N, RfSO. In particular, PF, AsF, S

2 2 2 3 2 2 3 6 6 bF, (RfSO) CH, (RfSO) C, (RfSO) N, RfSO are stable to polar compounds

6 2 2 2 3 2 2 3

 In addition, PF, AsF, and SbF force synthesis is simple and industrial.

 6 6 6

 As it is easy to obtain, it is particularly preferred to use spot strength.

 [0052] From the height of the activity, BF, B (C F), B (C H (CF)) force, especially B (C F), B (C H

 4 6 5 4 6 3 3 2 4 6 5 4 6 3

(CF)) is preferred. R is a hydrocarbon group containing a plurality of fluorine groups. These footings

3 2 4 f

 Elementary is necessary for non-coordinating the key-on, and the larger the number, the better. Examples of R f include, but are not limited to CF, C F, C F, C F, C F. Across

 3 2 5 4 9 8 17 6 5

 You can combine some!

 The late transition metal complex-based coordination polymerization catalyst represented by the general formula (3), (4) or (5) is known as a SHOP (Shell Higher Olefin Process) catalyst. Among (3), the following general formula (6):

[0054]

[0055] (wherein M is nickel, palladium, or platinum. E is oxygen or sulfur. X is phosphorus, arsenic, or antimony. R 1, R 2, and R 3 are each independently hydrogen or carbon number. 1

~ 20 hydrocarbon groups. R 1 and R 2 are each independently a fluorine atom or a fluorinated hydrocarbon group having 1 to 20 carbon atoms. The olefin polymerization catalyst represented by In particular, it has been reported that the R force S fluorinated hydrocarbon group exhibits high ethylene polymerization activity even in an emulsified system (Angew. Chem. Int. Ed. 2002, 41 卷, 544).

 [0056] By making R an electron-withdrawing fluorine atom or a fluorinated hydrocarbon group having 1 to 20 carbon atoms, a polyolefin having higher activity and / or higher molecular weight can be obtained. (3) is preferably prepared by the following reaction.

 [0057] [Chemical 12]

+ nL

 (In the reaction formula, M is nickel, palladium, or platinum. E is oxygen or sulfur. X is phosphorus, arsenic, or antimony. R 1, R 2, and R are each independently hydrogen or carbon. R is a hydrocarbon group having a prime number of 1 to 20. R is a fluorine atom or a fluorinated hydrocarbon group having a carbon number of 1 to 20. R is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a carbon number. 1 to 20 halogenated hydrocarbon groups, hydroxyl groups, ether groups consisting of 1 to 20 carbon atoms, ester groups, sulfonates or 1 to 20 carbon atoms that also have 1 to 20 carbon atoms. ML is a zero-valent nickel, palladium or platinum compound L is coordinated to M and maintains the valence of M to zero. (N is a natural number).

 [0059] Since these reactions easily proceed, M is preferably zero-valent nickel. E is preferably oxygen. X is preferably phosphorus.

[0060] R 1 and R 2 are preferably each independently a fluorinated hydrocarbon group having 1 to 20 carbon atoms. Specific examples include trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group, Examples thereof include a phenyl group substituted with a pentafluorophenyl group and a trifluoromethyl group. In particular, R is preferably a trifluoromethyl group. R is preferably a pentafluorophenol group.

 [0061] R 1, R 2, and R are each independently preferably a hydrocarbon group having 1 to 20 carbon atoms, particularly a substituted aromatic group. Most preferred as a substituted aromatic group is a phenyl group. The general formula (4) or the general formula (5) is preferably prepared by an in situ reaction using a ligand prepared in situ by the following compound.

 [0062] [Chemical 13]

+ Trick

 [0063] [Chemical 14]

 (In the reaction formula, M is nickel, palladium or platinum. E is oxygen or sulfur. X is phosphorus, arsenic or antimony. R 1, R 2 and R are each independently hydrogen or carbon. A hydrocarbon group having a prime number of 1 to 20. Y is a halogen atom, m is 1 to 3, ML is a zero-valent nickel, palladium or platinum compound, L is coordinated to M, There is no particular limitation as long as the valence of M is maintained at zero. N is a natural number.) Since these reactions are likely to proceed, M is preferably zero-valent nickel. E is preferably oxygen. U prefers that X is phosphorus.

[0065] Examples of the zero-valent nickel compound include bis (cyclooctagen) nickel and bis

(Cyclooctatetraene) nickel, bis (1,3,7-otatatriene) nickel, bis (cyclododecatriene) nickel, bis (aryl) nickel, bis (methallyl) nickel, triethylene Especially preferred is bis (cyclotagen) nickel, which is preferably nickel, bis (butadiene) nickel or bis (isoprene) nickel.

 [0066] These bis (cyclooctagen) nickel can be synthesized according to a known method, or may be used as a solution without taking out a solid (for example, Experimental Chemistry Course 4th edition, page 371). (Similarly, it can be synthesized from divalent nickel compounds, cyclooctagen, etc. and trialkylaluminum).

 [0067] Further, Y is preferably chlorine or fluorine, particularly fluorine! /. R, R, R are

 6 7 8 Each independently, a hydrocarbon group having 1 to 20 carbon atoms, particularly a substituted aromatic group is preferred. Most preferred as a substituted aromatic group is a phenyl group. In order to promote the reaction, phosphine, phosphine oxide, ketone, ester, ether, alcohol, nitrile, amine, pyridine, olefin and the like are preferably present together. Especially, it is preferable to have olefin coexist. Olefin contains an olefin monomer described below.

 [0068] The reaction temperature is preferably 0 to 100 ° C, and preferably 15 to 90 ° C. The reaction time is not particularly limited, but preferably 10 minutes to 24 hours. The reaction is preferably performed in an inert atmosphere such as argon and nitrogen. In some cases, trace amounts of oxygen and moisture may be present. The reaction is usually preferably carried out using a solvent, preferably an aliphatic or aromatic solvent, which may be halogenated! /.

 [0069] Examples include toluene, ethylbenzene, xylene, black benzene, dichlorobenzene, butane, isobutane, pentane, hexane, heptane, sucrose, decane, isododecane, cyclohexane, cycloheptane, methylcyclohexane, methyl Examples include cycloheptane, ethylcyclohexane, butyl chloride, methylene chloride, and chloroform. In general, the concentration of M in the solvent is preferably in the range of 1 to 20000 / ζ πιοΐΖ: ί, more preferably 10 to: LOOOO / z molZL.

[0070] In the reaction, the molar ratio of the ML Z ligand is preferably 5Zl to 1Zl, more preferably 3Zl to 2Zl. As specific examples of the general formula (3), (4), (5) of the olefin polymerization catalyst of the present invention, nickel is excellent in availability, and particularly preferred are compounds represented by the following general formula. The power that can be used is not limited to this. [0071] [Chemical 15]

[0072] [Chemical 16]

[0073] [Chemical 17]

 [In the formula, Ph is a phenyl group, R ′ is a hydrocarbon group having 1 to 6 carbon atoms, and n is 1 to 3).

 [0075] (Olefin monomer)

 The olefin monomer used in the present invention is an olefin compound having a carbon-carbon double bond capable of coordination polymerization. Preferred examples of olefin monomers include olefins having 2 to 20 carbon atoms such as ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-hexadecene, 1-eicosene, Examples include 4-methyl 1-pentene, 3-methyl-1-butene, vinylcyclohexane, cyclopentene, cyclohexene, cyclooctane, norbornene, and 5-fluoro-2 norbornene.

Of these, a-olefins having 10 or less carbon atoms are preferred because of their high polymerization activity, such as ethylene, propylene, 1-butene, 1-hexene, and 1-otaten. Ethylene is particularly preferred because of its high activity. These olefin-based monomers may be used alone or in combination of two or more. [0077] Also, 1,3-butadiene, isoprene, 1,4 monohexagen, 1,5-hexagen, 1,7-octagen, 1,9-decadiene, 1,11dodecadiene, 1,13-tetradecadiene 1, 15-hexadedecadiene, 1,5-cyclooctadiene, norbornagen, 5-bi-luo 2-norbornene, ethylidene norbornene, dimethanooctahydronaphthalene, dicyclopentagen, etc. But ... The amount of gen used is preferably 0 to 20 parts by weight per 100 parts by weight of the olefin monomer. By using Gen, the molecular weight, degree of branching, degree of crosslinking, etc. of polyolefin can be adjusted.

[0078] Generally, the coexistence of a bull monomer is not preferable because it lowers the polymerization activity. The amount of O-les fins monomers include, without limitation, a large molecular weight polymers from the viewpoint of obtaining good yield, O Les fins monomer / catalyst active species in a molar ratio 10 to 10 ^9, more 100 10 ⁷ , particularly 1000 to 10 ⁵ is preferable.

 [0079] (Olefin monomer polymerization)

 The method for polymerizing olefin monomers using the coordination polymerization catalyst of the present invention is not particularly limited as long as the resulting polymer can be obtained by latex (emulsion), but includes emulsion polymerization (minimal polymerization). There is a microsuspension polymerization method, which can be carried out in the system. For example, a coordination polymerization catalyst and olefin monomer can be uniformly dispersed in water and reacted. When the olefin monomer used is a gas at the reaction temperature, the system may be heated to the reaction temperature after being condensed or solidified at low temperature and charged to the reaction temperature, and charged as a liquid or gas under pressure. But it ’s okay.

 [0080] The entire amount of the olefin monomer and the coordination polymerization catalyst may be charged all at once or may be added continuously or intermittently after a part of the olefin monomer and the coordination polymerization catalyst are charged. Further, the mixture may be mixed with water and an emulsifier and charged with, for example, a homogenizer to prepare an emulsion.

[0081] Known emulsifiers can be used for emulsion polymerization or microsuspension polymerization, and any emulsifier having a ionic property, cationic property, or nonionic property can be used without any particular limitation. From the viewpoint of good emulsifying ability, alkali metal salts of alkylbenzenesulfonic acid, alkali metal salts of alkylsulfuric acid, alkali metal salts of alkylsulfosuccinic acid, etc. A diionic whey is preferred, more preferably sodium alkylbenzene sulfonate, sodium alkyl sulfate, sodium alkyl sulfosuccinate and the like. The amount of the emulsifier is not particularly limited and may be appropriately adjusted, but is preferably lgZL to 50 gZL, more preferably 2 gZL to 20 gZL, based on the water used.

