(META)acrylate-modified polyolefin resin

Abstract

The present invention addresses the problem of providing a novel modified polyolefin resin having photocurability and high adhesion to non-polar resin substrates such as polypropylene. The present invention pertains to a (meta)acrylate-modified polyolefin resin obtained by grafting a (meth)acrylate compound having a primary or secondary amino group onto a polyolefin resin modified with at least α,β-unsaturated carboxylic acid or a derivative thereof.

Description

(Meth)acrylate modified polyolefin resin

[0001] The present invention relates to a (meth)acrylate-modified polyolefin resin and uses thereof.

[0002] Polyolefin resins have many excellent properties, such as excellent mechanical properties such as tensile strength, tear strength, and impact strength, as well as excellent water resistance and chemical resistance, and are therefore 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, which makes them difficult to coat or adhere.

[0003] In the automotive industry, acid-modified polyolefin resins modified with highly adhesive α,β-unsaturated carboxylic acids or derivatives thereof are used as adhesion promoters for adhering poorly adhesive paints to polyolefin resins (in the automotive industry, paints that are composed mainly of adhesion promoters and that are applied directly to substrates are particularly called primer paints) (Patent Document 1).

[0004] On the other hand, in recent years, development of photocurable water-based paints that have photocurability and can be cured under limited drying conditions has been progressing, but it cannot be said that they have sufficient adhesion to non-polar resin substrates such as polypropylene.

[0005] Japanese Patent Application Laid-Open No. 2001-279048

[0006] An object of the present invention is to provide a novel modified polyolefin resin that has high adhesion to non-polar resin substrates such as polypropylene and photocurability (including ultraviolet curability, electron beam curability, etc.).

[0007] The present invention provides the following: [1] A (meth)acrylate-modified polyolefin resin obtained by grafting a (meth)acrylate compound having a primary or secondary amino group onto a polyolefin resin modified with at least an α,β-unsaturated carboxylic acid or a derivative thereof. [2] The (meth)acrylate-modified polyolefin resin according to [1] above, in which the (meth)acrylate compound having a primary or secondary amino group has two or more (meth)acryloyl groups per molecule. [3] The (meth)acrylate-modified polyolefin resin according to [1] or [2] above, in which the (meth)acrylate compound having a primary or secondary amino group has an amine value of 30 mgKOH / g to 200 mgKOH / g. [4] An aqueous dispersion comprising the (meth)acrylate-modified polyolefin resin according to any one of [1] to [3] above. [5] The aqueous dispersion according to [4] above, in which the solids content of the aqueous dispersion is 5% by weight to 60% by weight. [6] The aqueous dispersion according to [4] or [5] above, further comprising a neutralizing agent. [7] The aqueous dispersion according to any one of [4] to [6] above, further comprising an amphiphilic solvent. [8] A resin solution comprising the (meth)acrylate-modified polyolefin resin according to any one of [1] to [3] above and an organic solvent. [9] A primer comprising the (meth)acrylate-modified polyolefin resin according to any one of [1] to [3] above.

[10] An adhesive comprising the (meth)acrylate-modified polyolefin resin according to any one of [1] to [3] above.

[11] A paint or ink binder comprising the (meth)acrylate-modified polyolefin resin according to any one of [1] to [3] above.

[12] A method for producing a (meth)acrylate-modified polyolefin resin, comprising the following steps (1) and (2):Step (1): A step of modifying a polyolefin resin with an α,β-unsaturated carboxylic acid or a derivative thereof, or modifying a polyolefin resin with an α,β-unsaturated carboxylic acid or a derivative thereof and chlorinating the polyolefin resin in any order. Step (2): A step of grafting a (meth)acrylate compound having a primary or secondary amino group onto the modified polyolefin resin obtained in step (1) to obtain a (meth)acrylate-modified polyolefin resin.

[13] A method for producing a (meth)acrylate-modified polyolefin resin according to item

[12] above, wherein the amount of the α,β-unsaturated carboxylic acid or a derivative thereof added in step (1) is 1 to 20% by weight, based on 100% by weight of the polyolefin resin.

[14] A method for producing a (meth)acrylate-modified polyolefin resin according to item

[12] or

[13] above, wherein the amount of the (meth)acrylate compound having a primary or secondary amino group added in step (2) is 1 to 20% by weight, based on 100% by weight of the modified polyolefin resin obtained in step (1).

[15] A method for producing an aqueous dispersion, comprising the following steps (1) to (3): step (1): modifying a polyolefin resin with an α,β-unsaturated carboxylic acid or a derivative thereof, or modifying a polyolefin resin with an α,β-unsaturated carboxylic acid or a derivative thereof and chlorinating the polyolefin resin in any order; step (2): grafting a (meth)acrylate compound having a primary or secondary amino group onto the modified polyolefin resin obtained in step (1) to obtain a (meth)acrylate-modified polyolefin resin; and step (3): mixing a dispersion medium with the (meth)acrylate-modified polyolefin resin obtained in step (2) to obtain an aqueous dispersion.

[0008] According to the present invention, it is possible to provide a novel modified polyolefin resin that has high adhesion to non-polar resin substrates such as polypropylene and is photocurable.

[0009] The present invention provides a (meth)acrylate-modified polyolefin resin obtained by grafting a (meth)acrylate compound having a primary or secondary amino group onto a polyolefin resin modified with at least an α,β-unsaturated carboxylic acid or a derivative thereof. Such a (meth)acrylate-modified polyolefin resin exhibits high adhesion to non-polar resin substrates such as polypropylene and photocurability.

[0010] (1. (Meth)acrylate-Modified Polyolefin Resin) The (meth)acrylate-modified polyolefin resin of the present invention is obtained by grafting a (meth)acrylate compound having a primary or secondary amino group onto a polyolefin resin modified with at least an α,β-unsaturated carboxylic acid or a derivative thereof.

[0011] (1-1. Polyolefin Resin) Polyolefin resin is an olefin (α-olefin) polymer. Examples of α-olefins include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, and 1-octene.

[0012] The polyolefin resin may be a polymer of one type of olefin (α-olefin) or a copolymer of two or more types of olefins (α-olefins). When the polyolefin resin is a copolymer, the polyolefin resin may be a random copolymer or a block copolymer.

[0013] From the viewpoint of exhibiting sufficient adhesion to non-polar resin substrates such as polypropylene substrates, the polyolefin resin is preferably polypropylene (propylene homopolymer), ethylene-propylene copolymer, propylene-1-butene copolymer, or ethylene-propylene-1-butene copolymer.

[0014] Here, "polypropylene" refers to a polymer whose structural units are propylene-derived structural units. "Ethylene-propylene copolymer" refers to a copolymer containing ethylene-derived structural units and propylene-derived structural units as structural units. "Propylene-1-butene copolymer" refers to a copolymer containing propylene-derived structural units and butene-derived structural units as structural units. "Ethylene-propylene-1-butene copolymer" refers to a copolymer containing ethylene-derived structural units, propylene-derived structural units, and butene-derived structural units as structural units. These (co)polymers may contain small amounts of other olefin-derived structural units as structural units, as long as the amount does not significantly impair the inherent performance of the resin.

[0015] The polyolefin resin preferably contains 15 mol % or more, more preferably 50 mol % or more, of propylene-derived structural units in 100 mol % of all structural units. When the propylene-derived structural units are contained in the above range, adhesion to non-polar resin substrates such as propylene resins can be maintained.

[0016] When the ethylene-propylene copolymer or propylene-1-butene copolymer is a random copolymer, preferably, of all structural units (100 mol %), structural units derived from ethylene or structural units derived from butene account for 3 to 85 mol %, and structural units derived from propylene account for 15 to 97 mol %.

