Modified polyolefin resin composition

Abstract

A resin composition comprising a modified product obtained by modifying a polyolefin resin (A) having a melting point of 100°C or less with one or more compounds selected from the group consisting of α,β-unsaturated carboxylic acids and their derivatives, and a modified product obtained by modifying a polyolefin resin (B) having an extrapolated melting onset temperature (Tim) of 120°C or more with one or more compounds selected from the group consisting of α,β-unsaturated carboxylic acids and their derivatives, wherein the modified product of resin (B) is dispersed in the modified product of resin (A), and the average particle size of the modified product of resin (B) is 0.1 to 100 μm.

Description

[Technical field]

[0001] The present invention relates to a resin composition containing a modified polyolefin obtained by modification with an α,β-unsaturated carboxylic acid and / or a derivative thereof. [Background technology]

[0002] Polyolefin resins have many excellent properties, such as excellent mechanical properties such as tensile strength, tear strength, and impact strength, water resistance, and chemical resistance, as well as being lightweight, inexpensive, and easy to mold, and therefore are used in a variety of applications such as sheets, films, molded products, etc. However, unlike polar substrates such as polyurethane resins, polyamide resins, acrylic resins, and polyester resins, polyolefin resins are non-polar and crystalline, and therefore coating and adhesion can be difficult.

[0003] In the automotive industry, modified polyolefin resins that have been modified with highly adhesive α,β-unsaturated carboxylic acids or derivatives thereof are used as adhesion promoters for adhering paints that have poor adhesion to polyolefin resins (in the automotive industry, paints that are applied directly to substrates and contain an adhesion promoter as their main component are particularly called primer paints) (Patent Document 1). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2001-279048 A Summary of the Invention [Problem to be solved by the invention]

[0005] It has been known that modified polyolefin resins obtained by modifying polyolefin resins with relatively high melting points can achieve excellent heat-resistant adhesion to poorly adhesive substrates such as polyolefins. However, such resins have problems such as poor solution stability and poor handling.

[0006] An object of the present invention is to provide a resin composition having excellent heat resistance to adhesion to poorly adhesive substrates and excellent solution stability. [Means for solving the problem]

[0007] The present invention provides the following: [1] A modified product obtained by modifying a polyolefin resin (A) having a melting point of 100°C or less, measured at a heating rate of 10°C / min using a differential scanning calorimeter in accordance with JIS K7121-1987, with one or more compounds selected from the group consisting of α,β-unsaturated carboxylic acids and their derivatives, and A modified product obtained by modifying a polyolefin resin (B) having an extrapolated melting onset temperature (Tim) of 120°C or higher, measured at a heating rate of 10°C / min using a differential scanning calorimeter in accordance with JIS K7121-1987, with one or more compounds selected from the group consisting of α,β-unsaturated carboxylic acids and their derivatives. A resin composition comprising: The modified resin (B) is dispersed in the modified resin (A), A resin composition, wherein the modified resin (B) has an average particle size of 0.1 to 100 μm. [2] The resin composition according to the above [1], wherein the one or more compounds selected from the group consisting of α,β-unsaturated carboxylic acids and derivatives thereof include maleic anhydride. [3] The resin composition according to [1] or [2] above, wherein the one or more compounds selected from the group consisting of α,β-unsaturated carboxylic acids and derivatives thereof include a (meth)acrylic acid ester. [4] The resin composition according to any one of the above [1] to [3], wherein the melting point of the resin (B) is 140 to 200°C, as measured at a heating rate of 10°C / min using a differential scanning calorimeter in accordance with JIS K7121-1987. [5] The resin composition according to any one of the above [1] to [4], wherein a mass ratio of the modified resin (A) to the modified resin (B) (modified resin (A) : modified resin (B)) is 50:50 to 95:5. [6] The resin composition according to any one of the above [1] to [5], wherein the difference (Tem-Tim) between the extrapolated end temperature of melting (Tem) and the extrapolated onset temperature of melting (Tim) of the resin (B) measured at a heating rate of 10°C / min using a differential scanning calorimeter in accordance with JIS K7121-1987 is 5 to 20°C. [7] The resin composition according to any one of the above [1] to [6], further comprising a hydrophobic solvent. [8] A primer comprising the resin composition according to any one of the above [1] to [7]. [9] An adhesive comprising the resin composition according to any one of the above [1] to [7].

[10] A coating material comprising the resin composition according to any one of the above [1] to [7].

[11] An ink comprising the resin composition according to any one of the above [1] to [7].

[12] A method for producing the resin composition according to any one of the above [1] to [7], (1) A step of simultaneously modifying a mixture of resin (A) and resin (B) with one or more compounds selected from the group consisting of α,β-unsaturated carboxylic acids and derivatives thereof to obtain the resin composition, or (2) A method for producing a resin composition, comprising the steps of: modifying resin (A) with one or more compounds selected from the group consisting of α,β-unsaturated carboxylic acids and derivatives thereof to obtain a modified resin (A); modifying resin (B) with one or more compounds selected from the group consisting of α,β-unsaturated carboxylic acids and derivatives thereof to obtain a modified resin (B); and mixing the modified resin (A) and the modified resin (B) obtained to obtain the resin composition. Effect of the Invention

[0008] According to the present invention, it is possible to provide a resin composition that can exhibit excellent heat resistance adhesion and excellent solution stability with respect to a hardly adherent substrate.

Mode for Carrying Out the Invention

[0009] In the following description, unless otherwise specified, the description of "AA to BB" means "AA or more and BB or less". Here, "AA" and "BB" each represent a numerical value, and AA < BB. The unit of "AA" is the same as the unit attached to "BB" unless otherwise specified.

[0010] In the following description, unless otherwise specified, the term "(meth)acrylic acid" includes "acrylic acid", "methacrylic acid", and combinations thereof, and the term "(meth)acrylate" includes "acrylate", "methacrylate", and combinations thereof.

