(METH)acrylate-modified polyolefin resin

Abstract

To provide a (meth)acrylate-modified polyolefin resin that enables sufficient grafting of a (meth)acrylate compound and ensures excellent adhesion independent of the base material.SOLUTION: Provided is a (meth)acrylate-modified polyolefin resin produced by grafting a (meth)acrylate compound having a primary or secondary amino group onto a polyolefin resin that has been modified with at least an α,β-unsaturated carboxylic acid or a derivative thereof.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a (meth)acrylate-modified polyolefin resin and uses 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 have the disadvantage that they are difficult to paint or adhere to.

[0003] Patent Document 1 describes that by further graft polymerizing a (meth)acrylic compound onto a modified polyolefin obtained by modifying a polyolefin resin with maleic anhydride or the like, the solubility, compatibility with other resins, and adhesive strength of the polyolefin after graft polymerization can be further improved. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2012-207167 A Summary of the Invention [Problem to be solved by the invention]

[0005] However, under conventional graft polymerization conditions, it is difficult to efficiently graft-bond (meth)acrylic compounds to modified polyolefin resins, and polyolefin resins modified with conventional (meth)acrylate compounds may not necessarily exhibit adhesion to both resins and metals.

[0006] An object of the present invention is to provide a (meth)acrylate-modified polyolefin resin in which a (meth)acrylate compound is sufficiently graft-bonded and which exhibits good adhesion regardless of the substrate. [Means for solving the problem]

[0007] The present invention provides the following: [1] A modified polyolefin resin into which a modifying component containing an α,β-unsaturated carboxylic acid or its derivative has been introduced, (A) a (meth)acrylate compound having an amino group, and (B) (Meth)acrylate compound having no amino group are graft-bonded in this order. [2] The (meth)acrylate-modified polyolefin resin according to [1], having a graft efficiency of the (meth)acrylate compound calculated by the following formula (1) of 30% or more. Graft efficiency = (weight of (meth)acrylate compound contained in the (meth)acrylate-modified polyolefin resin after washing the (meth)acrylate-modified polyolefin resin with 50 parts by weight or more of acetone at 25°C / weight of unwashed (meth)acrylate-modified polyolefin resin) × 100 (1) [3] The (meth)acrylate-modified polyolefin resin according to [1] or [2], wherein the graft amount of the (meth)acrylate compound is 5% by weight or more based on the unmodified polyolefin resin. [4] A (meth)acrylate-modified polyolefin resin composition comprising the resin according to any one of [1] to [3] above and a solvent. [5] The composition according to [4], wherein the solvent includes an alcohol-based solvent and / or an ester-based solvent. [6] The (meth)acrylate-modified polyolefin resin composition according to [5], wherein the total amount of the alcohol-based solvent and the ester-based solvent contained in the solvent is 40% by weight or more. [7] The (meth)acrylate-modified polyolefin resin composition according to any one of [4] to [6], having a solid content of 30% by weight or less. [8] A coating material, a binder, an adhesive, or an ink, comprising the (meth)acrylate-modified polyolefin resin composition according to any one of [4] to [7]. [9] Step (1): A step of modifying a polyolefin resin with a modifying component containing an α,β-unsaturated carboxylic acid or a derivative thereof to obtain a modified polyolefin resin; and Step (2): A step of grafting (A) a (meth)acrylate compound having an amino group and (B) a (meth)acrylate compound in this order onto the modified polyolefin resin obtained in step (1) to obtain a (meth)acrylate-modified polyolefin resin. A method for producing the (meth)acrylate-modified polyolefin resin according to any one of [1] to [3], comprising:

[10] Step (1): A step of modifying a polyolefin resin with a modifying component containing an α,β-unsaturated carboxylic acid or a derivative thereof to obtain a modified polyolefin resin; and Step (2): grafting (A) a (meth)acrylate compound having an amino group and (B) a (meth)acrylate compound not having an amino group in this order onto the modified polyolefin resin obtained in step (1) to obtain a (meth)acrylate-modified polyolefin resin; and Step (3): A step of adding a solvent to the (meth)acrylate-modified polyolefin resin obtained in step (2) to obtain a resin solution. A method for producing the (meth)acrylate-modified polyolefin resin composition according to any one of [4] to [7], comprising: Effect of the Invention

[0008] According to the present invention, a (meth)acrylic acid-modified polyolefin resin having a (meth)acrylate graft bond is provided, which can achieve efficient introduction of (meth)acrylic acid and good grafting efficiency. The (meth)acrylic acid-modified polyolefin resin exhibits good adhesion to various substrates such as resins and metals, and can be used for applications such as paints, binders, adhesives, and inks. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] [1. (Meth)acrylate-modified polyolefin resin] The (meth)acrylate-modified polyolefin resin has a structure in which (meth)acrylate compounds (A) and (B) are graft-bonded in this order to a modified polyolefin resin.

[0010] [1-1. Polyolefin resin] Polyolefin resins, which are raw materials for modified polyolefin resins, are olefin (α-olefin) polymers. Examples of α-olefins include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, and 1-octene.

[0011] The polyolefin resin may be a polymer of one kind of olefin (α-olefin) or a copolymer of two or more kinds of olefins (α-olefins). When the polyolefin resin is a copolymer, the polyolefin resin may be a random copolymer or a block copolymer.

[0012] From the viewpoint of exhibiting sufficient adhesion to non-polar resin substrates such as polypropylene substrates, preferred polyolefin resins are polypropylene (propylene homopolymer), ethylene-propylene copolymer, propylene-1-butene copolymer, and ethylene-propylene-1-butene copolymer.

[0013] In this specification, "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 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 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.

