Modified polyolefin, thermoplastic resin composition, and molded article

Abstract

A modified polyolefin (X) satisfies the following (i)-(iii): (i) the weight average molecular weight (Mw) is 3,000-29,000; (ii) the weight average molecular weight (Mw) / the number average molecular weight (Mn) is 1.5 to 5.0 (exclusive of 5.0); and (iii) the modified polyolefin (X) is a hydrogenated polybutadiene having a hydroxyl group and a degree of hydrogenation of 60-100%.

Description

Modified Polyolefin, Thermoplastic Resin Composition and Molded Article

[0001] The present invention relates to a modified polyolefin, a thermoplastic resin composition and a molded article.

[0002] Thermoplastic resins, for example, polyolefin resins, are excellent in moldability, rigidity, heat resistance, chemical resistance, light weight and electrical insulation, and are widely used as materials for films, fibers, hollow fiber membranes and other molded articles of various shapes. On the other hand, for example, molded articles of polyolefin resins have problems in adhesiveness and paintability, for example, poor adhesion to paints, printing inks, adhesives and the like, and cannot be applied to painting and printing without post-processing surface treatment. Conventionally, as a method for improving adhesion, a method of performing corona treatment or plasma treatment on the surface of a molded article of a thermoplastic resin, for example, a polyolefin resin (see, for example, Patent Document 1) has been proposed.

[0003] Japanese Unexamined Patent Publication No. 2000-319426

[0004] However, the above technique has complicated processing and cannot be said to be sufficiently satisfactory in terms of adhesion. An object of the present invention is to provide a modified polyolefin that imparts excellent paint adhesion to a molded article obtained by molding a thermoplastic resin composition, a thermoplastic resin composition containing the modified polyolefin, and a molded article obtained by molding the thermoplastic resin composition.

[0005] The present inventors have intensively studied to solve the above problems, and as a result, arrived at the present invention. That is, the present invention provides a modified polyolefin (X) satisfying the following (i) to (iii): (i) a weight average molecular weight (Mw) of 3,000 to 29,000; (ii) a ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) of 1.5 or more and less than 5.0; (iii) the modified polyolefin (X) is a hydrogenated polybutadiene having a hydroxyl group and a hydrogenation rate of 60 to 100%; a thermoplastic resin composition (Y) containing the modified polyolefin (X) and a thermoplastic resin (E); and a molded article (Z) obtained by molding the thermoplastic resin composition (Y).

[0006] According to the present invention, it is possible to provide a modified polyolefin that provides excellent adhesion to paints to a molded article made by molding a thermoplastic resin composition, a thermoplastic resin composition containing the modified polyolefin, and a molded article made by molding the thermoplastic resin composition.

[0007] <Modified Polyolefin (X)> The modified polyolefin (X) of the present invention is a modified polyolefin (X) that satisfies the following (i) to (iii): (i) Weight-average molecular weight (Mw) is 3,000 to 29,000; (ii) Weight-average molecular weight (Mw) / Number-average molecular weight (Mn) is 1.5 or more and less than 5.0; (iii) The modified polyolefin (X) is a hydrogenated polybutadiene with hydroxyl groups and a hydrogenation rate of 60 to 100%.

[0008] The weight-average molecular weight (Mw) of the modified polyolefin (X) is 3,000 to 29,000, preferably 3,500 to 20,000, and more preferably 4,000 to 10,000, from the viewpoint of adhesion.

[0009] In this specification, "adhesion" means the property of a substrate to adhere to a coating film such as paint, printing ink, or adhesive.

[0010] In this invention, the number-average molecular weight (Mn) and weight-average molecular weight (Mw) are values ​​measured by GPC (gel permeation chromatography). The measurement conditions for Mw and Mn by GPC in this specification are as follows: • Apparatus: High-temperature gel permeation chromatograph ["Alliance GPC / V 2000", Waters Co., Ltd.] • Detection device: Refractive index detector • Solvent: Orthodichlorobenzene • Reference material: Polystyrene • Sample concentration: 3 mg / ml • Column stationary phase: PLgel 10 μm, MIXED-B 2 in series [Polymer Laboratories Co., Ltd.] • Column temperature: 135°C

[0011] The weight-average molecular weight (Mw) / number-average molecular weight (Mn) of the modified polyolefin (X) [hereinafter sometimes referred to as Mw / Mn] is 1.5 or more and less than 5.0, preferably 1.7 or more and less than 4.7, and more preferably 2.0 or more and less than 4.0, from the viewpoint of adhesion.

