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) comprising polyolefin (A) and a modifier (γ) as constituent raw materials, wherein the polyolefin (A) contains α-olefins having 3 to 8 carbon atoms as constituent monomers, and the modifier (γ) is a combination of unsaturated (poly)carboxylic acid (anhydride) (C) and a hydroxyl group-containing compound (F), a combination of carboxyl group-containing compound (k) and a hydroxyl group-containing compound (F), or a hydroxyl group-modified polyolefin (X) which is a hydroxyl group-containing compound (F).

Description

Technical Field

[0001] The present invention relates to a resin modifier.

Background Art

[0002] Thermoplastic resins, such as polyolefin resins, are excellent in formability, 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 performing corona treatment or plasma treatment on the surface of a thermoplastic resin, such as a polyolefin resin molded product (see, for example, Patent Document 1) has been proposed.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

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 modifier (γ) as constituent raw materials, wherein the polyolefin (A) comprises α-olefins having 3 to 8 carbon atoms as constituent monomers, and the modifier (γ) is a combination of an unsaturated (poly)carboxylic acid (anhydride) (C) and a hydroxyl group-containing compound (F), a combination of a carboxyl group-containing compound (k) and a hydroxyl group-containing compound (F), or a hydroxyl group-modified polyolefin (X) which is a hydroxyl group-containing compound (F). [Effects of the Invention]

[0006] The resin modifier (K) of the present invention provides the following effects. (1) Excellent adhesion to the substrate. (2) Provides excellent mechanical strength (impact resistance, flexural elasticity, etc.) to molded articles of resin compositions containing resin modifier (K). [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 polyolefin (A) described above may also contain other monomers besides α-olefins. In that case, based on the total weight of the monomers constituting the 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 20% by weight or less.

[0010] Other monomers that constitute the above polyolefin (A) include, for example, ethylene, 2-butene, C9-30 α-olefins (1-decene, 1-dodecene, etc.), and C4-30 unsaturated monomers 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 isotacticity of the α-olefin portion of the polyolefin (A) is preferably 1 to 65%, more preferably 1 to 50%, and more preferably 1 to 35%, from the viewpoint of the modifying effect of the modifier (K). The isotacticity of the α-olefin portion of the above polyolefin (A) tends to be directly reflected in the isotacticity of the α-olefin portion of the acid-modified polyolefin (AE) and hydroxyl-modified polyolefin (X) described later. The isotacticity of polyolefin (A) is 13 It can be measured using 1C-NMR.

[0012] 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.

[0013] 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: Two PLgel 10 μm, MIXED - B in series [manufactured by Polymer Laboratories, Ltd.] Column temperature: 135 °C

[0014] The number of double bonds per 1,000 carbon atoms in polyolefin (A) [the number of carbon - carbon double bonds at the molecular terminals 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 from 1.5 to 15, from the viewpoints of reactivity and productivity with the unsaturated carboxylic acid (B) described later. Here, the number of double bonds can be determined from the 1 1H - NMR spectrum of polyolefin (A). That is, by assigning the peaks in the spectrum and obtaining 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 to 6 ppm of polyolefin (A) and the integral value derived from polyolefin (A), the number of double bonds at the molecular terminals and / or in the molecular chain 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.

[0015] The method for producing polyolefin (A) in the present invention includes, for example, a method of thermally reducing a high - molecular - weight (preferably Mn is 60,000 to 400,000, more preferably Mn is 80,000 to 250,000) polyolefin (A0).

[0016] The thermal reduction method includes methods of heating the above high - molecular - weight polyolefin (A0) (1) in the absence of an organic peroxide, for example, at 300 to 450 °C for 0.5 to 10 hours, and (2) in the presence of an organic peroxide [e.g., 2,5 - dimethyl - 2,5 - di(t - butylperoxy)hexane], for example, at 180 to 300 °C for 0.5 to 10 hours, etc. Among these, from the industrial viewpoint and the viewpoint of 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 chain is preferred.

