Modified polyolefin resin composition and use for said resin composition

Abstract

The present invention provides a modified polyolefin resin composition which has excellent water resistance and excellent flex resistance and has sufficient flowability within a specific temperature range and which has excellent adhesiveness to polyolefin bases. Specifically, provided is a modified polyolefin resin composition that comprises an acid-modified polyolefin resin (A) and a compound (B) having a polymerizable unsaturated group, wherein the compound (B) having a polymerizable unsaturated group includes a compound (B-1) having a polymerizable unsaturated group which has a degree of elongation at break of 30% or higher.

Description

Modified polyolefin resin composition and uses of said resin composition

[0001] The present invention 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] 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.

[0004] 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.).

[0005] 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.

[0006] 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 paint is injected into the gap between the surface of a molded plastic body and the mold surface inside the mold, and then the paint is cured inside the mold by heat or the like to form a coating film.

[0007] 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.

[0008] Japanese Patent Publication No. 2002-201236 Japanese Patent Publication No. 2003-19731

[0009] 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.

[0010] The present invention has been made in view of the above, and an object of the present invention is to provide a modified polyolefin resin composition that has excellent water resistance, excellent flex resistance, sufficient fluidity within a specific temperature range, and excellent adhesion to polyolefin substrates.

[0011] In order to achieve the above object, the present inventors have conducted extensive research into dispersing and / or dissolving an acid-modified polyolefin resin in a compound having a polymerizable unsaturated group, and as a result have found that a modified polyolefin resin composition containing an acid-modified polyolefin resin and a compound having specific physical properties and a polymerizable unsaturated group can solve the above problems, thereby arriving at the present invention.

[0012] The present invention encompasses, for example, the subject matter described in the following items: Item 1. A modified polyolefin resin composition comprising an acid-modified polyolefin resin (A) and a compound (B) having a polymerizable unsaturated group, wherein the compound (B) having a polymerizable unsaturated group comprises a compound (B-1) having a polymerizable unsaturated group and having an elongation at break of 30% or more.

[0013] The modified polyolefin resin composition of the present invention has excellent water resistance, excellent flex resistance, sufficient fluidity within a specific temperature range, and excellent adhesion to polyolefin substrates. Because the modified polyolefin resin composition of the present invention exhibits sufficient fluidity within a specific temperature range, it can be suitably used as a liquid modified polyolefin resin composition in various applications.

[0014] Preferred embodiments of the present invention will be described in detail below. The following description of the components may be based on representative embodiments and specific examples, but the present invention is not limited to such embodiments.

[0015] In this specification, the expressions "contain" and "comprise" include the concepts of "contain," "include," "consist essentially of," and "consist only of."

[0016] In the numerical ranges described in stages in this specification, 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 specification, 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 an example. Furthermore, in this specification, a numerical value connected with "to" means a numerical range that includes the numbers before and after "to" as the upper and lower limits.

[0017] In this specification, "A and / or B" means "one of A and B" or "both A and B," and specifically means "A," "B," or "A and B."

[0018] As used herein, "n-" means "normal," "i-" or "iso-" means "iso," and "tert-" or "t-" means "tertiary."

[0019] In this specification, "(meth)acrylic" encompasses both acrylic and methacrylic, and "(meth)acrylate" encompasses both acrylate and methacrylate.

[0020] In this specification, 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.

[0021] In this specification, "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 represented by “CH ２ =C(CH ３ )C(=O)O-".

[0022] In this specification, 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 carbon atoms) 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.

[0023] In this specification, 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 carbon atoms) 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.

[0024] (Modified Polyolefin Resin Composition) The modified polyolefin resin composition of the present embodiment contains, as essential components, an acid-modified polyolefin resin (A) and a compound (B) having a polymerizable unsaturated group. The compound (B) having a polymerizable unsaturated group contains, as an essential component, a compound (B-1) having a polymerizable unsaturated group and having an elongation at break of 30% or more.

[0025] The modified polyolefin resin composition of the present embodiment usually has sufficient fluidity within a temperature range of 25° C. or higher and 80° C. In this specification, a resin composition having fluidity means, for example, a homogeneous liquid composition that does not contain coarse resin particles, aggregates, etc.

[0026] The modified polyolefin resin composition of the present embodiment 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 embodiment, 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.

[0027] <Acid-Modified Polyolefin Resin (A)> The present invention contains an acid-modified polyolefin resin (A). The acid-modified polyolefin resin (A) is a polymer obtained by graft polymerizing an α,β-unsaturated carboxylic acid and / or its acid anhydride onto a polyolefin resin. In other words, the acid-modified polyolefin resin (A) is a graft polymer having a structure in which an α,β-unsaturated carboxylic acid and / or its acid anhydride is grafted onto a polyolefin resin.

[0028] 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.

[0029] 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.

[0030] In one embodiment, the polyolefin resin is typically a petroleum-derived polyolefin resin, which is a polyolefin-based resin synthesized from petroleum-derived olefins.

[0031] 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.

[0032] In one embodiment, examples of the polyolefin resin constituting the acid-modified polyolefin resin (A) include homopolypropylene (propylene homopolymer), propylene-α-olefin copolymer, homopolyethylene (ethylene homopolymer), ethylene-α-olefin copolymer, homopoly-1-butene, 1-butene-α-olefin copolymer, etc. These polyolefin resins can be used alone or in combination of two or more. Among these polyolefin resins, homopolypropylene and / or propylene-α-olefin copolymer are preferred, and propylene-α-olefin copolymer is more preferred.

[0033] In one embodiment, the acid-modified polyolefin resin (A) is preferably a graft polymer having a structure in which an α,β-unsaturated carboxylic acid and / or an acid anhydride thereof is grafted onto a homopolypropylene or a propylene-α-olefin copolymer, and more preferably a graft polymer having a structure in which an α,β-unsaturated carboxylic acid and / or an acid anhydride thereof is grafted onto a propylene-α-olefin copolymer.

[0034] Propylene-α-olefin copolymers are copolymers of propylene and α-olefins. Examples of α-olefins include 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, and 1-eicosene, and other 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). These α-olefins can be used alone or in combination of two or more.

[0035] The content of the propylene component in the propylene-α-olefin copolymer is preferably 50 mol% or more, more preferably 55 mol% or more, even more preferably 60 mol% or more, still 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 this embodiment become even better.

[0036] 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.

[0037] The content of the ethylene component in the ethylene-α-olefin copolymer is preferably 75 mol% or more. When the content of the ethylene component in 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 this embodiment become even better.

[0038] 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.

[0039] 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 this embodiment to polyolefin substrates (particularly polypropylene substrates or poly-1-butene substrates) become even better.

[0040] In one embodiment, 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 biological resources (biomass). Biomass refers to a material formed from renewable biological organic resources excluding fossil resources.

[0041] 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.

[0042] Examples of the α,β-unsaturated carboxylic acid and / or its acid anhydride to be graft polymerized onto the polyolefin resin constituting the acid-modified polyolefin resin (A) 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.

[0043] 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 still more preferably 15 to 30. 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 embodiment becomes even better.

[0044] The acid value of the α,β-unsaturated carboxylic acid and its anhydride component 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 acid-modified polyolefin solution. －１and 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.

[0045] A wide variety of known methods can be used to graft polymerize an α,β-unsaturated carboxylic acid or anhydride thereof onto a polyolefin resin, including, for example, a melting method in which a polyolefin 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.

[0046] In one embodiment, the acid-modified polyolefin resin (A) may be an acid-modified chlorinated polyolefin resin that has been further chlorinated. Examples of the chlorination method include a method in which chlorine gas is blown into the acid-modified polyolefin resin to introduce chlorine atoms. More specifically, the acid-modified polyolefin resin is dispersed or dissolved in a solvent as needed, and then chlorination can be carried out by 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.

[0047] Examples of the solvent used in the chlorination include water and chlorine-based solvents (e.g., chloroform, methylene chloride, carbon tetrachloride, etc.), and chlorine-based solvents are preferred. The chlorine-based solvent may be distilled off under reduced pressure or the like after the chlorination is completed, or may be replaced with another organic solvent.

[0048] Examples of catalysts used in the chlorination include radical initiators, such as tert-butylperoxy-2-ethylhexanoate, tert-butylperoxyoctoate, di-tert-butylperoxide, and dicumyl peroxide.

[0049] When the acid-modified polyolefin resin (A) is chlorinated, the chlorine content in the acid-modified chlorinated polyolefin resin is preferably 5% by mass or more, more preferably 8% by mass or more, even more preferably 10% by mass or more, particularly preferably 12% by mass or more, and most preferably 14% by mass or more. When the chlorine content in the acid-modified chlorinated polyolefin resin is 5% by mass or more, the stability in the solution is improved, and the acid-modified chlorinated polyolefin resin is more likely to be emulsified.

[0050] The chlorine content in the acid-modified chlorinated polyolefin resin is preferably 40% by mass or less, more preferably 38% by mass or less, even more preferably 35% by mass or less, particularly preferably 32% by mass or less, and most preferably 30% by mass or less. When the chlorine content in the acid-modified chlorinated polyolefin resin is 40% by mass or less, the crystallinity of the acid-modified chlorinated polyolefin is increased, and the adhesion to polyolefin substrates is further improved.

[0051] When the acid-modified polyolefin resin (A) is chlorinated, the chlorine content in the acid-modified chlorinated polyolefin resin is preferably 5% by mass to 40% by mass, more preferably 8% by mass to 38% by mass, even more preferably 10% by mass to 35% by mass, still more preferably 12% by mass to 32% by mass, and particularly preferably 14% by mass to 30% by mass. When the chlorine content in the acid-modified chlorinated polyolefin resin is 5% by mass to 40% by mass, (I) the stability in solution is improved, making the acid-modified chlorinated polyolefin resin more easily emulsifiable, and (II) the crystallinity of the acid-modified chlorinated polyolefin is increased, thereby further improving adhesion to polyolefin substrates.

[0052] The chlorine content in the acid-modified chlorinated polyolefin resin can be measured in accordance with JIS K-7229-1995, i.e., by 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 amount is determined by titration.

[0053] The melting point of the acid-modified polyolefin resin (A) is preferably not more than 90° C., more preferably not more than 85° C., and particularly preferably not more than 80° C. When the melting point of the acid-modified polyolefin resin (A) is 90° C. or less, the adhesion to the polyolefin substrate is further improved.

[0054] The melting point of the acid-modified polyolefin resin (A) is preferably 50° C. or higher, more preferably 55° C. or higher, and particularly preferably 60° C. or higher. When the melting point of the acid-modified polyolefin resin (A) is 50° C. or higher, the adhesion to the polyolefin substrate is further improved.

[0055] 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, maintained in a molten state, cooled at a rate of 10°C / min, stabilized at -50°C, and then heated to 150°C at a rate of 10°C / min to melt the sample, at which the melting peak temperature is measured, and the melting peak temperature is evaluated as the melting point.

[0056] 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] The acid-modified polyolefin resin (A) may be further copolymerized with a radical-polymerizable monomer, as long as the effects of the present invention 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] 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).