[0012] Modified polyolefin (X) is hydrogenated polybutadiene with a hydrogenation rate of 60-100% having hydroxyl groups. In other words, the polyolefin chain contained in modified polyolefin (X) is hydrogenated polybutadiene with a hydrogenation rate of 60-100%. The polybutadiene has at least one of the group consisting of constituent units having 1,2-bonds, constituent units having cis-1,4-bonds, and constituent units having trans-1,4-bonds. From the viewpoint of adhesion, the above hydrogenation rate is preferably 65-95%, more preferably 70-90%. The hydrogenation rate (%) is a value defined by the following formula: Hydrogenation rate (%) = [A / (A + B)] × 100 In the formula, A is the number of moles of hydrogenated butadiene units constituting the hydrogenated polybutadiene, and B is the number of moles of unhydrogenated butadiene units constituting the hydrogenated polybutadiene. A and B are １ It is calculated using the integral ratio of H-NMR.

[0013] Modified polyolefins (X) can be produced, for example, by hydrogenation of hydroxyl group-containing polybutadiene (preferably polybutadiene polyol, more preferably polybutadiene diol) in the presence of a hydrogenation catalyst. Hereinafter, polybutadiene polyols having at least one hydroxyl group at their terminus may be referred to as hydroxyl-terminated polybutadiene (A). Modified polyolefins (X) may be produced using commercially available polybutadiene polyols, or commercially available modified polyolefins (X) (such as hydrogenated hydroxyl-terminated polybutadiene (A)) may be used.

[0014] The hydroxyl value of the modified polyolefin (X) is preferably 5 to 200 mg KOH / g, more preferably 10 to 180 mg KOH / g, and even more preferably 25 to 120 mg KOH / g, from the viewpoint of adhesion. The above hydroxyl values ​​were measured in accordance with JIS K 0070 (1992).

[0015] Modified polyolefin (X) may be used alone or in combination of two or more types. When two or more modified polyolefins (X) are used in combination, the Mw, Mw / Mn, and hydrogenation rate of the mixture satisfy the above conditions (i) to (iii). Furthermore, it is preferable that the hydroxyl value of the mixture is within the aforementioned range.

[0016] The modified polyolefin (X) of the present invention is suitable as a modifier for various thermoplastic resins (E), and is particularly suitable as a modifier for polyolefin resins as described later. Furthermore, the modified polyolefin (X) of the present invention is suitable as an adhesion enhancer to improve the adhesion of molded articles made by molding thermoplastic resin compositions to paints and the like.

[0017] <Thermoplastic resin composition (Y)> The thermoplastic resin composition (Y) of the present invention contains the modified polyolefin (X) of the present invention and a thermoplastic resin (E).

[0018] <Thermoplastic Resin (E)> Examples of thermoplastic resin (E) in the present invention include polyolefin resin and polystyrene resin. Of these, polyolefin resin is preferred.

[0019] Polyolefin resins include, for example, ethylene unit-containing (propylene unit-free) (co)polymers, propylene unit-containing (ethylene unit-free) (co)polymers, ethylene / propylene copolymers, and (co)polymers of olefins with 4 or more carbon atoms [sometimes abbreviated as C in this specification]. Among these, propylene unit-containing (ethylene unit-free) (co)polymers and ethylene / α-olefin copolymers are preferred, and polypropylene and ethylene / 1-butene copolymers are more preferred, as the effects of the present invention are more pronounced.

[0020] Examples of commercially available thermoplastic resins (E) include polypropylene such as Sun Allomer PM600A and PM771M manufactured by Sun Allomer Co., Ltd., and ethylene-based α-olefin copolymers such as Tuffmer® DF610 manufactured by Mitsui Chemicals, Inc. The thermoplastic resin (E) may be used alone or in combination of two or more types.

[0021] The manganese content (Mn) of the polyolefin resin is preferably 10,000 to 500,000, more preferably 20,000 to 400,000, and even more preferably 80,000 to 300,000, from the viewpoint of the mechanical strength and compatibility of the molded product.

