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 polyhydroxy compound component (C).

Description

Technical Field

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

[0002] Hitherto, polyolefin resins such as polypropylene, polyethylene, ethylene - propylene copolymer, ethylene - propylene - diene copolymer, polybutene, and poly(4 - methyl - 1 - pentene) have been used in fields such as automotive parts, electrical parts, building materials, and packaging films because of their relatively low prices and excellent properties such as chemical resistance, water resistance, and heat resistance.

[0003] On the other hand, since polyolefin resins are crystalline and non - polar, it is difficult to perform painting, adhesion, etc. on polyolefin resins.

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

[0005] In order to improve the adhesion (close contact property) of chlorinated polyolefin to a substrate or to compensate for defects such as limited adhesion targets of chlorinated polyolefin, mixtures of chlorinated polyolefin with acrylic resin, urethane resin, or polyester resin and adhesive compositions obtained by graft - polymerizing these resins onto chlorinated polyolefin are also widely used (refer to Patent Document 3 and Patent Document 4).

[0006] However, these mixtures and adhesive compositions are usually used in a state dissolved in organic solvents such as toluene and xylene. Therefore, a large amount of organic solvents are emitted into the atmosphere during painting, which is not preferable from the viewpoints of the environment and hygiene. Further, these mixtures and adhesive compositions have problems of poor fluidity and poor close contact property with polyolefin substrates.

[0007] Patent Document 5 describes a solvent - free in - mold coat coating composition for thermoplastic substrates, which contains an acrylic - modified polyolefin, a reactive monomer and / or a reactive oligomer, and a radical - polymerizable initiator in a specified ratio.

[0008] However, since the composition of Patent Document 5 requires the use of a large amount of solvents and a desolventization treatment in the manufacturing process, there is room for improvement from the viewpoints of the environment and hygiene. Further, the composition disclosed in Patent Document 5 has problems of poor fluidity and poor close contact property with polyallyl substrates. Prior Art Documents Patent Documents

[0009] Patent Document 1: Japanese Patent Laid - Open No. 59 - 75958 Patent Document 2: Japanese Patent Laid-Open Publication No. 60-99138 Patent Document 3: Japanese Patent Laid-Open Publication No. 6-16746 Patent Document 4: Japanese Patent Laid-Open Publication No. 8-12913 Patent Document 5: Japanese Patent Laid-Open Publication No. 2002-249680 Summary of the Invention Problems to be Solved by the Invention

[0010] The present invention has been completed in view of the above, and an object thereof is to provide a modified polyolefin resin composition that has sufficient fluidity within a specific temperature range and has sufficient adhesion to a polyolefin substrate. Means for Solving the Problems

[0011] As a result of repeatedly studying the dispersion and / or dissolution of an acid-modified polyolefin resin in a polyol in order to achieve the above object, the inventors of the present invention have found that a modified polyolefin resin composition containing an acid-modified polyolefin resin, a polyetheramine, and a polyol can solve the above problems, and thus have completed the present invention.

[0012] The present invention includes, for example, the subjects described in the following items. Item 1. A modified polyolefin resin composition containing an acid-modified polyolefin resin (A), a polyetheramine (B), and a polyol component (C). Effects of the Invention

[0013] The modified polyolefin resin composition of the present invention has sufficient fluidity within a specific temperature range and has sufficient adhesion to a polyolefin substrate. Since the modified polyolefin resin composition of the present invention exhibits sufficient fluidity within a specific temperature range, it can be applied as a liquid modified polyolefin resin composition to various uses. Detailed Description of the Invention

[0014] Hereinafter, preferred embodiments of the present invention will be described in detail. The description of the constituent elements described below is based on representative embodiments and specific examples in some cases, but the present invention is not limited to such embodiments.

[0015] In this specification, expressions such as "containing" and "comprising" include concepts such as "containing", "comprising", "substantially consisting of", and "consisting only of".

[0016] In the numerical ranges described stage by stage in this specification, the upper limit value or the lower limit value of the numerical range of a certain stage can be arbitrarily combined with the upper limit value or the lower limit value of the numerical range of other stages. Further, in the numerical ranges described in this specification, the upper limit value or the lower limit value of the numerical range can be replaced with the value shown in the examples or the value uniquely derived from the examples. Furthermore, in this specification, the numerical values connected by "~" refer to the numerical range including the numerical values before and after "~" as the lower limit value and the upper limit value.

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

[0018] In this specification, "(meth)acrylic acid" means acrylic acid or methacrylic acid. "(meth)acrylate" means acrylate or methacrylate.

[0019] <Modified polyolefin resin composition> The modified polyolefin resin composition of the present invention contains an acid-modified polyolefin resin (A), a polyetheramine (B), and a polyhydroxy compound component (C) as essential components.

[0020] The modified polyolefin resin composition of the present invention generally has sufficient fluidity in the range of 25°C or higher and 80°C or lower. In this specification, a resin composition having fluidity means, for example, a uniform liquid composition that does not contain coarse particles, aggregates, etc. of the resin.

[0021] The modified polyolefin resin composition of the present invention is generally a resin composition that flows when poured while tilting a glass bottle in the range of 25°C or higher and 80°C or lower. In the present invention, a resin composition having fluidity generally also includes a resin composition that flows by applying mechanical shear in the range of 25°C or higher and 80°C or lower.

[0022] As an embodiment of the present invention, the total content ratio of the acid-modified polyolefin resin (A), the polyetheramine (B), and the polyhydroxy compound component (C) relative to the total mass of the modified polyolefin resin composition exceeds 50% by mass, and is preferably 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 turn.

[0023] <Acid-modified polyolefin resin (A)> The present invention contains an acid-modified polyolefin resin (A). The acid-modified polyolefin resin (A) is a polymer obtained by graft-polymerizing an α,β-unsaturated carboxylic acid or its acid anhydride onto a polyolefin.

[0024] Examples of the polyolefin include: homopolypropylene (a homopolymer of propylene), a propylene-α-olefin copolymer, homopolyethylene (a homopolymer of ethylene), an ethylene-α-olefin copolymer, poly-1-butene, and a 1-butene-α-olefin copolymer, etc. These polyolefins can be used individually or in combination of two or more. Among these polyolefins, homopolypropylene and / or a propylene-α-olefin copolymer are preferred.

[0025] The propylene-α-olefin copolymer is a copolymer of propylene and an α-olefin. Examples of the α-olefin include: ethylene; α-olefins having 4 to 20 carbon atoms (4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20) such as 1-butene, isobutene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, etc. These α-olefins can be used individually or in combination of two or more.

[0026] The content of the propylene component in the propylene-α-olefin copolymer is preferably 50 mol% or more, more preferably 60 mol% or more, and even more preferably 70 mol% or more. When the content of the propylene component in the propylene-α-olefin copolymer is 50 mol% or more, the adhesion of the modified polyolefin resin composition of the present invention to a polyolefin substrate (especially a polypropylene substrate) becomes even better.

[0027] The ethylene-α-olefin copolymer is a copolymer of ethylene and an α-olefin. Examples of the α-olefin include: propylene, 1-butene, isobutene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, etc. 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 individually or in combination of two or more.

[0028] 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 adhesion of the modified polyolefin resin composition of the present invention to a polyolefin substrate (especially a polyethylene substrate) becomes even better.

[0029] 1-Butene-α-olefin copolymer refers to a copolymer of 1-butene and an α-olefin. As the α-olefin, for example, the following can be cited: ethylene, propylene; 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, 1-eicosene, etc. These α-olefins can be used individually or in combination of two or more.

[0030] The content of the 1-butene component in the 1-butene-α-olefin copolymer is preferably 65 mol% or more. When the content of the 1-butene component in the 1-butene-α-olefin copolymer is 65 mol% or more, the adhesion of the modified polyolefin resin composition of the present invention to a polyolefin substrate (especially a polypropylene substrate or a poly-1-butene substrate) becomes even better.

[0031] As the α,β-unsaturated carboxylic acid or its acid anhydride graft-polymerized on the polyolefin, for example, the following can be cited: maleic acid, maleic anhydride, fumaric acid, citraconic acid, citraconic anhydride, mesaconic acid, itaconic acid, itaconic anhydride, aconitic acid, aconitic anhydride, nadic anhydride, etc. Among these α,β-unsaturated carboxylic acids or their acid anhydrides, maleic acid, maleic anhydride and itaconic anhydride are preferred, and maleic acid and maleic anhydride are more preferred.

[0032] The total content of the α,β-unsaturated carboxylic acid and its acid anhydride components in the acid-modified polyolefin resin (A) is preferably 0.5 to 10% by mass, more preferably 0.7 to 7.5% by mass, still more preferably 0.8 to 3% by mass, and further preferably 1.0 to 2.0% by mass. When the total content of the α,β-unsaturated carboxylic acid and its acid anhydride components in the acid-modified polyolefin resin (A) is in the range of 0.5 to 10% by mass, the fluidity of the modified polyolefin resin composition of the present invention becomes even better.

[0033] As a method for graft-polymerizing an α,β-unsaturated carboxylic acid or its acid anhydride on a polyolefin, a well-known method can be widely adopted. For example, the following can be cited: a method of heating and melting the polyolefin above its melting point in the presence of a radical generator to make it react (melting method), a method of dissolving the polyolefin in an organic solvent and then heating and stirring it in the presence of a radical generator to make it react (solution method), etc.

[0034] In the present invention, the acid-modified polyolefin resin (A) may further be a chlorinated acid-modified chlorinated polyolefin resin. As a chlorination method, for example, a method of introducing chlorine atoms by blowing chlorine gas into the acid-modified polyolefin resin can be cited. More specifically, the acid-modified polyolefin resin can be dispersed or dissolved in a solvent as needed, and then chlorine gas is blown in under pressure or normal pressure in the presence of a catalyst or under ultraviolet irradiation within a temperature range of 50 to 150 °C to carry out chlorination.