[0059] Examples of the radical polymerizable monomer include (meth)acrylic compounds, vinyl compounds, etc. A (meth)acrylic compound is a compound containing at least one (meth)acryloyl group (acryloyl group and / or methacryloyl group) in the molecule.

[0060] 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, Examples of the alkyl acrylate include N-dimethylaminoethyl (meth)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)acryloylmorpholine, n-butyl vinyl ether, 4-hydroxybutyl vinyl ether, and dodecyl vinyl ether. Among these, methyl (meth)acrylate, ethyl (meth)acrylate, cyclohexyl (meth)acrylate, and lauryl (meth)acrylate are preferred, and these methacrylates, i.e., methyl methacrylate (methyl methacrylate), ethyl methacrylate (ethyl methacrylate), cyclohexyl methacrylate (cyclohexyl methacrylate), and lauryl methacrylate (lauryl methacrylate), are more preferred. The above-mentioned radical polymerizable monomers can be used either alone or in combination of two or more.

[0061] In one embodiment, the content of the acid-modified polyolefin resin (A) is preferably 10 to 50 parts by mass, more preferably 12 to 45 parts by mass, even more preferably 15 to 40 parts by mass, and still more preferably 18 to 35 parts by mass per 100 parts by mass of the compound (B) having a polymerizable unsaturated group, from the viewpoint of maintaining the fluidity of the modified polyolefin resin composition more favorably and further improving the water resistance and adhesion to a polyolefin substrate.

[0062] In one embodiment, the content of the acid-modified polyolefin resin (A) is preferably 5 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 polyolefin substrates.

[0063] <Compound (B) Having a Polymerizable Unsaturated Group> The present invention contains a compound (B) having a polymerizable unsaturated group as an essential component. The compound (B) having a polymerizable unsaturated group has one or more polymerizable unsaturated groups. In the present invention, the polymerizable unsaturated group means an unsaturated group capable of radical polymerization.

[0064] In one embodiment, the number of polymerizable unsaturated groups in the compound (B) having a polymerizable unsaturated group is usually 1, 2, 3, or 4, preferably 1, 2, or 3, and more preferably 1 or 2.

[0065] In one embodiment, the polymerizable unsaturated group in the compound (B) having a polymerizable unsaturated group is preferably 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.

[0066] In one embodiment, the polymerizable unsaturated group in the compound (B) having a polymerizable unsaturated group is preferably at least one selected from the group consisting of an acryloyl group, a methacryloyl group, an acryloyloxy group, and a methacryloyloxy group.

[0067] As an embodiment, it is more preferable that the polymerizable unsaturated group in the compound (B) having a polymerizable unsaturated group is an acryloyloxy group and / or a methacryloyloxy group.

[0068] <Compound (B-1) Having a Polymerizable Unsaturated Group with a Breaking Elongation of 30% or More> The compound (B) having a polymerizable unsaturated group includes a compound (B-1) having a polymerizable unsaturated group with a breakage elongation of 30% or more. By including the compound (B-1) having a polymerizable unsaturated group with a breakage elongation of 30% or more in the modified polyolefin resin composition, the modified polyolefin resin composition has excellent flex resistance.

[0069] In one embodiment, the breaking elongation of the compound (B-1) having a polymerizable unsaturated group is preferably 100% or more, more preferably 300%, and even more preferably 500% or more. In the present disclosure, the upper limit of the breaking elongation of the compound (B-1) having a polymerizable unsaturated group is usually 2000% or less, from the viewpoint of further improving the workability of film formation. The breaking elongation of the compound (B-1) having a polymerizable unsaturated group can be measured by the method described below in <Method for measuring breaking elongation of compound (B) having a polymerizable unsaturated group>.

[0070] In one embodiment, the compound (B-1) having a polymerizable unsaturated group and having an elongation at break of 30% or more is preferably at least one compound selected from the group consisting of urethane (meth)acrylate, epoxy (meth)acrylate, polyester (meth)acrylate, polyether (meth)acrylate, and vinyl ester, from the viewpoint of improving the flex resistance of the modified polyolefin resin composition.

[0071] In one embodiment, the compound (B-1) having a polymerizable unsaturated group with a breaking elongation of 30% or more is more preferably at least one compound selected from the group consisting of urethane (meth)acrylate, polyester (meth)acrylate, and vinyl ester, from the viewpoint of further improving the flex resistance of the modified polyolefin resin composition.

[0072] In one embodiment, the compound (B-1) having a polymerizable unsaturated group with a breaking elongation of 30% or more is more preferably a urethane (meth)acrylate and / or a vinyl ester, from the viewpoint of further improving the flex resistance of the modified polyolefin resin composition.

[0073] <Urethane (meth)acrylate> Urethane (meth)acrylate usually has a breaking elongation of 30% or more. Urethane (meth)acrylate is usually a compound having a urethane bond and a (meth)acrylate group in the molecule.

[0074] In one embodiment, examples of the urethane (meth)acrylate include: i) a compound obtained by reacting an equivalent amount of a compound having two or more isocyanate groups in the molecule with a compound having one or more hydroxyl groups and one or more double bond groups in the molecule; ii) a compound obtained by reacting a condensate of a polyol with a monobasic acid and / or polybasic acid and / or anhydride thereof with a compound having two or more isocyanate groups in the molecule, and then further reacting with a compound having one or more hydroxyl groups and one or more double bond groups in the molecule; and iii) a compound obtained by reacting a polyol with a compound having two or more isocyanate groups in the molecule, and then further reacting with a compound having one or more hydroxyl groups and one or more double bond groups in the molecule.

[0075] In the above i) to iii), examples of compounds having one or more hydroxyl groups and one or more double bond groups in the molecule include 2-hydroxy(meth)acrylate, 2-hydroxypropyl(meth)acrylate, 4-hydroxybutyl(meth)acrylate, pentaerythritol triacrylate, and dipentaerythritol pentaacrylate. In the above ii) to iii), examples of polyols that can be used include acrylic polyols, polyester polyols, polycarbonate polyols, and the like that are commonly used in this field. Specific examples of polyols include various low-molecular-weight diols such as ethylene glycol, butanediol, glycerin, pentaerythritol, neopentyl glycol, polyethylene glycol, polycarbonate diol, polytetramethylene glycol, and trimethylolpropane.

[0076] In the above i) to iii), examples of the compound having two or more isocyanate groups in the molecule include aromatic compounds such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, and metaxylylene diisocyanate; aliphatic compounds such as hexamethylene diisocyanate; alicyclic compounds such as isophorone diisocyanate; and polymers of the aromatic compounds, aliphatic compounds, or alicyclic compounds, such as biuret type, nurate type, and adduct type.

[0077] The polyurethane acrylate may partially contain a urea bond. To obtain a polyurethane acrylate having a urea bond, a polyamine compound may be used as a part of the polyurethane acrylate synthesis. Examples of usable polyamine compounds include aliphatic polyamines such as ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, triethylenetetramine, diethylenetriamine, triaminopropane, 2,2,4-trimethylhexamethylenediamine, 2-hydroxyethylethylenediamine, N-(2-hydroxyethyl)propylenediamine, (2-hydroxyethylpropylene)diamine, (di-2-hydroxyethylethylene)diamine, (di-2-hydroxyethylpropylene)diamine, (2-hydroxypropylethylene)diamine, (di-2-hydroxypropylethylene)diamine, and piperazine; Examples include alicyclic polyamines such as 1,2- and 1,3-cyclobutanediamine, 1,2-, 1,3- and 1,4-cyclohexanediamine, isophoronediamine (IPDA), methylenebiscyclohexane 2,4'- and / or 4,4'-diamine, and norbornanediamine; aromatic diamines such as phenylenediamine, xylylenediamine, 2,4-tolylenediamine, 2,6-tolylenediamine, diethyltoluenediamine, 3,3'-dichloro-4,4'-diaminodiphenylmethane, and 4,4'-bis-(sec-butyl)diphenylmethane; and dimer diamines in which the carboxyl groups of dimer acids have been converted to amino groups, and dendrimers having primary or secondary amino groups at the terminals.

[0078] In one embodiment, the number of polymerizable unsaturated groups contained per molecule in the urethane (meth)acrylate is preferably 1 to 20, and more preferably 1 to 10.

[0079] <Polyester (meth)acrylate> Polyester (meth)acrylate usually has a breaking elongation of 30% or more. The polyester (meth)acrylate can be obtained, for example, by reacting a polyester polycarboxylic acid obtained by polycondensation of a polybasic acid and a polyhydric alcohol with a hydroxyl group-containing (meth)acrylate or the like.

[0080] Examples of the polybasic acid include aliphatic polybasic acids, alicyclic polybasic acids, and aromatic polybasic acids. Examples of the aliphatic polybasic acids include aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, suberic acid, maleic acid, fumaric acid, dodecanedioic acid, pimelic acid, citraconic acid, glutaric acid, itaconic acid, succinic anhydride, and maleic anhydride. Anhydrides of these aliphatic dicarboxylic acids and derivatives of the acid anhydrides of these aliphatic dicarboxylic acids can also be used.

[0081] Examples of the polyhydric alcohol include an aliphatic diol compound and an alicyclic diol compound. Specific examples of the polyhydric alcohol include ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol, butylene glycol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-methyl-1,8-octanediol, 3,3'-dimethylolheptane, 2-butyl-2-ethyl-1,3-propanediol, polyoxyethylene glycol (addition mole number of 10 or less), polyoxypropylene glycol (addition mole number of 10 or less), propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, octanediol, butylethylpentanediol, 2-ethyl-1,3-hexanediol, cyclohexanediol, cyclohexanedimethanol, tricyclodecane dimethanol, cyclopentadiene dimethanol, and dimer diol. As the polyhydric alcohol, a polyol containing three or more hydroxyl groups, such as glycerin, trimethylolpropane, pentaerythritol, or dipentaerythritol, may be used in part.

[0082] Examples of the hydroxyl group-containing (meth)acrylate include 2-hydroxy(meth)acrylate, 2-hydroxypropyl(meth)acrylate, 4-hydroxybutyl(meth)acrylate, pentaerythritol triacrylate, and dipentaerythritol pentaacrylate.

[0083] The polyester (meth)acrylate preferably contains 1 to 20 polymerizable unsaturated groups per molecule, and more preferably 1 to 10 polymerizable unsaturated groups per molecule.

[0084] <Vinyl Ester> The vinyl ester generally has a breaking elongation of 30% or more. The vinyl ester is preferably a vinyl ester represented by the following formula (3), and more preferably a versatic acid vinyl ester.

