Modified polyolefin resin composition and uses of said resin composition

Abstract

The present disclosure provides a modified polyolefin resin composition which has sufficient water resistance, good bending resistance, and sufficient flowability within a specific temperature range, and which exhibits good adhesiveness to polyolefin base materials. The present disclosure specifically provides a modified polyolefin resin composition which contains an acid-modified polyolefin resin (A), a compound (B) that has a polymerizable unsaturated group, and a polyol component (C).

Description

Modified polyolefin resin composition and uses of said resin composition

[0001] The present disclosure relates to a modified polyolefin resin composition and uses of the resin composition.

[0002] BACKGROUND ART Polyolefin resins such as polypropylene and polyethylene have been widely used in the fields of automobile parts, electrical parts, construction materials, packaging films, etc. because they are relatively inexpensive and have excellent properties such as chemical resistance, water resistance, and heat resistance.

[0003] In particular, in automotive applications, the use of polyolefin resin substrates is increasing in order to reduce the weight of vehicle bodies in order to save energy. The substrates are coated with paint on their surfaces for design and protection purposes.

[0004] On the other hand, polyolefin resins generally have high crystallinity and low polarity, so that paints, printing inks, adhesives, etc. may not adhere well to them.

[0005] Therefore, a method is widely known in which a chlorinated polyolefin resin, an acrylic resin, or the like, which has good adhesion to polyolefin resins, is used as a primer, and a paint containing an organic solvent, an aqueous solvent, or the like is spray-applied (for example, Patent Document 1, etc.).

[0006] However, the method described in Patent Document 1 is undesirable from an environmental point of view because organic solvents are released into the atmosphere during spray coating.

[0007] Therefore, in recent years, attention has been drawn to an in-mold coating method, in which coating is performed inside a mold, as an alternative coating method to spray coating. The in-mold coating method is a technique in which a gap is created between the surface of a molded plastic body and the mold surface, a coating material is injected into the gap, and the coating material is then cured by heat or the like inside the mold to form a coating film.

[0008] For example, Patent Document 2 describes a method for producing an in-mold coated injection molded article by coating an injection molded article made of a thermoplastic resin as a raw material resin inside a mold to produce an in-mold coated injection molded article, the method including: a primary molding step in which heated and molten raw material resin is injected into a cavity formed by a set of molds consisting of a movable mold and a fixed mold and equipped with a heating device and a cooling device to form a primary molded article; a coating material injection step in which the movable mold and the fixed mold are relatively separated to form a secondary space between the movable mold and the primary molded article and inject a coating material into this secondary space; a heat-hardening step in which the mold is heated by the heating device and the injected coating material is hardened; and a cooling step in which the mold is cooled by the cooling device.

[0009] Japanese Patent Publication No. 2002-201236 Japanese Patent Publication No. 2003-19731

[0010] However, the in-mold coated injection molded article obtained by the manufacturing method described in Patent Document 2 has the problem of being poor in adhesion to polyolefin substrates and flex resistance.

[0011] The present disclosure has been made in view of the above, and aims to provide a modified polyolefin resin composition that has sufficient water resistance, good flex resistance, sufficient fluidity within a specific temperature range, and good adhesion to a polyolefin substrate.

[0012] In order to achieve the above object, the inventors have conducted extensive research into compositions for dispersing and / or dissolving an acid-modified polyolefin resin, and as a result have found that a modified polyolefin resin composition containing an acid-modified polyolefin resin, a compound (B) having a polymerizable unsaturated group, and a polyol component (C) achieves the above object, leading to the present disclosure.

[0013] The present disclosure encompasses, for example, the following subject matter: A modified polyolefin resin composition containing an acid-modified polyolefin resin (A), a compound having a polymerizable unsaturated group (B), and a polyol component (C).

[0014] The modified polyolefin resin composition of the present disclosure has sufficient water resistance, good flex resistance, sufficient fluidity within a specific temperature range, and good adhesion to polyolefin substrates. Because of these properties, the modified polyolefin resin composition of the present disclosure can be suitably used in a variety of applications.

[0015] Preferred embodiments of the present disclosure will be described in detail below. The following description of the components may be based on representative embodiments and specific examples, but the present disclosure is not limited to such embodiments.

[0016] In the present disclosure, the expressions "contain" and "comprise" include the concepts of "contain," "include," "consist essentially of," and "consist only of."

[0017] In the numerical ranges described in stages in this disclosure, the upper or lower limit of a certain numerical range can be arbitrarily combined with the upper or lower limit of another numerical range. Furthermore, in the numerical ranges described in this disclosure, the upper or lower limit of the numerical range may be replaced with a value shown in an example or a value that can be unambiguously derived from the example. Furthermore, in this disclosure, a numerical value connected with "to" means a numerical range that includes the numbers before and after "to" as the upper and lower limits.

[0018] In this disclosure, "A and / or B" means "one of A and B" or "both A and B," and specifically means "A," "B," or "A and B."

[0019] In this disclosure, "n-" means "normal," "i-" or "iso-" means "iso," and "tert-" or "t-" means "tertiary."

[0020] In this disclosure, "(meth)acrylic" encompasses both acrylic and methacrylic, and "(meth)acrylate" encompasses both acrylate and methacrylate.

[0021] In the present disclosure, the term "(meth)acryloyl group" encompasses both an acryloyl group and a methacryloyl group, and the term "(meth)acryloyloxy group" encompasses both an acryloyloxy group and a methacryloyloxy group.

[0022] In the present disclosure, "acryloyl group" means "CH ２ =CHC(=O)-" and "methacryloyl group" is "CH ２ =C(CH ３ )C(=O)-", and acryloyloxy group is "CH ２ =CHC(=O)O-" and the methacryloyloxy group is "CH ２ =C(CH ３ )C(=O)O-".

[0023] In the present disclosure, examples of the linear or branched alkyl group having 1 to 20 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, a cyclopentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, an n-tridecyl group, an n-tetradecyl group, an n-pentadecyl group, an n-hexadecyl group, an n-heptadecyl group, an n-octadecyl group, an n-nonadecyl group, and an n-icosyl group.

[0024] In the present disclosure, examples of the linear or branched alkylene group having 1 to 10 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9, or 10) include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group, an isobutylene group, a sec-butylene group, a tert-butylene group, an n-pentylene group, an isopentylene group, a neopentylene group, a cyclopentylene group, an n-hexylene group, an n-heptylene group, an n-octylene group, an n-nonylene group, and an n-decylene group.

[0025] (Modified Polyolefin Resin Composition) The modified polyolefin resin composition of the present disclosure contains, as essential components, an acid-modified polyolefin resin (A), a compound having a polymerizable unsaturated group (B), and a polyol component (C).

[0026] As one embodiment of the present disclosure, the modified polyolefin resin composition of the present disclosure typically has sufficient fluidity within a temperature range of 25° C. or higher and 80° C. In the present disclosure, a resin composition having fluidity means, for example, a homogeneous liquid composition that does not contain coarse resin particles, resin aggregates, etc.

[0027] In one embodiment of the present disclosure, the modified polyolefin resin composition is a resin composition that flows when placed in a glass bottle and tilted at a temperature in the range of 25° C. to 80° C. In the present disclosure, the resin composition having flowability also includes a resin composition that flows when mechanical shear is applied at a temperature in the range of 25° C. to 80° C.

[0028] In one embodiment of the present disclosure, the modified polyolefin resin composition of the present disclosure is a resin composition capable of dual curing. In this disclosure, "dual curing" refers to curing by two types of polymerization reactions: radical polymerization and polymerization via urethane bonds. In this disclosure, "dual cured product" refers to a cured product obtained by dual curing the modified polyolefin resin composition of the present disclosure.

[0029] <Acid-Modified Polyolefin Resin (A)> The modified polyolefin resin composition of the present disclosure contains an acid-modified polyolefin resin (A) as an essential component. In one embodiment of the present disclosure, the acid-modified polyolefin resin (A) is preferably a polymer obtained by graft polymerizing an α,β-unsaturated carboxylic acid or an acid anhydride thereof onto a polyolefin resin. In other words, in one embodiment of the present disclosure, the acid-modified polyolefin resin (A) is preferably a graft polymer having a structure in which an α,β-unsaturated carboxylic acid or an acid anhydride thereof is graft polymerized onto a polyolefin resin.

[0030] Polyolefin resins typically have structural units derived from α-olefins, such as α-olefins having 2 to 20 carbon atoms (2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms), such as ethylene, propylene, 1-butene, isobutene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene.

[0031] The polyolefin resin may be an olefin polymer containing one type of structural unit derived from an α-olefin, or may be a copolymer of an olefin polymer containing two or more types of structural units derived from an α-olefin.

[0032] In one embodiment of the present disclosure, the polyolefin resin is typically a petroleum-derived polyolefin resin, which is a polyolefin-based resin synthesized from petroleum-derived olefins.

[0033] Petroleum-derived olefins are olefins produced by thermal cracking of petrochemical raw materials such as naphtha, ethane, LPG (Liquefied Petroleum Gas), NGL (Natural Gas Liquid), and gas oil.

[0034] In one embodiment of the present disclosure, examples of polyolefin resins include homopolypropylene (propylene homopolymer), propylene-α-olefin copolymer, homopolyethylene (ethylene homopolymer), ethylene-α-olefin copolymer, homopoly-1-butene, and 1-butene-α-olefin copolymer, and these can be used alone or in combination of two or more.

[0035] In one embodiment of the present disclosure, the polyolefin resin is preferably homopolypropylene and / or propylene-α-olefin copolymer, more preferably propylene-α-olefin copolymer.

[0036] In one embodiment of the present disclosure, the acid-modified polyolefin resin (A) is preferably a graft polymer having a structure in which an α,β-unsaturated carboxylic acid or an acid anhydride thereof is grafted onto a homopolypropylene or a propylene-α-olefin copolymer.

[0037] As an embodiment of the present disclosure, it is even more preferable that the acid-modified polyolefin resin (A) is a graft polymer having a structure in which an α,β-unsaturated carboxylic acid or an acid anhydride thereof is grafted onto a propylene-α-olefin copolymer.

[0038] The propylene-α-olefin copolymer is a copolymer of propylene and an α-olefin. Examples of the α-olefin include ethylene; α-olefins having 4 to 20 carbon atoms (4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms), such as 1-butene, isobutene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene. These α-olefins can be used alone or in combination of two or more. In one embodiment of the present disclosure, the α-olefin in the propylene-α-olefin copolymer is preferably ethylene or 1-butene, and more preferably 1-butene.

[0039] In one embodiment of the present disclosure, the content of the propylene component in the propylene-α-olefin copolymer is preferably 50 mol% or more, more preferably 60 mol% or more, even more preferably 65 mol% or more, and particularly preferably 70 mol% or more. When the content of the propylene component in the propylene-α-olefin copolymer is 50 mol% or more, the water resistance and adhesion to polyolefin substrates (particularly polypropylene substrates) of the modified polyolefin resin composition of the present disclosure become even better.

[0040] The ethylene-α-olefin copolymer is a copolymer of ethylene and an α-olefin. Examples of the α-olefin include α-olefins having 3 to 20 carbon atoms (3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms), such as propylene, 1-butene, isobutene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene. These α-olefins can be used alone or in combination of two or more.

[0041] In one embodiment of the present disclosure, the ethylene content of the ethylene-α-olefin copolymer is preferably 75 mol% or more. When the ethylene content of the ethylene-α-olefin copolymer is 75 mol% or more, the water resistance and adhesion to polyolefin substrates (particularly polyethylene substrates) of the modified polyolefin resin composition of the present disclosure become even better.

[0042] The 1-butene-α-olefin copolymer is a copolymer of 1-butene and an α-olefin. Examples of the α-olefin include ethylene, propylene, and α-olefins having 5 to 20 carbon atoms (5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms), such as 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene. These α-olefins can be used alone or in combination of two or more.

[0043] In one embodiment of the present disclosure, the content of the 1-butene component in the 1-butene-α-olefin copolymer is preferably 65 mol% or more. When the content of the 1-butene component in the 1-butene-α-olefin copolymer is 65 mol% or more, the water resistance and adhesion of the modified polyolefin resin composition of the present disclosure to polyolefin substrates (particularly polypropylene substrates or poly-1-butene substrates) become even better.

[0044] In one embodiment of the present disclosure, a bio-derived polyolefin resin can be used as the polyolefin resin instead of a petroleum-derived polyolefin resin. The bio-derived polyolefin resin refers to a polyolefin resin produced from a biological resource (biomass). Biomass refers to a polyolefin resin formed from a renewable biological organic resource excluding fossil resources.

[0045] When a bio-derived polyolefin resin is used, it is preferable that the polyolefin resin contains a propylene structural unit. When a bio-derived polyolefin resin is used, the biomass degree of the polyolefin resin is usually 25% or more, preferably 27% or more, and more preferably 30% or more. The upper limit of the biomass degree is not particularly limited as long as it is 100% or less. The biomass degree of the polyolefin resin can be calculated, for example, from the content of carbon isotope with mass number 14 measured in accordance with ASTM D6866.

[0046] In the present disclosure, examples of the α,β-unsaturated carboxylic acid or acid anhydride thereof to be graft polymerized onto the polyolefin resin include maleic acid, maleic anhydride, fumaric acid, citraconic acid, citraconic anhydride, mesaconic acid, itaconic anhydride, aconitic acid, aconitic anhydride, himic anhydride, etc. Among these α,β-unsaturated carboxylic acids or acid anhydrides thereof, maleic acid, maleic anhydride, and itaconic anhydride are preferred, and maleic acid and maleic anhydride are more preferred.

[0047] In one embodiment of the present disclosure, the acid value of the α,β-unsaturated carboxylic acid and its anhydride component in the acid-modified polyolefin resin (A) is preferably 1 to 100 mgKOH / g, more preferably 5 to 50 mgKOH / g, even more preferably 10 to 40 mgKOH / g, and even more preferably 15 to 30 mgKOH / g. When the acid value of the α,β-unsaturated carboxylic acid and its anhydride component in the acid-modified polyolefin resin (A) is within the range of 1 to 100 mgKOH / g, the fluidity of the modified polyolefin resin composition of the present disclosure becomes even better.

[0048] The acid value of the α,β-unsaturated carboxylic acid and its anhydride components in the acid-modified polyolefin resin (A) was measured using a Fourier transform infrared spectrophotometer (FT-IR) by comparing the coefficient (f) obtained from a calibration curve prepared using a chloroform solution of maleic anhydride with the stretching peak (1780 cm) of the carbonyl (C═O) bond of succinic anhydride in the modified polyolefin solution. －１ and the absorbance (I) of the succinic anhydride solution, according to the following formula (i): Acid value (mg KOH / g) = [absorbance (I) × coefficient (f) × 2 × molecular weight of potassium hydroxide × 1000 (mg) / molecular weight of succinic anhydride] Formula (i) In the above formula (i), the molecular weight of succinic anhydride is 100.07, and the molecular weight of potassium hydroxide is 56.11.

