JP2009126920A - Modified polyolefin-based resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a modified polyolefin-based resin having an excellent bonding property to a hardly adhering base substrate by using a simple device and an easy method, a composition containing the resin, and its sheet and a film-shaped molded article. <P>SOLUTION: This modified polyolefin resin composition is provided by graft-reacting (b) an epoxy group-containing vinyl monomer and (c) an aromatic vinyl monomer or further (d) a (meth)acrylic acid ester with (a) a polyolefin-based resin, wherein the weight-average molecular weight of the graft chain including the grafted (b) epoxy group-containing vinyl monomer and (c) aromatic vinyl monomer or further (d) (meth)acrylic ester ranges from 200 to 10,000. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a resin composition obtained by graft-reacting an epoxy group-containing vinyl monomer and an aromatic vinyl monomer or a (meth) acrylic acid ester monomer to a polyolefin resin, The present invention relates to a composition having a weight average molecular weight of a graft chain of a resin composition in a specific range and a composition containing the resin. 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.

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-mentioned present situation, the present inventors grafted an epoxy group-containing vinyl monomer and an aromatic vinyl monomer, or further a (meth) acrylic acid ester monomer to a polyolefin resin. It has been found that a reacted resin composition having a weight average molecular weight of a graft chain of a modified polyolefin resin composition in a specific range can impart the above-mentioned physical properties. It came to complete.

That is, the present invention
(A) Resin composition obtained by graft reaction of (b) epoxy group-containing vinyl monomer and (c) aromatic vinyl monomer, or (d) (meth) acrylate monomer to polyolefin resin The weight of grafted chain comprising (b) an epoxy group-containing vinyl monomer and (c) an aromatic vinyl monomer, or (d) a (meth) acrylate monomer A modified polyolefin resin composition having an average molecular weight in the range of 200 to 10,000 (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.

  A polyolefin-based sheet or film-like molded article containing the modified polyolefin-based resin composition according to any one of claims 1 and 2 and having heat-weldability (Claim 3).

  A polyolefin resin composition containing 0.1 to 100 parts by weight of the modified polyolefin resin composition according to any one of claims 1 and 2 with respect to 100 parts by weight of the polyolefin resin (claim 4).

  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 and 2 (claim 5).

  A polyolefin-based sheet or film-like molded article comprising the polyolefin-based resin composition according to any one of claims 6 and 7 and having heat-weldability (Claim 6).

  The modified polyolefin resin composition according to any one of claims 1 and 2, the polyolefin resin composition according to any one of claims 4 and 5, and any one of claims 3 and 6. An adhesive body formed by adhering at least one selected from the group consisting of the polyolefin-based sheet or the film-like molded product according to the item (Claim 7).

  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 poly α-olefins such as polypentene-1 and polymethylpentene-1; ethylene or α-olefins such as a propylene / butene-1 copolymer having a propylene content of less than 75% by weight. / Α-olefin copolymer; ethylene or α-olefin / α-olefin / diene monomer copolymer such as ethylene / propylene / 5-ethylidene-2-norbornene copolymer having a propylene content of less than 75% by weight Polymer; Polydiene copolymer such as polybutadiene and polyisoprene; Vinyl monomer / diene monomer random copolymer such as styrene / butadiene random copolymer; Vinyl such as styrene / butadiene / styrene block copolymer Monomer / Diene monomer / Vinyl monomer block copolymer; Hydrogenation ( Hydrogenation such as styrene / butadiene random copolymer) (vinyl monomer / diene monomer random copolymer); Hydrogenation such as hydrogenation (styrene / butadiene / styrene block copolymer) (vinyl single unit) Monomer / diene monomer / vinyl monomer block copolymer); vinyl monomer / diene monomer such as acrylonitrile / butadiene / styrene graft copolymer, methyl methacrylate / butadiene / styrene graft copolymer / Vinyl monomer graft copolymer; vinyl polymers such as polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile, polyvinyl acetate, polyethyl acrylate, polybutyl acrylate, polymethyl methacrylate, polystyrene, etc .; vinyl chloride / Acrylonitrile copolymer, vinyl chloride / vinyl acetate copolymer, acrylonite Le / styrene copolymers, such as vinyl copolymers such as methyl methacrylate / styrene copolymer.