 [0082] Known dispersants can be used for the microsuspension polymerization. Specific examples include poorly water-soluble inorganic compounds such as calcium phosphate, calcium carbonate, aluminum hydroxide, and starch silica; nonionic high compounds such as polybutyl alcohol, polyethylene oxide, alkyl cellulose, and hydroxyalkyl cellulose. Molecular compounds: polyacrylic acid and salts thereof, polymethacrylic acid and salts thereof, and anionic polymer compounds such as copolymers of methacrylic acid esters and methacrylic acid and salts thereof.

 [0083] During polymerization, a small amount of an organic solvent may be added in order to increase the solubility of the olefin monomer and the coordination polymerization catalyst and promote the reaction. The solvent is not particularly limited, but aliphatic or aromatic solvents are preferred, and these may be halogenated. Examples include toluene, ethynolebenzene, xylene, black benzene, dichlorobenzene, pentane, hexane, heptane, octane, cyclohexane, methylcyclohexane, ethylcyclohexane, butyl chloride, methylene chloride, black mouth form. It is done.

 [0084] In addition, polar solvents such as tetrahydrofuran, dioxane, jetyl ether, acetone, ethanol, methanol, methyl ethyl ketone, methyl isobutyl ketone, and ethyl acetate may be used. It is particularly preferable that the solvent is relatively low in water solubility and the catalyst is easily dissolved. Examples of such particularly preferable examples include toluene, methylene chloride, chloroformate, butyl chloride, and chloroform benzene.

[0085] In the case of miniemulsion polymerization in which the entire system is preliminarily emulsified, a low water-soluble, aliphatic solvent such as pentadecane, hexadecane or heptadecane may be used to stabilize the emulsion (latex). Prefer U ,. A low water-soluble oligomer such as polybutene may be used. These solvents may be used alone or in combination. The total amount of the solvent used is preferably 30% by volume or less, more preferably 10% by volume or less, based on the total volume of the reaction solution. These solvents may be added as they are, or emulsified and added. [0086] The polyolefin latex of the present invention is usually produced at 30 to 200 ° C, preferably at 0 to 100 ° C, particularly preferably at 15 to 90 ° C. The polymerization time is not particularly limited, but usually 10 minutes to 24 hours, and the reaction pressure is not particularly limited, but is normal pressure to lOMPa. The temperature and pressure may be kept constant from the start to the end of the reaction, or may be changed continuously or stepwise during the reaction.

 [0087] When the olefin monomer used is a gas such as ethylene or propylene, the pressure may gradually decrease with the consumption of the monomer due to the polymerization reaction, but the reaction may be performed by changing the pressure as it is. The reaction may be carried out while maintaining a constant pressure by supplying monomers or heating. The polyolefin latex obtained according to the present invention is usually obtained as a latex. The particle size of the latex can be adjusted according to the amount of emulsifier, organic solvent, water used, and emulsification conditions. Point power such as stability of latex Preferably, the particle diameter force S20 nm to 5000 nm, more preferably 50 to 2000 nm is selected to obtain a condition, particularly preferably 100 to 1500 nm.

 [0088] The polyolefin latex produced by emulsion polymerization or microsuspension polymerization used in the present invention may be used as it is for the reaction with the butyl monomer, and may be diluted, concentrated, heat-treated, aged or the like as necessary. You may use it after adding operation, and you may use it, after adding ingredients, such as an emulsifier, an antifreezing agent, a stabilizer, and a pH adjuster. The polyolefin latex is preferably used as a latex having a solid content of 1 to 50% by weight, more preferably a latex having a solid content of 3 to 30% by weight. If the solid content is too high, latex particles agglomerate and the reaction becomes heterogeneous. If the solid content is too low, the total amount of the reaction solution increases, resulting in poor pot efficiency.

 [0089] (Bulomer)

The vinyl monomer referred to in the present invention is not particularly limited. For example, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, cycloacrylate acrylate Acrylic acid such as hexyl, methoxyethyl acrylate, cyclohexyl methacrylate, methyl methacrylate, ethyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, and benzyl methacrylate. Or alkyl esters of methacrylic acid, butyl aromatic compounds such as styrene and α-methylstyrene, halogenated butyls such as vinyl chloride and vinylidene chloride, unsaturated carboxylic acid amides such as acrylic amide, — ア ル キ ル -alkyl and Ζ or Ν-alkylol derivatives of unsaturated carboxylic acid amides such as methyl acrylamide, saturated carboxylic acid butyl esters such as vinyl acetate, acrylonitrile, metathalonitrile, vinylidene cyanide, a— Bullo-tolyl such as cyanoethyl acrylate, fumaro-tolyl, cyanostyrene and the like can be mentioned.

[0090] Among these butyl monomers, butyl acrylate, ethyl acrylate, and methoxyethyl acrylate are preferable because they have low Tg and thus improve low-temperature characteristics, softness, and oil resistance. A monomer having a nitrile group (bull-tolyl) is preferable because of its high dielectric constant and high frequency sealing properties. Bulle - When using a tolyl, the amount used in Bulle monomer, 5 to 100 weight _^0/0, further 20 to 100 weight _^0/0, especially 40 to: L 00% by weight.

[0091] Vinyl-tolyl is preferably used as at least one component of two or more monomers in combination. In that case, Bulle - trill Bulle monomer 100 wt _^0/0 in 10 to 80 wt%, more preferably 20 to 75 wt%. In particular, it is more preferable from the viewpoint of sealing property that the amount of bur-tolyl is 50 to 75% by weight, which is the largest component.

 The bulle monomer is preferably added to the reaction system in which the polyolefin latex obtained using a coordination polymerization catalyst is present for polymerization. In this case, it is preferable to use a water-soluble catalyst as a reaction catalyst, which is preferably preliminarily stored in the reaction system or used depending on the method of adding to the reaction system as appropriate through a different route from the bull monomer. U prefer. Also, the bulle monomer may be preferably emulsified in a system mixed with an organic solvent and a reaction catalyst in some cases! /, In a reaction system in which a polyolefin latex obtained using a coordination polymerization catalyst exists in a state. It is preferable to add ヽ. The method of addition can be added to the reaction system continuously or intermittently. The method of addition is continuous in the reaction system or is preferably dropped intermittently.

[0093] When the bull-tolyl is out of these ranges, the effect of improving the oil resistance tends to be reduced if the high frequency sealing property is exceeded. In particular, beacons represented by acrylonitrile and methacrylonitrile. Since ru-tolyl monomer has a large dielectric constant due to the nitrile group, its polymer is expected to have a great effect as a polar imparting agent. Functional group-containing vinyl monomers can also be used. Specifically, for example, in a molecule such as allylic methacrylate, allylic acrylate, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, ethylene glycol ditalylate, ethylene glycol dicyclopentaether ether methacrylate, etc. Monomers containing multiple unsaturated carbon bonds, epoxy group-containing polymers such as glycidyl methacrylate.

-Bulmonomer containing hydroxyl group such as 2-monoethyl methacrylate and 2-hydroxyethyl methacrylate.

 [0094] A gen monomer can also be used, and in this application, the gen monomer is included in the bull monomer for the sake of simplicity. Specific examples of the monomer include butadiene, isoprene, 1,4 pentagen, 1,4 monohexagen, 1,5 hexagen, 2,5-dimethyl-1,5 hexagen, 1,4 octagen, 1 4, 4-cyclohexagen, cyclooctagen, dicyclopentagen, 5-ethylidene-2-norbornene, 5-butylidene-2-norbornene, 2-methallyl-5-norbornene, 2-isopropylbenzene 5-norbornene, black mouth prene and the like. Of these gen-based monomers, butagenya isoprene is preferred because of its improved low-temperature properties and softness.

 [0095] The amount of the gen monomer used can be appropriately selected according to the characteristics to be expressed in the olefin copolymer. The amount used is preferably 5 to: L00% by weight, more preferably 10 to 100% by weight, particularly 20 to: L00% by weight in the vinyl monomer. Outside these ranges, the effect of improving low-temperature characteristics and softness is reduced. When vinyl monomers are used, in addition to high-frequency sealing properties, oil resistance, and oleic acid resistance, physical properties related to polarity such as low contact angle, high surface tension, wettability, adhesion, paintability, dyeability, and high dielectric constant. Can be expressed. In addition, when a monomer containing an unsaturated carbon bond in the molecule is used, a crosslink can be introduced into the olefin copolymer to develop rubber elasticity and rigidity, or to impart solvent resistance.

[0096] Depending on the characteristics that the olefin copolymer is desired to be expressed, these bur monomers may be used alone or in combination of two or more. The ratio between the polyolefin latex and the vinyl monomer can be arbitrarily set. 100 parts by weight of the vinyl monomer, the solid content of the polyolefin latex is preferably 1 to: L00 parts by weight, more preferably 2 to 4 parts. It is preferred to use 0 parts by weight, particularly 2 to 33 parts by weight.

 [0097] (Vinyl monomer copolymerization)

 The polyolefin copolymer of the present invention is a latex obtained by radical copolymerization of a bull monomer by an ordinary emulsion polymerization method (including a mini emulsion polymerization method) or a micro suspension polymerization method in the presence of a polyolefin latex. Can do.

 [0098] In the emulsion polymerization or microsuspension polymerization, the polymerization method is not particularly limited, but a method in which the reaction is started after mixing the polyolefin latex and the vinyl monomer is preferable. Bull monomer may be mixed as it is, or emulsified with a homogenizer, etc., but it may be mixed with emulsified latex in order to allow the olefin monomer to absorb the bull monomer. Is preferred. When the vinyl monomer is emulsified and mixed, the polyethylene monomer is uniformly absorbed by the polyethylene particles, and it is easy to form uniform particles immediately. Further, if the vinyl monomer is not sufficiently absorbed by the olefin latex, single particles derived from the vinyl monomer are likely to be generated. On the other hand, when copolymerizing in the presence of a polyolefin latex using a -tolyl group-containing monomer such as acrylonitrile, the vinyl monomer is used as it is or mixed with a solvent without being emulsified, and dropped into the reaction system. It is preferable to add and gently polymerize.

 [0099] There is no particular limitation on the amount of water used for emulsion polymerization or microsuspension polymerization, as long as it is an amount necessary to emulsify the vinyl monomer to be used. The weight may be used. If the amount of water used is too small, the proportion of the bulu monomer that is hydrophobic is too high, and the emulsion does not invert from WZO to OZW, making it difficult for water to form a continuous layer. If too much water is used, the stability will be poor and the efficiency of the pot will be low.