[0017] The weight ratio of the monomers constituting the above polyolefin (A) tends to maintain the weight ratio of the monomers constituting the high molecular weight polyolefin (A0) as it is. Moreover, the larger the thermal degradation temperature or the longer the thermal degradation time, the greater the tendency for the number of double bonds per 1,000 carbon atoms to increase. Furthermore, the larger the Mn of the high molecular weight polyolefin (A0), the higher the thermal degradation temperature, or the longer the thermal degradation time, the greater the tendency for the Mn of the polyolefin (A) to decrease. The polyolefin (A) may be used alone or in combination of two or more.

[0018] <Modifier (γ)> As the modifier (γ) in the present invention, preferably, it is a combination of an unsaturated (poly) carboxylic acid (anhydride) (C) and a hydroxyl group-containing compound (F), a combination of a carboxyl group-containing compound (k) and a hydroxyl group-containing compound (F), or a hydroxyl group-containing compound (F).

[0019] <Unsaturated (poly) carboxylic acid (anhydride) (C)> The unsaturated (poly) carboxylic acid (anhydride) (C) in the present invention means an unsaturated monocarboxylic acid, an unsaturated polycarboxylic acid, and / or an unsaturated polycarboxylic acid anhydride. The above unsaturated (poly) carboxylic acid (anhydride) (C) is preferably a C3-24 monocarboxylic acid having one polymerizable unsaturated group, a C4-24 polycarboxylic acid having one polymerizable unsaturated group, and / or a C4-24 polycarboxylic acid anhydride having one polymerizable unsaturated group. Among the unsaturated (poly)carboxylic acid (anhydride) (C), examples of unsaturated monocarboxylic acids include aliphatic monocarboxylic acids (C3-24, e.g., acrylic acid, methacrylic acid, α-ethylacrylic acid, crotonic acid, isocrotonic acid), alicyclic monocarboxylic acids (C6-24, e.g., cyclohexenecarboxylic acid); and examples of unsaturated poly(2-3 or more)carboxylic acids or their acid anhydrides include unsaturated dicarboxylic acids or their acid anhydrides [aliphatic dicarboxylic acids or their acid anhydrides (C4-24, e.g., maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, and their acid anhydrides), alicyclic dicarboxylic acids or their acid anhydrides (C8-24, e.g., cyclohexenedicarboxylic acid, cycloheptenedicarboxylic acid, bicycloheptenedicarboxylic acid, methyltetrahydrophthalic acid, and their acid anhydrides), etc.]. The unsaturated (poly)carboxylic acid (anhydride) (C) may be used alone or in combination of two or more. Of the above unsaturated (poly)carboxylic acids (anhydrides) (C), unsaturated dicarboxylic acid anhydrides are preferred, and maleic anhydride is more preferred, in terms of reactivity with polyolefins (A) and the modifying properties of the resin modifier (K) described later.

[0020] <Hydroxygroup-containing compound (F)> Examples of hydroxyl group-containing compounds (F) in the present invention include those having at least one hydroxyl group in the molecule and having a reactive functional group. Examples of reactive functional groups that hydroxyl group-containing compounds (F) have include primary amino groups, secondary amino groups, and mercapto groups.

[0021] Examples of hydroxyl group-containing compounds (F) include those with a molecular weight of 200 or less, such as 2-aminoethanol, 3-aminopropanol, 4-aminobutanol, 2- or 3-hydroxypiperazine, 2-, 3- or 4-aminocyclohexanol, 2-amino-1,3-propanediol, diethanolamine, diisopropanolamine, 2-, 3- or 4-aminophenol, 2- or 3-amino-p-cresol, 2- or 4-amino-m-cresol, 3- or 4-amino-o-cresol, and 2-mercaptoethanol. Of the above (F), preferred from the viewpoint of reactivity are 2-aminoethanol, 3-aminopropanol, 4-aminobutanol, 2-amino-1,3-propanediol, and 2-mercaptoethanol, and even more preferred are 2-aminoethanol, 2-amino-1,3-propanediol, and 2-mercaptoethanol.

