Resin modifier

Abstract

The object of the present invention is to provide a resin modifier that imparts excellent adhesion to paints, printing inks, adhesives, and the like to thermoplastic resins. [Solution] A resin modifier (K) containing a phenyl group-modified polyolefin (X), wherein the polyolefin (A) contains an α-olefin having 3 to 8 carbon atoms as a constituent monomer, and the modifier (γ) is an epoxy group-containing compound (P). Preferably, the number average molecular weight (Mn) of the epoxy group-modified polyolefin (X) is 1,000 to 60,000.

Description

【Technical Field】 【0001】 The present invention relates to a resin modifier. 【Background Art】 【0002】 Thermoplastic resins, such as polyolefin resins, are excellent in moldability, rigidity, heat resistance, chemical resistance, light weight, and electrical insulation, and are widely used as films, fibers, hollow fiber membranes, and molded products of various other shapes. On the other hand, for example, polyolefin resins have problems in adhesiveness and paintability. For example, they have poor adhesion to paints, printing inks, adhesives, etc., and there are problems such as being inapplicable without post-processing surface treatment. Conventionally, as a method for improving adhesion, a method of subjecting the surface of a thermoplastic resin, such as a polyolefin resin molded product, to corona treatment or plasma treatment (see, for example, Patent Document 1) has been proposed. 【Prior Art Documents】 【Patent Documents】 【0003】 【Patent Document 1】 Japanese Patent Application Laid-Open No. 2000-319426 【Summary of the Invention】 【Problems to be Solved by the Invention】 【0004】 However, in the above technology, the treatment is complicated, and the adhesion cannot be said to be sufficiently satisfactory. An object of the present invention is to provide a resin modifier that imparts excellent adhesion to thermoplastic resins with respect to paints, printing inks, adhesives, etc. 【Means for Solving the Problems】 【0005】 The present inventors have diligently studied to solve the above problems and have arrived at the present invention. That is, the present invention is a resin modifier (K) comprising a polyolefin (A) and a modifying agent (γ) as constituent raw materials, wherein the polyolefin (A) contains α-olefins having 3 to 8 carbon atoms as constituent monomers, and the modifying agent (γ) is an epoxy group-containing compound (P), and the present invention comprises an epoxy group-modified polyolefin (X). [Effects of the Invention] 【0006】 The resin modifier (K) of the present invention provides the following effects. (1) Excellent adhesion to the substrate. [Modes for carrying out the invention] 【0007】 <Polyolefin (A)> In the present invention, polyolefin (A) is a polyolefin containing an α-olefin having 3 to 8 carbon atoms as a constituent monomer. In the following text, "α-olefins with 3 to 8 carbon atoms" may be simply referred to as "α-olefins." 【0008】 Examples of the α-olefins mentioned above include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, and 1-octene. Of the α-olefins mentioned above, propylene is preferred. 【0009】 The above polyolefin (A) may also contain other monomers besides α-olefins. In that case, based on the total weight of the monomers constituting polyolefin (A), the weight of the other monomers is preferably 80% by weight or less, more preferably 50% by weight or less, and even more preferably 10% by weight or more and 20% by weight or less. 【0010】 Other monomers that make up the above polyolefin (A) include, for example, ethylene, 2-butene, α-olefins with 9 to 30 carbon atoms (hereinafter sometimes abbreviated as C) (1-decene, 1-dodecene, etc.), and unsaturated monomers with 4 to 30 carbon atoms other than α-olefins (for example, vinyl acetate). Of the other monomers mentioned above, ethylene is preferred. Furthermore, among polyolefins (A), propylene / ethylene copolymer, propylene / 1-butene copolymer, and ethylene / 1-octene copolymer are preferred, and propylene / ethylene copolymer is even more preferred. 【0011】 The number-average molecular weight (Mn) of polyolefin (A) is preferably 800 to 50,000, more preferably 1,500 to 40,000, and even more preferably 2,000 to 30,000. 