[0035] As the solvent used in chlorination, for example, the following can be cited: water, chlorine-based solvents (such as chloroform, dichloromethane, carbon tetrachloride, etc.), etc., and chlorine-based solvents are preferred. The chlorine-based solvent can be distilled off by reduced pressure or the like at the end of chlorination, or can be replaced with other organic solvents.

[0036] As the catalyst used in chlorination, for example, a radical initiator can be cited. As the radical initiator, for example, the following can be cited: tert-butyl 2-ethylhexanoate peroxide, tert-butyl octanoate peroxide, di-tert-butyl peroxide, cumene hydroperoxide, etc.

[0037] 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, further 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 solution stability becomes better, and thus the acid-modified chlorinated polyolefin resin becomes easier to emulsify. In addition, the chlorine content in the acid-modified chlorinated polyolefin resin is preferably 40% by mass or less, more preferably 38% by mass or less, further preferably 35% by mass or less, particularly preferably 32% by mass or less, and most preferably 30% by mass or less. When the chlorine content in the acid-modified chlorinated polyolefin resin is 40% by mass or less, the crystallinity of the acid-modified chlorinated polyolefin increases, and the close adhesion is further improved.

[0038] 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, still 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, particularly preferably 14% by mass or more and 30% by mass or less.

[0039] The chlorine content in the acid-modified chlorinated polyolefin resin can be measured in accordance with JIS K-7229-1995. That is, it can be measured by the "oxygen flask combustion method" in which the acid-modified chlorinated polyolefin resin is burned in an oxygen atmosphere, the generated chlorine gas is absorbed by water, and quantitative determination is carried out by titration.

[0040] 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, the adhesion to the polyolefin substrate becomes good.

[0041] 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 good.

[0042] The melting point of the acid-modified polyolefin resin (A) can be measured by a differential scanning calorimeter (DSC) in accordance with JIS K7121-2012. Specifically, using a DSC measuring device, the melting peak temperature is measured as follows: After maintaining and heating about 5 mg of the sample in a molten state at 150 °C for 10 minutes, it is cooled at a rate of 10 °C / minute, stably maintained at -50 °C, and further heated at a rate of 10 °C / minute to 150 °C and then melted. The melting peak temperature at this time is used as the melting point for evaluation.

[0043] 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, still more 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 in the range of 3,000 to 200,000, it has good fluidity. In addition, if Mw is in the range of 3,000 to 200,000, the cohesive force of the acid-modified polyolefin resin (A) further increases, and the adhesive force further 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 following examples.

[0044] Within the limit of not impairing the effects of the present invention, the acid-modified polyolefin resin (A) can be further copolymerized with a radically polymerizable monomer. With respect to 100 parts by mass of the acid-modified polyolefin resin (A), the content of the radically polymerizable monomer is usually 20 parts by mass or less, preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and further preferably 1 part by mass or less.

[0045] The form of the acid-modified polyolefin resin (A) when copolymerized with a radically polymerizable monomer is not limited. Examples of the copolymerization form include: random copolymerization, block copolymerization, graft copolymerization (graft modification), etc.

[0046] As radical polymerizable monomers, for example, the following can be mentioned: (meth)acrylic compounds, vinyl compounds, etc. A (meth)acrylic compound refers to a compound containing at least one (meth)acryloyl group (acryloyl group and / or methacryloyl group) in the molecule.

[0047] Examples of the radical polymerizable monomer include: (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-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, 2-hydroxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, acetoacetoxyethyl (meth)acrylate, N-methyl (meth)acrylamide, N-ethyl (meth)acrylamide, N-propyl (meth)acrylamide, N-isopropyl (meth)acrylamide, N-butyl (meth)acrylamide, N-isobutyl (meth)acrylamide, N-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)acryloylmorpholine, n-butyl vinyl ether, 4-hydroxybutyl vinyl ether, dodecyl vinyl ether, etc. Among these, methyl (meth)acrylate, ethyl (meth)acrylate, cyclohexyl (meth)acrylate, and lauryl (meth)acrylate are preferred, and their methyl acrylate esters, namely methyl methacrylate, ethyl methacrylate, cyclohexyl methacrylate, and lauryl methacrylate, are more preferred. The above-mentioned radical polymerizable monomers can be used individually or in combination of two or more.

[0048] In the present invention, from the viewpoint of further better maintaining the fluidity of the modified polyolefin resin composition and further improving the adhesion to the polyolefin substrate, the content of the acid-modified polyolefin resin (A) is preferably 5 to 60 parts by mass, more preferably 10 to 40 parts by mass, still more preferably 15 to 35 parts by mass, and further preferably 18 to 30 parts by mass, based on 100 parts by mass of the modified polyolefin resin composition.

[0049] In the present invention, from the viewpoint of further better maintaining the fluidity of the modified polyolefin resin composition and further improving the adhesion to the polyolefin substrate, the content of the acid-modified polyolefin resin (A) is usually 5 to 100 parts by mass, preferably 10 to 90 parts by mass, more preferably 12.5 to 80 parts by mass, still more preferably 15 to 70 parts by mass, further preferably 20 to 60 parts by mass, and particularly preferably 25 to 50 parts by mass, based on 100 parts by mass of the polyhydroxy compound component (C).

[0050] <Polyetheramine (B)> The present invention contains polyetheramine (B). Polyetheramine (B) is usually a compound having a polyether chain and an amino group.

[0051] In the present invention, polyetheramine (B) is preferably: having a polyether chain, which is a chain containing at least one selected from the group consisting of -(O-CH2CH2)x- (wherein x is an integer of 2 to 120), -(O-CH2CH(CH3))y1- (wherein y1 is an integer of 2 to 90), -(O-CH2CH2CH2)y2- (wherein y2 is an integer of 2 to 90), -(O-CH2CH2CH2CH2)z1- (wherein z1 is an integer of 2 to 80), -(O-CH(CH3)CH2CH2)z2- (wherein z2 is an integer of 2 to 80), -(O-CH2CH(CH3)CH2)z3- (wherein z3 is an integer of 2 to 80), and -(O-CH2CH2CH(CH3))z4- (wherein z4 is an integer of 2 to 80) constituting the structure of at least one kind in the group.

[0052] In the present invention, polyetheramine (B) is more preferably: having a polyether chain, which is a chain containing at least one selected from the group consisting of -(O-CH2CH2)x- (wherein x is an integer of 2 to 120), -(O-CH2CH(CH3))y1- (wherein y1 is an integer of 2 to 90), and -(O-CH2CH2CH2CH2)z1- (wherein z1 is an integer of 2 to 80) constituting the structure of at least one kind in the group.

[0053] In the present invention, the polyetheramine (B) is preferably one having a primary amino group or a secondary amino group at one end and having a weight-average molecular weight (Mw) of 200 to 50,000.

[0054] In the present invention, the polyetheramine (B) is more preferably one having a primary amino group or a secondary amino group at one end and having a weight-average molecular weight (Mw) of 200 to 5,000.

[0055] In the present invention, the polyetheramine (B) is further preferably one having a primary amino group at one end and having a weight-average molecular weight (Mw) of 500 to 5,000.

[0056] In the present invention, from the viewpoint of stably dissolving and / or dispersing the acid-modified polyolefin resin (A) in the polyhydroxy compound component (C), the polyetheramine (B) is generally a high-molecular compound having a weight-average molecular weight (Mw) in the range of 200 to 50,000. When the Mw of the polyetheramine (B) is within this range, steric repulsion of the polyetheramine (B) in the polyhydroxy compound component (C) is likely to increase, and the acid-modified polyolefin resin (A) can be stably dispersed and / or dissolved in the polyhydroxy compound component (C).

[0057] In the present invention, the weight-average molecular weight (Mw) of the polyetheramine (B) is generally 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.

[0058] The weight-average molecular weight (Mw) of the polyetheramine (B) in the present invention can be measured by GPC and converted by a calibration curve of polystyrene. In addition, GPC measurement can be performed using a commercially available apparatus by a conventionally known method using a solvent such as THF.

[0059] In the present invention, the HLB value of the polyetheramine (B) is preferably 2 to 19, more preferably 5 to 18, and even more preferably 8 to 17. When the HLB value is in the range of 2 to 19, good fluidity can be maintained.

[0060] In addition, in the present invention, the HLB value refers to a value indicating the degree of hydrophilicity or lipophilicity (hydrophobicity) of the polyetheramine (B), and can be obtained by the Griffin method represented by the following formula (1). HLB value = 20 × sum of formula weights of hydrophilic group moieties / molecular weight ··· formula (1)

[0061] The polyetheramine (B) can be combined with the acid-modified polyolefin resin (A) by various reaction methods. As such reaction methods, for example, reaction methods for forming covalent bonds and / or ionic bonds can be cited. More specifically, for example, amidation reactions of carboxylic anhydride groups with primary or secondary amino groups; imidization reactions, and neutralization reactions of carboxylic acid groups with primary or secondary amino groups can be cited.

[0062] As the polyetheramine (B), publicly known commercially available products can be widely used. As commercially available products of the polyetheramine (B), for example, “JEFFAMINE M-600 (MW = 600, HLB value = 2.1)”, “JEFFAMINE M-1000 (MW = 1000, HLB value = 16.1)”, “JEFFAMINE M-2005 (MW = 2000, HLB value = 2.7)”, “JEFFAMINE M-2070 (MW = 2000, HLB value = 13.8)”, “JEFFAMINE M-3085 (MW = 3000, HLB value = 16.8)”, “JEFFAMINE D-230 (MW = 230, HLB value = 3.6)”, “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., manufactured by HUNTSMAN can be cited. These commercially available products can be used individually or in combination of two or more.