[0085] In the above formula (3), R ４ and R ５ are each an alkyl group, and R ４ and R ５ At least one of R is an alkyl group having a branched structure. ４ The number of carbon atoms and R ５ The total number of carbon atoms in R is preferably 4 or more and 7 or less, and more preferably 4 or more and 6 or less. ４ and R ５Examples of the alkyl group constituting the formula (I) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a sec-butyl group, an isobutyl group, an n-pentyl group, an isopentyl group, a sec-pentyl group, a tert-pentyl group, an n-hexyl group, a 1,1-dimethylbutyl group, a 2-methylpentyl group, a 3-methylpentyl group, a 4-methylpentyl group, a 1-ethylbutyl group, a 2-ethylbutyl group, a 3-ethylbutyl group, and a 1-methyl-1-ethylpropyl group. Examples of the alkyl group having a branched structure include an isopropyl group (1-methylethyl group), a tert-butyl group (1,1-dimethylethyl group), a sec-butyl group (1-methylpropyl group), an isobutyl group (2-methylpropyl group), a tert-pentyl group (1,1-dimethylpropyl group), an isopentyl group (3-methylbutyl group), a sec-pentyl group (1-methylbutyl group), a 1,1-dimethylbutyl group, a 2-methylpentyl group, a 3-methylpentyl group, a 4-methylpentyl group, a 1-ethylbutyl group, a 2-ethylbutyl group, a 3-ethylbutyl group, and a 1-methyl-1-ethylpropyl group.

[0086] The versatic acid vinyl ester is preferably a compound represented by the formula (3) above, and is a compound having a total carbon number of 9 or more and 11 or less.

[0087] <Method for measuring breaking elongation of compound (B) having a polymerizable unsaturated group> The breaking elongation of compound (B) having a polymerizable unsaturated group can be measured by the following method: Compound (B) having a polymerizable unsaturated group and 1-hydroxycyclohexyl phenyl ketone are mixed in a mass ratio of compound (B) having a polymerizable unsaturated group / 1-hydroxycyclohexyl phenyl ketone = 100 / 3, and the mixture is irradiated with a high-pressure mercury lamp at an integrated light intensity of 800 mJ / cm. ２The cured coating film is irradiated with ultraviolet light under the conditions of (a) to (c) to obtain a cured coating film having a thickness of 100 μm. The elongation of the cured coating film until breakage is measured using a tensile tester (Tensilon RTM-100, manufactured by Orientec Corporation) under the following conditions: width 10 mm, chuck distance 30 mm, tensile speed 100 mm / min, temperature 20°C, relative humidity 65%. The breaking elongation of the compound (B) having a polymerizable unsaturated group is calculated using the following formula (9): Breaking elongation of the compound (B) having a polymerizable unsaturated group (%) = 100 × {(length at break) - (initial length before tensile test)} / initial length before tensile test ... formula (9)

[0088] <Compound (B-2) Having a Polymerizable Unsaturated Group with a Breaking Elongation of Less than 30%> In one embodiment, the compound (B) having a polymerizable unsaturated group preferably further contains a compound (B-2) having a polymerizable unsaturated group with a break elongation of less than 30%, in order to better maintain the fluidity of the modified polyolefin resin composition.

[0089] The breaking elongation of the compound (B-2) having a polymerizable unsaturated group is preferably 20% or less, more preferably 10% or less, from the viewpoint of maintaining the fluidity of the modified polyolefin resin composition even better. The breaking elongation of the compound (B-2) having a polymerizable unsaturated group can be measured by the method described above in <Method for measuring breaking elongation of compound (B) having a polymerizable unsaturated group>.

[0090] In one embodiment, the compound (B-2) having a polymerizable unsaturated group and a breaking elongation of less than 30% preferably includes a compound (B-21) having an alkyleneoxy group and / or a 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), and one or more (usually 1, 2, 3, or 4, preferably 1, 2, or 3, more preferably 1 or 2) polymerizable unsaturated groups. In this embodiment, 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) may have an alicyclic structure (preferably cyclohexyl) or an aromatic ring structure (preferably phenyl or naphthyl, more preferably phenyl). In this embodiment, the linear or branched alkyl group preferably has 1 to 10 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9, or 10).

[0091] From the viewpoint of maintaining the fluidity of the modified polyolefin resin composition more favorably and improving the adhesion to a polyolefin substrate, the content of the compound (B-21) having an alkyleneoxy group and / or a 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), and one or more (usually 1, 2, 3, or 4, preferably 1, 2, or 3, more preferably 1 or 2) polymerizable unsaturated groups, is preferably 1 to 80 mass%, more preferably 2 to 75 mass%, even more preferably 3 to 70 mass%, even more preferably 10 to 65 mass%, and still more preferably 15 to 60 mass%, relative to the total mass of the modified polyolefin resin composition.

[0092] In one embodiment, the alkyleneoxy group is typically represented by the following formula (4): -(Y １ -O)m- (4) [In formula (4): 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), and m represents an integer of 1 to 20.

[0093] In the above formula (4), Y １ is preferably a linear or branched alkylene group having 1 to 5 carbon atoms (1, 2, 3, 4 or 5).

[0094] In the above formula (4), m is preferably an integer of 2 to 15.

[0095] In one embodiment, the compound (B-21) having an alkyleneoxy group and / or a 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), and one or more (usually 1, 2, 3, or 4, preferably 1, 2, or 3, more preferably 1 or 2) polymerizable unsaturated groups, may further be represented by the following formula (4A): R ａ -R ｂ -R ｃ (4A) [In formula (4A): R ａ represents a polymerizable unsaturated group, and R ｃ represents a polymerizable unsaturated group, a linear or branched alkyl group having 1 to 10 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9, or 10), or a hydroxyl group. However, the linear or branched alkyl group having 1 to 10 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9, or 10) may have an alicyclic structure (preferably cyclohexyl) or an aromatic ring structure (preferably phenyl or naphthyl, more preferably phenyl). R ｂ is -(Y ２ represents a group represented by —O)n-. ２ represents a linear or branched alkylene group having 1 to 10 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9, or 10), and n represents an integer of 1 to 20.]; and / or a compound represented by the following formula (4B): [R ａ -R ｄ (4B) R ａ represents a polymerizable unsaturated group, and R ｄrepresents a 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), which may have a substituent. However, the substituent represents a hydroxyl group, a polymerizable unsaturated group, or an alkoxy group, and 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) may have an alicyclic structure (preferably cyclohexyl) or an aromatic ring structure (preferably phenyl or naphthyl, more preferably phenyl).

[0096] In the above formula (4A), Y ２ is preferably a linear or branched alkylene group having 1 to 5 carbon atoms (1, 2, 3, 4 or 5).

[0097] In the above formula (4A), n is preferably an integer of 2 to 15.

[0098] In one embodiment, the compound (B-2) having a polymerizable unsaturated group and having a breaking elongation of less than 30% more preferably includes the compound (B-21) and a compound represented by formula (4A) or (4B).

[0099] In one embodiment, the compound (B-21) preferably includes a compound having a (meth)acryloyloxy group as the polymerizable unsaturated group. Examples of the compound having a (meth)acryloyloxy group include a compound having one (meth)acryloyloxy group, a compound having two (meth)acryloyloxy groups, and a compound having three or more (meth)acryloyloxy groups. These compounds can be used alone or in combination of two or more.

[0100] 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; Examples of the compound include (meth)acrylates having an alicyclic structure such as cyclohexyl (meth)acrylate, 4-tert-butylcyclohexyl acrylate, and isobornyl (meth)acrylate; (meth)acrylates having an aromatic ring such as benzyl (meth)acrylate, phenoxyethyl acrylate, and phenoxyethyl methacrylate; 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, and 2-isopropoxyethyl (meth)acrylate. These compounds can be used alone or in combination of two or more.

[0101] 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, propylene 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.

[0102] Examples of the compound 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.

[0103] In one embodiment, 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 from the viewpoint of suppressing aggregation, the compound (B-21) is more preferably a compound having one or two (meth)acryloyloxy groups.

[0104] 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, phenoxydiethylene glycol (meth)acrylate, At least one selected from the group consisting of 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, behenyl (meth)acrylate, cyclohexyl (meth)acrylate, 4-tert-butylcyclohexyl acrylate, and isobornyl (meth)acrylate is preferred.

[0105] The compound having two (meth)acryloyloxy groups is preferably at least one selected from the group consisting of neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, tricyclodecanedimethylol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetrapropylene glycol di(meth)acrylate, and polypropylene glycol di(meth)acrylate.

[0106] In one embodiment, from the viewpoint of maintaining the fluidity of the modified polyolefin resin composition more favorably and improving the water resistance and adhesion to a polyolefin substrate, the compound (B-2) having a polymerizable unsaturated group and having an elongation at break of less than 30% preferably includes a compound (B-211) having a hydroxyl group and one or more (usually 1 to 4, preferably 1 to 3, more preferably 1 or 2, and even more preferably 2) polymerizable unsaturated groups. In this embodiment, the elongation at break of the compound (B-211) is usually less than 30%, preferably 20% or less, and more preferably 10% or less.

[0107] In one embodiment, the compound (B-2) having a polymerizable unsaturated group and an elongation at break of less than 30% more preferably includes a compound (B-21) having an alkyleneoxy group and / or a 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) and one or more (usually 1, 2, 3, or 4, preferably 1, 2, or 3, more preferably 1 or 2)) polymerizable unsaturated groups, and a compound (B-211) having a hydroxyl group and one or more (usually 1, 2, 3, or 4, preferably 1, 2, or 3, more preferably 1 or 2, and even more preferably 2) polymerizable unsaturated groups. In this embodiment, the number of polymerizable unsaturated groups in the compound (B-21) is preferably 1 to 3, more preferably 1 or 2, and even more preferably 1. In this embodiment, in the compound (B-21), 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 carbon atoms) may have an alicyclic structure (preferably cyclohexyl) or an aromatic ring structure (preferably phenyl or naphthyl, more preferably phenyl).

[0108] In one embodiment, from the viewpoint of further improving the water resistance and adhesion to a polyolefin substrate while further maintaining the fluidity of the modified polyolefin resin composition, the number of hydroxyl groups in the compound (B-211) having a hydroxyl group and one or more (usually 1 to 4, preferably 1 to 3, more preferably 1 or 2, and even more preferably 2) polymerizable unsaturated groups is preferably 1 or 2, and more preferably 1.

[0109] In one embodiment, from the viewpoint of maintaining the fluidity of the modified polyolefin resin composition more favorably and improving the water resistance and adhesion to a polyolefin substrate, the content of the compound (B-211) having a hydroxyl group and one or more (usually 1, 2, 3, or 4, preferably 1, 2, or 3, more preferably 1 or 2, and even more preferably 2) polymerizable unsaturated groups is preferably 1 to 50 mass%, more preferably 2 to 45 mass%, even more preferably 3 to 40 mass%, even more preferably 10 to 35 mass%, and even more preferably 15 to 30 mass%, relative to the total mass of the modified polyolefin resin composition.

[0110] Specific examples of the compound (B-211) having a hydroxyl group and one or more (usually 1, 2, 3, or 4, preferably 1, 2, or 3, more preferably 1 or 2, and even more preferably 2) polymerizable unsaturated groups include 2-hydroxy-3-methacrylpropyl acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 1,4-cyclohexanedimethanol monoacrylamide ...ethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 1,4-cyclohexanedimethanol monoacrylamide, 2-hydroxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, acrylate, 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, 2-hydroxy-1,3-dimethacryloxypropane, glycerin diacrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, and the like.