[0011] The present invention provides a resin composition containing a modified product obtained by modifying a polyolefin resin (A) having a melting point of 100°C or lower with an α,β-unsaturated carboxylic acid and / or its derivative, and a modified product obtained by modifying a polyolefin resin (B) having an extrapolated melting start temperature (Tim) of 120°C or higher with an α,β-unsaturated carboxylic acid and / or its derivative, wherein the modified product of resin (B) is dispersed in the modified product of resin (A), and the average particle diameter of the modified product of resin (B) is 0.1 to 100 μm. Such a resin composition can exhibit excellent heat resistance adhesion and solution stability with respect to a hardly adherent substrate. Hereinafter, resin (A) is also simply referred to as component (A), and resin (B) is also simply referred to as component (B).

[0012] (1. Polyolefin Resin) The resin composition of the present invention includes a modified product obtained by modifying a polyolefin resin (A) having a melting point of 100°C or less with an α,β-unsaturated carboxylic acid and / or a derivative thereof, and a modified product obtained by modifying a polyolefin resin (B) having an extrapolated melting onset temperature (Tim) of 120°C or more with an α,β-unsaturated carboxylic acid and / or a derivative thereof.

[0013] The polyolefin resin is an olefin (preferably an α-olefin) polymer, such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, or 1-octene.

[0014] The polyolefin resin may be a polymer of one kind of olefin (preferably α-olefin) or a copolymer of two or more kinds of olefins (preferably α-olefins). When the polyolefin resin is a copolymer, the polyolefin resin may be a random copolymer or a block copolymer.

[0015] The mass ratio of the modified product of component (A) to the modified product of component (B) (modified product of component (A) : modified product of component (B)) is preferably 40:60 to 95:5, more preferably 50:50 to 95:5, even more preferably 60:40 to 95:5, still more preferably 70:30 to 95:5, and particularly preferably 75:25 to 95:5.

[0016] (1-1. Component (A): Polyolefin resin with a melting point of 100°C or less) From the viewpoint of exhibiting sufficient adhesion, the polyolefin resin of component (A) is preferably polypropylene (propylene homopolymer), ethylene-propylene copolymer, propylene-1-butene copolymer, ethylene-propylene-1-butene copolymer, or a mixture thereof.

[0017] Here, "polypropylene" refers to a polymer whose constituent units are propylene-derived constituent units. "Ethylene-propylene copolymer" refers to a copolymer containing ethylene-derived constituent units and propylene-derived constituent units as constituent units. "Propylene-1-butene copolymer" refers to a copolymer containing propylene-derived constituent units and 1-butene-derived constituent units as constituent units. "Ethylene-propylene-1-butene copolymer" refers to a copolymer containing ethylene-derived constituent units, propylene-derived constituent units and 1-butene-derived constituent units as constituent units. These (co)polymers may contain small amounts of other olefin-derived constituent units as constituent units, as long as the amount does not significantly impair the inherent performance of the resin.

[0018] The polyolefin resin of component (A) preferably contains 15 mol % or more, and more preferably 50 mol % or more, of propylene-derived structural units out of 100 mol % of all structural units. When the propylene-derived structural units are contained in the above range, good adhesion can be maintained.

[0019] When the polyolefin resin of component (A) is an ethylene-propylene copolymer or a propylene-1-butene copolymer, preferably, out of 100 mol% of all structural units, the ethylene-derived structural units or 1-butene-derived structural units account for 3 to 85 mol% (more preferably 3 to 50 mol%) and the propylene-derived structural units account for 15 to 97 mol% (more preferably 50 to 97 mol%).

[0020] The lower limit of the melting point (Tm) of the polyolefin resin of component (A) is preferably 60°C or higher, more preferably 80°C or higher, even more preferably 90°C or higher, and particularly preferably 95°C or higher. When the melting point of the polyolefin resin of component (A) is within the above range, sufficient coating strength can be exhibited when the resin composition is used for applications such as ink and paint. Therefore, adhesion to the substrate can be sufficiently exhibited. In addition, when used as an ink, blocking during printing can be suppressed. The melting point (Tm) of the polyolefin resin of component (A) can be measured by a differential scanning calorimeter at a heating rate of 10°C / min in accordance with JIS K7121-1987.

[0021] The weight average molecular weight (Mw) of the polyolefin resin of component (A) is preferably 5,000 or more, more preferably 10,000 or more, even more preferably 30,000 or more, even more preferably 50,000 or more, and particularly preferably 100,000 or more, and the upper limit is preferably 200,000 or less, more preferably 180,000 or less, even more preferably 170,000 or less, even more preferably 160,000 or less, and particularly preferably 150,000 or less. The weight average molecular weight (Mw) can be measured by gel permeation chromatography (GPC) using polystyrene as a standard substance.

[0022] (1-2. Component (B): Polyolefin resin with an extrapolated melting temperature of 120°C or higher) The polyolefin resin of component (B) is preferably polypropylene (propylene homopolymer), ethylene-propylene copolymer, propylene-1-butene copolymer, ethylene-propylene-1-butene copolymer, or a mixture thereof.

[0023] The lower limit of the melting point (Tm) of the polyolefin resin of component (B) is preferably 140° C. or higher, more preferably 145° C. or higher, even more preferably 150° C. or higher, and particularly preferably 155° C. or higher, and the upper limit is preferably 200° C. or lower, more preferably 190° C. or lower, even more preferably 180° C. or lower, and particularly preferably 170° C. or lower. The melting point (Tm) of the polyolefin resin of component (B) can be measured by a differential scanning calorimeter at a heating rate of 10° C. / min in accordance with JIS K7121-1987.

[0024] The lower limit of the extrapolated melting onset temperature (Tim) of the polyolefin resin of component (B) is 120° C. or more, preferably 125° C. or more, more preferably 130° C. or more, even more preferably 135° C. or more, and particularly preferably 140° C. or more, and the upper limit is preferably 200° C. or less, more preferably 190° C. or less, even more preferably 180° C. or less, and particularly preferably 170° C. or less. The extrapolated melting onset temperature (Tim) of the polyolefin resin of component (B) can be measured by a differential scanning calorimeter at a heating rate of 10° C. / min in accordance with JIS K7121-1987.