[0017] The lower limit of the melting point of the polyolefin resin is preferably 20°C or higher, more preferably 60°C or higher, and the upper limit is preferably 180°C or lower, more preferably 170°C or lower, and even more preferably 165°C or lower. When the melting point of the polyolefin resin is 20°C or higher, sufficient coating film strength can be exhibited when the (meth)acrylate-modified polyolefin resin is used for applications such as inks and paints. Therefore, adhesion to the substrate can be sufficiently exhibited. Furthermore, when used as an ink, blocking during printing can be suppressed. When the melting point of the polyolefin resin is 180°C or lower, the coating film can be prevented from becoming too hard when the (meth)acrylate-modified polyolefin resin is used for applications such as inks and paints. Therefore, the coating film can exhibit appropriate flexibility.

[0018] The weight average molecular weight (Mw) of the polyolefin resin is preferably 5,000 or more, more preferably 10,000 or more, even more preferably 30,000 or more, still 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, still more preferably 200,000 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.

[0019] (1-2. Modification with α,β-unsaturated carboxylic acid or derivative thereof) In the (meth)acrylate-modified polyolefin resin, the target of modification with (meth)acrylate is a polyolefin resin that has been modified with at least an α,β-unsaturated carboxylic acid or a derivative thereof (hereinafter, sometimes referred to as an acid-modified polyolefin resin). Examples of the derivative of α,β-unsaturated carboxylic acid include α,β-unsaturated carboxylic anhydride and α,β-unsaturated carboxylic ester.

[0020] Examples of α,β-unsaturated carboxylic acids and derivatives thereof include maleic acid, maleic anhydride, fumaric acid, citraconic acid, citraconic anhydride, mesaconic acid, itaconic anhydride, aconitic acid, aconitic anhydride, himic anhydride, acrylic acid, methacrylic acid, acrylic acid esters, and methacrylic acid esters.

[0021] The graft weight (modification degree) of the α,β-unsaturated carboxylic acid or its derivative in the acid-modified polyolefin resin is preferably 50% by weight or less, more preferably 30% by weight or less, even more preferably 20% by weight or less, and even more preferably 10% by weight or less, relative to 100% by weight of the unmodified polyolefin resin. The lower limit is not particularly limited, but may be, for example, 0.01% by weight or more, or 1% by weight or more. The graft weight (% by weight) can be determined, for example, by alkali titration or Fourier transform infrared spectroscopy.

[0022] The acid-modified polyolefin resin is preferably an acid-modified polyolefin resin using at least maleic anhydride as an α,β-unsaturated carboxylic acid and its derivative, i.e., a maleic anhydride-modified polyolefin resin. Maleic anhydride-modified polyolefin resins typically have a polyolefin resin backbone and graft chains having a structure derived from maleic anhydride. The cyclic structures in the structure derived from maleic anhydride may be partially hydrolyzed and ring-opened. The ring-opening rate of the cyclic structures derived from maleic anhydride is preferably 30% or more, more preferably 40% or more, with the upper limit being preferably 95% or less, more preferably 90% or less. The ring-opening rate can be measured using the method described in Comparative Example 1 below.

[0023] (1-3. Chlorination) The acid-modified polyolefin resin may be chlorinated in addition to being modified with an α,β-unsaturated carboxylic acid or a derivative thereof (hereinafter sometimes referred to as "acid-modified"). Hereinafter, the chlorinated acid-modified polyolefin resin may be referred to as an acid-modified chlorinated polyolefin resin.

[0024] The degree of chlorination (chlorine content) of the acid-modified chlorinated polyolefin resin is preferably 60% by weight or less, more preferably 55% by weight or less, even more preferably 50% by weight or less, and even more preferably 45% by weight or less, based on 100% by weight of the polyolefin resin after acid modification and chlorination (after acid modification). The lower limit is preferably 5% by weight or more, more preferably 10% by weight or more, and even more preferably 15% by weight or more. This allows the polarity to be kept below a certain level, thereby achieving sufficient adhesion to non-polar substrates such as polyolefin substrates. The degree of chlorination can be measured in accordance with JIS-K7229. That is, it can be measured using the "oxygen flask combustion method," in which a chlorine-containing resin is burned in an oxygen atmosphere, the generated gaseous chlorine is absorbed with water, and the chlorine content is quantified by titration.

[0025] (1-4. (Meth)acrylate Compound Having a Primary or Secondary Amino Group) The (meth)acrylate-modified polyolefin resin of the present invention is obtained by grafting a (meth)acrylate compound having a primary or secondary amino group onto a polyolefin resin modified with at least an α,β-unsaturated carboxylic acid or a derivative thereof.

[0026] In one embodiment, the (meth)acrylate-modified polyolefin resin of the present invention may be obtained by amidating a primary or secondary amino group of a (meth)acrylate compound with a structure derived from an α,β-unsaturated carboxylic acid or a derivative thereof in the acid-modified polyolefin resin. For example, the (meth)acrylate-modified polyolefin resin has a structure in which a structural unit derived from an α,β-unsaturated carboxylic acid or a derivative thereof is graft-bonded to a polyolefin resin backbone, and one or more structural units derived from a (meth)acrylate compound are amide-bonded to the structural unit.

[0027] In one embodiment, the (meth)acrylate compound having a primary or secondary amino group preferably has two or more (meth)acryloyl groups in one molecule, more preferably has 2 to 10 (meth)acryloyl groups, even more preferably has 2 to 6 (meth)acryloyl groups, and even more preferably has 2 to 4 (meth)acryloyl groups in one molecule.

[0028] In a specific embodiment, the (meth)acrylate compound having a primary or secondary amino group preferably has 1 to 6, more preferably 1 to 4, and even more preferably 1 or 2 primary or secondary amino groups in one molecule.

[0029] The (meth)acrylate compound having a primary or secondary amino group is preferably a (meth)acrylate compound having a secondary amino group.

[0030] In a specific embodiment, the (meth)acrylate compound having a primary or secondary amino group preferably has a urethane structure (—NH—CO—O—).

[0031] The amine value of the (meth)acrylate compound having a primary or secondary amino group is preferably 30 mgKOH / g or more, more preferably 40 mgKOH / g or more, and even more preferably 50 mgKOH / g or more, and the upper limit is preferably 400 mgKOH / g or less, more preferably 200 mgKOH / g or less, and even more preferably 150 mgKOH / g or less. The amine value is the number of milligrams of potassium hydroxide equivalent to the amount of acid required to neutralize 1 g of sample, and can be measured by the method described in the Examples.

[0032] In a specific embodiment, the weight average molecular weight (Mw) of the (meth)acrylate compound having a primary or secondary amino group is preferably 300 to 10,000, more preferably 500 to 5,000, and even more preferably 700 to 3,500.

[0033] The (meth)acrylate compound having a primary or secondary amino group may be in the form of a salt.

[0034] Commercially available (meth)acrylate compounds having a primary or secondary amino group include, for example, "SARTOMER CN371" manufactured by Arkema, and "EBECRYL 80" and "EBECRYL 7100" manufactured by Daicel Corporation.

[0035] The graft weight (modification degree) of the (meth)acrylate compound having a primary or secondary amino group in the acid-modified polyolefin resin is preferably 50% by weight or less, more preferably 30% by weight or less, even more preferably 20% by weight or less, and even more preferably 10% by weight or less, based on 100% by weight of the acid-modified polyolefin resin. The lower limit is not particularly limited, but may be, for example, 0.01% by weight or more, 1% by weight or more. The graft weight (% by weight) can be determined, for example, by alkali titration, Fourier transform infrared (FT-IR) spectroscopy, or １ It can be determined by H-NMR.