[0063] In the present invention, from the viewpoints of further better 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 5 to 100 parts by mass, preferably 10 to 90 parts by mass, more preferably 12.5 to 80 parts by mass, still more preferably 15 to 70 parts by mass, further preferably 20 to 60 parts by mass, and particularly preferably 25 to 50 parts by mass, based on 100 parts by mass of the acid-modified polyolefin resin (A).

[0064] In the present invention, from the viewpoints of further better 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 preferably 1 to 40 parts by mass, more preferably 1.5 to 30 parts by mass, still more preferably 2 to 20 parts by mass, and further preferably 3 to 15 parts by mass, based on 100 parts by mass of the modified polyolefin resin composition.

[0065] <Polyhydroxy compound component (C)> The present invention contains a polyhydroxy compound component (C). The polyhydroxy compound component (C) generally contains a polyol (a compound having two or more hydroxyl groups in one molecule). The polyhydroxy compound component (C) is generally a reactive component that can be used as a resin for forming a coating film. The polyhydroxy compound component (C) can form a three-dimensional cured coating film by reacting with a curing agent by heating, for example.

[0066] As an embodiment of the present invention, the polyhydroxy compound component (C) preferably contains a single polyhydroxy compound component (C) or two or more polyhydroxy compound components (C) having different hydroxyl values, and more preferably contains a single polyhydroxy compound component (C) or two polyhydroxy compound components (C) having different hydroxyl values.

[0067] As other embodiments of the present invention, the polyhydroxy compound component (C) is preferably composed of a single polyhydroxy compound or two or more polyhydroxy compounds having different hydroxyl values, and more preferably composed of a single polyhydroxy compound or two polyhydroxy compound components having different hydroxyl values. It may contain a single polyhydroxy compound component (C) or two polyhydroxy compound components (C) having different hydroxyl values.

[0068] The polyhydroxy compound component (C) preferably contains at least one polyhydroxy compound selected from the group consisting of polyether polyhydroxy compounds, polyester polyhydroxy compounds, polyacrylate polyhydroxy compounds, polycaprolactone polyhydroxy compounds, polycarbonate polyhydroxy compounds, castor oil-modified polyhydroxy compounds, polyolefin polyhydroxy compounds, and polyalcohols.

[0069] The polyhydroxy compound component (C) more preferably contains at least one polyhydroxy compound selected from the group consisting of polyether polyhydroxy compounds, polyester polyhydroxy compounds, polyacrylate polyhydroxy compounds, polycaprolactone polyhydroxy compounds, polycarbonate polyhydroxy compounds, and polyalcohols.

[0070] The polyhydroxy compound component (C) still more preferably contains at least one polyhydroxy compound selected from the group consisting of polyether polyhydroxy compounds, polyester polyhydroxy compounds, polycaprolactone polyhydroxy compounds, polycarbonate polyhydroxy compounds, and polyalcohols.

[0071] The polyhydroxy compound component (C) more preferably contains at least one polyhydroxy compound selected from the group consisting of polypropylene glycol, polyester polyhydroxy compound, polyacrylate polyhydroxy compound, polycaprolactone polyhydroxy compound, polycarbonate polyhydroxy compound, and polyol.

[0072] The polyhydroxy compound component (C) particularly preferably contains a single polyether polyhydroxy compound; two or more polyether polyhydroxy compounds having different hydroxyl values; a polyether polyhydroxy compound and a polyester polyhydroxy compound; a polyether polyhydroxy compound and a polycaprolactone polyhydroxy compound; a polyether polyhydroxy compound and a polycarbonate polyhydroxy compound; or a polyether polyhydroxy compound and a polyol.

[0073] The polyhydroxy compound component (C) most preferably contains a single polypropylene glycol; two or more polypropylene glycols having different hydroxyl values; a polypropylene glycol and a polyester polyhydroxy compound; a polypropylene glycol and a polycaprolactone polyhydroxy compound; a polypropylene glycol and a polycarbonate polyhydroxy compound; or a polypropylene glycol and a polyol.

[0074] <Polyether polyhydroxy compound> The polyhydroxy compound component (C) may contain a polyether polyhydroxy compound. Examples of the polyether polyhydroxy compound include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and block copolymers thereof. These can be used individually or in combination of two or more.

[0075] The polyether polyhydroxy compound is preferably at least one selected from the group consisting of polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. The polyether polyhydroxy compound is more preferably polypropylene glycol.

[0076] The polyether polyhydroxy compound can be prepared, for example, by adding ethylene oxide and / or propylene oxide to a polyol compound. Thereby, a polyether polyhydroxy compound having 2, 3, or more hydroxyl groups in one molecule can be prepared.

[0077] As commercially available products of polyether polyhydroxy compounds, well-known commercially available products can be widely used. As commercially available products of polyether polyhydroxy compounds, for example, there can be mentioned: "SANNIX PP-200 (Mn = 200, hydroxyl value = 560 mg KOH / g)", "SANNIX PP-400 (Mn = 400, hydroxyl value = 280 mg KOH / g)", "SANNIX PP-600 (Mn = 600, hydroxyl value = 187 mg KOH / g)", "SANNIX PP-1000 (Mn = 1000, hydroxyl value = 112 mg KOH / g)", "SANNIX GP-250 (Mn = 250, hydroxyl value = 670 mg KOH / g)", "SANNIX GP-600 (Mn = 600, hydroxyl value = 280 mg KOH / g)", etc., manufactured by Sanyo Chemical Industries, Ltd. As commercially available products of polyether polyhydroxy compounds other than those manufactured by Sanyo Chemical Industries, Ltd., there can be mentioned: "EXCENOL series" manufactured by AGC Inc., "ADEKA polyether series" manufactured by ADEKA Corporation, "PTMG series" manufactured by Mitsubishi Chemical Corporation, etc. These commercially available products can be used individually or in combination of two or more kinds.

[0078] <Polyacrylate polyhydroxy compound> The polyhydroxy compound component (C) may contain a polyacrylate polyhydroxy compound. The polyacrylate polyhydroxy compound can be prepared, for example, by polymerizing an acrylate monomer composition containing an acrylate monomer having a hydroxyl group.

[0079] As the acrylate monomer having a hydroxyl group, there can be mentioned: 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, polytetramethylene glycol mono(meth)acrylate, etc.

[0080] As commercially available products of polyacrylate polyhydroxy compounds, well-known commercially available products can be widely used. As commercially available products of polyacrylate polyhydroxy compounds, for example, there can be mentioned: "ARUFON (registered trademark) UH-2000", "ARUFON (registered trademark) UH-2041", "ARUFON (registered trademark) UH-2170", "ARUFON (registered trademark) UH-2190", etc., manufactured by Toagosei Co., Ltd. These commercially available products can be used individually or in combination of two or more kinds.

[0081] <Polyester polyhydroxy compound> The polyhydroxy compound component (C) may contain a polyester polyhydroxy compound. The polyester polyhydroxy compound can be obtained, for example, by an esterification reaction of a dihydric or higher polyhydric alcohol compound and a dihydric or higher polycarboxylic acid.

[0082] Examples of the dihydric or higher polyhydric alcohol compound include: ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol (MPD), 2-butyl-2-ethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol (ND), 2-methyl-1,8-octanediol, 1,8-decanediol, octadecanediol, glycerol, trimethylolpropane (TMP), etc.

[0083] Examples of the dihydric or higher polycarboxylic acid include: succinic acid, methylsuccinic acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, 1,12-dodecanedioic acid, 1,14-tetradecanedioic acid, dimer acid, 2-methyl-1,4-cyclohexanedicarboxylic acid, 2-ethyl-1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, and acid anhydrides thereof, etc.

[0084] As commercially available products of the polyester polyhydroxy compound, well-known commercially available products can be widely used. Examples of the commercially available products of the polyester polyhydroxy compound include: "Kuraray Polyol P-510 (Mn = 500, hydroxyl value = 224 mgKOH / g)", "Kuraray Polyol P-1010 (Mn = 1000, hydroxyl value = 112 mgKOH / g)", "Kuraray Polyol P-530 (Mn = 500, hydroxyl value = 224 mgKOH / g)", "Kuraray Polyol P-2050 (Mn = 2000, hydroxyl value = 56 mgKOH / g)", "Kuraray Polyol F-510 (Mn = 500, hydroxyl value = 336 mgKOH / g)", etc. manufactured by Kuraray Co., Ltd. As other commercially available products, examples include: "POLYLITE series" manufactured by DIC Corporation, "Desmophen XP, VPLS series" manufactured by Covestro Japan Co., Ltd., etc. These commercially available products can be used individually or in combination of two or more.

[0085] <Polycaprolactone polyhydroxy compound> The polyhydroxy compound component (C) may contain a polycaprolactone polyhydroxy compound. The polycaprolactone polyhydroxy compound can be obtained, for example, by ring-opening polymerization of ε-caprolactone.

[0086] As commercially available products of polycaprolactone polyhydroxy compounds, well-known commercially available products can be widely used. As commercially available products of polycaprolactone polyhydroxy compounds, for example, “PLACCEL 205U (Mn = 530, hydroxyl value = 212 mgKOH / g)”, “PLACCEL 303 (Mn = 310, hydroxyl value = 541 mgKOH / g)” manufactured by Daicel Corporation, etc. can be cited. These commercially available products can be used individually or in combination of two or more kinds.

[0087] <Polycarbonate polyhydroxy compound> The polyhydroxy compound component (C) may contain a polycarbonate polyhydroxy compound. The polycarbonate polyhydroxy compound can be obtained, for example, by an esterification reaction of a dihydric or higher polyhydric alcohol compound and a carbonic acid diester compound.

