JP4699950B2 - Method for producing polyolefin-based molded body coated with polar polymer - Google Patents

Description

  The present invention relates to a polyolefin-based molded article coated with a polar polymer, a production method thereof and use thereof.

  Polyolefins such as polyethylene and polypropylene have the characteristics of being light and inexpensive and having excellent physical properties and processability. On the other hand, it provides high functionality such as printability, paintability, adhesiveness, heat resistance, impact resistance, hydrophilicity, stimuli response, and adhesion and compatibility with other polar polymers and metals. In view of this, its high chemical stability is an obstacle. As a method for compensating for this drawback and imparting functionality to the polyolefin, for example, a method of copolymerizing ethylene and a polar group-containing monomer such as vinyl acetate or methacrylate by a high-pressure radical polymerization method, or a polyolefin in the presence of a peroxide. In general, a method of grafting a polar group-containing monomer such as maleic anhydride on the surface is widely used. Further, in JP-A-06-172459, JP-A-07-149911, JP-A 2000-159843, or JP-A 2004-162054, the presence of a radical generator typified by peroxides is also disclosed. A method for modifying a polyolefin by melting and kneading a polymerizable monomer having a polar group or a polymer thereof with a polyolefin resin has been reported. On the other hand, in Japanese Patent Application Laid-Open No. 2004-131620 by the present applicants, a polar group in a polyolefin obtained by copolymerization of an olefin and a polar group-containing monomer is converted into a radical polymerization initiator such as an acrylate ester. A method of grafting a polar group-containing monomer by radical polymerization is disclosed. According to this method, it is possible to obtain a polyolefin-polymer hybrid polymer in which side reactions such as cross-linking and decomposition are suppressed and the presence of unreacted polymer such as a single polyolefin or a polymer unit is minimized. However, in molded products obtained from polyolefin materials obtained by these methods, polar groups or polar polymer segments exist both inside and on the surface of the polyolefin, so the properties of the surface of the polyolefin molded product are sufficiently modified. In addition to the difficulty of exhibiting the effect, there is a possibility that the inherent physical properties of the polyolefin may be impaired due to the dissimilar polymer dispersed therein.

On the other hand, a laminated film is manufactured by supplementing properties that cannot be possessed by polyolefin alone, such as strength, gas barrier properties, moisture resistance, heat sealability, appearance, etc., by a method of laminating films of different materials on the surface of a polyolefin molded body. This is generally done, and the products obtained in this way are widely used mainly for packaging materials. As a method for producing such a laminated film, there are a dry lamination method, a wet lamination method, a hot lamination method, an extrusion lamination method, a coextrusion lamination method, and the like, and these are applied according to the characteristics. In such a laminating method, the polyolefin molded body, which is essentially difficult to bond, and a film of a different material are bonded to each other, so that the surface of the polyolefin molded body is oxidized or ozone treated, or organic titanate, organic isocyanate, polyethylene A process of applying an imine adhesive or the like is necessary. Problems such as the complexity of the process, the limitation of the adaptive material due to the use of an adhesive, and the peeling due to poor interface adhesion or deterioration have been cited as problems.
Japanese Unexamined Patent Publication No. 06-172459 Japanese Unexamined Patent Publication No. 07-149911 JP 2000-159843 JP 2004-162054 A JP 2004-131620 A

  In such an actual situation, the problem to be solved by the present inventors is a novel structure in which a polar polymer is coated only on the surface of a polyolefin molded body, and a vinyl monomer or a small ring compound is polymerized on the surface. The concept is to provide a polyolefin-based molded article in which a polar segment layer is coated via a covalent bond, substantially without interfacial peeling, without impairing the properties of the polyolefin substrate.

  The polyolefin-based molded product coated with the polar polymer (B) according to the present invention is a polyolefin-based molded product in which the surface of the polyolefin molded product (A) is coated with the polar polymer (B). B) is a polyolefin-based molded article characterized in that it has a structure in which it is bonded to the surface of the polyolefin molded article (A) via a covalent bond.

