JP2009013230A - Modified polyolefin resin composition and its producing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a modified polyolefin resin composition as an intermediate for a polymer material requiring accurate molecule design that has improved wettability, printability, ink adhesion, adhesive property, oil resistance and welder processing performance by an easy method with the usage of a simple device, and to provide a method for producing the same. <P>SOLUTION: The modified polyolefin resin composition is prepared by melting and kneading (c) an unsaturated carboxylic acid monomer and (d) an aromatic vinyl monomer in the presence of (b) a radical polymerization initiator with respect to (a) the polyolefin resin, and more than half amount of (c) the unsaturated carboxylic acid monomer and (d) the aromatic vinyl monomer reacts to (a) the polyolefin resin. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention is obtained by adding an unsaturated carboxylic acid monomer and an aromatic vinyl monomer in the presence of a polyolefin-based resin and a radical polymerization initiator, and kneading and kneading the unsaturated carboxylic acid monomer and an aromatic vinyl monomer. The present invention relates to a modified polyolefin resin in which a majority of vinyl monomer components are reacted with a polyolefin resin component, a production method, and a composition containing the resin. In particular, the modified polyolefin resin has a carboxylic acid group and is useful as an intermediate for a polymer material that requires precise molecular design.

  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 are problems in properties, scratch resistance, oil resistance, and the like.

  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 modified resin is obtained by melting and kneading at least one monomer selected from styrene, isoprene and 1,3-butadiene, acrylic acid, and a radical polymerization initiator with respect to the polypropylene resin (Patent Document 1).

  (Ii) A polyolefin resin, maleic anhydride and an organic peroxide having a decomposition temperature of 150 to 200 ° C. with a half-life of 1 minute are melt-kneaded to obtain a modified polyolefin (Patent Document 2).

  However, in the method (i), acrylic acid is used in combination with at least one monomer selected from styrene, isoprene and 1,3-butadiene, but unsaturated carboxylic acid such as acrylic acid is highly efficient. In addition, no solution has been disclosed for introducing a high content of polypropylene resin.

  Further, in the method (ii), when the amount of maleic anhydride added is large, the production of unreacted products and by-products cannot be controlled. Not enough.

  As described above, it cannot be said that the polyolefin resin has been provided with a level of efficiency that satisfies the sufficient requirements for printability, ink adhesion, adhesion, and the like.

In addition, the production of unreacted products and by-products cannot be controlled while introducing a polar group at a high content, and the level of meeting the demand as an intermediate of a polymer material is not reached.
JP 10-2119014 A Japanese Patent Laid-Open No. 9-278956

  The present invention is a polymer material that has improved wettability, printability, ink adhesion, adhesiveness, oil resistance, welder processability, etc. by a simple method using a simple apparatus and requires precise molecular design. It is an object of the present invention to provide a modified polyolefin resin that is an intermediate of the above and a method for producing the same.

  As a result of intensive studies in view of the above-described present situation, the present inventors have added an unsaturated carboxylic acid monomer and an aromatic vinyl monomer in the presence of a polyolefin resin and a radical polymerization initiator, and then melt-kneaded. The present inventors have found that it is possible to suppress the formation of low molecular weight substances that do not contribute to grafting, introduce a carboxylic acid group into a polyolefin resin with high efficiency, and impart the above physical properties, thereby completing the present invention. It was.

That is, the present invention
(A) obtained by melt-kneading (c) an unsaturated carboxylic acid monomer and (d) an aromatic vinyl monomer in the presence of a radical polymerization initiator (b) with respect to a polyolefin-based resin, and (c A modified polyolefin resin composition wherein a majority of the unsaturated carboxylic acid monomer and (d) aromatic vinyl monomer are reacted with (a) a polyolefin resin. (Claim 1).

  The ratio of (c) unsaturated carboxylic acid monomer in a total of 100% by weight of (a) polyolefin resin, (c) unsaturated carboxylic acid monomer and (d) aromatic vinyl monomer is 2 to 50. The modified polyolefin resin composition according to claim 1, which is in the range of% by weight. (Claim 2).

  The modified polyolefin resin composition according to any one of claims 1 and 2, wherein (a) the polyolefin resin is a polypropylene resin having a majority of propylene units.

  The modified polyolefin-based composition according to any one of claims 1 to 3 has a multiphase structure, and (c) an unsaturated carboxylic acid monomer and (d) an aromatic vinyl in a phase comprising a polyolefin-based resin. The modified polyolefin resin composition according to any one of claims 1 to 3, wherein the monomer phase has an average particle size of 1 µm or less (claim 4).

