JP2009120787A - Modified polyolefin-based resin composition and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide: a modified polyolefin-based resin having excellent adhesiveness to a hardly adhesive base material; a composition containing the same; and a method for producing the composition, which is simple and uses a simple apparatus. <P>SOLUTION: The modified polyolefin-based resin composition is obtained by melting and kneading a polyolefin resin-based resin (a) together with an epoxy group-containing vinyl monomer (c) and isoprene monomer (d) in the presence of a radical polymerization initiator (b), and contains the epoxy group-containing vinyl monomer (c) in a ratio within a range of 0.1-50 wt.% based on the total amount (100 wt.%) of the polyolefin-based resin (a), the epoxy group-containing vinyl monomer (c) and the isoprene monomer (d). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention contains a modified polyolefin composition obtained by melt-kneading an epoxy group-containing vinyl monomer and an isoprene monomer in the presence of a polyolefin resin and a radical polymerization initiator, a production method, and the resin. Relates to the composition. Furthermore, it aims at providing the polyolefin-type sheet | seat or film-form molded object which has the outstanding adhesiveness with respect to a difficult-to-adhere base material, and its manufacturing method.

Polyolefin resins, such as polypropylene resins, have excellent moldability, rigidity, heat resistance, chemical resistance, electrical insulation, etc., and are inexpensive, so they can be used in films, fibers, and other shapes. Is widely used in a wide range of molded products. Polypropylene materials, on the other hand, are so-called non-polar and extremely inert polymer substances that do not have polar groups in the molecule, and have high crystallinity and extremely low solubility in solvents. There exists a subject that property, abrasion resistance, oil resistance, etc. are low.
In order to improve this defect, a method of producing a modified resin by graft polymerization of a polymerizable monomer having a polar functional group to an olefin resin has been proposed, and the following method has been proposed.
(I) A method in which a polyolefin resin particle dispersed in water is impregnated with a vinyl monomer and heated in the presence of a peroxide to produce a modified polyolefin (Patent Document 1).
(Ii) A method for producing a modified polyolefin by melt-kneading a polyolefin resin, maleic anhydride and an organic peroxide (Patent Document 2).
In the method (i), various vinyl monomers can be grafted onto the polyolefin resin. However, a monomer having a highly polar functional group such as an epoxy group is difficult to impregnate a polyolefin resin having a low polarity, so that the amount capable of copolymerization is limited. In addition, since a dissolution inhibitor for the monomer in water is required, the dissolution inhibitor remains in the modified polyolefin composition after the reaction, which impairs printability, ink adhesion, and adhesion. It was.

In the method (ii), the types of monomers that can be copolymerized with the polyolefin resin are limited. For example, when glycidyl methacrylate is used in place of maleic anhydride, the monomer is volatilized unreacted, the monomers are only polymerized and do not graft onto the polyolefin resin, or excess peroxide causes the main chain of the polyolefin. However, since the molecular weight is reduced by cutting, the mechanical properties are lowered, and it cannot be said that the level has been reached to meet the sufficient requirement for adhesion.
Japanese Patent Laid-Open No. 6-122738 Japanese Patent Laid-Open No. 9-278956

  An object of the present invention is to provide a modified polyolefin resin having excellent adhesiveness to a difficult-to-adhere substrate by using a simple apparatus and an easy method, a composition containing the resin, and a method for producing the same. To do.

  As a result of intensive studies in view of the above-described present situation, the present inventors have added an epoxy group-containing vinyl monomer and an isoprene monomer in the presence of a polyolefin-based resin and a radical polymerization initiator, and melt-kneaded the above. The present inventors have found that the physical properties can be imparted and have completed the present invention.

That is, the present invention
(A) obtained by melt-kneading (c) an epoxy group-containing vinyl monomer and (d) isoprene monomer in the presence of a radical polymerization initiator (b) with respect to a polyolefin-based resin, and (a) a polyolefin-based resin The ratio of (c) epoxy group-containing vinyl monomer in the total of 100% by weight of resin, (c) epoxy group-containing vinyl monomer and (d) isoprene monomer is in the range of 0.1 to 50% by weight. A modified polyolefin resin composition characterized in that it is present in claim 1.

