JP2019210359A - Modified polyolefin-based resin and its production method - Google Patents

Abstract

To improve the detergency when cleaning the inside of a coating machine with a cleaning solvent containing water.SOLUTION: A modified polyolefin-based resin is a modified polyolefin-based resin obtained by modifying a polyolefin resin (I) with α,β-unsaturated carboxylic acid or its derivative (II) and aminoalcohol (III) having primary or secondary amino group, when a peak height derived from an amino bond observed in infrared spectroscopy measurement is set to A, and a peak height derived from a methylene bond is set to B, a peak height ratio A/B×100 is 2.0% or larger.SELECTED DRAWING: None

Description

  The present invention relates to a modified polyolefin resin and a method for producing the same.

  Patent Document 1 discloses an ethylene compound-unsaturated carboxylic acid copolymer (B) 1 to 60 containing 40 to 99 parts by weight of a polyolefin resin (A) and 0.1 to 50% by mass of an unsaturated carboxylic acid derivative. A mixed resin consisting of parts by weight is graft-modified with an unsaturated carboxylic acid derivative and / or its anhydride (C), and has a weight average molecular weight of 20,000 to 150,000 and a graft weight of (C) of 0.00. The modified polyolefin resin composition which is 1-20 mass% is described.

JP 2001-279048 A

  A film-forming composition may be prepared using the modified polyolefin resin composition of Patent Document 1, and a film of the film-forming composition may be formed by a coating machine. In this case, after the coating machine is used, the coating film-forming composition and the modified polyolefin resin composition in a film-formed state remain in the coating machine, and it is necessary to wash them. However, when cleaning with a cleaning solvent containing water, there is room for improvement in cleaning properties.

  Then, an object of this invention is to provide the modified polyolefin resin which can improve the washability at the time of washing | cleaning the inside of a coating machine with the washing | cleaning solvent containing water.

  As a result of intensive studies, the present inventors have found that the above-mentioned problems can be solved by a modified polyolefin resin obtained by modifying a polyolefin resin with a specific modifying component, and completed the present invention.

That is, the present invention provides the following.
[1] A modified polyolefin resin obtained by modifying a polyolefin resin (I) with an α, β-unsaturated carboxylic acid or derivative thereof (II) and an amino alcohol (III) having a primary or secondary amino group. Because
The peak height ratio A / B × 100 is 2.0% or more, where A is the peak height derived from the amide bond and B is the peak height derived from the methylene bond observed in the infrared spectrum measurement. A modified polyolefin resin.
[2] The polyolefin resin (I) is at least one selected from the group consisting of polypropylene, ethylene-propylene copolymer, propylene-1-butene copolymer, and ethylene-propylene-1-butene copolymer. The modified polyolefin resin according to [1].
[3] The α, β-unsaturated carboxylic acid or derivative (II) thereof is at least one selected from the group consisting of maleic anhydride, itaconic anhydride, and maleic acid, [1] or [2] The modified polyolefin resin described in 1.
[4] The modified polyolefin resin has any one of [1] to [3], which has a weight average molecular weight of 10,000 to 200,000 as measured by gel permeation chromatography (GPC) according to polystyrene standards. The modified polyolefin resin described in 1.
[5] A primer comprising the modified polyolefin resin according to any one of [1] to [4].
[6] A paint containing the modified polyolefin resin according to any one of [1] to [4].
[7] An ink comprising the modified polyolefin resin according to any one of [1] to [4].
[8] An adhesive comprising the modified polyolefin resin according to any one of [1] to [4].
[9] When the peak height derived from the amide bond observed in the infrared spectroscopic spectrum measurement is A and the peak height derived from the methylene bond is B, the peak height ratio A / B × 100 is 2.0. % Is a method for producing a modified polyolefin resin,
Modifying the polyolefin resin (I) with an α, β-unsaturated carboxylic acid or derivative thereof (II) and an amino alcohol (III) having a primary or secondary amino group to obtain a modified polyolefin resin; A method for producing a modified polyolefin resin.

  According to the modified polyolefin resin of the present invention, it is possible to improve the cleaning performance when cleaning the interior of the coating machine with a cleaning solvent containing water.

<Modified polyolefin resin>
The modified polyolefin resin of the present invention is obtained by modifying a polyolefin resin (I) with an α, β-unsaturated carboxylic acid or derivative thereof (II) and an amino alcohol (III) having a primary or secondary amino group. It becomes. In the present specification, the α, β-unsaturated carboxylic acid or derivative thereof (II) and amino alcohol (III) having a primary or secondary amino group are also referred to as component (II) and component (III), respectively.

  Specifically, in the modified polyolefin resin of the present invention, component (II) is graft-polymerized to polyolefin resin (I). Furthermore, it is considered that an amide bond in which a carbonyl group derived from component (II) and a nitrogen atom derived from component (III) are bonded to each other at the graft polymerization site of component (II). Therefore, in the modified polyolefin resin of the present invention, it is considered that the hydroxyl group derived from the component (III) is introduced into the polyolefin resin (I) via the graft polymerization site of the component (II).

Moreover, it can also confirm from the infrared spectroscopy measurement that the hydroxyl group derived from component (III) is introduce | transduced in the modified polyolefin resin of this invention. That is, an amide bond-derived peak is observed in the infrared spectrum of the modified polyolefin resin of the present invention. Here, the peak derived from the amide bond is a peak appearing at wave numbers 1610 to 1680 cm ⁻¹ , and is attributed to C═O stretching vibration.

In the infrared spectrum of the modified polyolefin resin of the present invention, a peak derived from the methylene bond of the polyolefin resin (I) skeleton is also observed. Here, the peak derived from the methylene bond is a peak appearing at wave numbers 1420 to 1500 cm ⁻¹ and is attributed to C—H bending vibration. In the infrared spectroscopic spectrum, when the peak height derived from the amide bond is A and the peak height derived from the methylene bond is B, from the peak height ratio A / B × 100, the component ( The added amount of III) can be evaluated.

  That is, in the infrared spectrum, when the peak height derived from the amide bond is A and the peak height derived from the methylene bond is B, the lower limit of the peak height ratio A / B × 100 is 2.0%. Or more, preferably 3.0% or more, and more preferably 5.0% or more. When the peak height ratio A / B × 100 is in the above range, it can be said that the modified polyolefin resin of the present invention has hydroxyl groups introduced in a preferred amount.