[0014] 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, the resin can maintain adhesion to non-polar resin substrates such as propylene resins.

[0015] When the ethylene-propylene copolymer or propylene-1-butene copolymer is a random copolymer, preferably, in 100 mol % of all structural units, the ethylene-derived structural units or butene-derived structural units account for 3 to 85 mol % and the propylene-derived structural units account for 15 to 97 mol %.

[0016] 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, the (meth)acrylate-modified polyolefin resin can exhibit sufficient coating strength when used for ink, paint, etc. Therefore, the adhesion to the substrate can be sufficiently exhibited. In addition, when used as ink, blocking during printing can be suppressed. When the melting point of the polyolefin resin is 180°C or lower, the (meth)acrylate-modified polyolefin resin can be suppressed from becoming too hard when used for ink, paint, etc. Therefore, the coating film can exhibit moderate flexibility.

[0017] The weight average molecular weight (Mw) of the polyolefin resin is usually 5,000 or more, preferably 10,000 or more, more preferably 30,000 or more, even more preferably 40,000 or more, and even more preferably 50,000 or more. The upper limit is usually 500,000 or less, preferably 400,000 or less, and more preferably 300,000 or less. The weight average molecular weight (Mw) can be measured by gel permeation chromatography (GPC) using polystyrene as a standard substance.

[0018] [1-2. Denatured components] The modified polyolefin resin can be obtained by modifying a polyolefin resin with a modifying component. The modifying component can be, for example, an α,β-unsaturated carboxylic acid or a derivative thereof, or chlorine, and it is preferable that the modified polyolefin resin contains at least an α,β-unsaturated carboxylic acid or a derivative thereof. The modifying component usually does not contain a (meth)acrylate compound.

[0019] -α,β-unsaturated carboxylic acid or its derivative- Examples of the derivatives of α,β-unsaturated carboxylic acids include α,β-unsaturated carboxylic anhydrides and α,β-unsaturated carboxylic esters.

[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 acid, itaconic anhydride, aconitic acid, aconitic anhydride, himic acid anhydride, acrylic acid, methacrylic acid, acrylic acid esters, and methacrylic acid esters. Anhydrides of α,β-unsaturated carboxylic acids are preferred, and acid anhydrides having a cyclic structure (preferably a cyclic structure containing a -CO-O-CO- group) (maleic anhydride, citraconic anhydride, itaconic anhydride, and aconitic anhydride) are more preferred, with maleic anhydride being even more preferred.

[0021] The graft amount (degree of modification) of the α,β-unsaturated carboxylic acid or a derivative thereof is usually 50% by weight or less, preferably 30% by weight or less, more preferably 20% by weight or less, and even more preferably 10% by weight or less, based on 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, 1% by weight or more. The graft amount (% by weight) can be determined, for example, by alkali titration or Fourier transform infrared spectroscopy.

[0022] -Chlorination- Chlorine as a modifying component is preferably used together with an α,β-unsaturated carboxylic acid or a derivative thereof.

[0023] When the modified component contains chlorine, the chlorination degree (chlorine content) of the modified polyolefin resin is usually 60% by weight or less, preferably 55% by weight or less, more preferably 50% by weight or less, and even more preferably 45% by weight or less, based on 100% by weight of the modified polyolefin resin (after the modified component is introduced). The lower limit is usually 5% by weight or more, preferably 10% by weight or more, and more preferably 15% by weight or more. This makes it possible to suppress the polarity to a certain level or less, and to obtain sufficient adhesion to non-polar substrates such as polyolefin substrates. The chlorination degree 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 amount is quantified by titration.

[0024] [1-3. Modified polyolefin resin] The modified polyolefin resin is sufficient if the above-mentioned modifying component is introduced into the polyolefin resin, and is usually composed of a polyolefin skeleton and a graft chain derived from the modifying component bonded thereto. Hereinafter, in this specification, the modified polyolefin resin in which the modifying component contains an α,β-unsaturated carboxylic acid or a derivative thereof is referred to as an acid-modified polyolefin resin, and the modified polyolefin resin in which the modifying component contains an α,β-unsaturated carboxylic acid or a derivative thereof and chlorine is referred to as an acid-modified chlorinated polyolefin resin.

[0025] [1-4. (Meth)acrylate compounds] The (meth)acrylate modified polyolefin resin has a structure in which a (meth)acrylate compound is graft-bonded to the above-mentioned modified polyolefin resin. The (meth)acrylate compound is a compound having one or more (preferably one) (meth)acryloyl groups in one molecule (e.g., (meth)acrylic acid ester, (meth)acrylic acid amide), and may be in the form of a salt. It usually contains the following (A) and (B).

[0026] -(A): (meth)acrylate compound having an amino group- The (meth)acrylate compound (A) has an amino group. The (meth)acrylate compound having an amino group may be a (meth)acrylate compound having at least one amino group in one molecule. The number of amino groups in one molecule is usually 1 to 6, preferably 1 to 4, and more preferably 1 or 2. The amino group may be any of primary, secondary, and tertiary, and is preferably primary or secondary, and more preferably secondary. As the (meth)acrylate compound having an amino group, from the viewpoint of efficient graft bonding with the modified polyolefin resin, for example, a compound represented by general formula (1) is preferred. [ka]

[0027] In the formula, R 1R represents a hydrogen atom or a methyl group. 2 R represents an alkyl group having 1 to 5 carbon atoms, preferably 1 to 4, and more preferably 1 to 3 carbon atoms. 3 ~R 4 R each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably 1 to 4 carbon atoms, and more preferably 2 to 4 carbon atoms. 3 ~R 4 Any one of the above is preferably an alkyl group, more preferably an isobutyl group or a tert-butyl group, and even more preferably a t-butyl group, which can suppress side reactions such as crosslinking caused by reactions with multiple maleic anhydrides, and reduced stability such as thickening and gelation.