  The modified polyolefin resin composition according to claim 1, wherein (a) the polyolefin resin is a polypropylene resin having a majority of propylene units.

  The modified polyolefin-based composition according to claim 1 or 2 forms a multiphase structure, and (a) an epoxy group-containing vinyl monomer and (d) an isoprene monomer in a phase comprising (a) a polyolefin-based resin The modified polyolefin resin composition according to any one of claims 1 and 2, wherein the body phase has an average particle size of 1 µm or less (claim 3).

  (A) A polyolefin-based resin and (b) a radical polymerization initiator are melt-kneaded and then (c) an epoxy group-containing vinyl monomer and (d) an isoprene monomer are added and melt-kneaded. The manufacturing method of the modified polyolefin resin composition as described in any one of Claims 1-3 (Claim 4).

  A polyolefin-based sheet or film-like molded article containing the modified polyolefin-based resin composition according to any one of claims 1 to 3 and having heat-weldability (Claim 5).

  A method for producing a polyolefin-based sheet or film-like molded article, wherein the modified polyolefin-based resin according to any one of claims 1 to 3 is melt-kneaded and then molded into a sheet or film. ).

  The polyolefin resin composition which contains 0.1-100 weight part of modified polyolefin resin compositions as described in any one of Claims 1-3 with respect to 100 weight part of polyolefin resin (Claim 7).

  A polyolefin-based resin composition comprising a polypropylene-based resin having a majority of propylene units and the modified polyolefin-based resin composition according to any one of claims 1 to 3 (claim 8).

  A polyolefin-based sheet or film-like molded article comprising a polyolefin-based resin and the modified polyolefin-based resin composition according to any one of claims 1 to 3 and having heat-weldability (claim 9).

  The polyolefin-type sheet | seat or film-shaped molded object of Claim 9 whose propylene unit of polyolefin resin is a majority amount (Claim 10).

  A polyolefin sheet or a film-like molded article containing 0.1 to 100 parts by weight of the modified polyolefin resin according to any one of claims 1 to 3 with respect to 100 parts by weight of the polyolefin resin (claim 11).

  A polyolefin-based sheet or film-shaped molded article, wherein the modified polyolefin-based resin according to any one of claims 1 to 3 and a polyolefin-based resin are melt-kneaded and then molded into a sheet or film. Manufacturing method (Claim 12).

  The modified polyolefin resin composition according to any one of claims 1 to 3, the polyolefin resin composition according to any one of claims 8 to 9, and any one of claims 5, 9 to 11. An adhesive body formed by adhering at least one selected from the group consisting of a polyolefin-based sheet or a film-like molded article according to one item. (Claim 13).

  The modified polyolefin resin composition of the present invention can ensure excellent adhesion to difficult-to-adhere substrates, not only when used alone but also as an additive to polyolefin resins. It is suitably used in a wide range of fields such as packaging materials such as automobile parts, electric and electronic parts such as home appliances, and various industrial materials.

Details of the present invention will be described below.

<< About polyolefin resin >>
The (a) polyolefin resin is, for example, polyethylene, polypropylene, poly-1-butene, polyisobutylene, random copolymer or block copolymer in any ratio of propylene and ethylene and / or 1-butene, ethylene A cyclic polyolefin such as ethylene-propylene-diene terpolymer, polymethylpentene, a copolymer of cyclopentadiene and ethylene and / or propylene having a diene component of 50% by weight or less in any ratio of styrene and propylene, ethylene Alternatively, a random copolymer or a block copolymer of propylene and 50% by weight or less of a vinyl compound may be used.

  Among these, polypropylene, polyethylene, and polyisobutylene are preferable, and polypropylene is particularly preferable.