  By the way, the film forming composition containing the modified polyolefin resin of the present invention may be prepared, and the film of the film forming composition may be formed by a coating machine. In this case, after the use of the coating machine, the film forming composition and the modified polyolefin resin in a film-formed state remain in the coating machine, and these need to be washed. Since the modified polyolefin resin of the present invention has hydroxyl groups introduced in a preferred amount, it is excellent in cleanability when the inside of the coating machine is cleaned with a cleaning solvent containing water. This is presumed to be due to the fact that even a modified polyolefin resin in a film-formed state has a hydroxyl group on the surface of the coating, so that affinity with a cleaning solvent containing water is ensured.

  Moreover, using the composition for film formation containing the modified polyolefin resin of the present invention as a primer, an overcoat layer may be provided on the film obtained from the primer by an overcoat paint. As the top coating material, a urethane resin-based coating material is preferably used. This urethane resin-based coating usually includes a main component such as a polyol having a plurality of hydroxyl groups and a curing agent component such as isocyanate. When these are heated in the baking process, they undergo a crosslinking reaction to form urethane bonds. Since the modified polyolefin-based resin of the present invention has a hydroxyl group introduced in a preferable amount, this hydroxyl group may cause a crosslinking reaction with the above-mentioned curing agent component in the top coat at the coating interface. Thereby, the adhesiveness of a top coat layer and water-resistant adhesiveness can improve. Or even if it does not raise | generate a crosslinking reaction, the affinity with the urethane coating which is a polar substance improves by the hydroxyl group which is a polar group, and the adhesiveness of a topcoat layer and water-resistant adhesiveness can improve. Thus, when the modified polyolefin resin of the present invention is used as a primer, the coating performance of the topcoat layer can be improved.

  In the infrared spectroscopic spectrum, the upper limit of the peak height ratio A / B × 100 is preferably 15% or less, and more preferably 10% or less. When the peak height ratio A / B × 100 is in the above range, it can be said that hydroxyl groups are introduced in a more preferable amount into the modified polyolefin resin of the present invention. If the peak height ratio A / B × 100 exceeds the above range, the polarity of the modified polyolefin resin becomes too high due to the addition of hydroxyl groups, and the adhesion to nonpolar resin substrates such as polyolefin substrates is sufficient. Since there is a possibility of disappearing, it is preferable to be within the above range in consideration of the balance of adhesion to both the base material and the topcoat layer.

  The modified polyolefin resin of the present invention preferably has a weight average molecular weight of 10,000 to 200,000, preferably 30,000 to 150,000, as measured by gel permeation chromatography (GPC) using polystyrene standards. It is more preferable.

[Polyolefin resin (I)]
The polyolefin resin (I) used in the present invention is not particularly limited and may be a homopolymer of one olefin or a copolymer of two or more olefins. The copolymer may be a random copolymer or a block copolymer. As the olefin, an α-olefin is preferably used. Examples of the α-olefin include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, and 1-octene.

  As the polyolefin resin (I), polypropylene (propylene homopolymer), ethylene-propylene copolymer, propylene-1-, from the viewpoint of developing sufficient adhesion to a nonpolar resin substrate such as a polypropylene substrate. A butene copolymer and an ethylene-propylene-1-butene copolymer are more preferably used.

  In addition, in this specification, a polypropylene represents the polymer whose basic unit is a structural unit derived from propylene. An ethylene-propylene copolymer represents a copolymer whose basic unit is a structural unit derived from ethylene and propylene. The propylene-butene copolymer represents a copolymer whose basic unit is a structural unit derived from propylene and butene. These polymers may contain a small amount of structural units derived from olefins other than the above basic units. This content may be an amount that does not significantly impair the original performance of the resin. Such structural units derived from other olefins may be mixed in, for example, the process up to the production of the modified polyolefin resin.

  The polyolefin resin (I) preferably contains 60 mol% or more of propylene-derived structural units in 100 mol% of the structural units. When the structural unit derived from propylene is included in the above range, the adhesiveness to a nonpolar resin molded product such as propylene resin can be maintained.

  The polyolefin resin (I) is preferably obtained using a metallocene catalyst as a polymerization catalyst.

A well-known thing can be used as a metallocene catalyst. The metallocene catalyst is preferably obtained by combining the components (1) and (2) described below and (3) if necessary.
Component (1); a metallocene complex which is a transition metal compound of Groups 4 to 6 of the periodic table having at least one conjugated five-membered ring ligand;
-Component (2); ion-exchangeable layered silicate;
Component (3): an organoaluminum compound.

  Polyolefin resin (I) obtained using a metallocene catalyst has a narrow molecular weight distribution. Moreover, when polyolefin resin (I) is a copolymer, it is excellent in random copolymerizability, has a narrow composition distribution, and further has a wide range of comonomers that can be copolymerized. The polyolefin resin (I) having these characteristics is preferably used in the present invention.

  When the ethylene-propylene copolymer and the propylene-butene copolymer are random copolymers, the structural unit derived from ethylene or the structural unit derived from butene in an amount of 5 to 50 mol% in 100 mol% of the structural unit. Including propylene-derived structural units in an amount of 50 to 95 mol%.

  The molecular weight of the polyolefin resin (I) is not particularly limited. However, as described above, the weight average molecular weight of the modified polyolefin resin is preferably 10,000 to 200,000, more preferably 30,000 to 150,000. For this reason, when the weight average molecular weight of polyolefin resin (I) is 200,000 or more, it is preferable to adjust so that the weight average molecular weight of the modified polyolefin resin obtained may become the said range. Specifically, it is degraded in the presence of heat or radicals, and the molecular weight is adjusted to an appropriate range, for example, 200,000 or less. In the present specification, the weight average molecular weight is a value measured by gel permeation chromatography (GPC, standard substance: polystyrene).

  Polyolefin resin (I) may be used individually by 1 type, or may be used in combination of 2 or more type. When two or more types are used in combination, the ratio is not particularly limited.

