JP2008297407A - Modified polyolefin resin composition and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyolefin resin composition improved in printability, coating properties, adhesive properties, antistatic properties and the like by an easy method using a simple apparatus, and a molded item. <P>SOLUTION: The modified polyolefin resin composition is obtained by melt-kneading 100 pts.wt. of a polyolefin resin (component A), 10-150 pts.wt. of a compound (component B) having a polyoxyalkylene chain in the molecule and an ethylenically unsaturated double bond at its end and 0.01-10 pts.wt. of an organic peroxide (component C). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention is a modification characterized by being obtained by melt-kneading a polyolefin resin, a compound having a polyoxyalkylene chain in the molecule and having an ethylenically unsaturated double bond at the terminal, and an organic peroxide. The present invention relates to a polyolefin resin. The present invention also relates to a thermoplastic resin composition obtained by adding the modified polyolefin resin to a thermoplastic resin, and a molded body using the same.

  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. On the other hand, polypropylene-based materials are so-called non-polar, chemically highly inactive polymer substances that do not have polar groups in the molecule, and have high crystallinity and extremely low solubility in solvents. There are problems in properties, paintability, scratch resistance, oil resistance, antistatic properties and the like.

  For this reason, many surface modification methods such as printability, adhesiveness, paintability, and hydrophilicity have been proposed for polyethylene resins and polypropylene resins, which are particularly in high demand among polyolefin resins. It can be roughly divided into two. One is a method of imparting polarity by oxidizing the surface of the base resin by flame treatment, corona discharge treatment or the like. However, flame treatment, corona discharge treatment, and the like require special equipment, and there is a problem that the treatment effect becomes weak as time passes.

  The other method is a method in which a polar polymer is used as an additive to melt and knead the base resin to impart polarity. Specific examples of these methods include a method of adding a maleic anhydride-grafted polyolefin resin (see Patent Document 1) grafted with a polar monomer such as maleic acid and maleic anhydride, and an antistatic property such as a polyether ester amide. And a method in which an agent and an acid-modified polyolefin resin are used in combination (see Patent Document 2). However, these methods have many problems, such as the need to add a large amount and insufficient performance improvement.

  In response to such problems, recently, a polymer-type permanent antistatic agent by copolymerization of a polymer obtained by secondary modification of the end of a modified polyolefin and a polyfunctional hydrophilic polymer with the aim of further improving performance (Patent Document 3) However, this composition is effective for molded articles, but has a problem that performance is not stable for thin molded articles such as films and sheets.

As another method, an antistatic agent (see Patent Document 4) by a graft reaction between an acid-modified polyolefin resin and a specific monool-type polyoxyalkylene compound is disclosed. The multi-layer structure by extrusion exhibits performance, and when a molded body such as a sheet is obtained by kneading into a normal matrix resin, high performance cannot be obtained.
Japanese Patent Laid-Open No. 5-125111 JP-A-11-170456 JP 2001-278985 A JP 2006-188678 A

  The present invention provides a polyolefin resin composition capable of improving printability, paintability, adhesiveness, antistatic properties, etc. with a small amount of added parts by a simple method using a simple apparatus. Objective.

  As a result of intensive investigations in view of the above-described present situation, the present inventors have found that a polyolefin resin and a compound having a polyoxyalkylene chain in the molecule and having an ethylenically unsaturated double bond at the end are combined with an organic solvent. The present inventors have found that a modified polyolefin resin composition obtained by melt-kneading in the presence of an oxide is useful as an additive capable of imparting the above physical properties to a thermoplastic resin.

That is, the present invention
(Component A) 100 parts by weight of a polyolefin-based resin (Component B) 10 to 150 parts by weight of a compound having a polyoxyalkylene chain in the molecule and having an ethylenically unsaturated double bond at the terminal (Component C) Organic peroxidation A modified polyolefin resin composition obtained by melt-kneading 0.01 to 10 parts by weight of a product (Claim 1).
The modified polyolefin resin composition according to claim 1, wherein the component (B) has one ethylenically unsaturated double bond in the molecule (claim 2).
The modified polyolefin resin composition according to claim 1 or 2, wherein the polyoxyalkylene chain of (Component B) is a polyoxyethylene chain (Claim 3).
The number average molecular weight of (B component) is 100-10,000, The modified polyolefin resin composition of Claims 1-3 (Claim 4).
The modified polyolefin resin composition according to claim 1, wherein the (A component) polyolefin resin is a polypropylene resin (claim 5).