[0100] Known emulsifiers can be used for the emulsion polymerization or microsuspension polymerization, and any emulsifier having a ionic property, cationic property, or nonionic property can be used without any particular limitation. From the viewpoint of good emulsifying ability, anionic dairy agents such as alkali metal salts of alkylbenzene sulfonic acids, alkali metal salts of alkyl sulfates, and alkali metal salts of alkyl sulfosuccinic acids are more preferred. Is preferably sodium alkylbenzenesulfonate, sodium alkylsulfate, sodium alkylsulfosuccinate and the like. The emulsifier There is no particular limitation on the amount used, but it may be adjusted as appropriate, but it is preferably 10 parts by weight or less with respect to 100 parts by weight of the vinyl monomer. If the amount is too large, coloring may occur in the composition obtained by blending the resulting polyolefin copolymer with thermoplastic rosin.

 [0101] The average particle size of the polyolefin-based copolymer is obtained according to the particle size of the raw material polyolefin latex used and the amount of the reacted vinyl monomer. The average particle size is preferably 20 to 5000 nm, more preferably 50 to 2000 nm, particularly preferably 50 to 2000 nm from the viewpoint that when a polyolefin copolymer obtained after copolymerization is blended with a thermoplastic resin such as polypropylene, a good dispersion state is exhibited. Preferably, it is within the range of 100 to 1500 nm.

 [0102] A known dispersant can be used for the microsuspension polymerization. Specific examples include poorly water-soluble inorganic compounds such as calcium phosphate, calcium carbonate, aluminum hydroxide, and starch silica; nonionic high compounds such as polybutyl alcohol, polyethylene oxide, alkyl cellulose, and hydroxyalkyl cellulose. Molecular compounds: polyacrylic acid and salts thereof, polymethacrylic acid and salts thereof, and anionic polymer compounds such as copolymers of methacrylic acid esters and methacrylic acid and salts thereof.

 [0103] The polymerization initiator used for emulsion polymerization and microsuspension polymerization is not particularly limited, and known ones can be used. For example, persulfates such as potassium persulfate and ammonium persulfate; various organic peroxides (for example, alkyl hydride mouth peroxides such as t-butylnodide peroxide and tamennoide mouth peroxides); benzoylperoxide Diacyl peroxides such as oxides and lauroyl baroxides; Dialkyl peroxides such as di-t-butyl peroxide and t-butyl peroxide laurate); 2, 2, -azobisisobutyryl-tolyl, 2, 2, -azobis 2, 4 dimethylbare- And azo compounds such as tolyl. Of these, organic acid oxides are preferred because they have the ability to extract hydrogen and increase the graft efficiency of polyolefins and bur polymers.

[0104] The polymerization initiator used for suspension polymerization may be any known one without particular limitation. For example, azo compounds such as azobisisobutyoxy-tolyl, azobisisovalero-tolyl, and organic compounds such as diisopropylperoxydicarbonate, lauroyl peroxide, benzoyl peroxide, t-butylperoxybenzoate, and t-butylperoxide Examples include peracids.

 [0105] These initiators can also be used as a redox catalyst comprising a polymerization initiator, an activator (metal salt or metal complex), a chelating agent, and a reducing agent, in addition to the thermal decomposition method. The polymerization initiator may be a thermal decomposition method or a method using a redox catalyst. The pyrolytic method is suitable for obtaining a polymer having a low metal ion content because it is not necessary to add an additive such as a reducing agent or an activator. The method using a redox catalyst is advantageous in that the reaction rate is low, the reaction rate is high, and the reaction can be easily controlled.

 As the reducing agent constituting the redox catalyst, for example, glucose, dextrose, sodium sulfoxylate formaldehyde, sodium sulfite, sodium hydrogen sulfite, sodium thiosulfate, ascorbic acid, isoscorbic acid and the like can be preferably used. Of these, sodium formaldehyde sulfoxylate is particularly preferred because of its low cost and high activity.

 [0107] The chelating agent constituting the redox catalyst includes polyaminocarboxylates such as ethylenediamine tetraacetate, oxycarboxylic acids such as citrate, those that form water-soluble chelate compounds such as condensed phosphates, and dimethyldaroxime. , Oxine, dithizone and the like that form an oil-soluble chelate compound. Of these, polyaminocarboxylates such as ethylenediamine tetraacetate and oxycarboxylic acids such as citrate are preferred.

 [0108] Examples of the activator constituting the redox catalyst include metal salts such as iron, copper, manganese, silver, platinum, vanadium, nickel, chromium, palladium, cobalt, and metal chelates. Examples thereof include ferrous sulfate, copper sulfate, potassium hexocyano (III) and the like. The activator and chelating agent can be used as separate components or can be pre-reacted and used as a metal complex.

[0109] The combination of the initiator, the activator, the chelating agent, and the reducing agent is not particularly limited and may be arbitrarily selected. Preferred combination of activator Z reducing agent Z chelating agent, for example, ferrous sulfate Z glucose Z sodium pyrophosphate, ferrous sulfate Z dextrose Z sodium pyrophosphate, ferrous sulfate Z sodium sulfoxylate formaldehyde Z Ethylenediamine tetrasodium acetate, ferrous sulfate Z sodium sulfoxylate formaldehyde It is a combination of rudehydr z citrate, copper sulfate Z sodium sulfoxylate formaldehyde Z citrate.

 [oi io] A particularly preferred combination is ferrous sulfate Z sodium sulfoxylate formaldehyde Z ethylenediamin tetraacetate disodium, ferrous sulfate Z sodium formaldehyde sulfoformate formaldehyde Z citrate, etc. It is not limited. A preferred use amount of the initiator is 0.0005 to 0 parts by weight, more preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the bull monomer. If the amount is too small, the polymerization rate is too slow and the production efficiency is lowered. If the amount is too large, the heat of polymerization is increased and the reaction may be difficult to control.

 [0111] A chain transfer agent may be used in the emulsion polymerization as necessary. Any known chain transfer agent can be used without particular limitation. Specific examples include t-dodecyl mercaptan, n-dodecyl mercaptan, n-octyl mercaptan, n-hexyl mercaptan, and the like. There is no particular limitation on the reaction temperature during emulsion polymerization, but it is preferably 0 to 120 ° C, preferably 30 to 95 ° C.

 [0112] The polyolefin copolymer produced in the present invention may be a uniform particle composed of polyolefin and a vinyl polymer, or may be a multilayer structure particle such as a core-shell two-layer structure. It may be a salami-like multiphase structure in which other grease phases are dispersed in the matrix greave phase. In addition, the polyolefin copolymer produced in the present invention may or may not be grafted with polyolefin and a buule polymer. If it is used as a graft, the impact resistance of a composition comprising a polyolefin copolymer and a thermoplastic resin may be improved.

 [0113] The polyolefin copolymer obtained as described above or the latex containing the same is, for example, spray-dried, or calcium chloride, magnesium chloride, calcium sulfate, magnesium sulfate, aluminum sulfate. It is agglomerated with an electrolyte such as calcium formate, or after being subjected to such a precipitation process, washing 'dehydration (desolvation) • After processing such as drying, powder that also has a polyolefin copolymer strength, lumps or rubber It can be recovered as a mass.

[0114] The dried product of the polyolefin copolymer of the present invention is used as an extruder or a Banbury mixer. Or the like, or the hydrous (solvent-containing) coagulated fat obtained through precipitation (desolvation) from the precipitate is processed into a pellet by passing through a press dehydrator. Can also be recovered. As a method for hydrolysis to form a carboxylic acid group by hydrolysis, a base or an acid can be used.

 [0115] The base may be an alkali or alkaline earth metal hydroxide such as sodium hydroxide or potassium hydroxide, an alkali metal alcoholate such as sodium methylate, sodium ethylate, potassium methylate, Potassium ethylate and potassium tert-butylate, ammonia and amines such as triethylamine amine can be selected. The acid can also be selected from sulfuric acid, hydrochloric acid and p-toluenesulfonic acid. Also, a cation or ion-type ion exchange resin can be used. The hydrolysis is generally carried out at a temperature in the range of 5-100 ° C, preferably at a temperature in the range of 15-90 ° C.

[0116] (Coffin composition)

 The polyolefin copolymer of the present invention can be used as a raw material for producing a resin composition by blending with various thermoplastic resins or thermosetting resins.

[0117] Examples of the thermoplastic resin include generally used resins such as polypropylene, polyethylene, ethylene propylene rubber, ethylene propylene rubber, ethylene-grade rubber, polymethylpentene, ethylene cyclic olefin copolymer, Polyolefins such as ethylene vinyl acetate copolymer, ethylene glycidyl methacrylate copolymer, ethylene methyl methacrylate copolymer, polybutyl chloride, polystyrene, polymethyl methacrylate, methyl methacrylate-styrene copolymer styrene —Bur polymers such as acrylonitrile copolymer, styrene-acrylonitrile-1 N-phenolmaleimide copolymer, and at-methylstyrene acrylate-tolyl copolymer, polyester, polycarbonate, polyamide, polyphenylene ether Polystyrene conjugate, polyacetal, polyether ether ketone, engineering plastics such as polyether sulfone are preferably exemplified.

[0118] Preferred examples of the thermosetting resin include commonly used resins such as phenol resin, urea resin, melamine resin, unsaturated polyester resin, and epoxy resin. Is done. These thermoplastic or thermosetting resins may be used alone or in combination of two or more. Of these, polyolefins are preferred in view of the good dispersibility of the polyolefin copolymer of the present invention, such as polyethylene and polypropylene.

 [0119] The blending ratio of the thermoplastic resin or thermosetting resin and the polyolefin-based copolymer may be determined as appropriate so that the physical property S of the molded product is well balanced, but sufficient physical properties are obtained. For this purpose, the amount of the polyolefin-based copolymer is not less than 0.1 parts by weight, preferably not less than 5 parts by weight, based on 100 parts by weight of the thermoplastic or thermosetting resin. In order to maintain the properties of the curable resin, the amount of the polyolefin-based copolymer particles is 500 parts by weight or less, preferably 100 parts by weight or less with respect to 100 parts by weight of the thermoplastic resin.

 [0120] The blending ratio of the thermoplastic resin or thermosetting resin and the polyolefin-based copolymer may be appropriately determined so that the physical property S of the molded product can be obtained with good balance, but sufficient physical properties can be obtained. In order to achieve this, the amount of polyolefin-based copolymer should be 0.1 to 500 wt.% For a thermoplastic or thermosetting resin, or 0.1 to 500 wt. 0.1-: LOO part by weight, most preferably 5-: part by weight L00

 In the method for producing an olefin copolymer of the present invention, high polymerization activity can be maintained both in the polymerization of olefin with a coordination polymerization catalyst and in the radical polymerization of a bur monomer. In addition, the polyolefin copolymer contains a polyolefin component, so it exhibits good dispersibility even for low-polarity oils such as polyethylene and polypropylene, and since it contains a vinyl component, it can impart various functions. it can.