[0049] In the present disclosure, a wide variety of known methods can be employed as a method for graft polymerizing an α,β-unsaturated carboxylic acid or an anhydride thereof onto a polyolefin resin, including, for example, a melting method in which a polyolefin resin is heated to a temperature equal to or higher than its melting point in the presence of a radical generator to react with the α,β-unsaturated carboxylic acid or anhydride thereof, and a solution method in which a polyolefin is dissolved in an organic solvent and then heated and stirred in the presence of a radical generator to react with the α,β-unsaturated carboxylic acid or anhydride thereof.

[0050] In the present disclosure, the acid-modified polyolefin resin (A) may be chlorinated or unchlorinated. Examples of chlorination methods include blowing chlorine gas into the acid-modified polyolefin resin to introduce chlorine atoms. More specifically, chlorination can be carried out by dispersing or dissolving the acid-modified polyolefin resin in a solvent, if necessary, and then blowing chlorine gas into the resin in the presence of a catalyst or under ultraviolet irradiation, under pressure or under normal pressure (atmospheric pressure), at a temperature range of 50 to 150°C. Examples of solvents include water and chlorinated solvents (e.g., chloroform, methylene chloride, carbon tetrachloride, etc.), with chlorinated solvents being preferred. The chlorinated solvent may be distilled off under reduced pressure or the like upon completion of chlorination, or may be replaced with another organic solvent. Examples of catalysts include radical initiators. Examples of the radical initiator include tert-butylperoxy-2-ethylhexanoate, tert-butylperoxyoctoate, di-tert-butylperoxide, and dicumyl peroxide.

[0051] In one embodiment of the present disclosure, when the acid-modified polyolefin resin (A) is chlorinated, from the viewpoint of environmental friendliness, the chlorine content in the acid-modified chlorinated polyolefin resin (A) is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 1% by mass or less, per 100 parts by mass of the acid-modified polyolefin resin (A). In addition, it is also a preferred embodiment to use only a non-chlorinated acid-modified polyolefin that is not chlorinated.

[0052] In the present disclosure, the chlorine content in the acid-modified chlorinated polyolefin resin can be measured in accordance with JIS K-7229-1995, i.e., using the "oxygen flask combustion method" in which the acid-modified chlorinated polyolefin resin is burned in an oxygen atmosphere, the generated gaseous chlorine is absorbed with water, and the content is quantified by titration.

[0053] In one embodiment of the present disclosure, the melting point of the acid-modified polyolefin resin (A) is preferably 120° C. or lower, more preferably 100° C. or lower, and particularly preferably 80° C. or lower. When the melting point of the acid-modified polyolefin resin (A) is 120° C. or lower, the adhesion of the modified polyolefin resin composition to the polyolefin substrate becomes even better.

[0054] In the present disclosure, the acid-modified polyolefin resin (A) may be an amorphous resin that does not exhibit a melting peak. The melting point is more preferably 50° C. or higher, and particularly preferably 60° C. or higher. Even if the acid-modified polyolefin resin (A) does not exhibit a melting point, the adhesion to the polyolefin substrate is good.

[0055] In the present disclosure, the melting point of the acid-modified polyolefin resin (A) can be measured by a differential scanning calorimeter (DSC) in accordance with JIS K7121-2012. Specifically, using a DSC measurement device, about 5 mg of a sample is heated to 150°C for 10 minutes and maintained in a molten state, then cooled at a rate of 10°C / min, stabilized at -50°C, and further heated to 150°C at 10°C / min to melt, at which point the melting peak temperature is measured and evaluated as the melting point.

[0056] In one embodiment of the present disclosure, the weight average molecular weight (Mw) of the acid-modified polyolefin resin (A) is preferably 3,000 to 200,000, more preferably 10,000 to 150,000, even more preferably 20,000 to 120,000, even more preferably 30,000 to 100,000, and particularly preferably 40,000 to 90,000. When the weight average molecular weight (Mw) of the acid-modified polyolefin resin (A) is within the range of 3,000 to 200,000, the resin has good fluidity. Furthermore, when the Mw is within the range of 3,000 to 200,000, the cohesive strength of the acid-modified polyolefin resin (A) is further improved, resulting in even better adhesion. The weight average molecular weight (Mw) of the acid-modified polyolefin resin (A) can be measured by gel permeation chromatography (GPC). Specific measurement methods will be described in the examples below.

[0057] In the present disclosure, the acid-modified polyolefin resin (A) may be further copolymerized with a radical polymerizable monomer, as long as the effects of the present disclosure are not impaired. The content of the radical polymerizable monomer is usually 40 parts by mass or less, preferably 20 parts by mass or less, more preferably 5 parts by mass or less, and even more preferably 1 part by mass or less, per 100 parts by mass of the acid-modified polyolefin resin (A).

[0058] In the present disclosure, the form in which the acid-modified polyolefin resin (A) is copolymerized with a radically polymerizable monomer is not limited, and examples of the copolymerization form include random copolymerization, block copolymerization, and graft copolymerization (graft modification). Examples of the radically polymerizable monomer include (meth)acrylic compounds and vinyl compounds. A (meth)acrylic compound is a compound containing at least one (meth)acryloyl group (acryloyl group and / or methacryloyl group) in the molecule.

[0059] Examples of radical polymerizable monomers include (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, cyclohexyl (meth)acrylate, hydroxyethyl (meth)acrylate, isobornyl (meth)acrylate, glycidyl (meth)acrylate, octyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, stearyl (meth)acrylate, 4-tert-butylcyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, hydroxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, acrylate, acetoacetoxyethyl (meth)acrylate, N-methyl (meth)acrylamide, N-ethyl (meth)acrylamide, N-propyl (meth)acrylamide, N-isopropyl (meth)acrylamide, N-butyl (meth)acrylamide, N-isobutyl (meth)acrylamide, N-t-butyl (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, N,N-methylene-bis (meth)acrylamide, N-methylol (meth)acrylamide, hydroxyethyl (meth)acrylamide, (meth)acryloyl morpholine, n-butyl vinyl ether, 4-hydroxybutyl vinyl ether, dodecyl vinyl ether, and the like. These may be used alone or in combination of two or more.

[0060] In the present disclosure, the radical polymerizable monomer is preferably at least one selected from the group consisting of methyl (meth)acrylate, ethyl (meth)acrylate, cyclohexyl (meth)acrylate, and lauryl (meth)acrylate. In the present disclosure, the radical polymerizable monomer is more preferably at least one selected from the group consisting of methyl methacrylate (methyl methacrylate), ethyl methacrylate (ethyl methacrylate), cyclohexyl methacrylate (cyclohexyl methacrylate), and lauryl methacrylate (lauryl methacrylate).

[0061] In one embodiment of the present disclosure, the content of the acid-modified polyolefin resin (A) is preferably 10 to 150 parts by mass, more preferably 12 to 60 parts by mass, even more preferably 15 to 40 parts by mass, and still more preferably 18 to 35 parts by mass, relative to 100 parts by mass of the compound (B) having a polymerizable unsaturated group.

[0062] In one embodiment of the present disclosure, the content of the acid-modified polyolefin resin (A) is preferably 3 to 50 mass%, more preferably 7 to 45 mass%, even more preferably 10 to 40 mass%, and still more preferably 15 to 35 mass%, relative to the total mass of the modified polyolefin resin composition, from the viewpoint of maintaining the fluidity of the modified polyolefin resin composition even better and further improving the water resistance and adhesion to a polyolefin substrate.

[0063] In one embodiment of the present disclosure, the content of the acid-modified polyolefin resin (A) is preferably 5 to 100 parts by mass, more preferably 10 to 85 parts by mass, even more preferably 15 to 60 parts by mass, still more preferably 20 to 50 parts by mass, still more preferably 21 to 40 parts by mass, and particularly preferably 22 to 30 parts by mass, relative to 100 parts by mass of the total amount of the compound (B) having a polymerizable unsaturated group and the polyol component (C), from the viewpoint of maintaining the fluidity of the modified polyolefin resin composition even better and further improving the water resistance and adhesion to a polyolefin substrate.

[0064] <Compound (B) Having a Polymerizable Unsaturated Group> The modified polyolefin resin composition of the present disclosure contains a compound (B) having a polymerizable unsaturated group as an essential component. In the present disclosure, the compound (B) having a polymerizable unsaturated group usually has one or more (e.g., 1, 2, 3, or 4) polymerizable unsaturated groups. In the present disclosure, the polymerizable unsaturated group refers to an unsaturated group capable of radical polymerization.

[0065] In one embodiment of the present disclosure, the number of polymerizable unsaturated groups in the compound (B) having a polymerizable unsaturated group is preferably one or two.

[0066] As one embodiment of the present disclosure, it is preferable that the polymerizable unsaturated group in the compound (B) having a polymerizable unsaturated group is at least one selected from the group consisting of an acryloyl group, a methacryloyl group, an acryloyloxy group, a methacryloyloxy group, a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a maleimide group, and a vinyl ether group.

[0067] As an embodiment of the present disclosure, it is more preferable that the polymerizable unsaturated group in the compound (B) having a polymerizable unsaturated group is at least one selected from the group consisting of an acryloyl group, a methacryloyl group, an acryloyloxy group, and a methacryloyloxy group.

[0068] As an embodiment of the present disclosure, it is even more preferable that the polymerizable unsaturated group in the compound (B) having a polymerizable unsaturated group is at least one selected from the group consisting of an acryloyl group, an acryloyloxy group, and a methacryloyloxy group.

[0069] As one embodiment of the present disclosure, it is particularly preferable that the polymerizable unsaturated group in the compound (B) having a polymerizable unsaturated group is an acryloyl group or an acryloyloxy group.

[0070] In one embodiment of the present disclosure, the compound (B) having a polymerizable unsaturated group preferably has an alkyleneoxy group, in order to maintain the fluidity of the modified polyolefin resin composition more favorably.

[0071] In one embodiment of the present disclosure, the compound (B) having a polymerizable unsaturated group preferably includes a compound having an alkyleneoxy group and one or more (e.g., 1, 2, 3, or 4) polymerizable unsaturated groups. In this case, the number of polymerizable unsaturated groups is more preferably 1 or 2.

[0072] In the present disclosure, the alkyleneoxy group is preferably represented by the following formula 1: -(Y １ -O)m- Formula 1 [In formula 1: Y １ represents a linear or branched alkylene group having 1 to 10 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9, or 10), which may have a substituent. m represents an integer of 1 to 20 (1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20).

[0073] In Formula 1 of the present disclosure, Y １ is preferably a linear or branched alkylene group having 1 to 5 carbon atoms (1, 2, 3, 4 or 5).

[0074] In formula 1 of the present disclosure, m is preferably an integer from 1 to 15 (1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15), and more preferably an integer from 1 to 10 (1, 2, 3, 4, 5, 6, 7, 8, 9, or 10).

[0075] In Formula 1 of the present disclosure, Y １ Examples of the substituent that may be included include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a hydroxy group, a phosphate group, a phenyl group, a cyano group, a nitro group, an amino group, an ester group, a carboxy group, an epoxy group, and an isocyanate group. These substituents may be used either alone or in combination of two or more.

[0076] In one embodiment of the present disclosure, in order to further maintain the fluidity of the modified polyolefin resin composition and improve the crosslink density of the coating film, it is preferable to use a modified polyolefin resin having a structure in which Y １ The substituents that the group has are preferably one or two hydroxy groups, and more preferably one hydroxy group.

[0077] As an embodiment of the present disclosure, the compound (B) having a polymerizable unsaturated group preferably contains one or more compounds represented by the above formula 1.

[0078] In one embodiment of the present disclosure, from the viewpoint of maintaining the fluidity of the modified polyolefin resin composition more favorably and improving the crosslink density of the coating film, it is preferable that the compound (B) having a polymerizable unsaturated group has a hydroxyl group.

[0079] In one embodiment of the present disclosure, the compound (B) having a polymerizable unsaturated group preferably includes a compound having a hydroxyl group and one or more (e.g., 1, 2, 3, or 4) polymerizable unsaturated groups. In this case, the number of hydroxyl groups is preferably 1 or 2, more preferably 1.

[0080] In one embodiment of the present disclosure, the compound (B) having a polymerizable unsaturated group preferably includes a compound having a hydroxyl group and 1 to 3 (1, 2, or 3) polymerizable unsaturated groups. In this case, the number of hydroxyl groups is preferably 1 or 2, more preferably 1.

[0081] As an embodiment of the present disclosure, it is even more preferable that the compound (B) having a polymerizable unsaturated group includes a compound having one hydroxyl group and one polymerizable unsaturated group.

[0082] In one embodiment of the present disclosure, the compound (B) having a polymerizable unsaturated group preferably includes a compound having a linear or branched hydrocarbon group having 1 to 20 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms) and one or more (e.g., 1, 2, 3, or 4) polymerizable unsaturated groups. The hydrocarbon group may have a branched structure or a cyclic structure. In this case, the number of polymerizable unsaturated groups is preferably 1 or 2, and more preferably 1.

[0083] In one embodiment of the present disclosure, the compound (B) having a polymerizable unsaturated group preferably includes a compound having a (meth)acryloyloxy group as the polymerizable unsaturated group. Examples of the compound having one (meth)acryloyloxy group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 1,4-cyclohexanedimethanol monoacrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, polybutylene glycol mono(meth)acrylate, polyethylene glycol-polypropylene glycol mono(meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, Alkyl (meth)acrylates such as phenoxydiethylene glycol (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, i-propyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, t-butyl (meth)acrylate, n-hexyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, stearyl (meth)acrylate, and behenyl (meth)acrylate; (meth)acrylates having an alicyclic structure such as cyclohexyl (meth)acrylate, 4-tert-butylcyclohexyl acrylate, isobornyl (meth)acrylate, etc.; (meth)acrylates having an aromatic ring such as benzyl (meth)acrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, etc.; and (meth)acrylates containing an ether group such as methoxymethyl (meth)acrylate, ethoxymethyl (meth)acrylate, propoxymethyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 1-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 1-ethoxyethyl (meth)acrylate, 2-propoxyethyl (meth)acrylate, 2-isopropoxyethyl (meth)acrylate, etc.These compounds may be used alone or in combination of two or more.