  1 to 50 parts by weight of the modified polyolefin resin composition according to any one of claims 1 to 5 is added to 100 parts by weight of the thermoplastic resin (claim 6). .

  A polyolefin resin composition, wherein the thermoplastic resin according to claim 6 is a polyolefin resin (claim 7).

  The molded object using the resin composition of Claims 6-7 (Claim 8). It is.

  According to the present invention, since polar characteristics can be imparted to the polyolefin resin, wettability, printability, paint adhesion, adhesion, and antistatic properties are improved, and materials for automobiles, electrical and electronic materials, building materials, and packaging are improved. Industrially useful as materials, stationery, miscellaneous goods, etc.

  Details of the present invention will be described below.

<< About component A >>
The (component A) polyolefin resin used in the present invention is a homopolymer of an α-olefin having 2 to 12 carbon atoms or a copolymer containing them as a main component. Specific examples thereof include polyethylene, polypropylene, poly-1-butene, polyisobutylene, a random or block copolymer of propylene and ethylene, a random or block copolymer of propylene and 1-butene, and propylene and ethylene. Examples thereof include a random or block terpolymer with 1-butene. Further, vinyl acetate, acrylic acid, acrylic acid ester, alkyl acrylate ester, methacrylic acid, methacrylic acid ester, methacrylic acid alkyl ester, aromatic vinyl compound, etc. may be used as the monomer copolymerizable with the α-olefin. Random or block copolymers with these can also be used. Among these compounds, polypropylene or a compound having a polyoxyalkylene chain in the molecule whose random or block copolymer of propylene and ethylene is (component B) and having an ethylenically unsaturated double bond at the terminal Can be preferably used in terms of ease of introduction.

  In addition, the (component A) polyolefin-based resin of the present invention may be one in which one or more polar functional groups are introduced into the resin. The polar functional group described here is a generally known hydroxyl group, amino group, epoxy group, carboxyl group, acid anhydride group, silyl group, or the like. There is no restriction on the method of introducing a polar functional group into a polyolefin resin, but in general, a compound having a polymerizable unsaturated double bond present in the terminal or molecular chain is added simultaneously with the organic peroxide. A method of introducing by radical reaction can be exemplified. Specific examples of the compound having a polar functional group include allyl alcohol, ethylene glycol monoallyl ether, 2-hydroxymethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxy as a compound that can be used when a hydroxyl group is introduced. Examples include propyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxymethyl methacrylate, 2-hydroxyethyl metallate, 2-hydroxypropyl metallate, 4-hydroxybutyl methacrylate, and 1,4-cyclohexanedimethanol monoacrylate.

  In the case of introducing an amino group, allylamine, 2-aminoethyl acrylate, and 2-aminoethyl methacrylate are exemplified.

  When introducing an epoxy group, allyl glycidyl ether, glycidyl methacrylate, glycidyl acrylate, 4-hydroxybutyl acrylate glycidyl ether, aliphatic epoxy methacrylate, and aliphatic epoxy acrylate are exemplified.

  In the case of introducing a carboxyl group, acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, β-carboxyethyl acrylate, 2-acryloyloxypropyl hydrogen phthalate may be mentioned.

  In the case of an acid anhydride group, maleic anhydride, itaconic anhydride, citraconic anhydride, and tetrahydrophthalic anhydride can be mentioned. In the case of introducing a silyl group, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-methacryloxypropylmethyldiethoxysilane are exemplified. Among these, acid anhydride groups such as maleic anhydride, acrylic acid, methacrylic acid, and maleic acid are available because they can be obtained stably and inexpensively and polar functional groups can be introduced into polyolefin resins at a relatively high ratio. A polyolefin-based resin into which a carboxyl group is introduced is preferably used.