[0025] The lower limit of the extrapolated melting end temperature (Tem) of the polyolefin resin of component (B) is preferably 135° C. or higher, more preferably 140° C. or higher, even more preferably 145° C. or higher, and particularly preferably 150° C. or higher, and the upper limit is preferably 210° C. or lower, more preferably 200° C. or lower, even more preferably 190° C. or lower, and particularly preferably 180° C. or lower. The extrapolated melting end temperature (Tem) of the polyolefin resin of component (B) can be measured by a differential scanning calorimeter at a heating rate of 10° C. / min in accordance with JIS K7121-1987.

[0026] The difference (Tem-Tim) between the extrapolated melting end temperature (Tem) and the extrapolated melting initiation temperature (Tim) of the polyolefin resin of component (B) is preferably 5 to 20°C, more preferably 10 to 20°C, even more preferably 10 to 19°C, and particularly preferably 12 to 18°C.

[0027] The weight average molecular weight (Mw) of the polyolefin resin of component (B) is preferably 5,000 or more, more preferably 10,000 or more, even more preferably 30,000 or more, even more preferably 40,000 or more, and particularly preferably 50,000 or more, and the upper limit is preferably 500,000 or less, more preferably 400,000 or less, even more preferably 300,000 or less, even more preferably 200,000 or less, and particularly preferably 180,000 or less.

[0028] (2. Modification with α,β-unsaturated carboxylic acids and / or their derivatives) The resin composition of the present invention is, for example, (1) A method including a step of simultaneously modifying a mixture of component (A) and component (B) with an α,β-unsaturated carboxylic acid and / or a derivative thereof to obtain the resin composition of the present invention (hereinafter sometimes referred to as "simultaneous modification"); (2) A method including a step of modifying component (A) with an α,β-unsaturated carboxylic acid and / or a derivative thereof to obtain a modified product of component (A), a step of modifying component (B) with an α,β-unsaturated carboxylic acid and / or a derivative thereof to obtain a modified product of component (B), and a step of mixing the modified product of component (A) and the modified product of component (B) obtained to obtain the resin composition of the present invention (hereinafter sometimes referred to as "individual modification"). It can be produced by

[0029] The modification with an α,β-unsaturated carboxylic acid and / or a derivative thereof can be carried out, for example, by graft copolymerizing the α,β-unsaturated carboxylic acid or a derivative thereof onto the polyolefin chain of the raw material polyolefin resin. The modification with an α,β-unsaturated carboxylic acid and / or a derivative thereof can be carried out using a melting method.

[0030] The modification with α,β-unsaturated carboxylic acid and / or its derivative is preferably carried out, for example, by heating and melting the polyolefin resin to react with α,β-unsaturated carboxylic acid and / or its derivative. The temperature of the heat melting may be equal to or higher than the melting point of the raw polyolefin resin (component (B) in the case of simultaneous modification), preferably equal to or higher than the melting point of the raw polyolefin resin (component (B) in the case of simultaneous modification) and lower than 300°C, more preferably equal to or higher than the melting point of the raw polyolefin resin (component (B) in the case of simultaneous modification) and lower than 250°C, and particularly preferably equal to or higher than the melting point of the raw polyolefin resin (component (B) in the case of simultaneous modification) and lower than 200°C.

[0031] The modification with an α,β-unsaturated carboxylic acid and / or a derivative thereof can be carried out using equipment such as a Banbury mixer, a kneader, or an extruder, and is preferably carried out using an extruder (extrusion modification).

[0032] In the case of simultaneous modification, the extrusion modification method may include, for example, a method including a step of feeding a mixture of components (A) and (B) as raw materials to a feed section of an extruder (e.g., a co-rotating multi-screw extruder, a twin-screw extruder), mixing the raw materials, melt-kneading, reacting, and devolatilizing together with an α,β-unsaturated carboxylic acid and / or its derivative in the extruder, for example, at the above-mentioned heating and melting temperature, cooling, and further cooling (e.g., immersing in a water tank) the resin coming out of the tip die of the extruder to obtain the resin composition of the present invention. The progress of the modification reaction and kneading can be adjusted by adjusting the temperature of each part of the barrel of the extruder and the screw rotation speed.

[0033] In the case of individual modification, the extrusion modification method may include, for example, a step of supplying component (A) as a raw material to the supply section of an extruder, and in the extruder, mixing, melt-kneading, reacting, and devolatilizing the raw materials together with an α,β-unsaturated carboxylic acid and / or a derivative thereof, for example, at the above-mentioned heat-melting temperature, cooling, and further cooling the resin coming out of the tip die of the extruder to obtain a modified product of component (A); a step of supplying component (B) as a raw material to the supply section of an extruder, and in the extruder, mixing, melt-kneading, reacting, and devolatilizing the raw materials together with an α,β-unsaturated carboxylic acid and / or a derivative thereof, for example, at the above-mentioned heat-melting temperature, cooling, and further cooling the resin coming out of the tip die of the extruder to obtain a modified product of component (B); and a step of supplying the obtained modified product of component (A) and the obtained modified product of component (B) to the supply section of an extruder, and in the extruder, melt-kneading and cooling at the same temperature as the above-mentioned heat-melting temperature, for example, in the extruder, and further cooling the resin coming out of the tip die of the extruder to obtain the resin composition of the present invention. The progress of the modification reaction and kneading can be adjusted by adjusting the temperature at each portion of the barrel of the extruder and the screw rotation speed, as in the case of simultaneous modification.

[0034] Examples of the derivatives of α,β-unsaturated carboxylic acids include α,β-unsaturated carboxylic anhydrides, α,β-unsaturated carboxylic esters, α,β-unsaturated carboxylic amides, α,β-unsaturated carboxylic imides, etc. In the case of individual modification, the α,β-unsaturated carboxylic acid and its derivatives for modifying component (A) and the α,β-unsaturated carboxylic acid and its derivatives for modifying component (B) may be the same or different.