[0088] As the dihydric or higher polyhydric alcohol compound, for example, ethylene glycol, diethylene glycol, 1,2 - propanediol, 1,3 - propanediol, 1,3 - butanediol, 1,4 - butanediol, neopentyl glycol, 3 - methyl - 1,5 - pentanediol (MPD), 2 - butyl - 2 - ethyl - 1,3 - propanediol, 2,4 - diethyl - 1,5 - pentanediol, 1,2 - hexanediol, 1,6 - hexanediol, 1,8 - octanediol, 1,9 - nonanediol (ND), 2 - methyl - 1,8 - octanediol, 1,8 - decanediol, octadecanediol, glycerol, trimethylolpropane (TMP), etc. can be cited.

[0089] As the carbonic acid diester compound, for example, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate, ethyl butyl carbonate, ethylene carbonate, propylene carbonate, diphenyl carbonate, dibenzyl carbonate, etc. can be cited.

[0090] As commercially available products of polycarbonate polyhydroxy compounds, well-known commercially available products can be widely used. Examples of commercially available products of polycarbonate polyhydroxy compounds include: "DuraNol T5650E (Mn = 500, hydroxyl value = 225 mgKOH / g)" manufactured by Asahi Kasei Corporation, "Kuraray Polyol C-590 (Mn = 500, hydroxyl value = 224 mgKOH / g)", "Kuraray Polyol C-1090 (Mn = 1000, hydroxyl value = 112 mgKOH / g)", "Kuraray Polyol C-2090 (Mn = 2000, hydroxyl value = 56 mgKOH / g)" manufactured by Kuraray Co., Ltd., "ETERNACOLL PH-50 (Mn = 500, hydroxyl value = 225 mgKOH / g)", "ETERNACOLL PH-100 (Mn = 1000, hydroxyl value = 112 mgKOH / g)", "ETERNACOLL PH-200 (Mn = 2000, hydroxyl value = 56 mgKOH / g)" manufactured by Ube Industries, Ltd., etc. These commercially available products can be used individually or in combination of two or more kinds.

[0091] <Castor oil-modified polyhydroxy compound and polyolefin polyhydroxy compound> The polyhydroxy compound component (C) may contain a castor oil-modified polyhydroxy compound and / or a polyolefin polyhydroxy compound.

[0092] As commercially available products of castor oil-modified polyhydroxy compounds and polyolefin polyhydroxy compounds, well-known commercially available products can be widely used. Examples of commercially available products of castor oil-modified polyhydroxy compounds include "URIC series" manufactured by Ito Oil Co., Ltd., etc. Examples of commercially available products of polyolefin polyhydroxy compounds include "Poly bd, ip, EPOL series" manufactured by Idemitsu Kosan Co., Ltd., etc. These commercially available products can be used individually or in combination of two or more kinds.

[0093] <Polyol> The polyhydroxy compound component (C) may contain a polyol. Examples of the polyol include: ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, glycerol, trimethylolpropane, tetramethylene glycol, 1,2,5-hexanetriol, pentaerythritol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, cyclohexanedimethanol, 3-methyl-1,5-pentanediol, neopentyl glycol, sorbitol, etc. In the present invention, the polyol is preferably 3-methyl-1,5-pentanediol.

[0094] In the present invention, from the viewpoint of maintaining the fluidity of the modified polyolefin resin composition well, the polyhydroxy compound component (C) preferably contains a polyhydroxy compound having a number average molecular weight (Mn) of 5000 or less, more preferably contains a polyhydroxy compound having an Mn of 2000 or less, still more preferably contains a polyhydroxy compound having an Mn of 1500 or less, and further preferably contains a polyhydroxy compound having an Mn of 1000 or less. In the present invention, the polyhydroxy compound component (C) preferably contains a polyhydroxy compound having an Mn of 60 or more, more preferably contains a polyhydroxy compound having an Mn of 80 or more, still more preferably contains a polyhydroxy compound having an Mn of 110 or more, and further preferably contains a polyhydroxy compound having an Mn of 150 or more.

[0095] In the present invention, from the viewpoint of maintaining the fluidity of the modified polyolefin resin composition well, the polyhydroxy compound component (C) preferably contains a polyhydroxy compound having an Mn of 60 or more and 5000 or less, more preferably contains a polyhydroxy compound having an Mn of 80 or more and 2000 or less, still more preferably contains a polyhydroxy compound having an Mn of 110 or more and 1500 or less, and further preferably contains a polyhydroxy compound having an Mn of 150 or more and 1000 or less.

[0096] In the present invention, the hydroxyl value of the polyhydroxy compound contained in the polyhydroxy compound component (C) is preferably 50 to 1250 mgKOH / g, more preferably 100 to 1000 mgKOH / g, still more preferably 150 to 800 mgKOH / g, and further preferably 200 to 600 mgKOH / g. When the polyhydroxy compound component (C) contains a polyhydroxy compound having a hydroxyl value of 50 to 1250 mgKOH / g, the modified polyolefin resin composition of the present invention can maintain good fluidity for a longer period through the action of the polyether chain of the polyetheramine (B) and the polyhydroxy compound component (C).

[0097] The hydroxyl value of the polyhydroxy compound component (C) represents the value converted according to the solid content and can be evaluated in accordance with JIS K 1557-1:2007.

[0098] In the present invention, from the viewpoint of maintaining the fluidity of the modified polyolefin resin composition even better, the content of the polyhydroxy compound component (C) is preferably 10 to 90 parts by mass, more preferably 20 to 80 parts by mass, still more preferably 30 to 70 parts by mass, and further preferably 35 to 65 parts by mass with respect to 100 parts by mass of the modified polyolefin resin composition.

[0099] The modified polyolefin resin composition of the present invention may contain other resins for film formation other than the polyhydroxy compound component (C). Examples of the resin for film formation include: acrylic resin, polyester resin, alkyd resin, polyether resin, polyolefin resin, polyurethane resin, polycarbonate resin, melamine resin, epoxy resin, carbodiimide resin, etc. These resins can be used individually or in combination of two or more. With respect to 100 parts by mass of the modified polyolefin resin composition, the content of the above resin for film formation is preferably 10 to 30 parts by mass.

[0100] <Polyisocyanate compound> The modified polyolefin resin composition of the present invention may contain a polyisocyanate compound. The polyisocyanate compound is used as a curing agent for curing the polyhydroxy compound component (C) to form a resin for film formation. By using the polyisocyanate compound, the corrosion resistance and durability of the film are further improved.

[0101] As the polyisocyanate compound, polyisocyanate compounds for producing polyurethane, which have been widely known, can be used. For example, (i) aliphatic polyisocyanate compounds having 2 to 18 carbon atoms; (ii) alicyclic polyisocyanate compounds having 4 to 15 carbon atoms; (iii) aromatic polyisocyanate compounds having 8 to 15 carbon atoms; aromatic polyisocyanate compounds having 6 to 20 carbon atoms (excluding carbon in the NCO group, the same below) and their crude products; (iv) modified products of the polyisocyanate compounds of (i) to (iii) above (including modified products containing urethane group, carbodiimide group, urethane group, urea group, biuret group, uretdione group, ureimine group, isocyanurate group, modified products containing oxazolidinone group, etc.) and mixtures of two or more of these modified products, etc. These polyisocyanate compounds can be used individually or in combination of two or more. Among these polyisocyanate compounds, from the viewpoint of further improving corrosion resistance and durability, aliphatic polyisocyanate compounds having 2 to 18 carbon atoms and / or alicyclic polyisocyanate compounds having 4 to 15 carbon atoms are preferred.

[0102] Specific examples of the aliphatic polyisocyanate compound having 2 to 18 carbon atoms described above include: ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecanetriisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, methyl 2,6-diisocyanatohexanoate, bis(2-isocyanatoethyl) fumarate, bis(2-isocyanatoethyl) carbonate, 2-isocyanatoethyl 2,6-diisocyanatohexanoate, etc. These commercially available products can be used individually or in combination of two or more.

[0103] Specific examples of the alicyclic polyisocyanate compound having 4 to 15 carbon atoms described above include, for example: isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4'-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), 1,3-bis(isocyanatomethyl)cyclohexane, bis(2-isocyanatoethyl) 4-cyclohexene-1,2-dicarboxylate, 2,5-norbornane diisocyanate, 2,6-norbornane diisocyanate, etc. These can be used individually or in combination of two or more.

[0104] Specific examples of the aromatic polyisocyanate compound having 8 to 15 carbon atoms described above include, for example: m- and / or p-xylylene diisocyanate (XDI), α,α,α',α'-tetramethylxylylene diisocyanate (TMXDI), etc. These can be used individually or in combination of two or more.

[0105] Specific examples of the aromatic polyisocyanate compound having 8 to 15 carbon atoms described above include, for example: 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6-toluene diisocyanate (TDI), crude TDI, 2,4'- and / or 4,4'-diphenylmethane diisocyanate (MDI), 4,4'-biphenylene diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, 3,3'-dimethyl-4,4'-diisocyanatodiphenylmethane, crude MDI, 1,5-naphthalene diisocyanate, 4,4',4''-triphenylmethane triisocyanate, m- and p-isocyanatophenylsulfonyl isocyanate, 1,3-bis(isocyanatomethyl)benzene, etc. These can be used individually or in combination of two or more.

[0106] As a modified product of the above polyisocyanate compound, for example, the following can be cited: modified MDI (urethane-modified MDI, carbodiimide-modified MDI, trihydrocarbyl phosphate-modified MDI), urethane-modified TDI, biuret-modified HDI, isocyanurate-modified HDI, isocyanurate-modified IPDI and other polyisocyanate modified products; and mixtures of two or more of these [for example, the combined use of modified MDI and urethane-modified TDI (prepolymer containing isocyanate groups)]. Among these, isocyanurate-modified HDI is preferred.