[0022] The thermoplastic resin composition (Y) of the present invention may contain, as necessary, various additives (F) in addition to the modified polyolefin (X) and thermoplastic resin (E), provided that they do not impair the effects of the present invention. Examples of additives (F) include colorants (F1), flame retardants (F2), fillers (F3), lubricants (F4), antistatic agents (F5), dispersants (F6), antioxidants (F7), mold release agents (F8), antibacterial agents (F9), compatibilizers (F10), and ultraviolet absorbers (F11). One of these may be used, or two or more may be used in combination.

[0023] Examples of colorants (F1) include inorganic pigments (white pigments, cobalt compounds, iron compounds, sulfides, etc.) and organic pigments (azo pigments, polycyclic pigments, etc.).

[0024] Examples of flame retardants (F2) include halogen-containing flame retardants, nitrogen-containing flame retardants, sulfur-containing flame retardants, silicon-containing flame retardants, and phosphorus-containing flame retardants.

[0025] Examples of fillers (F3) include inorganic fillers (calcium carbonate, talc, clay, etc.) and organic fillers (urea, etc.).

[0026] Examples of lubricants (F4) include calcium stearate, butyl stearate, and oleamide.

[0027] Examples of antistatic agents (F5) include nonionic, cationic, anionic, or amphoteric surfactants described in U.S. Patent No. 3,929,678 and U.S. Patent No. 4,331,447.

[0028] Examples of dispersants (F6) include polymers with a Mn of 1,000 to 20,000, such as vinyl resins, poly(meth)acrylic acid esters [poly(meth)acrylate, etc.]; polyester resins [polyethylene terephthalate, etc.]; polyamide resins [6,6-nylon and 12-nylon, etc.]; polyether resins [polyethersulfone, etc.]; polycarbonate resins [polycondensates of bisphenol A and phosgene, etc.]; and block copolymers thereof.

[0029] Examples of antioxidants (F7) include phenol compounds [monocyclic phenols (2,6-di-t-butyl-p-cresol, etc.)] and bisphenols [2,2'-methylenebis(4-methyl-6-t-butylphenol, etc.)].

[0030] Examples of release agents (F8) include lower (C1-4) alcohol esters of fatty acids (C8-24) (such as butyl stearate), polyvalent (divalent to tetravalent or higher) alcohol esters of fatty acids (C2-24) (such as hydrogenated castor oil), and glycol (C2-8) esters of fatty acids (C2-24) (such as ethylene glycol monostearate).

[0031] Examples of antimicrobial agents (F9) include benzoic acid, sorbic acid, halogenated phenols, organic iodine, nitriles (such as 2,4,5,6-tetrachloroisophthalonitrile), thiocyanosides (methylenebisthianocyanate), N-haloalkylthioimide, copper compounds (such as 8-oxyquinoline copper), benzimidazole, benzothiazole, trihaloallyl, and triazole.

[0032] Examples of compatibilizers (F10) include modified vinyl polymers having sulfonic acid groups as described in Japanese Patent Publication No. 6-345927.

[0033] Examples of UV absorbers (F11) include benzotriazole [2-(2'-hydroxy-5'-methylphenyl)benzotriazole, etc.], benzophenone [2-hydroxy-4-methoxybenzophenone, etc.], salicylate [phenyl salicylate, etc.], and acrylate [2-ethylhexyl-2-cyano-3,3-diphenyl acrylate, etc.].

[0034] The total content of additives (F) in the thermoplastic resin composition (Y) is preferably, for example, 20% by weight or less, based on the total weight of the thermoplastic resin composition (Y), more preferably 0.05 to 10% by weight, and even more preferably 0.1 to 5% by weight, from the viewpoint of the expression of the function of each additive (F) and industrial viewpoint. The amount of each additive used based on the total weight of the thermoplastic resin composition (Y) is, for example, 5% by weight or less, preferably 0.1 to 3% by weight; for example, 8% by weight or less, preferably 1 to 3% by weight; for example, 10% by weight or less, preferably 5% by weight or less, preferably 0.1 to 1% by weight; for example, 8% by weight or less, preferably 1 to 5% by weight; for example, 8% by weight or less, preferably 1 to 3% by weight; for example, dispersant (F6) The amount of the main component is 1% by weight or less, preferably 0.1 to 0.5% by weight; the antioxidant (F7) is, for example, 2% by weight or less, preferably 0.05 to 0.5% by weight; the release agent (F8) is, for example, 5% by weight or less, preferably 0.01 to 3% by weight; the antibacterial agent (F9) is, for example, 25% by weight or less, preferably 0.5 to 20% by weight; the compatibilizer (F10) is, for example, 15% by weight or less, preferably 0.5 to 10% by weight; and the ultraviolet absorber (F11) is, for example, 2% by weight or less, preferably 0.05 to 0.5% by weight.