  In addition, a polyolefin resin into which a polar group is introduced can be used because it is easily compatible with an unsaturated carboxylic acid monomer having a polar group. Specific examples of polyolefin resins having polar groups introduced include acid-modified polypropylene such as maleic anhydride-modified polypropylene, maleic acid-modified polypropylene, and acrylic acid-modified polypropylene; ethylene / vinyl chloride copolymer, ethylene / vinylidene chloride copolymer , Ethylene / acrylonitrile copolymer, ethylene / methacrylonitrile copolymer, ethylene / vinyl acetate copolymer, ethylene / acrylamide copolymer, ethylene / methacrylamide copolymer, ethylene / acrylic acid copolymer, ethylene / Methacrylic acid copolymer, ethylene / maleic acid copolymer, ethylene / methyl acrylate copolymer, ethylene / ethyl acrylate copolymer, ethylene / isopropyl acrylate copolymer, ethylene / butyl acrylate copolymer, Ethylene / A Isobutyl acrylate copolymer, ethylene / 2-ethylhexyl acrylate copolymer, ethylene / methyl methacrylate copolymer, ethylene / ethyl methacrylate copolymer, ethylene / isopropyl methacrylate copolymer, ethylene / butyl methacrylate Copolymer, ethylene / isobutyl methacrylate copolymer, ethylene / 2-ethylhexyl methacrylate copolymer, ethylene / maleic anhydride copolymer, ethylene / ethyl acrylate / maleic anhydride copolymer, ethylene / acrylic acid Metal salt copolymer, ethylene / methacrylic acid metal salt copolymer, ethylene / vinyl acetate copolymer or saponified product thereof, ethylene / vinyl propionate copolymer, ethylene / glycidyl methacrylate copolymer ethylene / acrylic acid Ethyl / glycidyl methacrylate copolymer , Ethylene or α- olefin / vinyl monomer copolymers such as ethylene / vinyl acetate / glycidyl methacrylate copolymer; and chlorinated polyolefins such as chlorinated polypropylene chlorinated polyethylene. These polar group-introduced polyolefins can be used even if mixed.

  Polypropylene is preferred because it can be produced on an industrial scale at low cost.

  If necessary, another resin or rubber may be added to the raw material polyolefin resin as long as the effects of the present invention are not impaired.

  Examples of the other resin or rubber include polyethylene; poly α-olefins such as polypropylene, polybutene-1, polyisobutene, polypentene-1, and polymethylpentene-1; ethylene / propylene copolymer having a propylene content of less than 75% by weight. Copolymer, ethylene / butene-1 copolymer, ethylene or α-olefin / α-olefin copolymer such as propylene / butene-1 copolymer having a propylene content of less than 75% by weight; propylene content of 75% by weight Less than ethylene / propylene / 5-ethylidene-2-norbornene copolymer or ethylene- or α-olefin / α-olefin / diene monomer copolymer; polybutadiene copolymer such as polybutadiene and polyisoprene; styrene / Vinyl monomer such as butadiene random copolymer / Diene monomer random copolymer; vinyl monomer / diene monomer / vinyl monomer block copolymer such as styrene / butadiene / styrene block copolymer; hydrogenation (styrene / butadiene random) Hydrogenation (vinyl monomer / diene monomer random copolymer) such as copolymer); Hydrogenation (vinyl monomer / diene system) such as hydrogenation (styrene / butadiene / styrene block copolymer) Monomer / vinyl monomer block copolymer); vinyl monomer / diene monomer / vinyl monomer such as acrylonitrile / butadiene / styrene graft copolymer, methyl methacrylate / butadiene / styrene graft copolymer Polymer graft copolymer; polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile, polyvinyl acetate, polyethyl acrylate, poly Vinyl polymers such as butyl acrylate, polymethyl methacrylate, polystyrene; vinyl chloride / acrylonitrile copolymer, vinyl chloride / vinyl acetate copolymer, acrylonitrile / styrene copolymer, methyl methacrylate / styrene copolymer, etc. Examples thereof include vinyl copolymers.