  The polyolefin-based molded article of the present invention has a structure in which a polar polymer segment is coated via a covalent bond on the surface of the polyolefin molded article, and substantially does not impair the properties of the polyolefin base material. There is no delamination at the polar polymer segment interface.

  Hereinafter, a polyolefin-based molded body coated with the polar polymer according to the present invention and a method for producing the same will be described in detail. In the present invention, the term “coating” is defined as the surface of a polyolefin-based molded article being coated with a polar polymer layer via a covalent bond, and coating based on physical adhesion or ionic bond is defined in the present invention. It is out of the definition of “coating”.

  The polyolefin-based molded product coated with the polar polymer (B) according to the present invention is a polyolefin-based molded product in which the surface of the polyolefin molded product (A) is coated with the polar polymer (B). B) is a polyolefin-based molded article characterized in that it has a structure bonded to the surface of the polyolefin molded article (A) via a covalent bond.

Polyolefin molded product (A)
The polyolefin molded product (A) constituting the polyolefin-based molded product of the present invention is a molded product of one or more resins selected from the group consisting of the following (I) to (III).
(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, and 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 derivatives, tricyclo [4.3.0.1 ^2,5 ] -3-decene derivatives, and tricyclo [ 4.3.0.1 ^{2, 5]-3-undecene} derivative, tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene derivatives, pentacyclo [7.4.0.1 ^2,5 .1 ^9,12 .0 ^{8, 13]} -3-pentadecene derivatives, pentacyclo ^{[6.5.1.1 3,6 .0 2,7 .0 9,13]} -4- pentadecene derivatives, pentacyclo [8.4.0.1 ^2,3 .1 ^9,12 .0 ^{8, 13]} -3-hexadecene derivative, pentacyclo ^{[6.6.1.1 3,6 .0 2,7 .0 9,14]} -4- hexadecene derivatives, penta cyclopentadiene decadiene derivative, hexacyclo [6.6.1.1 ^{3, 6} .1 ^10,13 .0 ^2,7 .0 ^9,14] -4-heptadecene derivatives, heptacyclo ^{[8.7.0.1 3,6 .1 10,17 .1 12,15 .0} 2,7 .0 11,16] - 4-eicosene derivatives, heptacyclo-5-eicosene derivatives, heptacyclo ^{8.8.0.1 4,7 .1 11,18 .1 13,16 .0 3,8} .0 12,17] -5- heneicosene derivatives, octacyclo [8.8.0.1 ^2,9 .1 ^4,7 .1 ^{11, 18.1 13,16} .0 ^3,8 .0 ^12,17] -5-docosene derivatives, Nonashikuro ^{[10.9.1.1 4,7 .1 13,20 .1 15,18 .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) Homopolymer or copolymer of α-olefin compound represented by CH ₂ ═CH—C _x H _{2x + 1} (x is 0 or a positive integer) CH ₂ ═CH—C _x used in the present invention In a homopolymer or copolymer (A1) of an α-olefin compound represented by H _{2x + 1} (x is 0 or a positive integer), CH ₂ = CH—C _x H _{2x + 1} (x is 0 or positive) Specific examples of the α-olefin compound represented by an integer of 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-octadecene, 1-eicocene, etc., linear or branched having 4 to 20 carbon atoms These α-olefins may be mentioned. 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, polybutene, poly (4-methyl-1-pentene), poly (1-hexene), ethylene-propylene copolymers, ethylene-butene Copolymer, ethylene-hexene copolymer, ethylene-octene copolymer, ethylene- (4-methyl-1-pentene) copolymer And propylene-butene copolymer, propylene- (4-methyl-1-pentene) copolymer, propylene-hexene copolymer, propylene-octene copolymer and the like.

