JP2008095083A - Household molded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a household molded article comprised of a polyolefinic molded article coated with a polar polymer excellent in properties such as impact resistance, heat resistance, scratch resistance, transparency, paint property, paintability, adhesiveness, and low-temperature flexibility, etc. and to provide a use of the molded article. <P>SOLUTION: The household molded article is a molded polyolefinic article (A) whose surface is coated with a polar polymer (B), and has such a construction as the polar polymer (B) is attached to the surface of the molded polyolefinic article (A) through a covalent bond. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

The present invention relates to a miscellaneous product molded body, and more specifically, polar weight excellent in any performance such as impact resistance, heat resistance, scratch resistance, transparency, paintability, printability, adhesiveness, and low temperature flexibility. The present invention relates to a miscellaneous goods molded body comprising a polyolefin-based molded body coated with a coalescence.

Thermoplastic resins such as polyolefin, polyester, polyamide, polyacetal
Excellent processability, chemical resistance, electrical properties, mechanical properties, etc.
Processed into injection molded products, hollow molded products, films, sheets, etc., and used for various applications. However, depending on the miscellaneous goods use that requires designability, it may not be said that the balance of physical properties such as impact resistance, scratch resistance, paintability, printability, adhesiveness, low temperature flexibility, and moldability is sufficient.

Further, as a method for improving the balance of physical properties such as impact resistance and moldability of a molded article made of the thermoplastic resin as described above, for example, a modifier such as ethylene / α-olefin copolymer is added to the thermoplastic resin. A method of blending into a composition is known. However, conventional modifiers may not have a good balance between rigidity, surface hardness and impact resistance depending on the application.

The present invention has been made to solve the above-described problems in the prior art, and has impact resistance, heat resistance, scratch resistance, transparency, paintability, printability, adhesiveness, and low temperature flexibility. It is an object of the present invention to provide a polyolefin-based molded article coated with a polar polymer excellent in any performance such as property.

In such a situation, the problem to be solved by the present inventors is to provide a miscellaneous product molded body that satisfies various demands required for miscellaneous goods.

The miscellaneous goods molded body according to the present invention is a molded body in which the surface of the polyolefin molded body (A) is coated with the polar polymer (B), and the polar polymer (B) is covalently bonded to the surface of the polyolefin molded body (A). The present invention is characterized by having a structure coupled with a through hole, and provides an application as a miscellaneous product of this molded body.

The miscellaneous goods molded body of the present invention has a structure in which a polar polymer segment is coated via an organic bond on the surface of a polyolefin molded body, without impairing the properties of the polyolefin substrate,
Substantially no separation between the polyolefin molded body surface and the polar polymer segment interface occurs.

Hereinafter, the miscellaneous goods molded body according to the present invention will be specifically described. In the present invention, “
“Coating” is defined as the surface of a polyolefin-based molded article being coated with a polar polymer layer via a covalent bond. Coating based on mere physical adhesion or ionic bonding is the subject of “coating” according to the present invention. Outside. That is, a solution prepared by, for example, dissolving a polar polymer in an appropriate solvent, etc., simply applied to the surface of the polyolefin molded body and then dried cannot be said to be coated via a covalent bond. It is outside the scope of “coating” according to the present invention.

The miscellaneous goods molded body according to the present invention is a molded body in which the surface of the polyolefin molded body (A) is coated with the polar polymer (B), and the polar polymer (B) is covalently bonded to the surface of the polyolefin molded body (A). It is a molded object characterized by having a structure joined through the.

Polyolefin molded product (A)
The polyolefin molded product (A) constituting the miscellaneous product molded product of the present invention includes the following (I) to (III):
It is a molded body of resin consisting of one or more selected from the group consisting of.
(I) A homopolymer or copolymer resin of a monomer selected from the group consisting of the following (A1) to (A3).
(A1) A homopolymer or copolymer of an α-olefin compound represented by CH ₂ = CH—C _x H _{2x + 1} (x is 0 or a positive integer).
(A2) A copolymer of an α-olefin compound represented by CH ₂ ═CH—C _x H _{2x + 1} (x is 0 or a positive integer) and a monoolefin compound having an aromatic ring.
(A3) Copolymer of an α-olefin compound represented by CH ₂ ═CH—C _x H _{2x + 1} (x is 0 or a positive integer) and a cyclic monoolefin compound represented by the following general formula (1) .

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

In the general formula (1), R ^{1 to} R ¹⁸ and R ^a and R ^b each independently represent an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group.

Here, the halogen atom is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
Moreover, as a hydrocarbon group, a C1-C20 alkyl group, a C1-C20 halogenated alkyl group, or a C3-C15 cycloalkyl group is mentioned normally each independently. More specifically, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an amyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, and an octadecyl group. Examples of the halogenated alkyl include Examples include a group in which at least a part of hydrogen atoms forming such an alkyl group is substituted with a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and examples of the cycloalkyl group include a cyclohexyl group.

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

In the above examples, the carbon atoms assigned numbers 1 and 2 represent carbon atoms to which R ¹⁵ (R ¹⁶ ) or R ¹⁷ (R ¹⁸ ) are bonded in the general formula (1).