[0028] Examples of the (meth)acrylate compound having an amino group represented by formula (1) include alkylaminoalkyl (meth)acrylates such as 2-(tert-butylamino)ethyl (meth)acrylate, 2-(tert-butylamino)methyl (meth)acrylate, 2-(dimethylamino)ethyl (meth)acrylate, and 2-(dimethylamino)methyl (meth)acrylate.

[0029] -(B) (Meth)acrylate compound- The (meth)acrylate compound (B) does not have an amino group. Examples of the (meth)acrylic compound not having an amino group include 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, tetra ... Examples of such acrylic acid esters include ladecyl (meth)acrylate and stearyl (meth)acrylate, N-methyl (meth)acrylamide, N-ethyl (meth)acrylamide, N-propyl (meth)acrylamide, N-isopropyl (meth)acrylamide, N-butyl (meth)acrylamide, N-isobutyl (meth)acrylamide, Nt-butyl (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, N,N-methylene-bis (meth)acrylamide, N-methylol (meth)acrylamide, and hydroxyethyl (meth)acrylamide.

[0030] As the (meth)acrylate compound, (meth)acrylic acid or an ester thereof represented by the following general formula (2) is preferred. CH2=CR 1 COOR 2 (2) In the formula, R 1 is H or CH3, R 2 is a hydrogen atom, -C n H 2n+1 Or -(C m H 2m+1 O) p -R 3 n is an integer from 1 to 18 (preferably 1 to 10, 1 to 5, 1 to 3, 1 to 2), m is an integer from 1 to 3 (preferably 1 to 2), p is an integer from 1 to 18 (preferably 1 to 10, 1 to 5, 1 to 3, 1 to 2), R 3represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (preferably 1 to 2 carbon atoms).

[0031] The (meth)acrylate compound (B) may be one type or a combination of two or more types. (B) may be one type or a combination of two or more types of (meth)acrylic acid esters represented by the general formula (2), CH2=CR 1 COOC n H 2n+1 , CH2=CR 1 COOH, CH2=CR 1 COOC n H 2n+1 It is preferable that the compound contains any one of the above or two or more of the above.

[0032] [1-5. (Meth)acrylate-modified polyolefin resin] In the (meth)acrylate modified polyolefin resin, a (meth)acrylate compound is graft-bonded to the modified polyolefin resin. That is, the (meth)acrylate compounds are graft-bonded in the order of (A) and (B) to the modified component (a portion derived from an α,β-unsaturated carboxylic acid or its derivative) of the modified polyolefin. Therefore, the (meth)acrylate modified polyolefin resin is usually composed of a polyolefin skeleton and a graft chain bonded thereto, and the graft chain includes a portion derived from an α,β-unsaturated carboxylic acid or its derivative and a portion derived from two or more (meth)acrylate compounds ((A) and (B)) (a poly(meth)acrylic chain in which (A) and one or more (B) are linked), and the portion derived from an α,β-unsaturated carboxylic acid or its derivative is interposed between the polyolefin skeleton and the structural unit derived from (A) at the end of the portion derived from the (meth)acrylate compound. When the α,β-unsaturated carboxylic acid or a derivative thereof is an acid anhydride (e.g., maleic anhydride) having a cyclic structure (preferably a cyclic structure containing a -CO-O-CO- group), one of the hydroxyl groups formed by ring-opening is linked to the amino group of the (meth)acrylate compound via an amide bond formed by dehydration condensation.

[0033] - Graft amount of (meth)acrylate compound - The graft amount (modification degree) of the (meth)acrylate compound in the (meth)acrylate modified polyolefin resin is usually 5% by weight or more, preferably 7% by weight or more, and more preferably 10% by weight or more, based on 100% by weight of the polyolefin resin. The upper limit is not particularly limited, but may be, for example, 70% by weight or less. The graft amount (weight%) can be measured, for example, by Fourier transform infrared (FT-IR) spectroscopy or 1 It can be determined by H-NMR.

[0034] - Grafting efficiency - The graft efficiency in the (meth)acrylate modified polyolefin resin is usually 25% or more, preferably 30% or more, more preferably 35% or more, and even more preferably 40% or more. This confirms that the (meth)acrylate compound is efficiently grafted. The upper limit is not particularly limited, but is, for example, 100% or less, 90% or less. The graft efficiency is a value calculated by the following formula (1). Graft efficiency = (weight of (meth)acrylate compound contained in the (meth)acrylate-modified polyolefin resin after washing the (meth)acrylate-modified polyolefin resin with 50 parts by weight or more of acetone at 25°C / weight of unwashed (meth)acrylate-modified polyolefin resin) × 100 (1) The graft efficiency represents the ratio of the graft amount of the (meth)acrylate compound in the (meth)acrylate-modified polyolefin resin to the total amount of the (meth)acrylate compound used in the production thereof.

[0035] -Weight average molecular weight- The weight average molecular weight of the (meth)acrylate modified polyolefin resin is usually 5,000 or more, preferably 10,000 or more, more preferably 30,000 or more, even more preferably 40,000 or more, and even more preferably 50,000 or more. The upper limit is usually 500,000 or less, preferably 400,000 or less, more preferably 300,000 or less, even more preferably 200,000 or less, and even more preferably 150,000 or less. The weight average molecular weight (Mw) can be measured by GPC using polystyrene as a standard substance.