  The molecular weight of the (A) polyolefin resin used in the present invention is not particularly limited, but 500 to 100,000 is easy to improve paintability when the modified polyolefin resin is added to the polypropylene resin. Preferably, 1,000 to 30,000 is more preferable.

<< About B component >>
The compound having a polyoxyalkylene chain in the molecule (component B) of the present invention and having an ethylenically unsaturated double bond at the terminal has a polyoxyalkylene chain and an ethylenically unsaturated double bond in the molecule. Any chemical structure or chemical bond may be used as long as it has at least one. In the polyoxyalkylene chain, only one kind may be present in the molecule, or a plurality of polyoxyalkylene chains having different alkyl chains may be present. Specific examples of these compounds include polyalkylene glycol monoacrylates, polyalkylene glycol monomethacrylates, alkyl group-terminated polyalkylene glycol monoacrylates, alkyl group-terminated polyalkylene glycol monomethacrylates, polyalkylene glycol diacrylates, Examples include polyalkylene glycol dimethacrylates, bisphenol A skeleton-containing polyalkylene glycol diacrylates, bisphenol A skeleton-containing polyalkylene glycol dimethacrylates, and the like.

  Polyalkylene glycol monoacrylates include polyethylene glycol monoacrylate, polypropylene glycol monoacrylate, polytetramethylene glycol monoacrylate, poly (ethylene glycol / propylene glycol) monoacrylate, poly (ethylene glycol / tetramethylene glycol) monoacrylate, poly (Propylene glycol / tetramethylene glycol) monoacrylate, and the like.

  Polyalkylene glycol monomethacrylates include polyethylene glycol monomethacrylate, polypropylene glycol monomethacrylate, polytetramethylene glycol monomethacrylate, poly (ethylene glycol / propylene glycol) monomethacrylate, poly (ethylene glycol / tetramethylene glycol) monomethacrylate, poly (Propylene glycol / tetramethylene glycol) monomethacrylate and the like.

  Examples of alkyl group-terminated polyalkylene glycol monoacrylates include methoxy polyethylene glycol monoacrylate, ethoxy polyethylene glycol monoacrylate, propoxy polyethylene glycol monoacrylate, butoxy polyethylene glycol monoacrylate, hexoxy polyethylene glycol monoacrylate, octoxy polyethylene glycol monoacrylate, Such as desiloxy polyethylene glycol monoacrylate, lauroxy polyethylene glycol monoacrylate, myristoxy polyethylene glycol monoacrylate, palmitopolyethylene glycol monoacrylate, stearoxy polyethylene glycol monoacrylate, phenoxy polyethylene glycol monoacrylate And the like.

  Examples of alkyl group-terminated polyalkylene glycol monomethacrylates include methoxypolyethylene glycol monomethacrylate, ethoxypolyethyleneglycol monomethacrylate, propoxypolyethyleneglycolmonomethacrylate, butoxypolyethyleneglycolmonomethacrylate, hexoxypolyethyleneglycolmonomethacrylate, octoxypolyethyleneglycolmonomethacrylate, Decyloxy polyethylene glycol monomethacrylate, Lauroxy polyethylene glycol monomethacrylate, Myristoxy polyethylene glycol monomethacrylate, Palmitopolyethylene glycol monomethacrylate, Stearoxy polyethylene glycol monomethacrylate, Phenoxypolyethyleneglycol Such as over mono methacrylate, and the like.

  Polyalkylene glycol diacrylates include polyethylene glycol diacrylate, polypropylene glycol diacrylate, polytetramethylene glycol diacrylate, poly (ethylene glycol / propylene glycol) diacrylate, poly (ethylene glycol / tetramethylene glycol) diacrylate, poly (Propylene glycol / tetramethylene glycol) diacrylate, poly (ethylene glycol / propylene glycol / ethylene glycol) diacrylate, and the like.