【0012】 The number-average molecular weight (Mn) in this invention can be measured by GPC (gel permeation chromatography). The measurement conditions for Mn by GPC in this invention are as follows: Equipment: High-temperature gel permeation chromatograph ["Alliance GPC V2000", manufactured by Waters Co., Ltd.] Detection device: Refractive index detector Solvent: Orthodichlorobenzene Reference material: Polystyrene Sample concentration: 3 mg / ml Column stationary phase: PLgel 10μm, MIXED-B (2 tubes in series) [Manufactured by Polymer Laboratories, Inc.] Column temperature: 135℃ 【0013】 The number of double bonds per 1,000 carbon atoms of polyolefin (A) [the number of carbon-carbon double bonds at the molecular ends and / or in the molecular chain of polyolefin (A)] is preferably 0.5 to 20, more preferably 1.0 to 18, and even more preferably 1.5 to 15, from the viewpoint of reactivity with epoxy group-containing compound (P) and productivity. Here, the number of double bonds can be determined from the 1 1H-NMR spectrum. That is, by assigning the peaks in the spectrum and calculating the relative values of the number of double bonds and the number of carbon atoms of polyolefin (A) from the integral value derived from the double bond at 4.5 - 6 ppm and the integral value derived from polyolefin (A) in the spectrum of polyolefin (A), the number of double bonds at the molecular terminals and / or in the molecular chains per 1,000 carbon atoms of polyolefin (A) is calculated. The number of double bonds in the examples described later was determined according to this method. 【0014】 Examples of the method for producing polyolefin (A) in the present invention include a method of thermally reducing a high molecular weight (preferably Mn is 60,000 - 400,000, more preferably Mn is 80,000 - 250,000) polyolefin (A0). 【0015】 The thermal reduction method includes (1) a method of heating the above high molecular weight polyolefin (A0) at 300 - 450°C for 0.5 - 10 hours in the absence of an organic peroxide, and (2) a method of heating in the presence of an organic peroxide [e.g., 2,5-dimethyl-2,5-di(t-butylperoxy)hexane] at 180 - 300°C for 0.5 - 10 hours, etc. Among these, from the viewpoints of industrial aspects and the modification characteristics of the resin modifier (K), the method (1) that is more likely to obtain a larger number of double bonds at the molecular terminals and / or in the molecular chains is preferred. 【0016】 The weight ratio of the monomers constituting the above polyolefin (A) tends to be maintained as it is with the weight ratio of the monomers constituting the high molecular weight polyolefin (A0). Also, the higher the thermal reduction temperature or the longer the thermal reduction time, the more the number of double bonds per 1,000 carbon atoms tends to increase. Furthermore, the larger the Mn of the high molecular weight polyolefin (A0), the higher the thermal reduction temperature, or the longer the thermal reduction time, the smaller the Mn of polyolefin (A) tends to be. Polyolefin (A) may be used alone or in combination of two or more. 【0017】 <Modifier (γ)> The modifier (γ) in the present invention is an epoxy group-containing compound (P). 【0018】 <Epoxy group-containing compound (P)> The epoxy group-containing compound (P) in the present invention is an epoxide having one or more polymerizable unsaturated groups and having 3 to 30 carbon atoms. Examples of (P) include glycidyl (meth)acrylate, glycidyl group-containing (meth)acrylate having 6 to 20 carbon atoms such as β-methylglycidyl (meth)acrylate; alicyclic epoxy group-containing vinyl monomers having 6 to 20 carbon atoms such as 4-vinyl-1,2-epoxycyclohexane and 5-vinyl-2,3-epoxynorbornane; glycidyl group-containing acrylamides having 6 to 20 carbon atoms such as N-(4-(2,3-epoxypropoxy)-3,5-dimethylphenylmethyl)acrylamide, and the like. Among the above (P), glycidyl (meth)acrylate is preferable from the viewpoint of reactivity with the polyolefin (A). (P) may be used alone or in combination of two or more. 【0019】 <Epoxy group-modified polyolefin (X)> The epoxy group-modified polyolefin (X) in the present invention contains the above polyolefin (A) and epoxy group-containing compound (P) as constituent raw materials. The weight ratio [polyolefin (A) / epoxy group-containing compound (P)] of the polyolefin (A) and the epoxy group-containing compound (P) in the epoxy group-modified polyolefin (X) is preferably 80 / 20 to 99.5 / 0.5, more preferably 90 / 10 to 99 / 1, from the viewpoint of the modification characteristics of the resin modifier (K). 