[0036] 2. Method for producing (meth)acrylate-modified polyolefin resin The (meth)acrylate-modified polyolefin resin can be produced, for example, by a method including the following steps (1) and (2). Step (1): A step of modifying a polyolefin resin with a modifying component containing an α,β-unsaturated carboxylic acid or a derivative thereof to obtain a modified polyolefin resin. Step (2): A step of grafting (A) a (meth)acrylate compound having an amino group and (B) a (meth)acrylate compound not having an amino group in this order onto the modified polyolefin resin obtained in step (1) to obtain a (meth)acrylate-modified polyolefin resin.

[0037] 2-1. Step (1): Modification of polyolefin resin Step (1) is a step of modifying a polyolefin resin, and is usually a step of modifying the polyolefin resin with an α,β-unsaturated carboxylic acid or a derivative thereof (hereinafter sometimes referred to as "acid modification"), or further chlorinating the polyolefin resin. When both acid modification and chlorination are performed, the order of acid modification and chlorination is not particularly limited, but it is preferable to perform acid modification first and then chlorination, that is, modification with an α,β-unsaturated carboxylic acid or a derivative thereof and chlorination in this order.

[0038] -Chlorination- The chlorination may be carried out after dissolving the raw resin in a chlorine-based solvent such as chloroform in advance. The chlorination may be carried out, for example, by blowing chlorine gas into the reaction system. The pressure when blowing chlorine gas is not limited, and may be normal pressure or under pressure. The temperature when blowing chlorine gas is not particularly limited, and is, for example, 50 to 140°C.

[0039] The chlorine gas may be blown in under irradiation of ultraviolet rays or in the presence of a radical reaction initiator, but is preferably blown in the presence of a radical reaction initiator.

[0040] The radical reaction initiator may be, for example, a thermal polymerization initiator that generates free radicals when heated, and examples thereof include organic peroxides and azonitriles. Examples of the organic peroxides include aromatic organic peroxides such as di-tert-butyl peroxide, dicumyl peroxide, tert-butylcumyl peroxide, dibenzoyl peroxide, benzoyl m-tolyl peroxide, and di(m-tolyl)benzoyl peroxide; (2-ethylhexanoyl)(tert-butyl)peroxide, dilauryl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, cumene hydroperoxide, tert-butyl hydroperoxide, and 1,1-bis(2-methylphenyl)-1,1-dihydroperoxide. Examples of the non-aromatic organic peroxides include (tert-butylperoxy)-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-butylperoxyisopropylcarbonate, and cumylperoxyoctoate. 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). When using organic peroxides, non-aromatic organic peroxides are preferred because they can suppress the occurrence of side reactions such as coloring.

[0041] The amount of the radical reaction initiator used in the chlorination is preferably 0.001% by weight to 1% by weight, and more preferably 0.01% by weight to 0.1% by weight, based on 100% by weight of the raw material resin.

[0042] -Acid denaturation- For the acid modification, for example, a method can be used in which an α,β-unsaturated carboxylic acid or a derivative thereof is introduced into the polyolefin chain of the raw resin by graft copolymerization. The graft copolymerization is not particularly limited, and can be carried out by using a known method such as a melting method or a solution method. In the case of the melting method, the operation is simple and the reaction can be carried out in a shorter time. In the case of the solution method, there are few side reactions and a more uniform graft polymer can be obtained.

[0043] When the acid modification is carried out by the 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 temperature of the heat melting 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. When the heat melting is carried out, equipment such as a Banbury mixer, a kneader, and an extruder can be used, and it is preferable to use an extruder (extrusion modification). As a method of extrusion modification, for example, a method is given in which the raw material resin is blended, fed to the feed section of an extruder (for example, a co-rotating multi-screw extruder, a twin-screw extruder), and each step of raw material mixing, melt kneading, reaction, and devolatilization cooling is carried out in the extruder, 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.

[0044] When the acid modification is carried out by a solution method, for example, the raw material resin is dissolved in a hydrophobic solvent, and then heated and stirred in the presence of a radical reaction initiator to cause a reaction. 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. Examples of the hydrophobic solvent include aromatic hydrocarbon solvents such as benzene, o-xylene, m-xylene, p-xylene, and ethylbenzene; or aliphatic hydrocarbon solvents such as n-pentane, cyclopentane, n-hexane, isohexane, cyclohexane, n-heptane, methylcyclohexane, n-octane, ethylcyclohexane, n-nonane, and n-decane.

[0045] The amount of α,β-unsaturated carboxylic acid or its derivative added (used) to the reaction system is preferably 20% by weight or less, and more preferably 10% by weight or less, based on 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.

[0046] -Ring opening / closing process- In step (1), the modified polyolefin resin may be subjected to a ring-opening treatment or a ring-closing treatment. This allows the adjustment of the ring-opening rate / ring-closing rate. Examples of the ring-opening treatment include a treatment in which the modified polyolefin resin is immersed in water, and a treatment in which the modified polyolefin resin is placed under humidified conditions. Preferably, the modified polyolefin resin is placed under humidified conditions of 40 to 70°C and 2 to 10 days with a humidity of 90% or more, or is immersed in water. Examples of the ring-closing treatment include a dehydration reaction (e.g., a treatment of heating to 100°C or more).

[0047] [2-2. Step (2): Modification of modified polyolefin resin] Step (2) is a step of modifying the modified polyolefin resin obtained in step (1) with a (meth)acrylate compound to obtain a (meth)acrylate-modified polyolefin resin. For example, an amide bond can be formed by dehydrating and condensing an amino group of the (meth)acrylate compound (A) with a hydroxyl group derived from a cyclic structure of an α,β-unsaturated carboxylic acid or a derivative thereof, which is a modifying component of the modified polyolefin resin, and then a (meth)acrylate compound (B) can be bonded to the (meth)acryloyl group of the (meth)acrylate compound (A).