(A2) Copolymer of α-olefin compound represented by CH ₂ ═CH—C _x H _{2x + 1} (x is 0 or a positive integer) and monoolefin compound having an aromatic ring CH ₂ used in the present invention In the copolymer (A2) of an α-olefin compound represented by = CH-C _x H _{2x + 1} (x is 0 or a positive integer) and a monoolefin compound having an aromatic ring, CH ₂ = CH-C _x Examples of the α-olefin compound represented by H _{2x + 1} (x is 0 or a positive integer) include the same α-olefin compounds as described in the above section (A1), and a monoolefin having an aromatic ring Specific examples of the compound include styrene compounds such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid and 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) Copolymer of α-olefin compound represented by CH ₂ ═CH—C _x H _{2x + 1} (x is 0 or a positive integer) and cyclic monoolefin compound represented by the following general formula (II) The 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 and the cyclic monoolefin compound represented by the above general formula (I) In the polymer (A3), the α-olefin compound represented by CH ₂ = CH—C _x H _{2x + 1} (x is 0 or a positive integer) is the same as that described in the section (A1) above. An α-olefin compound is exemplified, and a 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, 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 acid esters such as butyl and isobutyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, and isobutyl methacrylate And an unsaturated carboxylic acid ester having 4 to 8 carbon atoms. These comonomers can be used alone or in combination of two or more.

  Among polyolefin resins consisting 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. A polystyrene-reduced number average molecular weight (Mn) measured by chromatography (GPC): 100 to 1,000,000, preferably 500 to 500,000, more preferably 1,000 to 100,000. It is preferable.

  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, ethyl (meth) 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, (meth) acrylic acid-2-ethylhexyl, Nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, phenyl (meth) acrylate, toluyl (meth) acrylate, Benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, Stearyl (meth) acrylate, glycidyl (meth) acrylate, 2-aminoethyl (meth) acrylate, 2- (dimethylamino) ethyl (meth) acrylate, γ- (methacryloyloxypropyl) trimethoxysilane, (meth ) Ethylene oxide adduct of acrylic acid, trifluoromethyl methyl (meth) acrylate, 2-trifluoromethyl ethyl (meth) acrylate, 2-perfluoroethyl ethyl (meth) acrylate, 2- (meth) acrylic acid 2- Perfluoroethyl-2-perfluorobutylethyl, (meth) acrylic acid 2-perfluoroethyl Perfluoromethyl (meth) acrylate, diperfluoromethyl methyl (meth) acrylate, 2-perfluoromethyl-2-perfluoroethyl methyl (meth) acrylate, 2-perfluorohexyl ethyl (meth) acrylate , (Meth) acrylic monomers such as 2-perfluorodecylethyl (meth) acrylate and 2-perfluorohexadecylethyl (meth) acrylate, styrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfone Styrene monomers such as acids and their salts, fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene and vinylidene fluoride, silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane, maleic anhydride, maleic Acid, maleic acid monoa Alkyl and dialkyl esters, fumaric acid, monoalkyl and dialkyl esters of fumaric acid, maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide Maleimide monomers such as nitrile group-containing vinyl monomers such as acrylonitrile and methacrylonitrile, (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N Amide group-containing vinyl such as isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide Monomers, vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, vinyl cinnamate and other olefin monomers, ethylene, propylene, butene and other olefin monomers, butadiene, isoprene and other diene monomers, vinyl chloride , Vinylidene chloride, allyl chloride, allyl alcohol, and the like, and further, a macromonomer having a carbon-carbon unsaturated bond such as an acroyl group, a methacryloyl group, or a styryl group at the terminal and having 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, the polar polymer (B) insoluble in the organic solvent and the polar polymer (B) having a non-smooth surface are not preferable.

  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-hydroxyvaleric acid, α-hydroxyisovaleric acid, α-hydroxycaproic acid, α-hydroxyisocaproic acid, α-hydroxy-β- And intermolecular cyclic diesters such as methyl valeric acid and α-hydroxyheptanoic acid. 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 (chloro Methyl) oxetane, 3- (trimethylsilyloxymethyl) oxetane, tetrahydrofuran, 2-methyl-tetrahydrofuran, 3-methyl-tetrahydrofuran, 2,5-dimethoxytetrahydrofuran, 2-ethoxytetrahydrofuran, Til tetrahydrofurfuryl ether, 2,3-dihydrobenzofuran, 2,3-dihydrofuran, 2,5-dihydrofuran, tetrahydrofuran acetic acid ethyl ester, tetrahydrofurfuryl chloride, tetrahydrofurfuryl acetate, tetrahydrofurfuryl propionate, Examples thereof include tetrahydrofurfuryl n-butyrate, tetrahydrofurfuryl methacrylate, and the like. Among these, ethylene oxide, propylene oxide, oxetane, and tetrahydrofuran are preferable because of easy availability of raw materials.