  (A) A polyolefin-based resin and (b) a radical polymerization initiator are melt-kneaded and then (c) an unsaturated carboxylic acid monomer and (d) an aromatic vinyl monomer are added and melt-kneaded. A process for producing a modified polyolefin resin composition according to any one of claims 1 to 4 (claim 5).

  The polyolefin resin composition which contains 0.1-100 weight part of modified polyolefin resin compositions as described in any one of Claims 1-4 with respect to 100 weight part of polyolefin resin (Claim 6).

  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 to 4 with respect to 100 parts by weight of a polypropylene resin having a majority of propylene units ( Claim 7).

  According to the present invention, an unsaturated carboxylic acid monomer can be grafted to a polyolefin resin with high efficiency by a simple method using a simple apparatus. In addition, since the carboxylic acid groups are introduced with high efficiency, these modified polyolefin resins can improve the wettability, printability, ink adhesion, adhesiveness, and oil resistance of the polyolefin resins. It is useful as an intermediate for polymer materials that require a particular molecular design. Furthermore, high-frequency processing (welder processing), which is difficult with a polyolefin resin alone, can be made possible.

  These modified polyolefin resins can be used not only independently but also as an additive to polyolefin resins to improve printability, ink adhesion, adhesiveness, and oil resistance, and impart high-frequency workability (welder processability). be able to.

  Details of the present invention will be described below.

  In the present invention, it is essential that the majority of (c) unsaturated carboxylic acid monomer and (d) aromatic vinyl monomer react with (a) polyolefin resin. The majority amount here means 50% by weight or more.

The amount of (c) unsaturated carboxylic acid monomer and (d) aromatic vinyl monomer reacted with (a) polyolefin resin can be measured by the following method. The extrudate pellets were dissolved by heating at 130 ° C. for 3 hours with about 50 times by weight of o-dichlorobenzene to remove insoluble matters, and then allowed to cool overnight to collect the re-precipitate by filtration. Residual solvent was removed by drying under reduced pressure at 80 ° C. overnight. The extruded pellet and reprecipitate were subjected to acid value measurement to determine the acid value, and the graft amount of the unsaturated carboxylic acid monomer was estimated. The acid value was measured by the following method. A sample (0.5 g) was dissolved in o-dichlorobenzene (40 mL), and ethanol (20 mL) was further added. A few drops of phenolphthalein in ethanol were added, followed by titration with 0.1N potassium hydroxide in ethanol. Regarding the graft amount of the aromatic vinyl monomer, the extruded pellet and the reprecipitate were each press-molded at 190 ° C. for about 7 minutes, and the obtained molded body was subjected to IR measurement with a transmission type, C—H The peak ratio of the group (1373 cm ⁻¹ ) and the aromatic C—H group (700 cm ⁻¹ ) was determined, and the graft amount of the aromatic vinyl monomer was estimated.

<< 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.

  Furthermore, stabilizers such as antioxidants, metal deactivators, phosphorus processing stabilizers, UV absorbers, UV stabilizers, fluorescent brighteners, metal soaps, and antacid adsorbents are optionally added to polyolefin resins. Or additives such as cross-linking agents, chain transfer agents, nucleating agents, lubricants, plasticizers, fillers, reinforcing materials, pigments, dyes, flame retardants, antistatic agents, etc. are added within a range that does not impair the effects of the present invention. May be.

  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.

  Further, when the above additive material (other resin, rubber, stabilizer and / or additive) is used, the polyolefin resin is melted even if the additive material is previously added to the polyolefin resin. It may be sometimes added, or 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.

<< Unsaturated Carboxylic Acid Monomer >>
(C) Specific examples of unsaturated carboxylic acid monomers include acrylic acid, cis-crotonic acid, trans-crotonic acid, cis-ethylacrylic acid, trans-ethylacrylic acid, cis-cinnamic acid, trans -One or more of cinnamic acid, methacrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride and the like. Among these, acrylic acid, methacrylic acid, and maleic anhydride are preferable in that they are inexpensive.