  The amount of other resin or rubber added to the polyolefin resin varies depending on the type of the resin or the type of the rubber and may be within the range not impairing the effects of the present invention as described above. It is preferable that it is about wt% or less.

  Further, these polyolefin resins (which may contain various additive materials) may be in the form of particles or pellets, and the size and shape are not particularly limited.

  In addition, when the above additive materials (other resins and rubbers) are used, this additive material is added when the polyolefin resin is melted, even if it is previously added to the polyolefin resin. The modified polyolefin resin may be added to the modified polyolefin resin by an appropriate method after the modified polyolefin resin is produced.

  Regarding the propylene component in the polyolefin resin, it is preferable that the propylene unit is a majority amount in that radicals are easily generated in the polyolefin resin. The majority amount here means that the propylene component with respect to the polyolefin resin is 50% by weight or more.

<< About epoxy group-containing vinyl monomers >>
Examples include glycidyl methacrylate, glycidyl acrylate, monoglycidyl maleate, diglycidyl maleate, monoglycidyl itaconate, diglycidyl itaconate, monoglycidyl allyl succinate, diglycidyl allyl succinate, p-styrene carboxylic acid glycidyl, allyl glycidyl ether , Epoxy olefins such as methallyl glycidyl ether, styrene-p-glycidyl ether, p-glycidyl styrene, 3,4-epoxy-1-butene, 3,4-epoxy-3-methyl-1-butene, vinylcyclohexene monooxide 1 type or 2 types or more, such as, are mentioned. Of these, glycidyl methacrylate and glycidyl acrylate are preferable in that they are inexpensive.

  The addition amount of the epoxy group-containing vinyl monomer is preferably 0.1 to 100 parts by weight, and 0.5 to 50 parts by weight with respect to 100 parts by weight of the (a) polyolefin resin. Further preferred. The ratio of the (c) epoxy group-containing vinyl monomer in the total of 100% by weight of the (a) polyolefin-based resin, (c) the epoxy group-containing vinyl monomer, and (d) the isoprene monomer is 0.00. The range is preferably 1 to 50% by weight, more preferably 0.5 to 40% by weight, and particularly preferably 1 to 30% by weight. If the addition amount is too small, the adhesiveness tends not to be sufficiently improved, and if the addition amount is too large, there is a tendency that it cannot be obtained as a resin composition having a suitable shape and appearance.

<< About Isoprene Monomer >>
(D) The amount of isoprene monomer added is preferably 0.1 to 50 parts by weight, more preferably 0.5 to 40 parts by weight, based on 100 parts by weight of (a) polyolefin resin. The amount is preferably 1 to 30 parts by weight. If the amount added is too small, the graft ratio of the epoxy group-containing vinyl monomer to the polyolefin resin tends to be poor. On the other hand, if the addition amount is too large, the grafting efficiency of the epoxy group-containing vinyl monomer reaches the saturation range, so it is preferable that the upper limit is 50 parts by weight.

<< About radical initiators >>
Examples of radical polymerization initiators generally include peroxides and azo compounds. Examples of the radical polymerization initiator include ketone peroxides such as methyl ethyl ketone peroxide and methyl acetoacetate peroxide; 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis Peroxyketals such as (t-butylperoxy) cyclohexane, n-butyl-4,4-bis (t-butylperoxy) valerate, 2,2-bis (t-butylperoxy) butane; permethane hydroper Hydroperoxides such as oxide, 1,1,3,3-tetramethylbutyl hydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide; dicumyl peroxide, 2,5-dimethyl-2,5-di ( t-Butylperoxy) hexane α, α′-bis (t-butylperoxy-m-isopropyl) benzene, t-butylcumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxide) Dialkyl peroxides such as oxy) hexyne-3; diacyl peroxides such as benzoyl peroxide; peroxys such as di (3-methyl-3-methoxybutyl) peroxydicarbonate and di-2-methoxybutylperoxydicarbonate Dicarbonate: t-butyl peroxyoctate, t-butyl peroxyisobutyrate, t-butyl peroxylaurate, t-butyl peroxy-3,5,5-trimethylhexanoate, t-butyl peroxy Isopropyl carbonate, 2,5-dimethyl-2,5-di (benzoylpa Oxy) hexane, t- butyl peroxy acetate, t- butyl peroxybenzoate, one or more organic peroxides such as peroxy esters such as di -t- butyl peroxy isophthalate and the like.