 [0121] The polyolefin system according to the present invention produced by radical polymerization of a butyl monomer in the presence of an olefin latex produced by emulsion polymerization or microsuspension polymerization of an olefin monomer in the presence of the coordination polymerization catalyst of the present invention. Copolymers (including compositions) are, for example, oil resistant, oleic acid resistant, low contact angle, high surface tension, surface wettability, adhesiveness, paintability, colorability, high dielectric constant, high frequency sealability, etc. Indicates a physical property that expresses polarity or a physical property that appears as a result of polarity.

[0122] Accordingly, a polarity imparting agent (for oil resistance, adhesion, (Paintability, dyeability, high frequency sealability, etc.), adhesives, primers, coating agents, paints, compatibilizers such as polymer alloys, surfactants for polyolefin / filler-based composite materials and polyolefin-based nanocomposites, etc. It is also compatible with thermoplastic elastomers, impact-resistant, and soft plastics that have polyolefin as a resin component and acrylic polymer as a rubber component (the rubber component can be cross-linked!). It can be used as a component or as a rubber component and compatible component.

 [0123] Further, the composition having a polyolefin copolymer power of the present invention is a conventional additive known in the plastics and rubber industries, for example, a plasticizer, a stabilizer, a lubricant, an ultraviolet absorber, and an antioxidant. Further, it may contain compounding agents such as flame retardant, flame retardant aid, pigment, glass fiber, filler, polymer processing aid.

 [0124] As a method for obtaining the polyolefin copolymer composition of the present invention, a method used for blending ordinary thermoplastic resins can be used. For example, the thermoplastic resin and the olefin copolymer of the present invention can be used. By melting and kneading the coalescence and optionally the additive component using a heating kneader, such as a single screw extruder, twin screw extruder, roll, Banbury mixer, Brabender, kneader, high shear mixer, etc. Can be manufactured. Further, the kneading order of each component is not particularly limited, and can be determined according to the apparatus used, workability, or physical properties of the obtained thermoplastic resin composition.

[0125] Further, when the thermoplastic resin was produced by an emulsion polymerization method, the thermoplastic resin and the polyolefin copolymer were blended in the state of V and the deviation in latex (emulsion). Thereafter, it can be obtained by co-precipitation (co-aggregation).

 As a method for molding a polyolefin copolymer composition obtained by force, for example, an injection molding method, an extrusion molding method, a blow molding method, a calendar molding method, etc., which are used for molding ordinary thermoplastic resin compositions, etc. The molding method is given.

 Example

 [0126] Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited by these.

[0127] [Polymerization conversion]

In emulsion polymerization, charged monomers, polyolefin (polyethylene), emulsifier and Then, the total weight of the initiator was divided by the total weight of the entire reaction solution to obtain the maximum solid content concentration when the monomer was 100% polymerized. About 0.5 to 2 g of the latex obtained after the reaction was collected in an ointment can and thermally dried in an oven at 100 ° C. to determine the remaining solid content, which was regarded as the solid content concentration in the latex. The time for heat drying is until the weight change becomes 1% or less even after heating for 30 minutes or longer (usually 30 minutes to 2 hours).

 Polymerization conversion rate (% by weight) = {(solid content concentration in latex) Z (maximum solid content concentration)} X 100 The polymerization conversion rate was calculated based on the above formula.

 [0128] [Tensile properties]

 A press sheet having a thickness of about 0.7 mm was prepared by blending a copolymer with polypropylene, and three 2 (lZ3) test pieces described in Appendix 1 of JIS K7113 were punched therefrom. Using an autograph (manufactured by Shimadzu, AUTOGRAPH AG-2000A), a tensile test was conducted at a tensile speed of 16.66 mmZmin, and the elastic modulus was measured. In addition, the maximum point stress (tensile strength) and maximum point elongation were measured and the average value of three specimens was adopted.

 [0129] [High frequency sealability]

 High-frequency welder device (transmitting frequency 40. 46MHz, high-frequency maximum output 5kw): Model Y TO— 5A (Yamamoto Bitter Co., Ltd., foot pedal type), current 0.22A, welding time 0.5 seconds The mold temperature was about 30 ° C, and the tuning position was automatically adjusted under the conditions of 100 10 approximately 0.2 mm size sheets. The welded sheet was pulled by hand and visually confirmed for welding. When it did not peel, it was judged that the high-frequency sealability was good (O), and when it peeled, the high-frequency sealability was poor (X). Even if it peeled off, it was judged as (△) if there were marks of adhesion on the two sheets.

 [0130] [Oil resistance test]

 A No. 2 (1/3) test piece described in Appendix 1 of JIS K7113 was punched from a press sheet of about 0.7 mm thickness. The dumbbells were wrapped in wire mesh SUS316, immersed in IRM903 oil (Nihon Sanseki Oil) at 100 ° C for 24 hours, and then visually observed.

 [0131] [IZOD impact strength test]

ASTM 1 dumbbells were injection molded using an 80t molding machine (Toshiba). Cut out a 3mm thick, 12mm long, 60mm long test piece from the dumbbell after injection molding and insert a notch An impact resistance test was conducted at 23 ° C and 50% RH according to ASTM D-256.

[0132] [Bending characteristics]

 An ASTM No. 1 bar was injection molded using an 80t molding machine (manufactured by Toshiba). Using a bar, the elastic modulus was measured by performing a bending test in accordance with ASTM D-790 at 23 ° C 50% RH and a test speed of 5 mmZmin.

[0133] [Measurement of particle diameter]

 The particle diameter was measured with a Microtrac particle size distribution measuring device (manufactured by Nikkiso Co., Ltd.). In addition, the particle diameter of this invention means a volume average value.

[0134] [Acne rain resistant]

 A 4.5 cm X 4.5 cm size sheet was cut from the approximately 0.2 mm thick press sheet. On top of that, oleic acid was dropped from 5 drops at a force point and left at room temperature for 24 hours, and the state was visually observed. If all the oleic acid droplets that do not change on the sheet are not flowing, it is judged as good (O), and the sheet is warped and the oleic acid droplets drips even at one point! If so, it was judged as bad (X).

[0135] [Yellow Index measurement]

 A sheet sample (approx. 0.2 mm thick press sheet) kneaded with the copolymer was cut into a size of about 7 mm square and measured. As a color difference meter, a Spectro Color Meter SE2000 manufactured by NIPPON DENSHOKU was used. The average value of both sides of the sheet was adopted as the yellow index of the sheet.

[0136] [Sheet wettability]

 As an evaluation method for paintability and printability, JIS K-6768 “Plastic film and sheet wetting tension test method” was used. For the evaluation sample, a press sheet having a thickness of about 0.7 mm was used. For each test, measurements were taken at six locations on the sheet, and the average value was used as an indicator of surface wettability. The higher the numerical value and the higher the wettability, the higher the polarity of the sheet surface.

[Synthesis Example 1] Synthesis of Ligand

 The following chemical formula

[0138] [Chemical 18]

 A palladium complex having a structure of [0139] (hereinafter also referred to as [N N] PdMeCl) was synthesized by a known method described in a literature such as J. Am. Chem. Soc. 1995, 117, 6414. [Ν 'N] PdMeCl 80mmolZL Jetyl ether solution 8mL and LiB (C F) 80mmolZ

 6 5 4

 Mix 8mL of L jetyl ether solution and precipitate LiCl. [N'N] PdMe'B (C F)

 16 mL of a 40 mmol ZL jetyl ether solution of 6 5 4 complex was prepared. (Hereafter, this palladium complex is referred to as Brookhart catalyst.) Next, after concentrating and drying the jethyl ether solution of this Brookhart catalyst, 16 mL of methylene chloride (manufactured by Wako Pure Chemical Industries, Ltd.) was added to the 40 mmol ZL stock solution. did. These catalysts were prepared by a normal Schlenk operation under an argon atmosphere.

 [Synthesis Example 2] Synthesis of Ligand

 In a nitrogen atmosphere, prepared with reference to Helvetica Chimica Acta. 1928, p. 76, 1993, 2.61 g of pentafluor benzyltriphenylphospho-mubromide and 11 ml of dry T HF (Wako Pure Chemical Industries, Ltd.) were charged. Cooled to 0 ° C. using an ice bath. Triethylamine (manufactured by Wako Pure Chemical Industries, Ltd.) 1. 5 ml was added and stirred for 15 minutes. Further, 0.78 ml of trifluoroacetic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise and reacted at 0 ° C for 1 hour and at room temperature (15 ° C) for 1 hour.

 [0141] The filtrate was concentrated, washed with 15 ml of distilled water (manufactured by Wako Pure Chemical Industries, Ltd.), and dried. The obtained product was dissolved in methanol at 60 ° C, gradually cooled to 0 ° C, and recrystallized. The yield after drying was 1.5 g. ^ Η— NMR (CDC1) shows that the benzyl proton has disappeared.

 Three

 It was confirmed that a compound represented by the following chemical formula was produced.

[0142] [Chemical 19]

 [0143] (In the formula, Ph represents a full group).

Example 1 Synthesis of PE—PBA Copolymer

 Degassed distilled water (manufactured by Wako Pure Chemical Industries, Ltd.) 150 ml was charged into a 300 ml autoclave (made by TAIATSU TECHNO, material SUS 316) purged with argon. Brookhart's catalyst in methylene chloride solution (4mmol / L) 0.3ml of sodium dodecyl sulfate (Wako Pure Chemical Industries, Ltd.) 30mg, pure water 3mL, dehydrated 1 hexene (Wako Pure Chemical Industries, Ltd.) 0.3ml The emulsion was emulsified with 2.7 ml of dehydrated methyl chloride using an ultrasonic homogenizer (manufactured by SMT company, ultrasonic disperser UH-600). The action time of ultrasonic waves during emulsification is about 10 seconds. The emulsified Brookhart catalyst solution was introduced by syringe into a 300 ml autoclave previously charged with distilled water.

 [0145] Thereafter, ethylene gas (manufactured by Sumitomo Seika Co., Ltd.) was introduced, the inside of the autoclave was set to 3 MPa, and the mixture was reacted at room temperature for 6 hours while stirring with a stirrer. The ethylene gas used here was a dehydration column (manufactured by Nikkasei Co., Ltd., dry column HDF 300—A3) and a deoxygenation ram (manufactured by Nikka Seie Co., Ltd., GASCLEAN GC—HDF 300—M). Purification was performed through After the reaction, unreacted ethylene gas was removed to obtain polyethylene latex. The obtained polyethylene latex had a particle size of 0.5 m (measured with a Microtrac particle size distribution measuring device (manufactured by Nikkiso Co., Ltd.)) and a solid content concentration (Sc) of 2%. In this reaction, the Turn Over Number (hereinafter abbreviated as TON), which is a measure of the catalyst activity and indicates the number of ethylene monomer incorporation per unit catalyst, was TON = 8548 [mol Ethylene / mol cat.]. It was.