[0035] Examples of α,β-unsaturated carboxylic acids and derivatives thereof include maleic acid, maleic anhydride, fumaric acid, citraconic acid, citraconic anhydride, mesaconic acid, itaconic acid, itaconic anhydride, aconitic acid, aconitic anhydride, himic anhydride, (meth)acrylic acid, (meth)acrylic acid esters, etc. The α,β-unsaturated carboxylic acids and derivatives thereof preferably include at least one selected from maleic anhydride and (meth)acrylic acid esters.

[0036] In one embodiment, the α,β-unsaturated carboxylic acid and / or its derivative more preferably includes a (meth)acrylic acid ester.As the (meth)acrylic acid ester, preferred are alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, 2,4,6-trimethylheptyl (meth)acrylate, undecyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, and stearyl (meth)acrylate. In one embodiment, the number of carbon atoms in the alkyl group of the alkyl (meth)acrylate is preferably 1 to 30, more preferably 4 to 20, further preferably 8 to 16, and particularly preferably 10 to 14. In one embodiment, the alkyl (meth)acrylate is most preferably lauryl (meth)acrylate.

[0037] In one embodiment, the α,β-unsaturated carboxylic acid and / or its derivative more preferably contains maleic anhydride. When the α,β-unsaturated carboxylic acid and / or its derivative contains maleic anhydride, the cyclic structure derived from the maleic anhydride contained in the modified polyolefin resin may be partially hydrolyzed to open the ring.

[0038] The content of maleic anhydride in the α,β-unsaturated carboxylic acid and / or its derivative is preferably 10% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and particularly preferably 50% by mass or more, when the total amount of the α,β-unsaturated carboxylic acid and / or its derivative is 100% by mass.

[0039] The amount of α,β-unsaturated carboxylic acid and / or its derivative used for modification with α,β-unsaturated carboxylic acid and / or its derivative is preferably 50 weight % or less, more preferably 30 weight % or less, even more preferably 20 weight % or less, and particularly preferably 10 weight % or less, relative to 100 weight % of the raw material polyolefin resin. The lower limit is not particularly limited, but is preferably 0.01 weight % or more, more preferably 0.1 weight % or more, even more preferably 1 weight % or more, and particularly preferably 3 weight % or more.

[0040] The modification with α,β-unsaturated carboxylic acid and / or its derivative is preferably carried out in the presence of a radical reaction initiator. The radical reaction initiator may be, for example, a thermal polymerization initiator that generates free radicals when heated, such as organic peroxides and azonitriles. Examples of organic peroxides include di-tert-butyl peroxide, dicumyl peroxide, tert-butylcumyl peroxide, dibenzoyl peroxide, benzoyl m-tolyl peroxide, di(m-tolyl)benzoyl, dilauryl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, cumene hydroperoxide, tert-butyl hydroperoxide, 1,1-bis(tert-butylperoxy)-3,5,5-trimethylcyclohexane, 1,1-bis(tert-butylperoxy)-cyclohexane, cyclohexanone peroxide, tert-butyl peroxybenzoate, tert-butyl peroxy isobutyrate, tert-butyl peroxy-3,5,5-trimethylhexanoate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxy isopropyl carbonate, and cumyl peroxy octoate. Examples of azonitriles include 2,2-azobis(2-methylbutyronitrile), 2,2-azobisisobutyronitrile, 2,2-azobis(2,4-dimethylvaleronitrile), and 2,2-azobis(4-methoxy-2,4-dimethylvaleronitrile).

[0041] The amount of the radical reaction initiator used for the modification with an α,β-unsaturated carboxylic acid and / or a derivative thereof is preferably 0.01 to 3% by weight, and more preferably 0.1 to 2% by weight, based on 100% by weight of the raw material polyolefin resin.

[0042] The mass ratio (component (A): component (B)) of the amount of the raw material component (A) required to obtain the resin composition of the present invention to the amount of the raw material component (B) is preferably 40:60 to 95:5, more preferably 50:50 to 95:5, even more preferably 60:40 to 95:5, even more preferably 70:30 to 95:5, and particularly preferably 75:25 to 95:5. In the case of simultaneous modification, a mixture of components (A) and (B) blended at the above mass ratio is used as a raw material to perform modification and obtain a resin composition. In the case of individual modification, the above mass ratio is used as the mass ratio of the raw materials used to perform modification of components (A) and (B) separately, and the obtained modified products are mixed to obtain a resin composition.

[0043] The total graft weight (degree of modification) of the α,β-unsaturated carboxylic acid and / or its derivative in the resin composition of the present invention is preferably 50% by weight or less, more preferably 30% by weight or less, even more preferably 20% by weight or less, and particularly preferably 10% by weight or less, when the total amount of the modified product of component (A) and the modified product of component (B) is taken as 100% by weight, and the lower limit is not particularly limited, but is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, and even more preferably 1% by weight or more. The graft weight (% by weight) can be measured, for example, by alkali titration, Fourier transform infrared spectroscopy, or a method for determining the graft weight (% by weight). 1 It can be determined by H-NMR or the like.

[0044] (3. Resin composition) The resin composition of the present invention is in a form in which the modified product of component (B) is dispersed in the modified product of component (A). The modified product of component (B) may be in a particulate form. The modified product of component (B) may be in a particulate form in which the unmodified polyolefin resin of component (B) and the modified polyolefin resin of component (B) are non-uniformly mixed.

[0045] The resin composition of the present invention may contain a hydrophobic solvent. The resin composition of the present invention includes a solid form in which the modified product of solid particulate component (B) is dispersed in the modified product of solid component (A), a liquid form in which the modified product of solid particulate component (B) is dispersed in a solution in which the modified product of component (A) is dissolved, and the like.