[0111] In one embodiment, from the viewpoint of maintaining the fluidity of the modified polyolefin resin composition more favorably, further suppressing aggregation, and further improving the water resistance and adhesion to a polyolefin substrate, the compound (B-2) having a polymerizable unsaturated group and having an elongation at break of less than 30% preferably includes a compound (B-22) having a unit having a carbonyl group and one or more (usually 1, 2, 3, or 4, preferably 1, 2, or 3, more preferably 1 or 2, and even more preferably 1) polymerizable unsaturated groups.

[0112] From the viewpoints of maintaining the fluidity of the modified polyolefin resin composition more favorably, further suppressing aggregation, and improving the water resistance and adhesion to a polyolefin substrate, the content of the compound (B-22) having a unit having a carbonyl group and one or more (usually 1, 2, 3, or 4, preferably 1, 2, or 3, more preferably 1 or 2, and even more preferably 1) polymerizable unsaturated groups is preferably 1 to 50 mass%, more preferably 2 to 48 mass%, even more preferably 3 to 45 mass%, even more preferably 10 to 42 mass%, and even more preferably 15 to 40 mass%, relative to the total mass of the modified polyolefin resin composition.

[0113] In one embodiment, in the compound (B-22) having a unit having a carbonyl group and one or more (usually 1, 2, 3, or 4, preferably 1, 2, or 3, more preferably 1 or 2, and still more preferably 1) polymerizable unsaturated groups, the unit having a carbonyl group is preferably a group represented by the following formula (1) or the following formula (2): In the formula (1), R １ represents a hydrogen atom or a methyl group. * represents a bond. In the formula (2), R ２ represents a hydrocarbon group having 1 to 10 (1, 2, 3, 4, 5, 6, 7, 8, 9 or 10) carbon atoms which may have a substituent. ３ represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9, or 10) which may have a substituent. * represents a bond. However, R ２ and R３ The hydrocarbon groups having 1 to 10 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9, or 10) which may have a substituent may each independently further have a branched structure, an alicyclic structure (preferably cyclohexyl), or an aromatic ring structure (preferably phenyl or naphthyl, more preferably phenyl).

[0114] In the above formula (2), R ２ Examples of the substituent include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom), an alkoxy group, and the like.

[0115] In the above formula (2), R ３ Examples of the substituent include an aldehyde group, an acetyl group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom), and an alkoxy group.

[0116] In one embodiment, compound (B-22) having a unit having a carbonyl group and one or more (usually 1, 2, 3, or 4, preferably 1, 2, or 3, more preferably 1 or 2, and even more preferably 1) polymerizable unsaturated groups more preferably includes one or more compounds (B-221) having a unit having a carbonyl group represented by formula (1) or (2) above and one or more (usually 1, 2, 3, or 4, preferably 1, 2, or 3, more preferably 1 or 2, and even more preferably 1) polymerizable unsaturated groups.

[0117] In one embodiment, compound (B-22) having a unit having a carbonyl group and one or more (usually 1, 2, 3, or 4, preferably 1, 2, or 3, more preferably 1 or 2, and even more preferably 1) polymerizable unsaturated groups is even more preferably compound (B-221) having a unit having a carbonyl group represented by formula (1) or (2) above and one or more (usually 1, 2, 3, or 4, preferably 1, 2, or 3, more preferably 1 or 2, and even more preferably 1) polymerizable unsaturated groups.

[0118] In one embodiment, the compound (B-22) having a unit having a carbonyl group and one or more (usually 1, 2, 3, or 4, preferably 1, 2, or 3, more preferably 1 or 2, and even more preferably 1) polymerizable unsaturated groups is more preferably a compound having a unit having a carbonyl group represented by the above formula (1) and one or more (usually 1, 2, 3, or 4, preferably 1, 2, or 3, more preferably 1 or 2, and even more preferably 1) polymerizable unsaturated groups.

[0119] Examples of the compound (B-221) having a unit having a carbonyl group represented by the above formula (1) or (2) and one or more (usually 1, 2, 3, or 4, preferably 1, 2, or 3, more preferably 1 or 2, and still more preferably 1) polymerizable unsaturated group include acrylic acid acetoacetic esters such as acetoacetoxy(meth)acrylate, acetoacetoxyethyl(meth)acrylate, acetoacetoxypropyl(meth)acrylate, allyl acetoacetate, acetoacetoxybutyl(meth)acrylate, and 2,3-di(acetoacetoxy)propyl(meth)acrylate; crotonic acid acetoacetic esters such as 2-acetoacetoxyethyl crotonate and 2-acetoacetoxypropyl crotonate; acetoacetic esters of N-alkylol(meth)acrylamides such as acetoacetoxy(meth)acrylamide, N-(acetoacetoxymethyl)(meth)acrylamide, and N-(acetoacetoxyethyl)(meth)acrylamide; Examples of suitable hydroxyl groups include acetoacetylated products of ethylenically unsaturated monomers having a hydroxyl group, such as 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, 2-hydroxy-3-chloropropyl methacrylate, 1,4-butylene glycol monoacrylate, 1,4-butylene glycol monomethacrylate, N-methylol acrylamide, N-methylol methacrylamide, and hydroxystyrene; and diacetone (meth)acrylamide. Among these, diacetone acrylamide and acetoacetoxyethyl methacrylate are preferred from the viewpoints of maintaining the fluidity of the modified polyolefin resin composition more favorably, further suppressing aggregation, and improving the water resistance and adhesion to polyolefin substrates.

[0120] In one embodiment, 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.

[0121] In one embodiment, from the viewpoint of stably dissolving and / or dispersing the acid-modified polyolefin resin (A) in the compound (B) having a polymerizable unsaturated group, the content of the compound (B) having a polymerizable unsaturated group is preferably 10 to 90 mass%, more preferably 20 to 85 mass%, and even more preferably 30 to 80 mass%, relative to the total mass of the modified polyolefin resin composition.

[0122] In one embodiment, when the compound (B) having a polymerizable unsaturated group comprises a compound (B-1) having a polymerizable unsaturated group with a breaking elongation of 30% or more and a compound (B-2) having a polymerizable unsaturated group with a breaking elongation of less than 30%, from the viewpoint of maintaining the fluidity of the modified polyolefin resin composition more favorably and from the viewpoint of improving the adhesion to a polyolefin substrate and the flex resistance, the mass ratio of the compound (B-1) having a polymerizable unsaturated group with a breaking elongation of 30% or more to the compound (B-2) having a polymerizable unsaturated group with a breaking elongation of less than 30% is preferably (B-1):(B-2)=99:1 to 5:95, more preferably (B-1):(B-2)=80:20 to 20:80, even more preferably (B-1):(B-2)=65:35 to 25:75, and even more preferably (B-1):(B-2)=40:60 to 60:40.

[0123] In one embodiment, the compound (B-2) having a polymerizable unsaturated group and a breaking elongation of less than 30% is selected from the group consisting of: a compound (B-21) having an alkyleneoxy group and / or a 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), and one or more (usually 1, 2, 3, or 4, preferably 1, 2, or 3, and more preferably 1 or 2) polymerizable unsaturated groups; a compound (B-211) having a hydroxyl group and one or more (usually 1, 2, 3, or 4, preferably 1, 2, or 3, and more preferably 1 or 2, and even more preferably 2) polymerizable unsaturated groups; and and compounds (B-221) each having a unit having a carbonyl group represented by the above formula (1) or (2) and one or more (usually 1, 2, 3, or 4, preferably 1, 2, or 3, more preferably 1 or 2, and still more preferably 1) polymerizable unsaturated groups.

[0124] <Polyetheramine (C)> The modified polyolefin resin composition of the present embodiment preferably contains polyetheramine (C). The polyetheramine (C) is usually a compound having a polyether chain and an amino group.

[0125] In one embodiment, the polyetheramine (C) has a polyether chain represented by the formula 5: —(O—CH ２ CH ２ )x- (wherein x is an integer of 2 to 120), a structure represented by Formula 6-1: -(O-CH ２ CH (CH ３ ))y １ -(In formula 6-1, y １ is an integer of 2 to 90), a structure represented by Formula 6-2: —(O—CH ２ CH ２ CH ２ ) y ２ -(In formula 6-2, y ２ is an integer of 2 to 90), a structure represented by Formula 7-1: -(O-CH ２ CH ２ CH ２ CH２ ) z １ -(In formula 7-1, z １ is an integer of 2 to 80), a structure represented by formula 7-2: -(O-CH(CH ３ ) CH ２ CH ２ ) z ２ -(In formula 7-2, z ２ is an integer of 2 to 80), a structure represented by formula 7-3: -(O-CH ２ CH (CH ３ ) CH ２ ) z ３ -(In formula 7-3, z ３ is an integer of 2 to 80), and a structure represented by formula 7-4: -(O-CH ２ CH ２ CH (CH ３ ))z ４ -(In formula 7-4, z ４ is an integer of 2 to 80).

[0126] In one embodiment, the polyetheramine (C) has a polyether chain represented by the formula 5: —(O—CH ２ CH ２ )x- (wherein x is an integer of 2 to 120), a structure represented by Formula 6-1: -(O-CH ２ CH (CH ３ ))y １ -(In formula 6-1, y １ is an integer of 2 to 90) and a structure represented by Formula 7-1: -(O-CH ２ CH ２ CH ２ CH ２ ) z １ -(In formula 7-1, z １ is an integer of 2 to 80).

[0127] In one embodiment, the polyetheramine (C) is represented by the following formula 5A: ６ -(O-R ７ ) a-R ８ Formula 5A (In formula 5A: R ６ and R８ R 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. ７ 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.

[0128] In the above formula 5A, 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.

[0129] In the above formula 5A, 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 -).

[0130] In the above formula 5A, R ６ 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 ７represents a linear or branched alkylene group having 2 to 4 (2, 3, or 4) carbon atoms, and R ８ represents an amino group, and a is preferably an integer of 1 to 120.

[0131] In one embodiment, the polyetheramine (C) preferably has a primary amino group or a secondary amino group at one terminal, and the weight average molecular weight (Mw) of the polyetheramine (C) is 200 to 50,000. In one embodiment, the polyetheramine (C) 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 (C) is 200 to 5,000. In one embodiment, the polyetheramine (C) still more preferably has a primary amino group at one terminal, and the weight average molecular weight (Mw) of the polyetheramine (C) is 500 to 5,000.

[0132] In one embodiment, from the viewpoint of stably dissolving and / or dispersing the acid-modified polyolefin resin (A) in the compound (B) having a polymerizable unsaturated group, the polyetheramine (C) 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 (C) is within this range, the steric repulsion of the polyetheramine (C) 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, the Mw of the polyetheramine (C) 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.

[0133] The weight average molecular weight (Mw) of the polyetheramine (C) in the present invention can be measured by GPC and converted from a polystyrene calibration curve. The GPC measurement is carried out by a conventionally known method using a commercially available apparatus and a solvent such as THF.