[Α, β-unsaturated carboxylic acid or derivative (II) (component (II))]
Among the components (II), examples of the α, β-unsaturated carboxylic acid include fumaric acid, maleic acid, itaconic acid, mesaconic acid, citraconic acid, aconitic acid, and nadic acid. Of these, unsaturated dicarboxylic acids are preferred. In addition, among the components (II), α, β-unsaturated carboxylic acid derivatives include acid anhydrides of the α, β-unsaturated carboxylic acid, monomethyl fumarate, monoethyl fumarate, monopropyl fumarate, Monobutyl fumarate, dimethyl fumarate, diethyl fumarate, dipropyl fumarate, dibutyl fumarate, monomethyl maleate, monoethyl maleate, monopropyl maleate, monobutyl maleate, dimethyl maleate, diethyl maleate, dipropyl maleate, malein Examples include dibutyl acid, maleimide, and N-phenylmaleimide. Of these, acid anhydrides are preferred.

  As the component (II), maleic anhydride, itaconic anhydride, and maleic acid are more preferably used from the viewpoint of introducing a hydroxyl group in a preferred amount into the modified polyolefin resin, that is, from the viewpoint of improving the detergency. Maleic anhydride is more preferably used.

  Component (II) is at least one selected from the group consisting of α, β-unsaturated carboxylic acids and derivatives thereof. As the component (II), an α, β-unsaturated carboxylic acid may be used alone, or the above derivatives may be used alone. Two or more α, β-unsaturated carboxylic acids may be used in combination, or two or more of the above derivatives may be used in combination. Further, one or more α, β-unsaturated carboxylic acids and one or more derivatives thereof may be used in combination. When two or more types are used in combination, the ratio is not particularly limited.

[Amino alcohol (III) (component (III))]
Component (III) has a primary or secondary amino group together with a hydroxyl group. Component (III) preferably has a primary amino group.

  As component (III), 2-aminoethanol, 3-amino-1-propanol, 4-amino-1-butanol, 5-amino-1-pentanol, 2-amino-1-butanol, 2-amino-2 -Methyl-1-propanol, 2-amino-2-methyl-1,3-propanediol, 2-methylamino-2-methyl-1-propanol, N-aminoethylethanolamine, 2- (2-aminoethoxy) Ethanol is mentioned. Of these, 2-aminoethanol, 2- (2-aminoethoxy) ethanol, 3-amino-propanol, 4-amino-1-butanol, and 2-amino-2-methyl-1-propanol are preferably used. .

  Component (III) may be used alone or in combination of two or more. When two or more types are used in combination, the ratio is not particularly limited.

[Method for producing modified polyolefin resin]
In the method for producing the modified polyolefin resin, the polyolefin resin (I) is modified with α, β-unsaturated carboxylic acid or a derivative thereof (II) and an amino alcohol (III) having a primary or secondary amino group. And a step of obtaining a modified polyolefin resin.

  The method for producing the modified polyolefin resin is not particularly limited as long as the modified polyolefin resin can be produced. However, the above-described steps are specifically the step (A) in which the polyolefin resin (I) is modified with the component (II) to obtain an acid-modified polyolefin resin, and the resulting acid-modified polyolefin resin is converted into the component (III). ) To obtain a modified polyolefin-based resin (B). Such a manufacturing method will be described in detail below.

  In the step (A) for obtaining the acid-modified polyolefin resin, the component (II) may be introduced into the polyolefin resin (I), and the component (II) is preferably introduced into the polyolefin resin (I) by graft polymerization. In the graft polymerization reaction, a radical generator may be used. As the step (A) for obtaining the acid-modified polyolefin resin, for example, a solution method in which the component (II) is heated and dissolved in a solvent such as toluene and a radical generator is added; Examples thereof include a melt-kneading method in which component (II) and a radical generator are added and kneaded. Here, when using 2 or more types of components (II), these may be added collectively or may be added sequentially. In the case of sequential addition, the order of which component (II) is first graft polymerized is not particularly limited. Moreover, when using 2 or more types of component (II), the ratio is not specifically limited.

  In the graft polymerization reaction, the component (II) is used in an amount of 0.5 to 20 parts by mass with respect to 100 parts by mass of the polyolefin resin (I) from the viewpoint of grafting the component (II) in a preferable amount. It is preferable.

  The radical generator can be appropriately selected from known ones, but organic peroxide compounds are preferred. Examples of organic peroxide compounds include di-t-butyl peroxide, dicumyl peroxide, t-butyl cumyl peroxide, benzoyl peroxide, dilauryl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, 1,1-bis (t-butylperoxy) -3,5,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) -cyclohexane, cyclohexanone peroxide, t-butylperoxybenzoate, t- Butyl peroxyisobutyrate, t-butyl peroxy-3,5,5-trimethylhexanoate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxyisopropyl carbonate, cumyl peroxy octoate 2,5-dimethyl- 5- bis (t-butylperoxy) hexane and the like. Of these, di-t-butyl peroxide, dilauryl peroxide, and 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane are preferable.

  The addition amount of the radical generator is preferably 1% by mass or more, more preferably 3% by mass or more, with respect to 100% by mass in total of the component (II) to be used. A graft ratio can be maintained as it is 1 mass% or more. The upper limit of the addition amount is preferably 100% by mass or less, more preferably 50% by mass or less. When it is 100% by mass or less, it is economical.

  In the step (A) for obtaining the acid-modified polyolefin resin, the component (II) that is not graft-polymerized to the polyolefin resin (I), that is, the unreacted product may be removed by extraction with a poor solvent, for example.

  Thus, an acid-modified polyolefin resin is obtained by the step (A). The graft amount of component (II) is not particularly limited, but is preferably more than 0% by mass and less than 20% by mass, more than 0% by mass and less than 10% by mass with respect to 100% by mass of the acid-modified polyolefin resin. preferable. The graft amount is determined by alkali titration method or Fourier transform infrared spectroscopy. When the graft amount is in the above range, the hydroxyl group can be introduced in a more preferable amount with respect to the finally obtained modified polyolefin resin. Therefore, the detergency can be further improved.

  The acid-modified polyolefin resin obtained in the step (A) has a weight average molecular weight measured by gel permeation chromatography (GPC) based on polystyrene standards so that the weight average molecular weight of the modified polyolefin resin is in the above-described preferred range. It is preferable that it is 10,000-200,000. The acid-modified polyolefin resin preferably has a melting point of 50 to 150 ° C. measured by a differential scanning calorimeter (DSC). The acid-modified polyolefin resin preferably has an acid value measured by an alkali titration method of 5 to 50 mgKOH / g. When the acid value is in the above range, hydroxyl groups can be introduced in a more preferable amount with respect to the finally obtained modified polyolefin resin. Therefore, the detergency can be further improved.