  The polar polymer (B) used in the invention may be one having a halogen atom or various molecules introduced at the terminal, a part of the functional group hydrolyzed, a metal, a low molecule or one introduced. Alternatively, it may be modified or cross-linked via a metal or a reactive group.

Polyolefin molded product of the present invention The polyolefin molded product of the present invention is a polyolefin molded product obtained by coating the surface of the polyolefin molded product (A) with the polar polymer (B), and the polar polymer (B). Has a structure in which the surface of the polyolefin molded body (A) is bonded via a covalent bond, so that 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. Moreover, it is preferable that the covalent bond is composed only of covalent bonds that are 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, a connecting portion between the polar polymer (B) and the surface of the polyolefin molded body (A). Is preferably composed of a carbon-carbon bond or a covalent bond formed by a chain thereof. The “covalent bond by carbon-carbon bond” means that the carbon atom [C _A ] on the surface of the polyolefin molded body (A) and the carbon atom [C _B ] on the surface of the polar polymer (B) are directly bonded. The term “covalent bond by a chain of carbon-carbon bonds” means that the carbon atom [C _A ] and the carbon atom [C _B ] are two groups such as a linear or branched alkylene group or an arylene group. It shows being connected through a divalent hydrocarbon group composed of the above carbon atoms. Usually, the carbon atom [C _A ] and the carbon atom [C _B ] are directly bonded.
For example, when the connecting part contains an ester bond, a siloxy group, or a bond through a metal, heat or moisture may be applied 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. In some cases, bond dissociation can easily occur due to the above, and cause peeling of the polar polymer (B).

  In the polyolefin-based molded article of the present invention, the surface of the polyolefin molded article (A) is coated with the polar polymer (B), but it is completely coated even if it is partially coated depending on the application. May be. 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 body (A) on the surface of the polyolefin-based molded body of the present invention is derived from the type, molecular weight, and number of molecules of the polar polymer, so that the intended use Is adjusted in accordance with the range of 1 nm to 5 mm, preferably 10 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.

Surface coated body and laminate comprising a polyolefin-based molded body coated with a polar polymer The polyolefin-based molded body of the present invention can be obtained by selecting the type of the polar polymer (B) coated on the surface via a covalent bond. Since it is possible to express adhesiveness with various materials, lamination of the polyolefin-based molded body in the form of a film or sheet and the polyolefin-based molded body in the same or different type of film or sheet It is possible to form a body or a surface covering or laminate with a material such as a thermoplastic resin, metal, glass, or thermosetting resin.

Production method of polyolefin-based molded article of the present invention The polyolefin-based molded article of the present invention is a polyolefin molded article obtained by polymerizing a polar compound (monomer) using a polymerization initiating group present on the surface of the polyolefin molded article (A) as an initiation reaction point. Only the surface of the body (A) 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. However, even if the polyolefin resin having the polymerization initiating group introduced in advance is molded, A molecule or a polymerization initiating group of a polymer may be surface-modified. 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 polyolefin-based molded product of the present invention, that is, a polyolefin-based molded product coated with a polar polymer (B), the polar compound (monomer) on the surface of the polyolefin molded product (A) into which a polymerization initiating group has been introduced. Depending on the difference in the polymerization process, the following two production methods (P-1) and (P-2) are preferably used.
(P-1) A method of coating a molded body comprising a polyolefin covalently bonded to a radical polymerization initiating group (A ′), on the surface, carbon-carbon starting from the radical polymerization initiating group present on the surface of (A ′) A method for producing a polymer by controlled radical polymerization of one or more monomers selected from organic compounds having at least one unsaturated bond.
(P-2) A method of coating a molded body made of polyolefin covalently bonded to a group consisting of heteroatoms (A ″) In the surface of (A ″), starting from the heteroatoms present on the surface of (A ″), the small ring compound Is produced by ring-opening polymerization.