[0036] (1-5. Method for Producing (Meth)acrylate-Modified Polyolefin Resin) The (meth)acrylate-modified polyolefin resin of the present invention can be produced by a method comprising the following steps (1) and (2). Step (1): A step of modifying a polyolefin resin with an α,β-unsaturated carboxylic acid or a derivative thereof, or a step of modifying a polyolefin resin with an α,β-unsaturated carboxylic acid or a derivative thereof and chlorinating the polyolefin resin in any order. Step (2): A step of grafting a (meth)acrylate compound having a primary or secondary amino group onto the modified polyolefin resin obtained in step (1) to obtain a (meth)acrylate-modified polyolefin resin.

[0037] Step (1) is a step in which a polyolefin resin is modified with an α,β-unsaturated carboxylic acid or a derivative thereof (hereinafter sometimes referred to as “acid modification”), or acid modification and chlorination are carried out in any order.

[0038] When both acid modification and chlorination are carried out in step (1), the order of acid modification and chlorination is not particularly limited. However, it is preferable to carry out acid modification first and then chlorination, that is, to carry out modification with an α,β-unsaturated carboxylic acid or a derivative thereof and chlorination in this order.

[0039] The chlorination in step (1) may be carried out after dissolving the raw material resin in a chlorine-based solvent such as chloroform in advance. The chlorination is carried out, for example, by blowing chlorine gas into the reaction system. The pressure during blowing chlorine gas is not limited, and may be normal pressure or under pressure. The temperature during blowing chlorine gas is not particularly limited, but is, for example, 50 to 140°C.

[0040] The chlorine gas may be blown in under irradiation with ultraviolet light or in the presence of a radical reaction initiator, but is preferably blown in the presence of a radical reaction initiator.

[0041] The radical reaction initiator may be, for example, a thermal polymerization initiator that generates free radicals upon heating, 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)- Examples of the azonitriles include 3,5,5-trimethylcyclohexane, 1,1-bis(tert-butylperoxy)cyclohexane, cyclohexanone peroxide, tert-butylperoxybenzoate, tert-butylperoxyisobutyrate, tert-butylperoxy-3,5,5-trimethylhexanoate, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxyisopropyl carbonate, and cumyl peroxyoctoate. Examples of the 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).

[0042] The amount of the radical reaction initiator used in the chlorination in step (1) is preferably 0.001 to 1% by weight, more preferably 0.01 to 0.1% by weight, based on 100% by weight of the raw material resin.

[0043] The acid modification in step (1) can be carried out, for example, by graft copolymerization of an α,β-unsaturated carboxylic acid or a derivative thereof into the polyolefin chain of the raw resin. The graft copolymerization is not particularly limited, and can be carried out using known methods such as a melting method or a solution method. The melting method is simple in operation and can complete the reaction in a shorter time. The solution method produces a more uniform graft polymer with fewer side reactions.

[0044] When the acid modification in step (1) is carried out by a melting method, for example, the raw material resin is heated and melted (heat-melted) in the presence of a radical reaction initiator to cause a reaction. The heat-melting temperature may be equal to or higher than the melting point, and is preferably equal to or higher than the melting point and equal to or lower than 300° C. Equipment such as a Banbury mixer, kneader, or extruder can be used for the heat-melting.

[0045] When the acid modification in step (1) is carried out by melting method, it is preferably carried out using an extruder (extrusion modification).As a method of extrusion modification, for example, raw material resin is compounded, and fed to the feed section of an extruder (for example, a co-rotating multi-screw extruder, a twin-screw extruder), and the raw material mixing, melt-kneading, reaction, and devolatilization cooling steps are carried out in the extruder sequentially, and the resin coming out of the tip die is cooled (for example, immersed in a water tank), to obtain a polyolefin resin modified with an acid component.The progress of the reaction can be adjusted by adjusting the temperature of each part of the barrel and the screw rotation speed.

[0046] When the acid modification in step (1) is carried out by a solution method, for example, the raw material resin is dissolved in a hydrophobic solvent and then reacted by heating and stirring in the presence of a radical reaction initiator. The temperature during the reaction is preferably 100 to 180° C. After the acid modification, the hydrophobic solvent in the system may be distilled off under reduced pressure, or the hydrophobic solvent may be removed using an extruder.

[0047] The hydrophobic solvent used when the acid modification in step (1) is carried out by a solution method is preferably an aromatic hydrocarbon solvent such as toluene, o-xylene, m-xylene, p-xylene, or ethylbenzene; or an aliphatic hydrocarbon solvent such as n-pentane, cyclopentane, n-hexane, isohexane, cyclohexane, n-heptane, methylcyclohexane, n-octane, ethylcyclohexane, n-nonane, or n-decane.

[0048] The amount of the α,β-unsaturated carboxylic acid or a derivative thereof used for acid modification in step (1) (amount used relative to the reaction system) is preferably 20% by weight or less, and more preferably 10% by weight or less, relative to 100% by weight of the (unmodified) polyolefin resin. The lower limit is not particularly limited, but may be, for example, 0.01% by weight or more, or 1% by weight or more.

[0049] In one embodiment, in step (1), the modified polyolefin resin is subjected to a ring-opening treatment. Examples of ring-opening treatments include immersing the modified polyolefin resin in water and placing the modified polyolefin resin under humidified conditions. The ring-opening rate can be adjusted by adjusting the treatment temperature, humidity, and treatment time. Preferably, the modified polyolefin resin is placed under humidified conditions at a humidity of 90% or higher at 40 to 70°C for 2 to 10 days, or is immersed in water.

[0050] Step (2) is a step of grafting a (meth)acrylate compound having a primary or secondary amino group onto the modified polyolefin resin obtained in step (1) to obtain a (meth)acrylate-modified polyolefin resin.

[0051] Step (2) may be carried out using an organic solvent. The organic solvent that can be used in step (2) is not particularly limited, but examples thereof include aliphatic hydrocarbon solvents such as n-pentane, cyclopentane, n-hexane, isohexane, cyclohexane, n-heptane, methylcyclohexane, n-octane, ethylcyclohexane, n-nonane, and n-decane; aromatic hydrocarbon solvents such as toluene, o-xylene, m-xylene, p-xylene, and ethylbenzene; hydrophobic solvents such as ester solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, and n-butyl acetate; methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, and sec-butyl alcohol. Examples of amphiphilic solvents that can be used include alcohol-based solvents such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monoisopropyl ether, propylene glycol monobutyl ether, ethyl cellosolve, n-propyl cellosolve, isopropyl cellosolve, n-butyl cellosolve, isobutyl cellosolve, and tert-butyl cellosolve; glycol-based solvents such as ethylene glycol; and ketone-based solvents such as acetone, methyl ethyl ketone, and methyl butyl ketone.

[0052] Step (2) is preferably carried out by dissolving 100% by weight of the modified polyolefin resin obtained in step (1) in 10% to 1000% by weight of an organic solvent.

[0053] When producing an aqueous dispersion, the organic solvent preferably contains an amphipathic solvent that can serve as a dispersion aid for the aqueous dispersion. When the organic solvent contains both an amphipathic solvent and a hydrophobic solvent, the weight ratio of the amphipathic solvent to the hydrophobic solvent (amphipathic solvent:hydrophobic solvent) is preferably 80:20 to 20:80, more preferably 60:40 to 40:60.

[0054] The reaction temperature in step (2) is not particularly limited, but is preferably 50° C. to 200° C., and more preferably 70° C. to 140° C. The reaction time in step (2) is not particularly limited, but is preferably 1 minute to 5 hours, and more preferably 10 minutes to 1 hour.

[0055] The amount of the (meth)acrylate compound having a primary or secondary amino group added in step (2) (amount added to the reaction system) is preferably 0.05 mol or more, more preferably 0.1 mol or more, and even more preferably 0.3 mol or more, relative to 1 mol of the amount of the α,β-unsaturated carboxylic acid or a derivative thereof added for acid modification in step (1). The upper limit is preferably 2 mol or less, more preferably 1.5 mol or less, and even more preferably 1 mol or less.