Specific examples of the cyclic olefin represented by the general formula (1) include bicyclo [2.2.1
] Hept-2-ene derivative, tricyclo [4.3.0.1 ^2,5 ] -3-decene derivative, tricyclo [4.
3.0.1 ^2,5] -3-undecene derivatives, tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3-dodecene derivatives, pentacyclo [7.4.0.1 ^2,5 .1 ^9,12 .0 ^{8, 13} ] -3-Pentadecene derivatives, pentacyclo [
6.5.1.1 ^3,6 .0 ^2,7 .0 ^9,13] -4- pentadecene derivatives, pentacyclo [8.4.0.1 ^2,3 .1 ^9,12 .0 ^{8
, 13]} -3-hexadecene derivative, pentacyclo ^{[6.6.1.1 3,6 .0 2,7 .0 9,14]} -4- hexadecene derivatives, penta cyclopentadiene decadiene derivative, hexacyclo [6.6.1.1 ^{3, 6.} 1 ^10,13 .0 ^{2
, 7.0 9,14]} -4-heptadecene derivatives, heptacyclo ^{[8.7.0.1 3,6 .1 10,17 .1 12,15 .0} 2,7 .0 1
^1,16 ] -4-eicosene derivatives, heptacyclo-5-eicosene derivatives, heptacyclo [8.8
.0.1 ^4,7 .1 ^11,18 .1 ^13,16 .0 ^3,8 .0 ^12,17] -5-heneicosene derivatives, octacyclo [8.8.0
.1 ^2,9 .1 ^4,7 .1 ^11,18 .1 ^13,16 .0 ^3,8 .0 ^12,17] -5-docosene derivatives, Nonashikuro [10.9.1.1 ^{4,
7.1 13,20} .1 ^15,18 .0 ^3,8 .0 ^2,10 .0 ^12,21 .0 ^14,19] -5-pentacosene derivatives, Nonashikuro [10
.10.1.1 ^5,8 .1 ^14,21 .1 ^16,19 .0 ^2,11 .0 ^4,9 .0 ^{13, 22} .0 ^15,20] -5-hexacosenoic derivatives.

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

(A1) α-olefin compound represented by CH ₂ = CH-C _x H _{2x + 1} (x is 0 or a positive integer)
Homopolymer or copolymer of α-olefin compound represented by CH ₂ ═CH—C _x H _{2x + 1} (x is 0 or a positive integer) used in the present invention (A1) ), The α-olefin compound represented by CH ₂ ═CH—C _x H _{2x + 1} (x is 0 or a positive integer) is specifically ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1- Examples thereof include linear or branched α-olefins having 4 to 20 carbon atoms such as octadecene and 1-eicosene. Among these exemplified olefins, it is preferable to use at least one olefin selected from ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene.

As the α-olefin compound homopolymer or copolymer (A1) represented by CH ₂ ═CH—C _x H _{2x + 1} (x is 0 or a positive integer) used in the present invention, the above α- There is no particular limitation as long as it is obtained by homopolymerization or copolymerization of an olefin compound, but ethylene heavy polymers such as low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, ultrahigh molecular weight polyethylene, etc. Propylene polymers such as polymers, propylene homopolymers, propylene random copolymers, propylene block copolymers, polybutenes, poly (
4-methyl-1-pentene), poly (1-hexene), ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-hexene copolymer, ethylene-octene copolymer, ethylene- (4-methyl) -1-pentene) copolymer, propylene-butene copolymer, propylene- (
4-methyl-1-pentene) copolymer, propylene-hexene copolymer, propylene-octene copolymer and the like are preferable.

(A2) α-olefin compound represented by CH ₂ = CH—C _x H _{2x + 1} (x is 0 or a positive integer)
Copolymer of monoolefin compound having an aromatic ring and an aromatic ring having an α-olefin compound represented by CH ₂ ═CH—C _x H _{2x + 1} (x is 0 or a positive integer) used in the present invention In copolymer (A2) with monoolefin compound, CH ₂ ═C
As the α-olefin compound represented by HC _x H _{2x + 1} (x is 0 or a positive integer),
The same α-olefin compounds as those described in the section A1) can be mentioned. Specific examples of monoolefin compounds having an aromatic ring include styrene, vinyltoluene, α-methylstyrene, chlorostyrene, and styrenesulfonic acid. And styrene compounds such as salts thereof and vinylpyridine.

As a copolymer (A2) of an α-olefin compound represented by CH ₂ ═CH—C _x H _{2x + 1} (x is 0 or a positive integer) and a monoolefin compound having an aromatic ring used in the present invention, As long as it is obtained by copolymerizing the above α-olefin compound and a monoolefin compound having an aromatic ring, there is no particular limitation.

(A3) α-olefin compound represented by CH ₂ ═CH—C _x H _{2x + 1} (x is 0 or a positive integer)
And a cyclic monoolefin compound represented by the following general formula (II): CH ₂ = CH-C _x H _{2x + 1} (x is 0 or a positive integer) used in the present invention Copolymer (A3) of olefin compound and cyclic monoolefin compound represented by general formula (I) above
), The α-olefin compound represented by CH ₂ ═CH—C _x H _{2x + 1} (x is 0 or a positive integer) is the same α-olefin compound as described in the above section (A1) The structural unit derived from the cyclic monoolefin compound is represented by the following general formula (2).

In the formula (2), n, m, q, R ^{1 to} R ¹⁸ and R ^a and R ^b have the same meanings as in the formula (1).
(II) ethylene-vinyl ester copolymer resin and (III) ethylene- (meth) acrylic ester copolymer resin.

Ethylene-vinyl ester copolymer resins and ethylene- (meth) acrylic ester copolymer resins can be produced by high-pressure radical polymerization, and are obtained by copolymerizing ethylene and a monomer capable of radical polymerization. It is done.

Examples of the vinyl ester of the ethylene-vinyl ester copolymer include vinyl acetate,
Examples include vinyl propionate and vinyl neonate.

Examples of the (meth) acrylic acid ester of the ethylene- (meth) acrylic acid ester-based copolymer include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, and acrylic acid t. -Acrylic esters such as butyl and isobutyl acrylate, methyl methacrylate, ethyl methacrylate, and methacrylic acid n
Examples thereof include methacrylic acid esters such as -propyl, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate and isobutyl methacrylate, and unsaturated carboxylic acid esters having 4 to 8 carbon atoms. These comonomers can be used alone or in combination of two or more.

Among polyolefin resins composed of one or more selected from the group consisting of (I) to (III) described above, preferred polyolefin resins include high density polyethylene, medium density polyethylene, ethylene elastomer, propylene elastomer, isotactic resin. Tick polypolypropylene, syndiotactic polypropylene, high-pressure low-density polyethylene and its acrylic acid, acrylate ester, copolymer with vinyl acetate, polyolefin ionomer, 4-methylpentene-1 polymer, ethylene-cycloolefin copolymer, etc. Is mentioned. In addition, a resin obtained by modifying the above-mentioned polyolefin resin by any technique, such as a polyolefin resin graft-modified with an acrylate ester or maleic anhydride in the presence of a peroxide, also constitutes the polyolefin molded article according to the present invention. Applicable as polyolefin resin.

