Modified polyolefin resin composition and use thereof

Abstract

Provided is a modified polyolefin resin composition containing an acid-modified polyolefin resin (A), a polyetheramine (B), and a compound (C) having a polymerizable unsaturated group.

Description

Technical Field

[0001] The present invention relates to a modified polyolefin resin composition and application of the resin composition. Background Art

[0002] Traditionally, polyolefin resins such as polypropylene, polyethylene, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, polybutene, and poly(4-methyl-1-pentene) have been used in a variety of fields, including automotive parts, electrical components, building materials, and packaging films, due to their relatively low cost and excellent chemical resistance, water resistance, and heat resistance.

[0003] On the other hand, polyolefin-based resins are crystalline and non-polar, and therefore, it is difficult to apply coating, bonding, etc. to polyolefin-based resins.

[0004] Therefore, chlorinated polyolefin resins having strong adhesion to polyolefin-based resins are widely used as binder resins (for example, Patent Document 1 and Patent Document 2).

[0005] From the perspective of improving the adhesion (closeness) of chlorinated polyolefin resins to substrates and compensating for the drawback that chlorinated polyolefin resins are limited in the adhesive targets, mixtures of chlorinated polyolefin resins with acrylic resins, polyurethane resins, or polyester resins, and adhesive compositions in which these resins are graft-polymerized onto chlorinated polyolefin resins are used (e.g., Patent Documents 3 and 4).

[0006] However, these mixtures and adhesive compositions are typically used dissolved in organic solvents such as toluene and xylene. Therefore, large amounts of organic solvent are released into the atmosphere during coating, which is undesirable from environmental and hygienic perspectives. Furthermore, these mixtures and adhesive compositions suffer from poor fluidity at low temperatures (e.g., -5°C) and poor adhesion to polyolefin substrates. [Prior art literature] [Patent Document]

[0007] Patent Document 1: Japanese Patent Application Laid-Open No. 59-75958 Patent Document 2: Japanese Patent Application Laid-Open No. 60-99138 Patent Document 3: Japanese Patent Application Laid-Open No. 6-16746 Patent Document 4: Japanese Patent Application Laid-Open No. 8-12913 Summary of the Invention [Problems to be Solved by the Invention]

[0008] The present invention has been made in view of the above, and an object thereof is to provide a modified polyolefin resin composition having sufficient water resistance and sufficient fluidity within a specific temperature range and sufficient adhesion to a polyolefin substrate. [Means for solving the problem]

[0009] To achieve the above-mentioned object, the present inventors have repeatedly conducted research on dispersing and / or dissolving an acid-modified polyolefin resin in a compound having a polymerizable unsaturated group. They have discovered that a modified polyolefin resin composition containing an acid-modified polyolefin resin, a polyetheramine, and a compound having a polymerizable unsaturated group can solve the above-mentioned problems, thereby completing the present invention.

[0010] The present invention includes the subject matter described in the following items. Item 1. A modified polyolefin resin composition comprising an acid-modified polyolefin resin (A), a polyetheramine (B), and a compound having a polymerizable unsaturated group (C). [Effects of the Invention]

[0011] The modified polyolefin resin composition of the present invention has sufficient water resistance and sufficient fluidity within a specific temperature range, and has sufficient adhesion to polyolefin substrates. Since the modified polyolefin resin composition of the present invention exhibits sufficient fluidity within a specific temperature range, it can be used as a liquid modified polyolefin resin composition in various applications. DETAILED DESCRIPTION

[0012] Hereinafter, preferred embodiments of the present invention will be described in detail. In the following description of the components, some are described based on representative embodiments and specific examples, but the present invention is not limited to such embodiments.

[0013] In this specification, the terms “comprising” and “including / include” include the concepts of “comprising”, “including / include”, “consisting / forming essentially of” and “consisting / forming only of”.

[0014] In the numerical ranges described in this specification, the upper limit or lower limit of the numerical range of a certain stage can be arbitrarily combined with the upper limit or lower limit of the numerical range of another stage. In addition, in the numerical ranges described in this specification, the upper limit or lower limit of the numerical range can also be replaced by the values ​​shown in the examples or the values ​​uniquely derived from the examples. In addition, in this specification, the numerical values ​​connected by "to" refer to the numerical ranges containing the numerical values ​​before and after "to" as the lower limit and upper limit.

[0015] 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”.

[0016] In the present specification, "n-" means "normal", "i-" or "iso-" means "iso", and "tert-" or "t-" means "tertiary", respectively.

[0017] In this specification, "(meth)acrylic acid" includes both acrylic acid and methacrylic acid, and "(meth)acrylate" includes both acrylate and methacrylate.

[0018] In this specification, “acryloyl” is represented by “CH2=CHC(=O)-”, “methacryloyl” is represented by “CH2=C(CH3)C(=O)-”, acryloyloxy is represented by “CH2=CHC(=O)O-”, and methacryloyloxy is represented by “CH2=C(CH3)C(=O)O-”.

[0019] (Modified polyolefin resin composition) The modified polyolefin resin composition of the present invention contains, as essential components, an acid-modified polyolefin resin (A), a polyetheramine (B), and a compound (C) having a polymerizable unsaturated group.

[0020] The modified polyolefin resin composition of the present invention generally has sufficient fluidity within a temperature range of -5°C to 80°C. In this specification, a fluid resin composition refers to a uniform liquid composition that does not contain coarse particles or aggregates of the resin.

[0021] The modified polyolefin resin composition of the present invention is a resin composition that flows when tilted in a glass bottle, typically within a temperature range of -5°C to 80°C. In the present invention, a resin composition having flowability also includes a resin composition that flows when mechanical shearing is applied, typically within a temperature range of -5°C to 80°C.

[0022] As one embodiment of the present invention, preferably, the modified polyolefin resin composition does not contain: (a) a hydrolyzable silyl group-containing polyether resin having a number average molecular weight of 18,000, a viscosity of 12,000 mPa·s at 25° C., and an average number of 1.4 hydrolyzable silyl groups per molecule, and / or (b) A hydrolyzable silyl group-containing acrylic polymer having a number average molecular weight of 9,000, a viscosity at 25° C. of 7,000 mPa·s, and an average number of 1.0 hydrolyzable silyl groups per molecule.

[0023] In one embodiment of the present invention, the content of the hydrolyzable silyl group-containing polyether resin and / or the hydrolyzable silyl group-containing acrylic polymer relative to the total mass of the modified polyolefin resin composition is preferably 55% by mass or less, 50% by mass or less, 45% by mass or less, 40% by mass or less, 35% by mass or less, 30% by mass or less, 25% by mass or less, 20% by mass or less, 15% by mass or less, 10% by mass or less, 7.5% by mass or less, 5% by mass or less, 2.5% by mass or less, 1% by mass or less, 0.5% by mass or less, and 0.1% by mass or less. Here, the "content ratio of the hydrolyzable silyl group-containing polyether resin and the hydrolyzable silyl group-containing acrylic polymer" refers to the total content ratio (mass %) of the hydrolyzable silyl group-containing polyether resin and the hydrolyzable silyl group-containing acrylic polymer relative to the total mass of the modified polyolefin resin composition. As one embodiment of the present invention, it is particularly preferred that the modified polyolefin resin composition does not contain a hydrolyzable silyl group-containing polyether resin and / or a hydrolyzable silyl group-containing acrylic polymer.

[0024] As one embodiment of the present invention, the total content ratio of the acid-modified polyolefin resin (A), the polyetheramine (B), and the compound having a polymerizable unsaturated group (C) relative to the total mass of the modified polyolefin resin composition is preferably 45% by mass, 50% by mass, more than 50% by mass, 55% by mass or more, 60% by mass or more, 65% by mass or more, 70% by mass or more, 75% by mass or more, 80% by mass or more, 85% by mass or more, 90% 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, 99.9% by mass or more, 99.95% by mass or more, and 99.99% by mass or more in this order.

[0025] <Acid-modified polyolefin resin (A)> The present invention comprises 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 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 anhydride is grafted onto a polyolefin resin.

[0026] Polyolefin resins generally have structural units derived from α-olefins. Examples of α-olefins include 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), such as ethylene, propylene, 1-butene, isobutylene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene.

[0027] The polyolefin resin may be an olefin polymer containing a single type of structural unit derived from an α-olefin, or may be a copolymer of olefin polymers containing two or more types of structural units derived from an α-olefin.

[0028] In the present invention, the polyolefin resin is generally a petroleum-derived polyolefin resin. The petroleum-derived polyolefin resin refers to a polyolefin-based resin synthesized from petroleum-derived olefins.

[0029] Petroleum-derived olefins are produced by thermally decomposing petrochemical raw materials such as naphtha, ethane, LPG (Liquefied Petroleum Gas), NGL (Natural Gas Liquid), and gas oil.

[0030] In the present invention, examples of polyolefin resins include homopolypropylene (homopolymer of propylene), propylene-α-olefin copolymers, homopolyethylene (homopolymer of ethylene), ethylene-α-olefin copolymers, polybutene-1, and 1-butene-α-olefin copolymers. These polyolefin resins can be used alone or in combination of two or more. Of these polyolefin resins, homopolypropylene and / or propylene-α-olefin copolymers are preferred.

[0031] In the present invention, 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 anhydride thereof is grafted onto homopolypropylene or a propylene-α-olefin copolymer.

[0032] Propylene-α-olefin copolymers are copolymers of propylene and α-olefins. Examples of α-olefins include ethylene; α-olefins having 4 to 20 carbon atoms (4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20), such as 1-butene, isobutylene, 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.

[0033] 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. When the content of the propylene component in the propylene-α-olefin copolymer is 50 mol% or more, the modified polyolefin resin composition of the present invention exhibits improved water resistance and adhesion to polyolefin substrates (particularly polypropylene substrates).

[0034] From the viewpoint of maintaining fluidity more satisfactorily, the isotacticity of the α-olefin portion in the propylene-α-olefin copolymer is preferably 30 to 100%, more preferably 50 to 100%, and even more preferably 70 to 100%.

[0035] Ethylene-α-olefin copolymers are copolymers of ethylene and α-olefins. Examples of α-olefins include propylene, 1-butene, isobutylene, 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, each 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). These α-olefins can be used alone or in combination of two or more.

[0036] 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 the present invention become better.

[0037] From the viewpoint of maintaining fluidity more satisfactorily, the isotacticity of the α-olefin portion in the ethylene-α-olefin copolymer is preferably 30 to 100%, more preferably 50 to 100%, and even more preferably 70 to 100%.

[0038] 1-Butene-α-olefin copolymers are copolymers of 1-butene and α-olefins. Examples of α-olefins 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), 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 greater. When the content of the 1-butene component in the 1-butene-α-olefin copolymer is 65 mol% or greater, the modified polyolefin resin composition of the present invention exhibits improved water resistance and adhesion to polyolefin substrates (particularly polypropylene substrates or poly-1-butene substrates).