[0146] In a three-necked flask equipped with a condenser, a stirrer, and a thermometer, 8 g of pure water, 5 g of n-butyl acrylate (manufactured by Nippon Shokubai Co., Ltd.), Parolyl L (manufactured by Nippon Oil & Fats Co., Ltd.) 0 025g, sodium dodecyl sulfate (manufactured by Wako Pure Chemical Industries, Ltd.) 0.05g emulsified (particle size 4 μm) and polyethylene When the particle diameter was measured by adding 54 g of latex (particle diameter 0.5 m), it was found to be a united latex having a particle diameter of 1 μm. The atmosphere was replaced with nitrogen, heated to 70 ° C with stirring, and reacted for 4 hours. An olefin-based copolymer latex having a polymerization conversion rate of 100% and a particle size of about 1 μm was obtained.

 [0147] To 50 g of the olefin copolymer latex obtained in Example 1, 5 g of a 10% calcium chloride aqueous solution was added for salting out. The obtained solid was washed 3 times with pure water and then vacuum-dried to obtain a polyolefin copolymer.

 In the obtained copolymer, the solid material having no sticky feeling peculiar to PBA was easily loosened.

 (Example 2) Preparation of a resin composition

4 g of the polyolefin-based copolymer obtained in Example 1 and 20 g of random PP (F232DC) (manufactured by Mitsui Chemicals, Inc.) were used at 200 ° C. for 10 minutes using plastmill (manufactured by Toyo Seiki Co., Ltd., LABOPLASTOMILL). A thermoplastic resin composition is obtained by melt-kneading at lOOrpm and pressed (conditions: 200 ° C, no pressure, 10min → 200 ° C,

10 min → room temperature, 50 kgfZ cm ² , 5 min), about 0.7 mm and about 0.2 mm thick sheets were prepared, and the tensile properties and oil resistance were evaluated using the 0.7 mm thick sheets.

 [0149] Tensile elongation: 378%, tensile strength: 14 MPa, tensile elastic modulus: 390 MPa. After the oil resistance test, it was deformed but dissolved. In addition, the evaluation of the high frequency sealing performance obtained by stacking two 0.2 mm thick sheets was poor. The Yellow Index of the sheet was 9.19. The sheet wettability was 32.

 [0150] TEM observation of the obtained resin composition confirmed that about 1 μm of uniform polyolefin copolymer particles were dispersed in the polypropylene resin matrix. . By mixing the emulsified monomer and the polyethylene latex, the monomer is quickly absorbed, and the monomer is uniformly absorbed by the polyethylene particles. As a result, a unified latex, that is, uniform particles, is formed. Conceivable.

 [0151] (Example 3) Synthesis of PE ^ PBA copolymer

In an argon atmosphere, 13.5 mg (25 μmol) of the compound obtained in Synthesis Example 2 and 29.9 mg (108 μmol) of bis (cyclooctagen) nickel (manufactured by Kanto Chemical Co., Inc.) (Made by Kojun Pharmaceutical Co., Ltd.) 2. Each was dissolved in 5 ml and stirred for 15 minutes. Thereafter, the respective toluene solutions were mixed, and 1.5 ml of dehydrated 1-hexene (manufactured by Wako Pure Chemical Industries, Ltd.) was added. This catalyst solution was emulsified with 250 mg sodium dodecyl sulfate (manufactured by Wako Pure Chemical Industries, Ltd.) and 7.5 mg pure water using an ultrasonic homogenizer (manufactured by SMT company, ultrasonic disperser UH-600). The ultrasonic action time during emulsification is about 10 seconds.

 [0152] Argon-substituted 1L autoclave (TAIATSU TECHNO, TAS-1 type autoclave, material SUS316), sodium dodecyl sulfate 2g, pure water 500ml, dehydrated toluene 50ml, hexadecane (Wako Pure Chemical Industries, Ltd.) )) Was deaerated, and a solution emulsified with an ultrasonic homogenizer (SMT company, Ultrasonic Disperser UH-600) for about 2 minutes was charged. The emulsified solution of the catalyst was injected there with a syringe. Thereafter, ethylene gas (manufactured by Sumitomo Seika Co., Ltd.) was introduced, the inside of the autoclave was set to 3 MPa, and the reaction was carried out at 750 rpm and 70 ° C. for 2 hours.

 [0153] The ethylene gas used here was a dehydration column (manufactured by Nikkasei Co., Ltd., dry column HDF 300—A3) and a deoxygenation column (manufactured by Nikkasei Co., Ltd., GASCLEAN GC—HDF 300— Purification was performed through M). After the reaction, unreacted ethylene gas was removed to obtain a polyethylene latex. The obtained polyethylene latex had a particle size of 0.8 m (measured with a microtrack particle size distribution analyzer (manufactured by Nikkiso Co., Ltd.)) and a solid content concentration (Sc) of 17%. In this reaction, TON = 280000 [mol Ethylene / mol cat.]

 [0154] In a three-necked flask equipped with a condenser, a stirrer, and a thermometer, 30 g of pure water, 15 g of n-butyl acrylate (manufactured by Nippon Shokubai Co., Ltd.), Parroyl L (manufactured by Nippon Oil & Fats Co., Ltd.) 15 g of sodium dodecyl sulfate (manufactured by Wako Pure Chemical Industries, Ltd.) 0.15 g emulsified and 18 g of polyethylene latex were charged and purged with nitrogen. The mixture was heated to 70 ° C with stirring for 5 hours. An olefin copolymer latex having a polymerization conversion of 83% and a particle size of about 1 μm was obtained.

[0155] To 10 g of the obtained olefin copolymer latex, 5 g of a 10% calcium chloride aqueous solution was added for salting out. The obtained solid was washed three times with pure water and then vacuum-dried to obtain a polyolefin copolymer. The obtained copolymer was a solid product that did not have the sticky feeling peculiar to PBA, and was easily loosened. [0156] The obtained polyolefin copolymer lOOmg was wrapped in a stainless steel net bag (φ 0. 025 X 500), allowed to stand in 100 ml of black mouth form at room temperature for 24 hours, then taken out and dried. When the IR (infrared absorption spectrum) of the residue in the stainless steel mesh bag was measured, a peak indicating a carbonyl group was present. Usually, the polymer of n-butyl acrylate is dissolved in black mouth form, so that it was confirmed that the synthesized olefin copolymer was grafted with polyethylene and polybutyl acrylate.

 (Example 4) Preparation of a resin composition

4 g of the polyolefin-based copolymer obtained in Example 3 and 20 g of random PP (F232DC) (manufactured by Mitsui Chemicals, Inc.) were used at 200 ° C. for 10 minutes using a plastmill (manufactured by Toyo Seiki Co., Ltd., LABOPLASTOMILL). A thermoplastic resin composition is obtained by melt-kneading at lOOrpm and pressed (conditions: 200 ° C, no pressure, 10min → 200 ° C,

10 min → room temperature, 50 kgfZ cm ² , 5 min), about 0.7 mm thick and about 0.2 mm thick sheets were prepared, and the tensile properties and oil resistance were evaluated using the 0.7 mm thick sheets.

 [0158] Tensile elongation: 710%, tensile strength: 28 MPa, tensile elastic modulus: 260 MPa. After the oil resistance test, it was deformed but dissolved. In addition, the high-frequency paper-nosiness obtained by stacking two sheets of about 0.2 mm thickness was poor. The oleic acid resistance was poor. The Yellow Index of the sheet was 7.09. The sheet wettability was 32.

 Example 5: Synthesis of PE ^ P (BA / AN) copolymer

 In a three-necked flask equipped with a condenser, stirrer, and thermometer, pure water 64 g, n-butyl acrylate (made by Nippon Shokubai Co., Ltd.) 14 g, acrylonitrile (made by Wako Pure Chemical Industries, Ltd.) 6 g, Parroyl L ( Nippon Oil & Fats Co., Ltd.) 0.2 g, sodium dodecyl sulfate (Wako Pure Chemical Industries, Ltd.) 0.2 g emulsified and polymerized in the same manner as in Example 3, Sc = 8.9% polyethylene Latex 45 g was charged and purged with nitrogen. The mixture was heated to 80 ° C with stirring and reacted for 5 hours. Polymerization conversion was 75%, and PE ^ P (BA / AN) copolymer latex was obtained.

 [0160] To 10 g of the obtained olefin copolymer latex, 5 g of a 10% calcium chloride aqueous solution was added for salting out. The obtained solid was washed with pure water three times and then vacuum-dried to obtain a Ρ ^ Ρ (BA / AN) copolymer.

[0161] (Example 6) Preparation of rosin composition The PE ^ P (BAZAN) copolymer 8g obtained in Example 5 and random PP (PC540R) (Sanomer Co., Ltd.) 20g were used at 200 ° using a plastomill (Toyo Seiki Co., Ltd., LABOPLASTOMILL). A thermoplastic resin composition is obtained by melt-kneading at lOOrpm for 10 minutes at C, and press (conditions: 200 ° C, no pressure, 10 min → 200 ° C, 50 kgf / cm ² , 10 min → room temperature, 5 Okgf / cm ² and 5 min), about 0.7 mm thick and about 0.2 mm thick sheets were prepared, and the tensile properties and oil resistance were evaluated using the approximately 0.7 mm thick sheets.

 [0162] Tensile elongation: 582%, tensile strength: 20 MPa, tensile modulus: 262 MPa. After the oil resistance test, it was deformed but dissolved. In addition, the evaluation of the high frequency sealing performance when two sheets having a thickness of about 0.2 mm were stacked was good.