  Polyalkylene glycol dimethacrylates include polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, polytetramethylene glycol dimethacrylate, poly (ethylene glycol / propylene glycol) dimethacrylate, poly (ethylene glycol / tetramethylene glycol) dimetallate, poly ( And propylene glycol / tetramethylene glycol) dimethacrylate and poly (ethylene glycol / propylene glycol / ethylene glycol) dimethacrylate.

  Examples of bisphenol A skeleton-containing polyalkylene glycol diacrylates include polyethylene glycol-bisphenol A-diacrylate, polypropylene propylene glycol-bisphenol A-diacrylate, and poly (ethylene glycol-propylene glycol) -bisphenol A-diacrylate. It is done.

  Examples of bisphenol A skeleton-containing polyalkylene glycol dimethacrylates include polyethylene glycol-bisphenol A-dimethacrylate, polypropylene propylene glycol-bisphenol A-dimethacrylate, poly (ethylene glycol-propylene glycol) -bisphenol A-dimethacrylate, and the like. It is done.

  Among these, from the viewpoint of promoting a stable reaction with few cross-linked products in the reaction with the polyolefin-based resin (component A), a polyalkylene glycol mono having only one ethylenically unsaturated double bond at the molecular end. Methacrylates, alkyl group-terminated polyalkylene glycol monomethacrylates, polyalkylene glycol monoacrylates, and alkyl group-terminated polyalkylene glycol monoacrylates are preferably used.

  Since the polyoxyalkylene chain in the (B component) of the present invention is a polyoxyethylene chain, the resin composition obtained by the reaction with the (A component) tends to modify the surface characteristics. preferable. The number average molecular weight of these (component B) is preferably in the range of 100 to 10,000, and more preferably in the range of 200 to 5,000. If the weight average molecular weight is lower than this range, the effects of the present invention tend not to be exhibited.If the weight average molecular weight exceeds this range, the compatibility is increased when the modified polyolefin resin composition of the present invention is added to the matrix resin. There is a tendency to decrease.

  The blending amount of (B component) with respect to (A component) of the present invention is in the range of 10 to 150 parts by weight, preferably 30 to 75 parts by weight, per 100 parts by weight of (A component). is there. When the blending amount of (B component) exceeds 10 parts by weight, there is a tendency to easily improve the target surface characteristics. On the other hand, if the blending amount exceeds the range, the reforming effect reaches the saturation region, so it is preferable that the upper limit is 150 parts by weight.

<< About C ingredient >>
The (C component) organic peroxide of the present invention is a component for extracting hydrogen from the polyolefin resin (A component) to generate radicals and reacting with the ethylenically unsaturated double bond in (B component). is there. In the present invention, the graft reaction of (A component) and (B component) is promoted by using an organic peroxide.

  Examples of the organic peroxide used in the present invention generally include peroxides and azo compounds. Specific examples of the organic peroxide include ketone peroxides such as methyl ethyl ketone peroxide and methyl acetoacetate peroxide; 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1, Peroxyketals such as 1-bis (t-butylperoxy) cyclohexane, n-butyl-4,4-bis (t-butylperoxy) valerate, 2,2-bis (t-butylperoxy) butane; Hydroperoxides such as methane hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide; dicumyl peroxide, 2,5-dimethyl-2,5 -Di (t-butylperoxy) hexa , Α, α′-bis (t-butylperoxy-m-isopropyl) benzene, t-butylcumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butyl) Peroxy) dialkyl peroxides such as hexyne-3; diacyl peroxides such as benzoyl peroxide; peroxydicarbonates such as di (3-methyl-3-methoxybutyl) peroxydicarbonate and di-2-methoxybutylperoxydicarbonate Oxydicarbonate; t-butyl peroxyoctate, t-butyl peroxyisobutyrate, t-butyl peroxylaurate, t-butyl peroxy-3,5,5-trimethylhexanoate, t-butyl peroxy Oxyisopropyl carbonate, 2,5-dimethyl-2,5-di (benzoyl) -Oxy) Peroxyesters such as hexane, t-butyl peroxyacetate, t-butyl peroxybenzoate, di-t-butyl peroxyisophthalate, and the like. These may be used alone or in combination of two or more. Also good.