  In the step (B) of obtaining the modified polyolefin resin, the acid-modified polyolefin resin obtained in the step (A) is heated and stirred at a temperature equal to or higher than the melting point, usually 50 to 200 ° C., and then the component (III) is added. . Thereby, a modified polyolefin resin is obtained. That is, it is considered that an amide bond in which a carbonyl group derived from the component (II) and a nitrogen atom derived from the component (III) are bonded to each other at the graft polymerization site of the component (II). Or it is thought that the ammonium salt of carboxylic acid produces | generates by component (III) in the graft polymerization location of component (II). Thus, in the modified polyolefin resin, it is considered that the hydroxyl group derived from the component (III) is introduced through the graft polymerization site of the component (II).

  More specifically, in the step (B) of obtaining the modified polyolefin resin, the modified polyolefin resin may be prepared as an aqueous dispersion composition in which the modified polyolefin resin is dispersed in an aqueous dispersion medium. In this case, first, the acid-modified polyolefin resin obtained in the step (A) is added to an organic solvent such as toluene or xylene to obtain a mixed solution.

You may add an amphiphilic solvent to this liquid mixture further. The amphiphilic solvent is, for example, a compound represented by the following general formula (1).
_{R-O- (C l H 2l} O) m H (1)

In the formula (1), R is C _n H _{2n + 1, n} is 1 to 10 integer. n is preferably 8 or less, more preferably 7 or less, further preferably 6 or less, particularly preferably 5 or less, and particularly preferably 4 or less. l is an integer of 1 to 5. l is preferably an integer of 4 or less, more preferably an integer of 3 or less, further preferably an integer of 2 or less, and particularly preferably 1.

  The compound represented by the general formula (1) has a structure in which a glycol alkyl group is ether-bonded, and has a hydrophobic group and a hydrophilic group in one molecule. For this reason, when an amphiphilic solvent is added, the modified polyolefin resin can be easily dispersed and emulsified in water, and the resulting aqueous dispersion composition exhibits good storage stability.

  Examples of the compound represented by the general formula (1) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, ethylene glycol mono -T-butyl ether, ethylene glycol monohexyl ether, ethylene glycol monodecyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether. Among these, ethylene glycol monobutyl ether (butyl cellosolve), propylene glycol monomethyl ether, and propylene glycol monopropyl ether are preferable, and ethylene glycol monobutyl ether and propylene glycol monopropyl ether are more preferable.

  The molecular weight of the compound represented by the general formula (1) is less than 200. Thereby, the raise of the boiling point of the obtained water dispersion composition is suppressed, and after producing a film using this composition, high temperature drying or long-time drying of a film can be omitted. The molecular weight of the compound represented by the general formula (1) is a molecular weight obtained from a relative atomic mass approved by the IUPAC atomic weight committee and set to 12C = 12.

  An amphiphilic solvent may be used individually by 1 type, or may be used in combination of 2 or more type. When two or more types are used in combination, the ratio is not particularly limited.

  The mixed solution is usually heated and stirred at 50 to 200 ° C. for a predetermined time.

  Next, the component (III) is further added to the heated and stirred liquid mixture, and the mixture is heated and stirred for a predetermined time. Next, a surfactant or an amphiphilic solvent may be added and heated and stirred for a predetermined time. Component (III) is preferably used in an amount of 1 to 20 parts by mass with respect to 100 parts by mass of the acid-modified polyolefin resin from the viewpoint of introducing a hydroxyl group in a preferable amount.

  As the surfactant, any of a nonionic surfactant and an anionic surfactant can be used. The nonionic surfactant is preferably used because the water dispersion of the resulting aqueous dispersion composition becomes better.

  Nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkylene alkyl ether, polyoxyethylene derivatives, polyoxyethylene fatty acid ester, polyoxyethylene polyhydric alcohol fatty acid ester, polyoxyethylene propylene polyol, polyoxyethylene sorbitan Examples include fatty acid esters, polyoxyethylene hydrogenated castor oil, polyoxyalkylene polycyclic phenyl ether, polyoxyethylene alkylamine, alkylalkanolamide, and polyalkylene glycol (meth) acrylate. Of these, polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and polyoxyethylene alkylamine are preferable.

  As an anionic surfactant, alkyl sulfate ester salt, polyoxyethylene alkyl ether sulfate, alkylbenzene sulfonate, α-olefin sulfonate, methyl taurate, sulfosuccinate, ether sulfonate, ether carboxylate, Examples include fatty acid salts, naphthalenesulfonic acid formalin condensates, alkylamine salts, quaternary ammonium salts, alkylbetaines, and alkylamine oxides. Of these, polyoxyethylene alkyl ether sulfate and sulfosuccinate are preferred.

  Next, after making the said liquid mixture normally into less than 100 degreeC, water, Preferably hot water is added. Further, the solid content may be prepared by distilling off the organic solvent or the amphiphilic solvent or adding water. The solid content of the aqueous dispersion composition is, for example, 15 to 50% by mass.

  In addition, when using an amphiphilic solvent when preparing an aqueous dispersion composition, the amphiphilic solvent is preferably 0.5% by mass or more, more preferably 1% by mass in the aqueous dispersion composition. Use in the amount of the above. In addition, the amphiphilic solvent is used in an amount of 15% by mass or less, more preferably 10% by mass or less in the aqueous dispersion composition. That is, the amphiphilic solvent is preferably used in an amount of 0.5 to 15% by mass, more preferably 1 to 10% by mass in the aqueous dispersion composition.

  Further, when a surfactant is used in preparing the aqueous dispersion composition, the amount of the surfactant added is preferably 0.1 to 30% by mass with respect to 100% by mass of the acid-modified polyolefin resin. More preferably, it is 3-20 mass%. When it exceeds 30 mass%, the film performance at the time of producing a film may be reduced by an excess emulsifier. Moreover, when it is set as a dry film, a plastic effect and a bleed phenomenon are caused and blocking may occur.