[0048] When modifying with a (meth)acrylate compound, an organic solvent may be used. The organic solvent is not particularly limited, but may be, for example, an aliphatic hydrocarbon solvent such as n-pentane, cyclopentane, n-hexane, isohexane, cyclohexane, n-heptane, methylcyclohexane, n-octane, ethylcyclohexane, n-nonane, or n-decane; an aromatic hydrocarbon solvent such as toluene, o-xylene, m-xylene, p-xylene, or ethylbenzene; a hydrophobic solvent such as an ester solvent such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, or n-butyl acetate; methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, or tert-butyl alcohol. Examples of the organic solvent that can be used include alcohol-based solvents such as 2-ethyl-hexanol, 1-pentanol, and glycol monoethers (e.g., propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monoisopropyl ether, and propylene glycol monobutyl ether); glycol monoether-based solvents such as ethyl cellosolve, n-propyl cellosolve, isopropyl cellosolve, n-butyl cellosolve, isobutyl cellosolve, and tert-butyl cellosolve; glycol-based solvents such as ethylene glycol; and amphipathic solvents such as ketone-based solvents such as acetone, methyl ethyl ketone, and methyl butyl ketone. The amount of the organic solvent used is usually 10 to 1000% by weight based on 100% by weight of the modified polyolefin resin.

[0049] When the resin is used in an aqueous dispersion, the organic solvent preferably contains an amphipathic solvent that can be 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.

[0050] In step (2), first, the (A) (meth)acrylate compound is charged into the system and reacted, and then the (B) (meth)acrylate compound (when a plurality of compounds are used, they may be added all at once or successively) is charged into the system and reacted. The amount of the (A) (meth)acrylate compound charged into the reaction system (amount used) is usually 0.05 mol or more, preferably 0.1 mol or more, more preferably 0.3 mol or more, per mol of the α,β-unsaturated carboxylic acid or its derivative. The upper limit is usually 2 mol or less, preferably 1.5 mol or less, more preferably 1 mol or less. The amount of the (B) (meth)acrylate compound charged into the reaction system (amount used: when two or more compounds are used, the total amount) is usually 50 to 95 / 50 to 5, preferably 55 to 90 / 45 to 10, more preferably 60 to 85 / 40 to 15 (the total of both is 100).

[0051] The reaction temperature is not particularly limited, but is usually 50° C. to 200° C., more preferably 70° C. to 140° C. The reaction time is not particularly limited, but is usually 1 minute to 5 hours, preferably 10 minutes to 1 hour.

[0052] 3. (Meth)acrylate-modified polyolefin resin composition The (meth)acrylate-modified polyolefin resin can constitute a composition together with other components such as a solvent, etc. The (meth)acrylate-modified polyolefin resin composition contains a (meth)acrylate-modified polyolefin resin.

[0053] [3-1. Resin solution] In one embodiment, the (meth)acrylate-modified polyolefin resin composition is a resin solution containing a (meth)acrylate-modified polyolefin resin and a solvent.

[0054] Examples of the solvent include the solvents exemplified in the above step (2), and preferably contain at least an ester-based solvent and / or an alcohol-based solvent, more preferably a combination of an ester-based solvent and / or an alcohol-based solvent with an aliphatic hydrocarbon-based solvent, and even more preferably a combination of butyl acetate and methylcyclohexane. This allows the viscosity of the resin solution to be adjusted to an appropriate range, and allows the solution stability to be maintained for a long period of time. In the case of a combination of an aliphatic hydrocarbon-based solvent with a glycol-based solvent and / or an aliphatic alcohol-based solvent, the total (weight ratio) of the aliphatic hydrocarbon-based solvent:glycol-based solvent and / or aliphatic alcohol-based solvent is 10-70:90-30, more preferably 20-60:80-40 (when the total of both is 100).

[0055] Examples of methods for producing the resin solution include a method in which a (meth)acrylate-modified polyolefin resin, the organic solvent described above, and, if necessary, other components other than the organic solvent described above are mixed together.

[0056] In the resin solution, the solid content is usually 30% by weight or less, preferably 27% by weight or less, and more preferably 25% by weight or more. This allows the viscosity of the resin solution to be adjusted to an appropriate range, and the solution stability can be maintained for a long period of time. There is no particular limit to the lower limit, but it is, for example, 3% by weight or more, 5% by weight or more.

[0057] [3-2. Aqueous dispersion] In one embodiment, the (meth)acrylate-modified polyolefin resin composition is an aqueous dispersion of a (meth)acrylate-modified polyolefin resin.

[0058] -Dispersion medium- The dispersion medium in the aqueous dispersion contains water. The dispersion medium may contain a component other than water, for example, an amphipathic solvent. The amphipathic solvent may function as a dispersion assistant to enhance the dispersibility of the (meth)acrylate-modified polyolefin resin. The amphipathic solvent used as the organic solvent in step (2) can be used as it 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.

[0059] When the aqueous dispersion further contains an amphipathic solvent, the weight ratio of water to the amphipathic solvent (water:amphipathic solvent) is preferably from 90:10 to 99.9:0.1, and more preferably from 95:5 to 99.9:0.1.

[0060] -Neutralizer- The aqueous dispersion 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. Tertiary amine compounds are preferred, and dimethylethanolamine (DMEA) is more preferred. The neutralizing agent may be one type or a combination of two or more types.

[0061] When the aqueous dispersion contains a neutralizing agent, the content of the neutralizing agent is preferably 0.1 to 10% by weight, and more preferably 0.5 to 10% by weight, based on 100% by weight of the total amount of the aqueous dispersion.