[0084] Examples of the compound having two (meth)acryloyloxy groups include alkanediol di(meth)acrylates such as 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and tricyclodecanedimethylol di(meth)acrylate; bisphenol-modified di(meth)acrylates such as bisphenol A ethylene oxide-modified di(meth)acrylate and bisphenol F ethylene oxide-modified di(meth)acrylate; ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, urethane di(meth)acrylate, epoxy di(meth)acrylate, and glycerin di(meth)acrylate. These compounds may be used alone or in combination of two or more.

[0085] Examples of compounds having three or more (meth)acryloyloxy groups include dipentaerythritol hexa(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate; ethylene oxide-modified (meth)acrylates such as ethylene oxide-modified dipentaerythritol hexa(meth)acrylate and ethylene oxide-modified pentaerythritol tetra(meth)acrylate; isocyanuric acid-modified tri(meth)acrylates such as ethylene oxide-modified tri(meth)acrylate and ε-caprolactone-modified tris(acryloxyethyl)isocyanurate; Examples of the urethane methacrylate include pentaerythritol tri(meth)acrylate hexamethylene diisocyanate urethane prepolymer, pentaerythritol tri(meth)acrylate toluene diisocyanate urethane prepolymer, and dipentaerythritol penta(meth)acrylate hexamethylene diisocyanate urethane prepolymer. These compounds can be used either alone or in combination of two or more.

[0086] In one embodiment of the present disclosure, the content of the compound (B) having a polymerizable unsaturated group is preferably 5 to 80 mass %, more preferably 15 to 75 mass %, even more preferably 30 to 70 mass %, and still more preferably 40 to 68 mass %, relative to the total mass of the modified polyolefin resin composition, from the viewpoint of maintaining the fluidity of the modified polyolefin resin composition even better and improving the adhesion to a polyolefin substrate.

[0087] In one embodiment of the present disclosure, from the viewpoint of maintaining the fluidity of the modified polyolefin resin composition even better and improving the crosslinking density of the coating film, the content of the compound having a hydroxyl group and a polymerizable unsaturated group is preferably 1 to 50 mass%, more preferably 3 to 45 mass%, even more preferably 6 to 40 mass%, and still more preferably 8 to 35 mass%, relative to the total mass of the modified polyolefin resin composition.

[0088] In one embodiment of the present disclosure, from the viewpoint of maintaining the fluidity of the modified polyolefin resin composition even better and improving the flexibility of the cured coating film, the content of the compound (B) having a polymerizable unsaturated group is preferably 1 to 99 parts by mass, more preferably 10 to 97 parts by mass, even more preferably 20 to 95 parts by mass, and still more preferably 35 to 93 parts by mass, relative to 100 parts by mass of the total of the compound (B) having a polymerizable unsaturated group and the polyol component (C).

[0089] Specific examples of the compound having a hydroxyl group and a polymerizable unsaturated group include 4-hydroxybutyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-1,3-dimethacryloxypropane, 2-hydroxy-3-methacrylpropyl acrylate, glycerin diacrylate, pentaerythritol di(meth)acrylate, and pentaerythritol tri(meth)acrylate.

[0090] In one embodiment of the present disclosure, the compound (B) having a polymerizable unsaturated group may contain a biomass-derived (meth)acrylic monomer component. The biomass-derived (meth)acrylic monomer component refers to a component composed of a biomass-derived (meth)acrylic acid or an ester of a biomass-derived alkanol with a biomass-derived or non-biomass-derived (meth)acrylic acid. Examples of biomass-derived alkanols include biomass ethanol and alkanols derived from plant materials such as palm oil, palm kernel oil, and coconut oil. When the biomass-derived alkanol has 3 or more carbon atoms, the alkanol may be linear or branched.

[0091] In one embodiment of the present disclosure, from the viewpoint of maintaining the fluidity of the modified polyolefin resin composition more favorably and further improving workability, the number average molecular weight (Mn) of the compound (B) having a polymerizable unsaturated group is preferably 3,000 or less, more preferably 2,000 or less, and even more preferably 1,000 or less.

[0092] In one embodiment of the present disclosure, from the viewpoint of maintaining the fluidity of the modified polyolefin resin composition more favorably and further improving workability, the number average molecular weight (Mn) of the compound (B) having a polymerizable unsaturated group is preferably 100 or more, more preferably 120 or more, and even more preferably 140 or more.

[0093] As an embodiment of the present disclosure, it is more preferable that the compound (B) having a polymerizable unsaturated group includes at least one selected from the group consisting of a compound having one acryloyl group, a compound having one acryloyloxy group, and a compound having two acryloyloxy groups.

[0094] As an embodiment of the present disclosure, it is even more preferable that the compound (B) having a polymerizable unsaturated group includes at least one selected from the group consisting of a compound having one acryloyl group and a morpholine group, a compound having one acryloyloxy group and an isobornyl group, a compound having one acryloyloxy group and one hydroxyl group, a compound having one acryloyloxy group, one hydroxyl group and one phenyl group, and a compound having two acryloyloxy groups.

[0095] As one embodiment of the present disclosure, it is particularly preferable that the compound (B) having a polymerizable unsaturated group includes at least one selected from the group consisting of a compound having one acryloyl group and a morpholine group, a compound having one acryloyloxy group and an isobornyl group, a compound having one acryloyloxy group and one hydroxyl group at a terminal of a side chain, a compound having one acryloyloxy group, one hydroxyl group and a phenyl group at a terminal of a side chain, and a compound having two acryloyloxy groups.

[0096] In the present disclosure, the functional group at the "end of the side chain" of the compound (B) having a polymerizable unsaturated group means the functional group located at the farthest position from the main chain of the compound (B) having a polymerizable unsaturated group.

[0097] In one embodiment of the present disclosure, the compound (B) having a polymerizable unsaturated group most preferably includes at least one compound selected from the group consisting of dipropylene glycol diacrylate, polyethylene glycol diacrylate, 4-hydroxybutyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, acryloylmorpholine, and isobornyl acrylate. <Polyol Component (C)> The modified polyolefin resin composition of the present disclosure contains polyol component (C) as an essential component. The polyol component (C) of the present disclosure typically contains a polyol (a compound having two or more hydroxyl groups per molecule). The polyol component (C) of the present disclosure is typically a reactive component that can be used as a resin for forming a coating film. The polyol component (C) of the present disclosure reacts with a curing agent, for example, by heating, to form a three-dimensional cured coating film.

[0098] In one embodiment of the present disclosure, the polyol component (C) preferably does not have a polymerizable unsaturated group (for example, an acryloyl group, a methacryloyl group, an acryloyloxy group, a methacryloyloxy group, a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a maleimide group, or a vinyl ether group).

[0099] In one embodiment of the present disclosure, the polyol component (C) may contain one kind of polyol component (C) alone or two or more kinds of polyol components (C) having different hydroxyl values.

[0100] In one embodiment of the present disclosure, from the viewpoint of maintaining the fluidity of the modified polyolefin resin composition more favorably and improving the flexibility of the cured coating film, the polyol component (C) preferably contains at least one polyol selected from the group consisting of polypropylene glycol, polyether polyol, polyester polyol, polyacrylate polyol, polycaprolactone polyol, polycarbonate polyol, castor oil-modified polyol, polyolefin polyol, and polyhydric alcohol.

[0101] As an embodiment of the present disclosure, the polyol component (C) more preferably includes at least one polyol selected from the group consisting of polypropylene glycol, polyether polyol, polyester polyol, polyacrylate polyol, polycaprolactone polyol, polycarbonate polyol, and polyhydric alcohol.

[0102] In one embodiment of the present disclosure, the polyol component (C) more preferably includes at least one polyol selected from the group consisting of polypropylene glycol, polyether polyol, polyester polyol, polycaprolactone polyol, polycarbonate polyol, and polyhydric alcohol.

[0103] In one embodiment of the present disclosure, the polyol component (C) more preferably includes at least one polyol selected from the group consisting of polypropylene glycol, polyester polyol, polyacrylate polyol, polycaprolactone polyol, polycarbonate polyol, and polyhydric alcohol.

[0104] In one embodiment of the present disclosure, the polyol component (C) particularly preferably contains at least one polyol selected from the group consisting of polypropylene glycol, polyester polyol, polycaprolactone polyol, and polycarbonate polyol.

[0105] In one embodiment of the present disclosure, the polyol component (C) most preferably comprises: polypropylene glycol and polyester polyol; polypropylene glycol and polycaprolactone polyol; or polypropylene glycol and polycarbonate polyol.

[0106] <Polyether polyol> The polyol component (C) of the present disclosure can contain a polyether polyol. Examples of polyether polyols include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and block copolymers thereof, and these can be used alone or in combination of two or more.

[0107] The polyether polyol is preferably at least one selected from the group consisting of polyethylene glycol, polypropylene glycol, and polytetramethylene glycol, and more preferably polypropylene glycol.

[0108] Polyether polyols can be prepared, for example, by adding ethylene oxide and / or propylene oxide to a polyhydric alcohol compound, thereby producing polyether polyols having two, three or more hydroxyl groups per molecule.

[0109] <Polyacrylate polyol> The polyol component (C) of the present disclosure can contain a polyacrylate polyol. The polyacrylate polyol can be obtained, for example, by polymerizing an acrylate monomer composition containing an acrylate monomer containing a hydroxyl group.

[0110] Examples of acrylate monomers having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and polytetramethylene glycol mono(meth)acrylate.

[0111] A wide variety of commercially available polyacrylate polyols can be used. Examples of commercially available polyacrylate polyols include "Alfon UH Series," "Alfon (registered trademark) UH-2000," "Alfon (registered trademark) UH-2041," "Alfon (registered trademark) UH-2170," and "Alfon (registered trademark) UH-2190," all manufactured by Toagosei Co., Ltd. These commercially available products can be used alone or in combination of two or more.

[0112] <Polyester Polyol> The polyol component (C) of the present disclosure can contain a polyester polyol. The polyester polyol can be obtained, for example, by an esterification reaction between a dihydric or higher polyhydric alcohol compound and a dihydric or higher polycarboxylic acid.

[0113] Examples of dihydric or higher polyhydric alcohol compounds include ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol (MPD), 2-butyl-2-ethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol (ND), 2-methyl-1,8-octanediol, 1,8-decanediol, octadecanediol, glycerin, and trimethylolpropane (TMP).

[0114] Examples of divalent or higher polyvalent carboxylic acids include succinic acid, methylsuccinic acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, 1,12-dodecanedioic acid, 1,14-tetradecanedioic acid, dimer acid, 2-methyl-1,4-cyclohexanedicarboxylic acid, 2-ethyl-1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, and acid anhydrides thereof.

[0115] <Polycaprolactone polyol> The polyol component (C) of the present disclosure may contain a polycaprolactone polyol, which can be obtained, for example, by ring-opening polymerization of ε-caprolactone.

[0116] As the commercially available polycaprolactone polyol, a wide variety of known commercially available products can be used. Examples of commercially available polycaprolactone polyols include "PLACCEL 205U (Mn=530, hydroxyl value=212 mgKOH / g)" and "PLACCEL 303 (Mn=310, hydroxyl value=541 mgKOH / g)" manufactured by Daicel Corporation. These commercially available products can be used alone or in combination of two or more.

[0117] <Polycarbonate polyol> The polyol component (C) of the present disclosure can contain a polycarbonate polyol. The polycarbonate polyol can be obtained, for example, by an esterification reaction between a dihydric or higher polyhydric alcohol compound and a carbonate diester compound.

[0118] Examples of dihydric or higher polyhydric alcohol compounds include ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol (MPD), 2-butyl-2-ethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol (ND), 2-methyl-1,8-octanediol, 1,8-decanediol, octadecanediol, glycerin, and trimethylolpropane (TMP).

[0119] Examples of the carbonate diester compound include dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate, ethyl butyl carbonate, ethylene carbonate, propylene carbonate, diphenyl carbonate, and dibenzyl carbonate.

[0120] <Castor Oil Modified Polyol and Polyolefin Polyol> The polyol component (C) of the present disclosure may contain a castor oil modified polyol and / or a polyolefin polyol.

[0121] As commercially available castor oil-modified polyols and polyolefin polyols, known commercially available products can be widely used. Examples of commercially available castor oil-modified polyols include the "URIC series" manufactured by Ito Oil Mills, Ltd. Examples of commercially available polyolefin polyols include the "Poly bd, ip, EPOL series" manufactured by Idemitsu Kosan Co., Ltd. These commercially available products can be used alone or in combination of two or more.

[0122] <Polyhydric Alcohol> The polyol component (C) of the present disclosure may contain a polyhydric alcohol. Examples of polyhydric alcohols include ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, glycerin, trimethylolpropane, tetramethylene glycol, 1,2,5-hexanetriol, pentaerythritol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, cyclohexanedimethanol, 3-methyl-1,5-pentanediol, neopentyl glycol, and sorbitol. In the present disclosure, the polyhydric alcohol is preferably 3-methyl-1,5-pentanediol.

[0123] In the present disclosure, from the viewpoint of maintaining good fluidity of the modified polyolefin resin composition, the polyol component (C) preferably contains a polyol having a number average molecular weight (Mn) of 5,000 or less, more preferably a polyol having an Mn of 2,000 or less, even more preferably a polyol having an Mn of 1,500 or less, and even more preferably a polyol having an Mn of 1,000 or less. In the present disclosure, the polyol component (C) preferably contains a polyol having an Mn of 60 or more, more preferably a polyol having an Mn of 80 or more, even more preferably a polyol having an Mn of 110 or more, and even more preferably a polyol having an Mn of 150 or more.

[0124] In the present disclosure, from the viewpoint of maintaining good fluidity of the modified polyolefin resin composition, the polyol component (C) preferably contains a polyol having an Mn of 60 or more and 5,000 or less, more preferably a polyol having an Mn of 80 or more and 2,000 or less, even more preferably a polyol having an Mn of 110 or more and 1,500 or less, and even more preferably a polyol having an Mn of 150 or more and 1,000 or less.

[0125] In the present disclosure, polyol component (C) preferably contains a polyol having a hydroxyl value of 50 to 1000 mgKOH / g, more preferably a polyol having a hydroxyl value of 100 to 800 mgKOH / g, even more preferably a polyol having a hydroxyl value of 150 to 700 mgKOH / g, and even more preferably a polyol having a hydroxyl value of 200 to 600 mgKOH / g. When polyol component (C) contains a polyol having a hydroxyl value of 50 to 1000 mgKOH / g, the action of the polyether chain of polyetheramine (D) and polyol component (C) enables the modified polyolefin resin composition of the present disclosure to maintain good fluidity for a long period of time.