[0046] When the resin composition of the present invention is obtained using the extrusion modification method, the resin composition obtained by cooling the resin coming out of the tip die of the extruder can be in a solid form in which the solid particulate modified product of component (B) is dispersed in the solid modified product of component (A). The solid resin composition thus obtained can be mixed with a hydrophobic solvent to form a liquid form in which the solid particulate modified product of component (B) is dispersed in a solution in which the modified product of component (A) is dissolved.

[0047] Examples of hydrophobic solvents include aromatic hydrocarbon solvents such as toluene and xylene; ester solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, and butyl acetate; ketone solvents such as acetone, methyl ethyl ketone, and methyl butyl ketone; alicyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane, and ethylcyclohexane; and aliphatic hydrocarbon solvents such as hexane, nonane, and decane.

[0048] The average particle size of the modified product of component (B) is 0.1 to 500 μm, and is not particularly limited, but is preferably 0.1 to 200 μm, more preferably 0.1 to 100 μm, even more preferably 0.3 to 50 μm, even more preferably 0.4 to 20 μm, and particularly preferably 0.5 to 10 μm. The average particle size of the modified product of component (B) may be a volume-based median diameter Dv50 (the maximum particle size below 50% of the sample volume). The average particle size of the modified product of component (B) can be measured and calculated, for example, as in Test Example 1 below.

[0049] The resin composition of the present invention has a low water vapor permeability when molded into a film. The resin composition of the present invention has a water vapor permeability of preferably 15 g / (m2) when molded into a film having a thickness of 30 μm. 2 ·24h) or less, preferably 12g / (m 2 24h) or less, usually 0g / (m 2 24h) or greater, 0.5g / (m 2 24 hours or more. The water vapor transmission rate can be measured by the method described in the Examples section based on JIS K 7129-1 (humidity sensor method).

[0050] The resin composition of the present invention can be used for primers, adhesives, paints, or inks. The primers, adhesives, paints, or inks may contain additives such as a hydrophobic solvent, a hydrophilic solvent, a curing agent, an adhesive component, a basic substance, an emulsifier, a crosslinking agent, a diluent, a light stabilizer, an ultraviolet absorber, a pigment, a dye, and an inorganic filler, in addition to the resin composition of the present invention.

[0051] Examples of hydrophilic solvents include water, glycol solvents such as ethylene glycol, alcohol solvents such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, tert-butyl alcohol, and 2-ethyl-hexanol, and glycol monoether solvents such as ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monoisopropyl ether, and propylene glycol monobutyl ether. The solvents may be used alone or in combination of two or more.

[0052] Examples of the curing agent include polyisocyanate compounds, epoxy compounds, polyamine compounds, polyol compounds, crosslinking agents in which the functional groups are blocked with protective groups, and combinations of two or more of these. The content of the curing agent may be appropriately selected depending on the content of the modified polyolefin resin. When using a curing agent, a catalyst such as an organic tin compound or a tertiary amine compound may be used in combination depending on the purpose. The curing agent may be used alone or in combination of two or more.

[0053] Examples of the adhesive component include known adhesive components such as polyester adhesives, polyurethane adhesives, acrylic adhesives, etc. The adhesive components may be used alone or in combination of two or more.

[0054] When using, for example, water, an alcohol-based solvent, a glycol-based solvent, a ketone-based solvent, or an ester-based solvent as the solvent, the resin composition preferably contains a basic substance. This allows the pH to be appropriately adjusted, and the dispersibility and storage stability of the resin in the solvent to be further improved. Examples of basic substances include sodium hydroxide, potassium hydroxide, ammonia, methylamine, propylamine, hexylamine, octylamine, ethanolamine, propanolamine, diethanolamine, N-methyldiethanolamine, dimethylamine, diethylamine, triethylamine, N,N-dimethylethanolamine, 2-dimethylamino-2-methyl-1-propanol, 2-amino-2-methyl-1-propanol, morpholine, dimethylethanolamine, and 2-amino-2-ethyl-1,3-propanediol, and preferably include ammonia, triethylamine, 2-amino-2-methyl-1-propanol, morpholine, dimethylethanolamine, and 2-amino-2-ethyl-1,3-propanediol. The basic substance may be used alone or in combination of two or more kinds.

[0055] When a hydrophobic solvent is used as the solvent, the resin composition preferably contains a diluent. This can improve storage stability. Examples of the diluent include alcohol and propylene-based glycol ether. Examples of the alcohol include methanol, ethanol, propanol, isopropanol, and butanol. Examples of the propylene-based glycol ether include propylene glycol methyl ether, propylene glycol ethyl ether, and propylene glycol-tert-butyl ether. The diluent may be used alone or in combination of two or more.

[0056] When a hydrophobic solvent is used as the solvent, the resin composition preferably contains a crosslinking agent. The crosslinking agent may be a compound that can react with groups such as hydroxyl groups, carboxyl groups, and amino groups present in the resin composition to form a crosslinked structure, and may be, for example, either a water-soluble crosslinking agent or a water dispersion of a crosslinking agent (a crosslinking agent dispersed in water by some method). Examples of the crosslinking agent include a blocked isocyanate compound, an aliphatic or aromatic epoxy compound, an amine compound, and an amino resin. The crosslinking agent may be used alone or in combination of two or more types.

[0057] When a hydrophilic solvent is used as the solvent, the resin composition preferably contains an emulsifier. Examples of the emulsifier include surfactants such as nonionic surfactants and anionic surfactants, and nonionic surfactants are preferred.

[0058] Examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene derivatives, polyoxyethylene fatty acid esters, polyoxyethylene polyhydric alcohol fatty acid esters, polyoxyethylene polyoxypropylene polyols, sorbitan fatty acid esters, polyoxyethylene hydrogenated castor oil, polyoxyalkylene polycyclic phenyl ethers, polyoxyethylene alkylamines, alkyl alkanolamides, polyalkylene glycol (meth)acrylates, etc. Preferred are polyoxyethylene alkyl ethers, polyoxyethylene fatty acid esters, polyoxyethylene sorbitan fatty acid esters, and polyoxyethylene alkylamines.