[0035] If a single compound functions as two or more additives from (F1) to (F11) above, the amount required to achieve the effect of each corresponding additive should not be applied individually. Instead, the total amount used should be adjusted according to the intended use, taking into consideration that the compound simultaneously achieves the effects of each additive.

[0036] The methods for producing the thermoplastic resin composition (Y) of the present invention include: (1) a method of mixing the entire amount of thermoplastic resin (E) and modified polyolefin (X), and optionally an additive (F), all at once to produce the thermoplastic resin composition (Y) (all-at-once method); and (2) a method of first preparing a masterbatch resin composition containing a high concentration of modified polyolefin (X) by mixing a portion of the thermoplastic resin (E), the entire amount of modified polyolefin (X), and optionally a portion or all of the additive (F), and then adding and mixing the remaining thermoplastic resin (E) and optionally the remaining additive (F) to produce the thermoplastic resin composition (Y) (masterbatch method). From the viewpoint of mixing efficiency of modified polyolefin (X), method (2) is preferred. The process may be appropriately changed depending on the raw materials used.

[0037] Specific mixing methods in the method for producing the thermoplastic resin composition (Y) described above include: (i) mixing each component to be mixed in a powder mixer [e.g., "Henschel Mixer" [product name "Henschel Mixer FM150L / B", manufactured by Nippon Coke Industries, Ltd.], "Nauta Mixer" [product name "Nauta Mixer DBX3000RX", manufactured by Hosokawa Micron Corporation], "Banbury Mixer" [product name "MIXTRON BB-16 MIXER", manufactured by Kobe Steel, Ltd.], etc.], and then kneading using a melt kneading device [batch kneader, continuous kneader (single-screw kneader, twin-screw kneader, etc.)] at a temperature of 120 to 220°C for 2 to 30 minutes; (ii) directly kneading each component to be mixed using the same melt kneading device as described above under the same conditions without pre-mixing the components as powders. Of these methods, method (i) is preferred from the viewpoint of mixing efficiency. Furthermore, the process may be modified as appropriate depending on the raw materials used.

[0038] The weight ratio [(X) / (E)] of the modified polyolefin (X) to the thermoplastic resin (E) in the thermoplastic resin composition (Y) of the present invention is preferably 0.3 / 99.7 to 10 / 90, and more preferably 0.5 / 99.5 to 5 / 95, from the viewpoint of adhesion and mechanical strength of the molded article.

[0039] <Molded Article (Z)> The molded article (Z) of the present invention is obtained by molding the thermoplastic resin composition (Y) of the present invention. That is, the molded article (Z) of the present invention is a molded body of the thermoplastic resin composition (Y) of the present invention. Examples of molding methods include injection molding, compression molding, calendering, slush molding, rotational molding, extrusion molding, blow molding, and film molding (casting method, tenter method, inflation method, etc.). Depending on the purpose, it can be molded by any method that incorporates means such as single-layer molding, multi-layer molding, or foam molding. Examples of the form of the molded article include plate-like, sheet-like, film-like, and fiber-like (including nonwoven fabrics, etc.).

[0040] The molded article (Z) of the present invention contains the modified polyolefin (X) having hydroxyl groups of the present invention, and due to its modification effect, it exhibits excellent affinity with paints, printing inks, adhesives, and the like, which have relatively high polarity.