  For the modified polyolefin resin, the peak height ratio (A / B × 100) determined by infrared spectroscopic spectrum measurement is the solvent type, the stirring temperature of the mixed solution, and the stirring time when preparing the aqueous dispersion composition. Adjustments can be made by appropriate changes. Specifically, for example, if the stirring temperature is increased or the stirring time is increased, the formation of amide bonds is promoted and A / B × 100 increases. Further, when water is further added after the addition of component (III), the formation of an ammonium salt by component (III) can be promoted when component (III) that does not produce an amide bond is present. Thereby, the electrostatic repulsion effect of an ammonium salt can be promoted and the stability as an aqueous dispersion composition can be improved.

<Film-forming composition containing modified polyolefin resin>
The film forming composition containing the modified polyolefin resin contains the modified polyolefin resin of the present invention and, if necessary, other components. Specifically, the film-forming composition is preferably used as a primer, paint, ink, or adhesive.

  The film-forming composition may be, for example, a dispersion composition in which a modified polyolefin resin is dispersed in a dispersion medium. The dispersion medium may be non-aqueous or aqueous (aqueous dispersion composition). Examples of the non-aqueous solvent include organic solvents such as xylene, toluene, and benzene.

  Other components that may be blended in the film-forming composition include urethane resins, epoxy resins, acrylic resins, phenol resins, alkyd resins, polyamide resins, polyimide resins, silicone resins, and nitrified cotton. Can be mentioned. Other resins may be blended as an aqueous product.

  Furthermore, the components that may be blended in the film forming composition include aqueous acrylic resins, aqueous urethane resins, lower alcohols, lower ketones, lower esters, preservatives, leveling agents, antioxidants, and light stability. Agents, ultraviolet absorbers, dyes, pigments, metal salts, acids.

  Moreover, when the said film formation composition is a water dispersion composition, you may mix | blend a crosslinking agent as another component. The cross-linking agent means a compound that reacts with a hydroxyl group, a carboxy group, an amino group, or the like present in a modified polyolefin resin, a surfactant, component (III) or the like to form a cross-linked structure. Examples of the crosslinking agent include blocked isocyanate compounds, aliphatic or aromatic epoxy compounds, amine compounds, and amino resins. The addition method of a crosslinking agent is not specifically limited. For example, it may be added in the middle of the aqueous treatment step or after the aqueous treatment.

  When the film forming composition is an aqueous dispersion composition, the pH of the aqueous dispersion composition is preferably 5 or more, and more preferably pH 6-11. When the pH is less than 5, neutralization is insufficient and the modified polyolefin resin may not be dispersed in water. Moreover, even if dispersed, precipitation and separation are likely to occur over time, and storage stability may deteriorate. On the other hand, if the pH exceeds 11, problems with compatibility with other components and work safety may occur. pH can be adjusted with the quantity of the component (III) added when preparing an aqueous dispersion composition.

  When the film forming composition is an aqueous dispersion composition, the average particle size of the resin emulsified and dispersed in water is preferably 300 nm or less, more preferably 200 nm or less. When it exceeds 300 nm, the storage stability of the aqueous dispersion composition and the compatibility with other resins may deteriorate. In addition, physical properties of the film such as adhesion to a substrate, solvent resistance, water resistance, and blocking resistance when a film is formed may be deteriorated. In addition, when the addition amount of an emulsifier is increased, the particle diameter can be reduced as much as possible. However, in this case, film properties such as adhesion to the substrate, water resistance, and gas hole resistance tend to be reduced. In this specification, the average particle size is a value obtained by particle size distribution measurement using a light diffusion method. The particle size can be adjusted by the amount and type of emulsifier added, the stirring force when emulsifying the resin in water, and the like.

  By the way, polyolefin resins such as polypropylene resins and polyethylene resins are widely used as molded articles such as sheets and films because they are excellent in moldability, chemical resistance, water resistance, electrical characteristics and the like. However, unlike polar base materials such as polyurethane-based resins, polyamide-based resins, acrylic resins, and polyester-based resins, polyolefin-based resin base materials are nonpolar and have crystallinity. Is difficult to attach.

  As a method for improving adhesion, a method has been proposed in which a primer capable of adhering to a polyolefin resin is undercoated on the surface of a substrate, and a urethane resin coating or the like is applied on the undercoat layer. Conventionally, a modified polyolefin resin to which a polar group (carboxy group, acid anhydride group, etc.) is added is used for this primer. By adding a polar group, not only the polyolefin resin base material but also the affinity with the urethane resin paint is improved, and the adhesion is improved. Conventional modified polyolefin resins are usually applied in the form of an organic solvent solution or a dispersion in water. However, in recent years, an aqueous dispersion is preferably used from the viewpoint of safety and hygiene and reduction of environmental pollution.

  Conventional aqueous dispersions of modified polyolefin resins are widely used as primers for resin substrates such as automobile bumpers. This is because the movement to reduce health and safety and environmental pollution is expanding also in the automobile industry, and volatile organic compounds (VOC) generated from paint factories are reduced.

  In a painting factory, when a plurality of coating colors are applied with the same coating machine, the procedure of draining the paint in the coating machine, cleaning the coating path with thinner, and supplying the next coating color to the path is repeated. The paint and thinner discarded at the time of color change contribute to an increase in VOC emissions. For this reason, if the paint to be used can be easily cleaned with a thinner, it is possible to save the cleaning thinner and greatly contribute to VOC reduction.

  However, in general, a resin for a primer is required to have high film formability in order to improve the strength and finish of the coating film. With solvent-based paints, even if a resin film is formed in the coating machine, it can be washed away with cleaning thinner relatively easily. is there. For this reason, a mixed liquid of water and an ether solvent is used as a cleaning solvent. In this case, the affinity between the formed resin and the cleaning solvent is low, and the resin with improved film forming property deteriorates the cleaning performance, and a large amount of cleaning solvent must be used. Therefore, it has been difficult for conventional modified polyolefin resins to achieve both coating film performance and coating machine washability.

  On the other hand, according to the film-forming composition (specifically, the aqueous dispersion composition) using the modified polyolefin resin of the present invention, it is possible to improve the coating machine washability. Moreover, it is excellent also in coating-film performances, such as adhesiveness of a topcoat layer and water-resistant adhesion of a topcoat layer. That is, it is possible to achieve both coating film performance and coater washability. This is because, as described above, the modified polyolefin resin of the present invention has hydroxyl groups introduced in a preferable amount.