【0020】 Preferably, the epoxy group-modified polyolefin (X) is obtained by reacting the above polyolefin (A) and epoxy group-containing compound (P) in the absence or presence of a radical initiator (C). Epoxy-modified polyolefins (X) can more preferably be produced by reacting the above polyolefin (A) and epoxy group-containing compound (P) in the presence of a radical initiator (C) with a suitable organic solvent as needed [for example, C3-18 hydrocarbons (hexane, heptane, octane, dodecane, benzene, toluene, xylene, etc.), C3-18 halogenated hydrocarbons (di-, tri-, or tetrachloroethane, dichlorobutane, etc.), C3-18 ketones (acetone, methyl ethyl ketone, di-t-butyl ketone, etc.), C3-18 ethers (ethyl-n-propyl ether, di-n-butyl ether, di-t-butyl ether, dioxane, etc.)]. 【0021】 The radical initiator (C) mentioned above is a known one, for example, an azo initiator (azobisisobutyronitrile, 1,1'-azobis(cyclohexane-1-carbonitride), etc.) or a peroxide initiator (dicumyl peroxide, etc.). Of the radical initiators (C) listed above, peroxide initiators are preferred. 【0022】 The reaction temperature is preferably 100 to 270°C, more preferably 120 to 250°C, and even more preferably 130 to 240°C, from the viewpoint of the reactivity and productivity of the polyolefin (A) and epoxy group-containing compound (P). 【0023】 The epoxy group content of the epoxy-modified polyolefin (X) [unit: mmol / g, only numerical values ​​may be shown below] is preferably 0.01 to 2 mmol / g (only numerical values ​​are shown below), more preferably 0.02 to 1.8, more preferably 0.03 to 1.7, and particularly preferably 0.1 to 1.0. The epoxy group content in this case can be measured by known methods (e.g., epoxy value). Furthermore, the epoxy group content can be appropriately adjusted by the number of double bonds in the polyolefin (A), the weight of the polyolefin (A), and the type and weight of the epoxy group-containing compound (P). 【0024】 The Mn content of epoxy-modified polyolefin (X) is preferably 1,000 to 60,000, more preferably 2,000 to 50,000, particularly preferably 3,000 to 40,000, and most preferably 5,000 to 20,000, from the viewpoint of balancing the modification characteristics. The Mn content of epoxy-modified polyolefin (X) can be measured by GPC in the same way as the Mn content of polyolefin (A) described above. Furthermore, the Mn content of the epoxy-modified polyolefin (X) can be adjusted as appropriate by the Mn content of the polyolefin (A). 【0025】 <Resin modifier (K)> The resin modifier (K) of the present invention contains the epoxy group-modified polyolefin (X) described above. The resin modifier (K) is suitably used as a modifier for various thermoplastic resins, particularly polyolefin resins (D) described later. Furthermore, it is suitable as an adhesion improver for paints and the like. The resin modifier (K) has excellent adhesion to the substrate and mechanical strength, and can be used in a variety of applications, providing excellent mechanical strength and modification effects to molded products of the thermoplastic resin composition (Y) described later. The resin modifier (K) may be used alone or in combination of two or more types. The content of the epoxy group-modified polyolefin (X) in the resin modifier (K) is preferably 50 to 100% by weight, more preferably 90 to 100% by weight. 【0026】 <Thermoplastic resin composition (Z)> The thermoplastic resin composition (Z) of the present invention contains the above-mentioned resin modifier (K) and thermoplastic resin (Y). 【0027】 <Thermoplastic resin (Y)> Examples of the thermoplastic resin (Y) in the present invention include polyolefin resin (D) and polystyrene resin. Of the above (Y), polyolefin resin (D) is preferred. 【0028】 Polyolefin resin (D) includes, 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 a C4 or higher. 【0029】 From the viewpoint of compatibility between the polyolefin resin (D) and the resin modifier (K), it is preferable that the constituent units of the polyolefin resin (D) and the polyolefin (A) constituting the resin modifier (K) are the same or similar. For this reason, a propylene unit-containing (co)polymer is preferred as the polyolefin resin (D), and an ethylene / propylene copolymer is particularly preferred. 【0030】 The Mn content of the polyolefin resin (D) 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 of the molded article of the present invention described later and compatibility with the resin modifier (K). 【0031】 The thermoplastic resin composition (Z) of the present invention may optionally contain various additives (F) as long as they do not impede the effects of the present invention. The additive (F) may be one or more selected from the group consisting of 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). 【0032】 Examples of colorants (F1) include inorganic pigments [white pigments, cobalt compounds, iron compounds, sulfides, etc.], organic pigments [azo pigments, polycyclic pigments, etc.], and dyes [azo, indigoid, sulfide, alizarin, acridine, thiazole, nitro, aniline, etc.]