The polyolefin molded body of the present invention is a molded body mainly composed of these polyolefin resins, and may contain any other materials, for example, resins other than the above polyolefin resins, flame retardants, inorganic filler components, and the like. Well, various additives such as softeners, stabilizers, fillers, antioxidants, crystal nucleating agents, waxes, thickeners, mechanical stability imparting agents, leveling agents, wetting agents, film-forming aids, crosslinking It may be a composition to which an agent, an antiseptic, a rust inhibitor, a pigment, a filler, a dispersant, an antifreezing agent, an antifoaming agent and the like are added.

Polar polymer (B)
The polar polymer (B) constituting the polyolefin-based molded product according to the present invention is an addition polymer of a vinyl monomer having a hetero atom or an aromatic ring or a ring-opening polymer of a small ring compound.

The polar polymer (B) comprising these polymers is a homopolymer or copolymer of one or more monomers selected from organic compounds having at least one carbon-carbon unsaturated bond, and is a gel permeation chromatography. Number average molecular weight (Mn) in terms of polystyrene measured by chromatography (GPC): 100 to 100000, preferably 500 to 500000, more preferably 1000 to 1000
A polar polymer of 00 is preferred.

Specific examples of one or more monomers selected from organic compounds having at least one carbon-carbon unsaturated bond include (meth) acrylic acid, methyl (meth) acrylate, (meth)
Ethyl acrylate, (meth) acrylic acid-n-propyl, (meth) acrylic acid isopropyl, (meth) acrylic acid-n-butyl, (meth) acrylic acid isobutyl, (meth) acrylic acid
-tert-butyl, (meth) acrylic acid-n-pentyl, (meth) acrylic acid-n-hexyl, (meth) acrylic acid cyclohexyl, (meth) acrylic acid-n-heptyl, (meth) acrylic acid-n- Octyl, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, phenyl (meth) acrylate, toluyl (meth) acrylate, (meth) Benzyl acrylate, (meth) acrylic acid
-2-methoxyethyl, (meth) acrylic acid-3-methoxybutyl, (meth) acrylic acid-2-
Hydroxyethyl, 2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, 2-aminoethyl (meth) acrylate, 2- (dimethylamino) ethyl (meth) acrylate , Γ- (methacryloyloxypropyl) trimethoxysilane, ethylene oxide adduct of (meth) acrylic acid, trifluoromethylmethyl (meth) acrylate, 2-trifluoromethylethyl (meth) acrylate, (meth) acrylic acid 2-perfluoroethylethyl, (meth) acrylic acid 2-perfluoroethyl-2-perfluorobutylethyl, (meth) acrylic acid 2-perfluoroethyl, (meth) acrylic acid perfluoromethyl, (meth) acrylic acid Diperfluoromethylmethyl, (
2-Perfluoromethyl-2-perfluoromethyl methyl methacrylate), 2-perfluorohexyl ethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, 2-perfluoro (meth) acrylic acid (Meth) acrylic acid monomers such as hexadecylethyl, styrene monomers such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid and their salts, perfluoroethylene, perfluoropropylene, vinylidene fluoride, etc. Fluorine-containing vinyl monomers, silicon-containing vinyl monomers such as vinyltrimethoxysilane, vinyltriethoxysilane, maleic anhydride, maleic acid, monoalkyl and dialkyl esters of maleic acid, fumaric acid, monoalkyl esters of fumaric acid and Zia Contains maleimide monomers such as kill ester, maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide, nitrile groups such as acrylonitrile, methacrylonitrile, etc. Vinyl monomers, (meth) acrylamide, N-methyl (meth)
Acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, N,
Amide group-containing vinyl monomers such as N-dimethyl (meth) acrylamide, vinyl acetate,
Vinyl ester monomers such as vinyl propionate, vinyl pivalate, vinyl benzoate and vinyl cinnamate, olefin monomers such as ethylene, propylene and butene, diene monomers such as butadiene and isoprene, vinyl chloride, vinylidene chloride and allyl chloride , Allyl alcohol, etc., and carbons such as an acroyl group, a methacryloyl group and a styryl group at the terminal
Examples thereof include a macromonomer having a carbon unsaturated bond and a molecular weight of 100 to 100,000.

As the polar polymer (B) comprising the addition polymer used in the present invention, one or more monomers selected from (meth) acrylic acid and derivatives thereof, (meth) acrylonitrile, styrene and derivatives thereof, Polymers obtained by copolymerization are preferred, (meth) acrylic acid esters, styrene, (meth) acrylamide, (meth) acrylonitrile, (meth) acrylic acid homopolymers and copolymers are more preferred, A homopolymer of methyl methacrylate, styrene, methyl acrylate, acrylonitrile, butyl acrylate and acrylamide, or a copolymer containing these as main monomers is preferred.

In addition, the coat layer made of the polar polymer (B) may be a polymer having a smooth surface when used in applications where affinity with other solvents or affinity with other resins is important. desirable. In this case, a polar polymer (B) insoluble in an organic solvent or a polar polymer (B
) Is not preferred.

On the other hand, the polar polymer (B) composed of a ring-opening polymer of a small ring compound includes small ring compounds such as one or more lactones, lactams, cyclic ethers, cyclic acid anhydrides or cyclic formals. A structure in which the ring is opened and they are added to each other is preferred.

The small ring compound for obtaining the ring-opening polymer is not particularly limited as long as it easily undergoes ring-opening polymerization, but lactones and cyclic ethers are preferable because of the ease of ring-opening polymerization. .