[0126] The hydroxyl value of the polyol component (C) is expressed as a value converted into solid content, and can be evaluated in accordance with JIS K 1557-1:2007.

[0127] In the present disclosure, from the viewpoint of maintaining good fluidity of the modified polyolefin resin composition, the content of the polyol component (C) is preferably 2 to 90 mass%, more preferably 3 to 60 mass%, even more preferably 4 to 30 mass%, particularly preferably 5 to 25 mass%, and most preferably 6 to 20 mass%, relative to the total mass of the modified polyolefin resin composition.

[0128] The modified polyolefin resin composition of the present disclosure may contain a film-forming resin other than the acid-modified polyolefin resin (A), the compound having a polymerizable unsaturated group (B), and the polyol component (C). Examples of the film-forming resin include acrylic resins, polyester resins, alkyd resins, polyether resins, polyolefin resins, polyurethane resins, polycarbonate resins, melamine resins, epoxy resins, and carbodiimide resins. These resins may be used alone or in combination of two or more.

[0129] In one embodiment of the present disclosure, when the modified polyolefin resin composition contains another coating film-forming resin, the content of the coating film-forming resin is preferably 10 to 30 mass % relative to the total mass of the modified polyolefin resin composition.

[0130] <Polyetheramine (D)> The modified polyolefin resin composition of the present disclosure preferably contains polyetheramine (D). The polyetheramine (D) is usually a compound having a polyether chain and an amino group.

[0131] In one embodiment of the present disclosure, the polyetheramine (D) has a polyether chain represented by Formula 2: —(O—CH ２ CH ２ )x- (wherein x is an integer of 2 to 120), a structure represented by Formula 3-1: -(O-CH ２ CH (CH ３ ))y １ -(In formula 3-1, y １ is an integer of 2 to 90), a structure represented by Formula 3-2: -(O-CH ２ CH ２ CH ２ ) y ２ -(In formula 3-2, y ２ is an integer of 2 to 90), a structure represented by Formula 4-1: -(O-CH ２ CH ２ CH ２ CH ２ ) z １ -(In formula 4-1, z １ is an integer of 2 to 80), a structure represented by formula 4-2: -(O-CH(CH３ ) CH ２ CH ２ ) z ２ -(In formula 4-2, z ２ is an integer of 2 to 80), a structure represented by formula 4-3: -(O-CH ２ CH (CH ３ ) CH ２ ) z ３ -(In formula 4-3, z ３ is an integer of 2 to 80), and a structure represented by formula 4-4: -(O-CH ２ CH ２ CH (CH ３ ))z ４ -(In formula 4-4, z ４ is an integer of 2 to 80), and

[0132] In one embodiment of the present disclosure, the polyetheramine (D) has a polyether chain represented by Formula 2: —(O—CH ２ CH ２ )x- (wherein x is an integer of 2 to 120), a structure represented by Formula 3-1: -(O-CH ２ CH (CH ３ ))y １ -(In formula 3-1, y １ is an integer of 2 to 90), and a structure represented by formula 4-1: -(O-CH ２ CH ２ CH ２ CH ２ ) z １ -(In formula 4-1, z １ is an integer of 2 to 80), and

[0133] In one embodiment of the present disclosure, the polyetheramine (D) is represented by the following formula 2A: １ -(O-R ２ ) a-R ３ Formula 2A (In formula 2A: R １ and R ３R each independently represents an amino group or a linear or branched alkyl group having 1 to 10 (1, 2, 3, 4, 5, 6, 7, 8, 9, or 10) carbon atoms which may have an amino group. ２ represents a linear or branched alkylene group having 2 to 4 carbon atoms (2, 3, or 4); and a is an integer of 2 to 120.

[0134] In Formula 2A of the present disclosure, examples of the linear or branched alkyl group having 1 to 10 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9, or 10) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, and an n-decyl group.

[0135] In Formula 2A of the present disclosure, the linear or branched alkylene group having 2 to 4 (2, 3, or 4) carbon atoms is preferably an ethylene group (—CH ２ CH ２ -), methylethylene group (-CH ２ CH (CH ３ )-), n-propylene group (—CH ２ CH ２ CH ２ -), 1-methylpropylene group (-CH(CH ３ ) CH ２ CH ２ -), 2-methylpropylene group, (-CH ２ CH (CH ３ ) CH ２ -), 3-methylpropylene group (-CH ２ CH ２ CH (CH ３ )-) or n-butylene group (-CH ２ CH ２ CH ２ CH ２ -).

[0136] In Formula 2A of the present disclosure, R １ represents a linear or branched alkyl group having 1 to 10 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9, or 10), and R ２represents a linear or branched alkylene group having 2 to 4 (2, 3, or 4) carbon atoms, and R ３ represents an amino group, and a is preferably an integer of 1 to 120.

[0137] In one embodiment of the present disclosure, the polyetheramine (D) preferably has a primary amino group or a secondary amino group at one terminal, and the weight average molecular weight (Mw) of the polyetheramine (D) is 200 to 50,000. In one embodiment of the present disclosure, the polyetheramine (D) more preferably has a primary amino group or a secondary amino group at one terminal, and the weight average molecular weight (Mw) of the polyetheramine (D) is 200 to 10,000. In one embodiment of the present disclosure, the polyetheramine (D) still more preferably has a primary amino group at one terminal, and the weight average molecular weight (Mw) of the polyetheramine (D) is 500 to 5,000.

[0138] In one embodiment of the present disclosure, from the viewpoint of stably dissolving and / or dispersing the acid-modified polyolefin resin (A) in the compound (B) having a polymerizable unsaturated group and / or the polyol component (C), the polyetheramine (D) is typically a polymer compound having a weight average molecular weight (Mw) in the range of 200 to 50,000. If the Mw of the polyetheramine (D) is within this range, the steric repulsion of the polyetheramine (D) in the compound (B) having a polymerizable unsaturated group tends to be large, making it possible to stably dissolve and / or disperse the acid-modified polyolefin resin (A) in the compound (B) having a polymerizable unsaturated group. In one embodiment of the present disclosure, the Mw of the polyetheramine (D) is typically 200 to 50,000, preferably 300 to 20,000, more preferably 350 to 10,000, even more preferably 450 to 7,000, and particularly preferably 500 to 5,000.

[0139] In one embodiment of the present disclosure, the weight average molecular weight (Mw) of the polyetheramine (D) can be measured by GPC and converted from a polystyrene calibration curve. The GPC measurement is performed by a conventionally known method using a commercially available apparatus and a solvent such as THF.

[0140] In one embodiment of the present disclosure, the polyetheramine (D) preferably has an HLB value of 2 to 20, more preferably 5 to 19, and even more preferably 8 to 18. When the HLB value is within the range of 2 to 20, the fluidity of the modified polyolefin resin composition can be maintained even better.

[0141] In one embodiment of the present disclosure, the HLB value refers to a value representing the degree of hydrophilicity or lipophilicity (hydrophobicity) of polyetheramine (D). In the present disclosure, the HLB value is a value calculated by the Griffin method. In the Griffin method, the HLB value is a value calculated based on the following formula (5): HLB value = 20 × sum of formula weights of hydrophilic group moieties / molecular weight ... formula (5).

[0142] The polyetheramine (D) can be bonded to the acid-modified polyolefin resin (A) by various reaction modes. Examples of such reaction modes include a reaction mode that forms a covalent bond and / or an ionic bond. More specifically, examples include an amidation reaction between a carboxylic acid anhydride group and a primary or secondary amino group; an imidization reaction; and a neutralization reaction between a carboxylic acid group and a primary or secondary amino group.

[0143] As the polyetheramine (D), a wide range of known commercially available products can be used. Commercially available polyetheramines (D) include, for example, "JEFFAMINE M-600 (Mw=600, HLB value=2.1)," "JEFFAMINE M-1000 (Mw=1000, HLB value=16.1)," "JEFFAMINE M-2005 (Mw=2000, HLB value=2.7)," "JEFFAMINE M-2070 (Mw=2000, HLB value=13.8)," "JEFFAMINE M-3085 (Mw=3000, HLB value=16.8)," "JEFFAMINE D-230 (Mw=230, HLB value=3.6)," and "JEFFAMINE D-400 (Mw = 430, HLB value = 1.7)," JEFFAMINE D-2000 (Mw = 2000, HLB value = 0.3)," JEFFAMINE D-4000 (Mw = 4000, HLB value = 0.2)," JEFFAMINE ED-600 (Mw = 600, HLB value = 13.4)," JEFFAMINE ED-900 (Mw = 900, HLB value = 12.5)," JEFFAMINE ED-2003 (Mw = 2000, HLB value = 16.7)," GENAMIN manufactured by CLARIANT M41 / 2000 (Mw=2000, HLB value=14.8), etc. These commercially available products may be used either alone or in combination of two or more.

[0144] In one embodiment of the present disclosure, when the modified polyolefin resin composition of the present disclosure contains polyetheramine (D), the content of polyetheramine (D) is preferably 6 to 100 parts by mass, more preferably 10 to 90 parts by mass, even more preferably 15 to 80 parts by mass, still more preferably 20 to 70 parts by mass, particularly preferably 25 to 60 parts by mass, and most preferably 30 to 55 parts by mass, per 100 parts by mass of the acid-modified polyolefin resin (A), from the viewpoint of maintaining the fluidity of the modified polyolefin resin composition even better and further improving the water resistance and adhesion to polyolefin substrates.

[0145] In one embodiment of the present disclosure, when the modified polyolefin resin composition of the present disclosure contains polyetheramine (D), the content of polyetheramine (D) is preferably 0.5 to 40 mass%, more preferably 1 to 35 mass%, even more preferably 2 to 30 mass%, even more preferably 5 to 25 mass%, and particularly preferably 6 to 20 mass%, relative to the total mass of the modified polyolefin resin composition, from the viewpoint of maintaining the fluidity of the modified polyolefin resin composition even better and further improving the water resistance and adhesion to polyolefin substrates.

[0146]

[0033] In one embodiment of the present disclosure, when the modified polyolefin resin composition of the present disclosure contains a polyetheramine (D), the total content of the acid-modified polyolefin resin (A), the compound (B) having a polymerizable unsaturated group, the polyol component (C), and the polyetheramine (D) is preferably 80% by mass or more, more preferably 85% by mass or more, even more preferably 90% by mass or more, still more preferably 95% by mass or more, still more preferably 97.5% by mass or more, and particularly preferably 99% by mass or more, based on the total mass of the modified polyolefin resin composition.

[0147] <Radical Polymerization Initiator (E)> The modified polyolefin resin composition of the present disclosure may contain a radical polymerization initiator (E) within a range that does not impair the effects of the present disclosure. By containing the radical polymerization initiator (E), the polymerization reaction of the polymerizable unsaturated group in the compound (B) having the polymerizable unsaturated group progresses, and a resin for forming a coating film can be formed. By using the polymerization initiator, the corrosion resistance and durability of the coating film can be further improved.

[0148] In one embodiment of the present disclosure, when the modified polyolefin resin composition of the present disclosure contains a radical polymerization initiator (E), the content of the radical polymerization initiator (E) is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, and even more preferably 2 to 5 parts by mass, relative to 100 parts by mass of the modified polyolefin resin composition, from the viewpoint of increasing the curing rate of a coating film obtained from the modified polyolefin resin composition.

[0149] As the radical polymerization initiator (E), a polymerization initiator capable of initiating a polymerization reaction of a polymerizable unsaturated group can be used, and examples thereof include a photopolymerization initiator that generates radicals by light, a thermal polymerization initiator that generates radicals by heat, etc. These radical polymerization initiators (E) can be used alone or in combination of two or more.

[0150] A photopolymerization initiator is a compound that generates radicals or acids upon irradiation with ultraviolet light or visible light, thereby initiating a chain polymerization reaction. Examples of the photopolymerization initiator include acetophenone-based photopolymerization initiators, benzoin-based photopolymerization initiators, benzophenone-based photopolymerization initiators, thioxanthone-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, and titanocene-based photopolymerization initiators. These may be used alone or in combination of two or more.

[0151] Specific examples of acetophenone-based photopolymerization initiators include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, benzyl dimethyl ketal, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-methyl-2-morpholino(4-thiomethylphenyl)propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone oligomer, etc. These can be used alone or in combination of two or more.

[0152] Specific examples of the benzoin-based photopolymerization initiator include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc. These may be used alone or in combination of two or more.

[0153] Specific examples of the benzophenone-based photopolymerization initiator include benzophenone, benzoylbenzoic acid, polyvinylbenzophenone, α-hydroxycyclohexylphenyl ketone, etc. These can be used either alone or in combination of two or more.

[0154] Specific examples of the thioxanthone-based photopolymerization initiator include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, dodecylthioxanthone, etc. These can be used either alone or in combination of two or more.

[0155] Specific examples of the acylphosphine oxide photopolymerization initiator include bis(2,4,6-trimethylbenzoyl)phenyl-phosphine oxide, ethoxyphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, etc. These can be used either alone or in combination of two or more.

[0156] Specific examples of titanocene photopolymerization initiators include bis(cyclopentadienyl)-bis[2,6-difluoro-3-(2-(1-pyl-1-yl)ethyl)phenyl]titanium, bis(cyclopentadienyl)-bis[2,6-difluoro-3-(3-(1-pyl-1-yl)propyl)phenyl]titanium, bis(cyclopentadienyl)-bis[2,6-difluoro-3-((1-pyl-1-yl)methyl)phenyl]titanium, and bis(methylcyclopentadienyl)-bis[2,6-difluoro-3-((1-pyl-1-yl)methyl)phenyl]titanium. Examples of such titanium compounds include bis(cyclopentadienyl)-bis[2,6-difluoro-3-((2,5-dimethyl-1-pyr-1-yl)methyl)phenyl]titanium, bis(cyclopentadienyl)-bis[2,6-difluoro-3-((2-isopropyl-5-methyl-1-pyr-1,6-yl)methyl)phenyl]titanium, and bis(cyclopentadienyl)-bis[2,6-difluoro-3-((2-(2-methoxyethyl)-5-methyl-1-pyr-1-yl)methyl)phenyl]titanium. These compounds may be used either alone or in combination of two or more.