[0134] In one embodiment, the polyetheramine (C) 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.

[0135] In this specification, the HLB value means a value representing the degree of hydrophilicity or lipophilicity (hydrophobicity) of the polyetheramine (C). The HLB value is a value calculated by the Griffin method. In the Griffin method, the HLB value is calculated based on the following formula (8): HLB value = 20 × sum of formula weights of hydrophilic group moieties / molecular weight ... formula (8).

[0136] The polyetheramine (C) can be bonded to the acid-modified polyolefin resin (A) by various reaction modes. Examples of such reaction modes include reaction modes that form covalent bonds and / or ionic bonds. 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.

[0137] As the polyetheramine (C), a wide range of known commercially available products can be used. Commercially available polyetheramines (C) 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 Examples of commercially available products include 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), and JEFFAMINE ED-2003 (MW = 2000, HLB value = 16.7). These commercially available products can be used alone or in combination of two or more.

[0138] In one embodiment, the content of the polyetheramine (C) is usually 6 to 100 parts by mass, preferably 10 to 90 parts by mass, more preferably 15 to 80 parts by mass, even more preferably 20 to 70 parts by mass, still more preferably 25 to 60 parts by mass, and particularly preferably 30 to 50 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 the polyolefin substrate.

[0139] In one embodiment, the content of the polyetheramine (C) is usually 0.5 to 40 mass%, preferably 1 to 30 mass%, more preferably 2 to 25 mass%, even more preferably 3 to 15 mass%, even more preferably 4 to 15 mass%, and particularly preferably 5 to 10 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.

[0140] In one embodiment, the total content of the acid-modified polyolefin resin (A) and the compound (B) having a polymerizable unsaturated group relative to the total mass of the modified polyolefin resin composition is preferably more than 50% by mass, 60% by mass or more, 70% by mass or more, 80% by mass or more, 85% by mass or more, 90% by mass or more, 91% by mass or more, 92% by mass or more, 92.5% by mass or more, 95% by mass or more, 97.5% by mass or more, 99% by mass or more, 99.5% by mass or more, and 99.9% by mass or more, in that order.

[0141] <Method for Measuring Breaking Elongation of a Cured Product Obtained by Curing a Modified Polyolefin Resin Composition> The breaking elongation of a cured coating film of a modified polyolefin resin composition can be measured by the following method. 2 parts by mass of tert-butyl-2-ethylperoxyhexanoate is mixed with 100 parts by mass of the compound (B) having a polymerizable unsaturated group, and the mixture is applied to a Teflon (registered trademark) sheet. The mixture is then cured at 110°C for 1 minute to produce a cured coating film with a thickness of 100 μm. The elongation until the hard coating film breaks is measured using a tensile tester (Tensilon RTM-100, manufactured by Orientec Corporation) under conditions of a width of 10 mm, a chuck distance of 30 mm, a pulling speed of 100 mm / min, a temperature of 20°C, and a relative humidity of 65%, and the breaking elongation of the modified polyolefin resin composition is calculated using the following formula (10): Breaking elongation (%) of modified polyolefin resin composition = 100 × {(length at break) - (initial length before tensile test)} / initial length before tensile test Formula (10)

[0142] <Polymerization initiator> In one embodiment, the modified polyolefin resin composition may contain a polymerization initiator within a range that does not impair the effects of the present invention. By containing a polymerization initiator, the polymerization reaction of the polymerizable unsaturated group of the compound (B) proceeds more smoothly, and a resin for forming a coating film can be more easily formed. In addition, the use of a polymerization initiator further improves the corrosion resistance and durability of the coating film.

[0143] The amount of the polymerization initiator used 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, from the viewpoint of increasing the curing rate of the coating film obtained from the modified polyolefin resin composition.

[0144] As the polymerization initiator, 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 polymerization initiators can be used alone or in combination of two or more.

[0145] 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 photopolymerization initiators can be used alone or in combination of two or more.

[0146] 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-hydroxycyclohexyl 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.

[0147] 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.

[0148] 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.

[0149] 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.

[0150] 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.

[0151] 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.

[0152] 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-butyl peroxy-2-ethylhexanoate, t-butyl peroxy-3,5,5-trimethylhexanoate, t-butyl peroxylaurate, t-butyl peroxybenzoate, di-t-butylperoxyisophthalate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexanoate Examples of organic peroxides include peroxyester compounds such as methyl peroxide, t-butyl peroxymaleic acid, t-butyl peroxyisopropyl carbonate, cumyl peroxyoctoate, t-hexyl peroxyneodecanoate, t-hexyl peroxypivalate, t-butyl peroxyneohexanoate, t-hexyl peroxyneohexanoate, and cumyl peroxyneohexanoate; acetylcyclohexylsulfonyl peroxide, and t-butyl peroxyallyl carbonate. These organic peroxides can be used either alone or in combination of two or more.

[0153] <Ultraviolet Absorber> In one embodiment, the modified polyolefin composition may contain an ultraviolet absorber, as long as the effects of the present invention are not impaired. Examples of the ultraviolet absorber include benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, triazine-based ultraviolet absorbers, salicylic acid-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, and benzoxazine-based ultraviolet absorbers. These ultraviolet absorbers may be used alone or in combination of two or more.

[0154] The amount of the ultraviolet absorber used is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the modified polyolefin resin composition.

[0155] <Light Stabilizer> In one embodiment, the modified polyolefin composition may contain a light stabilizer, as long as the effects of the present invention are not impaired. Examples of the light stabilizer include hindered amine light stabilizers.

[0156] 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.

[0157] The amount of the light stabilizer used 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.

[0158] <Sensitizer> The modified polyolefin composition of the present embodiment may contain a sensitizer within a range that does not impair the effects of the present invention. 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.

[0159] The amount of the sensitizer used is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the modified polyolefin resin composition.

[0160] <Surfactant> The modified polyolefin resin composition of the present embodiment may contain a surfactant within a range that does not impair the effects of the present invention. 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.

[0161] 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 alkylamine ethers, polyoxypropylene alkylamine ethers, 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.).

[0162] 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.).

[0163] The amount of the surfactant used 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 the coating film obtained from the modified polyolefin resin composition.

[0164] <Pigment> The coating material containing the modified polyolefin resin composition of the present embodiment may contain a pigment. As the pigment, a color pigment, an extender pigment, a conductive pigment, or the like may be used.

[0165] 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.

[0166] 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.

[0167] 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.

[0168] <Various Additives> The modified polyolefin resin composition of the present embodiment 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, and a wetting agent.

[0169] 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.

[0170] The amount of the tackifier used 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.

[0171] <Organic Solvent> The modified polyolefin resin composition of the present embodiment may or may not contain an organic solvent.

[0172] When the modified polyolefin resin composition of this embodiment contains an organic solvent, it is preferable that a small amount of organic solvent is contained from the viewpoints of environment and hygiene. 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, still 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. In one embodiment, when the modified polyolefin resin composition contains an organic solvent, the viscosity of the modified polyolefin resin composition is further reduced, which has the advantage of further improving the coatability.

[0173] When the modified polyolefin resin composition of this embodiment does not contain an organic solvent, the modified polyolefin resin composition of this embodiment can be suitably used as a base agent for a solventless radical curing binder. In this specification, "solventless" means that no organic solvent is intentionally added to the modified polyolefin resin composition of this embodiment, and the "solventless" includes an embodiment in which the organic solvent used in producing the acid-modified polyolefin resin (A) remains.

[0174] 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-based solvents such as methanol, ethanol, isopropyl alcohol, butanol, pentanol, 1-hexanol, 2-ethylhexanol, 2-methylcyclohexanol, phenol, and 2-heptyl alcohol; ketone-based solvents such as acetone, methyl isobutyl ketone, methyl ethyl ketone, pentanone, hexanone, cyclohexanone, isophorone, and acetophenone; cellosolve-based solvents such as methyl cellosolve and ethyl cellosolve; ester-based solvents such as methyl acetate, ethyl acetate, butyl acetate, methyl propionate, ethyl propionate, and butyl formate; Examples of such solvents include 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.

[0175] (Physical properties of modified polyolefin resin composition) The breaking elongation of the modified polyolefin resin composition of this embodiment is preferably 5% or more. In this case, the cured coating film produced from the resin composition has excellent flex resistance. The breaking elongation is more preferably 10% or more, and even more preferably 20%. From the viewpoint of further improving the workability of film formation, the upper limit of the breaking elongation of the modified polyolefin resin composition is preferably 2000% or less, more preferably 1500% or less, even more preferably 1000% or less, and even more preferably 750% or less. The breaking elongation of the modified polyolefin resin composition can be measured by the method described above in <Method for measuring breaking elongation of modified polyolefin resin composition>.

[0176] (Method for Producing Modified Polyolefin Resin Composition) A wide variety of known methods can be used to produce the modified polyolefin resin composition of this embodiment, and examples thereof include the method comprising the following steps (1) to (3). Step (1): The acid-modified polyolefin resin (A) and the compound (B) having a polymerizable unsaturated group are placed in a stirrer equipped with a heating device and kneaded while heating. Step (2): The polyetheramine (C) is further added to the stirrer and kneaded while heating. Step (3): The mixture is then cooled to room temperature and filtered to obtain a modified polyolefin resin composition.

[0177] In the above step (1), the heating temperature during kneading is usually 50 to 200° C., preferably 60 to 150° C., and more preferably 70 to 120° C. 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.

[0178] In the above step (2), the heating temperature during kneading is usually 50 to 200° C., preferably 60 to 150° C., and more preferably 70 to 120° C. 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 75 minutes.

[0179] In the above step (3), the filtration can be carried out using, for example, a wire mesh with an opening size of 50 μm to 300 μm.

[0180] (Cured Product) The cured product of this embodiment is a cured product obtained by curing the modified polyolefin resin composition of this embodiment. In other words, the cured product of this embodiment is a product obtained by curing the modified polyolefin resin composition of this embodiment. Hereinafter, the cured product will be simply referred to as the "cured product of this embodiment."

[0181] (Applications) The modified polyolefin resin composition of this embodiment and the cured product of this embodiment 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, and poly(4-methyl-1-pentene). The modified polyolefin resin composition of this embodiment and the cured product of this embodiment can be particularly suitably used for polypropylene substrates.

[0182] The modified polyolefin resin composition of this embodiment and the cured product of this embodiment 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 this embodiment and the cured product of this embodiment 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.

[0183] A coating film can be obtained from the modified polyolefin resin composition of the present embodiment. The coating film can be particularly suitably used for metal products, electronic devices, packaging materials, automobile parts, and the like.

[0184] Examples of methods for forming a coating film from the modified polyolefin resin composition of this embodiment include a method in which the modified polyolefin resin composition of this embodiment 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 this embodiment 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.