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 Method, i.e., Science, (1996), 272,866, Chem. Rev., 101, 2921 (2001), WO96 / 30421 publication, WO97 / 18247 publication, WO98 / 01480 publication, WO98 / 40415 publication, WO00 No. 156795 or Sawamoto et al., Chem. Rev., 101, 3689 (2001), JP-A-8-41117, JP-A-9-208616, JP-A-2000-264914, JP-A-2001-316410 No., JP-A No. 2002-80523, JP-A No. 2004-307872, and an organic halide or a sulfonyl halide compound as an initiator and a metal complex having a transition metal as a central metal as a catalyst. The method of radical polymerizing a radically polymerizable monomer is mentioned.

  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 introduced halogen atom are not particularly limited, but a brominated polyolefin having good stability and initiation efficiency of the atom transfer radical initiation skeleton is preferable.

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 Cole solvents, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate and dimethyl phthalate, ether solvents such as dimethyl ether, diethyl ether, di-n-amyl ether, tetrahydrofuran and dioxyanisole A solvent etc. can be mention | raise | lifted. Water can also be used as a solvent. These solvents may be used alone or in admixture of two or more.

  The polymerization temperature can be arbitrarily set as long as the temperature is such that the molded product (A ′) made of polyolefin having a radical polymerization initiating group introduced 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, specific examples include aromatic hydrocarbon solvents such as benzene, toluene and xylene, aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, nonane and decane, cyclohexane, methylcyclohexane and decahydronaphthalene. Alicyclic hydrocarbon solvents, chlorinated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, trichlorobenzene, methylene chloride, chloroform, carbon tetrachloride and tetrachloroethylene, and ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone Ester solvents such as ethyl acetate and dimethyl phthalate, ether solvents such as dimethyl ether, diethyl ether, di-n-amyl ether, tetrahydrofuran and dioxyanisole, etc. Kill. These solvents may be used alone or in admixture of two or more.

  The reaction temperature may be any temperature as long as the polyolefin molded product (A ″) to which a group consisting of heteroatoms is covalently bonded does not melt or swell and the ring-opening polymerization reaction proceeds. Although it is not uniform depending on the degree of polymerization and the type 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 ° C to 50 ° C. 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.