  Among these, a peroxide having a high hydrogen abstraction ability from the polyolefin resin as a base is preferable, and specific examples of such an organic peroxide include, for example, dicumyl peroxide, 2,5-dimethyl-2, 5-di (t-butylperoxy) hexane, α, α′-bis (t-butylperoxy-m-isopropyl) benzene, t-butylcumyl peroxide, di-t-butylperoxide, 2,5- Dialkyl peroxides such as dimethyl-2,5-di (t-butylperoxy) hexyne-3; diacyl peroxides such as benzoyl peroxide; t-butylperoxyoctate, t-butylperoxyisobutyrate, t -Butyl peroxylaurate, t-butyl peroxy-3,5,5-trimethylhexanoate, t Pars such as butyl peroxyisopropyl carbonate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxyacetate, t-butylperoxybenzoate, di-t-butylperoxyisophthalate An oxyester etc. are mentioned.

  The amount of the peroxide added is preferably in the range of 0.01 to 10 parts by weight, more preferably 0.05 to 8 parts by weight, especially 100 parts by weight of the polyolefin resin as the base. It is preferable that it exists in the range of 0.1-5 weight part. If it is less than 0.01 part by weight, the modification does not proceed sufficiently, and if it exceeds 10 parts by weight, the mechanical properties tend to be lowered.

  In the method for producing a modified polyolefin resin composition of the present invention, (component A) polyolefin resin, (component B) has a polyoxyalkylene chain in the molecule and has an ethylenically unsaturated double bond at the terminal. The melt kneading method with the compound and the (C component) organic peroxide is not particularly limited.

  Examples include a method in which the components are added and reacted in a device at a high temperature, or a method in which (A component) and (C component) are previously melted and (B component) is added and reacted later. . There is no limitation also about the apparatus used for reaction, For example, an autoclave, a separable flask with a stirring blade, a single screw extruder, a twin screw extruder, a plast mill, a kneader, a Banbury mixer, a heating roll, etc. are used suitably. The kneading conditions can be arbitrarily set depending on the type and combination of each component, but the reaction temperature is generally in the range of 150 ° C. to 250 ° C., and the reaction time is about 1 hour or less. And from the viewpoint of reaction efficiency and the like.

  When producing the modified polyolefin resin composition of the present invention, a small amount of components other than (A component) (B component) (C component) may be added. Specific examples of components other than (A component) (B component) (C component) that can be used are usually well-known stabilizers, inorganic flame retardants, organic flame retardants, flame retardant aids, ultraviolet absorbers, Light stabilizers, release agents, pigments, dyes, lubricants, plasticizers, and the like. These can be used alone or in combination of two or more. The amount of components other than (A component), (B component) and (C component) is not particularly limited as long as the effects of the present invention are not impaired, but is preferably based on 100 parts by weight of (A component). The amount is less than 1 part by weight, more preferably less than 0.1 part by weight, still more preferably less than 0.01 part by weight.

  By adding the modified polyolefin resin composition of the present invention to a thermoplastic resin, it is possible to improve the surface properties of the resin, in particular, adhesion, paintability, printability, antistatic properties, and the like. There are no particular restrictions on the type of thermoplastic resin. For example, in addition to polyolefin resins typified by polyethylene, polypropylene and polybutylene, polystyrene, polyacetal, polycarbonate, polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyamide, polyethylene naphthalate, poly Ether ketone, polyether ether ketone, polyether imide, polyether sulfone, polyphenylene sulfide, polyvinyl chloride, polyimide, polyarylate, acrylonitrile-styrene-butadiene copolymer (ABS), acrylonitrile-ethylene-styrene copolymer (AES) , Acrylonitrile-styrene-methyl acrylate copolymer (ASA) polyvinyl acetate, ethylene Yl acetate copolymer (EVA) and the like. These may be used alone or in combination as an alloy resin used in combination of two or more. Among these, since the polyolefin resin is excellent in balance including compatibility with the olefin resin composition of the present invention, the intended effect is easily exhibited.