  Of these, those having a particularly high hydrogen abstraction ability are preferred. Examples of such radical polymerization initiators include 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1. Peroxyketals such as bis (t-butylperoxy) cyclohexane, n-butyl-4,4-bis (t-butylperoxy) valerate, 2,2-bis (t-butylperoxy) butane; dicumyl Peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, α, α'-bis (t-butylperoxy-m-isopropyl) benzene, t-butylcumyl peroxide, di Dialkyl peroxides such as t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3; Diacyl peroxides such as nzoyl peroxide; t-butyl peroxyoctate, t-butyl peroxyisobutyrate, t-butyl peroxylaurate, t-butylperoxy-3,5,5-trimethylhexano Ate, t-butylperoxyisopropyl carbonate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxyacetate, t-butylperoxybenzoate, di-t-butylperoxyiso 1 type, or 2 or more types, such as peroxyesters, such as a phthalate, is mention | raise | lifted.

  The addition amount of the radical polymerization initiator is preferably in the range of 0.01 to 10 parts by weight and in the range of 0.2 to 5 parts by weight with respect to 100 parts by weight of the polyolefin resin. Further preferred. If it is less than 0.01 part by weight, the modification does not proceed sufficiently, and if it exceeds 10 parts by weight, fluidity and mechanical properties may be lowered.

<< Regarding Modified Polyolefin Resin Composition >>
The modified polyolefin resin composition of the present invention comprises (a) a polyolefin resin and (b) a radical polymerization initiator in the presence of a certain amount of (c) an epoxy group-containing vinyl monomer and (d) a single amount of isoprene. It is obtained by melting and kneading the body. By using melt kneading, the amount of the epoxy group-containing vinyl monomer can be increased as compared with the case of reacting by a method such as impregnation polymerization. Furthermore, (c) component in (c) epoxy group-containing vinyl monomer and (d) isoprene monomer, and (a) component, (c) component, and (d) component in a total of 100% by weight By making the ratio of 0.1 to 50% by weight, the grafting efficiency can be improved and the effects of the present invention can be obtained.

  Regarding the order and method of addition at the time of melt kneading, the addition order of melt kneading by adding an epoxy group-containing vinyl monomer and isoprene monomer to a mixture obtained by melting and kneading a polyolefin resin and a radical polymerization initiator is good. By carrying out in order, the production | generation of the low molecular weight body which does not contribute to a graft | grafting can be suppressed. In addition, the order and method of mixing and melt-kneading the materials added as necessary are not particularly limited.

  The heating temperature at the time of melt kneading is preferably 130 to 300 ° C. from the viewpoint that the polyolefin-based resin is sufficiently melted and is not thermally decomposed. The time for melt kneading (the time after mixing the radical polymerization initiator) is usually 30 seconds to 60 minutes.

  Further, as the melt kneading apparatus, an extruder, a Banbury mixer, a mill, a kneader, a heating roll, or the like can be used. From the viewpoint of productivity, a method using a single-screw or twin-screw extruder is preferred. Moreover, in order to mix each material sufficiently uniformly, the melt kneading may be repeated a plurality of times.

  The present invention is particularly effective when the modified polyolefin resin forms a multiphase structure and the phase composed of the epoxy group-containing vinyl monomer and the isoprene monomer in the phase composed of the polyolefin resin is finely dispersed. Is. Although depending on the reaction conditions such as heating temperature and melt kneading time, it is preferable that the phase composed of the epoxy group-containing vinyl monomer and the isoprene monomer in the phase composed of polyolefin resin is 1 μm or less on average. More preferably, it is 0.5 μm or less, and particularly preferably 0.3 μm or less. Since the epoxy group comprising the epoxy group-containing vinyl monomer is finely dispersed, the adhesiveness can be improved efficiently.