Specific examples of lactones include glycolide, lactide, α-hydroxybutyric acid, α-
Examples include intermolecular cyclic diesters such as hydroxyvaleric acid, α-hydroxyisovaleric acid, α-hydroxycaproic acid, α-hydroxyisocaproic acid, α-hydroxy-β-methylvaleric acid, α-hydroxyheptanoic acid and the like. Among these, glycolide and lactide are easily available, and the physical properties of these polymers are desirable, and are preferred lactones. Moreover, what has asymmetric carbon may be any of L-form, D-form, racemic form, and meso form.

Specific examples of cyclic ethers include ethylene oxide, propylene oxide, isobutylene oxide, cis-1,2-butylene oxide, trans-1,2-butylene oxide,
Styrene oxide, cyclopentene oxide, cyclohexene oxide, epichlorohydrin, glycidol, glycidyl phenyl ether, oxetane, 2-methyloxetane, 2,2-dimethyloxetane, 2-chloromethyloxetane, 3,3-dimethyloxetane, 3-methyl -3-chloromethyloxetane, 3,3-bis (chloromethyl) oxetane,
3- (trimethylsilyloxymethyl) oxetane, tetrahydrofuran, 2-methyl-tetrahydrofuran, 3-methyl-tetrahydrofuran, 2,5-dimethoxytetrahydrofuran, 2-ethoxytetrahydrofuran, methyltetrahydrofurfuryl ether, 2,
3-dihydrobenzofuran, 2,3-dihydrofuran, 2,5-dihydrofuran, tetrahydrofuran acetic acid ethyl ester, tetrahydrofurfuryl chloride, tetrahydrofurfuryl acetate, tetrahydrofurfuryl propionate, tetrahydrofurfuryl n-butyrate, Examples thereof include tetrahydrofurfuryl methacrylate. Of these, ethylene oxide, propylene oxide,
Oxetane and tetrahydrofuran are preferred.

The polar polymer (B) used in the invention may be modified with a halogen atom or various molecules at the terminal, and some of the monomer units are hydrolyzed, metal, low molecule or introduced reaction. It may be modified or cross-linked via a functional group.

Miscellaneous Goods Molded Article of the Present Invention The miscellaneous goods molded article of the present invention has a polar polymer (B) on the surface of the polyolefin molded article (A) described above.
Is a molded body coated with the polar polymer (B).
) Since the surface has a structure bonded through a covalent bond, the polar polymer (B) is hardly peeled off or eluted by various organic solvents.

For this covalent bond mode, the polar polymer (B) is preferably directly covalently bonded to the polyolefin chain (a) constituting the polyolefin molded body existing on the surface of the polyolefin molded body (A). It may have a short spacer connecting part (preferably less than 5% by weight based on the weight of the polar polymer (B)) that does not impair the properties of the polar polymer (B) that coats.

However, in this case, it is essential that all the linking parts are based on a covalent bond chain.
The bonding mode is preferably composed only of a covalent bond that is excellent in chemical stability against external stimuli such as light, heat, and moisture.

From this viewpoint, when the polar polymer (B) is an addition polymer of a monomer having at least one carbon-carbon unsaturated bond, and the connecting portion with the surface of the polyolefin molded body (A) is carbon-carbon sharing A preferred structure is that they are linked by a bond or a covalent bond formed by a chain thereof.

For example, when the connection includes a metal-mediated bond, it can be easily bonded by heat, moisture, etc. in the usage conditions of the molded body or in the process of processing for any application such as a laminate or coating of the molded body. It may cause dissociation and cause peeling of the polar polymer (B).

In the miscellaneous goods molded body of the present invention, the surface of the polyolefin molded body (A) is a polar polymer (B
However, it may be partially coated or completely coated depending on the application. Further, the coated part and the non-coated part may be regularly arranged two-dimensionally.

In addition, the thickness of the polar polymer (B) coated on the surface of the polyolefin molded product (A) on the surface of the miscellaneous product molded product of the present invention is attributable to the type, molecular weight, and number of molecules of the polar polymer, so that it is suitable for the intended use. Is adjusted accordingly, but in the range of 1 nm to 5 mm, preferably 1
0 nm to 1 mm. It is preferable that the polystyrene conversion number average molecular weight (Mn) of the polar polymer segment (B) which is a coating layer is 500-500000.

Production method of miscellaneous article molded article of the present invention The miscellaneous article molded article of the present invention is obtained by polymerizing a polar compound (monomer) with a polymerization initiation group present on the surface of the polyolefin molded article (A) as an initiating reaction point. A
) Only the surface can be coated with the polar polymer (B).

The molding method for preparing the polyolefin molded body (A) according to the present invention is not particularly limited, and is a molding method generally used for thermoplastic resins, that is, injection molding, extrusion molding, hollow molding, heat molding. Various molding methods such as molding and press molding can be applied.

The method for introducing the polymerization initiating group into the polyolefin molded body (A) is not particularly limited, but even if the polyolefin resin in which the polymerization initiating group is introduced in advance is molded,
The polyolefin molding may be surface-modified with a low-molecular or high-molecular polymerization initiating group. In addition, a polar compound (monomer) may be polymerized in a state where a polyolefin resin into which a polymerization initiating group has been introduced is coated on another resin film molded body, metal, paper, wood, etc., which is molded into a film or sheet. .

As a method for producing a miscellaneous article molded article of the present invention, that is, a molded article coated with a polar polymer (B), a polymerization step of a polar compound (monomer) on the surface of a polyolefin molded article (A) into which a polymerization initiating group has been introduced. Due to the difference, the following two production methods (P-1) and (P-2) are preferably used.

(P-1) A molded article made of polyolefin covalently bonded to radical polymerization initiating groups is coated.
In the surface of the method (A ′), the radical polymerization initiation group present on the surface of (A ′) is used as the starting point.
A process for producing a polymer by controlled radical polymerization of one or more monomers selected from organic compounds having at least one carbon-carbon unsaturated bond.

(P-2) A molded body made of polyolefin with covalently bonded groups of heteroatoms is coated.
A method of producing by ring-opening polymerization of a small ring compound on the surface of (A ″), starting from a heteroatom present on the surface of (A ″).