[0056] The amount of the (meth)acrylate compound having a primary or secondary amino group added in step (2) (amount added to the reaction system) is preferably 20% by weight or less, and more preferably 10% by weight or less, relative to 100% by weight of the (unmodified) polyolefin resin. The lower limit is not particularly limited, but may be, for example, 1% by weight or more, 2% by weight or more, 3% by weight or more, 4% by weight or more, or 5% by weight or more.

[0057] (1-6. Properties and Uses of (Meth)acrylate-Modified Polyolefin Resin) The weight-average molecular weight of the (meth)acrylate-modified polyolefin resin of the present invention is preferably 5,000 or more, more preferably 10,000 or more, even more preferably 30,000 or more, still 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, still more preferably 200,000 or less, and particularly preferably 150,000 or less. The weight-average molecular weight (Mw) can be measured by GPC using polystyrene as a standard substance.

[0058] The primer, adhesive, paint binder, and ink binder of the present invention each contain the (meth)acrylate-modified polyolefin resin of the present invention. The primer, adhesive, paint binder, and ink binder of the present invention may contain a photopolymerization initiator described below together with the (meth)acrylate-modified polyolefin resin of the present invention. Furthermore, the primer, adhesive, paint binder, and ink binder of the present invention may contain additives such as preservatives, leveling agents, antioxidants, light stabilizers, UV absorbers, dyes, pigments, metal salts, and acids together with the (meth)acrylate-modified polyolefin resin of the present invention.

[0059] (2. Aqueous Dispersion) The aqueous dispersion of the present invention contains the (meth)acrylate-modified polyolefin resin of the present invention. The aqueous dispersion of the present invention may be in a form in which the (meth)acrylate-modified polyolefin resin of the present invention is dispersed in a dispersion medium.

[0060] (2-1. Dispersion Medium) In the aqueous dispersion of the present invention, it is preferable that water is used as a dispersion medium and the (meth)acrylate-modified polyolefin resin is dispersed in water.

[0061] (2-2. Amphipathic Solvent) The aqueous dispersion of the present invention preferably further contains an amphipathic solvent. The amphipathic solvent can function as a dispersion aid to enhance the dispersibility of the (meth)acrylate-modified polyolefin resin. As the amphipathic solvent, the amphipathic solvent used as the organic solvent in step (2) can be used as is. Examples of amphipathic solvents include, but are not limited to, alcohol-based solvents such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, tert-butyl alcohol, 2-ethyl-hexanol, and 1-pentanol; glycol monoether-based solvents such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monoisopropyl ether, propylene glycol monobutyl ether, ethyl cellosolve, n-propyl cellosolve, isopropyl cellosolve, n-butyl cellosolve, isobutyl cellosolve, and tert-butyl cellosolve; glycol-based solvents such as ethylene glycol; and ketone-based solvents such as acetone, methyl ethyl ketone, and methyl butyl ketone.

[0062] When the aqueous dispersion of the present invention contains both water and an amphipathic solvent, the weight ratio of water to the amphipathic solvent (water:amphipathic solvent) is preferably 90:10 to 99.9:0.1, and more preferably 95:5 to 99.9:0.1.

[0063] (2-3. Neutralizing Agent) The aqueous dispersion of the present invention preferably further contains a neutralizing agent. Examples of the neutralizing agent include primary amine compounds such as methylamine, propylamine, hexylamine, octylamine, ethanolamine, propanolamine, 2-amino-2-methyl-1-propanol (AMP), and 2-amino-2-ethyl-1,3-propanediol; secondary amine compounds such as diethanolamine, dimethylamine, diethylamine, and morpholine; and tertiary amine compounds such as methyldiethanolamine, triethylamine, dimethylethanolamine (DMEA), and 2-(dimethylamino)-2-methyl-1-propanol. The neutralizing agent used may be one type or a combination of two or more types.

[0064] The neutralizing agent preferably comprises a tertiary amine compound, more preferably dimethylethanolamine (DMEA).

[0065] The content of the neutralizing agent in the aqueous dispersion of the present invention may be preferably 0.1 to 10% by weight, more preferably 0.5 to 10% by weight, when the total amount of the aqueous dispersion is taken as 100% by weight.

[0066] (2-4. Additives) The aqueous dispersion of the present invention may further contain additives as long as they do not impair the objects and effects of the present invention. Examples of additives include stabilizers, emulsifiers, crosslinking agents, diluents, and curing agents.

[0067] Examples of the stabilizer include epoxy-based stabilizers (compounds containing an epoxy group), etc. Examples of the epoxy-based stabilizer include epoxy compounds having an epoxy equivalent of about 100 to 500 and containing one or more epoxy groups per molecule. More specifically, examples of the epoxy compound include epoxidized soybean oil and epoxidized linseed oil obtained by epoxidizing vegetable oils having natural unsaturated groups with a peracid such as peracetic acid; epoxidized fatty acid esters obtained by epoxidizing unsaturated fatty acids such as oleic acid, tall oil fatty acid, and soybean oil fatty acid; epoxidized alicyclic compounds typified by epoxidized tetrahydrophthalate; monoepoxy compounds typified by condensation of bisphenol A or polyhydric alcohol with epichlorohydrin, such as bisphenol A glycidyl ether, ethylene glycol glycidyl ether, propylene glycol glycidyl ether, glycerol polyglycidyl ether, and sorbitol polyglycidyl ether; and butyl glycidyl ether, 2-ethylhexyl glycidyl ether, decyl glycidyl ether, stearyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, sec-butylphenyl glycidyl ether, tert-butylphenyl glycidyl ether, and phenol polyethylene oxide glycidyl ether.

[0068] The stabilizer may be a compound that does not contain an epoxy group, and examples thereof include metal soaps such as calcium stearate and lead stearate; organometallic compounds such as dibutyltin dilaurate and dibutyl maleate; hydrotalcite compounds; and oxetane compounds.

[0069] Examples of the emulsifier include surfactants such as nonionic surfactants and anionic surfactants.

[0070] 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, and polyalkylene glycol (meth)acrylates.

[0071] 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, naphthalenesulfonate-formalin condensates, alkylamine salts, quaternary ammonium salts, alkylbetaines, and alkylamine oxides.

[0072] (2-5. Photopolymerization Initiator) The aqueous dispersion of the present invention may further contain a photopolymerization initiator.

[0073] Examples of the photopolymerization initiator include α-hydroxyketone-based photopolymerization initiators such as 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, 2-hydroxy-2-methyl-1-phenylpropanone, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methylpropanone, and 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one; 2-methyl-1-phenyl-2-morpholinopropan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-methyl-1-(4-hexylphenyl)-2-morpholinopropan-1-one, and 2-ethyl-2-(dimethylamino)-1-(4-morpholinophenyl)butane-1 α-aminoketone photopolymerization initiators such as 2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one, 2-benzyl-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one, 2-(dimethylamino)-2-(4-methylphenylmethyl)-1-(4-morpholinophenyl)butan-1-one; phosphine oxide photopolymerization initiators such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, (2,4,6-trimethylbenzoyl)diphenylphosphine oxide, polyoxyethylene glycerin ether tris[phenyl(2,4,6-trimethylbenzoyl)phosphinate]; oxime ester photopolymerization initiators such as 2-(benzoyloxyimino)-1-[4-(phenylthio)phenyl]octan-1-one, and [1-[9-ethyl-6-(2-methylbenzoyl)carbazol-3-yl]ethylideneamino]acetate. The content of the photopolymerization initiator can be appropriately determined by a person skilled in the art.