Applications of polyolefin-based molded articles The polyolefin-based molded articles according to the present invention can be used for various applications, for example, the following applications.
(1) Film and sheet or laminate thereof The film and sheet comprising the polyolefin-based hybrid polymer according to the present invention are flexible, transparent, tacky, hydrophilic, anti-fogging, heat resistant, gas barrier, and adhesive. Excellent in separability, impact resistance, hydrophobicity, biocompatibility, strength, wear resistance, and conductivity.
(2) Laminate comprising at least one layer comprising the polyolefin-based molded product according to the present invention, such as agricultural film, wrapping film, shrink film, protective film, plasma component separation membrane, water selective pervaporation membrane, etc. Examples of separation membranes, selective separation membranes such as ion exchange membranes, battery separators, and optical separation membranes.
(3) Microcapsules, PTP packaging, chemical valves, drug delivery systems.
(4) Building materials and civil engineering materials For example, floor materials, floor tiles, floor sheets, sound insulation sheets, heat insulation panels, vibration-insulating materials, decorative sheets, baseboards, asphalt modifiers, gaskets / sealing materials, roofing sheets, Building materials such as water-proof sheets, resin for civil engineering, and moldings for building materials and civil engineering.
(5) Automotive interior / exterior material and gasoline tank The automotive interior / exterior material and gasoline tank made of the multi-branched polymer according to the present invention are excellent in rigidity, impact resistance, oil resistance, and heat resistance.
(6) Electrical insulating materials such as electricity and electronic components; Electronic component processing equipment; Containers such as magnetic recording media, binders for magnetic recording media, conductive films, sealing materials for electrical circuits, materials for home appliances, containers for microwave ovens, etc. Equipment, microwave oven film, polymer electrolyte substrate, conductive alloy substrate, etc. Connector, socket, resistor, relay case switch coil bobbin, condenser, variable capacitor case, optical pickup, optical connector, oscillator, various terminal boards, transformer, plug, printed wiring board, tuner, speaker, microphone, headphones, small motor, Electric / electronic parts such as magnetic head base, power module, housing, semiconductor, liquid crystal display parts, FDD carriage, FDD chassis, HDD parts, motor brush holder, parabolic antenna, computer related parts; VTR parts, TV parts, Iron, hair dryer, rice cooker parts, microwave oven parts, acoustic parts, audio equipment parts such as audio / laser disc (registered trademark) / compact disc, lighting parts, refrigerator parts, air conditioner Houses represented by parts, typewriter parts, word processor parts, office electrical product parts, office computer-related parts, telephone-related parts, facsimile-related parts, copier-related parts, electromagnetic shielding materials, speaker cone materials, speaker vibration elements etc.
(7) Surface-curing material: Since the molded article having the polyolefin-based molded article according to the present invention contains a polar monomer component on the surface, it has excellent affinity with acrylic monomers and polyfunctional monomers, and those photo-curing materials or Used as thermosetting material.
(8) Medical / hygiene material non-woven fabric, non-woven fabric laminate, electret, medical tube, medical container, infusion bag, prefill syringe, syringe and other medical supplies, medical material, cell culture platform, artificial organ, artificial muscle , Filtration membranes, food hygiene / health goods; retort bags, freshness keeping films, etc.
(9) Accessories desk mats, cutting mats, rulers, pen barrels, grips, caps, grips such as scissors and cutters, magnetic sheets, pen cases, paper folders, binders, label seals, tapes, whiteboards and other stationery : Clothing, curtains, sheets, carpets, doormats, bath mats, buckets, hoses, bags, planters, air conditioner and exhaust fan filters, dishes, trays, cups, lunch boxes, coffee siphon funnels, glasses frames, containers, storage cases Daily goods such as shoes, hangers, ropes, laundry nets: Sporting goods such as shoes, goggles, skis, rackets, balls, tents, underwater glasses, fins, fishing rods, cooler boxes, leisure seats, sports nets: Block, card, etc Ingredients: kerosene cans, drums, containers such as bottles, such as detergents and shampoos; signboard, pylon, plastic chain: display such as such.

  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 uses an SSX-100 type X-ray photoelectron spectrometer manufactured by SSI, and the bromine atom distribution state is an EPMA-1600 type manufactured by Shimadzu Corporation. An electron beam microanalyzer was used. In addition, ATR / IR analysis was performed using an FTS-6000 type infrared spectrophotometer manufactured by Biorad.

[Production Example 1]
[Preparation of polypropylene moldings having radical polymerization initiating groups on the surface (1)]
Propylene / 10-undecene-1-ol copolymer produced according to the method described in JP-A-2002-145944 (high molecular weight in terms of polypropylene by high-temperature GPC measurement Mw = 26400, Mw / Mn = 1.71, ¹ H-NMR measurement 170 g of comonomer content obtained from 1.0 mol%) was put into a 2 L glass polymerization vessel purged with deaerated nitrogen, 1700 mL of hexane and 9.2 mL of 2-bromoisobutyric acid bromide were added, and the temperature was raised to 60 ° C. The mixture was heated 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. The polymer was dried at 50 ° C. under a reduced pressure of 10 Torr for 10 hours to obtain a white polymer. As a result of ¹ H-NMR, it was a halogen atom-containing polypropylene in which 94% of the terminal OH groups were modified with 2-bromoisobutyric acid groups. This halogen atom-containing polypropylene was molded into a 1.0 mm thick sheet by a compression molding machine (180 ° C., 10 MPa).