[0185] The present invention provides the following aspects. Item 1. A modified polyolefin resin composition comprising an acid-modified polyolefin resin (A) and a compound (B) having a polymerizable unsaturated group, wherein the compound (B) having a polymerizable unsaturated group comprises a compound (B-1) having a polymerizable unsaturated group with an elongation at break of 30% or more. Item 2. The modified polyolefin resin composition according to Item 1, wherein the content of the acid-modified polyolefin resin (A) is preferably 10 to 50 parts by mass, more preferably 12 to 45 parts by mass, even more preferably 15 to 40 parts by mass, and still more preferably 18 to 35 parts by mass, per 100 parts by mass of the compound (B) having a polymerizable unsaturated group. Item 3. Item 4. The modified polyolefin resin composition according to any one of Items 1 to 3, wherein the compound (B-1) having a polymerizable unsaturated group and having an elongation at break of 30% or more is preferably at least one compound selected from the group consisting of urethane (meth)acrylate, epoxy (meth)acrylate, polyester (meth)acrylate, polyether (meth)acrylate, and vinyl ester, more preferably at least one compound selected from the group consisting of urethane (meth)acrylate, polyester (meth)acrylate, and vinyl ester, and even more preferably urethane (meth)acrylate and / or vinyl ester. Item 5. The modified polyolefin resin composition according to any one of Items 1 to 3, wherein the compound (B) having a polymerizable unsaturated group includes a compound (B-2) having a polymerizable unsaturated group and having an elongation at break of less than 30%. Item 5. The modified polyolefin resin composition according to Item 4, wherein the mass ratio of the compound (B-1) having a polymerizable unsaturated group and having an elongation at break of 30% or more to the compound (B-2) having a polymerizable unsaturated group and having an elongation at break of less than 30% is preferably (B-1):(B-2)=99:1 to 5:95, more preferably (B-1):(B-2)=80:20 to 20:80, even more preferably (B-1):(B-2)=65:35 to 25:75, and still more preferably (B-1):(B-2)=40:60 to 60:40.Item 6. The modified polyolefin resin composition according to Item 4 or 5, wherein the compound (B-2) having a polymerizable unsaturated group and having an elongation at break of less than 30% comprises a compound (B-21) having an alkyleneoxy group and / or a 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), and one or more (usually 1 to 4, preferably 1 to 3, more preferably 1 or 2) polymerizable unsaturated groups. Item 8. The modified polyolefin resin composition according to any one of Items 4 to 6, wherein the compound (B-2) having a polymerizable unsaturated group and having an elongation at break of less than 30% comprises a compound (B-211) having a hydroxyl group and one or more (usually 1 to 4, preferably 1 to 3, more preferably 1 or 2, and even more preferably 2) polymerizable unsaturated groups. Item 9. The modified polyolefin resin composition according to Item 8, wherein the compound (B-2) having a polymerizable unsaturated group and having an elongation at break of less than 30% comprises a compound (B-22) having a unit having a carbonyl group and one or more (usually 1 to 4, preferably 1 to 3, more preferably 1 or 2, and even more preferably 1) polymerizable unsaturated groups. Item 10. The modified polyolefin resin composition according to Item 8, wherein the unit having a carbonyl group is a group represented by the following formula (1) or (2): In the formula (1), R １ represents a hydrogen atom or a methyl group. * represents a bond. In the formula (2), R ２ represents a hydrocarbon group having 1 to 10 (1, 2, 3, 4, 5, 6, 7, 8, 9 or 10) carbon atoms which may have a substituent. ３ represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9, or 10) which may have a substituent. * represents a bond. However, R ２ and R ３The hydrocarbon groups having 1 to 10 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 carbon atoms) which may have a substituent each independently may further have a branched structure, an alicyclic structure (preferably cyclohexyl), or an aromatic ring structure (preferably phenyl or naphthyl, more preferably phenyl). Item 10. The modified polyolefin resin composition according to any one of Items 1 to 9, further comprising a polyetheramine (C). Item 11. The modified polyolefin resin composition according to Item 10, wherein the content of the polyetheramine (C) is usually 6 to 100 parts by mass, preferably 10 to 90 parts by mass, more preferably 15 to 80 parts by mass, even more preferably 20 to 70 parts by mass, still more preferably 25 to 60 parts by mass, and particularly preferably 30 to 50 parts by mass, per 100 parts by mass of the acid-modified polyolefin resin (A). Item 12. Item 10. The modified polyolefin resin composition according to Item 10 or 11, wherein the polyetheramine (C) 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 5,000, 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 13. The modified polyolefin resin composition according to any one of Items 1 to 12, wherein the acid-modified polyolefin resin (A) is a graft polymer having a structure in which an α,β-unsaturated carboxylic acid and / or an acid anhydride thereof is grafted to a polyolefin resin. Item 14. Item 14. The modified polyolefin resin composition according to Item 13, wherein the polyolefin resin is typically homopolypropylene (a homopolymer of propylene), propylene-α-olefin copolymer, homopolyethylene (a homopolymer of ethylene), ethylene-α-olefin copolymer, homopoly-1-butene, or 1-butene-α-olefin copolymer, preferably homopolypropylene and / or propylene-α-olefin copolymer, more preferably propylene-α-olefin copolymer.Item 15. The modified polyolefin resin composition according to Item 14, wherein the content of the propylene component in the propylene-α-olefin copolymer is preferably 50 mol% or more, more preferably 55 mol% or more, even more preferably 60 mol% or more, even more preferably 65 mol% or more, and particularly preferably 70 mol% or more. Item 16. The modified polyolefin resin composition according to any one of Items 1 to 15, wherein the content of the acid-modified polyolefin resin (A) is preferably 5 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 17. The modified polyolefin resin composition according to any one of Items 1 to 16, wherein the content of the compound (B) having a polymerizable unsaturated group is preferably 10 to 90 mass%, more preferably 20 to 85 mass%, and even more preferably 30 to 80 mass%, relative to the total mass of the modified polyolefin resin composition. Item 18. The modified polyolefin resin composition according to any one of Items 1 to 17, wherein the number of polymerizable unsaturated groups in the compound (B) having a polymerizable unsaturated group is usually 1, 2, 3, or 4, preferably 1, 2, or 3, and more preferably 1 or 2. Item 19. The modified polyolefin resin composition according to any one of Items 1 to 18, wherein the compound (B-1) having a polymerizable unsaturated group has a breaking elongation of preferably 100% or more, more preferably 300%, and even more preferably 500% or more. Item 20. The modified polyolefin resin composition according to any one of Items 1 to 19, wherein the compound (B-1) having a polymerizable unsaturated group has a breaking elongation of 2000% or less. Item 21. The modified polyolefin resin composition according to any one of Items 4 to 20, wherein the compound (B-2) having a polymerizable unsaturated group has a breaking elongation of preferably 20% or less, more preferably 10% or less.Item 22. The modified polyolefin resin composition according to any one of Items 4 to 21, wherein the combined content of the compound (B-1) having a polymerizable unsaturated group having an elongation at break of 30% or more and the compound (B-2) having a polymerizable unsaturated group having an elongation at break of less than 30% is usually more than 50% by mass, preferably 60% by mass or more, more preferably 65% ​​by mass or more, still more preferably 70% by mass or more, and even more preferably 72.5% by mass or more, relative to the total mass of the modified polyolefin resin composition. Item 23. The modified polyolefin resin composition according to any one of Items 1 to 22, wherein the combined content of the acid-modified polyolefin resin (A) and the compound (B) having a polymerizable unsaturated group is more than 50% by mass, 60% by mass or more, 70% by mass or more, 80% by mass or more, 85% by mass or more, 90% by mass or more, 91% by mass or more, 92% by mass or more, 92.5% by mass or more, 95% by mass or more, 97.5% by mass or more, 99% by mass or more, 99.5% by mass or more, and 99.9% by mass or more, relative to the total mass of the modified polyolefin resin composition. Item 24. The modified polyolefin resin composition according to any one of Items 4 to 23, wherein the total content of the acid-modified polyolefin resin (A), the compound (B-1) having a polymerizable unsaturated group and the compound (B-2) having a polymerizable unsaturated group and the breaking elongation of 30% or more is more than 50% by mass, 60% by mass or more, 70% by mass or more, 80% by mass or more, 85% by mass or more, 90% by mass or more, 91% by mass or more, 92% by mass or more, 92.5% by mass or more, 95% by mass or more, 97.5% by mass or more, 99% by mass or more, 99.5% by mass or more, and 99.9% by mass or more, in that order.Item 25. The compound (B-2) having a polymerizable unsaturated group and having an elongation at break of less than 30% is a compound (B-21) having an alkyleneoxy group and / or a 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), and one or more (usually 1 to 4, preferably 1 to 3, more preferably 1 or 2) polymerizable unsaturated groups; a compound (B-211) having a hydroxyl group and one or more (usually 1 to 4, preferably 1 to 3, more preferably 1 or 2, and even more preferably 2) polymerizable unsaturated groups; and Item 26. The modified polyolefin resin composition according to any one of Items 8 to 25, wherein the compound (B-22) is at least one compound selected from the group consisting of compounds (B-22) having a unit having a carbonyl group and one or more (usually 1, 2, 3, or 4, preferably 1, 2, or 3, more preferably 1 or 2, and even more preferably 1) polymerizable unsaturated groups. Item 26. The modified polyolefin resin composition according to any one of Items 8 to 25, wherein the compound (B-22) is a compound (B-221) having a group represented by Formula (1) or Formula (2) and one or more (usually 1, 2, 3, or 4, preferably 1, 2, or 3, more preferably 1 or 2, and even more preferably 1) polymerizable unsaturated groups. Item 27. Item 27. The weight average molecular weight (Mw) of the compound (B) having a polymerizable unsaturated group is usually 5,000 or less, preferably 3,000 or less, more preferably 2,000 or less, still more preferably 1,500 or less, and even more preferably 1,000 or less. The modified polyolefin resin composition according to any one of Items 1 to 26.Item 28. The modified polyolefin resin composition according to any one of Items 6 to 27, wherein the content of the compound (B-21) having an alkyleneoxy group and / or a 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), and one or more (usually 1 to 4, preferably 1 to 3, more preferably 1 or 2) polymerizable unsaturated groups, is preferably 1 to 80 mass%, more preferably 2 to 75 mass%, even more preferably 3 to 70 mass%, even more preferably 10 to 65 mass%, and still more preferably 15 to 60 mass%, relative to the total mass of the modified polyolefin resin composition. Item 30. The modified polyolefin resin composition according to any one of Items 7 to 28, wherein the content of the compound (B-211) having a hydroxyl group and one or more (usually 1 to 4, preferably 1 to 3, more preferably 1 or 2, and even more preferably 2) polymerizable unsaturated groups is preferably 1 to 50 mass%, more preferably 2 to 45 mass%, even more preferably 3 to 40 mass%, even more preferably 10 to 35 mass%, and even more preferably 15 to 30 mass%, relative to the total mass of the modified polyolefin resin composition. Item 30. The modified polyolefin resin composition according to any one of Items 8 to 29, wherein the content of the compound (B-22) having a unit having a carbonyl group and one or more (usually 1, 2, 3, or 4, preferably 1, 2, or 3, more preferably 1 or 2, and even more preferably 1) polymerizable unsaturated groups is preferably 1 to 50 mass%, more preferably 2 to 48 mass%, even more preferably 3 to 45 mass%, even more preferably 10 to 42 mass%, and even more preferably 15 to 40 mass%, relative to the total mass of the modified polyolefin resin composition.Item 31. The modified polyolefin resin composition according to any one of Items 26 to 30, wherein the content of the compound (B-221) having a group represented by formula (1) or formula (2) and one or more (usually 1, 2, 3, or 4, preferably 1, 2, or 3, more preferably 1 or 2, and even more preferably 1) polymerizable unsaturated groups is preferably 1 to 50% by mass, more preferably 2 to 48% by mass, even more preferably 3 to 45% by mass, even more preferably 10 to 42% by mass, and even more preferably 15 to 40% by mass, relative to the total mass of the modified polyolefin resin composition. Item 32. The modified polyolefin resin composition according to any one of Items 1 to 31, wherein the polymerizable unsaturated group is preferably 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, more preferably at least one selected from the group consisting of an acryloyl group, a methacryloyl group, an acryloyloxy group, and a methacryloyloxy group, and even more preferably an acryloyloxy group and / or a methacryloyloxy group. Item 33. The modified polyolefin resin composition according to any one of Items 6 to 32, wherein the compound (B-21) is at least one compound selected from the group consisting of: a compound having a 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), which optionally has an alicyclic structure (preferably cyclohexyl), and one or two (meth)acryloyloxy groups; and a compound having an alkyleneoxy group and one or two (meth)acryloyloxy groups. Item 34. The modified polyolefin resin composition according to any one of Items 7 to 33, wherein the compound (B-211) is a compound having one or two (preferably one) hydroxyl groups and one or two (preferably two) (meth)acryloyloxy groups.Item 35. The modified polyolefin resin composition according to any one of Items 8 to 34, wherein the compound (B-22) is a compound having a group represented by Formula (1) and one or two (more preferably one) (meth)acryloyloxy groups. Item 36. The modified polyolefin resin composition according to any one of Items 10 to 35, wherein the content of the polyetheramine (C) is usually 0.5 to 40 mass%, preferably 1 to 30 mass%, more preferably 2 to 25 mass%, even more preferably 3 to 20 mass%, even more preferably 4 to 15 mass%, and particularly preferably 5 to 10 mass%, relative to the total mass of the modified polyolefin resin composition. Item 37. The modified polyolefin resin composition according to any one of Items 10 to 36, wherein the HLB value of the polyetheramine (C) is preferably 2 to 20, more preferably 5 to 19, and even more preferably 8 to 18. Item 38. The polyetheramine (C) has a polyether chain, and the polyether chain is represented by the formula 5: —(O—CH. ２ CH ２ )x- (wherein x is an integer of 2 to 120), a structure represented by Formula 6-1: -(O-CH ２ CH (CH ３ ))y １ -(In formula 6-1, y １ is an integer of 2 to 90), a structure represented by Formula 6-2: —(O—CH ２ CH ２ CH ２ ) y ２ -(In formula 6-2, y ２ is an integer of 2 to 90), a structure represented by Formula 7-1: -(O-CH ２ CH ２ CH ２ CH ２ ) z １ -(In formula 7-1, z １ is an integer of 2 to 80), a structure represented by formula 7-2: -(O-CH(CH ３ ) CH ２ CH ２ ) z ２ -(In formula 7-2, z ２ is an integer of 2 to 80), a structure represented by formula 7-3: -(O-CH ２ CH (CH ３ ) CH２ ) z ３ -(In formula 7-3, z ３ is an integer of 2 to 80), and a structure represented by formula 7-4: -(O-CH ２ CH ２ CH (CH ３ ))z ４ -(In formula 7-4, z ４ Item 39. The modified polyolefin resin composition according to any one of Items 10 to 37, wherein the polyetheramine (C) has a polyether chain, and the polyether chain is represented by Formula 5: -(O-CH ２ CH ２ )x- (wherein x is an integer of 2 to 120), a structure represented by Formula 6-1: -(O-CH ２ CH (CH ３ ))y １ -(In formula 6-1, y １ is an integer of 2 to 90) and a structure represented by Formula 7-1: -(O-CH ２ CH ２ CH ２ CH ２ ) z １ -(In formula 7-1, z １ Item 40. The modified polyolefin resin composition according to any one of Items 10 to 38, wherein the polyetheramine (C) is a structure containing at least one selected from the group consisting of structures represented by the following formula 5A: ６ -(O-R ７ ) a-R ８ Formula 5A (In formula 5A: R ６ and R ８ R 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. ７ Item 41. The modified polyolefin resin composition according to any one of Items 10 to 39, wherein R represents a linear or branched alkylene group having 2 to 4 carbon atoms (2, 3, or 4). a represents an integer of 2 to 120. Item 42. The modified polyolefin resin composition according to any one of Items 10 to 39, wherein R represents a linear or branched alkylene group having 2 to 4 carbon atoms (2, 3, or 4). Item 43. The modified polyolefin resin composition according to any one of Items 10 to 39, wherein R represents a linear or branched alkylene group having 2 to 4 carbon atoms (2, 3, or 4). a represents an integer of 2 to 120. ６represents 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 ７ represents a linear or branched alkylene group having 2 to 4 (2, 3, or 4) carbon atoms, and R ８ represents an amino group, and a is an integer of 1 to 120. Item 42. A cured product obtained by curing the modified polyolefin resin composition according to any one of items 1 to 41. Item 43. An ink comprising the modified polyolefin resin composition according to any one of items 1 to 41 or the cured product according to item 42. Item 44. An adhesive comprising the modified polyolefin resin composition according to any one of items 1 to 41 or the cured product according to item 42. Item 45. A primer comprising the modified polyolefin resin composition according to any one of items 1 to 41 or the cured product according to item 42. Item 46. A paint comprising the modified polyolefin resin composition according to any one of items 1 to 41 or the cured product according to item 42. Item 47. A paint for in-mold coating comprising the modified polyolefin resin composition according to any one of items 1 to 41 or the cured product according to item 42.