First, the method for producing (P-1) according to the present invention will be described.
On the surface of the molded article (A ′) comprising a polyolefin covalently bonded to a radical polymerization initiating group, the monomer is polymerized using controlled radical polymerization, thereby controlling the molecular weight, molecular weight distribution and molecular end of the polar polymer (B), etc. It is possible to control the primary structure.

In the present invention, the type of the controlled radical polymerization method for introducing the polar polymer (B) is not particularly limited, but the ease of introduction of the polymerization initiating group into the polyolefin, the type of the polar polymer (B), the polymerization You can choose a more appropriate method of conditions.

For example, as disclosed in Trend Polym. Sci., (1996), 4, 456, a method in which a group having a nitroxide is bonded and a radical is generated by thermal cleavage, atom transfer radical polymerization (ATRP) and The method called, Science, (1996), 272,866, Chem. Rev., 101,
2921 (2001), WO96 / 30421 publication, WO97 / 18247 publication, WO98 / 01480 publication, WO98 / 40415 publication, WO00 / 156795 publication, or Sawamoto et al., Chem. Rev., 101, 3689 (2001) , JP-A-8-4
No. 1117, JP-A-9-208616, JP-A 2000-264914, JP-A 2001-316410,
As disclosed in JP-A-2002-80523 and JP-A-2004-307872, radical polymerization is performed using an organic halide or a sulfonyl halide as an initiator and a metal complex having a transition metal as a central metal as a catalyst. There is a method of radical polymerization of monomers.

The radical transfer polymerization polymerization method is an effective controlled radical polymerization method for introducing the polar polymer (B) according to the present invention because of the ease of introduction of the radical polymerization polymerization initiation terminal and the abundance of selectable monomer species. It is.

As a method for introducing the atom transfer radical polymerization initiator into the polyolefin, a functional group conversion method or a direct halogenation method is effective.

The functional group conversion method is a method of converting a functional group portion of a polyolefin into which a functional group such as a hydroxyl group, an acid anhydride group, a vinyl group, or a silyl group is introduced into an atom transfer radical initiator structure, for example, a published patent publication ( JP-A-2004-131620) is a method in which a hydroxyl group-containing polyolefin is modified with a low molecular compound such as 2-bromoisobutyric acid bromide.

The direct halogenation method is a method of obtaining a halogenated polyolefin having a carbon-halogen bond by directly acting a halogenating agent on the polyolefin.

The halogenating agent to be used and the kind of the halogen atom introduced are not particularly limited, but brominated polyolefin into which a bromine atom is introduced is preferable from the balance between the stability of the atom transfer radical initiation skeleton and the initiation efficiency.

Also, as shown in Science, (1996), 272,866, etc., the structure of atom transfer radical polymerization is preferably a structure having a low bond-dissociation energy of a carbon-halogen atom. A halogenating agent that easily develops a structure in which a halogen atom is introduced or a structure in which a halogen atom is introduced into a carbon atom bonded to an unsaturated carbon-carbon bond such as a vinyl group or vinylidene group is preferably used.

From this point of view, bromine (bromine) and N-bromosuccinimide (NBS) are preferably used as the halogenating agent in producing a halogenated polyolefin by a direct halogenation method.

In performing the controlled radical polymerization according to the present invention, a solvent may or may not be used.
As the solvent that can be used, any solvent can be used as long as it does not inhibit the polymerization reaction and does not dissolve the molded article (A ′) made of polyolefin into which a radical polymerization initiating group is introduced. , Aromatic hydrocarbon solvents such as toluene and xylene, aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, nonane and decane, and alicyclic hydrocarbons such as cyclohexane, methylcyclohexane and decahydronaphthalene Solvent, chlorinated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, trichlorobenzene, methylene chloride, chloroform, carbon tetrachloride and tetrachloroethylene, methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol And tert-butanol Solvent, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate and dimethyl phthalate, ethers such as dimethyl ether, diethyl ether, di-n-amyl ether, tetrahydrofuran and dioxyanisole Examples of the solvent include system solvents. Water can also be used as a solvent. These solvents may be used alone or in admixture of two or more.

The polymerization temperature is a molded article (A ′) made of polyolefin into which radical polymerization initiating groups are introduced.
Can be arbitrarily set as long as the temperature does not melt or swell and the radical polymerization reaction proceeds. Although it is not uniform depending on the degree of polymerization of the desired polymer and the kind and amount of the radical polymerization initiator and solvent used, it is usually -50 ° C to 150 ° C, preferably 0 ° C to 80 ° C, more preferably 0. It is 50 degreeC. In some cases, the polymerization reaction can be carried out under reduced pressure, normal pressure, or increased pressure. The polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon after oxygen is removed to suppress side reactions.

Next, (P-2) will be described.
In the present invention, the group consisting of heteroatoms in the molded article (A ″) made of polyolefin to which a group consisting of heteroatoms is covalently bonded is a group having the ability to initiate ring-opening polymerization of a small ring compound. That is, it is a group capable of generating an anion or a cation under a specific temperature condition or by addition of an acid or a base catalyst to generate an active species of ring-opening polymerization.
Specific examples include a hydroxyl group, a carboxyl group, an acid anhydride group, an epoxy group, an amino group, or a reaction product of these with a metal compound.
For example, when ring-opening polymerization of polylactide, which is a lactone, is performed by using a polyolefin molded body having a hydroxyl group covalently bonded to the surface, and in the presence of the monomer, a metal catalyst such as tin octoate is present on the surface to form polylactic acid. Can be obtained.

In performing the ring-opening polymerization of the present invention, a solvent may or may not be used. Any solvent can be used as long as it does not inhibit the polymerization reaction and dissolves the polyolefin molded article, but an aprotic solvent is preferred. For example, as a specific example:
Aromatic hydrocarbon solvents such as benzene, toluene and xylene, aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, nonane and decane, alicyclic hydrocarbons such as cyclohexane, methylcyclohexane and decahydronaphthalene Solvents, chlorinated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, trichlorobenzene, methylene chloride, chloroform, carbon tetrachloride and tetrachloroethylene, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ethyl acetate and dimethyl phthalate And ester solvents such as dimethyl ether, diethyl ether, di-n-amyl ether, tetrahydrofuran and dioxyanisole. These solvents may be used alone or in admixture of two or more.