[0041] The molded article (Z) of the present invention has excellent mechanical strength and excellent adhesion (good paintability, printability, adhesion, etc.) to coatings such as paints, printing inks, and adhesives. A molded article can be obtained by painting and / or printing on the molded article. Because the molded article (Z) has excellent adhesion to coatings, the coating on the molded article is less likely to peel off. Methods for painting the molded article include, but are not limited to, air spray painting, airless spray painting, electrostatic spray painting, dipping painting, roller painting, and brush painting. Examples of paints used for the molded article (Z) of the present invention include paints that are commonly used for painting plastics. For example, both highly polar resin-based paints (polyester melamine resin-based paints, epoxy melamine resin-based paints, acrylic melamine resin-based paints, urethane resin-based paints, etc.) and low-polarity resin-based paints (polyolefin resin-based paints, etc.) can be used. Among these, highly polar resin-based paints are preferred, and urethane resin-based paints are more preferred. The paint may be water-based or oil-based. The coating thickness (dry thickness) can be appropriately selected depending on the purpose, but for example, it is 10 to 50 μm.

[0042] As the printing ink used for the molded article (Z) of the present invention, those commonly used for plastic printing can be used, for example, gravure ink, flexographic ink, screen ink, pad ink, dry offset ink and offset ink. Further, as a method for printing on a molded article or a molded article that has been coated, any printing method generally used for plastic printing can be used, and examples thereof include gravure printing, flexographic printing, screen printing, pad printing, dry offset printing and offset printing.

[0043] As the adhesive used for the molded article (Z) of the present invention, those generally used for bonding plastics can be mentioned, for example, acrylate resin-based adhesives, epoxy resin-based adhesives, and urethane resin-based adhesives can be used.

[0044] The following matters are disclosed in the present specification. [1] A modified polyolefin (X) that satisfies the following (i) to (iii). (i) The weight average molecular weight (Mw) is 3,000 to 29,000; (ii) The weight average molecular weight (Mw) / number average molecular weight (Mn) is 1.5 or more and less than 5.0; (iii) The modified polyolefin (X) is a hydrogenated polybutadiene having a hydroxyl group and a hydrogenation rate of 60 to 100%. [2] The modified polyolefin (X) according to [1], wherein the hydrogenation rate of the hydrogenated polybutadiene is 70 to 90%. [3] The modified polyolefin (X) according to [1] or [2], which is an adhesion improver. [4] A thermoplastic resin composition (Y) containing the modified polyolefin (X) according to any one of [1] to [3] and a thermoplastic resin (E). [5] The thermoplastic resin composition (Y) according to [4], wherein the weight ratio [(X) / (E)] of the modified polyolefin (X) to the thermoplastic resin (E) is 0.3 / 99.7 to 10 / 90. [6] A molded article (Z) obtained by molding the thermoplastic resin composition (Y) according to [4] or [5].

[0045] The present invention will be further described below by way of examples, but the present invention is not limited thereto. "Parts" in the description represents parts by weight.

[0046] <Production Example 1> Into a reaction vessel equipped with a nitrogen introduction tube, a gas introduction tube, a dropping funnel, a thermometer, a cooling tube and a stirring blade, 230 parts of toluene, 27 parts of 2-mercaptoethanol, 8 parts of tert-dodecyl mercaptan, and 0.5 parts of iron(II) sulfide heptahydrate were charged. Next, 280 parts of 1,3-butadiene was introduced under nitrogen aeration, 2 parts of a 30 wt% aqueous hydrogen peroxide solution was injected, and the mixture was stirred at 60°C for 5 hours. Next, after cooling, 5 parts of methanol and 0.15 parts of acetic acid were added into the reaction vessel, and the mixture was stirred for several minutes to terminate the reaction. Thereafter, unreacted butadiene and the solvent were removed under reduced pressure to obtain hydroxyl-terminated polybutadiene (A-1).

[0047] <Production Examples 2 to 3> Each hydroxyl-terminated polybutadiene (A) was obtained in the same manner as in Production Example 1, except that the reaction was carried out in accordance with the reaction composition (parts) shown in Table 1. Table 1 shows the weight average molecular weight (Mw), number average molecular weight (Mn), Mw / Mn and hydroxyl value of each hydroxyl-terminated polybutadiene (A) measured by the aforementioned method.