[0186] Next, the present invention will be described in detail based on examples, but the present invention is not limited to the following examples. Hereinafter, "room temperature" means a temperature within the range of 20°C to 25°C.

[0187] (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.

[0188] (2) Measurement of melting point by differential scanning calorimetry (DSC) In accordance with JIS K7121-2012, 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 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 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.

[0189] (Production Example 1) 280 g of propylene-α-olefin copolymer (propylene content = 70 mol%), 70 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 mixture was reacted 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 modified polyolefin resin (MPO-1). Infrared absorption spectroscopy revealed that the acid values ​​of the maleic anhydride and maleic acid components in MPO-1 were 22.4 mgKOH / g. The total content of maleic anhydride and maleic acid components in MPO-1 was 2.0% by mass, the weight average molecular weight (Mw) measured by high-temperature GPC was 40,000, and the melting point measured by DSC was 70°C.

[0190] (Production Example 2) 280 g of propylene-α-olefin copolymer (propylene content = 94 mol%), 14 g of maleic anhydride, 5.6 g of dicumyl peroxide, and 420 g of toluene were placed in an autoclave equipped with a stirrer. After approximately 5 minutes of nitrogen substitution, the mixture was reacted 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. After drying under reduced pressure, 280 g of the resulting maleic anhydride-modified polyolefin resin and 2520 g of chloroform were placed in an autoclave equipped with a stirrer. After approximately 5 minutes of nitrogen substitution, the mixture was heated to 110°C to fully dissolve the resin. Next, 1.4 g of tert-butylperoxy-2-ethylhexanoate was added, and a predetermined amount of chlorine gas was blown in. The reaction solvent, chloroform, was distilled off under reduced pressure and dried to obtain a solid acid-modified chlorinated polyolefin resin (CPO-1). The weight average molecular weight (Mw) of CPO-1 measured by high-temperature GPC was 80,000, and the melting point measured by DSC was 75°C. The chlorine content in CPO-1 was 30% by mass, and the acid value of the maleic anhydride component was 16.8 mgKOH / g.

[0191] (Materials Used) The materials used in the Examples and Comparative Examples are as follows. The breaking elongation described in (B-1), (B-21), (B-211) and (B-22) below means the value measured by the above-mentioned <Method for measuring breaking elongation of compound (B) having a polymerizable unsaturated group>.

[0192] <Acid-Modified Polyolefin Resin (A)> MPO-1 obtained in Production Example 1 (total content of maleic anhydride component and maleic acid component=2.0% by mass, Mw measured by high-temperature GPC=40,000, melting point by DSC=70°C) CPO-1 obtained in Production Example 2 (chlorine content=30% by mass, content of maleic anhydride component=1.5% by mass, Mw measured by high-temperature GPC=80,000, melting point by DSC=75°C)

[0193] <Compounds (B-1) Having a Polymerizable Unsaturated Group with a Breaking Elongation of 30% or More> Urethane acrylate 1: KRM9276 (manufactured by Daicel-Allnex Corporation), breaking elongation=790% Urethane acrylate 2: EBECRYL8413 (manufactured by Daicel-Allnex Corporation), breaking elongation=460% Polyester acrylate: EBECRYL525 (manufactured by Daicel-Allnex Corporation), breaking elongation=50% Vinyl ester: VeoVa10 (manufactured by HEXION Corporation), breaking elongation=550%

[0194] <Compound (B-2) Having a Polymerizable Unsaturated Group with a Breaking Elongation of Less than 30%> [Compound (B-21) Having an Alkyleneoxy Group and / or a 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), and One or More Polymerizable Unsaturated Groups] (Compound Having a Branched Alkyl Group Having 10 Carbon atoms, an Alicyclic Structure, and One Polymerizable Unsaturated Group) 4-tert-butylcyclohexyl acrylate (Mw=210) (manufactured by Tokyo Chemical Industry Co., Ltd.), Breaking Elongation=1% (Compound Having an Alkyleneoxy Group and Two Polymerizable Unsaturated Groups) 1,9-Nonanediol diacrylate (Mw=268) (manufactured by Tokyo Chemical Industry Co., Ltd.), Breaking Elongation=12% Polypropylene glycol diacrylate (polypropylene glycol #700 diacrylate, number of repeating units = 12, Mw = 808, manufactured by Shin-Nakamura Chemical Co., Ltd., NK Ester (registered trademark) "APG-700"), breaking elongation = 9% [Compound (B-211) having a hydroxyl group and one or more polymerizable unsaturated groups] (Compound having one hydroxyl group and two polymerizable unsaturated groups) 2-hydroxy-3-methacrylpropyl acrylate (Mw = 214) (manufactured by Tokyo Chemical Industry Co., Ltd.), breaking elongation = 2% [Compound (B-221) having a unit having a carbonyl group represented by the above formula (1) and one or more polymerizable unsaturated groups] Acetoacetoxyethyl methacrylate (Mw = 214) (manufactured by Tokyo Chemical Industry Co., Ltd.), breaking elongation = 3%

[0195] <Polyetheramine (C)> "JEFFAMINE M-2070 (Mw = 2000, HLB value = 13.8)" manufactured by HUNTSMAN (number of primary amino groups = 1, number of secondary amino groups = 0) "JEFFAMINE M-1000 (Mw = 1000, HLB value = 16.1)" manufactured by HUNTSMAN (number of primary amino groups = 1, number of secondary amino groups = 0)

[0196] Example 1 A 200-milliliter four-neck flask equipped with a condenser, a thermometer, and a stirrer was charged with 20 g of CPO-1 obtained in Production Example 2 as the acid-modified polyolefin resin (A) and 80 g of urethane acrylate 1 as the compound (B) having a polymerizable unsaturated group, and the internal temperature was raised to 90°C and stirred for 1 hour. The mixture was then cooled to room temperature and filtered through a wire mesh with 149 μm openings to obtain a modified polyolefin resin composition (a). Note that no polyetheramine (C) was used in Example 1.