As a result of performing surface analysis of this polypropylene molded body by ATR / IR measurement, absorption of estecarbonyl stretching vibration can be confirmed at 1730 cm ⁻¹ , and 0.3 atm% bromine atoms may be present on the surface by XPS measurement. It became clear. 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 molded into a sheet having a thickness of 1.0 mm and 4 cm × 4 cm using a compression molding machine (180 ° C., 10 MPa). 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-1-ol copolymer produced according to the method described in JP-A-2002-145944 (polyethylene equivalent molecular weight by high-temperature GPC measurement Mw = 90400, Mw / Mn = 2.53, ¹ H-NMR measurement The comonomer content obtained from 3.9 mol% was molded into a sheet having a thickness of 1.0 mm and 4 cm × 4 cm by a compression molding machine (150 ° C., 10 MPa).
As a result of surface analysis of the polyethylene molded body by ATR / IR measurement, broad absorption was observed in the vicinity of 3500 cm ⁻¹ , confirming the presence of hydroxyl groups on the surface of the molded body.

[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, and immersed in a mixed solution of 250 mL of ethanol and 40 mL of methacrylic acid (2-hydroxyethyl) sufficiently bubbled with nitrogen. The reactor was further purged with nitrogen. To this was added a homogeneous solution of cuprous bromide (548 mg) and N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine in 2M xylene solution 3.75 mL and xylene 5.0 mL. Stir slowly for 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, it was confirmed that poly (methacrylic acid (2-hydroxyethyl)) was present on the surface of the polypropylene molded body. Moreover, from the photograph of the cross section of the molded body of a transmission electron microscope (TEM), it is found that poly (methacrylic acid (2-hydroxyethyl)) completely coats the surface of the polypropylene sheet with a thickness of about 10 μm to 20 μm. confirmed. 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.

[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 thereof was placed in a glass reactor and sufficiently bubbled with nitrogen. The reactor was immersed in a mixed solution of 150 mL of THF and 150 mL of methyl methacrylate, and the reactor was further purged with nitrogen. To this was added a homogeneous solution of cuprous bromide (548 mg), 3.75 mL of 2M xylene solution of N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine and 5.0 mL of xylene. Stir slowly for 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. 1730 cm ^-1 Analysis of the surface of the obtained polypropylene molded body ^{ATR / IR, 1270cm -1, 1242cm} -1, 1193cm -1, characteristic peaks of PMMA was observed at 1149cm ^-1, to the seat surface The presence of PMMA was confirmed.

  Moreover, it was confirmed from the photograph of the cross section of the molded body of the transmission electron microscope (TEM) that PMMA completely coats the surface of the polypropylene sheet with a thickness of about 40 μm to 60 μm. 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 improved.

[Polypropylene molded body coated with polymethyl methacrylate (= PMMA)]
The polypropylene molded product having the radical polymerization initiating group obtained in Production Example 2 on the surface is placed in a glass reactor, immersed in a mixed solution of 150 mL of THF and methyl methacrylate sufficiently bubbled with nitrogen, and the reactor is further immersed. Replaced with nitrogen. To this was added a homogeneous solution of cuprous bromide (548 mg), 3.75 mL of 2M xylene solution of N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine and 5.0 mL of xylene. Stir slowly for 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. 1730 cm ^-1 Analysis of the surface of the obtained polypropylene molded body ^{ATR / IR, 1270cm -1, 1242cm} -1, 1193cm -1, characteristic peaks of PMMA was observed at 1149cm ^-1, to the seat surface The presence of PMMA was confirmed. 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 improved.

[Comparative Example 1]
Polypropylene ([η] = 2.6) manufactured by Mitsui Chemicals, Inc. was molded into a sheet having a thickness of 1.0 mm and 4 cm × 4 cm using a compression molding machine (180 ° C., 10 MPa). On the polypropylene sheet-like molded body (hereinafter referred to as PP sheet), PMMA resin dissolved in toluene (manufactured by Aldrich, weight average molecular weight of about 15000) was applied and allowed to dry overnight at room temperature under reduced pressure. It was confirmed by ATR / IR measurement that PMMA was coated.

Evaluation of chemical stability of coated polar polymer Next, chemical stability (organic solvent and alkaline water) of the polar polymer layer coated on the polypropylene-based molded articles prepared in Examples and Comparative Examples. Evaluated.