[0074] (2-6. Method for Producing Aqueous Dispersion) The aqueous dispersion of the present invention can be produced by a method including step (3). Step (3): A step of mixing a dispersion medium (preferably water) with the (meth)acrylate-modified polyolefin resin of the present invention to obtain an aqueous dispersion.

[0075] The (meth)acrylate-modified polyolefin resin of the present invention used in step (3) may be the (meth)acrylate-modified polyolefin resin obtained in step (2) above.

[0076] In step (3), the temperature of the dispersion medium when it is mixed with the (meth)acrylate-modified polyolefin resin is preferably 40°C to 100°C, more preferably 70°C to 100°C.

[0077] Step (3) is preferably a step of mixing the (meth)acrylate-modified polyolefin resin of the present invention with a neutralizing agent (and optional additives) and a dispersion medium (preferably water) to obtain an aqueous dispersion.

[0078] In the step (3), it is preferable to mix the neutralizing agent (and additives, if necessary) with the (meth)acrylate-modified polyolefin resin, and then mix the dispersion medium therewith.

[0079] The (meth)acrylate-modified polyolefin resin used in step (3) can be used as a solution in which the (meth)acrylate-modified polyolefin resin is dissolved in the organic solvent used in step (2) without removing the organic solvent in step (2).

[0080] When the (meth)acrylate-modified polyolefin resin used in step (3) is in the form of a solution dissolved in an organic solvent containing the amphipathic solvent used in step (2), step (3) is preferably a step of mixing a neutralizer (and optional additives) and a dispersion medium (preferably water) with the solution of the (meth)acrylate-modified polyolefin resin of the present invention to obtain an aqueous dispersion. When the organic solvent further contains a hydrophobic solvent in addition to the amphipathic solvent, it is preferable to remove at least a portion of the amphipathic solvent or hydrophobic solvent after mixing the neutralizer (and optional additives) and the dispersion medium (preferably water). The method for removing at least a portion of the amphipathic solvent or hydrophobic solvent is not particularly limited, but for example, an azeotropic method, a reduced pressure method, etc. can be used.

[0081] In step (3), the (meth)acrylate-modified polyolefin resin is preferably mixed with the dispersion medium and the neutralizing agent (and, if necessary, additives) in a heated state. The heating temperature in step (3) is preferably 50°C to 150°C, more preferably 70°C to 140°C.

[0082] In step (3), the photopolymerization initiator may be added at any time, such as after at least a portion of the amphipathic solvent or hydrophobic solvent has been removed, together with the dispersion medium (preferably water), or together with the neutralizer (and, if necessary, additives).

[0083] (2-7. Properties of Aqueous Dispersion) The solid content of the aqueous dispersion of the present invention is preferably 1 wt % or more, more preferably 5 wt % or more, even more preferably 10 wt % or more, and particularly preferably 15 wt % or more. The upper limit of the solid content of the aqueous dispersion is preferably 70 wt % or less, more preferably 60 wt % or less, even more preferably 50 wt % or less, and particularly preferably 40 wt % or less. In one embodiment, the solid content of the aqueous dispersion is preferably 5 wt % to 60 wt %, more preferably 10 wt % to 50 wt %, and even more preferably 15 wt % to 40 wt %. This can improve stability over time. The solid content can be adjusted by changing the amount of dispersion medium used or the degree of reduced pressure.

[0084] The viscosity of the aqueous dispersion of the present invention at 25°C measured with a Brookfield viscometer is preferably 5 mPa s to 500 mPa s, more preferably 10 mPa s to 400 mPa s, even more preferably 10 mPa s to 350 mPa s, and particularly preferably 10 mPa s to 330 mPa s. The viscosity can be measured, for example, by the method of Test Example 2.

[0085] The average particle size of the particles constituting the aqueous dispersion of the present invention is preferably 10 nm to 300 nm, more preferably 30 nm to 200 nm, and even more preferably 50 nm to 170 nm. The average particle size can be measured, for example, by the method of Test Example 2.

[0086] (3. Resin Solution) The resin solution of the present invention contains a (meth)acrylate-modified polyolefin resin and an organic solvent. Examples of organic solvents include those exemplified in step (2) above. Preferably, the organic solvent contains one or more selected from aromatic hydrocarbon solvents, glycol solvents, and aliphatic alcohol solvents. Aromatic hydrocarbon solvents alone, or a combination of an aromatic hydrocarbon solvent with a glycol solvent and / or an aliphatic alcohol solvent, is more preferred. More preferably, the organic solvent contains one or more selected from toluene, butyl cellosolve, and isopropyl alcohol. In the case of a combination of an aromatic hydrocarbon solvent with a glycol solvent and / or an aliphatic alcohol solvent, the weight ratio of aromatic hydrocarbon solvent:glycol solvent and / or aliphatic alcohol solvent is preferably 10-70:90-30, more preferably 20-60:80-40 (assuming the total of both is 100). Examples of methods for producing the resin solution include mixing a (meth)acrylate-modified polyolefin resin with the organic solvent described above, and, if necessary, other components other than the organic solvent described above.

[0087] (4. Uses of Aqueous Dispersion and Resin Solution) The aqueous dispersion and resin solution of the present invention can be used as a primer, an adhesive, a paint binder, an ink binder, etc. When the aqueous dispersion and resin solution of the present invention are used for these purposes, they may contain additives such as preservatives, leveling agents, antioxidants, light stabilizers, ultraviolet absorbers, dyes, pigments, metal salts, and acids, as necessary.

[0088] The aqueous dispersion and resin solution of the present invention can be cured by irradiating them with active energy rays such as ultraviolet rays and electron beams. For irradiation of active energy rays such as ultraviolet rays and electron beams, a known light irradiation device commonly used in the relevant field can be used. The curing conditions for the aqueous dispersion of the present invention are not particularly limited, but for example, they can be cured by irradiating them with ultraviolet rays having a wavelength of 200 nm or more and 450 nm or less for 0.1 seconds or more and 60 seconds or less at a dose of 30 mJ / cm. ２ More than 5000mJ / cm ２ It can be cured by applying the following energy dose.

[0089] The present invention will be specifically described below using examples, but the present invention is not limited to these examples. The unit "parts" used below means "parts 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.

[0090] Comparative Example 1 Acid-Modified Polyolefin Resin (1') (a) Preparation of Raw Materials 100 parts of a polyolefin resin (propylene-butene random copolymer, propylene structural unit content: 70% by weight, butene structural unit content: 30% by weight, weight average molecular weight: 287,000, melting point: approximately 80°C) produced using a metallocene catalyst as a polymerization catalyst, 4 parts of maleic anhydride (α,β-unsaturated carboxylic acid anhydride), and 3 parts of di-tert-butyl peroxide (radical reaction initiator) were uniformly mixed and supplied to a twin-screw extruder (L / D = 60, diameter = 15 mm, 1st to 14th barrels).

[0091] The reaction was carried out under the following conditions: residence time: 10 minutes, rotation speed: 200 rpm, barrel temperatures: 100°C (barrels 1 and 2), 200°C (barrels 3 to 8), 90°C (barrels 9 and 10), and 110°C (barrels 11 to 14). Subsequently, a reduced pressure treatment was performed to remove unreacted maleic anhydride, yielding an acid-modified polyolefin resin (1') modified with maleic anhydride. The resulting acid-modified polyolefin resin (1') was further subjected to a ring-opening treatment by storing it in a sealed container at 50°C and 100% humidity for 3 days. The resulting acid-modified polyolefin resin (1') had a ring-opening rate of 70%, a weight-average molecular weight of 80,000, and a maleic anhydride graft weight (modification degree): 3.5 wt%.