  Polyolefin resins include polyethylene, polypropylene, poly-1-butene, polyisobutylene, random or block copolymers of propylene and ethylene, random or block copolymers of propylene and 1-butene, propylene and ethylene and 1 -Random or block terpolymer with butene and the like. In addition, as a monomer copolymerizable with the α-olefin, vinyl acetate, acrylic acid ester, acrylic acid alkyl ester, methacrylic acid ester, methacrylic acid alkyl ester, aromatic vinyl compound, and the like can be used. Or a block copolymer etc. are mention | raise | lifted, Furthermore, a polyolefin-type thermoplastic elastomer (TPO) is also mentioned. These may be used alone or in combination of two or more.

  The polyolefin-based thermoplastic elastomer is composed of an olefin-based copolymer rubber and a crystalline olefin-based polymer, and these forms include simple blend compositions, partially cross-linked blend compositions, and complete cross-linking (dynamic cross-linking). Examples thereof include a blend composition, but are preferably crosslinked. Specifically, a method of adding an organic peroxide to a kneaded product of an olefin copolymer rubber and a crystalline polyolefin polymer and partially crosslinking the two, a rubber obtained by kneading an olefin copolymer rubber and an organic oxide Examples include a method in which the phases are partially crosslinked and blended with the crystalline olefin polymer. Further, an organic peroxide may be added to the kneaded product of the olefin copolymer rubber and the crystalline polyolefin polymer, so that the olefin copolymer rubber component is completely cross-linked.

  The olefin copolymer rubber is an essentially amorphous rubbery copolymer consisting of a copolymer of at least one polyene (usually a diene) and two or more nonpolar α-olefin monomers. Preferred is ethylene-propylene-diene copolymer rubber (EPDM). The crystalline olefin polymer is a crystalline polymer obtained by polymerizing a nonpolar α-olefin monomer such as ethylene, propylene, butene-1, and pentene-1 by a conventional method. Specific examples include polyethylene and copolymers thereof, polypropylene and copolymers thereof, and polybutene. Polypropylene and copolymers thereof are preferred. The ratio of the olefin copolymer rubber and the crystalline olefin polymer is usually in the range of 40 to 80% by weight of the olefin copolymer rubber and 60 to 20% by weight of the crystalline olefin polymer with respect to the total amount of both components. preferable. Both components are kneaded at a melting point or higher to become a polyolefin-based thermoplastic elastomer.

  In addition, in order to impart properties useful as an elastomer, not only the organic peroxides described above as means for crosslinking the olefin copolymer rubber, but also phenol resins, sulfur, and the like can be used. The thermoplastic polyolefin-based elastomer may contain other components as long as the rubber properties are not impaired. Examples of other components include oil, filler, carbon black, stabilizer, and the like.

  Specific examples of these polyolefin-based thermoplastic elastomers are the commercially available “Milastomer” manufactured by Mitsui Chemicals, “Thermolan, Zelas” manufactured by Mitsubishi Chemical, “Excellen” manufactured by Sumitomo Chemical, and “Santoprene” manufactured by AES Japan. And Dow Chemical's “Versify”.

  The modified polyolefin resin composition of the present invention can contain 1 to 50 parts by weight with respect to 100 parts by weight of the thermoplastic resin. Preferably it is 1.5-30 weight part. When it contains more than this range, the crystallinity of polyolefin resin will be impaired and rigidity will fall, and when too small, the effect of this invention will not be expressed.

  The thermoplastic resin composition obtained by the present invention can be used as a molded article. The processing method for obtaining a molded body is not particularly limited, and generally used molding methods such as injection molding, in-mold molding, blow molding (hollow molding), extrusion molding (including co-extrusion molding), Vacuum forming, press forming, calendar forming, etc. can be applied. As a typical use of the molded body obtained by these molding methods, it can be used for modification of polypropylene members of automobiles.