[0157] A thermal polymerization initiator is a compound that generates radicals upon heating and initiates a chain polymerization reaction. Examples of the thermal polymerization initiator include organic peroxides; and inorganic peroxides such as potassium persulfate, ammonium persulfate, and hydrogen peroxide. Specific examples of organic peroxides include ketone peroxide compounds such as methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, methylacetoacetate peroxide, and acetylacetone peroxide; peroxyketal compounds such as 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, 2,2-bis(t-butylperoxy)octane, n-butyl-4,4-bis(t-butylperoxy)valerate, and 2,2-bis(t-butylperoxy)butane; Hydroperoxide compounds such as t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, and 1,1,3,3-tetramethylbutyl hydroperoxide; dialkyl peroxide compounds such as t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, α,α'-bis(t-butylperoxy-m-isopropyl)benzene, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, and 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3; diacyl peroxide compounds such as acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, succinic acid peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, and m-toluoyl peroxide;Peroxydicarbonate compounds such as diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-n-propyl peroxydicarbonate, bis-(4-t-butylcyclohexyl) peroxydicarbonate, dimyristyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, dimethoxyisopropyl peroxydicarbonate, di(3-methyl-3-methoxybutyl) peroxydicarbonate, and diallyl peroxydicarbonate; t-butyl peroxyacetate, t-butyl peroxyisobutyrate, t-butyl peroxypivalate, t-butyl peroxyneodecanoate, cumyl peroxyneodecanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butyl peroxylaurate, t-butyl peroxybenzoate, di-t-butylperoxyisophthalate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, t-butylperoxymaleic acid, t-butylperoxy peroxyester compounds such as cyclohexyl isopropyl carbonate, cumyl peroxyoctoate, t-hexyl peroxyneodecanoate, t-hexyl peroxypivalate, t-butyl peroxyneohexanoate, t-hexyl peroxyneohexanoate, cumyl peroxyneohexanoate, and tert-butyl-2-ethylperoxyhexanoate; acetylcyclohexylsulfonyl peroxide, and t-butyl peroxyallyl carbonate, which may be used alone or in combination of two or more;

[0158] <UV Absorber> In one embodiment of the present disclosure, the modified polyolefin resin composition of the present disclosure may contain an UV absorber, as long as the effects of the present disclosure are not impaired. Examples of the UV absorber include benzophenone-based UV absorbers, benzotriazole-based UV absorbers, triazine-based UV absorbers, salicylic acid-based UV absorbers, cyanoacrylate-based UV absorbers, and benzoxazine-based UV absorbers. These UV absorbers may be used alone or in combination of two or more.

[0159] In one embodiment of the present disclosure, when the modified polyolefin resin composition of the present disclosure contains an ultraviolet absorber, the content of the ultraviolet absorber is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the modified polyolefin resin composition.

[0160] <Light Stabilizer> The modified polyolefin composition of the present disclosure may contain a light stabilizer, for example, a hindered amine light stabilizer, as long as the effect of the present disclosure is not impaired.

[0161] Specific examples of the hindered amine light stabilizer include bis(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate, methyl(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate, 2,4-bis[N-butyl-N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)amino]-6-(2-hydroxyethylamine)-1,3,5-triazine, and decanedioic acid bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidinyl)ester. These may be used alone or in combination of two or more.

[0162] In one embodiment of the present disclosure, when the modified polyolefin resin composition of the present disclosure contains a light stabilizer, the content of the light stabilizer is preferably 0.01 to 10 parts by mass, and more preferably 0.1 to 1 part by mass, per 100 parts by mass of the modified polyolefin resin composition.

[0163] <Sensitizer> As an embodiment of the present disclosure, the modified polyolefin resin composition of the present disclosure may contain a sensitizer within a range that does not impair the effects of the present disclosure. Examples of sensitizers include unsaturated ketone compounds such as chalcone and dibenzalacetone, 1,2-diketone compounds such as benzil and camphorquinone, polymethine dyes such as benzoin compounds, fluorene compounds, naphthoquinone compounds, anthraquinone compounds, xanthene compounds, thioxanthene compounds, xanthone compounds, thioxanthone compounds, coumarin compounds, ketocoumarin compounds, cyanine compounds, merocyanine compounds, and oxonol compounds, acridine compounds, azine compounds, thiazine compounds, oxazine compounds, indoline compounds, azulene compounds, azulenium compounds, and squarylium compounds. Examples of such compounds include compounds such as porphyrin compounds, tetraphenylporphyrin compounds, triarylmethane compounds, tetrabenzoporphyrin compounds, tetrapyrazinoporphyrazine compounds, phthalocyanine compounds, tetraazaporphyrazine compounds, tetraquinoxalylporphyrazine compounds, naphthalocyanine compounds, subphthalocyanine compounds, pyrylium compounds, thiopyrylium compounds, tetraphyrin compounds, annulene compounds, spiropyran compounds, spirooxazine compounds, thiospiropyran compounds, metal arene complexes, organic ruthenium complexes, Michler's ketone compounds, and biimidazole compounds. These compounds may be used alone or in combination of two or more.

[0164] In one embodiment of the present disclosure, when the modified polyolefin resin composition of the present disclosure contains a sensitizer, the content of the sensitizer is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the modified polyolefin resin composition.

[0165] <Polyisocyanate Compound (F)> In one embodiment of the present disclosure, the modified polyolefin resin composition of the present disclosure may contain a polyisocyanate compound (F). The polyisocyanate compound is used as a curing agent for curing the polyol component (C) to form a resin for forming a coating film. Use of the polyisocyanate compound (F) further improves the corrosion resistance and durability of the coating film.

[0166] Examples of the polyisocyanate compound (F) include: (i) aliphatic polyisocyanate compounds having 2 to 18 carbon atoms; (ii) alicyclic polyisocyanate compounds having 4 to 15 carbon atoms; (iii) aromatic polyisocyanate compounds having 8 to 15 carbon atoms; aromatic polyisocyanate compounds having 6 to 20 carbon atoms (excluding carbon atoms in NCO groups, the same applies below) and crude products thereof; and (iv) modified products of the polyisocyanate compounds (i) to (iii) above (e.g., modified products containing urethane groups, carbodiimide groups, allophanate groups, urea groups, biuret groups, uretdione groups, uretoimine groups, isocyanurate groups, oxazolidone groups, etc.), and mixtures of two or more of these modified products. These polyisocyanate compounds (F) can be used alone or in combination of two or more. Among these polyisocyanate compounds (F), aliphatic polyisocyanate compounds having 2 to 18 carbon atoms and / or alicyclic polyisocyanate compounds having 4 to 15 carbon atoms are preferred in terms of further improving corrosion resistance and durability.

[0167] Specific examples of the aliphatic polyisocyanate compound having 2 to 18 carbon atoms include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethyl caproate, bis(2-isocyanatoethyl)fumarate, bis(2-isocyanatoethyl)carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate, etc. These may be used alone or in combination of two or more.

[0168] Specific examples of the alicyclic polyisocyanate compound (F) having 4 to 15 carbon atoms include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4'-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), 1,3-bis(isocyanatomethyl)cyclohexane, bis(2-isocyanatoethyl)-4-cyclohexene-1,2-dicarboxylate, 2,5-norbornane diisocyanate, 2,6-norbornane diisocyanate, etc. These can be used either alone or in combination of two or more.

[0169] Specific examples of the aromatic polyisocyanate compound having 8 to 15 carbon atoms include m- and / or p-xylylene diisocyanate (XDI), α,α,α',α'-tetramethylxylylene diisocyanate (TMXDI), etc. These can be used either alone or in combination of two or more.

[0170] Specific examples of the aromatic polyisocyanate compound having 8 to 15 carbon atoms include 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), crude TDI, 2,4'- and / or 4,4'-biphenylmethane diisocyanate (MDI), 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenylmethane, crude MDI, 1,5-naphthylene diisocyanate, 4,4',4''-triphenylmethane triisocyanate, m- and p-isocyanatophenylsulfonyl isocyanate, 1,3-bis(isocyanatomethyl)benzene, etc. These may be used alone or in combination of two or more.

[0171] Examples of the modified polyisocyanate compound include modified polyisocyanates such as modified MDI (urethane-modified MDI, carbodiimide-modified MDI, trihydrocarbyl phosphate-modified MDI), urethane-modified TDI, biuret-modified HDI, isocyanurate-modified HDI, and isocyanurate-modified IPDI; and mixtures of two or more of these [for example, a combination of modified MDI and urethane-modified TDI (isocyanate group-containing prepolymer)]. Among these, isocyanurate-modified HDI is preferred.

[0172] In one embodiment of the present disclosure, the modified polyolefin resin composition of the present disclosure may contain, in addition to the polyisocyanate compound (F) described above, a polyisocyanate compound in which the isocyanate group is blocked with a blocking agent. Examples of blocking agents include phenol compounds; oxime compounds; lactam compounds; alcohol compounds; mercaptan compounds; pyrazole compounds; and active methylene compounds such as diethyl malonate. When using a blocked polyisocyanate compound, it is preferable to use a dissociation catalyst for the blocking agent in combination. An unblocked polyisocyanate compound and a blocked polyisocyanate compound can also be used in combination.

[0173] The number average molecular weight (Mn) of the polyisocyanate compound (F) is preferably 3,000 or less, more preferably 100 to 1,500.

[0174] As the commercially available polyisocyanate compound (F), a wide variety of known commercially available products can be used, including, for example, "Bayhydur," "TP-LS2550," and "Sumidur N3300" manufactured by Sumika Bayer Urethane Co., Ltd., "TPA100" manufactured by Asahi Kasei Chemicals Corporation, and "BASONAT HI 100" manufactured by BASF Corporation. These commercially available products can be used either alone or in combination of two or more.

[0175] In one embodiment of the present disclosure, when the modified polyolefin resin composition of the present disclosure contains a polyisocyanate compound (F), the content of the polyisocyanate compound (F) may be such that the isocyanate groups (NCO) contained in the polyisocyanate compound (F) are generally in the range of 0.5 to 2.0 in terms of the NCO / OH equivalent ratio relative to the hydroxyl groups (OH) in the polyol component (C). <Other Curing Agents> The modified polyolefin resin composition of the present disclosure may contain a curing agent other than the polyisocyanate compound (F). Examples of other curing agents include amino resins, monomers or dimers of the above-mentioned isocyanate compounds, epoxy compounds, aziridine compounds, carbodiimide compounds, and oxazoline compounds. These may be used alone or in combination of two or more.

[0176] <Curing Catalyst> In one embodiment of the present disclosure, a curing catalyst can be used when curing the modified polyolefin resin composition of the present disclosure with the polyisocyanate compound (F). The use of the curing catalyst can accelerate the curing reaction. From the viewpoint of accelerating the curing reaction, the curing catalyst is preferably an organometallic catalyst containing at least one metal element selected from the group consisting of Bi, Zn, Al, Ti, Zr, and Sn.

[0177] Examples of organometallic catalysts containing Bi include bismuth carboxylic acid and bismuth carboxylate. Examples of organometallic catalysts containing Zn include zinc complex catalysts. Examples of organometallic catalysts containing Al include aluminum complex catalysts. Examples of organometallic catalysts containing Ti include titanium complex catalysts. Examples of organometallic catalysts containing Zr include zirconium chelate catalysts. Examples of organometallic catalysts containing Sn include dialkyltin dicarboxylates such as dibutyltin dilaurate, dioctyltin dilaurate, and dibutyltin diacetate; tin oxide compounds such as dibutyltin oxide; and tin carboxylates such as tin 2-ethylhexanoate.

[0178] Commercially available organometallic catalysts containing Bi include, for example, "K-KAT 348" and "K-KAT XK-640" manufactured by Kusumoto Chemicals Co., Ltd. Commercially available organometallic catalysts containing Zr include, for example, "K-KAT 4205", "K-KAT XC-9213", "K-KAT XC-A209", and "K-KAT 6212" manufactured by Kusumoto Chemicals Co., Ltd., and "Orgatix ZA and ZC series" manufactured by Matsumoto Fine Chemical Co., Ltd. Commercially available organometallic catalysts containing Al include, for example, "K-KAT 5218" manufactured by Kusumoto Chemicals Co., Ltd., and "Orgatix AL series" manufactured by Matsumoto Fine Chemical Co., Ltd. Commercially available organometallic catalysts containing Ti include, for example, "Orgatix TA and TC series" manufactured by Matsumoto Fine Chemical Co., Ltd. Commercially available organometallic catalysts containing Zn include, for example, K-KAT XK-314, K-KAT XK-635, K-KAT XK-639, and K-KAT XK-620 (all manufactured by Kusumoto Chemicals Co., Ltd.). Commercially available organometallic catalysts containing Sn include, for example, TVS TIN LAU (manufactured by Nitto Chemicals Co., Ltd.).

[0179] In one embodiment of the present disclosure, when a curing catalyst is used, the amount of the curing catalyst used is preferably 0.001 to 2.5 parts by mass, more preferably 0.05 to 2.0 parts by mass, even more preferably 0.1 to 1.5 parts by mass, and still more preferably 0.2 to 1.0 part by mass, relative to 100 parts by mass of the modified polyolefin resin composition.

[0180] <Surfactant> In one embodiment of the present disclosure, the modified polyolefin resin composition of the present disclosure may contain a surfactant within a range that does not impair the effects of the present disclosure. Examples of surfactants include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants. These surfactants can be used alone or in combination of two or more. Among these, from the viewpoint of further improving the stability of the modified polyolefin resin composition and the water resistance of the coating film obtained from the modified polyolefin resin composition, it is preferable to use a nonionic surfactant or anionic surfactant, and it is more preferable to use a nonionic surfactant.

[0181] Examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxypropylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxypropylene alkylphenyl ethers, polyoxyethylene styrenated phenyl ethers, polyoxypropylene styrenated phenyl ethers, polyoxyethylene fatty acid esters, polyoxypropylene fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxypropylene sorbitan fatty acid esters, polyoxyethylene lanolin alcohol ethers, polyoxypropylene lanolin alcohol ethers, polyoxyethylene lanolin fatty acid esters, polyoxypropylene lanolin fatty acid esters, (polyoxyethylene oxypropylene) block copolymers, etc. These can be used alone or in combination of two or more. Known commercially available products can be widely used as nonionic surfactants, such as the Emulmin series (manufactured by Sanyo Chemical Industries, Ltd.), the Noigen series (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), and the Brownon series (manufactured by Aoki Oil & Fat Industries Co., Ltd.).

[0182] Examples of anionic surfactants include higher alkyl sulfates, alkylaryl polyoxyethylene sulfates, higher fatty acid salts, alkylaryl sulfonates, and alkyl phosphates. These can be used alone or in combination of two or more. A wide variety of known commercially available anionic surfactants can be used, including, for example, the Neocol series (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) and the Hitenol series (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.).

[0183] In one embodiment of the present disclosure, when the modified polyolefin resin composition of the present disclosure contains a surfactant, the content of the surfactant is preferably 1 to 60 parts by mass, more preferably 3 to 40 parts by mass, and even more preferably 5 to 30 parts by mass, per 100 parts by mass of the acid-modified polyolefin resin (A), from the viewpoint of further improving the stability of the modified polyolefin resin composition and the water resistance of a coating film obtained from the modified polyolefin resin composition.