[0092] (Ring Opening Rate) The infrared absorption spectrum of the acid-modified polyolefin resin was measured, and the horizontal axis was plotted as wave number (cm －１ ), and on a spectrum chart with the vertical axis being absorbance, －１ The peak present in the vicinity was determined to be a peak specific to the closed ring structure (formula: -(C=O)-O-(C=O)-), and the peak height of the structure was calculated to be Aa. －１The peak present in the vicinity was determined as the peak specific to the ring-opened structure (formula: -COOH), and the peak height of the structure was calculated as Ac. The values ​​Aa and Ac were substituted into the following formula (1) to determine the ring-opening rate of the structure. Ring-opening rate = Ac / (Aa + Ac) × 100 (%) (1)

[0093] (Weight-average molecular weight (Mw)) Measurement was carried out by GPC under the following conditions. Apparatus: HLC-8320GPC (manufactured by Tosoh Corporation) Column: TSK-gel G-6000 HXL, G-5000 HXL, G-4000 HXL, G-3000 HXL, G-2000 HXL (manufactured by Tosoh Corporation) Eluent: THF Flow rate: 1 mL / min Temperature: Pump oven, column oven 40°C Injection volume: 100 μL Standard substance: Polystyrene EasiCal PS-1 (manufactured by Agilent Technology)

[0094] (Graft Weight of Maleic Anhydride (Degree of Modification)) The degree of modification was calculated according to JIS K-0070 (1992) by the following procedure. Approximately 0.5 g of precisely weighed modified polyolefin resin and approximately 100 g of toluene were placed in a 300 ml separable flask equipped with a condenser and a thermometer, and the mixture was stirred and dissolved while being heated on a hot stirrer so that the internal temperature reached 80°C. After the resin was dissolved, 15 ml of methanol was added and the mixture was held for 5 minutes. Five to six drops of an indicator (1% phenolphthalein-methanol solution) were added, and the mixture was titrated with a 0.1 mol / L potassium hydroxide-ethanol solution. The degree of modification of the modified polyolefin resin was calculated from the titration amount required for neutralization using the following formula: K={B×f×F / (S×1000)}×100 Here, K represents the degree of modification (% by weight when the weight of the raw material unmodified polyolefin resin is taken as 100% by weight), B represents the titration amount (ml) of the potassium hydroxide-ethanol solution, f represents the factor of the 0.1 mol / L potassium hydroxide-ethanol solution, F represents the formula weight of the α,β-unsaturated carboxylic acid derivative×1 / 10, and S represents the weight (g) of the modified polyolefin resin.

[0095] (Graft Weight (Degree of Modification) of (Meth)acrylate Compound) The degree of modification was measured by the following method. 2 g of weighed modified polyolefin resin was dissolved in 18 g of toluene, and the solution was poured into approximately 150 g of acetone weighed in a 300 ml beaker while stirring with a stirrer, held for 30 minutes, and the precipitate collected by filtration was dissolved in toluene to obtain a solution with a solid content of 10%. FT-IR measurement was performed using the obtained solution, and the following peak area ratio was applied to the calibration curve to calculate the degree of modification (graft ratio) of the (meth)acrylate compound. Peak area ratio value=1730 cm －１ Peak area / 1450 cm －１ Peak area of ​​1730 cm －１ is a peak derived from the carbonyl group of the polymerized (meth)acrylate compound, and 1450 cm －１ is a peak derived from the raw material polyolefin, the graft weight (wt%) of the (meth)acrylate compound can be calculated from the above area ratio value.

[0096] (b) Preparation of organic solution 100 parts of acid-modified polyolefin resin (1') was weighed into a glass bottle, 186 parts of toluene was added, the temperature was raised to about 80°C in a water bath, and the contents were stirred by hand until homogeneous, to obtain a toluene solution of acid-modified polyolefin resin (1').

[0097] (c) Preparation of Aqueous Dispersion (DMEA) 100 parts of the acid-modified polyolefin resin (1') was dissolved in 18 parts of toluene and 42 parts of n-butyl cellosolve, and 6.5 parts of a neutralizer (dimethylethanolamine (DMEA)) and 20 parts of an emulsifier ("Leox CL-90" manufactured by Lion Corporation) were added at 100°C with stirring. Hot water (80 to 100°C) was added until the solid content reached 20% by weight, and the mixture was evaporated under reduced pressure (0.02 to 0.1 MPa) to obtain an aqueous dispersion having a solid content of 30% by weight.

[0098] Comparative Example 2 Acid-Modified Chlorinated Polyolefin Resin (2') (a) Preparation of Raw Materials 100 parts of a polyolefin resin (propylene-ethylene random copolymer, propylene structural unit content: 94% by weight, ethylene structural unit content: 6% by weight, weight average molecular weight: 80,000, melting point: 125°C) produced using a metallocene catalyst as a polymerization catalyst, 4 parts of maleic anhydride (α,β-unsaturated carboxylic acid anhydride), and 3 parts of di-tert-butyl peroxide (radical reaction initiator) were uniformly mixed and supplied to a twin-screw extruder (L / D=60, diameter=15 mm, 1st to 14th barrels).

[0099] The reaction was carried out under conditions of a residence time of 10 minutes, a rotation speed of 200 rpm, and barrel temperatures of 100°C (first and second barrels), 200°C (third to eighth barrels), 90°C (ninth and tenth barrels), and 110°C (eleventh to fourteenth barrels). Thereafter, a reduced pressure treatment was carried out to remove unreacted maleic anhydride, yielding an acid-modified polyolefin resin modified with maleic anhydride.

[0100] 100 parts of the acid-modified polyolefin resin was placed in a glass-lined reactor. Chloroform was added and the mixture was heated to 2 kgf / cm. ２ After the resin was fully dissolved at a temperature of 110°C under a pressure of 1.0 kgf / cm, 2 parts of 2,2-azobisisobutyronitrile (radical reaction initiator) was added, and the pressure inside the vessel was increased to 2 kgf / cm. ２ Chlorination was carried out by blowing in chlorine gas while controlling the temperature.

[0101] After the reaction was completed, 6 parts of an epoxy compound (Denacol EX-146, manufactured by Nagase ChemteX Corporation) was added as a stabilizer, and the mixture was fed to a vented extruder equipped with a desolvation suction section on the screw shaft, where the solvent was removed and solidified to obtain acid-modified chlorinated polyolefin resin (2'). The obtained acid-modified chlorinated polyolefin resin (2') was further subjected to ring-opening treatment by storing it in a sealed container at 50°C and 100% humidity for 3 days. The obtained acid-modified chlorinated polyolefin resin (2') had a ring-opening rate of 70%, a weight-average molecular weight of 80,000, a maleic anhydride graft amount of 4% by weight, and a chlorine content of 22% by weight.

[0102] (Degree of chlorination (chlorine content)) Measured in accordance with JIS-K7229. The value is based on the weight of the modified polyolefin resin after chlorination taken as 100% by weight.

[0103] (b) Preparation of organic solution 100 parts of acid-modified chlorinated polyolefin resin (2') was weighed into a glass bottle, 186 parts of toluene was added, the temperature was raised to about 80°C in a water bath, and the contents were stirred by hand until homogeneous, to obtain a toluene solution of acid-modified chlorinated polyolefin resin (2').

[0104] Comparative Example 3: Amino group-containing acrylate compound (3') "SARTOMER CN371" (amine value 136 mg KOH / g) manufactured by Arkema was prepared as the amino group-containing acrylate compound (3'). 100 parts of the amino group-containing acrylate compound (3') was weighed into a glass bottle, 186 parts of toluene was added, and the mixture was heated to about 80°C in a water bath and stirred by hand until the contents became homogeneous, thereby obtaining a toluene solution of the amino group-containing acrylate compound (3').