[0022] <Carboxyl group-containing compound (k)> Examples of carboxyl group-containing compounds (k) in the present invention include those that do not have an unsaturated group, have at least one carboxyl group in the molecule, and have a functional group other than the carboxyl group that can react with polyolefin (A). Examples of carboxyl group-containing compounds (k) include mercaptoacetic acid, 3-mercaptopropanoic acid, and 2-mercaptopropanoic acid. Of the above carboxyl group-containing compounds (k), mercaptoacetic acid is preferred.

[0023] <Hydroxy-modified polyolefin (X)> The hydroxyl-modified polyolefin (X) in the present invention comprises the above-mentioned polyolefin (A) and a modifying agent (γ) as constituent raw materials.

[0024] Examples of hydroxyl-modified polyolefins (X) include the following: (1) A reaction product of polyolefin (A) and a hydroxyl group-containing compound (F). (2) A reaction product obtained by reacting a polyolefin (A) with an unsaturated (poly)carboxylic acid (anhydride) (C) in the absence or presence of a radical initiator to obtain an acid-modified polyolefin (AE), which is then reacted with a hydroxyl group-containing compound (F) (a combination of an unsaturated (poly)carboxylic acid (anhydride) (C) and a hydroxyl group-containing compound (F)). (3) A reaction product obtained by reacting a polyolefin (A) with a carboxyl group-containing compound (k) in the absence or presence of a radical initiator to obtain an acid-modified polyolefin (AE), which is then reacted with a hydroxyl group-containing compound (F) (a combination of carboxyl group-containing compound (k) and hydroxyl group-containing compound (F)).

[0025] The acid value (mgKOH / g) of the above acid-modified polyolefin (AE) is preferably 1 to 100 mgKOH / g, more preferably 3 to 75 mgKOH / g, and particularly preferably 5 to 50 mgKOH / g, from the viewpoint of productivity. The above acid value is measured in accordance with JIS K0070 (1992). Furthermore, the above acid value can be appropriately adjusted depending on the number of double bonds in the polyolefin (A), the weight of the polyolefin (A), or the type and weight of the unsaturated (poly)carboxylic acid (anhydride) (C) or carboxyl group-containing compound (k).

[0026] The hydroxyl value of the hydroxyl-modified polyolefin (X) is preferably 1 to 100 mg KOH / g, more preferably 3 to 40 mg KOH / g, and particularly preferably 5 to 25 mg KOH / g. The above hydroxyl value is measured in accordance with JIS K0070 (1992). The above hydroxyl value can be adjusted as appropriate, for example, depending on the type and weight of polyolefin (A) and the type and weight of each modifying agent (γ).

[0027] The manganese (Mn) content of the hydroxyl-modified polyolefin (X) is preferably 1,000 to 60,000, more preferably 2,000 to 40,000, and particularly preferably 3,000 to 20,000. If the Mn content is less than 1,000, the mechanical strength of the molded product is poor, and if it exceeds 60,000, the modification characteristics of the resin modifier (K) are poor. The Mn content of the hydroxyl-modified polyolefin (X) can be measured by GPC in the same way as the Mn content of the polyolefin (A) described above. Furthermore, the Mn content of the hydroxyl-modified polyolefin (X) can be appropriately adjusted by controlling the Mn content of polyolefin (A), the type and amount of each modifying agent (γ), and the reaction between polyolefin (A) and each modifying agent (γ).

[0028] <Resin modifier (K)> The resin modifier (K) of the present invention contains the hydroxyl-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 hydroxyl-modified polyolefin (X) in the resin modifier (K) is preferably 50 to 100% by weight, more preferably 90 to 100% by weight.