  More specifically, a film-forming composition (specifically, an aqueous dispersion composition) using the modified polyolefin resin of the present invention has a low adhesiveness and is difficult to apply a coating material such as a paint, for example, It can function as an intermediate medium for non-polar resin molded products. For example, it is also useful as an adhesive between polyolefin-based substrates such as polypropylene and polyethylene having poor adhesion. It can be used with or without surface treatment with plasma, corona or the like on the surface of a substrate such as a nonpolar resin molded product. It is also suitable for polar substrates such as polyesters such as polyethylene terephthalate, polyurethanes and polyamides. Therefore, as described above, the film-forming composition is suitably used as an adhesive, a primer, a paint binder, an ink binder, or the like.

  In addition, when the said film forming composition is a water dispersion composition, it can manufacture by the method demonstrated by the manufacturing method of the said modified polyolefin resin. Specifically, it can be produced by further blending the above-mentioned other components according to the intended use. Alternatively, the film forming composition may be produced by emulsifying the modified polyolefin resin of the present invention later. For example, it can be produced by a known method such as forced emulsification, phase inversion emulsification, D phase emulsification, or gel emulsification. Specifically, an organic solvent such as toluene or xylene and a surfactant or an amphiphilic solvent are mixed with a modified polyolefin resin, and water is added. When mixing components other than water, you may heat (for example, 50-200 degreeC) as needed. Next, the above-mentioned other components can be blended depending on the intended use. Here, the details of the surfactant and the amphiphilic solvent are as described in the method for producing the modified polyolefin resin.

[Example 1]
Anhydrous propylene-butene random copolymer [P-B] (propylene component 70 mol%, butene component 30 mol%) in a four-necked flask equipped with a stirrer, condenser, dropping funnel and nitrogen air supply tube Maleic acid [MAH] -modified polyolefin resin (weight average molecular weight [Mw] 70,000, Tm = 75 ° C., MAH grafting amount = 2-5% by mass) 60 g, toluene 9.6 g, ethylene glycol monobutyl ether (molecular weight = 18.2) 28.8 g was added, the air in the flask was replaced with nitrogen at room temperature, and the mixture was stirred for 30 minutes at 125 ° C. while maintaining the nitrogen. Next, after adding 4.3 g of 2-amino-2-methyl-1-propanol [AMP] and stirring for 120 minutes, an alkylamine emulsifier (trade name: Pureamyl (registered trademark)) at a flask internal temperature of 95 ° C. 3 g of CCS-80 (manufactured by Sanyo Chemical Industries, Ltd.) was added and stirred for 30 minutes. Then, 209 g of 90 ° C. deionized water was added over 120 minutes at a flask internal temperature of 75 ° C. After the addition of deionized water was completed, the flask was cooled with stirring until the temperature inside the flask reached 30 ° C. Subsequently, the flask was heated with stirring until the temperature inside the flask reached 95 ° C., and a part of toluene and ethylene glycol monobutyl ether was distilled off under reduced pressure. Then, it cooled, stirring to room temperature, and adjusted so that solid content might be 30 wt% with deionized water. As a result, an aqueous dispersion composition containing the modified polyolefin resin was obtained.

[Example 2]
Anhydrous propylene-butene random copolymer [P-B] (propylene component 80 mol%, butene component 20 mol%) in a four-necked flask equipped with a stirrer, condenser, dropping funnel and nitrogen air supply tube Maleic acid [MAH] modified polyolefin resin (weight average molecular weight [Mw] 70,000, Tm = 85 ° C., MAH grafting amount = 2 to 5% by mass) 60 g, toluene 9.6 g, ethylene glycol monobutyl ether (molecular weight = 18.2) 28.8 g was added, the air in the flask was replaced with nitrogen at room temperature, and the mixture was stirred for 30 minutes at 125 ° C. while maintaining the nitrogen. Next, 3 g of 2-amino-2-methyl-1-propanol [AMP] was added and stirred for 120 minutes, and then an alkylamine emulsifier (trade name: Pureamyl (registered trademark) CCS-) at a flask internal temperature of 95 ° C. 80, manufactured by Sanyo Chemical Industries, Ltd.) was added and stirred for 30 minutes. Then, 211 g of 90 ° C. deionized water was added over 120 minutes at a flask internal temperature of 75 ° C. After the addition of deionized water was completed, the flask was cooled with stirring until the temperature inside the flask reached 30 ° C. Subsequently, the flask was heated with stirring until the internal temperature of the flask reached 95 ° C., and a part of toluene and ethylene glycol monobutyl ether was distilled off under reduced pressure. Then, it cooled, stirring to room temperature, and adjusted so that solid content might be 30 wt% with deionized water. As a result, an aqueous dispersion composition containing the modified polyolefin resin was obtained.

Example 3
Anhydrous propylene-butene random copolymer [P-B] (propylene component 65 mol%, butene component 35 mol%) in a four-necked flask equipped with a stirrer, condenser, dropping funnel and nitrogen air supply tube Maleic acid [MAH] -modified polyolefin resin (weight average molecular weight [Mw] 100,000, Tm = 85 ° C., MAH grafting amount = 2-5% by mass) 60 g, toluene 9.6 g, ethylene glycol monobutyl ether (molecular weight = 18.2) 28.8 g was added, the air in the flask was replaced with nitrogen at room temperature, and the mixture was stirred for 30 minutes at 125 ° C. while maintaining the nitrogen. Next, 3 g of 2-amino-2-methyl-1-propanol [AMP] was added and stirred for 120 minutes, and then an alkylamine emulsifier (trade name: Pureamyl (registered trademark) CCS-) at a flask internal temperature of 95 ° C. 80, manufactured by Sanyo Chemical Industries, Ltd.) was added and stirred for 30 minutes. Then, 211 g of 90 ° C. deionized water was added over 120 minutes at a flask internal temperature of 75 ° C. After the addition of deionized water was completed, the flask was cooled with stirring until the temperature inside the flask reached 30 ° C. Subsequently, the flask was heated with stirring until the internal temperature of the flask reached 95 ° C., and a part of toluene and ethylene glycol monobutyl ether was distilled off under reduced pressure. Then, it cooled, stirring to room temperature, and adjusted so that solid content might be 30 wt% with deionized water. As a result, an aqueous dispersion composition containing the modified polyolefin resin was obtained.