[0062] The solid content of the aqueous dispersion is preferably 1% by weight or more, more preferably 5% by weight or more, even more preferably 10% by weight or more, and particularly preferably 15% by weight or more. The upper limit of the solid content of the aqueous dispersion is preferably 70% by weight or less, more preferably 60% by weight or less, even more preferably 50% by weight or less, and particularly preferably 40% by weight or less. In one embodiment, the solid content of the aqueous dispersion is preferably 5% by weight to 60% by weight, more preferably 10% by weight to 50% by weight, and even more preferably 15% by weight to 40% by weight. This can improve the stability over time. The solid content can be adjusted by changing the amount of the dispersion medium used or the degree of reduced pressure.

[0063] The viscosity of the aqueous dispersion 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 still more preferably 10 mPa·s to 330 mPa·s.

[0064] The average particle size of the particles constituting the aqueous dispersion is preferably 10 nm to 300 nm, more preferably 30 nm to 200 nm, and further preferably 50 nm to 170 nm.

[0065] [3-3.Optional ingredients] The (meth)acrylic acid-modified polyolefin resin composition 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, curing agents, photopolymerization initiators, other resin components, unreacted raw materials, and other additive components, and can be selected as needed.

[0066] -Stabilizer- Examples of the stabilizer include epoxy stabilizers (compounds containing an epoxy group). Examples of the epoxy stabilizer include epoxy compounds having an epoxy equivalent of about 100 to 500 and containing one or more epoxy groups in one molecule. More specifically, examples of the epoxy compounds include epoxidized soybean oil and linseed oil obtained by epoxidizing vegetable oils having natural unsaturated groups with peracids 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 such as epoxidized tetrahydrophthalate; monoepoxy compounds such as bisphenol A glycidyl ether, ethylene glycol glycidyl ether, propylene glycol glycidyl ether, glycerol polyglycidyl ether, and sorbitol polyglycidyl ether, which are obtained by condensing bisphenol A or polyhydric alcohol with epichlorohydrin; and monoepoxy compounds such as 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.

[0067] 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 malate; hydrotalcite compounds; and oxetane compounds.

[0068] -emulsifier- Examples of the emulsifier include surfactants such as nonionic surfactants and anionic surfactants.

[0069] 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.

[0070] Examples of anionic surfactants include alkyl sulfate salts, polyoxyethylene alkyl ether sulfate salts, alkylbenzene sulfonates, α-olefin sulfonates, methyl tauryl salts, sulfosuccinates, ether sulfonates, ether carboxylates, fatty acid salts, naphthalenesulfonate-formalin condensates, alkylamine salts, quaternary ammonium salts, alkylbetaines, and alkylamine oxides.

[0071] 4. Method for Producing Composition The (meth)acrylic acid modified polyolefin resin composition can be produced using the (meth)acrylic acid modified polyolefin resin obtained by the above-mentioned production method, and is preferably produced by a method including the step (3) or (4). Step (3): A step of adding a solvent to the (meth)acrylate-modified polyolefin resin and mixing as necessary to obtain a resin solution. Step (4): A step of adding a dispersion medium to the (meth)acrylate-modified polyolefin resin and mixing as necessary to obtain an aqueous dispersion.

[0072] In step (3), the solvent used in the reaction up to step (2) may be used as it is, or the solvent used in the reaction may be recovered and a desired solvent may be added separately. When obtaining a resin solution, stirring may be performed as necessary. Temperature control may also be performed by heating or the like.

[0073] When the (meth)acrylate-modified polyolefin resin is added to the dispersion medium in step (4), the temperature of the resin and / or the dispersion medium may be adjusted in advance (the resin is adjusted to, for example, 50°C to 150°C, preferably 70°C to 140°C; the dispersion medium is adjusted to, for example, 40°C to 100°C, preferably 70°C to 100°C). When an additive such as a neutralizing agent is used, it may be added to the resin first or to the dispersion medium. It may also be added gradually or all at once.

[0074] In step (4), the (meth)acrylate-modified polyolefin resin solution (a solution dissolved in an organic solvent containing the amphipathic solvent and hydrophobic solvent used in step (2)) may be added directly to the dispersion medium. In this case, at least a part of the organic solvent may be removed as necessary. Examples of the removal method include an azeotropic method and a reduced pressure method.

[0075] In steps (3) and (4), additives can be added at any time, if necessary. For example, additives can be added together with a solvent or a dispersion medium, or can be added to a prepared resin solution or aqueous dispersion. When two or more additives are used, they do not need to be added at the same time, and each can be added at any time.

[0076] 5. Uses of the composition The (meth)acrylate-modified polyolefin resin and the (meth)acrylate-modified polyolefin resin composition can be used as a primer, an adhesive, a paint binder, an ink binder, and the like. EXAMPLES

[0077] 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." The temperature conditions in the following description are at room temperature (25°C) unless otherwise specified, and the pressure conditions are at normal pressure (760 mmHg) unless otherwise specified.

[0078] [Production Example 1: Maleic anhydride modified polyolefin resin] 100 parts of polyolefin resin (propylene-1-butene random copolymer, propylene constituent unit content: 64% by weight, 1-butene constituent unit content: 36% by weight, melting point: 76°C, weight average molecular weight: 287,000) produced using a metallocene catalyst as a polymerization catalyst, 2 parts of maleic anhydride (α,β-unsaturated carboxylic anhydride), 1.5 parts of S-lauryl methacrylate (mixture of lauryl methacrylate and tridecyl methacrylate) manufactured by Mitsubishi Gas Chemical Company, and 3 parts of di-tert-butyl peroxide (radical reaction initiator) were uniformly mixed and fed to a twin-screw extruder (L / D=60, diameter=15mm, 1st barrel to 14th barrel).