[0040] The total content of the α,β-unsaturated carboxylic acid and its anhydride components in the acid-modified polyolefin resin (A) is preferably 0.5 to 10% by mass, more preferably 0.7 to 6% by mass, even more preferably 0.8 to 3% by mass, and even more preferably 1 to 2% by mass. When the total content of the α,β-unsaturated carboxylic acid and its anhydride components in the acid-modified polyolefin resin (A) is within the range of 0.5 to 10% by mass, the flowability of the modified polyolefin resin composition of the present invention is further improved.

[0041] In the present invention, bio-derived polyolefin resins may be used as polyolefin resins instead of petroleum-derived polyolefin resins. Bio-derived polyolefin resins refer to polyolefin resins produced from biological resources (biomass). Biomass refers to materials formed from organic resources (excluding fossil resources) derived from renewable organisms.

[0042] When using a bio-derived polyolefin resin, the polyolefin resin preferably contains propylene structural units. When using a bio-derived polyolefin resin, the biomass content of the polyolefin resin is generally 25% or greater, preferably 27% or greater, and more preferably 30% or greater. The upper limit of the biomass content is not particularly limited, as long as it is 100% or less. The biomass content of the polyolefin resin can be calculated, for example, based on the carbon isotope content with a mass number of 14 as measured according to ASTM D6866.

[0043] Examples of the α,β-unsaturated carboxylic acid or its anhydride to be graft-polymerized onto the polyolefin resin include maleic acid, maleic anhydride, fumaric acid, citraconic acid, citraconic anhydride, mesaconic acid, itaconic acid, itaconic anhydride, aconitic acid, aconitic anhydride, and humic anhydride. Among these α,β-unsaturated carboxylic acids or their anhydrides, maleic acid, maleic anhydride, and itaconic anhydride are preferred, and maleic acid and maleic anhydride are more preferred.

[0044] The acid value of the α,β-unsaturated carboxylic acid and its anhydride component in the acid-modified polyolefin resin (A) is preferably 1 to 100 mgKOH / g, more preferably 5 to 50 mgKOH / g, even more preferably 10 to 40 mgKOH / g, and even more preferably 15 to 30 mgKOH / g. When the acid value of the α,β-unsaturated carboxylic acid and its anhydride component in the acid-modified polyolefin resin (A) is within the range of 1 to 100 mgKOH / g, the modified polyolefin resin composition of the present invention exhibits improved fluidity.

[0045] The acid value of the α,β-unsaturated carboxylic acid and its anhydride component in the acid-modified polyolefin resin (A) can be determined using a Fourier transform infrared spectrophotometer (FT-IR) using the coefficient (f) obtained from a calibration curve prepared using a chloroform solution of maleic anhydride, the stretching peak (1780 cm) of the carbonyl (C=O) bond of succinic anhydride in the acid-modified polyolefin solution, and the peak of the carbonyl (C=O) bond of the succinic anhydride in the acid-modified polyolefin solution. -1 ) was calculated using the following formula (i). Acid value (mgKOH / g) = [absorbance (I) × coefficient (f) × 2 × molecular weight of potassium hydroxide × 1000 (mg) / molecular weight of succinic anhydride] ···Formula (i) It should be noted that, in the above formula (i), the molecular weight of succinic anhydride is 100.07, and the molecular weight of potassium hydroxide is 56.11.

[0046] As a method for graft-polymerizing an α,β-unsaturated carboxylic acid or its anhydride onto a polyolefin resin, a wide range of known methods can be employed. Examples of such methods include a method in which a polyolefin is heated and melted to a temperature above its melting point in the presence of a free radical generator to react with the α,β-unsaturated carboxylic acid or its anhydride (melt method); and a method in which a polyolefin is dissolved in an organic solvent and then heated and stirred in the presence of a free radical generator to react with the α,β-unsaturated carboxylic acid or its anhydride (solution method).

[0047] In the present invention, the acid-modified polyolefin resin (A) may be an acid-modified chlorinated polyolefin resin that has been further chlorinated. Examples of chlorination methods include blowing chlorine gas into the acid-modified polyolefin resin to introduce chlorine atoms. More specifically, chlorination can be achieved by dispersing or dissolving the acid-modified polyolefin resin in a solvent, as needed, and then blowing chlorine gas in the presence of a catalyst or under ultraviolet irradiation, under pressure or at normal pressure (atmospheric pressure), at a temperature range of 50 to 150°C.

[0048] As the solvent used in the chlorination, for example, water, chlorine-based solvents (such as chloroform, dichloromethane, carbon tetrachloride, etc.) can be mentioned, and chlorine-based solvents are preferred. The chlorine-based solvent can be removed by distillation under reduced pressure or replaced with other organic solvents after the chlorination is completed.

[0049] Examples of the catalyst used in the chlorination include free radical initiators, such as tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxyoctanoate, di-tert-butyl peroxide, and dicumyl peroxide.

[0050] 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 acid-modified chlorinated polyolefin resin is easily emulsified because its stability in solution is improved.

[0051] The chlorine content of 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 of the acid-modified chlorinated polyolefin resin is 40% by mass or less, the crystallinity of the acid-modified chlorinated polyolefin is increased, further improving adhesion to polyolefin substrates.

[0052] 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 and 40% by mass or less, more preferably 8% by mass or more and 38% by mass or less, even more preferably 10% by mass or more and 35% by mass or less, further preferably 12% by mass or more and 32% by mass or less, and particularly preferably 14% by mass or more and 30% by mass or less.

[0053] The chlorine content in the acid-modified chlorinated polyolefin resin can be measured according to JIS K-7229-1995. Specifically, the chlorine content can be measured 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 chlorine content is quantitatively determined by titration.

[0054] The melting point of the acid-modified polyolefin resin (A) is preferably 90° C. or lower, more preferably 85° C. or lower, and particularly preferably 80° C. or lower. When the melting point of the acid-modified polyolefin resin (A) is 90° C. or lower, adhesion to the polyolefin substrate is further improved.

[0055] 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 becomes better.

[0056] The melting point of the acid-modified polyolefin resin (A) can be measured using a differential scanning calorimeter (DSC) in accordance with JIS K7121-2012. Specifically, using a DSC apparatus, approximately 5 mg of a sample is heated and molten at 150°C for 10 minutes, then cooled at a rate of 10°C / minute, held steady at -50°C, and then heated to 150°C at a rate of 10°C / minute. The melting peak temperature is measured during melting, and this melting peak temperature is used as the melting point for evaluation.

[0057] 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, further preferably 20,000 to 120,000, further preferably 30,000 to 100,000, and particularly preferably 40,000 to 90,000. If the weight average molecular weight (Mw) of the acid-modified polyolefin resin (A) is within the range of 3,000 to 200,000, it has good fluidity. In addition, if Mw is within the range of 3,000 to 200,000, the cohesive force of the acid-modified polyolefin resin (A) is further improved, and the adhesion becomes better. The weight average molecular weight (Mw) of the acid-modified polyolefin resin (A) can be measured by gel permeation chromatography (GPC). The specific measurement method will be described in the examples described below.

[0058] In the present invention, the tensile modulus of the acid-modified polyolefin resin (A) is preferably 10 MPa or more, more preferably 50 MPa or more, and even more preferably 100 MPa or more. When the tensile modulus is 10 MPa or more, the adhesion of the coating film obtained from the modified polyolefin resin composition tends to be further improved. The upper limit is not particularly limited, but is preferably 2000 MPa or less, more preferably 1000 MPa or less, even more preferably 500 MPa or less, and even more preferably 300 MPa or less. It should be noted that the specific determination method of the tensile modulus is described in the Examples described below.

[0059] The acid-modified polyolefin resin (A) may be further copolymerized with a radically polymerizable monomer, unless the effects of the present invention are impaired. The content of the radically polymerizable monomer is generally 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, relative to 100 parts by mass of the acid-modified polyolefin resin (A).

[0060] The form of copolymerization of the acid-modified polyolefin resin (A) with the radical polymerizable monomer is not limited, and examples of the copolymerization form include random copolymerization, block copolymerization, and graft copolymerization (graft modification).

[0061] Examples of the radical polymerizable monomer include (meth)acrylic compounds and vinyl compounds. A (meth)acrylic compound is a compound containing at least one (meth)acryloyl group (acryloyl group and / or methacryloyl group) in the molecule.

[0062] Examples of the radical polymerizable monomer 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, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, hydroxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and (meth)acrylate. -N,N-dimethylaminoethyl ester, 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-tert-butyl (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, N,N-methylene-bis (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, hydroxyethyl (meth)acrylamide, (meth)acryloyl morpholine, n-butyl vinyl ether, 4-hydroxybutyl vinyl ether, dodecyl vinyl ether, etc. Among them, 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. These free radical polymerizable monomers can be used alone or in combination of two or more.

[0063] In the present invention, the content of the acid-modified polyolefin resin (A) is usually 5 to 120 parts by mass, preferably 10 to 90 parts by mass, more preferably 12.5 to 70 parts by mass, further preferably 15 to 50 parts by mass, further preferably 17.5 to 40 parts by mass, and particularly preferably 20 to 35 parts by mass, relative to 100 parts by mass of the compound (C) having a polymerizable unsaturated group.

[0064] In the present invention, from the perspective of further maintaining the fluidity of the modified polyolefin resin composition and further improving the water resistance and adhesion to the polyolefin substrate, the content ratio of the acid-modified polyolefin resin (A) relative to the total mass of the modified polyolefin resin composition is preferably 1 to 60 mass%, more preferably 4 to 50 mass%, further preferably 7 to 40 mass%, further preferably 10 to 35 mass%, and particularly preferably 15 to 30 mass%.

[0065] <Polyetheramine (B)> The present invention contains a polyetheramine (B). The polyetheramine (B) is generally a compound having a polyether chain and an amino group.

[0066] In the present invention, preferably, the polyetheramine (B) has a polyether chain, and the polyether chain is a structure containing at least one selected from the following structures: Formula 1: a structure represented by -(O-CH2CH2)x- (in Formula 1, x is an integer of 2 to 120), Formula 2-1: a structure represented by -(O-CH2CH(CH3))y1- (in Formula 2-1, y1 is an integer from 2 to 90), Formula 2-2: a structure represented by -(O-CH2CH2CH2)y2- (in Formula 2-2, y2 is an integer from 2 to 90), Formula 3-1: a structure represented by -(O-CH2CH2CH2CH2)z1- (in Formula 3-1, z1 is an integer from 2 to 80), Formula 3-2: a structure represented by -(O-CH(CH3)CH2CH2)z2- (in Formula 3-2, z2 is an integer from 2 to 80), Formula 3-3: a structure represented by -(O-CH2CH(CH3)CH2)z3- (in Formula 3-3, z3 is an integer from 2 to 80), and Formula 3-4: A structure represented by -(O-CH2CH2CH(CH3))z4- (in Formula 3-4, z4 is an integer of 2 to 80).

[0067] In the present invention, more preferably, the polyetheramine (B) has a polyether chain, and the polyether chain is a structure containing at least one selected from the following structures: Formula 1: a structure represented by -(O-CH2CH2)x- (in Formula 1, x is an integer of 2 to 120), Formula 2-1: a structure represented by -(O-CH2CH(CH3))y1- (in Formula 2-1, y1 is an integer from 2 to 90), and Formula 3-1: A structure represented by -(O-CH2CH2CH2CH2)z1- (in Formula 3-1, z1 is an integer of 2 to 80).