Example 4
Anhydrous propylene-butene random copolymer [P-B] (propylene component 65 mol%, butene component 35 mol%) in a four-necked flask equipped with a stirrer, condenser, dropping funnel and nitrogen air supply tube Maleic acid [MAH] -modified polyolefin resin (weight average molecular weight [Mw] 120,000, Tm = 85 ° C., MAH grafting amount = 2-5% by mass) 60 g, toluene 9.6 g, ethylene glycol monobutyl ether (molecular weight = 18.2) 28.8 g was added, the air in the flask was replaced with nitrogen at room temperature, and the mixture was stirred for 30 minutes at 125 ° C. while maintaining the nitrogen. Next, 5.4 g of 2-amino-2-methyl-1-propanol [AMP] was added and stirred for 120 minutes, and then the alkylamine emulsifier (trade name: Pureamyl (registered trademark)) at a flask internal temperature of 95 ° C. 3 g of CCS-80 (manufactured by Sanyo Chemical Industries, Ltd.) was added and stirred for 30 minutes. Thereafter, 208 g of 90 ° C. deionized water was added over 120 minutes at a flask internal temperature of 75 ° C. After the addition of deionized water was completed, the flask was cooled with stirring until the temperature inside the flask reached 30 ° C. Subsequently, the flask was heated with stirring until the temperature in the flask reached 95 ° C., and a part of toluene and ethylene glycol monobutyl ether was distilled off under reduced pressure. Then, it cooled, stirring to room temperature, and adjusted so that solid content might be 30 wt% with deionized water. As a result, an aqueous dispersion composition containing the modified polyolefin resin was obtained.

[Comparative Example 1]
Maleic anhydride [MAH] modified polyolefin resin (weight average molecular weight [Mw] 70,000, Tm = 75 ° C., MAH grafting amount) in a four-necked flask equipped with a stirrer, condenser, dropping funnel, and nitrogen air supply tube = 2 to 5 mass%) 60 g, toluene 6.6 g, ethylene glycol monobutyl ether (molecular weight = 118.2) 19.8 g was added, and the flask was stirred for 30 minutes at 95 ° C. Next, 4.4 g of N, N-dimethylethanolamine [DMEA] was added and stirred for 30 minutes, and then an alkylamine emulsifier (trade name: Pureamyl (registered trademark) CCS-80, manufactured by Sanyo Chemical Industries, Ltd. ) 3g was added and stirred for another 30 minutes. Thereafter, 221 g of deionized water at 90 ° C. was added over 120 minutes. After the addition of deionized water was completed, a portion of toluene and ethylene glycol monobutyl ether was distilled off under reduced pressure. Then, it cooled, stirring to room temperature, and adjusted so that solid content might be 30 wt% with deionized water. This obtained the water dispersion composition containing acid-modified polyolefin resin.

[Comparative Example 2]
In a four-necked flask equipped with a stirrer, condenser, dropping funnel, and nitrogen air supply tube, maleic anhydride [MAH] modified polyolefin resin (weight average molecular weight [Mw] 70,000, Tm = 85 ° C., MAH graft amount = 2 to 5% by mass) 60 g, toluene 9.6 g, ethylene glycol monobutyl ether (molecular weight = 118.2) 28.8 g were added, and the flask was stirred at a temperature of 95 ° C for 30 minutes. Next, 3 g of N, N-dimethylethanolamine [DMEA] was added and stirred for 30 minutes, and then an alkylamine emulsifier (trade name: Pureamyl (registered trademark) CCS-80, manufactured by Sanyo Chemical Industries, Ltd.) 3 g Was added and stirred for an additional 30 minutes. Thereafter, 211 g of 90 ° C. deionized water was added over 120 minutes. After the addition of deionized water was completed, a portion of toluene and ethylene glycol monobutyl ether was distilled off under reduced pressure. Then, it cooled, stirring to room temperature, and adjusted so that solid content might be 30 wt% with deionized water. This obtained the water dispersion composition containing acid-modified polyolefin resin.

[Comparative Example 3]
Maleic anhydride [MAH] modified polyolefin resin (weight average molecular weight [Mw] 100,000, Tm = 85 ° C., MAH grafting amount) in a four-necked flask equipped with a stirrer, a condenser, a dropping funnel and a nitrogen gas feeding tube = 2 to 5 mass%) 60 g, toluene 12 g, and ethylene glycol monobutyl ether (molecular weight = 118.2) 36 g were added, and the mixture was stirred at a flask internal temperature of 95 ° C for 30 minutes. Next, 3 g of N, N-dimethylethanolamine [DMEA] was added and stirred for 30 minutes, and then an alkylamine emulsifier (trade name: Pureamyl (registered trademark) CCS-80, manufactured by Sanyo Chemical Industries, Ltd.) 3 g Was added and stirred for an additional 30 minutes. Thereafter, 257 g of deionized water at 90 ° C. was added over 120 minutes. After the addition of deionized water was completed, a portion of toluene and ethylene glycol monobutyl ether was distilled off under reduced pressure. Then, it cooled, stirring to room temperature, and adjusted so that solid content might be 30 wt% with deionized water. This obtained the water dispersion composition containing acid-modified polyolefin resin.

[Comparative Example 4]
Maleic anhydride [MAH] modified polyolefin resin (weight average molecular weight [Mw] 120,000, Tm = 85 ° C., MAH grafting amount) in a four-necked flask equipped with a stirrer, condenser, dropping funnel, and nitrogen air supply tube = 2 to 5 mass%) 60 g, toluene 12 g, and ethylene glycol monobutyl ether (molecular weight = 118.2) 36 g were added, and the mixture was stirred at a flask internal temperature of 95 ° C for 30 minutes. Next, 6 g of N, N-dimethylethanolamine [DMEA] was added, and after stirring for 30 minutes, 3 g of an alkylamine emulsifier (trade name: Pureamyl (registered trademark) CCS-80, manufactured by Sanyo Chemical Industries, Ltd.) Was added and stirred for an additional 30 minutes. Thereafter, 254 g of deionized water at 90 ° C. was added over 120 minutes. After the addition of deionized water was completed, a portion of toluene and ethylene glycol monobutyl ether was distilled off under reduced pressure. Then, it cooled, stirring to room temperature, and adjusted so that solid content might be 30 wt% with deionized water. This obtained the water dispersion composition containing acid-modified polyolefin resin.