. 【0033】 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. 【0034】 Examples of fillers (F3) include inorganic fillers (calcium carbonate, talc, clay, etc.) and organic fillers (urea, calcium stearate, etc.). 【0035】 Examples of lubricants (F4) include calcium stearate, butyl stearate, oleamide, polyolefin wax, and paraffin wax. 【0036】 Examples of antistatic agents (F5) include nonionic, cationic, anionic, or amphoteric surfactants as described below and in U.S. Patents No. 3,929,678 and 4,331,447. 【0037】 Examples of dispersants (F6) include polymers with a Mn of 1,000 to 20,000, such as vinyl resins, and other vinyl resins besides the polyolefin (A) mentioned above [polyhalogenated vinyl [polyvinyl chloride and polybrominated vinyl, etc.], polyvinyl acetate, polyvinyl alcohol, polymethyl vinyl ether, poly(meth)acrylic acid, poly(meth)acrylic acid ester [poly(meth)acrylate, etc.]; polyester resin [polyethylene terephthalate, etc.], polyamide resin [6,6-nylon and 12-nylon, etc.], polyether resin [polyethersulfone, etc.], polycarbonate resin [polycondensate of bisphenol A and phosgene, etc.] and block copolymers thereof. 【0038】 Examples of antioxidants (F7) include phenol compounds [monocyclic phenols (2,6-di-t-butyl-p-cresol, etc.), bisphenols [2,2'-methylenebis(4-methyl-6-t-butylphenol), etc.], polycyclic phenols [1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, etc.]], sulfur compounds (dilauryl 3,3'-thiodipropionate, etc.), phosphorus compounds (triphenyl phosphite, etc.), and amine compounds (octylated diphenylamine, etc.). 【0039】 Examples of release agents (F8) include lower (C1-4) alcohol esters of fatty acids (C8-24) (such as butyl stearate), polyhydric (2-4 or higher) alcohol esters of fatty acids (C2-24) (such as hydrogenated castor oil), glycol (C2-8) esters of fatty acids (C2-24) (such as ethylene glycol monostearate), and liquid paraffin. 【0040】 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, triazole, organic nitrogen sulfur compounds (such as Slaoff 39), quaternary ammonium compounds, and pyridine compounds. 【0041】 Examples of compatibilizers (F10) include modified vinyl polymers having sulfonic acid groups as described in Japanese Patent Publication No. 6-345927, and block polymers having a polyolefin portion and an aromatic vinyl polymer portion. 【0042】 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-diphenylacrylate, etc.]. 【0043】 The total content of additives (F) in the thermoplastic resin composition (Z) is preferably 20% by weight or less, based on the total weight of the thermoplastic resin composition (Z), 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 considerations. The amount of each additive used based on the total weight of the thermoplastic resin composition (Z) is, for example, 5% by weight or less, preferably 0.1 to 3% by weight; (F2) is, for example, 8% by weight or less, preferably 1 to 3% by weight; (F3) is, for example, 5% by weight or less, preferably 0.1 to 1% by weight; (F4) is, for example, 8% by weight or less, preferably 1 to 5% by weight; (F5) is, for example, 8% by weight or less, preferably 1 to 3% by weight; (F6) is, for example, 1% (F7) is, for example, 2% by weight or less, preferably 0.05% by weight or less; (F8) is, for example, 5% by weight or less, preferably 0.01%% by weight or less; (F9) is, for example, 25% by weight or less, preferably 0.5%% by weight or less; (F10) is, for example, 15% by weight or less, preferably 0.5%% by weight or less; (F11) is, for example, 2% by weight or less, preferably 0.05%% by weight or less. 【0044】 If the compounds are the same and overlap between (F1) and (F11) above, the amount used should not be the same as the amount that produces the corresponding additive effect for each compound. Instead, the amount used should be adjusted according to the purpose of use, taking into consideration that the effects of other additives may also be obtained simultaneously. 【0045】 The method for producing the thermoplastic resin composition (Z) of the present invention is as follows: (1) A method of mixing the entire amounts of (Y) and the resin modifier (K) and (F) as needed to make a resin composition (bulk method); (2) A method (masterbatch method) is used in which a masterbatch resin composition containing a high concentration of resin modifier (K) is first prepared by mixing a portion of (Y), the entire amount of resin modifier (K), and, if necessary, a portion or all of additive (F), and then the remaining (Y) and, if necessary, the remaining amount of additive (F) are added and mixed to form a resin composition. From the viewpoint of the mixing efficiency of the resin modifier (K), method (2) is preferred. 