[0107] In addition to the above polyisocyanate compounds, the modified polyolefin resin composition of the present invention may contain a polyisocyanate compound in which the isocyanate group is blocked with a blocking agent. As the blocking agent, for example, the following can be cited: phenol compounds; oxime compounds; lactam compounds; alcohol compounds; thiol compounds; pyrazole compounds; active methylene compounds such as diethyl malonate. When using a blocked polyisocyanate compound, a dissociation catalyst for the blocking agent is preferably used in combination. An unblocked polyisocyanate compound and a blocked polyisocyanate compound can also be used in combination.

[0108] The number average molecular weight of the polyisocyanate compound is preferably 3000 or less, more preferably 100 to 1500.

[0109] As commercially available products of polyisocyanate compounds, publicly known commercially available products can be widely used. For example, the following can be cited: "Bayhydur (バイヒジュール)", "TP-LS2550", "SUMIDURN3300" manufactured by Sumitomo Bayer Urethane Co., Ltd., "TPA100" manufactured by Asahi Kasei Chemicals Corporation, "BASONAT (バソナート) HI 100" manufactured by BASF SE, etc. These commercially available products can be used individually or in combination of two or more.

[0110] The amount of the polyisocyanate compound used is usually in the range of 0.5 to 2.0 in terms of the equivalent ratio of NCO / OH of the isocyanate group (NCO) contained in the polyisocyanate compound to the hydroxyl group (OH) in the polyhydroxy compound component (C).

[0111] <Other curing agents> The modified polyolefin resin composition of the present invention may contain other curing agents other than polyisocyanate compounds. As other curing agents, for example, the following can be cited: amino resins, monomers or dimers of the above isocyanate compounds, epoxy compounds, aziridine compounds, carbodiimide compounds, oxazoline compounds, etc. These can be used alone or in combination of two or more.

[0112] <Curing catalysts> When curing the modified polyolefin resin composition of the present invention with a polyisocyanate compound, a curing catalyst can be used. By using a curing catalyst, the curing reaction can be promoted. From the viewpoint of promoting the curing reaction, as the curing catalyst, an organometallic catalyst containing at least one metal element selected from the group consisting of Bi, Zn, Al, Ti, Zr, and Sn is preferably used.

[0113] Examples of the organometallic catalyst containing Bi include bismuth carboxylic acid, bismuth carboxylate, etc. Examples of the organometallic catalyst containing Zn include zinc complex catalysts, etc. Examples of the organometallic catalyst containing Al include aluminum complex catalysts, etc. Examples of the organometallic catalyst containing Ti include titanium complex catalysts, etc. Examples of the organometallic catalyst containing Zr include zirconium chelate catalysts, etc. Examples of the organometallic catalyst containing Sn include: dialkyl tin dicarboxylates such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin diacetate; tin oxide compounds such as dibutyltin oxide; tin carboxylates such as tin 2-ethylhexanoate, etc.

[0114] Examples of commercially available products of the organometallic catalyst containing Bi include: "K-KAT 348", "K-KAT XK-640", etc. manufactured by Kusumoto Chemical Co., Ltd. Examples of commercially available products of the organometallic catalyst containing Zr include: "K-KAT 4205", "K-KAT XC-9213", "K-KAT XC-A209", "K-KAT6212" manufactured by Kusumoto Chemical Co., Ltd.; "ORGATIX ZA, ZC series" manufactured by Matsumoto Fine Chemical Co., Ltd., etc. Examples of commercially available products of the organometallic catalyst containing Al include: "K-KAT 5218" manufactured by Kusumoto Chemical Co., Ltd.; "ORGATIX AL series" manufactured by Matsumoto Fine Chemical Co., Ltd., etc. Examples of commercially available products of the organometallic catalyst containing Ti include: "ORGATIX TA, TC series" manufactured by Matsumoto Fine Chemical Co., Ltd. Examples of commercially available products of the organometallic catalyst containing Zn include: K-KAT XK-314, K-KAT XK-635, K-KAT XK-639, K-KAT XK-620 (manufactured by Kusumoto Chemical Co., Ltd. above). Examples of commercially available products of the organometallic catalyst containing Sn include: TVS TIN LAU (manufactured by Nitto Kasei Co., Ltd.).

[0115] With respect to 100 parts by mass of the modified polyolefin resin composition, the amount of the curing catalyst used is preferably 0.001 to 2.5 parts by mass, more preferably 0.05 to 2.0 parts by mass, still more preferably 0.1 to 1.5 parts by mass, and further preferably 0.2 to 1.0 parts by mass.

[0116] <Surfactant> The modified polyolefin resin composition of the present invention may contain a surfactant. Examples of the surfactant include: nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, and the like. These surfactants can be used alone or in combination of two or more. Among these surfactants, from the viewpoint of further improving the water resistance of the coating film, nonionic surfactants and anionic surfactants are preferred, and nonionic surfactants are more preferred.

[0117] Examples of the nonionic surfactant include: polyoxyethylene alkyl ether, polyoxypropylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxypropylene alkyl phenyl 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 alkylamide, polyoxypropylene alkylamide, polyoxyethylene lanolin alcohol ether, polyoxypropylene lanolin alcohol ether, polyoxyethylene lanolin fatty acid ester, polyoxypropylene lanolin fatty acid ester, (polyoxyethylene oxypropylene) block copolymer, and the like. These can be used alone or in combination of two or more. As the nonionic surfactant, well-known commercially available products can be widely used. Examples include: EMULMIN series manufactured by Sanyo Chemical Industries, Ltd., NOIGEN series manufactured by Daiichi Kogyo Seiyaku Co., Ltd., BLAUNON series manufactured by Aoki Yushi Industry Co., Ltd., and the like.

[0118] Examples of the anionic surfactant include: higher alkyl sulfates, alkylaryl polyoxyethylene sulfates, higher fatty acid salts, alkylaryl sulfonates, alkyl phosphate salts, and the like. These can be used alone or in combination of two or more. As the anionic surfactant, well-known commercially available products can be widely used. Examples include: NEOCOL series, HITENOL series manufactured by Daiichi Kogyo Seiyaku Co., Ltd., and the like.

[0119] From the viewpoints of the stability of the modified polyolefin resin composition and the water resistance of the coating film, with respect to 100 parts by mass of the acid-modified polyolefin resin (A), the amount of the surfactant used is preferably 1 to 60 parts by mass, more preferably 3 to 40 parts by mass, still more preferably 5 to 30 parts by mass.

[0120] <Various additives> As needed, the modified polyolefin resin composition of the present invention may contain various additives. Examples of various additives include: tackifiers, film-forming aids, defoamers, anti-sagging agents, wetting agents, ultraviolet absorbers, etc.

[0121] Examples of tackifiers include: rosin, dammar resin, polymerized rosin, hydrogenated rosin, ester rosin, rosin-modified maleic resin, polyterpene resin, petroleum resin, cyclopentadiene resin, phenolic resin, xylene resin, coumarone-indene resin, etc. The amount of the tackifier used is preferably 5 to 100 parts by mass, more preferably 10 to 50 parts by mass, relative to 100 parts by mass of the modified polyolefin resin composition.

[0122] <Organic solvent> The modified polyolefin resin composition of the present invention may or may not contain an organic solvent.

[0123] As an embodiment of the present invention, when the present invention contains an organic solvent, from the viewpoints of environmental and hygiene aspects, the present invention preferably contains a small amount of the organic solvent. The amount of the organic solvent used at this time is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, still more preferably 5 parts by mass or less, further 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. When the present invention contains an organic solvent, since the viscosity of the modified polyolefin resin composition is further decreased, there is an advantage that the coatability is further improved.

[0124] As other embodiments of the present invention, when the present invention does not contain an organic solvent, the present invention can be suitably used as the main component of a solventless two-component curable polyurethane adhesive. In addition, in this specification, solventless means that no organic solvent is intentionally added to the modified polyolefin resin composition of the present invention, and embodiments such as residual organic solvents used in the production of the acid-modified polyolefin resin (A) are included in solventless.

[0125] As organic solvents, for example, the following can be cited: 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 monobutyl ether, ethylene glycol mono-isobutyl ether, ethylene glycol mono-tert-butyl ether, diethylene glycol monobutyl ether, diethylene glycol mono-isobutyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, dibenzyl ether, diphenyl ether, and butyl phenyl ether, etc. These can be used individually or in combination of two or more.

[0126] <Method for manufacturing modified polyolefin resin composition> As the method for manufacturing the modified polyolefin resin composition of the present invention, known methods can be widely adopted. For example, the following methods can be cited. Step (1): Put the acid-modified polyolefin resin (A) and the polyhydroxy compound component (C) into a blender equipped with a heating device, and carry out kneading while heating. Step (2): Further add the polyetheramine (B) to the blender, and carry out kneading while heating. Step (3): Then, cool to room temperature, and the modified polyolefin resin composition can be obtained by filtration.

[0127] In the above step (1), the heating temperature during kneading is usually 50 to 200 °C, preferably 60 °C to 150 °C, more preferably 70 °C to 120 °C. The kneading time varies depending on the heating temperature and the like, and is usually 10 minutes to 120 minutes, preferably 15 minutes to 90 minutes, more preferably 20 minutes to 60 minutes. Step (1) can be carried out in a nitrogen atmosphere, for example, to remove moisture.

[0128] In the above step (2), the heating temperature during kneading is usually 50 to 200 °C, preferably 60 °C to 150 °C, more preferably 70 °C to 120 °C. The kneading time varies depending on the heating temperature and the like, and is usually 10 minutes to 120 minutes, preferably 15 minutes to 90 minutes, more preferably 20 minutes to 75 minutes. Step (2) can be carried out in a nitrogen atmosphere, for example, to remove moisture.

[0129] In the above step (3), filtration can be performed using a metal mesh with a mesh size of 50 μm to 300 μm, for example. Step (3) can be performed in a nitrogen atmosphere to remove moisture, for example.