[0048]

[0049] <Example 1> Into a reaction vessel equipped with a nitrogen introduction tube, a gas introduction tube, a thermometer, a cooling tube and a stirring blade, 250 parts of hydroxyl-terminated polybutadiene (A-1) and 25 parts of a carbon-supported ruthenium catalyst (ruthenium content: 5% by weight, manufactured by FUJIFILM Wako Pure Chemical Corporation) were charged. Under nitrogen substitution, hydrogen gas was fed until the gas pressure reached 5 MPaA. Next, the temperature of the autoclave was raised to 100°C, hydrogen gas was supplied so that the total pressure was maintained at 5 MPaA, and a hydrogenation reaction was carried out for 3 hours. Next, hydrogen was removed, the catalyst was separated by filtration, the product was precipitated in methanol and then dried to obtain modified polyolefin (X-1).

[0050] <Examples 2 to 4> Each modified polyolefin (X) was obtained in the same manner as in Example 1, except that the reaction was carried out in accordance with the reaction composition (parts) and hydrogenation reaction (time) shown in Table 2.

[0051] [Hydrogenation Rate] Of hydroxyl-terminated polybutadiene and modified polyolefin (X) under the following measurement conditions １ 1H-NMR measurement was carried out. The hydrogenation rate was determined by the aforementioned method. < １H-NMR measurement conditions > Apparatus: 400YH (manufactured by JEOL) Solvent: Deuterium toluene Table 2 shows the weight-average molecular weight (Mw), Mw / Mn, hydrogenation rate, and hydroxyl value of each modified polyolefin (X) measured by the method described above.

[0052]

[0053] <Example 5> In a reaction vessel equipped with a nitrogen inlet tube, a dropping funnel, a thermometer, a cooling tube, and a stirring blade, 30 parts of polyolefin (X0-1) [hydroxyl-terminated polybutadiene, trade name "NISSO PB GI-1000", manufactured by Nippon Soda Co., Ltd., Mw: 3,400, Mw / Mn: 2.52] and 70 parts of polyolefin (X0-2) [hydroxyl-terminated polybutadiene, trade name "NISSO PB GI-3000", manufactured by Nippon Soda Co., Ltd., Mw: 5,600, Mw / Mn: 1.30] were melt-kneaded at 100°C for 1 hour under nitrogen aeration to obtain modified polyolefin (X-5). The weight-average molecular weight (Mw) of the modified polyolefin (X-5) was 5,000, the Mw / Mn ratio was 2.09, the hydrogenation rate was 100%, and the hydroxyl value was 40 mgKOH / g.

[0054] <Examples 6-7, Comparative Example 1> Modified polyolefins (X) were obtained in the same manner as in Example 5, except that the raw materials were used according to Table 3. The weight-average molecular weight (Mw), Mw / Mn, hydrogenation rate, and hydroxyl value of each modified polyolefin (X) measured by the method described above are shown in Table 3.

[0055]

[0056] <Examples 11-19, Comparative Examples 2-3> According to the formulations in Table 4, each modified polyolefin (X) and thermoplastic resin (E) was melt-kneaded in a twin-screw extruder [product name "KZW45TW", manufactured by Technovel Co., Ltd.] at 230°C and 100 rpm to obtain each thermoplastic resin composition (Y). Note that thermoplastic resin (E-2) is a mixture obtained by melt-kneading polypropylene [product name "Sun Allomer PM771M", manufactured by Sun Allomer Co., Ltd., MFR: 9.5] (70 parts by weight), elastomer [product name "Toughmer DF610", manufactured by Mitsui Chemicals, Inc., MFR: 2.2] (20 parts by weight), and talc (10 parts by weight) in a twin-screw extruder at 230°C and 100 rpm. Each thermoplastic resin composition (Y) was injection molded using an injection molding machine [product name "PS40E5ASE", manufactured by Nissei Plastics Co., Ltd.] at a nozzle temperature of 230°C and a mold temperature of 50°C to obtain molded products (Z). The molded products (Z) were evaluated according to the evaluation method described below. The results are shown in Table 4.