【0046】 The weight ratio [(K) / (Y)] of the resin modifier (K) to the thermoplastic resin (Y) in the thermoplastic resin composition (Z) of the present invention is preferably 1 / 99 to 30 / 70, and more preferably 3 / 97 to 10 / 90, from the viewpoint of the modification characteristics of the resin modifier (K) and the mechanical strength of the molded article described later. 【0047】 A specific mixing method in the method for producing the above thermoplastic resin composition (Z) is: (i) A method in which each component to be mixed is mixed using a powder mixer [e.g., "Henschel Mixer" [product name "Henschel Mixer FM150L / B", manufactured by Mitsui Mining Co., Ltd., and later Nippon Coke Industries Co., Ltd.], "Nauta Mixer" [product name "Nauta Mixer DBX3000RX", manufactured by Hosokawa Micron Corporation], "Banbury Mixer" [product name "MIXTRON BB-16MIXER", manufactured by Kobe Steel Ltd.], etc.], and then kneaded using a melt kneading device [batch kneader, continuous kneader (single-screw kneader, twin-screw kneader, etc.)] for, for example, 120 to 220°C for 2 to 30 minutes; (ii) A method in which each component to be mixed is directly kneaded 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. 【0048】 [Molded products, molded articles] The molded article of the present invention is a molded article of the above thermoplastic resin composition (Z). In other words, the molded article of the present invention is a molded article of the above thermoplastic resin composition (Z). 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, molding can be done using any method that incorporates single-layer molding, multi-layer molding, or foam molding. Molded products can take the form of plates, sheets, films, fibers (including nonwoven fabrics, etc.). Since the molded article of the present invention contains the above-mentioned epoxy group-containing resin modifier (K), it exhibits excellent affinity with paints, inks, and the like, which have relatively high polarity, due to its modifying effect. 【0049】 The molded articles of the present invention have excellent mechanical strength, as well as good paintability and printability, and molded articles can be obtained by painting and / or printing on the molded articles. Methods for painting the molded product include, but are not limited to, air spray painting, airless spray painting, electrostatic spray painting, dipping, roller painting, and brush painting. Examples of paints include those commonly used for coating plastics, such as polyester melamine resin paint, epoxy melamine resin paint, acrylic melamine resin paint, and acrylic urethane resin paint. Both these paints, which have relatively high polarity, and paints with low polarity (such as olefin-based paints) can be used. The paint film thickness (dry film thickness) can be appropriately selected depending on the purpose, but for example, it is 10 to 50 μm. 【0050】 Furthermore, any printing method commonly used for printing on plastics can be used for the molded product or the molded product after it has been painted, such as gravure printing, flexographic printing, screen printing, pad printing, dry offset printing, and offset printing. As printing inks, known inks used for printing on plastics, such as gravure inks, flexographic inks, screen printing inks, pad inks, dry offset inks, and offset inks can be used. [Examples] 【0051】 The present invention will be further described by the following examples, but the present invention is not limited thereto. In the examples, parts represent parts by weight. In the examples, the number average molecular weight (Mn), the number of double bonds in the polyolefin, and the epoxy group content were measured by the method described above. 【0052】 <Manufacturing Example 1> 100 parts of high molecular weight polyolefin (A0-1) [trade name "Vistamaxx6102", manufactured by Exxonmobil] were charged into a reaction vessel. The mixture was heated and melted using a mantle heater while nitrogen was aerated into the liquid phase, and thermal degeneration was carried out at 350°C for 10 minutes with stirring to obtain polyolefin (A-1). The manganese content of polyolefin (A-1) was 30,000, and the number of double bonds per 1,000 carbon atoms was 0.5. 