[0068] In the present invention, it is further preferred that the polyetheramine (B) is a compound represented by the following formula 1A: R 1 -(OR 2 )aR 3 Formula 1A (In Formula 1A: R 1 and R 3 Each independently represents an amino group or a linear or branched alkyl group having 1 to 10 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9 or 10) which may have an amino group. R 2 It represents a linear or branched alkylene group having 2 to 4 carbon atoms. a is an integer from 1 to 120. ).

[0069] In the above formula 1A, examples of the alkyl group having 1 to 10 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9 or 10) include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl.

[0070] In the above formula 1A, the linear or branched alkylene group having 2 to 4 (2, 3 or 4) carbon atoms is preferably an ethylene group (-CH2CH2-), a methylethylene group (-CH2CH(CH3)-), a n-propylene group (-CH2CH2CH2-), a 1-methylpropylene group (-CH(CH3)CH2CH2-), a 2-methylpropylene group (-CH2CH(CH3)CH2-), a 3-methylpropylene group (-CH2CH2CH(CH3)-) or a n-butylene group (-CH2CH2CH2CH2-).

[0071] In the above formula 1A, preferably, R 1 represents a linear or branched alkyl group having 1 to 10 (1, 2, 3, 4, 5, 6, 7, 8, 9 or 10) carbon atoms, R 2 represents a linear or branched alkylene group having 2 to 4 carbon atoms, R 3 represents an amino group, and a is an integer of 1 to 120.

[0072] In the present invention, from the perspective of stably dissolving and / or dispersing the acid-modified polyolefin resin (A) in the compound (C) having a polymerizable unsaturated group, the polyetheramine (B) preferably has a primary or secondary amino group at a single terminal and has a weight average molecular weight (Mw) of 200 to 50,000. In the present invention, it is more preferred that the polyetheramine (B) has a primary or secondary amino group at a single terminal and has a weight average molecular weight (Mw) of 300 to 10,000. In the present invention, it is even more preferred that the polyetheramine (B) has a primary amino group at a single terminal and has a weight average molecular weight (Mw) of 500 to 5,000.

[0073] In the present invention, from the perspective of stably dissolving and / or dispersing the acid-modified polyolefin resin (A) in the compound (C) having a polymerizable unsaturated group, the polyetheramine (B) is generally a polymer compound having a weight-average molecular weight (Mw) within the range of 200 to 50,000. When the Mw of the polyetheramine (B) is within this range, the steric repulsion of the polyetheramine (B) in the compound (C) having a polymerizable unsaturated group tends to be increased, thereby enabling the acid-modified polyolefin resin (A) to be stably dispersed and / or dissolved in the compound (C) having a polymerizable unsaturated group.

[0074] In the present invention, the weight average molecular weight (Mw) of the polyetheramine (B) is usually 200 to 50,000, preferably 300 to 20,000, more preferably 350 to 10,000, further preferably 450 to 7,000, and particularly preferably 500 to 5,000.

[0075] The weight average molecular weight (Mw) of the polyetheramine (B) in the present invention can be measured by GPC and converted from a polystyrene calibration curve. Note that GPC measurement is performed using THF or the like as a solvent using a commercially available apparatus according to a conventionally known method.

[0076] In the present invention, the HLB value of the polyetheramine (B) is preferably 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 more satisfactorily.

[0077] In the present invention, the HLB value is a value indicating the degree of hydrophilicity or lipophilicity (hydrophobicity) of the polyetheramine (B). In the present invention, the HLB value is a value calculated using the Griffin method. In the Griffin method, based on the following formula (ii): HLB value = 20 × total formula weight of hydrophilic group part / molecular weight ... formula (ii) Calculate the HLB value.

[0078] The polyetheramine (B) can be bonded to the acid-modified polyolefin resin (A) through various reaction methods. Examples of such reaction methods include those that form covalent bonds and / or ionic bonds. More specifically, examples include amidation reactions between carboxylic anhydride groups and primary or secondary amino groups; imidization reactions; and neutralization reactions between carboxylic acid groups and primary or secondary amino groups.

[0079] As the polyetheramine (B), a wide range of known commercial products can be used. Examples of commercially available polyetheramine (B) include: "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)" "JEFFAMINE D-400 (MW = 430, HLB value = 1.7)" "JEFFAMINE D-2000 (MW = 2000, HLB value = 0.3)" "JEFFAMINE D-4000 (MW = 4000, HLB value = 0.2)" "JEFFAMINE ED-600 (MW=600, HLB value=13.4)", "JEFFAMINE ED-900 (MW=900, HLB value=12.5)", "JEFFAMINE ED-2003 (MW = 2000, HLB value = 16.7)" etc. These commercial products can be used alone or in combination of two or more.

[0080] In the present invention, from the perspective of further maintaining the fluidity of the modified polyolefin resin composition and further improving the adhesion to the polyolefin substrate, the content of the polyetheramine (B) 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, even more preferably 25 to 60 parts by mass, and particularly preferably 30 to 50 parts by mass, relative to 100 parts by mass of the acid-modified polyolefin resin (A).

[0081] In the present invention, from the perspective of further maintaining the fluidity of the modified polyolefin resin composition and further improving the adhesion to the polyolefin substrate, the content of the polyetheramine (B) is generally 0.5 to 40% by mass, preferably 1 to 30% by mass, more preferably 2 to 20% by mass, further preferably 3 to 15% by mass, further preferably 4 to 12.5% ​​by mass, and particularly preferably 5 to 10% by mass relative to the total mass of the modified polyolefin resin composition.

[0082] <Compound (C) Having a Polymerizable Unsaturated Group> The present invention contains a compound (C) having a polymerizable unsaturated group. The compound (C) having a polymerizable unsaturated group generally has one or more (e.g., one, two, three, or four) polymerizable unsaturated groups. In the present invention, a polymerizable unsaturated group refers to an unsaturated group that can be free radical polymerized. In the present invention, the number of polymerizable unsaturated groups in the compound (C) having a polymerizable unsaturated group is preferably one or two.

[0083] In the present invention, preferably, the polymerizable unsaturated group in the compound (C) having a polymerizable unsaturated group is at least one selected from 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.

[0084] In the present invention, more preferably, the polymerizable unsaturated group in the compound (C) having a polymerizable unsaturated group is at least one selected from the group consisting of an acryloyl group, a methacryloyl group, an acryloyloxy group, and a methacryloyloxy group.

[0085] In the present invention, it is more preferred that the polymerizable unsaturated group in the compound (C) having a polymerizable unsaturated group is an acryloyloxy group and / or a methacryloyloxy group.

[0086] In the present invention, preferably, the compound (C) having a polymerizable unsaturated group includes a compound having a hydroxyl group and one or more (e.g., one, two, three, or four) polymerizable unsaturated groups. In this case, the number of hydroxyl groups is preferably one or two, more preferably one. In the present invention, more preferably, the compound (C) having a polymerizable unsaturated group includes a compound having a hydroxyl group and one to three (one, two, or three) polymerizable unsaturated groups. In this case, the number of hydroxyl groups is preferably one or two, more preferably one.

[0087] In the present invention, from the perspective of further maintaining the fluidity of the modified polyolefin resin composition, the compound (C) having a polymerizable unsaturated group preferably comprises a compound 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 (e.g., 1, 2, 3, or 4) polymerizable unsaturated groups. In this case, the number of polymerizable unsaturated groups is preferably 1 or 2, more preferably 2.

[0088] In the present invention, the compound (C) having a polymerizable unsaturated group preferably comprises 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) and one or more (e.g., 1, 2, 3, or 4) polymerizable unsaturated groups. In this case, the number of polymerizable unsaturated groups is preferably 1 or 2, more preferably 1.

[0089] In the present invention, preferably, the compound (C) having a polymerizable unsaturated group comprises: a compound having a hydroxyl group and one or more (e.g., one, two, three, or four) polymerizable unsaturated groups, and A compound 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 (e.g., 1, 2, 3 or 4) polymerizable unsaturated groups. In the present invention, more preferably, the compound (C) having a polymerizable unsaturated group comprises: A compound having a hydroxyl group and one or two polymerizable unsaturated groups, and A compound 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 two polymerizable unsaturated groups.

[0090] In the present invention, the alkyleneoxy group is generally a structure represented by the following formula 4: -(Y 1 -O)m-Formula 4 [In formula 4: Y 1 It represents a linear or branched alkylene group having 1 to 10 (1, 2, 3, 4, 5, 6, 7, 8, 9 or 10) carbon atoms. m represents an integer from 1 to 20].

[0091] In the above formula 4, Y 1 It is preferably a linear or branched alkylene group having 1 to 5 (1, 2, 3, 4 or 5) carbon atoms.

[0092] In the above formula 4, m is preferably an integer of 2 to 15.

[0093] In the present invention, preferably, the compound (C) having a polymerizable unsaturated group includes a compound represented by the following formula 5: R a -R b -R c Formula 5 [In formula 5: R a represents a polymerizable unsaturated group, R c represents a polymerizable unsaturated group or a methyl group. R b Indicated by -(Y 2 -O)n-, or a linear or branched alkylene 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). Y 2 It represents a linear or branched alkylene group having 1 to 10 (1, 2, 3, 4, 5, 6, 7, 8, 9 or 10) carbon atoms. n represents an integer from 1 to 20. ].

[0094] In the above formula 5, Y 2 It is preferably a linear or branched alkylene group having 1 to 5 (1, 2, 3, 4 or 5) carbon atoms.

[0095] In the above formula 5, n is preferably an integer of 2 to 15.

[0096] In the present invention, it is more preferred that the compound (C) having a polymerizable unsaturated group contains one or two or more compounds represented by Formula 5 above.

[0097] In the present invention, the compound (C) having a polymerizable unsaturated group preferably includes a compound having a (meth)acryloyloxy group as a polymerizable unsaturated group. Examples of the compound having a (meth)acryloyloxy group include compounds having one (meth)acryloyloxy group, compounds having two (meth)acryloyloxy groups, and compounds having three or more (meth)acryloyloxy groups. These compounds can be used alone or in combination of two or more.

[0098] 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 ( Alkyl (meth)acrylates such as (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-hexyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, stearyl (meth)acrylate, and behenyl (meth)acrylate; (Meth)acrylates having an alicyclic structure, such as cyclohexyl (meth)acrylate and isobornyl (meth)acrylate; (Meth)acrylates having an aromatic ring, such as benzyl (meth)acrylate, phenoxyethyl acrylate, and phenoxyethyl methacrylate; (Meth)acrylates having an amino group, such as dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, tert-butylaminoethyl (meth)acrylate, methylethylaminoethyl (meth)acrylate, dimethylaminostyrene, diethylaminostyrene, pentamethylpiperidinyl (meth)acrylate, and tetramethylpiperidinyl (meth)acrylate; (Meth)acrylates containing epoxy groups, such as glycidyl (meth)acrylate and 3,4-epoxycyclohexyl (meth)acrylate; (Meth)acrylates containing ether groups, 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, can be used alone or in combination of two or more.