  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. Further, (a) polyolefin resin, (b) epoxy group-containing vinyl monomer, (c) aromatic vinyl monomer, and (d) (meth) acrylic acid ester monomer in a total amount of 100% by weight ( b) The proportion of the epoxy group-containing vinyl monomer is preferably in the range of 0.1 to 50% by weight, more preferably in the range of 0.5 to 40% by weight, and 1 to 30% by weight. A range is particularly preferred. 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 the aromatic vinyl monomer >>
For example, styrene; methyl styrene such as o-methyl styrene, m-methyl styrene, p-methyl styrene, α-methyl styrene, β-methyl styrene, dimethyl styrene, trimethyl styrene; o-chloro styrene, m-chloro Chlorostyrene such as styrene, p-chlorostyrene, α-chlorostyrene, β-chlorostyrene, dichlorostyrene, trichlorostyrene; o-bromostyrene, m-bromostyrene, p-bromostyrene, dibromostyrene, tribromostyrene, etc. Bromostyrene; fluorostyrene such as o-fluorostyrene, m-fluorostyrene, p-fluorostyrene, difluorostyrene, trifluorostyrene; o-nitrostyrene, m-nitrostyrene, p-nitrostyrene, dinitrostyrene, Nitrostyrenes such as renitrostyrene; vinylphenols such as o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, dihydroxystyrene, trihydroxystyrene; o-divinylstyrene, m-divinylstyrene, p-divinylstyrene, etc. 1 type, or 2 or more types, such as divinyl styrene; diisopropenylbenzene, such as o-diisopropenylbenzene, m-diisopropenylbenzene, p-diisopropenylbenzene; Of these, methylstyrene such as styrene, α-methylstyrene, and p-methylstyrene, a divinylbenzene monomer, or a divinylbenzene isomer mixture is preferable in that it is inexpensive.

  The amount of the (c) aromatic vinyl monomer added is preferably 0.1 to 50 parts by weight, and 0.5 to 40 parts by weight with respect to 100 parts by weight of the (a) polyolefin resin. More preferably, the amount is 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 (meth) acrylic acid ester monomer >>
Although it does not restrict | limit especially as a (meth) acrylic acid ester, Preferably it is C4-C20, More preferably, it is a C4-10 (meth) acrylic acid ester. Specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, (meth) acrylic Examples thereof include tert-butyl acid, benzyl (meth) acrylate, phenylethyl (meth) acrylate, naphthyl (meth) acrylate, and the like. Among these, methyl (meth) acrylate is preferable because it is inexpensive.

  The addition amount of the (d) (meth) acrylic acid ester monomer is preferably 0.01 to 50 parts by weight, and 0.05 to 40 parts by weight with respect to 100 parts by weight of the (a) polyolefin resin. Part is more preferable, and 0.1 to 30 parts by weight is particularly preferable. 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 amount added is too large, a free polymer that does not contribute to grafting tends to be produced as a by-product, so the upper limit is preferably set to the same part by weight as the aromatic vinyl monomer.

<< About radical initiators >>
When copolymerizing (a) polyolefin resin, (b) epoxy group-containing vinyl monomer, (c) aromatic vinyl monomer, (d) (meth) acrylate monomer, the reaction is accelerated. Therefore, a radical polymerization initiator can be added.

  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 the amount is less than 0.01 part by weight, the modification does not proceed sufficiently, and if it exceeds 10 parts by weight, the fluidity and mechanical properties are lowered.

<< Regarding Modified Polyolefin Resin Composition >>
The modified polyolefin resin composition of the present invention is a resin composition in which (a) a polyolefin resin is grafted with a short graft chain composed of two or more monomers including (b) an epoxy group-containing vinyl monomer. It is a thing. As a monomer, (b) an epoxy group-containing vinyl monomer and (c) an aromatic vinyl monomer are used as essential components, and (d) a (meth) acrylic acid ester monomer is optionally used. May be. Furthermore, the effect of this invention is acquired by making the weight average molecular weight of a graft chain into the range of 200-10000.