[0130] The present invention is a cured product obtained by curing a modified polyolefin resin composition. In other words, this cured product is a substance obtained by curing the modified polyolefin resin composition of the present invention. Hereinafter, the above-mentioned cured product will be briefly referred to as "the cured product of the present invention".

[0131] <Uses of the Present Invention> The modified polyolefin resin composition of the present invention and the cured product of the present invention can be suitably used for polyolefin substrates. As polyolefin substrates, for example, those obtained by processing polyolefins into blocks (such as plates, rods, spheres, etc.), sheets, films, wires, fabrics (such as woven fabrics, knitted fabrics, and non-woven fabrics), etc. can be cited. Among these polyolefin substrates, sheets and films are preferred from the viewpoint of manufacturing. As the thickness of the film, a film with a thickness of 5 μm to 100 μm can be used. As polyolefins, for example, polypropylene, polyethylene, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, 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 suitably used for polypropylene substrates.

[0132] The modified polyolefin resin composition of the present invention and the cured product of the present invention can be suitably used for coatings for molded articles; inks; adhesives; sealants; primer coatings: coating agents, coatings for in-mold coating, etc. The modified polyolefin resin composition of the present invention and the cured product of the present invention can be particularly suitably used for inks for polyolefin substrates, adhesives for polyolefin substrates, primer coatings for polyolefin substrates, coatings for polyolefin substrates, and in-mold coating coatings for polyolefin substrates.

[0133] A coating film can be obtained from the modified polyolefin resin composition of the present invention. The coating film can be particularly suitably used for applications such as metal products, electronic devices, packaging materials, and automotive parts.

[0134] As a method for forming a coating film from the modified polyolefin resin composition of the present invention, for example, a method of uniformly coating the modified polyolefin resin composition of the present invention on the surface of various substrates for heat treatment (such as baking treatment, etc.) can be cited. Thus, a uniform coating film can be formed on the surface of various substrates. As the coating method, for example, the following can be cited: gravure coating method, curtain coating method, wire bar coating method, dip coating method, brush coating method, roll coating method, spraying method, etc. The amount of the modified polyolefin resin composition coated on the substrate is not particularly limited and can be appropriately selected according to its use. Preferably, the dry coating film is in the range of 1 μm to 100 μm. The heat treatment can be carried out using a hot air circulation type furnace, an infrared heater, etc. In addition, a method of forming a coating film by injecting the modified polyolefin resin composition of the present invention between a mold and a substrate, applying heat and pressure after forming a plastic substrate in the mold can be cited. The heating temperature when forming the coating film is usually 60 to 200 °C. The heating time when forming the coating film is usually 15 seconds to 20 minutes. Examples

[0135] Next, the present invention will be specifically described based on examples, but the present invention is not limited to the following examples. Hereinafter, "room temperature" means a temperature in the range of 20 °C to 25 °C.

[0136] (1) Measurement of weight-average molecular weight (Mw) using high-temperature GPC As a solvent, orthodichlorobenzene was used, and the measurement was carried out at 140 °C using a GPC150-Cplus type manufactured by Waters Corporation (chromatographic column: "GMH6-HT" + "GMH6-HTL" manufactured by Tosoh Corporation). For the weight-average molecular weight (Mw), it can be calculated using polystyrene with a known molecular weight as a standard substance.

[0137] (2) Measurement of melting point using differential scanning calorimeter (DSC) According to JIS K7121-2012, using a DSC measuring device (manufactured by Seiko Instruments Inc.), after maintaining and heating about 5 mg of the sample in a molten state at 150 °C for 10 minutes, cooling was carried out at a rate of 10 °C / min, stably maintained at -50 °C, and further heating was carried out at a rate of 10 °C / min to 150 °C. The melting peak temperature during melting was measured, and this melting peak temperature was used as the melting point for evaluation.

[0138] (Production Example 1) 280 g of an ethylene-α-olefin copolymer (ethylene content = 70 mol%), 62 g of maleic anhydride, 7 g of diisopropylbenzene peroxide, and 420 g of toluene were added to an autoclave equipped with a stirrer. After nitrogen replacement for about 5 minutes, the mixture was heated and stirred while reacting at 140°C for 5 hours. After the reaction, the reaction solution was poured 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. By subjecting the obtained resin to reduced-pressure drying, a solid of the acid-modified polyolefin resin (MPO-1) was obtained. According to the results of infrared absorption spectrum measurement, the total content of maleic anhydride component and maleic acid component in MPO-1 was 2.0 mass%. In addition, the weight-average molecular weight of MPO-1 measured by high-temperature GPC was 70,000, and the melting point based on DSC was 70°C.

[0139] (Production Example 2) 280 g of a homopolymer of propylene (homopolypropylene, propylene content = 100 mol%), 36 g of maleic anhydride, 5.6 g of diisopropylbenzene peroxide, and 420 g of toluene were added to an autoclave equipped with a stirrer. After nitrogen replacement for about 5 minutes, the mixture was heated and stirred while reacting at 140°C for 5 hours. After the reaction, the reaction solution was poured 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. By subjecting the obtained resin to reduced-pressure drying, a solid of the acid-modified polyolefin resin (MPO-2) was obtained. According to the results of infrared absorption spectrum measurement, the total content of maleic anhydride component and maleic acid component in MPO-2 was 1.8 mass%. In addition, the weight-average molecular weight of MPO-2 measured by high-temperature GPC was 40,000, and the melting point based on DSC was 75°C.

[0140] (Production Example 3) 280 g of an ethylene-α-olefin copolymer (ethylene content = 94 mol%), 14 g of maleic anhydride, 5.6 g of diisopropylbenzene peroxide, and 420 g of toluene were added to an autoclave equipped with a stirrer. After nitrogen replacement for about 5 minutes, the mixture was heated and stirred, and the reaction was carried out at 140 °C for 5 hours. After the reaction was completed, the reaction solution was poured 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. After drying under reduced pressure, 280 g of the obtained maleic anhydride-modified polyolefin resin and 2520 g of chloroform were added to an autoclave equipped with a stirrer. After nitrogen replacement for about 5 minutes, the mixture was heated to 110 °C to dissolve the resin completely. Then, 1.4 g of tert-butyl peroxy-2-ethylhexanoate was added, and a specified amount of chlorine gas was blown in. The reaction solvent chloroform was distilled off under reduced pressure to dry it, and a solid (CPO-1) of the acid-modified chlorinated polyolefin resin was obtained. The weight-average molecular weight of CPO-1 measured by high-temperature GPC was 80,000, and the melting point based on DSC was 75 °C. In addition, the chlorine content in CPO-1 was 21% by mass, and the content of maleic anhydride was 1.5% by mass.

[0141] <Example 1 (Manufacture of Modified Polyolefin Resin Composition (a))> 20 g of MPO-1 prepared in Production Example 1 as an acid-modified polyolefin resin (A) and 60 g of a polyhydroxy compound polypropylene glycol ["SANNIX PP-200 (Mn = 200, hydroxyl value = 560 mgKOH / g)" manufactured by Sanyo Chemical Industries, Ltd.] as a polyhydroxy compound component (C) were charged into a 200-ml four-necked flask equipped with a cooler, a thermometer, and a stirrer. Under a nitrogen atmosphere, the internal temperature was heated to 90 °C and heated for 30 minutes to dissolve. Then, 8 g of "JEFFAMINE M-2070 (MW = 2000, HLB value = 13.8)" manufactured by HUNTSMAN Corporation as a polyetheramine (B) (primary amino group number = 1, secondary amino group number = 0) was added, and the mixture was stirred at 90 °C for 1 hour. Then, it was cooled to room temperature, and the modified polyolefin resin composition (a) was obtained by filtering through a metal mesh with a mesh size of 154 μm.

[0142] <Example 2 (Manufacture of Modified Polyolefin Resin Composition (b))> Except for using MPO-2 prepared in Production Example 2 as the acid-modified polyolefin resin (A), the modified polyolefin resin composition (b) was obtained by the same method as in Example 1.

[0143] <Example 3 (Manufacture of Modified Polyolefin Resin Composition (c))> Except for using the CPO-1 obtained in Production Example 3 as the acid-modified polyolefin resin (A), a modified polyolefin resin composition (c) was obtained in the same manner as in Example 1.

[0144] <Example 4 (Production of Modified Polyolefin Resin Composition (d))> Except for using the CPO-1 obtained in Production Example 3 as the acid-modified polyolefin resin (A) and using "JEFFAMINE M-1000 (MW = 1000, HLB value = 16.1)" manufactured by HUNTSMAN Corporation (number of primary amino groups = 1, number of secondary amino groups = 0) as the polyetheramine (B), a modified polyolefin resin composition (d) was obtained in the same manner as in Example 1.

[0145] <Example 5 (Production of Modified Polyolefin Resin Composition (e))> Except for using "JEFFAMINE M-2005 (MW = 2000, HLB value = 2.7)" manufactured by HUNTSMAN Corporation (number of primary amino groups = 1, number of secondary amino groups = 0) as the polyetheramine (B), a modified polyolefin resin composition (e) was obtained in the same manner as in Example 1.

[0146] <Example 6 (Production of Modified Polyolefin Resin Composition (f))> Except for changing the amount of the polyetheramine (B) used to 15 g and changing the amount of the polyhydroxy compound component (C) used to 30 g, a modified polyolefin resin composition (f) was obtained by the same method as in Example 1.

[0147] <Example 7 (Production of Modified Polyolefin Resin Composition (g))> Except for changing the amount of the polyetheramine (B) used to 15 g, a modified polyolefin resin composition (g) was obtained by the same method as in Example 1.