[0099] 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 tricyclodecane dihydroxymethyl 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, glycerol di(meth)acrylate, etc. These compounds can be used alone or in combination of two or more.

[0100] 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 isocyanuric acid ethylene oxide-modified tri(meth)acrylate and ε-caprolactone-modified tri(acryloyloxyethyl)isocyanurate; Urethane methacrylates such as 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 can be used alone or in combination of two or more.

[0101] In the present invention, from the viewpoint of stably dissolving and / or dispersing the acid-modified polyolefin resin (A) in the compound (C) having a polymerizable unsaturated group and suppressing the formation of aggregates, it is more preferred that the compound (C) having a polymerizable unsaturated group contains a compound having two (meth)acryloyloxy groups.

[0102] The compound having two (meth)acryloyloxy groups is preferably at least one selected from neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, tricyclodecane dihydroxymethyl di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetrapropylene glycol di(meth)acrylate and polypropylene glycol di(meth)acrylate.

[0103] In the present invention, specific examples of the compound (C) having a polymerizable unsaturated group include, in addition to the above, (meth)acrylamide, N-methoxymethyl-(meth)acrylamide, N-ethoxymethyl-(meth)acrylamide, N-propoxymethyl-(meth)acrylamide, N-butoxymethyl-(meth)acrylamide, N-pentyloxymethyl-(meth)acrylamide, N,N-bis(methoxymethyl)acrylamide, N-ethoxymethyl-N-methoxymethyl methacrylamide, N,N-bis(ethoxymethyl)acrylamide, N-ethoxymethyl-N-propoxymethyl methacrylamide, N,N-bis(propoxymethyl)acrylamide, N-butoxymethyl-N Compounds having an amide group, such as -(propyloxymethyl)methacrylamide, N,N-bis(butoxymethyl)acrylamide, N-butoxymethyl-N-(methoxymethyl)methacrylamide, N,N-bis(pentyloxymethyl)acrylamide, N-methoxymethyl-N-(pentyloxymethyl)methacrylamide, N,N-dimethylaminopropylacrylamide, N,N-diethylaminopropylacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, and diacetone(meth)acrylamide; aromatic vinyl compounds, such as styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, vinylnaphthalene, and indene; (meth)acrylonitrile, acryloylmorpholine, and the like.

[0104] From the perspective of further maintaining the fluidity of the modified polyolefin resin composition and further improving the water resistance and adhesion to the polyolefin substrate, the content ratio of the compound (C) having a polymerizable unsaturated group in the present invention is usually 10 to 90 mass %, preferably 20 to 85 mass %, more preferably 30 to 80 mass %, further preferably 40 to 77 mass %, and particularly preferably 50 to 75 mass %, relative to the total mass of the modified polyolefin resin composition.

[0105] In the present invention, from the perspective of further maintaining the fluidity of the modified polyolefin resin composition and further improving water resistance and adhesion to polyolefin substrates, the compound (C) having a polymerizable unsaturated group preferably includes a compound having a hydroxyl group and one or more (e.g., one, two, three, or four) polymerizable unsaturated groups. In this case, from the perspective of further maintaining the fluidity of the modified polyolefin resin composition and further improving water resistance and adhesion to polyolefin substrates, the content ratio of the compound having a hydroxyl group and one or more (e.g., one, two, three, or four) polymerizable unsaturated groups relative to the total mass of the modified polyolefin resin composition is preferably 1 to 50% by mass, more preferably 2 to 45% by mass, and even more preferably 3 to 40% by mass.

[0106] In the present invention, from the perspective of further maintaining the fluidity of the modified polyolefin resin composition and further improving the water resistance and adhesion to the polyolefin substrate, it is more preferred that the compound (C) having a polymerizable unsaturated group contains a compound having a hydroxyl group and one or two polymerizable unsaturated groups.

[0107] Specific examples of the compound having a hydroxyl group and one or more (e.g., one, two, three, or four) polymerizable unsaturated groups include 2-hydroxy-1,3-dimethacryloyloxypropane, 2-hydroxy-3-methacryloylpropyl acrylate, glycerol diacrylate, pentaerythritol di(meth)acrylate, and pentaerythritol tri(meth)acrylate.

[0108] In the present invention, from the perspective of further maintaining the fluidity of the modified polyolefin resin composition, the compound (C) having a polymerizable unsaturated group preferably includes: a compound having a unit having a carbonyl group and one or more (for example, 1, 2, 3 or 4) polymerizable unsaturated groups.

[0109] In the present invention, the compound (C) having a polymerizable unsaturated group more preferably includes a compound having a unit having a carbonyl group represented by the following formula (1) or the following formula (2) and one or more (e.g., one, two, three, or four) polymerizable unsaturated groups.

[0110] [Chemistry 1] (In formula (1), R1 represents a hydrogen atom or a methyl group. * indicates a bond.)

[0111] In the above formula (1), the bond is preferably to an oxygen atom.

[0112] In the above formula (1), preferably, R1 is a methyl group.

[0113] In the above formula (1), more preferably, R1 is a methyl group, and the bond is to an oxygen atom.

[0114] [Chemistry 2] (In formula (2), R2 represents a hydrocarbon group having 1 to 10 carbon atoms, a hydrocarbon group having 1 to 10 carbon atoms containing a substituent such as a halogen atom (F, Cl, Br or I) or an alkoxy group. R3 represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a hydrocarbon group having 1 to 10 carbon atoms containing a substituent such as an aldehyde group, an acetyl group, a halogen atom (F, Cl, Br, or I), or an alkoxy group. * indicates a bond. The hydrocarbon group may contain a branched structure, an alicyclic structure such as a cyclohexyl group, or an aromatic ring structure such as a phenyl group or a naphthyl group.

[0115] In the above formula (2), the bonding bond is preferably bonded to an oxygen atom.

[0116] In the present invention, it is more preferred that the compound having a unit having a carbonyl group and one or more polymerizable unsaturated groups contains one or more of the following compounds: a compound having a unit having a carbonyl group represented by the above-mentioned formula (1) or formula (2) and one or more (for example, 1, 2, 3 or 4) polymerizable unsaturated groups.

[0117] In the present invention, it is more preferred that the compound (C) having a polymerizable unsaturated group contains a compound having a unit having a carbonyl group represented by the above formula (1) and one or more (eg, one, two, three, or four) polymerizable unsaturated groups.

[0118] In the present invention, it is more preferred that the compound (C) having a polymerizable unsaturated group contains a compound having a unit having a carbonyl group represented by the above formula (1) and one polymerizable unsaturated group.

[0119] Examples of the compound having a unit having a group represented by the above formula (1) or formula (2) and one or more (e.g., one, two, three, or four) polymerizable unsaturated groups include acetoacetoxy (meth)acrylate, acetoacetoxyethyl (meth)acrylate, acetoacetoxypropyl (meth)acrylate, allyl acetoacetate, acetoacetoxybutyl (meth)acrylate, and 2,3-bis (acetoacetoxy)propyl (meth)acrylate; Crotonic acid acetoacetates such as 2-acetoacetoxyethyl crotonate and 2-acetoacetoxypropyl crotonate; Acetoacetate esters of N-alkanol (meth)acrylamides such as acetoacetoxy (meth)acrylamide, N-(acetoacetoxymethyl) (meth)acrylamide, and N-(acetoacetoxyethyl) (meth)acrylamide; Acetylated products of ethylenically unsaturated monomers having a hydroxyl group, such as 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, 2-hydroxy-3-chloropropyl methacrylate, 1,4-butanediol monoacrylate, 1,4-butanediol monomethacrylate, N-hydroxymethyl acrylamide, N-hydroxymethyl methacrylamide, and hydroxystyrene; Among them, from the perspectives of maintaining the fluidity of the modified polyolefin resin composition more satisfactorily, suppressing agglomerates, and improving water resistance and adhesion to polyolefin substrates, diacetone (meth)acrylamide and acetoacetoxyethyl (meth)acrylate are preferred, acetoacetoxyethyl (meth)acrylate is more preferred, and acetoacetoxyethyl methacrylate is even more preferred.

[0120] In the present invention, the compound (C) having a polymerizable unsaturated group may contain a biomass-derived (meth)acrylic acid monomer component. The biomass-derived (meth)acrylic acid monomer component refers to a substance composed of biomass-derived (meth)acrylic acid, a biomass-derived alkanol, and an ester of biomass-derived or non-biomass-derived (meth)acrylic acid. Examples of biomass-derived alkanols include alkanols derived from plant materials such as bioethanol, 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 the present invention, from the perspective of further maintaining the fluidity of the modified polyolefin resin composition and further improving workability, the weight average molecular weight (Mw) of the compound (C) having a polymerizable unsaturated group is preferably 5000 or less, more preferably 2000 or less, and even more preferably 1000 or less.

[0122] In the present invention, from the perspective of further maintaining the fluidity of the modified polyolefin resin composition and further improving workability, the weight average molecular weight (Mw) of the compound (C) having a polymerizable unsaturated group is preferably 100 or more, more preferably 150 or more, and even more preferably 160 or more.

[0123] In the present invention, from the perspective of further maintaining the fluidity of the modified polyolefin resin composition and further improving the workability, the weight average molecular weight (Mw) of the compound (C) having a polymerizable unsaturated group is preferably 100 or more and 5000 or less, more preferably 150 or more and 2000 or less, and even more preferably 160 or more and 1000 or less.

[0124] In the present invention, it is preferred to contain a compound having a polymerizable unsaturated group with an SP value of 9 or greater. By containing a compound having a polymerizable unsaturated group with an SP value of 9 or greater, it is possible to suppress the increase in viscosity during long-term storage, and to further maintain the fluidity of the modified polyolefin resin composition. In this specification, the SP value is defined by the Fedors method, and the unit of the SP value is cal / cm 3 . It is more preferred to contain a compound (C) having a polymerizable unsaturated group having an SP value of 9.2 or more, and further preferred to contain a compound (C) having a polymerizable unsaturated group having an SP value of 9.5 or more. It should be noted that in the present disclosure, there is no particular restriction on the upper limit of the SP value, but from the perspective of the water resistance of the cured coating film, for example, the upper limit of the SP value of the compound (C) having a polymerizable unsaturated group is 15 or less. The compound (C) having a polymerizable unsaturated group having an SP value of 9 or more can be used alone, or two or more types can be used in combination. In addition, it can be used in combination with a compound having a polymerizable unsaturated group having an SP value of 9 or less.

[0125] The modified polyolefin resin composition of the present invention may contain other film-forming resins other than the compound (C) having a polymerizable unsaturated group. Examples of the film-forming resin include acrylic resins, polyester resins, alkyd resins, polyether resins, polyolefin resins, polyurethane resins, polycarbonate resins, melamine resins, epoxy resins, and carbodiimide resins. These resins may be used alone or in combination of two or more. The content of the film-forming resin is preferably 10 to 30 parts by mass relative to 100 parts by mass of the modified polyolefin resin composition.