【0053】 <Manufacturing Examples 2-7> In Production Example 1, thermal desorption was performed in the same manner as in Production Example 1, except that the high molecular weight polyolefin (A0) and thermal desorption conditions (temperature, time) were changed according to Table 1, to obtain each polyolefin (A-2) to (A-7). The results are shown in Table 1. 【0054】 [Table 1] 【0055】 <Example 1> 100 parts of (A-1) were placed in the reaction vessel, and after purging with nitrogen, the mixture was heated to 180°C under nitrogen aeration to dissolve it. Two parts of glycidyl methacrylate (P-1) were added and mixed uniformly. Then, a solution of 0.3 parts of a radical initiator [dicumyl peroxide, trade name "Perkmyl D", manufactured by NOF Corporation] (C-1) dissolved in three parts of xylene was added dropwise over 10 minutes, and stirring was continued at 180°C for 3 hours. After that, the xylene and unreacted glycidyl methacrylate were removed by distillation under reduced pressure (1.5 kPa, the same applies hereafter) to obtain a resin modifier (K-1) containing epoxy group-modified polyolefin (X-1). (X-1) had an epoxy group content of 0.036 mmol / g and a manganese content of 30,100. 【0056】 <Examples 2-7> In Example 1, the reaction was carried out in the same manner as in Example 1, except that it was carried out according to Table 2, to obtain each resin modifier (K) containing each epoxy group-modified polyolefin (X). The results are shown in Table 2. 【0057】 <Comparative Example 1> For comparison, commercially available acid-modified polyolefins listed in Table 3 were used as resin modifiers (ratio K-1). 【0058】 [Table 2] 【0059】 <Examples 11-18, Comparative Example 11> According to the compound composition (parts) in Table 3, each resin modifier (K) and thermoplastic resin (Y) were 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 (Z). Each thermoplastic resin composition (Z) 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, and evaluated according to the evaluation method described below. The results are shown in Table 3. 【0060】 (1) Paint adhesion (evaluation of adhesion to the substrate) Paintability (adhesion to the paint) was evaluated using epoxy-based paints. Epoxy-based paint was applied to a test piece (100 × 100 × 2 mm) using an applicator to achieve a dry film thickness of 30 μm. After drying at 80°C for 30 minutes, a grid peel test was performed on the painted surface according to the method specified in JIS K 5600-5-6 (1999). The number of areas where the paint film did not peel off out of 100 grid squares was counted and evaluated according to the following criteria. 【0061】 <Evaluation Criteria> ◎: 100 were not peeled off. ○+: Number of non-peeling items was 95-99 ○: Number of non-peeling individuals was 90-94 ○-: Number of non-peeling individuals was 81-89 △: The number of items that did not peel off was 50-80. ×: Number of non-peeling items: 0-49 【0062】 [Table 3] 【0063】 The results in Tables 1-3 show that the resin modifier (K) of the present invention has superior modification properties for thermoplastic resins, particularly in terms of substrate adhesion, compared to the comparative agent. [Industrial applicability] 【0064】 The resin modifier (K) of the present invention can impart excellent adhesion to paints, printing inks, adhesives, etc., to thermoplastic resins without impairing their mechanical properties.

Claims

[Claim 1] A resin modifier (K) comprising an epoxy-modified polyolefin (X), wherein the polyolefin (A) contains an α-olefin having 3 to 8 carbon atoms as a constituent monomer, and the modifier (γ) is an epoxy-containing compound (P). [Claim 2] The resin modifier (K) according to claim 1, wherein the polyolefin (A) has 0.5 to 20 carbon-carbon double bonds per 1,000 carbon atoms. [Claim 3] The resin modifier (K) according to claim 1, wherein the epoxy group content of the epoxy group-modified polyolefin (X) is 0.01 to 2 mmol / g. [Claim 4] The resin modifier (K) according to claim 1, wherein the number average molecular weight (Mn) of the epoxy group-modified polyolefin (X) is 1,000 to 60,000. [Claim 5] A thermoplastic resin composition (Z) comprising the resin modifier (K) and a thermoplastic resin (Y) as described in claim 1. [Claim 6] The thermoplastic resin composition (Z) according to claim 5, wherein the weight ratio [(K) / (Y)] of the resin modifier (K) to the thermoplastic resin composition (Y) is 1 / 99 to 30 / 70. [Claim 7] A molded article obtained by molding the thermoplastic resin composition (Z) according to claim 5 or 6. [Claim 8] A molded article obtained by coating and / or printing on a molded article as described in claim 7.

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