[0184] <Pigment> The coating composition of the present disclosure may contain a pigment. As the pigment, a color pigment, an extender pigment, a conductive pigment, etc. may be used.

[0185] Examples of coloring pigments include titanium oxide, carbon black, yellow lead, yellow ochre, Hansa Yellow, Pigment Yellow, Chrome Orange, Permanent Orange, Permanent Red, Fast Violet, Methyl Violet Lake, Prussian Blue, Cobalt Blue, Phthalocyanine Blue, Pigment Green, Naphthol Green, and aluminum paste, and these can be used alone or in combination of two or more.

[0186] Examples of extender pigments include barium sulfate, talc, silica, and calcium carbonate, and these can be used alone or in combination of two or more.

[0187] The conductive pigment is not particularly limited as long as it can impart conductivity to the coating film, and any shape such as particles, flakes, or fibers (including whiskers) can be used. Examples include conductive carbon, carbon nanotubes, carbon nanofibers, silver, nickel, copper, graphite, aluminum, antimony-doped tin oxide, phosphorus-doped tin oxide, acicular titanium oxide surface-coated with tin oxide / antimony, antimony oxide, zinc antimonate, and indium tin oxide, and these can be used alone or in combination of two or more.

[0188] <Various Additives> The modified polyolefin resin composition of the present disclosure may contain various additives as needed. Examples of the various additives include a tackifier, a film-forming aid, an antifoaming agent, an anti-sagging agent, a wetting agent, etc.

[0189] Examples of tackifiers include rosin, dammar, polymerized rosin, hydrogenated rosin, ester rosin, rosin-modified maleic acid resin, polyterpene-based resin, petroleum-based resin, cyclopentadiene-based resin, phenol-based resin, xylene-based resin, coumarone-indene-based resin, etc. These may be used alone or in combination of two or more.

[0190] In one embodiment of the present disclosure, when the modified polyolefin resin composition of the present disclosure contains a tackifier, the content of the tackifier is preferably 1 to 50 parts by mass, more preferably 10 to 25 parts by mass, per 100 parts by mass of the modified polyolefin resin composition.

[0191] <Organic Solvent> The modified polyolefin resin composition of the present disclosure may or may not contain an organic solvent. When the modified polyolefin resin composition of the present disclosure contains an organic solvent, it is preferable that the modified polyolefin resin composition of the present disclosure contain a small amount of organic solvent from the standpoint of environmental and hygienic aspects. In this case, the amount of organic solvent used is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, even more preferably 5 parts by mass or less, even more preferably 3 parts by mass or less, and particularly preferably 1 part by mass or less, per 100 parts by mass of the modified polyolefin resin composition of the present disclosure. When the modified polyolefin resin composition of the present disclosure contains an organic solvent, the viscosity of the modified polyolefin resin composition of the present disclosure is further reduced, thereby providing the benefit of improved coatability. When the modified polyolefin resin composition of the present disclosure does not contain an organic solvent, the modified polyolefin resin composition of the present disclosure can be suitably used as a base agent for a dual-cure binder, such as a solvent-free radical-cure binder and / or a solvent-free curable polyurethane binder. In the present disclosure, solvent-free means that no organic solvent is intentionally added to the modified polyolefin resin composition of the present disclosure, and an embodiment in which the organic solvent used in producing the acid-modified polyolefin resin (A) remains is included in the term solvent-free.

[0192] Examples of organic solvents include aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as hexane, heptane, octane, and decane; alicyclic hydrocarbons such as cyclohexane, cyclohexene, methylcyclohexane, and ethylcyclohexane; halogenated hydrocarbons such as trichloroethylene, dichloroethylene, chlorobenzene, and chloroform; alcohol solvents such as methanol, ethanol, isopropyl alcohol, butanol, pentanol, 1-hexanol, 2-ethylhexanol, 2-methylcyclohexanol, phenol, and 2-heptyl alcohol; acetone, methyl isobutyl ketone, methyl ethyl ketone, pentanone, hexanone, cyclohexanone, isophorone, Examples of such solvents include ketone solvents such as acetophenone, cellosolve solvents such as methyl cellosolve and ethyl cellosolve, ester solvents such as methyl acetate, ethyl acetate, butyl acetate, methyl propionate, ethyl propionate, and butyl formate, and ether solvents such as ethylene glycol mono-n-butyl ether, ethylene glycol mono-iso-butyl ether, ethylene glycol mono-tert-butyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol mono-iso-butyl ether, triethylene glycol mono-n-butyl ether, tetraethylene glycol mono-n-butyl ether, dibenzyl ether, diphenyl ether, and butylphenyl ether. These may be used alone or in combination of two or more.

[0193] <Method for Producing Modified Polyolefin Resin Composition> As an embodiment of the present disclosure, a wide variety of known methods can be used as a method for producing the modified polyolefin resin composition of the present disclosure, and examples thereof include the methods described in the following <Example 1>, <Example 2>, <Example 3>, and <Example 4>. <Example 1> Step (1-1): The acid-modified polyolefin resin (A) and the compound (B) having a polymerizable unsaturated group are placed in a mixer equipped with a heater and kneaded while heating. Step (1-2): The mixture is then cooled to room temperature, and the polyol component (C) is added and kneaded. The mixture is then filtered to obtain a modified polyolefin resin composition. <Example 2> Step (2-1): The acid-modified polyolefin resin (A), the compound (B) having a polymerizable unsaturated group, the polyol component (C), and the polyetheramine (D) are placed in a mixer equipped with a heater and kneaded while heating. Step (2-2): The mixture is then cooled to room temperature and filtered to obtain a modified polyolefin resin composition. Example 3 Step (3-1): The acid-modified polyolefin resin (A), the compound (B) having a polymerizable unsaturated group, and the polyol component (C) are placed in a mixer equipped with a heater and kneaded while heating. Step (3-2): The polyetheramine (D) is further added to the mixer and kneaded while heating. Step (3-3): The mixture is then cooled to room temperature and filtered to obtain a modified polyolefin resin composition. Example 4 Step (4-1): The acid-modified polyolefin resin (A), the compound (B) having a polymerizable unsaturated group, and the polyetheramine (D) are added and kneaded while heating. The mixture is then cooled to room temperature and filtered to obtain a modified polyolefin resin composition. Step (4-2): The acid-modified polyolefin resin (A), the polyol component (C), and the polyetheramine (D) are added and kneaded while heating. The mixture is then cooled to room temperature and filtered to obtain a modified polyolefin resin composition. Step (4-3): The modified polyolefin resin compositions obtained in Step (4-1) and Step (4-2) are mixed to obtain a modified polyolefin resin composition.

[0194] In the above <Example 1>, <Example 2>, <Example 3> and <Example 4>, the temperature during kneading is usually 20 to 200°C, preferably 40 to 150°C, and more preferably 60 to 120°C. In the above <Example 1>, <Example 2>, <Example 3> and <Example 4>, the kneading time varies depending on the heating temperature and the like, but is usually 10 to 120 minutes, preferably 15 to 90 minutes, and more preferably 20 to 60 minutes. Kneading can be carried out, for example, under a nitrogen atmosphere to remove moisture.

[0195] In the above <Example 1>, <Example 2>, <Example 3> and <Example 4>, filtration can be carried out using, for example, a wire mesh with an opening of 50 μm to 300 μm, and may be carried out under a nitrogen atmosphere to remove moisture.

[0196] The cured product of the present disclosure is a cured product obtained by curing the modified polyolefin resin composition of the present disclosure. In other words, the cured product is a product obtained by curing the modified polyolefin resin composition of the present disclosure. Hereinafter, the cured product will be simply referred to as the "cured product of the present disclosure."

[0197] <Applications of the Present Disclosure> The modified polyolefin resin composition of the present disclosure contains a compound (B) having a polymerizable unsaturated group that can be radically polymerized by light or heat, and a polyol component (C) that reacts with a curing agent by heat, and therefore is capable of dual curing by light or heat. Therefore, the cured product of the present disclosure can be suitably used in various applications.

[0198] The modified polyolefin resin composition of the present disclosure and the cured product of the present disclosure can be suitably used for polyolefin substrates. Examples of polyolefin substrates include polyolefins processed into blocks (plates, rods, spheres, etc.), sheets, films, yarns, fabrics (woven fabrics, knitted fabrics, nonwoven fabrics, etc.), etc. Among these polyolefin substrates, sheets and films are preferred from the viewpoint of manufacturing. Films with a thickness of 5 μm to 100 μm can be used. Examples of polyolefins include polypropylene, polyethylene, ethylene-propylene copolymers, ethylene-propylene-diene copolymers, polybutene, poly(4-methyl-1-pentene), etc. The modified polyolefin resin composition of the present disclosure and the cured product of the present disclosure can be particularly suitably used for polypropylene substrates.

[0199] The modified polyolefin resin composition of the present disclosure and the cured product of the present disclosure can be suitably used in paints for molded articles, inks, adhesives, sealants, primers, coating agents, paints for in-mold coating, etc. The modified polyolefin resin composition of the present disclosure and the cured product of the present disclosure can be particularly suitably used in inks for polyolefin substrates, adhesives for polyolefin substrates, primers for polyolefin substrates, paints for polyolefin substrates, and in-mold coating paints for polyolefin substrates.

[0200] A coating film can be obtained from the modified polyolefin resin composition of the present disclosure, and the coating film can be particularly suitably used for metal products, electronic devices, packaging materials, automobile parts, and the like.

[0201] Examples of methods for forming a coating film from the modified polyolefin resin composition of the present disclosure include a method in which the modified polyolefin resin composition of the present disclosure is uniformly applied to the surface of various substrates and then subjected to a heat treatment (e.g., baking treatment, etc.). This allows for the formation of a uniform coating film on the surface of various substrates. Examples of coating methods include gravure coating, curtain flow coating, Mayer bar coating, dip coating, brush coating, roll coating, and spray coating. The amount of the modified polyolefin resin composition applied to the substrate is not particularly limited and is selected appropriately depending on the application. Preferably, the dried coating film has a thickness in the range of 1 μm to 100 μm. Heat treatment can be performed using a hot air circulating oven, an infrared heater, or the like. Another method includes molding a plastic substrate in a mold, injecting the modified polyolefin resin composition of the present disclosure between the mold and the substrate, and applying heat and pressure to form a coating film. The heating temperature is typically 60 to 200°C. The heating time is typically 15 seconds to 20 minutes.