[0126] Preferred embodiments of the modified polyolefin resin composition of the present invention (hereinafter referred to as "Aspect A") include the following: The modified polyolefin resin composition comprises an acid-modified polyolefin resin (A), a polyetheramine (B) and two or three "compounds having a polymerizable unsaturated group (C)". (a) When containing two compounds (C) having polymerizable unsaturated groups, (a1) the two compounds (C) having a polymerizable unsaturated group are one compound having one polymerizable unsaturated group and one compound having two polymerizable unsaturated groups; (a2) Two compounds having polymerizable unsaturated groups (C) are two compounds having two polymerizable unsaturated groups, (b) When containing three types of compounds (C) having polymerizable unsaturated groups, The three compounds (C) having a polymerizable unsaturated group are one compound having one polymerizable unsaturated group and two compounds having two polymerizable unsaturated groups.

[0127] In the above embodiment A, preferably, the compound having one polymerizable unsaturated group is: Compounds having a hydroxyl group and one polymerizable unsaturated group; 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) and one polymerizable unsaturated group, or A compound having a unit having a carbonyl group represented by the above formula (1) or (2) and one polymerizable unsaturated group.

[0128] In the above embodiment A, more preferably, the compound having one polymerizable unsaturated group is: Compounds having a hydroxyl group and one polymerizable unsaturated group; A compound having a linear or branched alkyl group having 1 to 10 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9 or 10) and one polymerizable unsaturated group; or A compound having a unit having a carbonyl group represented by the above formula (1) and one polymerizable unsaturated group.

[0129] In the above embodiment A, preferably, the compound having two polymerizable unsaturated groups is: A compound having an alkyleneoxy group represented by the above formula 4 and two polymerizable unsaturated groups; or A compound having a hydroxyl group and two polymerizable unsaturated groups.

[0130] In the above embodiment A, the 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, and more preferably an acryloyloxy group and / or a methacryloyloxy group.

[0131] As another preferred embodiment of the modified polyolefin resin composition of the present invention (hereinafter referred to as "Aspect B"), the following embodiments can be mentioned: The modified polyolefin resin composition comprises an acid-modified polyolefin resin (A), a polyetheramine (B) and a compound having a polymerizable unsaturated group (C). The compound (C) having a polymerizable unsaturated group is at least one compound selected from neopentyl glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, 2-ethylhexyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxy-3-methylacrylate and acetoacetoxyethyl methacrylate.

[0132] <Polymerization Initiator> The modified polyolefin resin composition of the present invention may contain a polymerization initiator as long as the effects of the present invention are not impaired. The inclusion of a polymerization initiator allows the polymerization reaction of the polymerizable unsaturated group of compound (C) to proceed, thereby forming a coating film-forming resin. The use of a polymerization initiator further improves the corrosion resistance and durability of the coating film.

[0133] From the perspective of increasing the curing speed of the coating film obtained from the modified polyolefin resin composition, 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.

[0134] As the polymerization initiator, a polymerization initiator capable of initiating the polymerization reaction of the polymerizable unsaturated group can be used, for example, a photopolymerization initiator that generates free radicals using light, a thermal polymerization initiator that generates free radicals using heat, etc. These polymerization initiators can be used alone or in combination of two or more.

[0135] A photopolymerization initiator is a compound that generates free radicals or acids upon exposure to ultraviolet light or visible light, thereby initiating a chain polymerization reaction. Examples of photopolymerization initiators 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.

[0136] Specific examples of acetophenone-based photopolymerization initiators include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-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, and 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone oligomers. These can be used alone or in combination of two or more.

[0137] 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 can be used alone or in combination of two or more.

[0138] Specific examples of the benzophenone-based photopolymerization initiator include benzophenone, benzoylbenzoic acid, polyvinylbenzophenone, α-hydroxycyclohexylphenyl ketone, etc. These can be used alone or in combination of two or more.

[0139] Specific examples of thioxanthone-based photopolymerization initiators include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, and dodecylthioxanthone. These can be used alone or in combination of two or more.

[0140] Specific examples of the acylphosphine oxide-based photopolymerization initiator include bis(2,4,6-trimethylbenzoyl)-phenyl-phosphine oxide and ethoxyphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, etc. These can be used alone or in combination of two or more.

[0141] Specific examples of titanocene-based photopolymerization initiators include: Bis(cyclopentadienyl)-bis[2,6-difluoro-3-(2-(1-pyrrol-1-yl)ethyl)phenyl]titanium, Bis(cyclopentadienyl)-bis[2,6-difluoro-3-(3-(1-pyrrol-1-yl)propyl)phenyl]titanium, Bis(cyclopentadienyl)-bis[2,6-difluoro-3-((1-pyrrol-1-yl)methyl)phenyl]titanium, Bis(methylcyclopentadienyl)-bis[2,6-difluoro-3-((1-pyrrol-1-yl)methyl)phenyl]titanium, Bis(cyclopentadienyl)-bis[2,6-difluoro-3-((2,5-dimethyl-1-pyrrol-1-yl)methyl)phenyl]titanium, Bis(cyclopentadienyl)-bis[2,6-difluoro-3-((2-isopropyl-5-methyl-1-pyrrol-1,6-yl)methyl)phenyl]titanium, Bis(cyclopentadienyl)-bis[2,6-difluoro-3-((2-(2-methoxyethyl)-5-methyl-1-pyrrol-1-yl)methyl)phenyl]titanium, etc. These can be used alone or in combination of two or more.

[0142] Thermal polymerization initiators are compounds that generate free radicals upon heating, thereby initiating a chain polymerization reaction. Examples of thermal polymerization initiators include organic peroxides; inorganic peroxides such as potassium persulfate, ammonium persulfate, and hydrogen peroxide; and ketone peroxide compounds such as methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, methyl acetoacetate peroxide, and acetylacetone peroxide. Peroxyketal compounds such as 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-butylperoxy)cyclohexane, 2,2-bis(tert-butylperoxy)octane, n-butyl-4,4-bis(tert-butylperoxy)valerate, and 2,2-bis(tert-butylperoxy)butane; Hydroperoxide compounds such as tert-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 tert-butyl peroxide, tert-butyl cumyl peroxide, dicumyl peroxide, α,α'-bis(tert-butylperoxy-m-isopropyl)benzene, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, and 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3-ol; Acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, succinic acid peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, m-toluoyl peroxide and other diacyl peroxide compounds; Peroxydicarbonate compounds such as diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-n-propyl peroxydicarbonate, bis-(4-tert-butylcyclohexyl) peroxydicarbonate, dimyristyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, dimethoxyisopropyl peroxydicarbonate, di(3-methyl-3-methoxybutyl) peroxydicarbonate, and diallyl peroxydicarbonate; Peroxyester compounds such as tert-butyl peroxyacetate, tert-butyl peroxyisobutyrate, tert-butyl peroxypivalate, tert-butyl peroxyneodecanoate, cumyl peroxyneodecanoate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxy-3,5,5-trimethylhexanoate, tert-butyl peroxylaurate, tert-butyl peroxybenzoate, di-tert-butyl peroxyisophthalate, 2,5-dimethyl-2,5-di(benzoylperoxide)hexane, tert-butyl peroxymaleate, tert-butyl peroxyisopropylcarbonate, cumyl peroxyoctanoate, tert-hexyl peroxyneodecanoate, tert-hexyl peroxypivalate, tert-butyl peroxyneohexanoate, tert-hexyl peroxyneohexanoate, and cumyl peroxyneohexanoate; acetylcyclohexylsulfonyl peroxide, and tert-butyl peroxyallylcarbonate. These organic peroxides can be used alone or in combination of two or more.

[0143] <Ultraviolet absorber> The modified polyolefin composition of the present invention may contain a UV absorber as long as the effects of the present invention are not impaired. Examples of UV absorbers include benzophenone-based UV absorbers, benzotriazole-based UV absorbers, triazine-based UV absorbers, salicylic acid-based UV absorbers, cyanoacrylate-based UV absorbers, and benzoxazine-based UV absorbers. These UV absorbers can be used alone or in combination of two or more.

[0144] 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, relative to 100 parts by mass of the modified polyolefin resin composition.

[0145] <Light Stabilizer> The modified polyolefin composition of the present invention 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-based light stabilizers.

[0146] Specific examples of hindered amine light stabilizers include bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, methyl(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 2,4-bis[N-butyl-N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)amino]-6-(2-hydroxyethylamino)-1,3,5-triazine, and bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidyl) decanedioate. These can be used alone or in combination of two or more.

[0147] The amount of the light stabilizer used is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 1 part by mass, relative to 100 parts by mass of the modified polyolefin resin composition.

[0148] <Sensitizer> The modified polyolefin composition of the present invention may contain a sensitizer as long as the effects of the present invention are not impaired. Examples of the sensitizer include unsaturated ketone compounds such as chalcone and dibenzalacetone, 1,2-diketone compounds such as benzyl and camphorquinone, benzoin compounds, fluorene compounds, naphthoquinone compounds, anthraquinone compounds, xanthene compounds, thioxanthene compounds, xanthone compounds, thioxanthene compounds, coumarin compounds, ketocoumarin compounds, cyanine compounds, merocyanine compounds, polymethine pigments such as oxonol compounds, acridine compounds, azine compounds, thiazine compounds, oxazine compounds, indoline compounds, azulene compounds, azulenium compounds, and the like. compounds), squarylium compounds, porphyrin compounds, tetraphenylporphyrin compounds, triarylmethane compounds, tetrabenzoporphyrin compounds, tetrapyrazinoporphyrazine compounds, phthalocyanine compounds, tetraazaporphyrazine compounds, tetraquinoxalinoporphyrazine 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 or Michler's ketone compounds, biimidazole compounds, etc. These can be used alone or in combination of two or more.

[0149] The amount of the sensitizer used is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the modified polyolefin resin composition.

[0150] <Surfactant> The modified polyolefin resin composition of the present invention may contain a surfactant as long as it does not impair the effects of the present invention. Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants. These surfactants may be used alone or in combination of two or more. From the perspective 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 preferred to use a nonionic surfactant or anionic surfactant, and more preferably a nonionic surfactant.

[0151] As nonionic surfactant, for example, polyoxyethylene alkyl ether, polyoxypropylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxypropylene alkylphenyl ether, polyoxyethylene styrenated phenyl ether, polyoxypropylene styrenated phenyl ether, polyoxyethylene fatty acid ester, polyoxypropylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxypropylene sorbitan fatty acid ester, polyoxyethylene alkylamine ether, polyoxypropylene alkylamine ether, polyoxyethylene lanolin alcohol ether, polyoxypropylene lanolin alcohol ether, polyoxyethylene lanolin fatty acid ester, polyoxypropylene lanolin fatty acid ester, (polyoxyethylene oxygen propylene) block copolymer etc. can be enumerated.They can be used alone or two or more are used in combination respectively.As nonionic surfactant, known commercially available products can be widely used, for example, Emulmin series (manufactured by Sanyo Chemical Industries, Ltd.), Noigen series (manufactured by Daiichi Industrial Pharmaceutical Co., Ltd.), Blaunon series (manufactured by Aoki Oil & Fats Industry Co., Ltd.) etc. can be enumerated.