[0057] (1) Adhesion to paint (20°C) The paintability (adhesion to paint) was evaluated using the adhesion of urethane-based paint. A molded product (Z) was cut to a size of 100 mm x 100 mm x 2 mm to obtain a test piece. Urethane-based paint (product name "Retan PG80", manufactured by Kansai Paint Co., Ltd.) was applied to the test piece using an applicator to a film thickness of 30 μm after drying, and dried at 80°C for 30 minutes to obtain a coated object. After temperature-controlled the coated object at 20°C for 24 hours, a grid peel test was performed on the coated surface at 20°C using the method specified in JIS K 5600-5-6 (1999), with cloth adhesive tape [LS No. 123, manufactured by Nichiban Co., Ltd.] instead of transparent pressure-sensitive adhesive tape. The number of areas where the paint film did not peel off out of 100 grid squares was measured and evaluated according to the following criteria.

[0058] <Evaluation Criteria> ◎ (Excellent): Number of eyes that did not peel off is 100 ○ (Good): Number of eyes that did not peel off is 95-99 △ (Acceptable): Number of eyes that did not peel off is 80-94 × (Poor): Number of eyes that did not peel off is 0-79

[0059] (2) Adhesion to paint (40°C) The paintability (adhesion to paint) was evaluated using the adhesion of urethane-based paint. Urethane-based paint (product name "Retan PG80", manufactured by Kansai Paint Co., Ltd.) was applied to the test piece obtained by the method described in "Adhesion to paint (20°C)" above using an applicator so that the film thickness after drying was 30 μm, and the coated material was dried at 80°C for 30 minutes. After the coated material was temperature-controlled at 40°C for 24 hours, a grid peel test was performed on the coated surface at 40°C using the method specified in JIS K 5600-5-6 (1999), with cloth adhesive tape [LS No. 123, manufactured by Nichiban Co., Ltd.] instead of transparent pressure-sensitive adhesive tape. The number of areas where the paint film did not peel off out of 100 grid squares was measured and evaluated according to the following criteria.

[0060] <Evaluation Criteria> ◎ (Excellent): Number of eyes that did not peel off is 100 ○ (Good): Number of eyes that did not peel off is 95-99 △ (Acceptable): Number of eyes that did not peel off is 80-94 × (Poor): Number of eyes that did not peel off is 0-79

[0061] (3) Izod Impact Strength The Izod impact strength of the molded articles of the thermoplastic resin composition (Y) of the example was measured in accordance with JIS K 7110 (1999), and the improvement rate (%) of the Izod impact strength was calculated using the following formula: Improvement rate (%) of Izod impact strength = (Izod impact strength of the molded article (Z) of the example) × 100 / (Izod impact strength of the comparative molded article) The Izod impact strength of the comparative molded article is the Izod impact strength measured in the same manner as in each example, by manufacturing a molded article using the modified polyolefin of Comparative Example 1 (ratio X-1) as the modified polyolefin in the compound composition of each example and comparative example. Next, the improvement rate (%) of the Izod impact strength calculated above was evaluated according to the following <evaluation criteria>. <Evaluation criteria> ◎ (Excellent): Over 100% ○ (Good): Over 90%, 100% or less △ (Acceptable): Over 80%, 90% or less × (Poor): 80% or less

[0062]

[0063] The results in Table 4 show that the modified polyolefin (X) of each example provides superior adhesion and high mechanical strength to the molded article (Z) of thermoplastic resin (E) over a wide temperature range, compared to the comparative example.

Claims

1. Modified polyolefin (X) satisfying the following conditions (i) to (iii): (i) Weight-average molecular weight (Mw) is 3,000 to 29,000; (ii) Weight-average molecular weight (Mw) / Number-average molecular weight (Mn) is 1.5 or more and less than 5.0; (iii) Modified polyolefin (X) is hydrogenated polybutadiene with hydroxyl groups and a hydrogenation rate of 60 to 100%.

2. The modified polyolefin (X) according to claim 1, wherein the hydrogenation rate of the hydrogenated polybutadiene is 70 to 90%.

3. The modified polyolefin (X) according to claim 1, which is an adhesion improving agent.

4. A thermoplastic resin composition (Y) containing a modified polyolefin (X) according to any one of claims 1 to 3 and a thermoplastic resin (E).

5. The thermoplastic resin composition (Y) according to claim 4, wherein the weight ratio [(X) / (E)] of the modified polyolefin (X) to the thermoplastic resin (E) is 0.3 / 99.7 to 10 / 90.

6. A molded article (Z) obtained by molding the thermoplastic resin composition (Y) according to claim 4.

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