[0029] <Thermoplastic resin composition (Z)> The thermoplastic resin composition (Z) of the present invention contains the above-mentioned resin modifier (K) and thermoplastic resin (Y).

[0030] <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.

[0031] 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.

[0032] 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.

[0033] 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).

[0034] 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).

[0035] 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.].

[0036] 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.

[0037] Examples of fillers (F3) include inorganic fillers (calcium carbonate, talc, clay, etc.) and organic fillers (urea, calcium stearate, etc.).

[0038] Examples of lubricants (F4) include calcium stearate, butyl stearate, oleamide, polyolefin wax, and paraffin wax.

[0039] 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.

[0040] 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.

[0041] 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.).

[0042] 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.

[0043] 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.

[0044] 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.

[0045] 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.].

[0046] 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.

[0047] 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.

[0048] 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.

[0049] 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, more preferably 2 / 98 to 5 / 95, from the viewpoint of the modification characteristics of the resin modifier (K) and the mechanical strength of the molded article described later.

[0050] 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 in a powder mixer, for example, a "Henschel Mixer" [product name "Henschel Mixer FM150L / B", manufactured by Mitsui Mining Co., Ltd., and later Nippon Coke Industries Co., Ltd.], a "Nauta Mixer" [product name "Nauta Mixer DBX3000RX", manufactured by Hosokawa Micron Corporation], a "Banbury Mixer" [product name "MIXTRON BB-16MIXER", manufactured by Kobe Steel Ltd.], etc.], and then mixed using a melting and kneading device [batch kneader, continuous kneader (single-screw kneader, twin-screw kneader, etc.)], usually at 120-220°C for 2-30 hours; (ii) A method in which the components to be mixed are directly kneaded using the same melt kneading apparatus as described above under the same conditions, without pre-mixing each component as a powder. Of these methods, method (i) is preferred from the viewpoint of mixing efficiency.

[0051] <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 resin modifier (K) having a hydroxyl group, it exhibits excellent affinity with paints, inks, and the like, which have relatively high polarity, due to its modifying effect.

[0052] 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.

[0053] 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. Printing inks commonly 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]

[0054] 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 of the polyolefin, the hydroxyl value, and the acid value were measured by the method described above.

[0055] <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, the number of double bonds per 1,000 carbon atoms was 0.5, and the isotacticity was 28%.

[0056] <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.

[0057] [Table 1]

[0058] <Manufacturing Example 11> 100 parts of polyolefin (A-1), 1 part of maleic anhydride (C-1), and 1 part of dicumyl peroxide (f-1) were charged into a reaction vessel. The mixture was heated to 200°C under nitrogen aeration and stirred for 10 hours. After that, the unreacted maleic anhydride was removed by distillation under reduced pressure (1.5 kPa) to obtain acid-modified polyolefin (AE-1). Furthermore, the acid-modified polyolefin (AE-1) had an acid value of 2.0 mgKOH / g and a manganese content of 30,100.

[0059] <Manufacturing Examples 12-15> In Production Example 11, the reaction was carried out in the same manner as in Production Example 11, except that the polyolefin, unsaturated (poly)carboxylic acid (anhydride) (C), and radical initiator (f) were changed according to Table 2, to obtain acid-modified polyolefins (AE-2) to (AE-5). The results are shown in Table 2.

[0060] <Manufacturing Example 16> In a reaction vessel, 100 parts of polyolefin (A-6) and 1 part of mercaptoacetic acid (k-1) were charged, followed by 200 parts of xylene. The mixture was heated to 160°C under nitrogen aeration, and 1 part of 1,1'-azobis(cyclohexane-1-carbonitride)(f-2) was added. The mixture was stirred for 10 hours. Subsequently, the xylene and unreacted mercaptoacetic acid were removed under reduced pressure (1.5 kPa) to obtain acid-modified polyolefin (AE-6). Furthermore, the acid-modified polyolefin (AE-6) had an acid value of 0.2 mg KOH / g and a manganese content of 180,000.