Specifically, front and rear bumpers, fender protectors, radiator grilles, engine and transmission under covers, linear fishers, over fenders, side moldings, aero parts, air duct covers, air duct hoses, weather strips, glass run channels, window moldings, Door seals, timing belt covers, sunroof housings, door mirrors, instrument panels, console boxes, seat frames, seat belt components, trims (door trims, interior trims, etc.), molded ceilings, sun visors, reaction covers, steering pads, consoles, Pillars, lamp housing, fan shroud, air conditioning case, air conditioning door, child seat, meter case, seat material Interior seat, instrument panel skin, glass shade, decorative sheet, sun visor sheet, shift lever skin, armrest skin, etc.), but such as air bag cover and the like, but is not limited to these.
Other than automotive applications, construction field (waterproofing materials for civil engineering and construction, joint materials, covering materials for decorative steel sheets, etc.), electrical field (non-slip for various housings and home appliances, gaskets, packing, grips, etc.), sports Can be used in the supplies, stationery and sundries fields.

Specific examples are shown below, but the present invention is not limited to the following examples.
The main raw materials used in Examples and Comparative Examples are summarized below.

(material)
(Component A) Polyolefin resin (A-1) Maleic anhydride grafted polypropylene (H-1100P: manufactured by Toyo Kasei Kogyo Co., Ltd., number average molecular weight 24,000, maleic anhydride conversion rate 4.5 wt%).
(A-2) Homopolypropylene (F113G: manufactured by Prime Polymer Co., Ltd., MFR (230 ° C.) = 3 g / 10 min)
(Component B) Compound having a polyoxyalkylene chain in the molecule and having an ethylenically unsaturated double bond at the terminal (B-1) Methoxypolyethylene glycol acrylate: Number average molecular weight 1,000
(B-2) Methoxypolyethylene glycol methacrylate: number average molecular weight 1,000
(B-3) Methoxypolyethylene glycol methacrylate: Number average molecular weight 4,000
(C component) Organic peroxide (C-1) α, α'-bis (t-butylperoxy-m-isopropyl) benzene (E component) and others (E-1) stearyl acrylate (wetting tension test)
JIS K-6768 “Plastic-film and sheet-wetting tension test method” was followed. As the evaluation sample, the evaluation pellet obtained by the extruder was sandwiched between press plates set at 200 ° C., and a press sheet having a thickness of about 300 μm was used. A polyimide film was sandwiched inside the press plate so that the evaluation sheet was easily released.

(Paintability test)
The tape peeling test by UV curable ink application was performed. As the evaluation sample, the evaluation pellet obtained by the extruder was sandwiched between press plates set at 200 ° C., and a press sheet having a thickness of about 300 μm was used. A polyimide film was sandwiched inside the press plate so that the evaluation sheet was easily released. As a detailed test method, UV ink having a length of 5 cm and a width of 1 cm was applied on an evaluation sheet having a length of 10 cm and a width of 20 cm, and the ink was cured with a UV curing apparatus. Thereafter, a cellophane tape was applied vertically to the cured UV ink and pulled up vertically to evaluate the degree of ink peeling. Judgment is as follows.

○: Ink does not peel Δ: Ink peels slightly (peeling 20% or less)
X: Ink peels off (20% to 100% peeling)
(Example 1 of modified polyolefin resin)
(A-1) Same direction in which 100 parts by weight of maleic anhydride grafted polypropylene and 1.5 parts by weight of (C-1) α, α′-bis (t-butylperoxy-m-isopropyl) benzene were set at 180 ° C. It is added from the hopper of a twin screw extruder (TEX30: L / D = 28, manufactured by Nippon Steel), and 40 parts by weight of (B-1) methoxypolyethylene glycol acrylate is added by side feed from the middle of the cylinder to perform melt kneading. The modified polyolefin resin composition (D-1) was obtained. In addition, as a result of analyzing the obtained composition by transmission IR, it was confirmed that an ether bond signal was formed in the vicinity of 1105 cm ⁻¹ , and the reaction products of both were present.

(Examples 2 to 4 of modified polyolefin resin)
A sample was prepared in the same manner as in Example 1 of the modified polyolefin resin based on the number of blending parts described in Table 1.

(Comparative example 1 of modified polyolefin resin)
A sample was prepared in the same manner as in Example 1 of the modified polyolefin resin based on the number of blending parts described in Table 1.