[0152] As anionic surfactant, for example, can enumerate high alkyl sulfate salt, alkyl aryl polyoxyethylene sulfate salt, higher fatty acid salt, alkyl aryl sulfonate, alkyl phosphate salt etc..They can be used alone or two or more are used in combination respectively.As anionic surfactant, can widely use known commercially available product, for example, can enumerate Neocol series (Daiichi Industrial Pharmaceutical Co., Ltd. manufactures), Hitenol series (Daiichi Industrial Pharmaceutical Co., Ltd. manufactures) etc.

[0153] From the perspective 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, 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 relative to 100 parts by mass of the acid-modified polyolefin resin (A).

[0154] <Various additives> The modified polyolefin resin composition of the present invention may contain various additives as needed. Examples of the various additives include tackifiers, film-forming aids, defoaming agents, anti-sagging agents, and wetting agents.

[0155] Examples of the tackifier include rosin, dammar resin, polymerized rosin, hydrogenated rosin, ester rosin, rosin-modified maleic acid resin, polyterpene resin, petroleum resin, cyclopentadiene resin, phenol resin, xylene resin, and coumarone-indene resin. These can be used alone or in combination of two or more.

[0156] The amount of the tackifier used is preferably 1 to 50 parts by mass, more preferably 10 to 25 parts by mass, based on 100 parts by mass of the modified polyolefin resin composition.

[0157] <Organic Solvents> The modified polyolefin resin composition of the present invention may contain an organic solvent or may not contain an organic solvent.

[0158] When the present invention contains an organic solvent, it is preferably a small amount for environmental and hygienic reasons. In this case, the amount of organic solvent used is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, even more preferably 5 parts by mass or less, even more preferably 3 parts by mass or less, and particularly preferably 1 part by mass or less, relative to 100 parts by mass of the modified polyolefin resin composition. The inclusion of an organic solvent in the present invention further reduces the viscosity of the modified polyolefin resin composition, thereby further improving its coating properties.

[0159] When the present invention does not contain an organic solvent, the present invention can be preferably used as the main agent of a solvent-free two-component curable polyurethane adhesive. It should be noted that, in this specification, "solvent-free" means that no organic solvent is intentionally added to the modified polyolefin resin composition of the present invention. The term "solvent-free" also includes the residual organic solvent used in the production of the acid-modified polyolefin resin (A).

[0160] Examples of the organic solvent include: Aromatic hydrocarbons such as benzene, toluene, and xylene; Aliphatic hydrocarbons such as hexane, heptane, octane, and decane; Alicyclic hydrocarbons such as cyclohexane, cyclohexene, methylcyclohexane, and ethylcyclohexane; Halogenated hydrocarbons such as trichloroethylene, dichloroethylene, chlorobenzene, and chloroform; Alcohol solvents such as methanol, ethanol, isopropanol, butanol, pentanol, 1-hexanol, 2-ethylhexanol, 2-methylcyclohexanol, phenol, and 2-heptanol; Ketone solvents such as acetone, methyl isobutyl ketone, methyl ethyl ketone, pentanone, hexanone, cyclohexanone, isophorone, and acetophenone; Cellosolve solvents such as methyl cellosolve and ethyl cellosolve; Ester solvents such as methyl acetate, ethyl acetate, butyl acetate, methyl propionate, ethyl propionate, and butyl formate; Ether solvents such as ethylene glycol mono-n-butyl ether, ethylene glycol mono-isobutyl ether, ethylene glycol mono-tert-butyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol mono-isobutyl ether, triethylene glycol mono-n-butyl ether, tetraethylene glycol mono-n-butyl ether, dibenzyl ether, diphenyl ether, and butylphenyl ether can be used alone or in combination of two or more.

[0161] (Method for producing modified polyolefin resin composition) As a method for producing the modified polyolefin resin composition of the present invention, a wide range of known methods can be adopted, and for example, the methods described in the following steps (1) to (3) can be mentioned. Step (1): The acid-modified polyolefin resin (A) and the compound (C) having a polymerizable unsaturated group are placed in a stirrer equipped with a heating device and kneaded while heating. Step (2): The polyetheramine (B) is further added to the stirrer and kneaded while heating. Step (3): Then, the mixture is cooled to room temperature and filtered to obtain a modified polyolefin resin composition.

[0162] 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, etc., but is usually 10 to 120 minutes, preferably 15 to 90 minutes, and more preferably 20 to 60 minutes.

[0163] 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, etc., but is usually 10 to 120 minutes, preferably 15 to 90 minutes, and more preferably 20 to 75 minutes.

[0164] In the above step (3), filtration can be performed using, for example, a metal mesh having a mesh size of 50 μm to 300 μm.

[0165] The present invention is a cured product formed by curing a modified polyolefin resin composition. In other words, the cured product is a product obtained by curing the modified polyolefin resin composition of the present invention. Hereinafter, the cured product will be referred to simply as the "cured product of the present invention."

[0166] (Application of the present invention) The modified polyolefin resin composition of the present invention and the cured product of the present invention can be preferably used for polyolefin substrates. As polyolefin substrates, for example, materials obtained by processing polyolefin into blocks (plates, rods, spheres, etc.), sheets, films, yarns, cloths (woven fabrics, braided fabrics, and non-woven fabrics, etc.) can be cited. Among these polyolefin substrates, sheets and films are preferred from the perspective of manufacturing. As the thickness of the film, a film thickness of 5 μm to 100 μm can be used. As polyolefins, for example, polypropylene, polyethylene, ethylene propylene copolymers, ethylene propylene diene copolymers, polybutene, poly(4-methyl-1-pentene), etc. can be cited. The modified polyolefin resin composition of the present invention and the cured product of the present invention can be particularly suitable for use in polypropylene substrates.

[0167] The modified polyolefin resin composition and cured product of the present invention can be suitably used in coatings for molded articles, inks, adhesives, sealants, primers, coating agents, and in-mold coatings. The modified polyolefin resin composition and cured product of the present invention can be particularly suitably used in inks for polyolefin substrates, adhesives for polyolefin substrates, primers for polyolefin substrates, coatings for polyolefin substrates, and in-mold coatings for polyolefin substrates.

[0168] A coating film can be obtained from the modified polyolefin resin composition of the present invention and can be particularly suitably used in metal products, electronic devices, packaging materials, automotive parts, and the like.

[0169] As a method for forming a coating film from the modified polyolefin resin composition of the present invention, for example, there can be mentioned a method of uniformly coating the modified polyolefin resin composition of the present invention on the surface of various substrates and subjecting it to a heat treatment (for example, a baking treatment, etc.). In this way, a uniform coating film can be formed on the surface of various substrates. As a coating method, for example, there can be mentioned a gravure coating method, a curtain coating method, a Meyer bar method, a dip coating method, a brush coating method, a roller coating method, a spray coating method, etc. The amount of the modified polyolefin resin composition applied to the substrate is not particularly limited and can be appropriately selected according to its use. The dry coating film is preferably in the range of 1 μm to 100 μm. The heating treatment can be carried out using a hot air circulation oven, an infrared heater, etc. In addition, there can be mentioned a method of forming a plastic substrate in a mold, injecting the modified polyolefin resin composition of the present invention between the mold and the substrate, and forming a coating film by heating and pressurizing. The heating temperature is usually 60 to 200°C. The heating time is usually 15 seconds to 20 minutes.