[0079] The reaction was carried out under the following conditions: residence time: 10 minutes, rotation speed: 200 rpm, barrel temperature: 100°C (1st and 2nd barrels), 200°C (3rd to 8th barrels), 90°C (9th and 10th barrels), 110°C (11th to 14th barrels). After that, the unreacted maleic anhydride was removed by a reduced pressure treatment, and maleic anhydride-modified polyolefin resin a was obtained. The maleic anhydride-modified polyolefin resin a obtained had a weight average molecular weight of 140,000 and a ring closure rate of 70%.

[0080] [Example 1: Preparation of acrylic modified polyolefin resin solution A-1] 100 parts of the maleic anhydride-modified polyolefin resin obtained in Production Example 1 was dissolved in a mixed solvent of 122 parts of methylcyclohexane and 122 parts of butyl acetate, and 1.3 parts of 2-(tert-butylamino)ethyl methacrylate as (A) (meth)acrylate compound was added at 100°C in a nitrogen atmosphere, and the mixture was held for 1.5 hours. After that, 66.7 parts of methyl methacrylate as (B) (meth)acrylate compound and 3.3 parts of NOF Corp.'s Perbutyl (registered trademark) O ((2-ethylhexanoyl) (tert-butyl) peroxide) as a radical reaction initiator were added, and the mixture was held for 5 hours. Then, a resin solution of acrylic-modified polyolefin resin A-1 was obtained with methylcyclohexane and butyl acetate, with a solid content of 25% and a final solvent composition of methylcyclohexane / butyl acetate = 50 / 50. The weight average molecular weight of resin A-1 was 117,000. The graft amount of the acrylic monomer in 100 parts of Resin A-1 was 21% by weight, and the graft efficiency was 50%.

[0081] [Example 2] The same procedure as in Example 1 was carried out except that the amount of methyl methacrylate added was adjusted so that the ratio (weight ratio) of the amount of acid-modified polyolefin resin a / methyl methacrylate added was 80 / 20, and a resin solution of acrylic-modified polyolefin resin A-2 was obtained. The weight average molecular weight of resin A-2 was 125,000. The graft amount of acrylic monomer in 100 parts of resin A-2 was 11.3% by weight, and the graft efficiency was 51%.

[0082] [Example 3] A resin solution of acrylic modified polyolefin resin A-3 was obtained in the same manner as in Example 2, except that methyl methacrylate, 2-methoxyethyl acrylate and methacrylic acid were used as the (B) (meth)acrylate compound in the weight percentages shown in Table 1. The weight average molecular weight of resin A-3 was 133,000. The graft amount of acrylic monomer in 100 parts of resin A-3 was 13.3 weight%, and the graft efficiency was 60%.

[0083] [Example 4] The same procedure as in Example 3 was carried out except that the solid content concentration was 20%, to obtain a resin solution of acrylic modified polyolefin resin A-4. The weight average molecular weight of resin A-4 was 133,000. The graft amount of acrylic monomer in 100 parts of resin A-4 was 13.3% by weight, and the graft efficiency was 60%.

[0084] [Comparative Example 1] The same procedure as in Example 1 was carried out except that modification with a (meth)acrylate compound was not performed, to obtain a resin solution of acrylic-modified polyolefin resin A-5. The weight average molecular weight of resin A-5 was 110,000. The graft amount of acrylic monomer in 100 parts of resin A-5 was 0.3% by weight, and the graft efficiency was 20%.

[0085] [Comparative Example 2] The same procedure as in Example 1 was carried out except that the addition of 2-(tert-butylamino)ethyl methacrylate and the subsequent retention were omitted, and o-xylene was used as the solvent, to obtain a resin solution of acrylic modified polyolefin resin A-6. The weight average molecular weight of resin A-6 was 146,000. The graft amount of acrylic monomer in 100 parts of resin A-5 was 4.9% by weight, and the graft efficiency was 23%.

[0086] [Table 1]

[0087] [Table 1 Footnotes] a: Acid-modified polyolefin resin a prepared in Production Example 1 x: 2-(tert-butylamino)ethyl methacrylate MMA: Methyl methacrylate 2MTA: 2-Methoxyethyl acrylate MAA: Methacrylic acid MCH: Methylcyclohexane

[0088] [Measurement method] -Weight average molecular weight (Mw)- Measurement was performed by GPC under the following conditions. Equipment: HLC-8320GPC (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: 1mL / min Temperature: Pump oven, column oven 40℃ Injection volume: 100μL Standard material: Polystyrene EasiCal PS-1 (Agilent Technology)

[0089] -Maleic anhydride graft amount (modification degree)- The degree of modification was calculated according to the following procedure in accordance with JIS K-0070 (1992). Approximately 0.5 g of the modified polyolefin resin and approximately 100 g of toluene were weighed and placed in a 300 ml separable flask equipped with a cooling tube and a thermometer, and stirred and dissolved while heating on a hot stirrer so that the internal temperature reached 80° C. After the resin was dissolved, 15 ml of methanol was added and held for 5 minutes, 5 to 6 drops of an indicator (1% phenolphthalein-methanol solution) were added, and titration was performed with 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 (weight % when the weight of the raw material unmodified polyolefin resin is taken as 100 weight %), B represents the titration amount (ml) of potassium hydroxide-ethanol solution, f represents the factor of 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.

[0090] -Graft amount (modification degree) of (meth)acrylate compound- 2 g of a weighed (meth)acrylate-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 recovered by filtration was dissolved in toluene to obtain a solution with a solid content of 10%.