 [0163] (Example 7) Synthesis of PE ^ P (IP / AN) copolymer

 Nitrogen-substituted 1L autoclave, pure water 500g, isoprene (made by Wako Pure Chemical Industries, Ltd.) 87.5g, acrylonitrile (made by Wako Pure Chemical Industries, Ltd.) 37.5g, sodium dodecyl sulfate (Wako Pure Chemical Industries, Ltd.) 1.25g, sodium hydrogen carbonate (Wako Pure Chemical Industries, Ltd.) 1. 178g of polyethylene latex (sc = 14%) polymerized in the same way as in Example 3 with emulsified 25g (as polyethylene) 25 g) was added, and potassium persulfate (manufactured by Wako Pure Chemical Industries, Ltd.) 1. An aqueous solution prepared by dissolving 25 g in 8 g of pure water was added and the cap was closed. The mixture was heated to 80 ° C with stirring at 750 rpm and reacted for 5 hours. A ラ テ ッ ク ス ^ Ρ (ΙΡΖΑΝ) copolymer latex was obtained at a polymerization conversion rate of 96%. From the polymerization conversion value, the obtained polymer can be calculated as 144 g.

 [0164] To 700 g of the obtained olefin-based copolymer latex, 12 Og of 10% calcium chloride aqueous solution was added for salting out. The obtained solid was washed with pure water three times and then vacuum-dried to obtain a PE ^ P (IPZAN) copolymer. The ratio of PEZP (IPZAN) can be calculated as 25Z (144—25) = 1 7Z83.

[0165] About 1 lg of PE ^ P (IPZAN) obtained on a cylindrical filter paper that had been vacuum-dried at 80 ° C for 1 hour or longer was placed and weighed precisely (Wl). Then, 80 ml of toluene and a stirring bar were placed in a 100 ml flask, and the mixture was heated and stirred at 100 ° C for 3 hours. Thereafter, vacuum drying was performed at 80 ° C., and the weight of the copolymer remaining on the cylindrical filter paper was precisely weighed (W2). The insoluble content (W2ZW1 × 100) was also calculated for these weight forces. Compared to the P (IP / AN) content (83%) of the PE ^ P (IP / AN) copolymer, the insoluble content was 78%, so most PE grafted to P (IPZAN) There I understood.

 (Example 8) Preparation of a resin composition

° ^ プ ラ ス (ΙΡΖΑΝ) copolymer 8g obtained in Example 7 and random PP (PC540R) (Sanomer Co., Ltd.) 20g were used at 200 ° using a plastmill (Toyo Seiki Co., Ltd., LABOPLASTOMILL). A thermoplastic resin composition is obtained by melt-kneading at lOOrpm for 10 minutes at C, and press (conditions: 200 ° C, no pressure, 10 min → 200 ° C, 50 kgf / cm ² , 10 min → room temperature, 5 Okgf / cm ² and 5 min), about 0.7 mm thick and about 0.2 mm thick sheets were prepared, and the tensile properties and oil resistance were evaluated using the approximately 0.7 mm thick sheets.

 [0167] Tensile elongation: 229%, tensile strength: 10 MPa, tensile modulus: 176 MPa. After the oil resistance test, it was deformed but dissolved. In addition, the evaluation of the high frequency sealing performance when two sheets having a thickness of about 0.2 mm were stacked was good.

 (Example 9) Preparation of a resin composition

 280 g of PE ^ P (IP / AN) copolymer obtained by repeating Example 7 and 700 g of random PP (P C540R) (manufactured by Sanalomar Co., Ltd.) are twin-screw extruder (manufactured by Nippon Steel Works) , TEX30 HSS-25.5PW-2V) was used for melt kneading to obtain a thermoplastic resin composition. ASTM1 dumbbells and bars were injection molded using an 80t molding machine (manufactured by Toshiba) to evaluate impact resistance and bending properties. The value of Izod was 20jZm and the flexural modulus was 280MPa.

[Example 10] Synthesis of PE ^ P (IP / AN) copolymer

 Nitrogen-substituted 1 L autoclave with pure water 200 g, isoprene (manufactured by Wako Pure Chemical Industries, Ltd.) 105 g, acrylonitrile (manufactured by Wako Pure Chemical Industries, Ltd.) 45 g, sodium dodecyl sulfate (manufactured by Wako Pure Chemical Industries, Ltd.) 1 5 g, Permenta H (manufactured by NOF Corporation) 0.75 g of emulsified oil and 476 g of polyethylene latex of Sc = 6.3% 3% polymerized in the same manner as in Example 3 (30 g as polyethylene) Charge 3 g of 0.1% aqueous solution of FeSO7Η O / EDTA 2Na = l / 4.

 4 2

 Thereafter, 30 g of an SFS 1.0% aqueous solution was added. After closing, the mixture was heated to 50 ° C with stirring at 500 rpm and reacted for 5 hours. PE ^ P (IPZAN) copolymer latex was obtained with a polymerization conversion of 85%. From the value of the polymerization conversion rate, the obtained polymer can be calculated as 153 g.

The ratio of PE / P (IP / AN) can be calculated as 30Z (153-30) = 20Z80. [0170] To 700 g of the obtained olefin copolymer latex, 12 Og of a 10% calcium chloride aqueous solution was added for salting out. The obtained solid was washed three times with pure water and then vacuum-dried to obtain a PE P (IP / AN) copolymer.

 [0171] Since the insoluble matter obtained by the same operation as in Example 7 was 81%, PE was grafted to P (IPZAN), and the grafting efficiency of PE was (81—80) 720 X 100 = 5 Can be calculated as%

(Example 11) Preparation of a resin composition

 280 g of PE ^ P (IP / AN) copolymer obtained by repeating Example 10 and 700 g of random PP (PC540R) (manufactured by Sanalomar Co., Ltd.) are twin-screw extruder (manufactured by Nippon Steel Works, Ltd.) A thermoplastic resin composition was obtained by melt-kneading using TEX30 HSS-25.5PW-2V). ASTM1 dumbbells and bars were injection molded using an 80t molding machine (manufactured by Toshiba) to evaluate impact resistance and bending properties. The Izod value was 36jZm and the flexural modulus was 330MPa.

[Example 12] Synthesis of PE ^ PtBMA copolymer

 In a three-necked flask equipped with a condenser, stirrer, and thermometer, add 45 g of pure water, 14 g of pure water (manufactured by Nippon Shokubai Co., Ltd.), Parroyl L (manufactured by Nippon Oil & Fats Co., Ltd.) 0 14 g, sodium dodecyl sulfate (manufactured by Wako Pure Chemical Industries, Ltd.) 0.1.14 g of emulsified emulsion and 25 g of Sc = 11.0% polyethylene latex polymerized in the same manner as in Example 3 were charged with nitrogen. Replaced. The mixture was heated to 80 ° C with stirring and reacted for 5 hours. A PE ^ -PtBMA copolymer latex was obtained at a polymerization conversion of 93%.

 [0174] 40 ml of 1N hydrochloric acid was added, and the mixture was heated at 95 ° C for 2 hours. After returning to room temperature, Na SO aqueous solution

 twenty four

15 g was added for salting out. The obtained solid content was washed with pure water three times, and then vacuum-dried to obtain a PE PtBMA copolymer. In the IR measurement, a peak indicating a hydroxyl group was observed, indicating that it was hydrolyzed.

[Example 13] Preparation of a resin composition

10g at 200 ° C using 4g of PE ^ PtBMA copolymer obtained in Example 12 and 20g of random PP (PB363W) (manufactured by Sun Aroma Co., Ltd., LABOPLASTOMILL) (Toyo Seiki Co., Ltd.) The thermoplastic resin composition is melt kneaded at lOOrpm for 1 minute. The resulting press (conditions: 200 ° C, without pressure, 10min → → 200 ° C 50kgf / cm 2, 10min at room ^{temperature, 5 Okgf / cm 2, 5min} ) and create about 0. 2 mm thick sheet, resistant Orein An acidity test was performed. The oleic acid resistance was good. (Example 14) PE40 part P (BA 30 part ZAN70 part) Copolymer synthesis

 A 300 mL four-necked flask equipped with a Dimroth cooler, a stirrer, and a thermometer was preliminarily placed in a nitrogen atmosphere by nitrogen flow. On the other hand, 3 g of butyl acrylate and 7 g of acrylonitrile, oil-soluble initiator Parroyl LO. Lg, 0. lg of sodium dodecyl sulfate, and 20 g of pure water were emulsified with an ultrasonic homogenizer (SMT company, ultrasonic disperser UH-600). . The ultrasonic action time during emulsification is about 1.5 minutes. This vinyl monomer emulsion was put into a flask, and 125 g of a polymer latex polymerized in the same manner as in Example 3 (solid content: 3.2% in use) (125 g of polyethylene in this polyethylene latex was 4 g). Heating and stirring were started. The reaction system was heated with a oil bath until the temperature reached 60 ° C. The temperature reached 60 ° C in 1 hour at room temperature.

 [0176] After reaching 60 ° C, the reaction system was continuously heated and stirred, and reacted for 5 hours. When the temperature reached 60 ° C and the force was 4 hours, the polymerization conversion rate calculated from the solid content measurement was 67%. After polymerization, PE-P (BAZAN) latex was charged with 15 mL of a 10% calcium chloride aqueous solution to salt out the polymer. The obtained solid content was washed with pure water three times and then vacuum-dried to obtain a PEP (BAZAN) copolymer. The copolymer obtained by salting this PE-P (BAZAN) latex was 8.7 g, and the scale deposited during the polymerization was 1.7 g. 75%.

[0177] In addition, IR measurement of the obtained PE ^ P (BAZAN) copolymer was conducted, and the peak area derived from the nitrile group (2220 cm- ¹ 2270 cm ^_1 ) was absorbed into the area derived from polyethylene (27 50 cm - ¹ divided by 3000 cm ^_1) was 0.034. This value is a reference value for knowing the abundance of a certain functional group in the obtained copolymer.

(Example 15) Preparation of resin composition [0178] PE ^ P (BAZAN) copolymer obtained in Example 14 3.3g and random PP (PC540R, manufactured by Sanalomer) 16. A thermoplastic resin composition was obtained by melting and kneading at 200 ° C. lOOrpm for 10 minutes using LABOPLASTOMILL (Toyo Seiki Co., Ltd.). Furthermore, this thermoplastic resin composition is pressed. (Condition: 200 ° C, no pressure, 10 min → 200 ° C, 50 kgf / cm ² , 10 min → room temperature, 50 kgf 5 min) Create a sheet of about 0.7 mm thickness and perform a tensile elongation test with a thickness of about 0.2 mm This sheet was prepared and a high frequency sealing test was conducted. After the oil resistance test, there was deformation but it did not dissolve.

 Tensile elongation: 7%, tensile strength: 14 MPa, tensile modulus: 404 MPa. In addition, the evaluation of the high frequency sealing performance when two sheets having a thickness of about 0.2 mm were overlapped was poor.