[0170] The present invention provides the following aspects of the invention. Item 1. A modified polyolefin resin composition comprising an acid-modified polyolefin resin (A), a polyetheramine (B), and a compound having a polymerizable unsaturated group (C). Item 2. The modified polyolefin resin composition according to Item 1, wherein the content of the acid-modified polyolefin resin (A) is generally 5 to 120 parts by mass, preferably 10 to 90 parts by mass, more preferably 12.5 to 70 parts by mass, further preferably 15 to 50 parts by mass, more preferably 17.5 to 40 parts by mass, and particularly preferably 20 to 35 parts by mass, relative to 100 parts by mass of the compound (C) having a polymerizable unsaturated group. Item 3. The modified polyolefin resin composition according to Item 1 or 2, wherein The compound (C) having a polymerizable unsaturated group preferably includes a compound having a hydroxyl group and one or more polymerizable unsaturated groups. More preferably, it contains a compound having a hydroxyl group and 1 to 4 (1, 2, 3 or 4) polymerizable unsaturated groups, More preferably, the compound contains a compound having a hydroxyl group and one or two polymerizable unsaturated groups. Item 4. The modified polyolefin resin composition according to any one of Items 1 to 3, wherein The compound (C) having a polymerizable unsaturated group preferably comprises a compound 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. More preferably, the compound contains 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 1 to 4 (1, 2, 3 or 4) polymerizable unsaturated groups. More preferably, the compound contains 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 two polymerizable unsaturated groups. Item 5. The modified polyolefin resin composition according to any one of Items 1 to 4, wherein the content of the polyetheramine (B) is generally 6 to 100 parts by mass, preferably 10 to 90 parts by mass, more preferably 15 to 80 parts by mass, further preferably 20 to 70 parts by mass, further preferably 25 to 60 parts by mass, and particularly preferably 30 to 50 parts by mass, relative to 100 parts by mass of the acid-modified polyolefin resin (A). Item 6. The modified polyolefin resin composition according to any one of Items 1 to 5, wherein The polyetheramine (B) has a polyether chain, The polyether chain is a structure comprising at least one selected from the following structures: -(O-CH2CH2)x- (x is an integer from 2 to 120), -(O-CH2CH(CH3))y1- (y1 is an integer from 2 to 90), -(O-CH2CH2CH2)y2- (y2 is an integer from 2 to 90), -(O-CH2CH2CH2CH2)z1- (z1 is an integer from 2 to 80), -(O-CH(CH3)CH2CH2)z2- (z2 is an integer from 2 to 80), -(O-CH2CH(CH3)CH2)z3- (z3 is an integer from 2 to 80), and A structure represented by -(O-CH2CH2CH(CH3))z4- (z4 is an integer from 2 to 80). Item 7. The modified polyolefin resin composition according to any one of Items 1 to 6, wherein The polyetheramine (B) preferably has a primary or secondary amino group at a single terminal and has a weight average molecular weight (Mw) of 200 to 50,000. More preferably, it has a primary or secondary amino group at a single terminal and a weight average molecular weight (Mw) of 300 to 10,000. More preferably, it has a primary amino group at a single terminal and has a weight average molecular weight (Mw) of 500 to 5,000. Item 8. The modified polyolefin resin composition according to any one of Items 1 to 7, wherein The HLB value of the polyetheramine (B) is preferably 2-20, more preferably 5-19, and even more preferably 8-18. Item 9. The modified polyolefin resin composition according to any one of Items 1 to 8, wherein The weight average molecular weight (Mw) of the compound (C) having a polymerizable unsaturated group is 5,000 or less. Item 10. The modified polyolefin resin composition according to any one of Items 1 to 9, wherein The compound (C) having a polymerizable unsaturated group comprises: A compound having a hydroxyl group and one or more polymerizable unsaturated groups, and A compound 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. Item 11. The modified polyolefin resin composition according to any one of Items 1 to 10, wherein The acid-modified polyolefin resin (A) is a graft polymer having a structure in which an α,β-unsaturated carboxylic acid and / or anhydride thereof is grafted onto a polyolefin resin. Item 12. The modified polyolefin resin composition according to Item 11, wherein The polyolefin resin: It is preferably at least one copolymer selected from homopolypropylene, propylene-α-olefin copolymer, homopolyethylene, ethylene-α-olefin copolymer, poly-1-butene and 1-butene-α-olefin copolymer, More preferably, homopolypropylene and / or propylene-α-olefin copolymer, Even more preferably, it is homopolypropylene or a propylene-α-olefin copolymer. Item 13. The modified polyolefin resin composition according to any one of Items 1 to 12, wherein the content ratio of the acid-modified polyolefin resin (A) relative to the total mass of the modified polyolefin resin composition is preferably 1 to 60 mass %, more preferably 4 to 50 mass %, further preferably 7 to 40 mass %, further preferably 10 to 35 mass %, and particularly preferably 15 to 30 mass %. Item 14. The modified polyolefin resin composition according to any one of Items 1 to 13, wherein The polyetheramine (B) has a polyether chain, The polyether chain is a structure comprising at least one selected from the following structures: Formula 1: a structure represented by -(O-CH2CH2)x- (in Formula 1, x is an integer of 2 to 120), Formula 2-1: a structure represented by -(O-CH2CH(CH3))y1- (in Formula 2-1, y1 is an integer from 2 to 90), and Formula 3-1: A structure represented by -(O-CH2CH2CH2CH2)z1- (in Formula 3-1, z1 is an integer of 2 to 80). Item 15. The modified polyolefin resin composition according to any one of Items 1 to 14, wherein The polyetheramine (B) is represented by the following formula 1A: R 1 -(OR 2 )aR 3 Formula 1A (In Formula 1A: R 1 and R 3 Each independently represents an amino group or a linear or branched alkyl group having 1 to 10 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9 or 10) which may have an amino group. R 2 It represents a linear or branched alkylene group having 2 to 4 carbon atoms. a is an integer from 1 to 120.) Represents the compound. Item 16. The modified polyolefin resin composition according to Item 15, wherein In Formula 1A, R 1 represents a linear or branched alkyl group having 1 to 10 (1, 2, 3, 4, 5, 6, 7, 8, 9 or 10) carbon atoms, R 2 represents a linear or branched alkylene group having 2 to 4 carbon atoms, R 3 represents an amino group, and a is an integer of 1 to 120. Item 17. The modified polyolefin resin composition according to any one of Items 1 to 16, wherein The content of the polyetheramine (B) is generally 0.5 to 40% by mass, preferably 1 to 30% by mass, more preferably 2 to 20% by mass, further preferably 3 to 15% by mass, further preferably 4 to 12.5% ​​by mass, and particularly preferably 5 to 10% by 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 weight average molecular weight (Mw) of the compound (C) having a polymerizable unsaturated group is preferably 100 or more and 5000 or less, more preferably 150 or more and 2000 or less, and further preferably 160 or more and 1000 or less. Item 19. The modified polyolefin resin composition according to any one of Items 1 to 18, wherein The modified polyolefin resin composition contains two or three compounds (C) having a polymerizable unsaturated group. Item 20. The modified polyolefin resin composition according to Item 19, wherein (a) When two compounds (C) having polymerizable unsaturated groups are contained, (a1) the two compounds (C) having a polymerizable unsaturated group are one compound having one polymerizable unsaturated group and one compound having two polymerizable unsaturated groups; or (a2) Two compounds having polymerizable unsaturated groups (C) are two compounds having two polymerizable unsaturated groups, (b) When three compounds (C) having polymerizable unsaturated groups are contained, The three compounds (C) having a polymerizable unsaturated group are one compound having one polymerizable unsaturated group and two compounds having two polymerizable unsaturated groups. Item 21. The modified polyolefin resin composition according to any one of Items 3 to 20, wherein The number of the hydroxyl groups is preferably 1 or 2, more preferably 1. Item 22. The modified polyolefin resin composition according to any one of Items 1 to 21, wherein The content of the compound (C) having a polymerizable unsaturated group is generally 10 to 90% by mass, preferably 20 to 85% by mass, more preferably 30 to 80% by mass, further preferably 40 to 77% by mass, and particularly preferably 50 to 75% by mass, 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 polymerizable unsaturated group: It is preferably at least one selected from the group consisting of acryloyl, methacryloyl, acryloyloxy, methacryloyloxy, vinyl, allyl, propenyl, isopropenyl, maleimide and vinyl ether groups, More preferably, it is at least one selected from acryloyl, methacryloyl, acryloyloxy and methacryloyloxy, More preferably, it is an acryloyloxy group and / or a methacryloyloxy group. Item 24. The modified polyolefin resin composition according to any one of Items 1 to 23, wherein The total content ratio of the acid-modified polyolefin resin (A), the polyetheramine (B), and the compound having a polymerizable unsaturated group (C) relative to the total mass of the modified polyolefin resin composition is preferably 45% by mass, 50% by mass, greater than 50% by mass, 55% by mass or more, 60% by mass or more, 65% by mass or more, 70% by mass or more, 75% by mass or more, 80% by mass or more, 85% by mass or more, 90% 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, 99.9% by mass or more, 99.95% by mass or more, and 99.99% by mass or more in this order. Item 25. A cured product obtained by curing the modified polyolefin resin composition according to any one of Items 1 to 24. Item 26. An ink comprising the modified polyolefin resin composition according to any one of Items 1 to 24 or the cured product according to Item 11. Item 27. An adhesive comprising the modified polyolefin resin composition according to any one of Items 1 to 24 or the cured product according to Item 11. Item 28. A primer comprising the modified polyolefin resin composition according to any one of Items 1 to 24 or the cured product according to Item 11. 29. A coating material comprising the modified polyolefin resin composition according to any one of items 1 to 24 or the cured product according to item 11. Item 30. A coating material for in-mold coating, comprising the modified polyolefin resin composition according to any one of Items 1 to 24 or the cured product according to Item 11. Example

[0171] The present invention will be described in detail below based on examples, but the present invention is not limited to the following examples. Hereinafter, "room temperature" refers to a temperature within the range of 20°C to 25°C.

[0172] (1) Determination of weight average molecular weight (Mw) by high temperature GPC The analysis was performed using o-dichlorobenzene as a solvent at 140°C using a GPC150-CPLUS manufactured by Waters (columns: "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.

[0173] (2) Determination of melting point by differential scanning calorimetry (DSC) According to JIS K 7121-2012, a DSC measuring apparatus (manufactured by Seiko Electronics Industries) was used to measure the melting temperature of approximately 5 mg of a sample at 150°C for 10 minutes. The sample was then cooled at a rate of 10°C / minute, held at -50°C, and then heated to 150°C at a rate of 10°C / minute. The peak melting temperature during melting was measured and evaluated as the melting point.

[0174] (3) Determination of tensile elastic modulus (MPa) The modified polyolefin resin composition shown in the following manufacturing example was dissolved in toluene to obtain a solution. The obtained solution was applied to a Teflon (registered trademark) sheet to a film thickness of approximately 50 μm, and the toluene was dried to obtain a dry coating. The coating was cut into pieces with a width of 10 mm and a length of 70 mm to prepare test pieces. The tensile modulus of the obtained test piece was measured using a tensile testing machine (Tensilon RTM-100, manufactured by Orientec Corporation) with a distance between the clamps of 50 mm.

[0175] (Production Example 1) 280g of propylene-α-olefin copolymer (propylene content = 70 mol%), 62g of maleic anhydride, 7g of dicumyl peroxide and 420g of toluene were added to an autoclave equipped with a stirrer, and after nitrogen substitution for about 5 minutes, the mixture was reacted at 140°C for 5 hours while heating and stirring. After the reaction, the reaction solution was added to a large amount of methyl ethyl ketone to precipitate the resin. The resin was further washed several times with methyl ethyl ketone to remove unreacted maleic anhydride. The obtained resin was dried under reduced pressure to obtain a solid substance (MPO-1) of an acid-modified polyolefin resin. According to the results of infrared absorption spectrum measurement, the acid value of the maleic anhydride component and the maleic acid component in MPO-1 was 22.4mgKOH / g. In addition, the weight average molecular weight (Mw) of MPO-1 obtained by high-temperature GPC measurement was 70,000, and the melting point obtained by DSC was 70°C. In addition, the tensile modulus of MPO-1 was 190MPa.

[0176] (Production Example 2) 280g of propylene homopolymer (homopolypropylene, propylene content = 100 mol%), 36g of maleic anhydride, 5.6g of dicumyl peroxide and 420g of toluene were placed in an autoclave equipped with a stirrer, and after nitrogen substitution for about 5 minutes, the mixture was reacted at 140°C for 5 hours while heating and stirring. After the reaction, the reaction solution was put into a large amount of methyl ethyl ketone to precipitate the resin. The resin was further washed several times with methyl ethyl ketone to remove unreacted maleic anhydride. The obtained resin was dried under reduced pressure to obtain a solid substance (MPO-2) of an acid-modified polyolefin resin. According to the results of infrared absorption spectrum measurement, the acid value of the maleic anhydride component and the maleic acid component in MPO-2 was 20.2mgKOH / g. In addition, the weight average molecular weight (Mw) of MPO-2 obtained by high-temperature GPC measurement was 40,000, and the melting point obtained by DSC was 75°C. In addition, the tensile modulus of MPO-2 was 130MPa.

[0177] (Production Example 3) 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 added to an autoclave equipped with a stirrer, and after nitrogen substitution for about 5 minutes, the reaction was carried out at 140°C while heating and stirring for 5 hours. After the reaction was completed, the reaction solution was added to a large amount of methyl ethyl ketone to precipitate the resin. The resin was further washed several times with methyl ethyl ketone to remove unreacted maleic anhydride. After drying under reduced pressure, 280 g of the obtained maleic anhydride-modified polyolefin resin and 2520 g of chloroform were placed in an autoclave equipped with a stirrer, and after nitrogen substitution for about 5 minutes, the resin was heated to 110°C to fully dissolve the resin. Next, 1.4 g of tert-butyl peroxy-2-ethylhexanoate was added, and a specified amount of chlorine gas was blown in. The chloroform as the reaction solvent was removed by vacuum distillation and dried to obtain a solid substance (CPO-1) of the acid-modified chlorinated polyolefin resin. The weight-average molecular weight (Mw) of CPO-1 as measured by high-temperature GPC was 80,000, and its melting point as measured by DSC was 75°C. Furthermore, the chlorine content in CPO-1 was 21% by mass, and the acid value of the maleic anhydride component was 16.8 mgKOH / g. Furthermore, the tensile modulus of CPO-1 was 18 MPa.