The reaction temperature may be any temperature as long as the ring-opening polymerization reaction proceeds at a temperature at which the polyolefin molded body (A ″) to which a group consisting of heteroatoms is covalently bonded does not melt or swell,
Although it is not uniform depending on the polymerization degree of the desired polymer and the kind and amount of the radical polymerization initiator and solvent to be used, it is usually -50 ° C to 150 ° C. Preferably it is 0 degreeC-80 degreeC, More preferably, it is 0 degreeC-50 degreeC. In some cases, the reaction can be performed under reduced pressure, normal pressure, or increased pressure.

In carrying out the ring-opening polymerization, it is preferable that the small ring compound, the solvent, and the catalyst component to be used are purified. In particular, in order not to cause the ring-opening homopolymer as a by-product, water is sufficiently removed. The polymerization is preferably carried out in the system.

Uses of the molded product The miscellaneous product molded product according to the present invention has excellent properties such as impact resistance, heat resistance, scratch resistance, transparency, paintability, printability, adhesiveness, and low temperature flexibility. It is useful in a wide range of fields as miscellaneous goods.

EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples. The X-ray photoelectron spectroscopic analysis of the surface of the molded body shown in this example is S
ATR / IR analysis was performed using an SSX-100 type X-ray photoelectron spectrometer manufactured by SI.
The measurement was performed using an FTS-6000 type infrared spectrophotometer manufactured by ad company.

The Rockwell hardness (HR) is measured using a square plate having a thickness of 2 mm, a length of 120 mm and a width of 130 mm in accordance with ASTM D785, and the flexural modulus (FM) is measured according to ASTM D.
In accordance with 790, using a test piece having a thickness of 1/8 inch, span 51 mm, bending speed 2
Measured under the condition of 0 mm / min, the heat distortion temperature (HDT) is ASTM D648 (4.6 k).
g / cm ² ), and measurement was performed using a test piece having a thickness of ¼ inch.

[Production Example 1]
[Preparation of polypropylene moldings having radical polymerization initiating groups on the surface (1)]
Propylene / 10-undecene produced according to the method described in JP-A-2002-145944
-1-All copolymer (polypropylene equivalent molecular weight measured by high temperature GPC Mw = 2
6400, Mw / Mn = 1.71, comonomer content 1.0 obtained from ¹ H-NMR measurement
mol%,) 170 g was put into a 2 L glass polymerization vessel purged with nitrogen and hexane 1
700 mL, 9.2 mL of 2-bromoisobutyric acid bromide was added, and the temperature was raised to 60 ° C. and stirred for 2 hours. After the reaction slurry-like polymer solution returned to room temperature was filtered with a Kiriyama funnel, the polymer on the funnel was rinsed with 200 mL of methanol three times. 50 polymers
The polymer was dried at 10 ° C. under reduced pressure at 10 ° C. for 10 hours to obtain a white polymer. ¹ H-N
As a result of MR, 94% of terminal OH groups were halogen atom-containing polypropylene modified with 2-bromoisobutyric acid groups. This halogen atom-containing polypropylene was compressed into a compression molding machine (180 ° C.
, 10 MPa) to form a sheet having a thickness of 3.0 mm.
As a result of surface analysis of this polypropylene molded body by ATR / IR measurement, 1730c
Absorption of estecarbonyl stretching vibration can be confirmed at m ⁻¹ , and it is 0.3 atm by XPS measurement
% Bromine atoms were found on the surface. From this, it was confirmed that an atom transfer radical polymerization initiation terminal is present on the surface of the polypropylene molded body.

[Production Example 2]
[Preparation of polypropylene molded body having radical polymerization initiation group on the surface (2)]
Polypropylene ([η] = 2.6) manufactured by Mitsui Chemicals, Inc. was compressed into a compression molding machine (180 ° C., 1
0 MPa) to form a sheet having a thickness of 1.0 mm and 4 cm × 4 cm. The molded body was immersed in 50 mL of butyl acetate solvent, and the inside of the reactor was purged with nitrogen by nitrogen bubbling. Then, 0.5 mL of dry bromine (bromine) was added, heated to 50 ° C., and slowly stirred with a stirrer chip. . After reacting for 24 hours, it was cooled to room temperature, the polypropylene sheet was pulled up, and the surface was washed with acetone. As a result of conducting a surface analysis of the polypropylene molded body by XPS measurement, it was revealed that 0.5 atm% bromine atoms exist on the surface.

[Production Example 3]
[Preparation of polyethylene molded product having ring-opening polymerization initiation group on the surface (1)]
Ethylene / 10-undecene produced according to the method described in JP-A-2002-145944
1-ol copolymer (polyethylene equivalent molecular weight by high temperature GPC measurement Mw = 904
00, Mw / Mn = 2.53, comonomer content obtained from ¹ H-NMR measurement 3.9 mo
l%) using a compression molding machine (150 ° C., 10 MPa), thickness 1.0 mm, 4 cm × 4 cm
Molded into a sheet.
As a result of conducting surface analysis of this polyethylene molding by ATR / IR measurement, 3500 cm ⁻¹
Since broad absorption was observed in the vicinity, it was confirmed that a hydroxyl group was present on the surface of the molded body.