[Chemical stability evaluation method 1 (THF treatment)]
The polypropylene molded sheet (hereinafter referred to as PP sheet) whose surface is coated with MMA prepared in Examples 1 to 3 and Comparative Example 1 is placed in a glass container, and tetrahydrofuran (THF) is used so that the PP-sheet is sufficiently immersed. Soaked in. After slowly stirring with a stirrer overnight at 50 ° C., the PP sheet was taken out with tweezers and the surface was washed several times with THF. The obtained PP sheet was dried at 50 ° C. for 10 hours under a reduced pressure of 10 Torr. Table 2 shows the ATR / IR results of the obtained sheet surface.

[Chemical stability evaluation method 2 (alkali treatment)]
The polypropylene molded sheet (hereinafter referred to as PP sheet) whose surface was coated with MMA prepared in Examples 2 and 3 was placed in a glass container, and tetrahydrofuran (THF) and 1M hydroxylation were used so that the PP-sheet was sufficiently immersed. It was immersed in a mixed solution of sodium aqueous solution (volume ratio 9: 1). After slowly stirring with a stirrer overnight at 45 ° C., the PP sheet was taken out with tweezers and the surface was washed several times with THF. The obtained PP sheet was dried at 50 ° C. for 10 hours under a reduced pressure of 10 Torr. Table 2 shows the ATR / IR results of the obtained sheet surface.

  From Table 2, the polypropylene-based molded products obtained in Examples 1 to 3 were not changed in the absorption band of the polar segment in the ATR / IR measurement by the treatment with THF, and the peeling of the polar polymer was substantially caused by the THF treatment. It became clear that it would not happen. On the other hand, in the polypropylene-based molded article after the alkali treatment, the molded articles of Examples 1 and 2 and Comparative Example 1 were observed to have a decrease or disappearance of absorption bands attributed to the polar segments on the surface. In the molded product of No. 3, no change in the PMMA absorption band was observed by the alkali treatment. In Examples 1 and 2, it is considered that the ester bond at the bonding portion was hydrolyzed by treatment under alkaline conditions, and part or all of the polar polymer was peeled off. From the above results, the connection through the covalent bond between the polyolefin molded body (A) and the polar polymer (B) due to the presence of the covalent bond according to the present invention is one of the features of the chemical stability of the molded body. It became clear that it contributed to retention. Further, it was shown that a molded article having a linking group composed of a carbon-carbon bond that does not contain a hydrolyzable ester bond is particularly excellent in chemical stability.

[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, 1 mL of a toluene solution of triethylaluminum (1M) was gently poured 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 article was dried at 40 ° C. under a reduced pressure of 10 Torr for 10 hours, and subjected to surface analysis by ATR / IR measurement. As a result, absorption due to ester carbonyl stretching vibration was observed at 1760 cm ^−1. From this, it was observed that polylactic acid was present on the surface of the molded body.

[Polyethylene molded product 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, 1 mL of a toluene solution of triethylaluminum (1M) was gently poured 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 molded product 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.

Claims (3)

Polyolefin molded body and (A), said consist polar polymer disposed on the surface of the polyolefin molded body (A) (B), producing a polyolefin molded body closed with a coating layer having a thickness of 10 nm to 1 mm, a Because
Preparing a polyolefin molded body (A ′) in which a polymerization initiating group is directly bonded to a carbon atom of polyolefin;
Using the polymerization initiation group as a polymerization initiation point, radically polymerizing one or more polar monomers to form the coating layer;
The manufacturing method of the polyolefin-type molded object containing this. The polymerization initiating group is a halogen atom;
The method for producing a polyolefin-based molded article according to claim 1, wherein the polar monomer is a monomer having at least one carbon-carbon unsaturated bond. The polymerization initiating group is a hydroxyl group, a carboxyl group, an acid anhydride group, an epoxy group, an amino group, or a group obtained by reacting them with a metal compound,
The method for producing a polyolefin-based molded article according to claim 1, wherein the polar monomer is a small ring compound.