  The graft polymerization reaction used in the present invention is not particularly limited, and solution polymerization, impregnation polymerization, melt polymerization and the like can be used. In particular, melt polymerization is simple and preferable.

  About the addition order and method at the time of melt kneading, the addition order of melt-kneading the epoxy group-containing vinyl monomer and the aromatic vinyl monomer to the mixture obtained by melt-kneading the polyolefin resin and the radical polymerization initiator is good, By performing in this addition 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.

  In the present invention, a modified polyolefin-based resin forms a graft structure, and a graft chain composed of an epoxy group-containing vinyl monomer and an aromatic vinyl monomer or a (meth) acrylic acid ester monomer with respect to the polyolefin-based resin is present. This is particularly effective when the control is short. Depending on reaction conditions such as epoxy group-containing vinyl monomer, aromatic vinyl monomer, (meth) acrylic acid ester monomer, radical polymerization initiator charge amount, heating temperature, melt kneading time for polyolefin resin, The length of the graft chain can be controlled. It is preferable that the weight average molecular weight of the graft chain consisting of an epoxy group-containing vinyl monomer and an aromatic vinyl monomer or a (meth) acrylic acid ester monomer for the polyolefin-based resin is 200 to 10,000, It is more preferable that it is 7000, and it is especially preferable that it is 200-5000. Since the graft chain is short, a fine phase structure can be formed in the phase of the polyolefin resin, and 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 added to the (a) polyolefin resin in advance, and (a) when the (b) to (e) components are grafted to the polyolefin resin. It may be added, or 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 polyolefin 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, acrylic acid alkyl ester, aromatic vinyl Random copolymers with vinyl compounds such as rubber, polyolefin-based thermoplastic elastomer block copolymers, olefin-based thermoplastic elastomers (simple polypropylene / ethylene / propylene copolymer or ethylene-propylene-diene terpolymer) A mixture, a partially cross-linked product thereof, or a completely cross-linked product thereof) and the like. These may 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.

(Measurement of graft chain length / weight average molecular weight)
The graft chain length was considered to be the same as the chain length of the free polymer that did not contribute to grafting in the modified polyolefin resin, and was calculated as follows. The extrudate pellets were dissolved by heating at 130 ° C. for 3 hours using about 50 times by weight of o-dichlorobenzene, and after removing insolubles, the crystals were allowed to cool overnight and the crystallized product was filtered off. Collection and concentration to dryness gave a free polymer. This was dissolved in chloroform, and the weight average molecular weight was measured by GPC (gel per emission chromatography).

Moreover, it confirmed that the epoxy group containing vinyl monomer and the aromatic vinyl monomer were copolymerized by polyolefin resin by the following method. The extruded pellet was heated and dissolved using o-dichlorobenzene to remove insolubles, and then allowed to cool overnight to obtain a reprecipitate. About the reprecipitation, the epoxy value measurement was performed and the graft | grafting of the epoxy group containing vinyl monomer was confirmed. Furthermore, the IR spectrum measurement of the press sheet of the reprecipitate was performed, and the graft of the aromatic vinyl monomer was confirmed from the peak at 700 cm ⁻¹ (aromatic ring).