[Production Example 4]
[Polypropylene molded product coated with poly (methacrylic acid (2-hydroxyethyl)) (= PHEMA)]
The polypropylene molded body having the radical polymerization initiating group obtained in Production Example 1 on the surface is placed in a glass reactor, immersed in 250 mL of ethanol and 40 mL of methacrylic acid (2-hydroxyethyl) sufficiently bubbled with nitrogen, and further reacted. The vessel was purged with nitrogen. Here, cuprous bromide (5
48 mg) and 3.75 mL of a 2M xylene solution of N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine and 5.0 mL of xylene were added and the mixture was stirred slowly at 25 ° C. for 24 hours. The immersed polypropylene molded body was taken out, washed with acetone several times, and then dried at 50 ° C. for 10 hours under a reduced pressure of 10 Torr. To 3200cm ^-1 ~3600cm ^-1 Analysis of the surface of the obtained polypropylene molded body ATR / IR, broad absorber due to OH stretching vibration absorber due to the ester carbonyl stretching vibration in the vicinity of 1730 cm ^-1 is From the observation, poly (methacrylic acid (
It was confirmed that 2-hydroxyethyl)) was present. Transmission electron microscope (
From the photograph of the cross section of the molded body of TEM), poly (methacrylic acid (2-hydroxyethyl)) is
It was confirmed that the surface of the polypropylene sheet was completely coated with a thickness of about 10 μm to 20 μm. Even if this polypropylene molded body is treated with THF, no change in weight is observed. Therefore, poly (methacrylic acid (2-hydroxyethyl)) is coated on the polypropylene main chain existing on the substrate surface via a covalent bond. Indicated. From the results of the water contact angle measurement on the surface (Table 1), it was revealed that the hydrophilicity of the surface of the polypropylene molded body was remarkably improved.

[Production Example 5]
[Polypropylene molded body coated with polymethyl methacrylate (= PMMA)]
The polypropylene molded body having the radical polymerization initiating group obtained in Production Example 1 on the surface is placed in a glass reactor, and 150 mL of THF and methyl methacrylate 150 sufficiently bubbled with nitrogen.
It was immersed in mL and the reactor was further purged with nitrogen. Here, cuprous bromide (548 mg) and N, N
, N ′, N ″, N ″ -pentamethyldiethylenetriamine in 2M xylene solution 3.75 m
A homogeneous solution of L and xylene (5.0 mL) was added, and the mixture was slowly stirred at 60 ° C. for 10 hours. The polypropylene molded body in which the polymerization solution was returned to room temperature was taken out, the surface was washed several times with acetone, and then dried at 50 ° C. for 10 hours under a reduced pressure of 10 Torr. When the surface of the polypropylene molded body obtained by ATR / IRR was analyzed, 1730 cm ⁻¹ , 1270 cm ⁻¹ , 124
2cm ^-1, 1193cm ^-1, characteristic peaks of PMMA to 1149cm ^-1 was observed, the presence of PMMA on the sheet surface was observed.
Moreover, from the photograph of the cross section of the molded body of the transmission electron microscope (TEM), PMMA is about 40 μm.
It was confirmed that the surface of the polypropylene sheet was completely coated with a thickness of ˜60 μm.

[Production Example 6]
[Polypropylene molded body coated with polymethyl methacrylate (= PMMA)]
The polypropylene molded body having the radical polymerization initiating group obtained in Production Example 2 on the surface is put into a glass reactor, and 150 mL of THF and methyl methacrylate 150 sufficiently bubbled with nitrogen.
It was immersed in mL and the reactor was further purged with nitrogen. Here, cuprous bromide (548 mg) and N, N
, N ′, N ″, N ″ -pentamethyldiethylenetriamine in 2M xylene
A homogeneous solution of mL and xylene 5.0 mL was added and stirred slowly at 60 ° C. for 10 hours. The polypropylene molded body in which the polymerization solution was returned to room temperature was taken out, the surface was washed several times with acetone, and then dried at 50 ° C. for 10 hours under a reduced pressure of 10 Torr. When the surface of the polypropylene molded body obtained by ATR / IR was analyzed, 1730 cm ⁻¹ , 1270 cm ⁻¹ , 124
2cm ^-1, 1193cm ^-1, characteristic peaks of PMMA to 1149cm ^-1 was observed, the presence of PMMA on the sheet surface was observed.

[Production Example 7]
[Polylactic acid-coated polyethylene-based molded product]
50 mL of dehydrated toluene was poured into a 200 mL flat bottom separable flask equipped with a magnetic stirrer, and one sheet-like polyethylene molded product obtained in Production Example 3 was allowed to stand, and the flask was sufficiently purged with nitrogen. To this flask was added a toluene solution of triethylaluminum (
1M) 1 mL was poured gently using a syringe, and the mixture was slowly stirred at 40 ° C. in a nitrogen atmosphere to sufficiently bring the polyethylene molded product and triethylaluminum into contact with each other in the system. After 30 minutes, toluene and excess triethylaluminum in the flask were removed by decantation in a nitrogen atmosphere, and the polyethylene molded article was washed twice with 100 mL of dehydrated toluene.
After sufficiently removing the solvent in the flask, 50 mL of dehydrated acetone was poured, and 4.0 g of DL-lactide was added, followed by reaction at 40 ° C. for 24 hours in a nitrogen atmosphere. After completion of the reaction, the polyethylene molded product in the flask was taken out and washed with 300 mL of methanol. The obtained polyethylene molded body was dried at 40 ° C. under a reduced pressure of 10 Torr for 10 hours, and subjected to surface analysis by ATR / IR measurement. Absorption due to ester carbonyl stretching vibration was observed at A1760 cm ^−1. Therefore, it was observed that polylactic acid was present on the surface of the molded body.

[Production Example 8]
[Polyethylene molded body coated with poly (ε-caprolactone)]
50 mL of dehydrated toluene was poured into a 200 mL flat bottom separable flask equipped with a magnetic stirrer, and one sheet-like polyethylene molded product obtained in Production Example 3 was allowed to stand, and the flask was sufficiently purged with nitrogen. To this flask was added a toluene solution of triethylaluminum (
1M) 1 mL was poured gently using a syringe, and the mixture was slowly stirred at 40 ° C. in a nitrogen atmosphere to sufficiently bring the polyethylene molded product and triethylaluminum into contact with each other in the system. After 30 minutes, toluene and excess triethylaluminum in the flask were removed by decantation in a nitrogen atmosphere, and the polyethylene molded article was washed twice with 100 mL of dehydrated toluene.
After sufficiently removing the solvent in the flask, 60 mL of dehydrated acetone was poured, 5.5 g of ε-caprolactone was added, and the mixture was reacted at 40 ° C. for 24 hours in a nitrogen atmosphere. After completion of the reaction, the polyethylene molded product in the flask was taken out and washed with 300 mL of methanol. The obtained polyethylene molding was dried at 40 ° C. under a reduced pressure of 10 Torr for 10 hours. When the surface of the obtained molded body was analyzed by ATR / IR measurement, absorption attributable to ester carbonyl stretching vibration was observed at 1740 cm ⁻¹ , so that poly (εcaprolactone) was present on the surface of the molded body. It was observed.