[実施例５]
（Ａ−２）ホモポリプロピレン（Ｆ１１３Ｇ）１００重量部に対し、（Ｄ−１）改質ポリオレフィン系樹脂１２重量部を２００℃に設定した同方向二軸押出機（ＴＥＸ３０：Ｌ／Ｄ＝２８、日本製鋼所製）のホッパーより添加し、ポリオレフィン系樹脂組成物を得た。得られたペレットは、濡れ評価試験および塗装性試験に用いた。

[Example 5]
(A-2) Co-directional twin-screw extruder (TEX30: L / D = 28, 12 parts by weight of modified polyolefin resin (D-1) set to 200 ° C. with respect to 100 parts by weight of homopolypropylene (F113G) A polyolefin resin composition was obtained by adding from a hopper of Nippon Steel Works. The obtained pellets were used for a wetness evaluation test and a paintability test.

[Examples 6 to 9 and Comparative Examples 2 to 5]
For Examples 6 to 9 and Comparative Examples 2 to 5, samples were prepared in the same manner as in Example 5 with respect to the number of blending parts shown in Table 2, and a wet tension test was performed. In addition, Examples 8 and 9 and Comparative Examples 2 and 35 were subjected to a paintability test.

実施例５〜９については、本発明の請求範囲内における改質ポリオレフィン系樹脂組成物をポリオレフィン系樹脂に配合しているので、濡れ性は高い。一方で比較例２〜５については、いずれもポリオレフィン系樹脂に対して、本発明の改質ポリオレフィン系樹脂を添加していないので濡れ性は実施例に対して低い。

About Examples 5-9, since the modified polyolefin resin composition in the claim of this invention is mix | blended with polyolefin resin, wettability is high. On the other hand, in Comparative Examples 2 to 5, since the modified polyolefin resin of the present invention is not added to the polyolefin resin, the wettability is low compared to the examples.

実施例５、８、９については、本発明の請求範囲内における改質ポリオレフィン系樹脂組成物をポリオレフィン系樹脂に配合しているので、塗装性は高い。一方で比較例２、３、５については、いずれもポリオレフィン系樹脂に対して、本発明の改質ポリオレフィン系樹脂を添加していないので塗装性の改質効果は実施例に対して低い。

In Examples 5, 8, and 9, since the modified polyolefin resin composition in the claims of the present invention is blended with the polyolefin resin, the paintability is high. On the other hand, in Comparative Examples 2, 3, and 5, since the modified polyolefin resin of the present invention is not added to the polyolefin resin, the effect of improving the paintability is low compared to the examples.

  According to the present invention, it is possible to produce a polyolefin-based resin composition excellent in printability, paintability, adhesiveness, and antistatic property, and industrially such as automotive materials, packaging materials, building materials, stationery, and miscellaneous goods. Useful. It is also suitable for a recycling-oriented society such as excellent recyclability.

Claims (8)

(Component A) 100 parts by weight of a polyolefin-based resin (Component B) 10 to 150 parts by weight of a compound having a polyoxyalkylene chain in the molecule and having an ethylenically unsaturated double bond at the terminal (Component C) Organic peroxidation A modified polyolefin resin composition obtained by melt-kneading 0.01 to 10 parts by weight of a product. The modified polyolefin resin composition according to claim 1, wherein the (B component) has one ethylenically unsaturated double bond in the molecule. The modified polyolefin resin composition according to any one of claims 1 to 2, wherein the polyoxyalkylene chain of (Component B) is a polyoxyethylene chain. The number average molecular weight of (B component) is 100-10,000, The modified polyolefin resin composition of any one of Claims 1-3 characterized by the above-mentioned. The modified polyolefin resin composition according to claim 1, wherein the (A component) polyolefin resin is a polypropylene resin.   1 to 50 parts by weight of the modified polyolefin resin composition according to any one of claims 1 to 5 is added to 100 parts by weight of a thermoplastic resin.   The polyolefin resin composition according to claim 6, wherein the thermoplastic resin is a polyolefin resin.   The molded object using the resin composition of any one of Claims 6-7.