 Example 16 Synthesis of PE40 part P (BA70 part ZAN30 part) copolymer

 95 g of polyethylene latex polymerized in the same manner as in Example 3 (solid content 4.2% in use) in a 300 mL four-necked flask equipped with a Dimroth condenser, dropping funnel, stirring device, and thermometer (in this polyethylene latex) The weight of polyethylene was 4 g), and sodium dodecyl sulfate (manufactured by Wako Pure Chemical Industries, Ltd.) 0.73 g was charged. The flask was pre-flowed with nitrogen so that the system was in a nitrogen atmosphere. Heat to 70 ° C in an oil bath while stirring, and when the polyethylene latex reaches 70 ° C, an aqueous solution of potassium persulfate (manufactured by Wako Pure Chemical Industries, Ltd.), a water-soluble initiator, is added to 5 mL of pure water. Dissolved) was added. The temperature drop in the system due to the addition of the potassium persulfate aqueous solution was about 3 ° C. When the temperature in the system returned to 70 ° C again, a mixture of butyl monomer (7 g of butyl acrylate and 3 g of acrylonitrile) was obtained. ) Was added dropwise.

[0180] The time required for dropping 10 g (approximately 10 mL) of this bull monomer was 1 hour and 30 minutes (dropping rate 0. lmL / min) ₀ 2 hours after the start of dropping of the bull monomer, the bull monomer was dropped. 30 minutes after the end of the addition, the solid content in the reaction system was measured, and the polymerization conversion was calculated to be 85%. The reaction was further continued at 70 ° C for 3 hours, and the heating and stirring was stopped to complete the polymerization. The polymer was salted out by adding 10 mL of 10% aqueous solution of calcium chloride to PE-P (BAZAN) latex after polymerization. The obtained solid content was washed with pure water three times and then vacuum-dried to obtain a PE P (BAZAN) copolymer. The copolymer obtained by salting this PE-P (BAZ AN) latex was 9.5 g, and the scale deposited during the polymerization was 3.7 g. Was 94%.

[0181] (Example 17) Preparation of rosin composition 14.3 g of the PE ^ P (BAZAN) copolymer obtained in Example 16 and 5. 7 g of random PP (PC540R, manufactured by San Aromar) Toyo Corporation A thermoplastic resin composition was obtained by melt-kneading at 200 ° C. lOOrpm for 10 minutes using a LABOPLASTOMILL manufactured by Seiki. Furthermore, this thermoplastic resin composition is pressed (conditions: 200 C, no pressure, 10 min → 200 C 50 kgf / cm ² 10 min → room temperature, 50 kgf Zcm ² 5 min) to create a sheet about 0.7 mm thick and pull it For the elongation test, a sheet having a thickness of about 0.2 mm was prepared and a high frequency sealing property test was conducted.

 [0182] Tensile elongation: 472%, tensile strength: 16 MPa, tensile modulus: 330 MPa. In addition, the evaluation of the high frequency sealing performance obtained by stacking two sheets of about 0.2 mm thickness was good. After the oil resistance test, it was deformed but not dissolved.

 Example 18 Synthesis of PE40 part P (BA 30 part ZAN70 part) copolymer

 Polyethylene latex polymerized in the same manner as in Example 3 in a 300 mL four-necked flask equipped with a Dimroth cooler, dropping funnel, stirrer, thermometer, and 92 g (in this polyethylene latex) The weight of polyethylene was 8 g), and sodium dodecyl sulfate (manufactured by Wako Pure Chemical Industries) 0.8 g was charged. The flask was preliminarily subjected to nitrogen flow so that the system was in a nitrogen atmosphere. While stirring, heat up to 70 ° C in an oil bath, and when the polyethylene latex reaches 70 ° C, an aqueous solution of 400 mg of pure water (400 mg of pure water, manufactured by Wako Pure Chemical Industries, Ltd.) Was dissolved). The temperature drop in the system due to the addition of the potassium persulfate aqueous solution was about 3 ° C. When the temperature in the system returned to 70 ° C again, a mixture of butyl monomer (6 g of butyl acrylate and 14 g of acrylonitrile) was obtained. (Liquid) was added dropwise.

[0184] The time required for dropping 20 g (approximately 20 mL) of this bull monomer was 1 hour and 30 minutes (dropping rate 0.2 mL / min) ₀ 2 hours after the start of dropping of the bull monomer, the bull monomer was dropped. 30 minutes after the completion of the addition, the solid content in the reaction system was measured and the polymerization conversion was calculated to be 95%. The reaction was further continued at 70 ° C for 1 hour, and the heating and stirring was stopped to complete the polymerization. The polymer was salted out by adding 15 mL of 10% aqueous calcium chloride solution to the PE-P (BAZAN) latex after polymerization. The obtained solid content was washed with pure water three times and then vacuum-dried to obtain a PE P (BAZAN) copolymer. The copolymer obtained by salting out this PE-P (BAZ AN) latex was 24. lg, and the scale deposited during the polymerization was 2.9 g. Was 99%. [0185] In addition, IR measurement of the obtained ΡΕ ^ Ρ (ΒΑ / ΑΝ) copolymer was performed, and the peak area derived from the nitrile group (2220 cm – ¹ to 2270 cm ^_1 ) was determined as the absorption area derived from polyethylene. The value divided by (27 50 cm- ¹ to 3000 cm ^_1 ) was 0.065. From this, it was confirmed that in the polymerization method shown in this (Example 18), the amount of -tolyl group contained in the polyolefin copolymer was larger than that in (Example 14).

(Example 19) Preparation of a resin composition [0186] PE ^ P (BAZAN) copolymer obtained in Example 18 3.3g and random PP (PC540R, manufactured by Sanalomar) 16. A thermoplastic resin composition was obtained by melt-kneading at 200 ° C and lOOrpm for 10 minutes using LABOPLASTOMILL (Toyo Seiki Co., Ltd.). Further, this thermoplastic resin composition is pressed (conditions: 200. C, no pressure, 10 min → 200. C, 50 kgf / cm ² , 10 min → room temperature, 50 kgfZcm ² , 5 min), and a sheet having a thickness of about 0.7 mm. A tensile elongation test was performed, and a sheet with a thickness of about 0.2 mm was prepared and a high frequency sealability test was performed.

 [0187] Tensile elongation: 23%, tensile strength: 15 MPa, tensile elastic modulus: 468 MPa. In addition, the evaluation of the high frequency sealing performance obtained by stacking two sheets having a thickness of about 0.2 mm was good. After the oil resistance test, it was deformed but not dissolved.

 [0188] (Comparative Example 1) Synthesis of PBA ^ PE copolymer

In an 8 L glass separable flask equipped with a stirrer, a thermometer, and a reflux condenser, 1.4 L of pure water and 226 g of sodium nitrite (manufactured by Wako Pure Chemical Industries, Ltd.) were charged to dissolve sodium nitrite. Next, in a separate 10L stainless steel container, 1.7L of pure water, butyl acrylate (manufactured by Nippon Shokubai Co., Ltd.) 1.96kg, methacrylic acid (Mitsubishi Rayon) 9.8g, stearyl methacrylate ( Wako Pure Chemical Industries, Ltd.) 19.6 g, Lauroyl peroxide (Nippon Yushi Co., Ltd., Parroyl L) 10 g, and sodium dodecylbenzenesulfonate aqueous solution (Kao Corporation, Neopelex G15, 15 mass ⁰ / ₀ ) 39.2 g was added and stirred with a homogenizer (manufactured by Tokushu Kika Kogyo Co., Ltd.) at 14000 rpm for 50 minutes to obtain a uniform emulsion.

[0189] Here, the emulsified monomer solution was placed in the 8 L glass separable flask. The emulsified liquid adhering to the wall of the stainless steel container was washed out with 200 mL of pure water and poured into the same 8 L separable flask. When this reaction solution was heated to 60 ° C in a water bath to start the reaction, the reaction was completed in about 5 hours, the solid content concentration was 35%, and the particle size was 0.7. A macromonomer latex solution of / zm polybutyl acrylate was obtained.

 [0190] After 750 ml of the above acrylic latex was degassed, it was charged into an argon-substituted 1 L autoclave (TAIATSU TECHNO, TAS-1 type autoclave, material SUS 316). Brookhart catalyst in methylene chloride solution (4mmolZL) l. 5mL sodium dodecyl sulfate (manufactured by Wako Pure Chemical Industries, Ltd.) 150mg, pure water 15mL, dehydrated 1 hexene (manufactured by Wako Pure Chemical Industries, Ltd.) 0.3ml, dehydrated The mixture was emulsified with 13.5 ml of methylene chloride using an ultrasonic homogenizer (manufactured by SMT company, ultrasonic disperser UH-600). The action time of ultrasonic waves during emulsification is about 10 seconds. The emulsified Brookhart catalyst solution was previously charged with distilled water! It was introduced into the 1 L autoclave with a syringe.

 [0191] Thereafter, ethylene gas (manufactured by Sumitomo Seika Co., Ltd.) was introduced, and the inside of the autoclave was set to 3 MPa and reacted at room temperature for 6 hours. The ethylene gas used here was a dehydration column (manufactured by Nikkasei Co., Ltd., dry column HDF 300-A3) and a deoxygenation column (manufactured by Nikkasei Co., Ltd., GASCL EAN GC-HDF 300-M). Purification was done through.

 [0192] After the reaction, unreacted ethylene gas was removed to obtain an olefin-based copolymer latex.

 The obtained polyolefin copolymer latex had a particle size of 0.7 / ζ πι and a solid content concentration of 22%. TON was TON = 1635 [mol Ethylene / mol cat.]. Compared to Example 1, the catalyst activity is greatly reduced.

 [0193] To 50 g of the obtained polyolefin copolymer latex, 5 g of a 10% calcium chloride aqueous solution was added for salting out. The obtained solid was washed three times with pure water and then vacuum-dried to obtain an olefin copolymer. The obtained copolymer had a sticky feeling peculiar to PBA, and the solid was aggregated in one lump.

 [0194] (Comparative Example 2) Preparation of a resin composition

 A sheet was prepared and evaluated in the same manner as in Example 2 except that the polyolefin-based copolymer obtained in Comparative Example 1 was used, and the following results were obtained. Tensile elongation: 390%, tensile strength: 20 MPa, tensile modulus: 387 MPa. After the oil resistance test, there was deformation, but the dissolution was strong. Moreover, the high frequency scenery was poor. The Yellow Index of the sheet was 14.43. The sheet wettability was 32.