[Production Example 9]
[Polypropylene molded body coated with polymethyl methacrylate (= PMMA)]
The polypropylene sheet having the radical polymerization initiating group obtained in Production Example 1 on the surface is put into a glass reactor, and MMA, 1-butanone and ethyl (2-bromoisobutyric acid) are put therein and the film is completely immersed in the liquid. I let you. Subsequently, argon gas (about 10 L / h) was passed through the liquid from the syringe needle, and the atmosphere was purged with argon by slowly stirring (30 minutes). Copper (I) bromide weighed in a glove box is placed in an ethanol solution of 0.20MN, N, N ', N ", N" -pentamethyldiethylenetriamine (PMDETA) prepared in an argon-substituted Schlenk, and about The mixture was stirred for 10 minutes, and when the CuBr / PMDETA complex was completely dissolved, it was injected into the polymerization vessel with a syringe. Copper (I) bromide at the start of polymerization was 5.0 mM, and the molar ratio of charge was adjusted to [CuBr] ₀ / [PMDETA] ₀ / [BiBB] ₀ / [MMA] ₀ = 1/2 / 0.30 / 600 . After polymerization at room temperature for 8 hours, the film was taken out from the polymerization vessel, immersed in 300 mL of 1-butanone, and ultrasonic cleaning was repeated twice to completely remove EBiB-initiated PMMA attached to the film surface. On the other hand, silica gel powder was put into a polymerization solution of EBiB-initiated PMMA (PMMA-BiB) and stirred slowly (10 minutes). When the copper complex was adsorbed, the silica gel was filtered off and the filtrate was dried under reduced pressure. As a result of GPC measurement of PMMA-BiB obtained by drying the obtained solid under reduced pressure, the number average molecular weight was Mn = 53700 and Mw / Mn = 1.55. Moreover, it was confirmed from the photograph of the cross section of the molded body of a transmission electron microscope (TEM) that PMMA completely coated the surface of the polypropylene sheet with a thickness of 60.5 ± 2.7 (nm). (Figure 1)

When a test piece was prepared from the molded body obtained in Production Example 5 and a Martens hardness scratch hardness tester manufactured by Tokyo Shiki Co., Ltd. was used, a test indenter 20 g was applied to the 3 mm thick test piece and the sample was scratched. The resulting groove width was measured, and the reciprocal thereof was calculated to be 18 (1 / mm).
Further, the obtained molded article had a flexural modulus (FM) of 1350 MPa, a Rockwell hardness (HR) of 95, and a heat distortion temperature (HDT) of 105 ° C.

Scratch resistance test The molded body (sheet) obtained in Production Example 9 was fixed to the stage of Tribostation Type 32 made by Shinto Kagaku, and a stainless steel sphere having a diameter of 10 mm was brought into contact with the surface to make a vertical load of 0.49 N (50 gf). Under the conditions of a sliding speed of 90 mm / min and a stroke of 20 mm, 30 reciprocating runs were performed. The surface of the sheet after sliding was observed with an optical microscope, and scratch resistance was evaluated. A photograph is shown in FIG.

[Comparative Example 1]
Scratch resistance test of PMMA spin-coated PP sheet On the polypropylene sheet of Production Example 1, PMMA (Mn 53700, 0.1 wt%) dissolved in chloroform was applied and coated on the surface using a spin coater. At this time, the spin coater was rotated at 600 rpm × 30 seconds and 2000 rpm × 5 minutes. A PMMA surface coat film having a thickness of 60 to 70 nm was obtained by TEM observation. The PMMA surface coat curtain was tested for scratch resistance in the same manner as in Example 2. FIG. 3 shows an optical micrograph of the sheet surface after sliding. FIG. 3 shows that PMMA on the surface layer is worn by friction with a stainless steel ball, and there is a wear mark of about 125 μm, whereas FIG. 2 is compared with FIG. It can be seen that the wear scar is small and difficult to be damaged. Thus, by introducing the PMMA chain chemically bonded via a covalent bond onto the polypropylene molded body (sheet), the scratch resistance is remarkably improved as compared with a general surface coat (non-chemical bond) film. Became clear.

A polyolefin-based molded article coated with a polar polymer with excellent performance such as impact resistance, heat resistance, scratch resistance, transparency, paintability, printability, adhesion, and low temperature flexibility is provided. The

FIG. 4 is a transmission electron microscope (TEM) photograph of a cross-section of the molded body obtained in Production Example 9. These are the optical microscope photographs of the sheet | seat surface after carrying out the scratch resistance test of the molded object in Example 1. FIG. These are the optical microscope photographs of the sheet | seat surface after carrying out the scratch resistance test of the molded object in the comparative example 1. FIG.

Claims (4)

Molded product comprising a molded product obtained by coating the surface of a polyolefin molded product (A) with a polar polymer (B), and the polar polymer (B) is chemically bonded to the surface of the polyolefin molded product (A) via a covalent bond. A miscellaneous goods molded body characterized by comprising a body. The miscellaneous goods molded article according to claim 1, wherein the polar polymer (B) is an addition polymer of a monomer having at least one carbon-carbon unsaturated bond. The polar polymer (B) is an addition polymer of a monomer having at least one carbon-carbon unsaturated bond, and the connecting portion with the surface of the polyolefin molded body (A) is formed by a carbon-carbon covalent bond or a chain thereof. The miscellaneous goods molded body according to claim 1, wherein the miscellaneous article is connected by covalent bond. 3. The miscellaneous goods molded article according to claim 1, wherein the polar polymer (B) is a ring-opening polymer.