  As necessary, the modified polyolefin resin composition includes antioxidants, metal deactivators, phosphorus processing stabilizers, UV absorbers, UV stabilizers, fluorescent brighteners, metal soaps, antacid adsorbents, etc. Additives such as stabilizers, cross-linking agents, chain transfer agents, nucleating agents, lubricants, plasticizers, fillers, reinforcing materials, pigments, dyes, flame retardants, antistatic agents, etc., within a range not impairing the effects of the present invention It may be added. When these stabilizers and additives are used, they may be previously added to the (a) polyolefin resin, and (a) the components (b) to (d) are added to the polyolefin resin and melt-kneaded. The modified polyolefin resin may be added to the modified polyolefin resin by an appropriate method after the modified polyolefin resin is produced.

  Even if the modified polyolefin resin of the present invention is added to a polyolefin resin as an additive, the adhesion can be improved.

  Examples of the polyolefin resin in which the modified polyolefin resin of the present invention is blended include polypropylene homopolymer, high density polyethylene, low density polyethylene, linear low density polyethylene, poly-1-butene, polyisobutylene, propylene and ethylene, and Random copolymers or block copolymers in any ratio with 1 / butene, ethylene-propylene-diene terpolymers having a diene component of 50% by weight or less in any ratio of ethylene and propylene, poly Cyclic polyolefins such as methylpentene, a copolymer of cyclopentadiene and ethylene and / or propylene, ethylene or propylene and 50% by weight or less of vinyl acetate, alkyl methacrylate, alkyl acrylate, isopre Random copolymers with vinyl compounds, etc., polyolefin-based thermoplastic elastomer block copolymers, olefin-based thermoplastic elastomers (simple mixtures of polypropylene and ethylene / propylene copolymer or ethylene-propylene-diene terpolymer) , A partially crosslinked product thereof, or a completely crosslinked product thereof, and the like. These can be used alone or in admixture of two or more.

  A polypropylene homopolymer is preferable from the viewpoint of high rigidity and low cost, and a block copolymer of propylene and another monomer is preferable from the viewpoint of high rigidity and impact resistance. When flexibility is required, a polyolefin-based thermoplastic elastomer is preferable.

  When the modified polyolefin resin of the present invention is blended with the polyolefin resin, the blending amount is not particularly limited, but is 0.1 to 100 parts by weight, more preferably 0.1 to 70 parts by weight with respect to 100 parts by weight of the polyolefin resin. It is preferable to include parts by weight. More preferably, it is 0.3-50 weight part, More preferably, it is 0.5-20 weight part. If the amount is less than this range, the modification effect of the present invention tends not to be obtained with respect to the polyolefin resin. On the other hand, if the amount is too large, the original mechanical properties of the polyolefin-based resin may deteriorate, and economic problems may occur.

<< About sheet or film-like molded article >>
The modified polyolefin resin composition of the present invention can be made into a polyolefin sheet or film-like molded article having heat-welding properties. A polyolefin resin composition obtained by adding the modified polyolefin resin composition of the present invention to a polyolefin resin can also be made into a polyolefin sheet or film-like molded article having heat-weldability. The heat-weldability referred to in the present invention refers to the property of melting with heat and joining to the adherend. The sheet or film-like molded product of the present invention can be exemplified by a thickness of 3 μm to 3 mm, preferably 10 μm to 1 mm, and can be used as a sheet or film.

  The method for producing the heat-bondable polyolefin sheet or film-like molded product of the present invention is not particularly limited. For example, the polyolefin resin of the present invention and the modified polyolefin resin are dry blended or melt-kneaded. Later, it can be formed into a sheet-like molded body using various types of extrusion molding machines, injection molding machines, calendar molding machines, inflation molding machines, roll molding machines, or hot press molding machines.