(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) 90 parts by weight of random polypropylene (manufactured by Prime Polymer Co., Ltd., J229E, MFR = 50), 1,3-di (t-butylperoxyisopropyl) benzene (manufactured by NOF Corporation: perbutyl P, halved for 1 minute (Phase 175 ° C.) 0.5 parts by weight was supplied to a twin-screw extruder (TEX 30: L / D = 28, manufactured by Nippon Steel Works) set to 200 ° C. and melt-kneaded, and then from the middle of the cylinder (b) 5 parts by weight of glycidyl methacrylate and 5 parts by weight of (c) styrene were added and melt-kneaded to obtain a modified polyolefin resin pellet (A-1). The weight average molecular weight of the graft chain composed of glycidyl methacrylate and styrene (A-1) was 1300. 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-1) 40 parts by weight of random polypropylene (J229E manufactured by Prime Polymer Co., Ltd., MFR = 50), (a-2) 40 parts by weight of polypropylene ethylene rubber (V3401, MFR = 8 manufactured by Dow Chemical), 1,3- A twin screw extruder (TEX30: L / D =) in which 1.5 parts by weight of di (t-butylperoxyisopropyl) benzene (Nippon Yushi Co., Ltd .: Perbutyl P, 1 minute half-life 175 ° C.) is set to 200 ° C. 28, manufactured by Nippon Steel Works), melt-kneaded, and then (b) 10 parts by weight of glycidyl methacrylate and (c) 10 parts by weight of styrene were melted and kneaded from the middle of the cylinder, and modified polyolefin resin pellets ( A-2) was obtained. The weight average molecular weight of the graft chain consisting of glycidyl methacrylate and styrene (A-2) was 1,800. 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)
(A) 90 parts by weight of polypropylene ethylene rubber (D340 Chemicals, V3401, MFR = 8), 1,3-di (t-butylperoxyisopropyl) benzene (manufactured by NOF Corporation: Perbutyl P, 1 minute half-life 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, and then (b) methacrylic acid from the middle of the cylinder 5 parts by weight of glycidyl and 5 parts by weight of (c) styrene were added and melt-kneaded to obtain modified polyolefin resin pellets (A-3). The weight average molecular weight of the graft chain composed of glycidyl methacrylate and styrene of (A-3) was 1300. 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 4
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.

(Comparative Example 2)
Into a 10 L autoclave, 200 parts by weight of water, 0.05 part by weight of an emulsifier (Kao Lattemul PS) and 1.5 parts by weight of a dispersant (Taihei Sangyo Tricalcium Phosphate) are added to form an aqueous medium. 70 parts by weight of polypropylene (J226EA manufactured by Prime Polymer Co., Ltd., MFR = 20), 1,3-di (t-butylperoxyisopropyl) benzene (manufactured by NOF Corporation: Perbutyl P, half-life 175 ° C. for 1 minute) 0.4 parts by weight, (c) 6 parts by weight of glycidyl methacrylate, and (d) 24 parts by weight of styrene were added. Next, after stirring at 100 ° C. for 1 hour, the mixture was stirred at 150 ° C. for 3 hours to complete the polymerization. After the reaction, the solid content was taken out and washed with water to obtain a modified polyolefin resin pellet (A-4). The weight average molecular weight of the graft chain composed of glycidyl methacrylate and styrene (A-4) was 63,000. 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.

実施例１〜３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、比較例２は含浸重合で製造された変性ポリオレフィン系樹脂である。実施例４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り、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１〜４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 to 3 are modified polyolefin resins of the present invention produced by melt kneading, and Comparative Example 2 is a modified polyolefin resin produced by impregnation polymerization. Example 4 is the polyolefin resin of the present invention containing the modified polyolefin resin of the present invention, and Comparative Example 1 is a polyolefin resin not containing the modified polyolefin resin. About Examples 1-4, 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 (7)

  (A) Resin composition obtained by graft reaction of (b) epoxy group-containing vinyl monomer and (c) aromatic vinyl monomer, or (d) (meth) acrylate monomer to polyolefin resin The weight of grafted chain comprising (b) an epoxy group-containing vinyl monomer and (c) an aromatic vinyl monomer, or (d) a (meth) acrylate monomer A modified polyolefin resin composition having an average molecular weight in the range of 200 to 10,000.   The modified polyolefin resin composition according to claim 1, wherein (a) the polyolefin resin is a polypropylene resin having a majority of propylene units.   A polyolefin sheet or film-like molded article comprising the modified polyolefin resin composition according to any one of claims 1 and 2 and having heat-weldability.   The polyolefin resin composition which contains 0.1-100 weight part of modified polyolefin resin compositions as described in any one of Claim 1, 2 with respect to 100 weight part of polyolefin resin.   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 and 2.   A polyolefin-based sheet or film-like molded article comprising the polyolefin-based resin composition according to any one of claims 6 and 7, and having heat-weldability.   The modified polyolefin resin composition according to any one of claims 1 and 2, the polyolefin resin composition according to any one of claims 4 and 5, and any one of claims 3 and 6. An adhesive body formed by bonding with at least one selected from the group consisting of the polyolefin-based sheet or the film-like molded body described in 1.