[0202] The present disclosure provides the following aspects. Item 1. A modified polyolefin resin composition containing an acid-modified polyolefin resin (A), a compound (B) having a polymerizable unsaturated group, and a polyol component (C). Item 2. The modified polyolefin resin composition according to Item 1, further containing a polyetheramine (D). Item 3. The modified polyolefin resin composition according to Item 1 or 2, wherein the content of the acid-modified polyolefin resin (A) is 5 to 100 parts by mass per 100 parts by mass of the compound (B) having a polymerizable unsaturated group and the polyol component (C). Item 4. The modified polyolefin resin composition according to any one of Items 1 to 3, wherein the content of the compound (B) having a polymerizable unsaturated group is 1 to 99 parts by mass per 100 parts by mass of the compound (B) having a polymerizable unsaturated group and the polyol component (C). Item 5. Item 6. The modified polyolefin resin composition according to any one of Items 1 to 4, wherein the compound (B) having a polymerizable unsaturated group has an alkyleneoxy group. Item 7. The modified polyolefin resin composition according to any one of Items 1 to 5, wherein the compound (B) having a polymerizable unsaturated group has a hydroxyl group. Item 8. The modified polyolefin resin composition according to any one of Items 1 to 6, wherein the polyol component (C) comprises at least one polyol selected from the group consisting of polyether polyols, polyacrylate polyols, polyester polyols, polycaprolactone polyols, polycarbonate polyols, castor oil-modified polyols, polyolefin polyols, and polyhydric alcohols. Item 9. The modified polyolefin resin composition according to any one of Items 1 to 7, further comprising a radical polymerization initiator (E). Item 10. The modified polyolefin resin composition according to any one of Items 1 to 8, further comprising a polyisocyanate compound (F). Item 11. Item 10. The modified polyolefin resin composition according to any one of Items 1 to 9, wherein the acid value of the α,β-unsaturated carboxylic acid or anhydride component thereof in the acid-modified polyolefin resin (A) is preferably 1 to 100 mgKOH / g, more preferably 5 to 50 mgKOH / g, still more preferably 10 to 40 mgKOH / g, and even more preferably 15 to 30 mgKOH / g.Item 11. The modified polyolefin resin composition according to any one of Items 1 to 10, wherein the weight average molecular weight of the acid-modified polyolefin resin (A) is preferably 3,000 to 200,000, more preferably 10,000 to 150,000, even more preferably 20,000 to 120,000, still more preferably 30,000 to 100,000, and particularly preferably 40,000 to 90,000. Item 12. The modified polyolefin resin composition according to any one of Items 1 to 11, wherein the content of the acid-modified polyolefin resin (A) is preferably 10 to 150 parts by mass, more preferably 12 to 60 parts by mass, even more preferably 15 to 40 parts by mass, and even more preferably 18 to 35 parts by mass, per 100 parts by mass of the compound (B) having a polymerizable unsaturated group. Item 13. Item 14. The modified polyolefin resin composition according to any one of Items 1 to 13, wherein the content of the acid-modified polyolefin resin (A) is preferably 3 to 50 mass%, more preferably 7 to 45 mass%, even more preferably 10 to 40 mass%, and even more preferably 15 to 35 mass%, relative to the total mass of the modified polyolefin resin composition. Item 15. The modified polyolefin resin composition according to any one of Items 1 to 13, wherein the content of the acid-modified polyolefin resin (A) is more preferably 10 to 85 parts by mass, even more preferably 15 to 60 parts by mass, even more preferably 20 to 50 parts by mass, even more preferably 21 to 40 parts by mass, and particularly preferably 22 to 30 parts by mass, relative to 100 parts by mass of the total of the compound (B) having a polymerizable unsaturated group and the polyol component (C). Item 15. Item 15. The acid-modified polyolefin resin (A) is a graft polymer having a structure in which an α,β-unsaturated carboxylic acid or an acid anhydride thereof is graft polymerized onto a polyolefin resin. Modified polyolefin resin composition according to any one of Items 1 to 14.Item 16. The modified polyolefin resin composition according to Item 15, wherein the polyolefin resin is preferably at least one selected from the group consisting of homopolypropylene, propylene-α-olefin copolymer, homopolyethylene, ethylene-α-olefin copolymer, homopoly-1-butene, and 1-butene-α-olefin copolymer, more preferably homopolypropylene and / or propylene-α-olefin copolymer, even more preferably propylene-α-olefin copolymer, particularly preferably propylene-ethylene copolymer or propylene-1-butene copolymer, most preferably propylene-1-butene copolymer. Item 17. The modified polyolefin resin composition according to Item 16, wherein the content of the propylene component in the propylene-α-olefin copolymer is preferably 50 mol% or more, more preferably 60 mol% or more, even more preferably 65 mol% or more, and particularly preferably 70 mol%. Item 18. Item 19. The modified polyolefin resin composition according to any one of Items 15 to 17, wherein the α-olefin is ethylene, 1-butene, isobutene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, or 1-eicosene. Item 20. The modified polyolefin resin composition according to any one of Items 15 to 18, wherein the α,β-unsaturated carboxylic acid or its acid anhydride is preferably maleic acid, maleic anhydride, or itaconic anhydride, more preferably maleic acid or maleic anhydride. Item 20. The modified polyolefin resin composition according to any one of Items 1 to 19, wherein the content of the compound (B) having a polymerizable unsaturated group is preferably 5 to 80 mass%, more preferably 15 to 75 mass%, even more preferably 30 to 70 mass%, and still more preferably 40 to 68 mass%, relative to the total mass of the modified polyolefin resin composition.Item 21. The modified polyolefin resin composition according to any one of Items 1 to 20, wherein the content of the compound (B) having a polymerizable unsaturated group is more preferably 10 to 97 parts by mass, even more preferably 20 to 95 parts by mass, and even more preferably 35 to 93 parts by mass, per 100 parts by mass of the total of the compound (B) having a polymerizable unsaturated group and the polyol component (C). Item 22. The modified polyolefin resin composition according to any one of Items 1 to 21, wherein the polymerizable unsaturated group is more preferably at least one selected from the group consisting of an acryloyl group, a methacryloyl group, an acryloyloxy group, and a methacryloyloxy group, even more preferably at least one selected from the group consisting of an acryloyl group, an acryloyloxy group, and a methacryloyloxy group, and particularly preferably an acryloyl group or an acryloyloxy group. Item 23. Item 23. The modified polyolefin resin composition according to any one of Items 1 to 22, wherein the compound (B) having a polymerizable unsaturated group comprises one or more compounds represented by Formula 1 of the present disclosure. Item 24. The modified polyolefin resin composition according to any one of Items 1 to 23, wherein the compound (B) having a polymerizable unsaturated group preferably has one or two hydroxyl groups, more preferably one hydroxyl group. Item 25. The modified polyolefin resin composition according to any one of Items 1 to 24, wherein the number average molecular weight (Mn) of the compound (B) having a polymerizable unsaturated group is preferably 100 or more and 3,000 or less, more preferably 120 or more and 2,000 or less, and even more preferably 140 or more and 1,000 or less.Item 26. The compound (B) having a polymerizable unsaturated group more preferably includes at least one selected from the group consisting of a compound having one acryloyl group, a compound having one acryloyloxy group, and a compound having two acryloyloxy groups, and even more preferably includes at least one selected from the group consisting of a compound having one acryloyl group and a morpholine group, a compound having one acryloyloxy group and an isobornyl group, a compound having one acryloyloxy group and one hydroxyl group, a compound having one acryloyloxy group, one hydroxyl group, and one phenyl group, and a compound having two acryloyloxy groups. Item 26. The modified polyolefin resin composition according to any one of Items 1 to 25, particularly preferably containing at least one compound selected from the group consisting of a compound having one acryloyl group and a morpholine group, a compound having one acryloyloxy group and an isobornyl group, a compound having one acryloyloxy group and a hydroxyl group at a terminal of a side chain, a compound having one acryloyloxy group, one hydroxyl group and a phenyl group at a terminal of a side chain, and a compound having two acryloyloxy groups, and most preferably containing at least one compound selected from the group consisting of dipropylene glycol diacrylate, polyethylene glycol diacrylate, 4-hydroxybutyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, acryloylmorpholine, and isobornyl acrylate. Item 27. The modified polyolefin resin composition according to any one of Items 1 to 26, wherein the polyol component (C) does not contain a polymerizable unsaturated group. Item 28. Item 28. The modified polyolefin resin composition according to any one of Items 1 to 27, wherein the polyol component (C) preferably contains a polyol having a number average molecular weight (Mn) of 60 or more and 5,000 or less, more preferably a polyol having an Mn of 80 or more and 2,000 or less, even more preferably a polyol having an Mn of 110 or more and 1,500 or less, and even more preferably a polyol having an Mn of 150 or more and 1,000 or less.Item 29. The modified polyolefin resin composition according to any one of Items 1 to 28, wherein the polyol component (C) preferably contains a polyol having a hydroxyl value of 50 to 1000 mgKOH / g, more preferably a polyol having a hydroxyl value of 100 to 800 mgKOH / g, even more preferably a polyol having a hydroxyl value of 150 to 700 mgKOH / g, and even more preferably a polyol having a hydroxyl value of 200 to 600 mgKOH / g. Item 30. The modified polyolefin resin composition according to any one of Items 1 to 29, wherein the content of the polyol component (C) is preferably 2 to 90 mass%, more preferably 3 to 60 mass%, even more preferably 4 to 30 mass%, particularly preferably 5 to 25 mass%, and most preferably 6 to 20 mass%, relative to the total mass of the modified polyolefin resin composition. Item 31. 31. The modified polyolefin resin composition according to any one of Items 1 to 30, wherein the polyol component (C) more preferably comprises at least one polyol selected from the group consisting of polypropylene glycol, polyether polyol, polyester polyol, polyacrylate polyol, polycaprolactone polyol, polycarbonate polyol, and polyhydric alcohol; even more preferably comprises at least one polyol selected from the group consisting of polypropylene glycol, polyether polyol, polyester polyol, polycaprolactone polyol, polycarbonate polyol, and polyhydric alcohol; still more preferably comprises at least one polyol selected from the group consisting of polypropylene glycol, polyester polyol, polyacrylate polyol, polycaprolactone polyol, polycarbonate polyol, and polyhydric alcohol; particularly preferably comprises at least one polyol selected from the group consisting of polypropylene glycol, polyester polyol, polycaprolactone polyol, and polycarbonate polyol; and most preferably comprises polypropylene glycol and polyester polyol; polypropylene glycol and polycaprolactone polyol; or polypropylene glycol and polycarbonate polyol.Item 32. The modified polyolefin resin composition according to any one of Items 2 to 31, wherein the content of polyetheramine (D) is preferably 6 to 100 parts by mass, more preferably 10 to 90 parts by mass, even more preferably 15 to 80 parts by mass, even more preferably 20 to 70 parts by mass, particularly preferably 25 to 60 parts by mass, and most preferably 30 to 55 parts by mass, relative to 100 parts by mass of the acid-modified polyolefin resin (A). Item 33. The modified polyolefin resin composition according to any one of Items 2 to 32, wherein the content of polyetheramine (D) is preferably 0.5 to 40% by mass, more preferably 1 to 35% by mass, even more preferably 2 to 30% by mass, even more preferably 5 to 25% by mass, and particularly preferably 6 to 20% by mass, relative to the total mass of the modified polyolefin resin composition. Item 34. Item 34. The modified polyolefin resin composition according to any one of Items 2 to 33, wherein the total content of the acid-modified polyolefin resin (A), the compound having a polymerizable unsaturated group (B), the polyol component (C), and the polyetheramine (D) is preferably 80% by mass or more, more preferably 85% by mass or more, even more preferably 90% by mass or more, even more preferably 95% by mass or more, still more preferably 97.5% by mass or more, and particularly preferably 99% by mass or more, relative to the total mass of the modified polyolefin resin composition. Item 35. The modified polyolefin resin composition according to any one of Items 2 to 34, wherein the polyetheramine (D) is a compound represented by Formula 2A of the present disclosure. Item 36. Item 36. The modified polyolefin resin composition according to any one of Items 2 to 35, wherein the polyetheramine (D) preferably has a primary amino group or a secondary amino group at one end and a weight average molecular weight (Mw) of 200 to 50,000, more preferably has a primary amino group or a secondary amino group at one end and a weight average molecular weight (Mw) of 200 to 10,000, and even more preferably has a primary amino group at one end and a weight average molecular weight (Mw) of 500 to 5,000. Item 37. The modified polyolefin resin composition according to any one of Items 2 to 36, wherein the HLB value of the polyetheramine (D) is preferably 2 to 20, more preferably 5 to 19, and even more preferably 8 to 18.Item 38. The modified polyolefin resin composition according to any one of Items 8 to 37, wherein the content of the radical polymerization initiator (E) is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, and even more preferably 2 to 5 parts by mass, per 100 parts by mass of the modified polyolefin resin composition. Item 39. The modified polyolefin resin composition according to any one of Items 9 to 38, wherein the equivalent ratio of isocyanate groups in the polyisocyanate compound (F) to hydroxyl groups in the polyol component (C) [isocyanate groups in the polyisocyanate compound (F) / hydroxyl groups in the polyol component (C)] is 0.5 to 2.0. Item 40. A cured product obtained by curing the modified polyolefin resin composition according to any one of Items 1 to 39. Item 41. An ink comprising the modified polyolefin resin composition according to any one of Items 1 to 39 or the cured product according to Item 40. Item 42. Item 42. An adhesive comprising the modified polyolefin resin composition according to any one of items 1 to 39 or the cured product according to item 40. Item 43. A primer comprising the modified polyolefin resin composition according to any one of items 1 to 39 or the cured product according to item 40. Item 44. A paint comprising the modified polyolefin resin composition according to any one of items 1 to 39 or the cured product according to item 40. Item 45. A paint for in-mold coating comprising the modified polyolefin resin composition according to any one of items 1 to 39 or the cured product according to item 40.

[0203] The present disclosure will be described in more detail below based on examples, but the present disclosure is not limited to these examples. In the following examples and comparative examples, "room temperature" means a temperature within the range of 20°C to 25°C.

[0204] (1) Measurement of weight-average molecular weight (Mw) by high-temperature GPC Measurement was performed using orthodichlorobenzene as a solvent and a Waters GPC150-C Plus model at 140°C. (Column: "GMH6-HT" + "GMH6-HTL" manufactured by Tosoh Corporation.) The weight-average molecular weight (Mw) was calculated using polystyrene of known molecular weight as a standard substance.

[0205] (2) Measurement of melting point by differential scanning calorimetry (DSC) In accordance with JIS K 7121-2012, a DSC measuring device (manufactured by Seiko Instruments Inc.) was used. Approximately 5 mg of a sample was heated to 150°C for 10 minutes and kept in a melted state, then cooled at a rate of 10°C / min, stabilized at -50°C, and further heated to 150°C at a rate of 10°C / min to melt, at which point the melting peak temperature was measured, and the melting peak temperature was evaluated as the melting point.

[0206] (Production Example 1) 280 g of propylene-1-butene copolymer (propylene content: 70 mol%, 1-butene content: 30 mol%), 38 g of maleic anhydride, 7 g of dicumyl peroxide, and 420 g of toluene were added to an autoclave equipped with a stirrer. After approximately 5 minutes of nitrogen substitution, the reaction was carried out at 140°C for 5 hours with heating and stirring. After completion of the reaction, the reaction solution was poured into a large amount of methyl ethyl ketone to precipitate a resin. This resin was further washed several times with methyl ethyl ketone to remove unreacted maleic anhydride. The resulting resin was dried under reduced pressure to obtain a solid acid-modified polyolefin resin (MPO-1). Infrared absorption spectroscopy revealed that the total content of maleic anhydride and maleic acid components in MPO-1 was 1.6% by mass, and the acid values ​​of the maleic anhydride and maleic acid components were 17.9 mgKOH / g. The weight average molecular weight (Mw) of MPO-1 measured by high-temperature GPC was 75,000, and the melting point measured by DSC was 70°C.

[0207] (Production Example 2) 280 g of propylene-1-butene copolymer (propylene component content = 70 mol%, 1-butene component content: 30 mol%), 62 g of maleic anhydride, 12 g of tert-butylperoxyisopropyl carbonate, and 420 g of toluene were added to an autoclave equipped with a stirrer. After approximately 5 minutes of nitrogen substitution, the reaction was carried out at 140°C for 5 hours with heating and stirring. After completion of the reaction, the reaction solution was poured into a large amount of methyl ethyl ketone to precipitate a resin. This resin was further washed several times with methyl ethyl ketone to remove unreacted maleic anhydride. The resulting resin was dried under reduced pressure to obtain a solid acid-modified polyolefin resin (MPO-2). Infrared absorption spectroscopy revealed that the total content of maleic anhydride and maleic acid components in MPO-2 was 2.0% by mass, and the acid values ​​of the maleic anhydride and maleic acid components were 22.4 mgKOH / g. The weight average molecular weight (Mw) of MPO-2 measured by high-temperature GPC was 90,000, and the melting point measured by DSC was 70°C.

[0208] (Production Example 3) 280 g of propylene-1-butene copolymer (propylene component content = 70 mol%, 1-butene component content: 30 mol%), 70 g of maleic anhydride, 12 g of di-tert-butyl peroxide, and 420 g of toluene were added to an autoclave equipped with a stirrer. After approximately 5 minutes of nitrogen substitution, the reaction was carried out at 140°C for 5 hours with heating and stirring. After completion of the reaction, the reaction solution was poured into a large amount of methyl ethyl ketone to precipitate a resin. This resin was further washed several times with methyl ethyl ketone to remove unreacted maleic anhydride. The resulting resin was dried under reduced pressure to obtain a solid acid-modified polyolefin resin (MPO-3). Infrared absorption spectroscopy revealed that the total content of maleic anhydride and maleic acid components in MPO-3 was 2.5% by mass, and the acid values ​​of the maleic anhydride and maleic acid components were 28.0 mgKOH / g. The weight average molecular weight (Mw) of MPO-2 measured by high-temperature GPC was 50,000, and the melting point measured by DSC was 67°C.