[0105] Example 1: Acrylate-modified polyolefin resin (1) (a) Preparation of organic solution 100 parts of the acid-modified polyolefin resin (1') obtained in Comparative Example 1(a) was dissolved in 186 parts of toluene, and a solution of 8.4 parts of an amino group-containing acrylate ("SARTOMER CN371" manufactured by Arkema, amine value 136 mg KOH / g) dissolved in 15.6 parts of toluene was added at 100°C in a nitrogen atmosphere, and the reaction was carried out at 100°C for 1 hour to obtain a toluene solution of acrylate-modified polyolefin resin (1). The graft weight of the amino group-containing acrylate of the obtained acrylate-modified polyolefin resin (1) was 2.2 wt%.

[0106] [Example 2: Acrylate-modified polyolefin resin (2)] (a) Preparation of organic solution A toluene / n-butylcellosolve solution of acrylate-modified polyolefin resin (2) was obtained in the same manner as in Example 1(a), except that the solvent for dissolving 100 parts of the acid-modified polyolefin resin (1') obtained in Comparative Example 1(a) was changed from 186 parts of toluene to a mixed solvent of 56 parts of toluene and 130 parts of n-butylcellosolve. The graft weight of the amino group-containing acrylate in the obtained acrylate-modified polyolefin resin (2) was 2.2 wt%.

[0107] (b) Preparation of aqueous dispersion (DMEA) To the toluene / n-butylcellosolve solution of the acrylate-modified polyolefin resin (2) obtained in Example 2(a), 6.5 parts of a neutralizing agent (dimethylethanolamine (DMEA)) and 20 parts of an emulsifier ("Leox CL-90" manufactured by Lion Corporation) were added with stirring at 100°C, and hot water (80 to 100°C) was added until the solids content reached 20% by weight, followed by evaporation under reduced pressure (0.02 to 0.1 MPa) to obtain an aqueous dispersion of acrylate-modified polyolefin resin (2) with a solids content of 30% by weight.

[0108] (c) Preparation of aqueous dispersion (morpholine) An aqueous dispersion of acrylate-modified polyolefin resin (2) was obtained in the same manner as in Example 2(b), except that 6.5 parts of morpholine was used as the neutralizing agent instead of 6.5 parts of dimethylethanolamine (DMEA).

[0109] (d) Preparation of aqueous dispersion (AMP) An aqueous dispersion of acrylate-modified polyolefin resin (2) was obtained in the same manner as in Example 2(b), except that 6.5 parts of 2-amino-2-methyl-1-propanol (AMP) was used as the neutralizing agent instead of 6.5 parts of dimethylethanolamine (DMEA).

[0110] [Example 3: Acrylate-modified polyolefin resin (3)] (a) Preparation of organic solution A toluene / n-butylcellosolve solution of acrylate-modified polyolefin resin (3) was obtained in the same manner as in Example 2(a), except that 19 parts of an amino group-containing acrylate ("EBECRYL 80" manufactured by Daicel Corporation, amine value 60 mgKOH / g) was used instead of 8.4 parts of the amino group-containing acrylate ("SARTOMER CN371" manufactured by Arkema, amine value 136 mgKOH / g). The graft weight of the amino group-containing acrylate in the obtained acrylate-modified polyolefin resin (3) was 4.0 wt%.

[0111] (b) Preparation of aqueous dispersion (DMEA) An aqueous dispersion of acrylate-modified polyolefin resin (3) was obtained in the same manner as in Example 2(b), except that the toluene / n-butylcellosolve solution of acrylate-modified polyolefin resin (3) obtained in Example 3(a) was used instead of the toluene / n-butylcellosolve solution of acrylate-modified polyolefin resin (2).

[0112] Example 4: Acrylate-modified polyolefin resin (4)] (a) Preparation of organic solution A toluene / n-butylcellosolve solution of acrylate-modified polyolefin resin (4) was obtained in the same manner as in Example 2(a), except that 8.4 parts of an amino-group-containing acrylate ("EBECRYL 7100" manufactured by Daicel Corporation, amine value 140 mgKOH / g) was used instead of 8.4 parts of the amino-group-containing acrylate ("SARTOMER CN371" manufactured by Arkema, amine value 136 mgKOH / g). The graft weight of the amino-group-containing acrylate in the obtained acrylate-modified polyolefin resin (4) was 2.7 wt%.

[0113] (b) Preparation of aqueous dispersion (DMEA) An aqueous dispersion of acrylate-modified polyolefin resin (4) was obtained in the same manner as in Example 2(b), except that the toluene / n-butylcellosolve solution of acrylate-modified polyolefin resin (4) obtained in Example 4(a) was used instead of the toluene / n-butylcellosolve solution of acrylate-modified polyolefin resin (2).

[0114] Example 5: Acrylate-modified polyolefin resin (5) (a) Preparation of organic solution 100 parts of the acid-modified chlorinated polyolefin resin (2') obtained in Comparative Example 2 (a) was dissolved in a mixed solvent of 90 parts toluene and 90 parts isopropyl alcohol, and in a nitrogen atmosphere at 100 ° C., a solution of 4.2 parts of an amino group-containing acrylate ("SARTOMER CN371" manufactured by Arkema, amine value 136 mg KOH / g) dissolved in 7.8 parts toluene was added, and the reaction was carried out at 100 ° C. for 1 hour to obtain a toluene / isopropyl alcohol solution of acrylate-modified polyolefin resin (5). The graft weight of the amino group-containing acrylate of the obtained acrylate-modified polyolefin resin (5) was 1.4 wt%.

[0115] (b) Preparation of aqueous dispersion (DMEA) An aqueous dispersion of acrylate-modified polyolefin resin (5) was obtained in the same manner as in Example 2(b), except that the toluene / n-butylcellosolve solution of acrylate-modified polyolefin resin (5) obtained in Example 5(a) was used instead of the toluene / n-butylcellosolve solution of acrylate-modified polyolefin resin (2).

[0116] (c) Preparation of aqueous dispersion (morpholine) An attempt was made to prepare an aqueous dispersion of acrylate-modified polyolefin resin (5) in the same manner as in Example 2(c), except that a toluene / isopropyl alcohol solution of acrylate-modified polyolefin resin (5) obtained in Example 5(a) was used instead of the toluene / n-butylcellosolve solution of acrylate-modified polyolefin resin (2). However, an aqueous dispersion could not be obtained.

[0117] Test Example 1: Evaluation of Organic Solutions The properties, photocurability (ultraviolet curability), and adhesion of the solutions obtained in Examples 1 to 5(a), Comparative Example 1(b), Comparative Example 2(b), and Comparative Example 3 were evaluated by the following methods.

[0118] (1) Solution Properties The solution was adjusted to a temperature of 20° C., and the solution properties were visually evaluated according to the following criteria.

[0119] Evaluation criteria: "○": No precipitates or gelation, and good fluidity is confirmed. "×": Precipitations, gelation, thickening, etc. are confirmed.

[0120] (2) Photocurability (UV curability) The solution was poured into a 30 cc glass tube, and 1 part by weight of a photopolymerization initiator (Irgacure 184, 1-hydroxycyclohexyl phenyl ketone) was added to 100 parts by weight of the solution. The mixture was stirred until homogeneous, and then UV irradiation was carried out five times in total using a UV irradiation device under the following irradiation conditions, and the photocurability (UV curability) was evaluated according to the following evaluation criteria.

[0121] Irradiation conditions: High-pressure mercury lamp (without cut filter), Conveyor speed: 3 m / min, Irradiation distance: 12.5 cm, Accumulated light intensity: 460 mJ / cm ２ (3m / min×1Pass)

[0122] Evaluation criteria: "Good": The solution was completely solidified and lost its fluidity. "Good": The solution was partially solidified, but when the glass tube was tilted, it partially flowed. "Poor": The fluidity remained the same as before irradiation.