  The material of the adherend used in the present invention is, for example, a material that can adhere to the adhesive resin layer of the adhesive film of the present invention. Specifically, for example, metals such as gold, silver, copper, iron, tin, lead, aluminum and silicon, inorganic materials such as glass and ceramics; cellulosic polymer materials such as paper and cloth, melamine resins and acrylics -Synthetic polymer materials such as urethane resins, urethane resins, (meth) acrylic resins, styrene / acrylonitrile copolymers, polycarbonate resins, phenol resins, alkyd resins, epoxy resins, and silicon resins.

  Two or more different materials may be mixed and combined as the material of the adherend. When the laminate is formed by adhering two different adherends via the adhesive film of the present invention, the materials constituting the two adherends may be the same type of material but different types. Any of the materials may be used. The property of the adherend is not particularly limited, and examples thereof include a film shape, a sheet shape, a plate shape, and a fiber shape. In addition, the adherend may be subjected to a surface treatment such as a release agent, a coating such as plating, a coating with a paint, surface modification with plasma or laser, surface oxidation, etching, etc., if necessary. Good. Specific examples of adherends include automotive parts such as trims (door trims, interior trims, etc.), molded ceilings, sheet materials (interior sheets, instrument panel skins, decorative sheets, etc.), indoor doors, partitions, interior wall panels, Examples include, but are not limited to, decorative films used in housing materials such as furniture and system kitchens.

  Specific examples are shown below, but the present invention is not limited to the following examples. In the following examples and comparative examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively.

(Particle size measurement)
The particle size was measured by observation with a transmission electron microscope. As a transmission electron microscope, JEOL JEM-1200EX was used and the acceleration voltage was 80 kV. The sample was prepared by freezing ultrathin section method after ruthenium oxide staining.

(T-shaped peeling evaluation)
T-peel evaluation was performed at 23 ° C. with a tensile test speed of 50 mm / min using AG-2000A manufactured by Shimadzu Corporation. The test sample was created by the following method. A film was sandwiched between two aluminum plates (25 mm × 150 mm) and adhered by a press (press temperature 200 ° C., press time 1 minute) to obtain a test sample.

Example 1
(A) 100 parts by weight of random polypropylene (J229E manufactured by Prime Polymer Co., Ltd., MFR = 50), (b) 1,3-di (t-butylperoxyisopropyl) benzene (manufactured by NOF Corporation: Perbutyl P, 1 minute half-life of 175 ° C.) 0.5 parts by weight was supplied to a twin-screw extruder (TEX30: L / D = 28, manufactured by Nippon Steel Works) set to 200 ° C. and melt-kneaded. (C) 5 parts by weight of glycidyl methacrylate and (d) 5 parts by weight of isoprene were added and melt-kneaded to obtain a modified polyolefin resin pellet (A-1). The obtained resin composition was supplied to a T-die to obtain a film having a thickness of 0.1 mm. The results are shown in Table 1.

(Example 2)
(A) 100 parts by weight of random polypropylene (J229E manufactured by Prime Polymer Co., Ltd., MFR = 50), (b) 1,3-di (t-butylperoxyisopropyl) benzene (manufactured by NOF Corporation: Perbutyl P, (1 minute half-life 175 ° C.) 1 part by weight was supplied to a twin-screw extruder (TEX 30: L / D = 28, manufactured by Nippon Steel Works) set at 200 ° C. and melt-kneaded. ) 10 parts by weight of glycidyl methacrylate and 10 parts by weight of (d) isoprene were added and melt-kneaded to obtain a modified polyolefin resin pellet (A-2). The obtained resin composition was supplied to a T-die to obtain a film having a thickness of 0.1 mm. The results are shown in Table 1.

(Example 3)
100 parts by weight of random polypropylene (manufactured by Prime Polymer Co., Ltd. J229E, MFR = 50) and 20 parts by weight of the modified polyolefin resin pellet (A-1) of Example 1 are supplied to a T die set at 200 ° C. and melt-kneaded. Thus, a film having a thickness of 0.1 mm was obtained. The results are shown in Table 1.