[0148] <Example 8 (Production of Modified Polyolefin Resin Composition (h))> Except for changing the amount of the acid-modified polyolefin resin (A) used to 10 g and changing the amount of the polyetheramine (B) used to 1.5 g, a modified polyolefin resin composition (h) was obtained by the same method as in Example 1.

[0149] <Example 9 (Production of Modified Polyolefin Resin Composition (i))> Except for changing the amount of the polyetheramine (B) used to 1.5 g, a modified polyolefin resin composition (i) was obtained by the same method as in Example 1.

[0150] <Example 10 (Production of Modified Polyolefin Resin Composition (j))> Except for using 72 g of polyhydroxy compound polypropylene glycol ["SANNIX PP-400 (Mn = 400, hydroxyl value = 280 mgKOH / g)" manufactured by Sanyo Chemical Industries, Ltd.] as the polyhydroxy compound component (C), a modified polyolefin resin composition (j) was prepared by the same method as in Example 1.

[0151] <Example 11 (Manufacture of Modified Polyolefin Resin Composition (k))> Except for using 40 g of polypropylene glycol ["SANNIX PP-200 (Mn = 200, hydroxyl value = 560 mgKOH / g)" manufactured by Sanyo Chemical Industries, Ltd.] as the polyhydroxy compound and 32 g of polypropylene glycol ["SANNIX PP-1000 (Mn = 1000, hydroxyl value = 112 mgKOH / g)" manufactured by Sanyo Chemical Industries, Ltd.] as the polyhydroxy compound component (C), a modified polyolefin resin composition (k) was prepared by the same method as in Example 1.

[0152] <Example 12 (Manufacture of Modified Polyolefin Resin Composition (l))> Except for using 40 g of polypropylene glycol ["SANNIX PP-400 (Mn = 400, hydroxyl value = 280 mgKOH / g)" manufactured by Sanyo Chemical Industries, Ltd.] as the polyhydroxy compound and 32 g of polyester polyhydroxy compound ["Kuraray Polyol P-510 (Mn = 500, hydroxyl value = 224 mgKOH / g)" manufactured by Kuraray Co., Ltd.] as the polyhydroxy compound component (C), a modified polyolefin resin composition (l) was prepared by the same method as in Example 1.

[0153] <Example 13 (Manufacture of Modified Polyolefin Resin Composition (m))> Except for using 40 g of polypropylene glycol ["SANNIX PP-400 (Mn = 400, hydroxyl value = 280 mgKOH / g)" manufactured by Sanyo Chemical Industries, Ltd.] as the polyhydroxy compound and 32 g of polyester polyhydroxy compound ["Kuraray Polyol F-510 (Mn = 500, hydroxyl value = 336 mgKOH / g)" manufactured by Kuraray Co., Ltd.] as the polyhydroxy compound component (C), a modified polyolefin resin composition (m) was prepared by the same method as in Example 1.

[0154] <Example 14 (Manufacture of Modified Polyolefin Resin Composition (n))> Except for using 40 g of polypropylene glycol [“SANNIX PP-400 (Mn = 400, hydroxyl value = 280 mgKOH / g)” manufactured by Sanyo Chemical Industries, Ltd.] as the polyhydroxy compound and using 32 g of polyester polyhydroxy compound [“Kuraray Polyol P-2050 (Mn = 2000, hydroxyl value = 56 mgKOH / g)” manufactured by Kuraray Co., Ltd.] as the polyhydroxy compound component (C), a modified polyolefin resin composition (n) was prepared by the same method as in Example 1.

[0155] <Example 15 (Manufacture of Modified Polyolefin Resin Composition (o))> Except for using 40 g of polypropylene glycol [“SANNIX PP-400 (Mn = 400, hydroxyl value = 280 mgKOH / g)” manufactured by Sanyo Chemical Industries, Ltd.] as the polyhydroxy compound and using 32 g of polycaprolactone polyhydroxy compound [“PLACCEL 205U (Mn = 530, hydroxyl value = 212 mgKOH / g)” manufactured by Daicel Corporation] as the polyhydroxy compound component (C), a modified polyolefin resin composition (o) was prepared according to the same method as in Example 1.

[0156] <Example 16 (Manufacture of Modified Polyolefin Resin Composition (p))> Except for using 40 g of polypropylene glycol [“SANNIX PP-400 (Mn = 400, hydroxyl value = 280 mgKOH / g)” manufactured by Sanyo Chemical Industries, Ltd.] and changing the polycarbonate polyhydroxy compound [“Kuraray Polyol C590 (Mn = 500, hydroxyl value = 224 mgKOH / g)” manufactured by Kuraray Co., Ltd.] to 32 g as the polyhydroxy compound component (C), a modified polyolefin resin composition (p) was prepared by the same method as in Example 1.

[0157] <Example 17 (Manufacture of Modified Polyolefin Resin Composition (q))> Except for using 40 g of polypropylene glycol [“SANNIX PP-200 (Mn = 200, hydroxyl value = 560 mgKOH / g)” manufactured by Sanyo Chemical Industries, Ltd.] and using 32 g of polyol [3-methyl-1,5-pentanediol (Mn = 91, hydroxyl value = 1230 mgKOH / g)] as the polyhydroxy compound component (C), a modified polyolefin resin composition (q) was prepared according to the same method as in Example 1.

[0158] <Comparative Example 1> Into a 200 mL four-necked flask equipped with a cooler, a thermometer, and a stirrer, 20 g of MPO-1 prepared in Production Example 1 was charged as the acid-modified polyolefin resin (A), and 60 g of the polyhydroxy compound polypropylene glycol ["SANNIX PP-200 (Mn = 200, hydroxyl value = 560 mgKOH / g)" manufactured by Sanyo Chemical Industries, Ltd.] was charged as the polyhydroxy compound component (C). Under a nitrogen atmosphere, the internal temperature was heated to 90°C and heated for 30 minutes for dissolution. Thereafter, without adding the polyetheramine (B), stirring was carried out at 90°C for 1 hour. Thereafter, it was cooled to room temperature, but the resin precipitated and a modified polyolefin resin composition could not be obtained.

[0159] <Comparative Example 2> Into a 200 mL four-necked flask equipped with a cooler, a thermometer, and a stirrer, 20 g of MPO-1 prepared in Production Example 1 was charged as the acid-modified polyolefin resin (A), and 60 g of the polyhydroxy compound polypropylene glycol ["SANNIX PP-200 (Mn = 200, hydroxyl value = 560 mgKOH / g)" manufactured by Sanyo Chemical Industries, Ltd.] was charged as the polyhydroxy compound component (C). Under a nitrogen atmosphere, the internal temperature was heated to 90°C and heated for 30 minutes for dissolution. Thereafter, instead of adding the polyetheramine (B), polyoxyethylene alkyl ether (Mn = 1050, HLB value = 15.3) as a surfactant was added, and stirring was carried out at 90°C for 1 hour. Thereafter, it was cooled to room temperature, but the resin precipitated and a modified polyolefin resin composition could not be obtained.

[0160] <Comparative Example 3 (Production of modified polyolefin resin composition (r))> Into a 200 mL four-necked flask equipped with a cooler, a thermometer, and a stirrer, only 60 g of the polyhydroxy compound polypropylene glycol ["SANNIX PP-200 (Mn = 200, hydroxyl value = 560 mgKOH / g)" manufactured by Sanyo Chemical Industries, Ltd.] was charged as the polyhydroxy compound component (C). Under a nitrogen atmosphere, the internal temperature was heated to 90°C and heated for 30 minutes for dissolution. Thereafter, 8 g of "JEFFAMINE M-2070 (MW = 2000, HLB value = 13.8)" was added as the polyetheramine (B), and stirring was carried out at 90°C for 1 hour. Thereafter, it was cooled to room temperature, and the modified polyolefin resin composition (r) was prepared by filtering through a metal mesh with a mesh size of 154 μm. In addition, in Comparative Example 3, the acid-modified polyolefin resin (A) was not used.

[0161] (1) Evaluation of fluidity at 25°C and 80°C For the modified polyolefin resin compositions prepared in the examples and comparative examples, visually evaluate the fluidity at 25°C and 80°C immediately after manufacturing, the fluidity at 25°C and 80°C the next day (24 hours after the start of manufacturing), and the fluidity at 25°C and 80°C after 1 week (168 hours after the start of manufacturing). Evaluate the case with fluidity after 1 week as ◎, the case with fluidity the next day as 〇, the case with fluidity only immediately after manufacturing as △, and the case without fluidity immediately after manufacturing as ×.

[0162] (2) Evaluation of adhesion Add 0.015 g of dibutyltin dilaurate as a curing catalyst and "SUMIDUR N3300" manufactured by Sumitomo Bayer Urethane as a polyisocyanate compound to the modified polyolefin resin compositions prepared in the examples and comparative examples to OH / NCO = 1.2, and stir with a magnetic stirrer for 30 seconds. Apply the stirred mixture to a substrate for a PP (polypropylene) bumper cleaned with isopropyl alcohol with a No. 16 rod coater at room temperature until the dry film thickness becomes about 10 μm. After baking at 120°C for 10 minutes, place it in an atmosphere of 25°C × relative humidity 60% for 72 hours to obtain a test plate. Make 100 squares reaching the substrate at 1 mm intervals on the test plate, attach a transparent tape thereto, and repeat tearing at an angle of 90 degrees with respect to the coated surface 3 times. Evaluate the case where there is no peeling after repeating the tearing 3 times as ○, the case where peeling occurs at the 3rd tearing as △, and the case where peeling occurs at the 1st or 2nd tearing as ×.

[0163] The raw materials used in each example and each comparative example, their usage amounts, the evaluation results of the obtained modified polyolefin resin compositions (a) to (r), etc. are shown in Table 1 below. In addition, for Comparative Example 1 and Comparative Example 2, since a modified polyolefin resin composition could not be obtained, the adhesion is "not evaluable".