[0209] (Production Example 4) 280 g of propylene-1-butene copolymer (propylene component content = 70 mol%, 1-butene component content: 30 mol%), 20 g of maleic anhydride, 12 g of di-tert-butyl peroxide, and 420 g of toluene were added to an autoclave equipped with a stirrer, and after approximately 5 minutes of nitrogen substitution, the reaction was carried out at 140°C for 5 hours with heating and stirring. After completion of the reaction, the reaction solution was poured into a large amount of methyl ethyl ketone to precipitate a resin. This resin was further washed several times with methyl ethyl ketone to remove unreacted maleic anhydride. The resulting resin was dried under reduced pressure to obtain a solid acid-modified polyolefin resin (MPO-4). Infrared absorption spectroscopy revealed that the total content of maleic anhydride and maleic acid components in MPO-4 was 0.8% by mass, and the acid values ​​of the maleic anhydride and maleic acid components were 9.0 mgKOH / g. The weight average molecular weight (Mw) of MPO-4 measured by high-temperature GPC was 100,000, and the melting point measured by DSC was 73°C.

[0210] (Production Example 5) 280 g of propylene-1-butene copolymer (propylene component content = 70 mol%, 1-butene component content: 30 mol%), 62 g of maleic anhydride, 24 g of di-tert-butyl peroxide, and 420 g of toluene were added to an autoclave equipped with a stirrer. After approximately 5 minutes of nitrogen substitution, the mixture was reacted at 160°C for 5 hours with heating and stirring. After completion of the reaction, the reaction solution was poured into a large amount of methyl ethyl ketone to precipitate a resin. This resin was further washed several times with methyl ethyl ketone to remove unreacted maleic anhydride. The resulting resin was dried under reduced pressure to obtain a solid acid-modified polyolefin resin (MPO-5). Infrared absorption spectroscopy revealed that the total content of maleic anhydride and maleic acid components in MPO-5 was 2.0% by mass, and the acid values ​​of the maleic anhydride and maleic acid components were 22.4 mgKOH / g. The weight average molecular weight (Mw) of MPO-5 measured by high-temperature GPC was 31,000, and the melting point measured by DSC was 65°C.

[0211] (Materials Used) The materials used in the examples and comparative examples are as follows. <Acid-Modified Polyolefin Resin (A)> MPO-1 obtained in Production Example 1 (total content of maleic anhydride component and maleic acid component=1.6% by mass, Mw measured by high-temperature GPC=75,000, melting point by DSC=70°C) MPO-2 obtained in Production Example 2 (total content of maleic anhydride component and maleic acid component=2.0% by mass, Mw measured by high-temperature GPC=90,000, melting point by DSC=70°C) MPO-3 obtained in Production Example 3 (total content of maleic anhydride component and maleic acid component=2.5% by mass, Mw measured by high-temperature GPC=50,000, melting point by DSC=67°C) MPO-4 obtained in Production Example 4 (total content of maleic anhydride component and maleic acid component=0.8% by mass, Mw measured by high-temperature GPC=100,000, melting point by DSC=73°C) MPO-5 obtained in Production Example 5 (total content of maleic anhydride component and maleic acid component=2.0% by mass, Mw measured by high-temperature GPC=31,000, melting point measured by DSC=65° C.) <Compound (B) having a polymerizable unsaturated group> Dipropylene glycol diacrylate (Mn=242) (manufactured by Tokyo Chemical Industry Co., Ltd.) Polyethylene glycol diacrylate (Mn=302) (manufactured by NOF Corporation) 4-hydroxybutyl acrylate (Mn=144) (manufactured by Tokyo Chemical Industry Co., Ltd.) 2-hydroxy-3-phenoxypropyl acrylate (Mn=222) (manufactured by Tokyo Chemical Industry Co., Ltd.) Acryloylmorpholine (Mn=141) (manufactured by Tokyo Chemical Industry Co., Ltd.) Isobornyl acrylate (Mn=208) (manufactured by Tokyo Chemical Industry Co., Ltd.) <Polyol component (C)> Polypropylene glycol (Mn=400, hydroxyl value=280 mgKOH / g) (manufactured by Sanyo Chemical Industries, Ltd.) Polyester polyol (Mn=500, hydroxyl value=224 mgKOH / g) (manufactured by Kuraray Co., Ltd.) Polycaprolactone polyol (Mn=530, hydroxyl value=212 mgKOH / g) (manufactured by Daicel Corporation) Polycarbonate polyol (Mn=500, hydroxyl value=224 mgKOH / g) (manufactured by Kuraray Co., Ltd.) <Polyetheramine (D)> "JEFFAMINE M-2070 (Mw=2000, HLB value=13.8)" (number of primary amino groups=1, number of secondary amino groups=0) manufactured by HUNTSMANCLARIANT "GENAMIN M41 / 2000 (Mw = 2000, HLB value = 14.8)" (number of primary amino groups = 1, number of secondary amino groups = 0)

[0212] Example 1 (Production of Modified Polyolefin Resin Composition (a)) To a 200-milliliter four-neck flask equipped with a condenser, a thermometer, and a stirrer were added 20 g of the MPO-1 obtained in Production Example 1 as the acid-modified polyolefin resin (A), 45 g of dipropylene glycol diacrylate, 10 g of polyethylene glycol diacrylate, and 10 g of 4-hydroxybutyl acrylate as the compound having a polymerizable unsaturated group (B), 4 g of polypropylene glycol (Mn=400) and 3 g of polyester polyol as the polyol component (C), and 8 g of "JEFFAMINE M-2070" manufactured by HUNTSMAN as the polyetheramine (D), and the mixture was stirred at 90°C for 1 hour. Thereafter, the mixture was cooled to room temperature and filtered through a wire mesh with 154 μm mesh openings, to obtain a modified polyolefin resin composition (a).

[0213] Examples 2 to 13 Modified polyolefin resin compositions (b) to (m) were obtained in the same manner as in Example 1, except that the amounts and types of the acid-modified polyolefin (A), the compound having a polymerizable unsaturated group (B), the polyol component (C), and the polyetheramine (D) used were changed as shown in Table 1 below.

[0214] Example 14 (Production of Modified Polyolefin Resin Composition (n)) To a 200-milliliter four-neck flask equipped with a condenser, a thermometer, and a stirrer, 20 g of MPO-5 obtained in Production Example 1 as the acid-modified polyolefin resin (A), 64 g of isobornyl acrylate as the compound (B) having a polymerizable unsaturated group, 10 g of polypropylene glycol (Mn=400) as the polyol component (C), and 6 g of polyester polyol were added and stirred at 90°C for 1 hour. The mixture was then cooled to room temperature and filtered through a wire mesh with 154 μm openings to obtain a modified polyolefin resin composition (n). Note that in Example 14, polyetheramine (D) was not used.

[0215] Comparative Example 1 (Production of Resin Composition (o)) A 200-milliliter four-neck flask equipped with a condenser, thermometer, and stirrer was charged with 24 g of dipropylene glycol diacrylate, 6 g of polyethylene glycol diacrylate, and 6 g of 4-hydroxybutyl acrylate as the compound (B) having a polymerizable unsaturated group, and 20 g of polypropylene glycol (Mn=400) and 16 g of polyester polyol as the polyol component (C). The internal temperature was raised to 90°C, and dissolution was carried out by heating for 1 hour. The mixture was then cooled to room temperature and filtered through a wire mesh with 154 μm openings to obtain a resin composition (o). In Comparative Example 1, no acid-modified polyolefin resin (A) was used.

[0216] Comparative Example 2 (Production of Modified Polyolefin Resin Composition (p)) A 200-milliliter four-neck flask equipped with a condenser, thermometer, and stirrer was charged with 20 g of the MPO-1 obtained in Production Example 1 as the acid-modified polyolefin resin (A), and 45 g of dipropylene glycol diacrylate, 10 g of polyethylene glycol diacrylate, 10 g of 4-hydroxybutyl acrylate, and 8 g of polyetheramine (D) as the compound (B) having a polymerizable unsaturated group, and the internal temperature was raised to 90°C, followed by heating and dissolution for 1 hour. The mixture was then cooled to room temperature and filtered through a wire mesh with 154 μm openings to obtain a resin composition (p). In Comparative Example 2, no polyol component (C) was used.

[0217] Comparative Example 3 (Production of Modified Polyolefin Resin Composition (q)) A 200-milliliter four-neck flask equipped with a condenser, thermometer, and stirrer was charged with 20 g of the MPO-5 obtained in Production Example 1 as the acid-modified polyolefin resin (A), and 40 g of polypropylene glycol (Mn=400), 32 g of polyester polyol, and 8 g of polyether amine (D) as the polyol component (C), and the internal temperature was heated to 90°C, followed by heating and dissolution for 1 hour. The mixture was then cooled to room temperature and filtered through a wire mesh with 149 μm openings to obtain a resin composition (q). In Comparative Example 3, the compound (B) having a polymerizable unsaturated group was not used.

[0218] (1) Evaluation of fluidity at 25°C and 80°C The modified polyolefin resin compositions obtained in the examples and the resin compositions obtained in the comparative examples were visually evaluated for fluidity at 25°C and 80°C immediately after production, the next day (24 hours after production) at 25°C and 80°C, and one week later (168 hours after production) at 25°C and 80°C. A case where fluidity was present one week later was evaluated as ○, a case where fluidity was present only immediately after production was evaluated as △, and a case where no fluidity was present from immediately after production was evaluated as ×.

[0219] (2) Evaluation of Adhesion 5 g of the modified polyolefin resin composition obtained in the Examples or 5 g of the resin composition obtained in the Comparative Examples was added with 2% of tert-butyl-2-ethylperoxyhexanoate as a radical polymerization initiator, and Sumidur N3300, a polyisocyanate compound manufactured by Sumika Bayer Urethane Co., Ltd., which is an isocyanurate-modified hexamethylene diisocyanate, in an amount to give an NCO / OH equivalent ratio of 1.2. 0.6 equivalents of dibutyltin dilaurate as a curing catalyst relative to the polyol component (C) were added and stirred for 30 seconds at room temperature using a magnetic stirrer. The resulting mixture was applied to a PP (polypropylene) bumper substrate washed with isopropyl alcohol at room temperature and baked at 110 ° C for 1 minute to obtain a cured coating film with a film thickness of 300 μm. The mixture was then left for 72 hours in an atmosphere of 25 ° C and 60% relative humidity to prepare a test plate. One hundred squares were made on this test plate at 1 mm intervals, reaching down to the substrate, and cellophane tape was pressed onto them and peeled off three times at an angle of 90 degrees to the coated surface. If no peeling occurred after three peeling attempts, it was evaluated as ○, if peeling occurred on the third peeling attempt, it was evaluated as △, and if peeling occurred on the first or second peeling attempt, it was evaluated as ×.

[0220] (3) Evaluation of Water Resistance Test plates were prepared in the same manner as in the evaluation of adhesion in (2), and the resulting test plates were immersed in 40°C warm water for 10 days (240 hours). After immersion, 100 grids were made on the test plate at 1 mm intervals, reaching down to the substrate, and cellophane tape was pressed onto the grids and peeled off three times at an angle of 90 degrees to the coating surface. Evaluation was performed with a circle if no peeling occurred after three peeling attempts, a triangle if peeling occurred after the third peeling attempt, and an x ​​if peeling occurred after the first or second peeling attempt.

[0221] (4) Evaluation of Flex Resistance Test plates were prepared in the same manner as in the evaluation of adhesion in (2). Among the methods in accordance with JIS K 5600-5-1:1999 (flex resistance), the bending of the test plate was changed to a 90° bending, and a φ20 mm cylindrical mandrel was used to conduct a flex resistance test, and the flex resistance of the test plate was evaluated based on the following criteria: ○: No cracks occurred when bent at 90° △: Cracks occurred when bent at 45° or more and less than 90° ×: Cracks occurred when bent at 1° or more and less than 45°

[0222] The evaluation results of each example and each comparative example are shown in Table 1 below.

[0223]

[0224] [Discussion of the results in Table 1] The modified polyolefin resin compositions (a) to (n) obtained in Examples 1 to 14 were shown to maintain fluidity immediately after production at both 25°C and 80°C. Furthermore, the dual cured products of the modified polyolefin resin compositions (a) to (n) obtained in Examples 1 to 14 were shown to have excellent adhesion to a PP (polypropylene) bumper substrate. Furthermore, the dual cured products of the modified polyolefin resin compositions (a) to (n) obtained in Examples 1 to 14 were shown to have good water resistance. Furthermore, the dual cured products of the modified polyolefin resin compositions (a) to (n) obtained in Examples 1 to 14 were shown to have excellent flex resistance.

[0225] On the other hand, the resin composition (o) obtained in Comparative Example 1 did not use the acid-modified polyolefin resin (A), and therefore the adhesion and water resistance were significantly inferior. The modified polyolefin resin composition (p) obtained in Comparative Example 2 did not use the polyol component (C), and therefore the flex resistance was significantly inferior. The modified polyolefin resin composition (q) obtained in Comparative Example 3 did not use the compound (B) having a polymerizable unsaturated group, and therefore the water resistance was poor.

Claims

1. A modified polyolefin resin composition containing an acid-modified polyolefin resin (A), a compound having a polymerizable unsaturated group (B), and a polyol component (C).

2. The modified polyolefin resin composition according to claim 1, further comprising a polyetheramine (D).

3. The modified polyolefin resin composition according to claim 1, wherein the content of the acid-modified polyolefin resin (A) is 5 to 100 parts by mass per 100 parts by mass of the total of the compound (B) having a polymerizable unsaturated group and the polyol component (C).

4. The modified polyolefin resin composition according to claim 1, wherein the content of the compound (B) having a polymerizable unsaturated group is 1 to 99 parts by mass per 100 parts by mass of the total of the compound (B) having a polymerizable unsaturated group and the polyol component (C).

5. The modified polyolefin resin composition according to claim 1, wherein the compound (B) having a polymerizable unsaturated group has an alkyleneoxy group.

6. The modified polyolefin resin composition according to claim 1, wherein the compound (B) having a polymerizable unsaturated group has a hydroxyl group.

7. The modified polyolefin resin composition according to claim 1, wherein the polyol component (C) comprises at least one polyol selected from the group consisting of polyether polyols, polyacrylate polyols, polyester polyols, polycaprolactone polyols, polycarbonate polyols, castor oil-modified polyols, polyolefin polyols, and polyhydric alcohols.

8. The modified polyolefin resin composition according to claim 1, further comprising a radical polymerization initiator (E).

9. The modified polyolefin resin composition according to claim 1, further comprising a polyisocyanate compound (F).

10. A cured product obtained by curing the modified polyolefin resin composition according to any one of claims 1 to 9.

11. An ink containing the modified polyolefin resin composition according to any one of claims 1 to 9.

12. An adhesive containing the modified polyolefin resin composition according to any one of claims 1 to 9.

13. A primer containing the modified polyolefin resin composition according to any one of claims 1 to 9.

14. A paint containing the modified polyolefin resin composition according to any one of claims 1 to 9.

15. A paint for in-mold coating, comprising the modified polyolefin resin composition according to any one of claims 1 to 9.

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