  The amount of the (c) unsaturated carboxylic acid monomer added is preferably 3 to 100 parts by weight, more preferably 3 to 50 parts by weight, based on 100 parts by weight of the (a) polyolefin resin. preferable. Further, (c) the unsaturated carboxylic acid monomer in (a) the polyolefin resin, (c) the unsaturated carboxylic acid monomer and (d) the aromatic vinyl monomer being 100% by weight in total. The ratio is preferably in the range of 2 to 50% by weight, more preferably in the range of 2 to 40% by weight, and particularly preferably in the range of 2 to 30% by weight. If the addition amount is too small, the adhesiveness and paintability tend not to be improved sufficiently, 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 >>
(D) Specific examples of the aromatic vinyl monomer include styrene; o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, β-methylstyrene, dimethylstyrene, and trimethylstyrene. Methyl styrene such as o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, α-chlorostyrene, β-chlorostyrene, dichlorostyrene, trichlorostyrene and the like; o-bromostyrene, m-bromostyrene, Bromostyrene such as p-bromostyrene, dibromostyrene, tribromostyrene; fluorostyrene such as o-fluorostyrene, m-fluorostyrene, p-fluorostyrene, difluorostyrene, trifluorostyrene; o-nitrostyrene, m-nitro Styrene, p- Nitrostyrene such as trostyrene, dinitrostyrene, trinitrostyrene; vinylphenols such as o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, dihydroxystyrene, trihydroxystyrene; o-divinylstyrene, m-divinylstyrene, 1 type, or 2 or more types, such as divinyl styrene, such as p-divinyl styrene; diisopropenyl benzene, such as o-diisopropenyl benzene, m-diisopropenyl benzene, and p-diisopropenyl benzene; 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 (d) aromatic vinyl monomer added is preferably 3 to 50 parts by weight with respect to 100 parts by weight of the polyolefin resin. If the amount added is too small, the graft ratio of the unsaturated carboxylic acid 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 unsaturated carboxylic acid monomer reaches the saturation region, so it is preferable to set the upper limit to 50 parts by weight.

<< About radical initiators >>
(B) The radical polymerization initiator generally includes peroxides or 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; 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.

  About the addition order and method at the time of melt kneading, the addition order of melt kneading the unsaturated carboxylic acid monomer and 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.

  The present invention relates to the case where the modified polyolefin resin forms a multiphase structure and the phase composed of the unsaturated carboxylic acid monomer and the aromatic vinyl monomer in the phase composed of the polyolefin resin is finely dispersed. It is particularly effective. Although depending on the reaction conditions such as heating temperature and melt kneading time, it is preferable that the average phase of the unsaturated carboxylic acid monomer and aromatic vinyl monomer in the phase consisting of polyolefin resin is 1 μm or less. . Since the carboxylic acid group composed of the unsaturated carboxylic acid is finely dispersed, the compatibility with the material having a reactive functional group is improved and it can be used as an intermediate of the polymer material. Further, it is possible to efficiently improve printability, ink adhesion, adhesion, and oil resistance, and to impart high-frequency workability (welder workability).

  Even if the modified polyolefin resin of the present invention is added to a polyolefin resin as an additive, it can improve printability, ink adhesion, adhesion, and oil resistance, and can impart high-frequency workability (welder processability). it can.

  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, alkyl acrylate, aromatic Random copolymers with vinyl compounds such as nil, 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.

  The modified polyolefin resin obtained by the present invention can be used for modification of polypropylene and polyolefin-based thermoplastic elastomer members for 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, armrest, 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 / architecture, jointing materials, covering materials for decorative steel sheets, etc.), electrical field (non-slip for various housings and home appliances, gaskets, packing, grips, etc.), sports In the articles, stationery and sundries fields, it can be used to modify polypropylene and polyolefin-based thermoplastic elastomer members as well.

  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.

(Analysis of graft amount and graft ratio of unsaturated carboxylic acid)
The graft amount and graft ratio of the unsaturated carboxylic acid of the modified polyolefin resin were calculated by the following methods. The extrudate pellets were dissolved by heating at 130 ° C. for 3 hours with about 50 times by weight of o-dichlorobenzene to remove insoluble matters, and then allowed to cool overnight to collect the re-precipitate by filtration. Residual solvent was removed by drying under reduced pressure at 80 ° C. overnight. About the reprecipitation, the acid value was measured, the acid value was calculated | required, and the graft amount was estimated. Moreover, the graft ratio was estimated from the acid value of the extruded pellet and the re-precipitate. The acid value was measured by the following method. A sample (0.5 g) was dissolved in o-dichlorobenzene (40 mL), and ethanol (20 mL) was further added. A few drops of phenolphthalein in ethanol were added, followed by titration with 0.1N potassium hydroxide in ethanol.

(Wetting tension test)
As an evaluation method for paintability and printability, it was carried out in accordance with JIS K-6768 “Plastic-film and sheet-wetting tension test method”. For the evaluation sample, a press sheet having a thickness of 0.3 mm was used.