[0178] (Materials used) The materials used in Examples and Comparative Examples are as follows. <Acid-modified polyolefin resin (A)> MPO-1 obtained in Production Example 1 (total content of maleic anhydride and maleic acid components = 2.0% by mass, Mw as measured by high-temperature GPC = 70,000, melting point as measured by DSC = 70°C) MPO-2 obtained in Production Example 2 (total content of maleic anhydride and maleic acid components = 1.8% by mass, Mw as measured by high-temperature GPC = 40,000, melting point as measured by DSC = 75°C) CPO-1 obtained in Production Example 3 (chlorine content = 21% by mass, maleic anhydride content = 1.5% by mass, Mw as measured by high-temperature GPC = 80,000, melting point as measured by DSC = 75°C) <Polyetheramine (B)> "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) "JEFFAMINE M-2005 (Mw = 2000, HLB value = 2.7)" manufactured by HUNTSMAN (number of primary amino groups = 1, number of secondary amino groups = 0) <Compound (C) Having a Polymerizable Unsaturated Group> [Compound having an alkyleneoxy group and two polymerizable unsaturated groups] Neopentyl glycol diacrylate (Mw = 212, SP value = 9.4) (manufactured by Tokyo Chemical Industry Co., Ltd.) Tripropylene glycol diacrylate (Mw=300, SP value=9.2) (manufactured by Tokyo Chemical Industry Co., Ltd.) Polypropylene glycol diacrylate (polypropylene glycol #700 diacrylate, number of repeating units = 12, Mw = 808, SP value = 8.9, manufactured by Shin-Nakamura Chemical Industry Co., Ltd., NK Ester (registered trademark) "APG-700") [Compound having a branched alkyl group having 8 carbon atoms and one polymerizable unsaturated group] 2-Ethylhexyl acrylate (Mw=184, SP value=8.6) (manufactured by Tokyo Chemical Industry Co., Ltd.) [Compound having a hydroxyl group and one polymerizable unsaturated group] 4-Hydroxybutyl acrylate (Mw=144, SP value=11.6) (manufactured by Tokyo Chemical Industry Co., Ltd.) [Compound having a hydroxyl group and two polymerizable unsaturated groups] 2-Hydroxy-3-methacryloylpropyl acrylate (Mw=214, SP value=12.2) (manufactured by Tokyo Chemical Industry Co., Ltd.) [Compound having a unit having a carbonyl group represented by formula (1) and one polymerizable unsaturated group] Acetoacetoxyethyl methacrylate (Mw=214, SP value=10) (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0179] (Example 1) A 200 ml four-necked flask equipped with a cooler, thermometer, and stirrer was charged with 20 g of MPO-1 as the acid-modified polyolefin resin (A), 50 g of neopentyl glycol diacrylate as the compound having a polymerizable unsaturated group (C), and 30 g of 2-hydroxy-3-methacryloylpropyl acrylate. The internal temperature was raised to 90°C and heated for 30 minutes to dissolve. Then, 8 g of "JEFFAMINE M-2070" as the polyetheramine (B) was added and stirred at 90°C for 1 hour. The mixture was then cooled to room temperature and filtered through a metal mesh with a mesh size of 149 μm to obtain a modified polyolefin resin composition (a).

[0180] (Example 2 to Example 16) Modified polyolefin resin compositions (b) to (p) were obtained in the same manner as in Example 1 except that the amounts of the acid-modified polyolefin resin (A), polyetheramine (B) and compound having a polymerizable unsaturated group (C) used were changed as shown in Table 1 below.

[0181] (Comparative Example 1) In a 200 ml four-necked flask equipped with a cooler, thermometer, and stirrer, 50 g of neopentyl glycol diacrylate as the polymerizable unsaturated group compound (C) and 30 g of 2-hydroxy-3-methacryloylpropyl acrylate were placed. The internal temperature was raised to 90°C and heated to dissolve for 30 minutes. Then, 8 g of "JEFFAMINE M-2070" was added as the polyetheramine (B) and stirred at 90°C for 1 hour. The mixture was then cooled to room temperature and filtered through a metal mesh with a mesh size of 149 μm to obtain a resin composition (q). It should be noted that in Comparative Example 1, no acid-modified polyolefin resin (A) was used.

[0182] (Comparative Example 2) A 200 ml four-necked flask equipped with a cooler, thermometer, and stirrer was charged with 20 g of MPO-1 as the acid-modified polyolefin resin (A), 50 g of neopentyl glycol diacrylate as the compound having a polymerizable unsaturated group (C), and 30 g of 2-hydroxy-3-methacryloylpropyl acrylate. The internal temperature was raised to 90°C and heated for 30 minutes to dissolve the mixture. The mixture was then stirred at 90°C for 1 hour without adding the polyetheramine (B). The mixture was then cooled to room temperature, but no resin precipitation occurred, and a modified polyolefin resin composition was not obtained.

[0183] (1) Evaluation of fluidity at -5°C and 80°C The modified polyolefin resin compositions obtained in the Examples and the resin compositions obtained in the Comparative Examples were visually evaluated for fluidity at -5°C and 80°C immediately after production, fluidity at -5°C and 80°C the next day (24 hours after production), and fluidity at -5°C and 80°C one week after production (168 hours after production). A rating of ⊚ indicates that fluidity was present after one week, ⊚ indicates that fluidity was present the next day, ⊚ indicates that fluidity was present only immediately after production, and × indicates that no fluidity was present immediately after production.

[0184] (2) Evaluation of adhesion 0.15 g of tert-butyl-2-ethylperoxycaproate was added to 5 g of the modified polyolefin resin composition obtained in the example and 5 g of the resin composition obtained in the comparative example, and the mixture was stirred at room temperature for 30 minutes using a magnetic stirrer. The stirred mixture was applied to a PP (polypropylene) bumper substrate washed with isopropyl alcohol using a No. 16 rod coater at room temperature so that the coating thickness after drying was approximately 10 μm. After baking at 110°C for 10 minutes, the mixture was placed in an atmosphere of 25°C and 60% relative humidity for 72 hours to prepare a test plate. 100 grids were made on the test plate at 1 mm intervals, reaching the substrate. Cellophane tape was pressed onto the test plate and peeled off repeatedly three times at a 90-degree angle relative to the coated surface. A score of ○ was given if no peeling occurred even after three peelings, a score of △ was given if peeling occurred during the third peeling, and a score of × was given if peeling occurred during the first or second peeling.

[0185] (3) Evaluation of water resistance 0.15 g of tert-butyl-2-ethylperoxyhexanoate was added to 5 g of the modified polyolefin resin composition obtained in the example and 5 g of the resin composition obtained in the comparative example, and the mixture was 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 using a No. 16 bar coater at room temperature, so that the coating thickness after drying was approximately 10 μm. After baking at 110°C for 10 minutes, the mixture was placed in an atmosphere of 25°C and 60% relative humidity for 72 hours to prepare a test plate. The resulting test plate was immersed in warm water at 40°C for 10 days (240 hours). On the immersed test plate, 100 grids were made at 1 mm intervals, reaching the substrate. Cellophane tape was pressed onto the grids and peeled off repeatedly three times at a 90-degree angle relative to the coated surface. A score of ○ was given if no peeling occurred even after three peeling attempts. A score of △ was given if peeling occurred during the third peeling attempt. A score of × was given if peeling occurred during the first or second peeling attempt.

[0186] The raw materials used in each example and each comparative example and their amounts, the evaluation results of the modified polyolefin resin compositions (a) to (p) obtained in Examples 1 to 16, and the evaluation results of the resin composition (q) obtained in Comparative Example 1 are shown in Table 1 below. Note that, for Comparative Example 2, no modified polyolefin resin composition could be obtained, and therefore, the adhesion and water resistance were rated "not evaluable."

[0187] [Table 1]

[0188] [Review of the results of Table 1] The modified polyolefin resin compositions (a) to (p) obtained in Examples 1 to 16 showed that fluidity was maintained immediately after production at both -5°C and 80°C. In addition, the modified polyolefin resin compositions (a) to (p) obtained in Examples 1 to 16 showed sufficient adhesion to the PP (polypropylene) bumper substrate. In addition, the modified polyolefin resin compositions (a) to (p) obtained in Examples 1 to 16 showed sufficient water resistance. On the other hand, in the resin composition (q) obtained in Comparative Example 1, since the modified polyolefin resin (A) was not used, the adhesion was greatly deteriorated. In addition, in Comparative Example 2, since the polyetheramine (B) was not used, the resin could not be precipitated, and the modified polyolefin resin composition itself could not be produced.

Claims

1. A modified polyolefin resin composition comprising an acid-modified polyolefin resin A, a polyetheramine B, and a compound C having a polymerizable unsaturated group.

2. The modified polyolefin resin composition according to claim 1, wherein The content of the acid-modified polyolefin resin A is 5 to 120 parts by mass relative to 100 parts by mass of the compound C having a polymerizable unsaturated group.

3. The modified polyolefin resin composition according to claim 1, wherein The compound C having a polymerizable unsaturated group includes a compound having a hydroxyl group and one or more polymerizable unsaturated groups.

4. The modified polyolefin resin composition according to claim 1, wherein The compound C having a polymerizable unsaturated group includes a compound 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.

5. The modified polyolefin resin composition according to claim 1, wherein The content of the polyetheramine B is 6 to 100 parts by mass relative to 100 parts by mass of the acid-modified polyolefin resin A.

6. The modified polyolefin resin composition according to claim 1, wherein The polyetheramine B has a polyether chain, The polyether chain is a structure comprising at least one selected from the following structures: -(O-CH2CH2)x-, wherein x is an integer from 2 to 120. -(O-CH2CH(CH3))y1-, y1 is an integer from 2 to 90, -(O-CH2CH2CH2)y2-, wherein y2 is an integer from 2 to 90. -(O-CH2CH2CH2CH2)z1-, ​​z1 is an integer from 2 to 80, -(O-CH(CH3)CH2CH2)z2-, wherein z2 is an integer from 2 to 80. -(O-CH2CH(CH3)CH2)z3-, z3 is an integer from 2 to 80, and The structure represented by -(O-CH2CH2CH(CH3))z4-, wherein z4 is an integer from 2 to 80.

7. The modified polyolefin resin composition according to claim 1, wherein The polyetheramine B has a primary or secondary amino group at a single terminal, The weight average molecular weight Mw of the polyetheramine B is 200 to 50,000.

8. The modified polyolefin resin composition according to claim 1, wherein The HLB value of the polyetheramine B is 3-20.

9. The modified polyolefin resin composition according to claim 1, wherein The weight average molecular weight Mw of the compound C having a polymerizable unsaturated group is 5,000 or less.

10. The modified polyolefin resin composition according to claim 1, wherein The compound C having a polymerizable unsaturated group comprises: A compound having a hydroxyl group and one or more polymerizable unsaturated groups, and A compound 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. 11 . A cured product obtained by curing the modified polyolefin resin composition according to claim 1 . 12 . An ink comprising the modified polyolefin resin composition according to claim 1 . 13 . An adhesive comprising the modified polyolefin resin composition according to claim 1 .

14. A primer comprising the modified polyolefin resin composition according to any one of claims 1 to 10. 15 . A coating material comprising the modified polyolefin resin composition according to claim 1 .

16. A paint for in-mold coating, comprising the modified polyolefin resin composition according to any one of claims 1 to 10.

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