[0059] Examples of anionic surfactants include alkyl sulfates, polyoxyethylene alkyl ether sulfates, alkylbenzene sulfonates, α-olefin sulfonates, methyl taurates, sulfosuccinates, ether sulfonates, ether carboxylates, fatty acid salts, naphthalene sulfonate-formaldehyde condensates, alkylamine salts, quaternary ammonium salts, alkyl betaines, and alkylamine oxides.Preferably, polyoxyethylene alkyl ether sulfates and sulfosuccinates.Emulsifiers may be used alone or in combination of two or more. EXAMPLES

[0060] The present invention will be described in detail below using examples, but the present invention is not limited to these examples. In the following, the unit "parts" means "parts by weight". In addition, unless otherwise specified, "%" means % by weight. In the following description, the temperature conditions are at room temperature (25°C) unless otherwise specified, and the pressure conditions are at normal pressure (760 mmHg) unless otherwise specified.

[0061] <Example 1> 90 parts of propylene-butene copolymer (Tm=97°C) as component (A), 10 parts of polyolefin-based thermoplastic elastomer (Tm=166°C, Tim=152°C, Tem=169°C) as component (B), 4 parts of maleic anhydride, 4 parts of lauryl methacrylate, and 1.5 parts of di-tert-butyl peroxide were kneaded in a twin-screw extruder set at a reaction temperature of 170°C to carry out a reaction. The reaction was carried out in the extruder under reduced pressure to remove any remaining unreacted material. After the reaction, the mixture was cooled to room temperature to obtain a modified polyolefin resin composition. The total graft weight of maleic anhydride in the modified polyolefin resin composition was 3.0% by weight, with the total amount of the modified polyolefin resin being 100% by weight. The total graft weight of maleic anhydride was measured by alkali titration. The same applies below.

[0062] The melting point (Tm) of component (A) and the melting point (Tm), extrapolated melting onset temperature (Tim) and extrapolated melting end temperature (Tem) of component (B) were measured using a differential scanning calorimeter at a heating rate of 10°C / min in accordance with JIS K7121-1987.

[0063] <Example 2> A modified polyolefin resin composition was obtained in the same manner as in Example 1, except that the amount of propylene-butene copolymer (Tm=97°C) used was changed from 90 parts to 80 parts, and the amount of polyolefin thermoplastic elastomer (Tm=166°C, Tim=152°C, Tem=169°C) used was changed from 10 parts to 20 parts. The total graft weight of maleic anhydride in the modified polyolefin resin composition was 2.9% by weight, with the total amount of modified polyolefin resin being 100% by weight.

[0064] <Example 3> A modified polyolefin resin composition was obtained in the same manner as in Example 1, except that 10 parts of a polyolefin thermoplastic elastomer (Tm=164°C, Tim=153°C, Tem=170°C) was used instead of 10 parts of a polyolefin thermoplastic elastomer (Tm=166°C, Tim=152°C, Tem=169°C). The total graft weight of maleic anhydride in the modified polyolefin resin composition was 3.4% by weight, with the total amount of the modified polyolefin resin being 100% by weight.

[0065] <Example 4> A modified polyolefin resin composition was obtained in the same manner as in Example 1, except that 10 parts of a propylene homopolymer (Tm=156°C, Tim=152°C, Tem=165°C) was used instead of 10 parts of a polyolefin thermoplastic elastomer (Tm=166°C, Tim=152°C, Tem=169°C). The total graft weight of maleic anhydride in the modified polyolefin resin composition was 3.1% by weight, with the total amount of the modified polyolefin resin being 100% by weight.

[0066] <Example 5> A modified polyolefin resin composition (1) was obtained in the same manner as in Example 1, except that the amount of propylene-butene copolymer (Tm=97°C) used was changed from 90 parts to 100 parts, and polyolefin-based thermoplastic elastomer (Tm=166°C, Tim=152°C, Tem=169°C) was not used. A modified polyolefin resin composition (2) was obtained in the same manner as in Example 1, except that 100 parts of propylene-ethylene copolymer (Tm=142°C, Tim=140°C, Tem=155°C) was used instead of 90 parts of propylene-butene copolymer (Tm=97°C), and polyolefin-based elastomer (Tm=166°C, Tim=152°C, Tem=169°C) was not used. 90 parts of the above resin composition (1) as a modified product of component (A) and 10 parts of the above resin composition (2) as a modified product of component (B) were kneaded in a twin-screw extruder set at a reaction temperature of 170°C. After kneading, the mixture was cooled to room temperature to obtain a modified polyolefin resin composition. The total graft weight of maleic anhydride in the modified polyolefin resin composition was 3.0% by weight, with the total amount of the modified polyolefin resin being 100% by weight.

[0067] <Example 6> Except for not using lauryl methacrylate, a modified polyolefin resin composition was obtained in the same manner as in Example 1. The total graft weight of maleic anhydride in the modified polyolefin resin composition was 2.9% by weight, with the total amount of the modified polyolefin resin being 100% by weight.

[0068] <Comparative Example 1> A modified polyolefin resin composition was obtained in the same manner as in Example 1, except that the amount of propylene-butene copolymer (Tm=97°C) was changed from 90 parts to 100 parts, and polyolefin-based thermoplastic elastomer (Tm=166°C, Tim=152°C, Tem=169°C) was not used. The total graft weight of maleic anhydride in the modified polyolefin resin composition was 3.1% by weight, with the total amount of modified polyolefin resin being 100% by weight.

[0069] <Comparative Example 2> A modified polyolefin resin composition was obtained in the same manner as in Example 1, except that 100 parts of a propylene-ethylene copolymer (Tm = 105°C) was used instead of 90 parts of a propylene-butene copolymer (Tm = 97°C) and no polyolefin-based thermoplastic elastomer (Tm = 166°C, Tim = 152°C, Tem = 169°C) was used. The total graft weight of maleic anhydride in the modified polyolefin resin composition was 3.0% by weight, with the total amount of the modified polyolefin resin being 100% by weight.