(Paintability test)
As an evaluation method of paintability, it was performed as follows. For the evaluation sample, a press sheet having a thickness of 0.3 mm was used. First, UV curable ink of 5 cm in length and 1 cm in width was applied on the evaluation sheet, and the ink was cured with a UV curable apparatus. A cellophane tape was applied vertically to the cured ink, and then the cellophane tape was peeled off 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
(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.) 1.5 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) 9 parts by weight of methacrylic acid and (d) 9 parts by weight of styrene were added and melt-kneaded to obtain modified polyolefin resin pellets (A-1). The average particle diameter of the domain consisting of the components of (A-1) methacrylic acid and styrene was 0.5 μm. The graft amount of (A-1) was 4%, and the graft ratio was 79% (reprecipitate yield 91%). (A-1) was used as a sample for evaluation. The results are shown in Table 1.

(Example 2)
(A-1) 100 parts by weight obtained in Example 1, (b) 1,3-di (t-butylperoxyisopropyl) benzene (manufactured by NOF Corporation: Perbutyl P, 1 minute half-life 175 ° C. ) After supplying 1.3 parts by weight to a twin-screw extruder (TEX30: L / D = 28, manufactured by Nippon Steel Works) set to 200 ° C. and melt-kneading, then (c) methacrylic acid 8 from the middle of the cylinder Part by weight and (d) 8 parts by weight of styrene were added and melt-kneaded to obtain modified polyolefin resin pellets (A-2). The average particle size of the domain consisting of the components of (A-2) methacrylic acid and styrene was 0.3 μm. The graft amount of (A-2) was 11%, and the graft ratio was 100% (reprecipitate yield 90%). (A-2) was used as a sample for evaluation. The results are shown in Table 1.

(Examples 3 and 4)
Laboplast mill (blade shape: roller type R60) in which 100 parts by weight of homopolypropylene (Prime Polymer F113G, MFR = 3.8) and 20 parts by weight of modified polyolefin resins of Examples 1 and 2 were set to 200 ° C. The resin composition obtained was kneaded for about 5 minutes with Toyo Seiki Co., Ltd. (20C200) and used as an evaluation sample. The results are shown in Table 1.

(Comparative Example 1)
Homopolypropylene (Prime Polymer F113G, MFR = 3.8) was used as an evaluation sample. Results are shown.

実施例１〜４については、本発明の請求範囲内における変性ポリオレフィン系樹脂及び樹脂組成物であり、その濡れ張力は高い。また、インキ密着性にも優れている。一方で比較例では濡れ張力は低く、インキ密着性に劣ることが判る。濡れ張力が大きいと表面張力が大きな液体でも塗ることができ、この様な液体を含むインキ、塗料、接着剤を用いた際、印刷性、インキ密着性、接着性を向上させる点で好ましい。

Examples 1 to 4 are modified polyolefin resins and resin compositions within the scope of the present invention, and their wetting tension is high. In addition, the ink adhesion is excellent. On the other hand, it can be seen that the comparative example has a low wetting tension and poor ink adhesion. When the wetting tension is large, a liquid having a large surface tension can be applied. When an ink, a paint, or an adhesive containing such a liquid is used, it is preferable in terms of improving printability, ink adhesion, and adhesiveness.

Claims (7)

  (A) obtained by melt-kneading (c) an unsaturated carboxylic acid monomer and (d) an aromatic vinyl monomer in the presence of a radical polymerization initiator (b) with respect to a polyolefin-based resin, and (c A modified polyolefin resin composition wherein a majority of the unsaturated carboxylic acid monomer and (d) aromatic vinyl monomer are reacted with (a) a polyolefin resin.   The ratio of (c) unsaturated carboxylic acid monomer in a total of 100% by weight of (a) polyolefin resin, (c) unsaturated carboxylic acid monomer and (d) aromatic vinyl monomer is 2 to 50. The modified polyolefin resin composition according to claim 1, which is in the range of% by weight.   The modified polyolefin resin composition according to any one of claims 1 and 2, wherein (a) the polyolefin resin is a polypropylene resin having a majority of propylene units.   The modified polyolefin-based composition according to any one of claims 1 to 3 has a multiphase structure, and (c) an unsaturated carboxylic acid monomer and (d) an aromatic vinyl in a phase comprising a polyolefin-based resin. The modified polyolefin resin composition according to any one of claims 1 to 3, wherein the monomer phase has an average particle size of 1 µm or less.   (A) A polyolefin-based resin and (b) a radical polymerization initiator are melt-kneaded and then (c) an unsaturated carboxylic acid monomer and (d) an aromatic vinyl monomer are added and melt-kneaded. The manufacturing method of the modified polyolefin resin composition as described in any one of Claims 1-4 characterized by these.   The polyolefin resin composition which contains 0.1-100 weight part of modified polyolefin resin compositions as described in any one of Claims 1-4 with respect to 100 weight part of polyolefin resin.   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 4 with respect to 100 parts by weight of a polypropylene resin having a majority of propylene units.