[0091] The obtained solution was subjected to FT-IR measurement, and the following peak area ratio was applied to a calibration curve to calculate the degree of modification (graft amount) of the (meth)acrylate compound. Peak area ratio value = 1730 cm -1 Peak area / 1450cm -1 Peak area of 1730cm -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 amount (wt %) of the (meth)acrylate compound can be calculated from the above area ratio value.

[0092] - Grafting efficiency - 1 part by weight of each (meth)acrylate-modified polyolefin resin was dissolved in 5 parts by weight of toluene, and then washed with 100 parts by weight of acetone. Then, FT-IR measurement was performed on each of the (meth)acrylate-modified polyolefin resins before and after washing, and the weight of the (meth)acrylate compound contained in each was calculated.

[0093] [Test Example 1: Solution Stability Test] Each resin solution of the acrylic modified polyolefin resins A-1 to A-6 placed in a glass bottle was allowed to stand in a refrigerator set at 5° C., and the solution properties were visually evaluated after a predetermined time.

[0094] Evaluation criteria "Good": The liquid remains the same as it was immediately after production, and no solidification or thickening is observed. "Good △": The liquid remains almost the same as immediately after production, but some viscosity increase is observed. "X": Completely solidified and not suitable for practical use

[0095] [Test Example 2: Heat seal test] Each resin solution of acrylic modified polyolefin resins A-1 to A-6 was applied to the non-glossy side of an aluminum film (Nikkin Glossy OP Coat, 20 μm) using a Meyer bar #10 and dried with hot air. The films were then laminated and heat sealed using the following procedure to prepare test specimens.

[0096] CPP / AL: After laminating the coated aluminum film to a CPP film (Idemitsu Kosan Super Pure Ray, 0.25 mm), heat sealing was performed at a temperature of 140°C and a pressure of 2 kgf / cm for 3 seconds, or at a temperature of 200°C and a pressure of 1 kgf / cm for 1 second.

[0097] The heat-sealed test piece was left to stand at 25°C and 50% humidity for at least 2 days, and then a Tensilon tensile tester was used to perform a peel test by pulling one of the films of the test piece (the aluminum surface of CPP / Al) in the 180° direction.

[0098] [Table 2]

[0099] Evaluation criteria (CPP / Al) "A": Peel strength exceeds 8N / 15mm. "B": Peel strength is 7N / 15mm or more and 8N / 15mm or less "C": Peel strength is below 7N / 15mm

[0100] Compared with Comparative Examples 1 and 2, which did not use a (meth)acrylic compound, each of the resins in Examples 1 to 4 exhibited good peel strength under each temperature condition in the heat seal test and had good solution stability (Table 2). These results show that the (meth)acrylate-modified polyolefin resin and its composition of the present invention can exhibit high adhesion to substrates such as metals and resins, and can also exhibit good solution stability.

Claims

1. A modified polyolefin resin into which a modifying component containing an α,β-unsaturated carboxylic acid or a derivative thereof has been introduced, (A) a (meth)acrylate compound having an amino group, and (B) (Meth)acrylate compound having no amino group are graft-bonded in this order.

2. 2. The (meth)acrylate-modified polyolefin resin according to claim 1, wherein the graft efficiency of the (meth)acrylate compound calculated by the following formula (1) is 30% or more. Graft efficiency = (weight of (meth)acrylate compound contained in the resin after washing the (meth)acrylate-modified polyolefin resin with 50 parts by weight or more of acetone at 25°C / weight of unwashed (meth)acrylate-modified polyolefin resin) x 100 ... (1)

3. 3. The (meth)acrylate-modified polyolefin resin according to claim 1, wherein the graft amount of the (meth)acrylate compound is 5% by weight or more based on the weight of the unmodified polyolefin resin.

4. A (meth)acrylate-modified polyolefin resin composition comprising the resin according to claim 1 or 2 and a solvent.

5. The composition of claim 4 , wherein the solvent comprises an alcohol-based solvent and / or an ester-based solvent.

6. The (meth)acrylate-modified polyolefin resin composition according to claim 5, wherein the total amount of the alcohol-based solvent and the ester-based solvent contained in the solvent is 40% by weight or more.

7. The (meth)acrylate-modified polyolefin resin composition according to claim 4, having a solids content of 30% by weight or less.

8. A paint, binder, adhesive, or ink comprising the (meth)acrylate-modified polyolefin resin composition according to claim 4.

9. Step (1): A step of modifying a polyolefin resin with a modifying component containing an α,β-unsaturated carboxylic acid or a derivative thereof to obtain a modified polyolefin resin; and Step (2): A step of grafting (A) a (meth)acrylate compound having an amino group and (B) a (meth)acrylate compound not having an amino group in this order onto the modified polyolefin resin obtained in step (1) to obtain a (meth)acrylate-modified polyolefin resin. The method for producing the (meth)acrylate-modified polyolefin resin according to claim 1 or 2, comprising:

10. Step (1): A step of modifying a polyolefin resin with a modifying component containing an α,β-unsaturated carboxylic acid or a derivative thereof to obtain a modified polyolefin resin; and Step (2): A step of grafting (A) an amino group-containing (meth)acrylate compound and (B) a (meth)acrylate compound in this order onto the modified polyolefin resin obtained in step (1) to obtain a (meth)acrylate-modified polyolefin resin; and Step (3): A step of adding a solvent to the (meth)acrylate-modified polyolefin resin obtained in step (2) to obtain a resin solution. A method for producing the (meth)acrylate-modified polyolefin resin composition according to claim 4, comprising:

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