[0164] [Table 1]

[0165] [Examination of the results in Table 1] As shown in Table 1, among the modified polyolefin resin compositions (a) to (q) prepared in Examples 1 to 17, fluidity was maintained since just after production, and good adhesion to a base material for a PP (polypropylene) bumper was confirmed. On the other hand, in Comparative Example 1, since polyethylamine (B) was not used, resin precipitation occurred and the modified polyolefin resin composition itself could not be produced. In Comparative Example 2, polyoxyethylene alkyl ether, which is a nonionic surfactant, was used instead of polyethylamine (B), but as in Comparative Example 1, resin precipitation occurred and the modified polyolefin resin composition itself could not be produced. In the modified polyolefin resin composition (k) obtained in Comparative Example 3, since the acid-modified polyolefin resin (A) was not used, the adhesion was significantly deteriorated as a result.

[0166] The present invention provides an invention in the following-described embodiments. Item 1. A modified polyolefin resin composition containing an acid-modified polyolefin resin (A), a polyetheramine (B), and a polyhydroxy compound component (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 100 parts by mass, preferably 10 to 90 parts by mass, more preferably 12.5 to 80 parts by mass, still more preferably 15 to 70 parts by mass, further preferably 20 to 60 parts by mass, and particularly preferably 25 to 50 parts by mass with respect to 100 parts by mass of the polyhydroxy compound component (C). Item 3. The modified polyolefin resin composition according to Item 1 or 2, wherein the content of the polyetheramine (B) is generally 5 to 100 parts by mass, preferably 10 to 90 parts by mass, more preferably 12.5 to 80 parts by mass, still more preferably 15 to 70 parts by mass, further preferably 20 to 60 parts by mass, and particularly preferably 25 to 50 parts by mass with respect to 100 parts by mass of the acid-modified polyolefin resin (A). Item 4. The modified polyolefin resin composition according to any one of Items 1 to 3, wherein the polyetheramine (B) has a polyether chain, and the polyether chain is: a chain containing a chain represented by -(O-CH2CH2)x- (wherein x is an integer of 2 to 120), a chain represented by -(O-CH2CH(CH3))y1- (wherein y1 is an integer of 2 to 90), a chain represented by -(O-CH2CH2CH2)y2- (wherein y2 is an integer of 2 to 90), a chain represented by -(O-CH2CH2CH2CH2)z1- (wherein z1 is an integer of 2 to 80), a chain represented by -(O-CH(CH3)CH2CH2)z2- (wherein z2 is an integer of 2 to 80). - (O-CH2CH(CH3)CH2)z3- (where z3 is an integer from 2 to 80) and - (O-CH2CH2CH(CH3))z4- (where z4 is an integer from 2 to 80). Item 5. The modified polyolefin resin composition according to any one of Items 1 to 4, wherein the polyetheramine (B) has a primary amino group or a secondary amino group at one terminal, and the weight average molecular weight (Mw) of the polyetheramine (B) is 200 to 50,000. Item 6. The modified polyolefin resin composition according to any one of Items 1 to 5, wherein the polyhydroxy compound component (C) comprises at least one polyhydroxy compound selected from the group consisting of polyether polyhydroxy compounds, polyester polyhydroxy compounds, polyacrylate polyhydroxy compounds, polycaprolactone polyhydroxy compounds, polycarbonate polyhydroxy compounds, castor oil-modified polyhydroxy compounds, polyolefin polyhydroxy compounds, and polyols. Item 7. The modified polyolefin resin composition according to any one of Items 1 to 6, wherein the polyhydroxy compound component (C) comprises a polyhydroxy compound having a number average molecular weight (Mn) of 5000 or less. Item 8. The modified polyolefin resin composition according to any one of Items 1 to 7, wherein the polyetheramine (B) has a polyether chain, and the polyether chain is: comprising at least one structure selected from the group consisting of - (O-CH2CH2)x- (where x is an integer from 2 to 120), - (O-CH2CH(CH3))y1- (where y1 is an integer from 2 to 90), and - (O-CH2CH2CH2CH2)z1- (where z1 is an integer from 2 to 80). Item 9. The modified polyolefin resin composition according to any one of Items 1 to 8, wherein, relative to 100 parts by mass of the modified polyolefin resin composition, the content of the acid-modified polyolefin resin (A) is preferably 5 to 60 parts by mass, more preferably 10 to 40 parts by mass, still more preferably 15 to 35 parts by mass, and further preferably 18 to 30 parts by mass. Item 10. The modified polyolefin resin composition according to any one of Items 1 to 9, wherein the polyetheramine (B) has a primary amino group at one terminal, and the weight average molecular weight (Mw) of the polyetheramine (B) is 500 to 5000. Item 11. The modified polyolefin resin composition according to any one of Items 1 to 10, wherein the HLB value of the polyetheramine (B) is preferably 2 to 19, more preferably 5 to 18, still more preferably 8 to 17, and the HLB value is in the range of 2 to 19. Item 12. The modified polyolefin resin composition according to any one of Items 1 to 11, the content of the polyetheramine (B) is preferably 1 to 40 parts by mass, more preferably 1.5 to 30 parts by mass, still more preferably 2 to 20 parts by mass, and further preferably 3 to 15 parts by mass, based on 100 parts by mass of the modified polyolefin resin composition. Item 13. The modified polyolefin resin composition according to any one of Items 1 to 12, the number average molecular weight (Mn) of the polyhydroxy compound contained in the polyhydroxy compound component (C) is preferably 60 or more and 5000 or less, more preferably 80 or more and 2000 or less, still more preferably 110 or more and 1500 or less, and further preferably 150 or more and 1000 or less. Item 14. The modified polyolefin resin composition according to any one of Items 1 to 13, the polyhydroxy compound component (C) contains at least one polyhydroxy compound selected from the group consisting of polyether polyhydroxy compounds, polyester polyhydroxy compounds, polyacrylate polyhydroxy compounds, polycaprolactone polyhydroxy compounds, polycarbonate polyhydroxy compounds, and polyols. Item 15. The modified polyolefin resin composition according to any one of Items 1 to 14, the polyhydroxy compound component (C) contains a single polyether polyhydroxy compound; Two or more polyether polyhydroxy compounds having different hydroxyl values; A polyether polyhydroxy compound and a polyester polyhydroxy compound; A polyether polyhydroxy compound and a polycaprolactone polyhydroxy compound; A polyether polyhydroxy compound and a polycarbonate polyhydroxy compound; or A polyether polyhydroxy compound and a polyol. Item 16. The modified polyolefin resin composition according to any one of Items 6 to 15, the polyether polyhydroxy compound is preferably at least one selected from the group consisting of polyethylene glycol, polypropylene glycol, and polytetramethylene glycol, more preferably polyethylene glycol, polypropylene glycol, or polytetramethylene glycol, and still more preferably polypropylene glycol. Item 17. The modified polyolefin resin composition according to any one of Items 1 to 16, the hydroxyl value of the polyhydroxy compound contained in the polyhydroxy compound component (C) is preferably 50 to 1250 mgKOH / g, more preferably 100 to 1000 mgKOH / g, still more preferably 150 to 800 mgKOH / g, and further preferably 200 to 600 mgKOH / g. Item 18. The modified polyolefin resin composition according to any one of Items 1 to 17, the content of the polyhydroxy compound component (C) is preferably 10 to 90 parts by mass, more preferably 20 to 80 parts by mass, still more preferably 30 to 70 parts by mass, and further preferably 35 to 65 parts by mass, based on 100 parts by mass of the modified polyolefin resin composition. Item 19. The modified polyolefin resin composition according to any one of Items 1 to 18, the total content ratio of the acid-modified polyolefin resin (A), the polyetheramine (B), and the polyhydroxy compound component (C) based on the total mass of the modified polyolefin resin composition exceeds 50% by mass, and is preferably 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 sequence. Item 20. The modified polyolefin resin composition according to any one of Items 1 to 19, which further contains a polyisocyanate compound. Item 21. A cured product, which is cured from the modified polyolefin resin composition according to any one of Items 1 to 20. Item 22. An ink, which contains the modified polyolefin resin composition according to any one of Items 1 to 20. Item 23. An adhesive, which contains the modified polyolefin resin composition according to any one of Items 1 to 20. Item 24. An undercoat, which contains the modified polyolefin resin composition according to any one of Items 1 to 20. Item 25. A coating, which contains the modified polyolefin resin composition according to any one of Items 1 to 20. Item 26. A coating for in-mold coating, which contains the modified polyolefin resin composition according to any one of Items 1 to 20.

Claims

1. A modified polyolefin resin composition containing an acid-modified polyolefin resin (A), a polyetheramine (B), and a polyhydroxy compound component (C).

2. The modified polyolefin resin composition according to claim 1, wherein the content of the acid-modified polyolefin resin (A) is 5 to 100 parts by mass relative to 100 parts by mass of the polyhydroxy compound component (C).

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

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

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

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

7. The modified polyolefin resin composition according to claim 1, wherein the polyhydroxy compound component (C) comprises a polyhydroxy compound having a number-average molecular weight Mn of 5000 or less.

8. The modified polyolefin resin composition according to claim 1, which further contains a polyisocyanate compound.

9. A cured product obtained by curing the modified polyolefin resin composition according to any one of claims 1 to 8.

10. An ink containing the modified polyolefin resin composition according to any one of claims 1 to 8.

11. An adhesive containing the modified polyolefin resin composition according to any one of claims 1 to 8.

12. An undercoat paint containing the modified polyolefin resin composition according to any one of claims 1 to 8.

13. A coating material containing the modified polyolefin resin composition according to any one of claims 1 to 8.

14. A coating material for in-mold coating containing the modified polyolefin resin composition according to any one of claims 1 to 8.

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