[0061] <Manufacturing Example 17> In Production Example 16, the reaction was carried out in the same manner as in Production Example 16, except that the polyolefin and radical initiator (f) were changed according to Table 2, to obtain acid-modified polyolefin (AE-7). The results are shown in Table 2.

[0062] [Table 2]

[0063] <Example 1> 100 parts of acid-modified polyolefin (AE-1) and 1 part of 2-aminoethanol (F-1) were charged into a reaction vessel, and the mixture was heated to 180°C under nitrogen aeration and stirred for 10 hours. Subsequently, stirring was continued under reduced pressure (1.5 kPa) for 10 hours to obtain a resin modifier (K-1) containing hydroxyl-modified polyolefin (X-1). Furthermore, the hydroxyl-modified polyolefin (X-1) had a hydroxyl value of 2.0 mgKOH / g and a manganese content of 30,100.

[0064] <Examples 2-8> 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 3, to obtain each resin modifier (K) containing each hydroxyl-modified polyolefin (X). The results are shown in Table 3.

[0065] <Comparative Example 1> For comparison, commercially available acid-modified polyolefins listed in Table 3 were used as resin modifiers (ratio K-1).

[0066] [Table 3]

[0067] <Example 9> In a reaction vessel, 100 parts of polyolefin (A-1), 2 parts of 2-mercaptoethanol (F-3), and 200 parts of xylene were charged. Under nitrogen aeration, the mixture was heated to 160°C, 1 part of dicumyl peroxide (f-1) was added, and stirring was continued for 10 hours. Subsequently, the xylene and unreacted 2-mercaptoethanol (F-3) were removed by distillation under reduced pressure (1.5 kPa) to obtain a resin modifier (K-9) containing hydroxyl-modified polyolefin (X-9). Furthermore, the hydroxyl-modified polyolefin (X-9) had a hydroxyl value of 2.0 mgKOH / g and a manganese content of 30,100. The results are shown in Table 4.

[0068] [Table 4]

[0069] <Examples 11-20, Comparative Example 11> According to the compound composition (parts) in Table 5, 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 5.

[0070] (1) Paint adhesion (evaluation of adhesion to the substrate) Regarding paintability (adhesion to the paint), the adhesion to urethane-based paints was evaluated. Urethane-based paint was applied to a test piece (100 × 100 × 2 mm) using an applicator to achieve a film thickness of 30 μm after drying. 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 K5600-5-6 (1999). The number of areas where the paint film did not peel out of 100 grid squares was counted and evaluated according to the following criteria.

[0071] <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

[0072] [Table 5]

[0073] The results in Tables 1-5 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. It also exhibits superior mechanical strength. [Industrial applicability]

[0074] 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

1. A resin modifier (K) comprising a polyolefin (A) and a modifier (γ) as constituent raw materials, wherein the polyolefin (A) contains α-olefins having 3 to 8 carbon atoms as constituent monomers, and the modifier (γ) is a combination of an unsaturated (poly)carboxylic acid (anhydride) (C) and a hydroxyl group-containing compound (F), a combination of a carboxyl group-containing compound (k) and a hydroxyl group-containing compound (F), or a hydroxyl group-modified polyolefin (X) which is the hydroxyl group-containing compound (F).

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.

3. The resin modifier (K) according to claim 1, wherein the hydroxyl value of the hydroxyl-modified polyolefin (X) is 1 to 100 mg KOH / g.

4. The resin modifier (K) according to claim 1, wherein the number average molecular weight (Mn) of the hydroxyl-modified polyolefin (X) is 1,000 to 60,000.

5. A thermoplastic resin composition (Z) comprising the resin modifier (K) and a thermoplastic resin (Y) as described in claim 1.

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.

7. A molded article obtained by molding the thermoplastic resin composition (Z) according to claim 5 or 6.

8. A molded article obtained by coating and / or printing on a molded article as described in claim 7.

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