[0123] (3) Adhesion The solution was applied to an IPA-wiped OPP film (manufactured by Futamura Chemical, 60 μm) using a Meyer bar #10, dried with warm air, and then irradiated with UV light twice using a UV irradiation device under the following irradiation conditions to prepare a test coating film.

[0124] Irradiation conditions: High-pressure mercury lamp (without cut filter), Conveyor speed: 3 m / min, Irradiation distance: 12.5 cm, Accumulated light intensity: 460 mJ / cm ２ (3m / min×1Pass)

[0125] A cellophane tape (manufactured by Nichiban, width 20 mm) was applied to the surface of the test coating film, and after strongly peeling it off, the coating film was visually evaluated for adhesion according to the following evaluation criteria.

[0126] Evaluation criteria: "○": No peeling; "△": Peeling occurred in less than 25% of the total area; "×": Peeling occurred in 25% or more of the total area.

[0127] Test Example 2: Evaluation of aqueous dispersions The aqueous dispersions obtained in Examples 2(b) to (d), 3(b), 4(b), 5(b), and Comparative Example 1(c) were evaluated for photocurability (ultraviolet curability) and adhesion by the following methods, and the average particle size and viscosity were measured by the following methods. Note that, for Examples 2(b) to (d), 3(b), 4(b), 5(b), and Comparative Example 1(c), in which aqueous dispersions were obtained, the emulsifiability was evaluated as "○", and for Example 5(c), in which an aqueous dispersion could not be obtained, the emulsifiability was evaluated as "×".

[0128] (1) Photocurability (UV-curability) The photocurability (UV-curability) of the aqueous dispersion was evaluated in the same manner as in Test Example 1(2) above, using the same evaluation criteria as in Test Example 1(2) above.

[0129] (2) Adhesion The aqueous dispersion was evaluated for adhesion in the same manner as in Test Example 1(3) above, using the same evaluation criteria as in Test Example 1(3) above.

[0130] (3) Average Particle Diameter The aqueous dispersion was diluted with pure water to a concentration of about 1 / 1000, and the average particle diameter (nm) was measured by dynamic light scattering using a Malvern Zetasizer.

[0131] (4) Viscosity The aqueous dispersion placed in a glass bottle was immersed in a thermostatic bath at 25°C for 6 hours or more to adjust the temperature, and then the viscosity (mPa s) was measured at 60 rpm in an environment of 25°C using a Brookfield viscometer ("BM-II" manufactured by Toki Sangyo Co., Ltd.).

[0132] In the following Table 1, the column "Modified polyolefin resin" summarizes the degree of chlorination, weight average molecular weight (Mw), and ring-opening rate of the modified polyolefin resin used in the Examples and Comparative Examples; the column "(meth)acrylate compound" summarizes the number of (meth)acryloyl groups and amine value of the (meth)acrylate compound used in the Examples and Comparative Examples; the column "Organic solution" summarizes the solvent used in the organic solution obtained in the Examples and Comparative Examples, the properties of the organic solution, and the evaluation results of photocurability (UV curability) and adhesion; and the column "Organic solution" summarizes the neutralizing agent used in the aqueous dispersion obtained in the Examples and Comparative Examples, the average particle size of the aqueous dispersion, the measurement results of viscosity, and the evaluation results of emulsifiability, photocurability (UV curability), and adhesion.

[0133] (Amine Value) 50 mL of acetic acid was added to 0.5 g of a sample to dissolve the sample, and the solution was titrated with 0.1 mol / L perchloric acid by electrometric titration (potentiometric titration). The titration value was then substituted into the following formula to calculate the amine value: Amine value = (a / c) × 5.611, where a: consumption amount (mL) of 0.1 mol / L perchloric acid, and c: amount of sample (g).

[0134]

[0135] The above results show that the organic solution of (meth)acrylate-modified polyolefin resin has adhesion equivalent to that of the raw material modified polyolefin resin and photocurability (UV curability) equivalent to that of a (meth)acrylate compound having a primary or secondary amino group. Furthermore, the aqueous dispersion of the (meth)acrylate-modified-acid-modified polyolefin resin exhibits a good balance of various physical properties, including average particle size, viscosity, photocurability, adhesion, and water dispersibility (emulsification ability, viscosity, and average particle size), and was particularly evaluated as excellent when DMEA was used as a neutralizing agent. Furthermore, the aqueous dispersion of the (meth)acrylate-modified-acid-modified chlorinated polyolefin resin also exhibited higher adhesion and photocurability (UV curability) when DMEA was used as a neutralizing agent.

Claims

1. A (meth)acrylate-modified polyolefin resin obtained by grafting a (meth)acrylate compound having a primary or secondary amino group onto a polyolefin resin modified with at least an α,β-unsaturated carboxylic acid or a derivative thereof.

2. 2. The (meth)acrylate-modified polyolefin resin according to claim 1, wherein the (meth)acrylate compound having a primary or secondary amino group has two or more (meth)acryloyl groups in one molecule.

3. 2. The (meth)acrylate modified polyolefin resin according to claim 1, wherein the amine value of the (meth)acrylate compound having a primary or secondary amino group is 30 mg KOH / g to 200 mg KOH / g.

4. An aqueous dispersion comprising the (meth)acrylate-modified polyolefin resin according to claim 1.

5. 5. The aqueous dispersion according to claim 4, wherein the solids content of the aqueous dispersion is from 5% by weight to 60% by weight.

6. The aqueous dispersion of claim 4 further comprising a neutralizing agent.

7. The aqueous dispersion of claim 4 further comprising a neutralizing agent.

8. A resin solution comprising the (meth)acrylate-modified polyolefin resin according to claim 1 and an organic solvent.

9. A primer comprising the (meth)acrylate-modified polyolefin resin according to claim 1.

10. An adhesive comprising the (meth)acrylate-modified polyolefin resin according to claim 1 .

11. A paint or ink binder comprising the (meth)acrylate-modified polyolefin resin according to claim 1.

12. A method for producing a (meth)acrylate-modified polyolefin resin, comprising the following steps (1) and (2): Step (1): A step of modifying a polyolefin resin with an α,β-unsaturated carboxylic acid or a derivative thereof, or modifying the polyolefin resin with an α,β-unsaturated carboxylic acid or a derivative thereof and chlorinating the polyolefin resin in any order. Step (2): A step of grafting a (meth)acrylate compound having a primary or secondary amino group onto the modified polyolefin resin obtained in step (1) to obtain a (meth)acrylate-modified polyolefin resin.

13. The method for producing a (meth)acrylate-modified polyolefin resin according to claim 12, wherein the amount of the α,β-unsaturated carboxylic acid or its derivative added in the step (1) is 1% by weight to 20% by weight based on 100% by weight of the polyolefin resin.

14. The method for producing a (meth)acrylate-modified polyolefin resin according to claim 12, wherein the amount of the (meth)acrylate compound having a primary or secondary amino group added in step (2) is 1% by weight to 20% by weight based on 100% by weight of the modified polyolefin resin obtained in step (1).

15. A method for producing an aqueous dispersion, comprising the following steps (1) to (3): Step (1): A step of modifying a polyolefin resin with an α,β-unsaturated carboxylic acid or a derivative thereof, or modifying the polyolefin resin with an α,β-unsaturated carboxylic acid or a derivative thereof and chlorinating the polyolefin resin in any order. Step (2): A step of grafting a (meth)acrylate compound having a primary or secondary amino group onto the modified polyolefin resin obtained in step (1) to obtain a (meth)acrylate-modified polyolefin resin. Step (3): A step of mixing a dispersion medium with the (meth)acrylate-modified polyolefin resin obtained in step (2) to obtain an aqueous dispersion.