[0070] <Comparative Example 3> A modified polyolefin resin composition was obtained in the same manner as in Example 1, except that 10 parts of a polyolefin thermoplastic elastomer (Tm=143°C, Tim=120°C, Tem=154°C) was used instead of 10 parts of a polyolefin thermoplastic elastomer (Tm=166°C, Tim=152°C, Tem=169°C). The total graft weight of maleic anhydride in the modified polyolefin resin composition was 3.0% by weight, with the total amount of the modified polyolefin resin being 100% by weight.

[0071] <Comparative Example 4> A modified polyolefin resin composition was obtained in the same manner as in Example 1, except that 10 parts of a polyolefin thermoplastic elastomer (Tm=135°C, Tim=112°C, Tem=153°C) was used instead of 10 parts of a polyolefin thermoplastic elastomer (Tm=166°C, Tim=152°C, Tem=169°C). The total graft weight of maleic anhydride in the modified polyolefin resin composition was 2.9% by weight, with the total amount of the modified polyolefin resin being 100% by weight.

[0072] <Comparative Example 5> A modified polyolefin resin composition was obtained in the same manner as in Example 1, except that 10 parts of a polyolefin thermoplastic elastomer (Tm=132°C, Tim=118°C, Tem=139°C) was used instead of 10 parts of a polyolefin thermoplastic elastomer (Tm=166°C, Tim=152°C, Tem=169°C). The total graft weight of maleic anhydride in the modified polyolefin resin composition was 3.2% by weight, with the total amount of the modified polyolefin resin being 100% by weight.

[0073] <Test Example 1: Measurement and calculation of average particle size of modified component (B)> The volumetric particle size distribution was measured using a Malvern Mastersizer 3000, and the average particle size was calculated as the volumetric median diameter Dv50 (the maximum particle size below which 50% of the sample volume falls). The measurement sample was prepared by adding a solution sample of the modified polyolefin resin composition obtained in the examples and comparative examples (solid content: 15% by weight, solvent composition: methylcyclohexane / MEK=80 / 20 (w / w)) to a dispersion solvent (solvent composition: methylcyclohexane / MEK=80 / 20 (w / w)) so that the laser scattering intensity was about 12%.

[0074] In the measurement sample for measuring the particle size distribution, it was confirmed by the following procedure that the modified product of resin (A) was completely dissolved and the modified product of resin (B) was not dissolved and existed as particles. 50 g of the solution sample of the modified polyolefin resin composition obtained in the examples (solid content: 15 wt %, solvent composition: methylcyclohexane / MEK=80 / 20 (w / w)) was taken into a centrifuge tube (250 cc) and centrifuged at 10,000 rpm (centrifugal force 15600×g) and 15° C. for 3 hours. The resulting supernatant and precipitate were each dried and then subjected to differential scanning calorimetry (DSC). The melting point peak of resin (A) was observed from the solid obtained from the supernatant, and the melting point peak of resin (B) was observed from the solid obtained from the precipitate (i.e., the solid that was not dissolved and existed as particles). In addition, the Fourier transform infrared spectroscopy (FT-IR) spectra (ATR method) of the supernatant and precipitate obtained in the same manner were measured. As a result, peaks derived from the carbonyl groups of the α,β-unsaturated carboxylic acid anhydride were observed in both the solid obtained from the supernatant and the solid obtained from the precipitate, confirming that the dissolved resin was a modified product of resin (A) and that the undissolved resin present as particles was a modified product of resin (B). Details of the melting point measurement by DSC are as follows. According to JIS K7121 (1987), a DSC measuring device (e.g., "DISCOVERY DSC2500" manufactured by TA Instruments Japan) is used to heat and melt approximately 5 mg of a sample at 150°C for 10 minutes. The temperature is then lowered at a rate of 10°C / min and the sample is stably held at -50°C for 5 minutes. The sample is then heated to 150°C at a rate of 10°C / min, and the melting peak temperature is measured when the sample melts, and this temperature is taken as the melting point. The details of the FT-IR (ATR) measurement are as follows: -1 The infrared absorption spectrum was observed. Analysis was performed using the attached software ("Spectro Manager", JASCO Corporation). Wavenumber: 1700-1750 cm -1 The peaks appearing at wavenumbers of 1750 to 1820 cm are attributed to the carbonyl groups of ring-opened α,β-unsaturated carboxylic anhydrides. -1 The peak appearing in the above figure was assigned to that derived from the carbonyl group of the unopened α,β-unsaturated carboxylic acid anhydride.

[0075] <Test Example 2: Measurement of adhesive strength (heat-resistant adhesion) using Tensilon peel test> 0.52 g of HDI isocyanurate (100% solids, 20% NCO content) was added as a curing agent to the solution sample of the modified polyolefin resin composition obtained in the examples and comparative examples (solids: 15%, solvent composition: methylcyclohexane / MEK=80 / 20 (w / w)) and mixed, and this was applied to aluminum foil as an adhesive with a #16 Meyer bar so that the resin dry film thickness was 3 μm. The coating film was then dried in a thermostatic dryer adjusted to 100 ° C, and the coated aluminum foil was laminated with a non-oriented polypropylene (CPP) sheet, and thermocompression bonding was performed under conditions of 200 ° C, 0.1 MPa, and 1 second, and then aging was performed for 3 days in a thermostatic dryer adjusted to 60 ° C. Test pieces were cut out to a width of 15 mm, and the laminate adhesive strength was measured under conditions of a peel angle of 180 °, a peel speed of 100 mm / min, and an atmosphere of 120 ° C.

[0076] <Test Example 3: Evaluation of solution stability> 10 g of the solution samples of the modified polyolefin resin compositions obtained in the Examples and Comparative Examples (solid content: 15%, solvent composition: methylcyclohexane / MEK=80 / 20 (w / w)) were placed in a screw tube and allowed to stand at 23°C, and the change in the solution state was observed. The evaluation criteria were as follows: samples that maintained fluidity after standing for one day were rated as "G", and samples that had no fluidity and were gel-like or solidified were rated as "NG".