[Method for measuring physical properties]
The weight average molecular weight, melting point, and acid value were measured using an acid-modified polyolefin resin. The infrared spectroscopic spectrum and the average particle size were measured using a modified polyolefin resin aqueous dispersion composition.
(1) Weight average molecular weight (Mw): Measured with GPC (manufactured by Tosoh Corporation, standard material: polystyrene resin).
(2) Melting point (Tm): Measured with DSC (manufactured by TA Instruments Japan Co., Ltd.).
(3) Acid value: determined by alkali titration method.
(4) Infrared spectroscopy spectrum: The modified polyolefin resin aqueous dispersion composition was dried at 40 ° C. for 24 hours, and the obtained dried product was dissolved in an organic solvent to obtain a solution. The above solution was applied to a KBr plate, dried to form a thin film, and measured with FT-IR (manufactured by JASCO Corporation). This ^gave the infrared absorption spectrum of the 400cm ^-1 ~4000cm -1. The analysis was performed using the attached software (Spectro Manager, JASCO Corporation).
Peak appearing in the wavenumber 1610～1680Cm ^-1 is assigned to a peak derived from an amide bond, a peak appearing in the wavenumber 1420～1500Cm ^-1 it is assigned to a peak derived from a methylene bond.
The peak height ratio A / B × 100 was determined with A as the peak height derived from the amide bond and B as the peak height derived from the methylene bond.
(5) Average particle size: Measured with a particle size distribution measuring device (manufactured by Malvern Instruments).

[Detergency test]
[Paint preparation]
The water-based urethane paint was stirred at about 1,000 rpm for 20 minutes using a disper. Thereafter, about 67 g of the paint is taken into a mayonnaise bottle, about 13 g of the modified polyolefin resin aqueous dispersion composition is added using a pipette while stirring at about 1,200 rpm, and then the test paint is stirred by stirring for 5 minutes. Obtained.
[Procedure of test]
In a temperature-controlled and humidity-controlled laboratory (23 ° C., 50% Rh), a test paint was applied to the base material (steel plate: high top) with a # 30 bar coater (target wet film thickness: 50 μm). After air drying for 60 minutes, it was immersed in a cleaning solvent (n-butyl cellosolve / deionized water = 30/70) for 5 minutes. Thereafter, the test piece was taken out and allowed to stand for 1 hour in a standing state, and the state of the coating film after standing was evaluated.
Evaluation was made according to the following criteria.
○: Paint film 3/4 or more peeled △: Paint film part (less than 3/4) peeled ×: No peeling

[Cross-cut adhesion test]
[Preparation of test piece]
The surface of the ultra-high-rigidity polypropylene plate was degreased with isopropyl alcohol, and the modified polyolefin resin aqueous dispersion composition was spray-coated so that the dried coating film had a thickness of 10 to 15 μm, and preheated at 80 ° C. for 5 minutes. Next, the base paint was spray-coated and allowed to stand for 10 minutes, after which a clear paint was applied and allowed to stand for 10 minutes. Then, the baking process for 30 minutes was performed at 90 degreeC, and the test piece was produced.
[Procedure of test]
After leaving the test piece to stand at room temperature for 3 days, 100 square grid-like cuts that reach the substrate at intervals of 2 mm were made on the coating film with a cutter knife, and the cellophane adhesive tape was stuck on top of it and the angle of 180 ° Was peeled 10 times, and the remaining coating film was determined. Specifically, the number of remaining cells was counted.

(Water adhesion test)
A test piece was prepared in the same manner as in the cross-cut adhesion test. After immersing the test piece in 40 ° C warm water for 10 days, visually observing the blister state of the coating surface (blister), and using a cutter knife to form a 100 grid pattern that reaches the substrate at 2 mm intervals A cut was made and a cellophane adhesive tape was applied thereon, and then peeled off at an angle of 180 °, and the degree of remaining coating was determined. Moreover, about the sample which did not peel all by this test, the same test was continuously performed 10 times and the residual of the coating film after 10 times peeling was determined. Specifically, the number of remaining cells was counted.
Blisters were evaluated according to the following criteria.
Diameter: (Large) 1-10 (Small)
Frequency: (small) F, FM, M, MD, D, DD (many)
○: No blister ×: With blister

  Table 1 shows the evaluation results for Examples and Comparative Examples.

Claims (9)

A modified polyolefin resin obtained by modifying a polyolefin resin (I) with an α, β-unsaturated carboxylic acid or derivative thereof (II) and an amino alcohol (III) having a primary or secondary amino group. ,
The peak height ratio A / B × 100 is 2.0% or more, where A is the peak height derived from the amide bond and B is the peak height derived from the methylene bond observed in the infrared spectrum measurement. A modified polyolefin resin.   The polyolefin resin (I) is at least one selected from the group consisting of polypropylene, ethylene-propylene copolymer, propylene-1-butene copolymer, and ethylene-propylene-1-butene copolymer. Item 2. A modified polyolefin resin according to Item 1.   The modified polyolefin according to claim 1 or 2, wherein the α, β-unsaturated carboxylic acid or derivative (II) thereof is at least one selected from the group consisting of maleic anhydride, itaconic anhydride, and maleic acid. Resin.   The modified polyolefin resin according to any one of claims 1 to 3, wherein the modified polyolefin resin has a weight average molecular weight of 10,000 to 200,000 as measured by gel permeation chromatography (GPC) according to polystyrene standards. Resin.   The primer containing the modified polyolefin resin of any one of Claims 1-4.   The coating material containing the modified polyolefin resin of any one of Claims 1-4.   The ink containing the modified polyolefin resin of any one of Claims 1-4.   The adhesive agent containing the modified polyolefin resin of any one of Claims 1-4. The peak height ratio A / B × 100 is 2.0% or more, where A is the peak height derived from the amide bond and B is the peak height derived from the methylene bond observed in the infrared spectrum measurement. A method for producing a modified polyolefin resin,
Modifying the polyolefin resin (I) with an α, β-unsaturated carboxylic acid or derivative thereof (II) and an amino alcohol (III) having a primary or secondary amino group to obtain a modified polyolefin resin; A method for producing a modified polyolefin resin.