[0195] (Comparative Example 3) Random PP Random PP (F232DC) was melt-kneaded at 200 ° C for 10 minutes at lOOrpm using a plastomill (Toyo Seiki Co., Ltd., LABOPLASTOMILL), and pressed (conditions: 200 ° C, no pressure, 10 m in → 200.C, 50kgfZcm ² , 10min → room temperature,

5 min), sheets of about 0.7 mm thickness and about 0.2 mm thickness were prepared, and the tensile properties and oil resistance were evaluated using the 0.7 mm thickness sheet.

 [0196] Tensile elongation: 790%, tensile strength: 43 MPa, tensile modulus: 730 MPa. After the oil resistance test, it was deformed but dissolved. In addition, the evaluation of the high frequency sealing performance when two sheets having a thickness of about 0.2 mm were overlapped was poor. Sheet wettability was 30 or less

[0197] (Comparative Example 4) Random PP

Random PP (PC540R) was melt-kneaded at 200 ° C for 10 minutes at lOOrpm using a Plastomill (Toyo Seiki Co., Ltd., LABOPLASTOMILL) and pressed (conditions: 200 ° C, no pressure, 10 m in → 200 ° C, 50 kgfZcm ² , 10 min → room temperature, 50 kgfZcm ² , 5 min), about 0.7 mm thickness and about 0.2 mm thickness sheets were prepared and used to evaluate the tensile properties and oil resistance.

 [0198] Tensile elongation: 750%, tensile strength: 29 MPa, tensile modulus: 310 MPa. After the oil resistance test, it was deformed but dissolved. In addition, the evaluation of the high frequency sealing performance when two sheets having a thickness of about 0.2 mm were overlapped was poor.

 [0199] (Comparative Example 5) EVA

Ethylene acetate butyl copolymer (EVA) (EV460) (manufactured by Mitsui DuPont Polychemical Co., Ltd.) is melt-kneaded at 200 ° C for 10 minutes at lOOrpm using a plast mill (manufactured by Toyo Seiki Co., Ltd., LABOPLASTOMILL) Conditions: 200 ° C, no pressure, 10min → 200 ° C, 50kgf / cm ² , 10min → room temperature, 50kgfZcm ² , 5min) to create a sheet of about 0.7mm thickness and about 0.2mm thickness, . Tensile properties and oil resistance were evaluated using 7mm thick sheets.

 [0200] Tensile elongation: 966%, tensile strength: 28 MPa, tensile modulus: 38 MPa. It dissolved after the oil resistance test. In addition, the evaluation of the high frequency sealability obtained by stacking two sheets of about 0.2 mm thickness was good. Moreover, the oleic acid resistance was poor.

 [0201] (Comparative Example 6) Reactor TPO

Reactor TPO (RTPO) (Q100F) (manufactured by Sanalomar Co., Ltd.) LABOPLASTOMILL), melt kneaded at 200 ° C for 10 minutes at lOOrpm, and press (conditions: 200 ° C, no pressure, 10min → 200 ° C, 50kgf / cm ² , 10min → room temperature, 50kgf 5min) Sheets of about 0.7 mm thickness and about 0.2 mm thickness were prepared, and tensile properties and oil resistance were evaluated using a 0.7 mm thickness sheet.

 [0202] Tensile elongation: 888%, tensile strength: 23 MPa, tensile modulus: 80 MPa. It dissolved after the oil resistance test. In addition, the evaluation of the high frequency sealing performance obtained by stacking two sheets of about 0.2 mm thickness was poor. Moreover, the oleic acid resistance was poor.

[0203] [Table 1]

§S ^

[0205] [Table 3]

 [0206] From Example 1 and Comparative Example 1, in the production method of the present invention, the radical polymerization of the bull monomer proceeds with high efficiency, and the polymerization of the olefin monomer by the coordination polymerization catalyst is also highly active (TON value). As a result, it can be seen that the polyolefin copolymer can be produced with high efficiency.

 [0207] Further, from Example 2 and Comparative Example 2, when the olefin-based copolymer obtained by the production method of the present invention was added as a modifier of polyolefin, emulsion polymerization of olefin was carried out in the presence of acrylic latex. The same physical properties as those obtained by adding the olefin copolymer obtained by the method to be carried out can be expressed.

 [0208] In Example 56, the use of a -tolyl group-containing monomer as a butyl monomer, and the combined use with butyl acrylate, can provide high frequency sealing properties in addition to softness. I got it. It is considered that a highly polar -tolyl group-containing monomer is effective in developing high-frequency sealability.

 [0209] In Examples 78, it can be seen that the softness is improved by using isoprene instead of butyl acrylate.

 [0210] From Examples 9 and 11, when the graft efficiency of the PE ^ P (IPZAN) copolymer was improved, the impact resistance was improved.

 [0211] Furthermore, by using PE PtBMA hydrolyzate (Example 12 13), the oleic acid resistance can be improved.

[0212] From (Example 5) and (Example 16), when the emulsified monomer is reacted with the polyethylene latex and when the non-emulsified monomer is added dropwise, the resulting polyolefin series is obtained. It was confirmed from the resin composition kneaded that the copolymer had the same effect as a polarity-imparting agent (Example 6 17) [0213] Also, from (Example 14) and (Example 18), when nitrile nitrile, which is a monomer containing a nitrile group, is polymerized in the presence of polyethylene latex, the monomer is emulsified and charged all at once. Compared to the polymerization force by adding monomers dropwise without emulsification, the polymerization rate of talli-tolyl is good, and the presence of -tolyl groups in polyolefin copolymers with good IR measurement ability Was confirmed to be large. Also, when these polyolefin copolymers obtained in (Example 14) and (Example 18) were kneaded to 20 parts by weight with respect to 100 parts by weight of random PP, monomers were added dropwise for polymerization (Example 18). ) The kneading of the polyolefin-based copolymer showed good high frequency sealability.

 [0214] Therefore, the olefin-based copolymer having higher functionality can be produced by the production method of the present invention. Various functionalities can be expressed by selecting a vinyl monomer according to the desired physical properties.

Claims

Claims [1] A polyolefin copolymer produced by radical polymerization of a butyl monomer in the presence of a polyolefin latex obtained using a coordination polymerization catalyst. [2] The coordination polymerization catalyst is any one of the following general formulas (1) to (5), which is one type of late transition metal complex-based coordination polymerization catalyst. The polyolefin copolymer described.

 [Chemical 1]

(In the formula, M is palladium or nickel. R 1 and R 2 each independently represent 1 to 4 carbon atoms.

 14

 It is a hydrocarbon group. R 1 and R 2 are each independently a hydrogen atom or a methyl group. R is

 2 3 5 A halogen atom, a hydrogen atom, or an organic group having 1 to 20 carbon atoms. X is an organic group having a heteroatom that can be coordinated to M, and may be connected to R, or X does not exist

 Five

 May be. L— is an arbitrary anion. )

[Chemical 2]

(In the formula, M is palladium or nickel. R 1 and R 2 each independently represent 1 to 4 carbon atoms.

 14

It is a hydrocarbon group. R is a halogen atom, a hydrogen atom, or an organic group having 1 to 20 carbon atoms

 Five

It is. X is an organic group with a heteroatom that can coordinate to M,

 Five

X or X may not be present. L is an arbitrary key. )

[Chemical 3]

 (Wherein M is nickel, palladium or platinum. E is oxygen or sulfur. X is phosphorus, arsenic or antimony. R 1, R 2 and R 3 are each independently hydrogen or carbon number 1.

 6 7 8

 ~ 20 hydrocarbon groups. R is a fluorine atom or a fluorinated hydrocarbon having 1 to 20 carbon atoms fl

It is a basic group. R is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a hydroxyl group, an ether group that also has a hydrocarbon group having 1 to 20 carbon atoms, a carbon number of 1 to 20 Ester group, sulfonate, or carbon number of 1-2 It is a sulfonic acid ester group that also has zero hydrocarbon group power. )

 [Chemical 4]

 (Wherein M is nickel, palladium or platinum. E is oxygen or sulfur. X is phosphorus, arsenic or antimony. R 1, R 2 and R 3 are each independently hydrogen or carbon number 1.

 6 7 8

 ~ 20 hydrocarbon groups. Y is a halogen atom. m is 1-3. )

[3] The polyolefin copolymer according to any one of claims 1 and 2, wherein the bulle monomer is a (meth) acrylic monomer.

[4] The polyolefin copolymer according to [3], which is a (meth) acrylic monomer strength tert-butyl (meth) acrylic ester.

[5] The monomer having a -tolyl group is used as the bull monomer. The polyolefin copolymer according to any one of -4.

[6] A monomer having a nitrile group is 5% by weight to 100% by weight in 100% by weight of the whole bull monomer

6. The polyolefin copolymer according to claim 5, wherein the polyolefin copolymer is%.

[7] The polyolefin copolymer according to [1], wherein the bulle monomer is a gen-based monomer.

[8] The polyolefin copolymer according to [7], wherein the gen-based monomer is isoprene or butadiene.

[9] The polyolefin copolymer according to any one of [1] to [8], wherein the polyolefin and graft polymer are grafted.

[10] The polyolefin copolymer according to any one of claims 1 to 9, wherein the butyl monomer is radically polymerized in the presence of the polyolefin latex obtained using the coordination polymerization catalyst. Production method.

[11] The vinyl monomer is pre-emulsified when the butyl monomer is radically polymerized in the presence of the polyolefin latex obtained using the coordination polymerization catalyst.

A method for producing a polyolefin copolymer according to 0.

[12] The polyolefin copolymer according to any one of [10] to [12], wherein the polyolefin latex obtained using a coordination polymerization catalyst and a butyl monomer are mixed in advance and then radical polymerization is performed. Manufacturing method.

[13] The polyolefin co-polymer according to any one of [10] or [11], wherein a butyl monomer is added dropwise to the polyolefin latex obtained using the coordination polymerization catalyst without emulsification, and the polymerization is performed. A method for producing a polymer.

[14] The water-soluble initiator may be used when radically polymerizing the butyl monomer in the presence of the polyolefin latex obtained using the coordination polymerization catalyst. The manufacturing method of the polyolefin-type copolymer of description.

[15] The method for producing a polyolefin copolymer according to any one of [10] to [13], wherein the polyolefin copolymer obtained by radical polymerization is further hydrolyzed.

[16] The polio according to claim 16, wherein a carboxylic acid group is generated by hydrolysis. A method for producing a refin copolymer.

 [17] A thermoplastic resin composition comprising the polyolefin copolymer according to any one of [1] to [9] and a thermoplastic resin.

[18] A thermoplastic resin composition comprising a polyolefin-based copolymer obtained by the method according to any one of claims 10 to 17 and a thermoplastic resin.

[19] A molded article comprising the thermoplastic resin composition according to any one of claims 18 and 19.