[0077] Table 1 below summarizes the melting points, extrapolated melting start temperatures, and extrapolated melting end temperatures of the raw materials used in Examples 1 to 6 and Comparative Examples 1 to 5, as well as the evaluation and measurement results of Test Examples 1 to 3.

[0078] <Test Example 4: Evaluation of water vapor permeability> <How to prepare evaluation samples> A solution sample of the prepared resin composition (solid content: 15 wt%, solvent composition: methylcyclohexane / MEK=80 / 20 (w / w)) was applied to a 12 μm thick polyethylene terephthalate (PET) film using a Mayer bar and dried at room temperature to prepare a sample for evaluation.

[0079] <Evaluation method><Calculation method of values> The water vapor permeation rate was measured using the Lyssy L80-5000. The measurement conditions were 40°C and 90% RH, and the sample was set so that the coated surface was the detector side (low humidity side). The measurement was performed according to JIS K 7129-1 (humidity sensor method), and the water vapor permeation rate measurement results were obtained. Based on the results of the 12 μm-thick PET film single layer and each evaluation sample, the water vapor permeability of each evaluation sample (sample having a layer structure of 12 μm-thick PET film / coating film) was calculated to determine how many μm thick the PET film is. The difference between the calculated value and the thickness of the coated PET film, 12 μm, was then taken to calculate the water vapor permeability of the coating film itself. The thickness of the coating film at the location actually used for measurement on the evaluation sample was measured at three points using a JIS-type paper thickness measuring instrument MEI-10 manufactured by CITIZEN Watch Co., Ltd., and the average value was taken to calculate the average film thickness of the measured parts. From the calculated permeability of the coating film itself and the average film thickness of the measured parts, the water vapor permeability (g / (m2) was calculated assuming that the resin composition was a 30 μm film. 2 ·24h)) was calculated. The results of Test Example 4 are summarized in Table 2 below.

[0080] The abbreviations in Table 1 have the following meanings. Tim: extrapolated melting onset temperature Tem: extrapolated melting end temperature Adhesive strength: Tensilon peel test adhesive strength

[0081] [Table 1]

[0082] [Table 2]

[0083] From the above results, it can be seen that the resin composition of the present invention, which contains a modified product obtained by modifying polyolefin resin (A) having a melting point of 100°C or less with an α,β-unsaturated carboxylic acid and / or a derivative thereof, and a modified product obtained by modifying polyolefin resin (B) having an extrapolated melting onset temperature (Tim) of 120°C or more with an α,β-unsaturated carboxylic acid and / or a derivative thereof, wherein the modified product of component (B) is dispersed in the modified product of component (A) and the average particle size of the modified product of component (B) is 0.1 to 100 μm, can exhibit excellent heat-resistant adhesion to poorly adhesive substrates such as polypropylene sheets and metal materials, as well as excellent solution stability. It is also clear that the resin compositions according to the examples have significantly smaller water vapor permeation amounts than the resin composition according to Comparative Example 1.

Claims

1. A modified product obtained by modifying a polyolefin resin (A) having a melting point of 100° C. or less, as measured at a heating rate of 10° C. / min using a differential scanning calorimeter in accordance with JIS K7121-1987, with one or more compounds selected from the group consisting of α,β-unsaturated carboxylic acids and derivatives thereof; and A modified product obtained by modifying a polyolefin resin (B) with one or more compounds selected from the group consisting of α,β-unsaturated carboxylic acids and derivatives thereof, the polyolefin resin (B) having an extrapolated melting onset temperature (Tim) of 120°C or higher as measured at a heating rate of 10°C / min using a differential scanning calorimeter in accordance with JIS K7121-1987, and a difference (Tem-Tim) between the extrapolated melting end temperature (Tem) as measured at a heating rate of 10°C / min using a differential scanning calorimeter in accordance with JIS K7121-1987 and the extrapolated melting onset temperature (Tim) of 5 to 20°C. A resin composition comprising: The modified resin (B) is dispersed in the modified resin (A), A resin composition, wherein the modified resin (B) has an average particle size of 0.1 to 100 μm.

2. 2. The resin composition according to claim 1, wherein the one or more compounds selected from the group consisting of α,β-unsaturated carboxylic acids and derivatives thereof include maleic anhydride.

3. 2. The resin composition according to claim 1, wherein the one or more compounds selected from the group consisting of α,β-unsaturated carboxylic acids and derivatives thereof include a (meth)acrylic acid ester.

4. The resin composition according to claim 1, wherein the melting point of the resin (B) is 140 to 200° C., as measured at a temperature rise rate of 10° C. / min using a differential scanning calorimeter in accordance with JIS K7121-1987.

5. The resin composition according to claim 1, wherein the mass ratio of the modified resin (A) to the modified resin (B) is 50:50 to 95:

5.

6. The resin composition according to claim 1 , further comprising a hydrophobic solvent.

7. A primer comprising the resin composition according to any one of claims 1 to 6.

8. An adhesive comprising the resin composition according to any one of claims 1 to 6.

9. A coating material comprising the resin composition according to any one of claims 1 to 6.

10. An ink comprising the resin composition according to any one of claims 1 to 6.

11. A method for producing the resin composition according to any one of claims 1 to 6, (1) A step of simultaneously modifying a mixture of resin (A) and resin (B) with one or more compounds selected from the group consisting of α,β-unsaturated carboxylic acids and derivatives thereof to obtain the resin composition, or (2) A method for producing a resin composition, comprising the steps of: modifying resin (A) with one or more compounds selected from the group consisting of α,β-unsaturated carboxylic acids and derivatives thereof to obtain a modified resin (A); modifying resin (B) with one or more compounds selected from the group consisting of α,β-unsaturated carboxylic acids and derivatives thereof to obtain a modified resin (B); and mixing the modified resin (A) and the modified resin (B) obtained to obtain the resin composition.