(Comparative Example 1)
Random polypropylene (J229E manufactured by Prime Polymer Co., Ltd., MFR = 50) was supplied to the T-die to obtain a 0.1 mm thick film. Results are shown.

実施例１、２は溶融混練で製造された本発明の変性ポリオレフィン系樹脂であり、実施例３は本発明の変性ポリオレフィン系樹脂を含有する本発明のポリオレフィン系樹脂である。比較例１は変性ポリオレフィン系樹脂を含有しないポリオレフィン系樹脂である。実施例１〜３については、その接着性は高い。一方で比較例ではＴ字剥離強度は低く、接着性に劣ることが判る。

Examples 1 and 2 are modified polyolefin resins of the present invention produced by melt-kneading, and Example 3 is a polyolefin resin of the present invention containing the modified polyolefin resin of the present invention. Comparative Example 1 is a polyolefin resin that does not contain a modified polyolefin resin. About Examples 1-3, the adhesiveness is high. On the other hand, in the comparative example, it can be seen that the T-shaped peel strength is low and the adhesiveness is poor.

Claims (13)

  (A) obtained by melt-kneading (c) an epoxy group-containing vinyl monomer and (d) isoprene monomer in the presence of a radical polymerization initiator (b) with respect to a polyolefin-based resin, and (a) a polyolefin-based resin The ratio of (c) epoxy group-containing vinyl monomer in the total of 100% by weight of resin, (c) epoxy group-containing vinyl monomer and (d) isoprene monomer is in the range of 0.1 to 50% by weight. The modified polyolefin resin composition characterized by being in.   The modified polyolefin resin composition according to claim 1, wherein (a) the polyolefin resin is a polypropylene resin having a majority of propylene units.   The modified polyolefin-based composition forms a multiphase structure, and (a) a phase composed of a polyolefin-based resin contains (c) an epoxy group-containing vinyl monomer and (d) a phase composed of an isoprene monomer on average of 1 μm. The modified polyolefin resin composition according to any one of claims 1 and 2, wherein the modified polyolefin resin composition has the following particle size.   (A) A polyolefin-based resin and (b) a radical polymerization initiator are melt-kneaded and then (c) an epoxy group-containing vinyl monomer and (d) an isoprene monomer are added and melt-kneaded. The manufacturing method of the modified polyolefin resin composition as described in any one of Claims 1-3.   A polyolefin-based sheet or film-like molded article containing the modified polyolefin-based resin composition according to any one of claims 1 to 3 and having heat-weldability.   A method for producing a polyolefin-based sheet or film-shaped molded article, comprising melt-kneading the modified polyolefin-based resin according to any one of claims 1 to 3 and then molding the sheet into a sheet or film.   A polyolefin resin composition comprising a polyolefin resin and the modified polyolefin resin composition according to any one of claims 1 to 3.   A polyolefin resin composition comprising 0.1 to 100 parts by weight of the modified polyolefin resin composition according to any one of claims 1 to 3 with respect to 100 parts by weight of a polypropylene resin having a majority of propylene units. .   A polyolefin-based sheet or film-shaped molded article comprising a polyolefin-based resin and the modified polyolefin-based resin composition according to any one of claims 1 to 3 and having heat-weldability.   The polyolefin-type sheet | seat or film-form molded object of Claim 9 whose propylene unit of polyolefin resin is a majority amount.   A polyolefin sheet or film-like molded article containing 0.1 to 100 parts by weight of the modified polyolefin resin according to any one of claims 1 to 3 with respect to 100 parts by weight of the polyolefin resin.   A polyolefin-based sheet or film-shaped molding, wherein the modified polyolefin-based resin composition according to any one of claims 1 to 3 and a polyolefin-based resin are melt-kneaded and then molded into a sheet or film. Body manufacturing method.   The modified polyolefin resin composition according to any one of claims 1 to 3, the polyolefin resin composition according to any one of claims 8 to 9, and any one of claims 5, 9 to 11. An adhesive body formed by adhering at least one selected from the group consisting of a polyolefin-based sheet or a film-like molded article according to one item.