[0197] (Examples 2 to 16 and Comparative Example 2) Modified polyolefin resin compositions (b) to (p) and (r) were obtained in the same manner as in Example 1, except that the amounts of the acid-modified polyolefin (A), the compound having a polymerizable unsaturated group (B), and the polyetheramine (C) used were changed as shown in Table 1 below. In Examples 2 to 8, 20 g of the CPO-1 obtained in Production Example 2 was used, and in Examples 9 to 16, 20 g of the MPO-1 obtained in Production Example 1 was used. In Examples 2 to 7 and Comparative Example 2, no polyetheramine (C) was used, while in Examples 8 to 15, 8 g of polyetheramine (C) was used, and in Example 16, 4 g of polyetheramine (C) was used.

[0198] Comparative Example 1: 100 g of urethane acrylate 1 was placed in a 200 ml four-neck flask equipped with a condenser, thermometer, and stirrer as a compound (B) having a polymerizable unsaturated group and a breaking elongation of 30% or more. The internal temperature was raised to 90°C and the mixture was heated and dissolved for 1 hour. The mixture was then cooled to room temperature and filtered through a wire mesh with a mesh size of 149 μm to obtain a resin composition (q). In Comparative Example 1, neither the acid-modified polyolefin resin (A) nor the polyetheramine (C) was used.

[0199] (1) Evaluation of fluidity at 25°C and 80°C The modified polyolefin resin compositions obtained in Examples 1 to 16 and Comparative Example 2 and the resin composition obtained in Comparative Example 1 were visually evaluated for fluidity at 25°C and 80°C immediately after production, fluidity at 25°C and 80°C the next day (24 hours after production), and fluidity at 25°C and 80°C one week later (168 hours after production). A case where fluidity was present one week later was evaluated as ⊚, a case where fluidity was present the next day 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 x.

[0200] (2) Evaluation of Adhesion To 5 g of the compound (B) having a polymerizable unsaturated group in the modified polyolefin resin compositions obtained in Examples 1 to 16 and Comparative Example 2 and 5 g of the compound (B) having a polymerizable unsaturated group in the resin composition obtained in Comparative Example 1, 2% tert-butyl-2-ethylperoxyhexanoate was added and stirred at room temperature for 30 minutes using a magnetic stirrer. The resulting mixture was applied to a PP (polypropylene) bumper substrate washed with isopropyl alcohol at room temperature to a coating thickness of approximately 100 μm after drying. After baking at 110°C for 3 minutes, the test plate was left for 72 hours in an atmosphere of 25°C and 60% relative humidity to produce a cured coating film, which was used as a test plate. One hundred squares were created on the test plate at 1 mm intervals, reaching down to the substrate. Cellophane tape was then pressed onto the squares and peeled off at a 90° angle to the coating surface three times. When peeling was repeated three times, no peeling occurred, and the evaluation was ◯. When peeling occurred on the third peeling, the evaluation was △. When peeling occurred on the first or second peeling, the evaluation was ×.

[0201] (3) Evaluation of Water Resistance To 5 g of the compound (B) having a polymerizable unsaturated group in the modified polyolefin resin compositions obtained in Examples 1 to 16 and Comparative Example 2 and 5 g of the compound (B) having a polymerizable unsaturated group in the resin composition obtained in Comparative Example 1, 2% of tert-butyl-2-ethylperoxyhexanoate was added and stirred at room temperature for 30 minutes using a magnetic stirrer. The resulting mixture was applied to a PP (polypropylene) bumper substrate washed with isopropyl alcohol at room temperature so that the coating thickness after drying would be approximately 100 μm. After baking at 110 °C for 3 minutes, the coating was left for 72 hours in an atmosphere at a temperature of 25 °C and a relative humidity of 60%, producing a cured coating film, which was used as a test plate. The resulting test plate was immersed in warm water at 40 °C 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 coated 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.

[0202] (4) Flex Resistance A cured coating film prepared in the same manner as in the adhesion evaluation performed in (2) was subjected to a flex resistance test using a φ20 mm cylindrical mandrel in accordance with JIS K 5600-5-1:1999 (flex resistance). The flex resistance of the cured coating film was evaluated based on the following criteria: ○: No cracks occurred △: Cracks occurred in a small area ×: Cracks occurred over the entire surface

[0203] (5) Breaking Elongation 2% of tert-butyl-2-ethylperoxyhexanoate was added to 10 g of the compound (B) having a polymerizable unsaturated group in 10 g of the modified polyolefin resin composition obtained in Examples 1 to 16 and Comparative Example 2, and to 10 g of the compound (B) having a polymerizable unsaturated group in 10 g of the resin composition obtained in Comparative Example 1, and the mixture was stirred at room temperature for 30 minutes using a magnetic stirrer. The mixed solution was applied to a Teflon (registered trademark) sheet and heated at 110°C for 1 minute to produce a cured coating film with a thickness of 100 μm. The elongation to break of the cured coating film produced was measured using a tensile tester (Tensilon RTM-100, manufactured by Orientec Corporation) under conditions of a width of 10 mm, a chuck distance of 30 mm, a pulling speed of 100 mm / min, a temperature of 20°C, and a relative humidity of 65%, and the breaking elongation of the modified polyolefin resin compositions obtained in Examples 1 to 16 and Comparative Example 2 and the resin composition obtained in Comparative Example 1 was calculated using the following method. Breaking elongation (%) = 100 × {(length at break) - (initial length before tensile test)} / initial length before tensile test

[0204] The raw materials and amounts used in each Example and Comparative Example, the evaluation results of the modified polyolefin resin compositions (a) to (p) obtained in Examples 1 to 16, the evaluation results of the resin composition (q) obtained in Comparative Example 1 and the modified polyolefin resin composition (r) obtained in Comparative Example 2, etc. are shown in Table 1 below.

[0205]

[0206] [Discussion of the Results in Table 1] The modified polyolefin resin compositions obtained in Examples 1 to 16 were shown to maintain fluidity immediately after production at both 25°C and 80°C. The modified polyolefin resin compositions obtained in Examples 1 to 16 were also shown to have good adhesion to PP (polypropylene) bumper substrates. Furthermore, the modified polyolefin resin compositions obtained in Examples 1 to 16 were also shown to have good water resistance. Furthermore, the modified polyolefin resin compositions obtained in Examples 1 to 16 were also shown to have excellent flex resistance. On the other hand, the resin composition obtained in Comparative Example 1 did not contain an acid-modified polyolefin resin (A), resulting in significantly inferior adhesion and water resistance. Furthermore, Comparative Example 2 did not contain a compound (B-1) having a polymerizable unsaturated group with a breaking elongation of 30% or more, resulting in significantly inferior flex resistance.

Claims

1. A modified polyolefin resin composition comprising an acid-modified polyolefin resin (A) and a compound (B) having a polymerizable unsaturated group, wherein the compound (B) having a polymerizable unsaturated group comprises a compound (B-1) having a polymerizable unsaturated group with a breaking elongation of 30% or more.

2. The modified polyolefin resin composition according to claim 1, wherein the content of the acid-modified polyolefin resin (A) is 10 to 50 parts by mass per 100 parts by mass of the compound (B) having a polymerizable unsaturated group.

3. The modified polyolefin resin composition according to claim 1, wherein the compound (B-1) having a polymerizable unsaturated group with a breaking elongation of 30% or more is at least one compound selected from the group consisting of urethane (meth)acrylates, epoxy (meth)acrylates, polyester (meth)acrylates, polyether (meth)acrylates and vinyl esters.

4. The modified polyolefin resin composition according to claim 1, wherein the compound (B) having a polymerizable unsaturated group includes a compound (B-2) having a polymerizable unsaturated group having a breaking elongation of less than 30%.

5. The modified polyolefin resin composition according to claim 4, wherein the mass ratio of the compound (B-1) having a polymerizable unsaturated group and having a breaking elongation of 30% or more to the compound (B-2) having a polymerizable unsaturated group and having a breaking elongation of less than 30% is (B-1):(B-2)=99:1 to 5:

95.

6. The modified polyolefin resin composition according to claim 4, wherein the compound (B-2) having a polymerizable unsaturated group with a breaking elongation of less than 30% comprises a compound (B-21) having an alkyleneoxy group and / or a linear or branched alkyl group having 1 to 20 carbon atoms, and one or more polymerizable unsaturated groups.

7. The modified polyolefin resin composition according to claim 4, wherein the compound (B-2) having a polymerizable unsaturated group and having a breaking elongation of less than 30% includes a compound (B-211) having a hydroxyl group and one or more polymerizable unsaturated groups.

8. The modified polyolefin resin composition according to claim 4, wherein the compound (B-2) having a polymerizable unsaturated group and having a breaking elongation of less than 30% includes a compound (B-22) having a unit having a carbonyl group and one or more polymerizable unsaturated groups.

9. The modified polyolefin resin composition according to claim 8, wherein the unit having a carbonyl group is a group represented by the following formula (1) or (2): In the formula (1), R １ represents a hydrogen atom or a methyl group. * represents a bond. In the formula (2), R ２ R represents a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent. ３ represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent. * represents a bond. ２ and R ３ The hydrocarbon groups having 1 to 10 carbon atoms which may have a substituent in the above formula may each independently further have a branched structure, an alicyclic structure or an aromatic ring structure.

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

11. The modified polyolefin resin composition according to claim 10, wherein the content of the polyetheramine (C) is 6 to 100 parts by mass per 100 parts by mass of the acid-modified polyolefin resin (A).

12. The modified polyolefin resin composition according to claim 10, wherein the polyetheramine (C) has a primary amino group or a secondary amino group at one end, and the weight average molecular weight (Mw) of the polyetheramine (C) is 200 to 50,000.

13. A cured product obtained by curing the modified polyolefin resin composition according to any one of claims 1 to 12.

14. An ink comprising the modified polyolefin resin composition according to any one of claims 1 to 12.

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

16. A primer comprising the modified polyolefin resin composition according to any one of claims 1 to 12.

17. A coating material comprising the modified polyolefin resin composition according to any one of claims 1 to 12.

18. A paint for in-mold coating, comprising the modified polyolefin resin composition according to any one of claims 1 to 12.