JP2023146023A - Modified polyolefin resin composition - Google Patents

Abstract

To provide a modified polyolefin resin composition that has excellent adhesion and can show excellent emulsion stability regardless of the type of solvent.SOLUTION: A modified polyolefin resin composition includes a graft resin (IV) with a graft chain including (I) a constitutional unit derived from α,β-unsaturated carboxylic acid and a derivative thereof, (II) a constitutional unit derived from an amino alcohol with a primary or secondary amino group, and (III) a constitutional unit derived from a compound with an isocyanate group and an oxyalkylene group.SELECTED DRAWING: None

Description

The present invention relates to a modified polyolefin resin composition.

Aqueous modified polyolefin resin compositions modified with unsaturated carboxylic acids and/or their anhydrides are used as pre-painting agents or adhesives for hard-to-adhere substrates such as polyolefin resin substrates (for example, Patent Document 1).

Japanese Patent Application Publication No. 2017-160375

The quality of physical properties required of modified polyolefin resins is increasing. Under these circumstances, there is a desire to develop modified polyolefins that have even higher adhesion to difficult-to-adhere substrates.

The present invention was created in view of the above-mentioned problems, and it is an object of the present invention to provide a modified polyolefin resin composition that has good adhesion and can exhibit good emulsion stability regardless of the type of solvent. With the goal.

（一般式（１）中、
Ｒ^１は、オキシアルキレン基及び－ＮＨ－ＣＯＯ－で表される基を含む基であり、
Ｒ^２は、水素原子または炭素原子数１～２０のアルキル基であり、
Ｒ^３は、ポリオレフィン樹脂であり、
Ｒ^４は、炭素原子数１０以下のアルキル基であり、
Ａ^１Ｏは、同一若しくは異なっていてもよい、オキシアルキレン基であり、
ｎ１は、１以上の整数であり、
ａは、１以上の整数である。）

（一般式（２）中、
Ｒ^５は、水素原子またはアルキル基であり、
Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ａ^１Ｏ、ｎ１、ａは、一般式（１）と同様である。）
［５］ 水分散体組成物である、［１］～［４］のいずれか１項に記載の水分散体組成物。
［６］ グリコール系溶剤をさらに含む、［５］に記載の水分散体組成物。
［７］ アルキルエーテル系界面活性剤をさらに含む、［５］または［６］に記載の水分散体組成物。
［８］ ［１］～［４］のいずれか１項に記載の変性ポリオレフィン樹脂組成物を含む、塗料、バインダー、接着剤、インキ。
［９］ ［５］～［７］のいずれか１項に記載の水分散体組成物を含む、塗料、バインダー、接着剤、インキ。
［１０］ 以下の工程を含む、変性ポリオレフィン樹脂組成物の製造方法。
（ア）：ポリオレフィン樹脂を、（Ｉ）α，β－不飽和カルボン酸及びその誘導体で変性し、酸変性ポリオレフィン樹脂を得る工程
（イ）：得られる酸変性ポリオレフィン樹脂を、（ＩＩ）一級または二級のアミノ基を有するアミノアルコールで変性し、アミド化変性ポリオレフィン樹脂を得る工程
（ウ）：アミド化変性ポリオレフィン樹脂に、（ＩＩＩ）イソシアネート基及びオキシアルキレン基を有する化合物を反応させて、グラフト樹脂（ＩＶ）を含む変性ポリオレフィン樹脂組成物を得る工程 The present invention provides the following [1] to [10].
[1] (I) Constituent unit derived from α,β-unsaturated carboxylic acid and its derivatives,
(II) a structural unit derived from an amino alcohol having a primary or secondary amino group; and (III) a graft resin (IV) having a graft chain containing a structural unit derived from a compound having an isocyanate group and an oxyalkylene group. A modified polyolefin resin composition comprising.
[2] The modified polyolefin resin composition according to [1], wherein the compound having an isocyanate group and an oxyalkylene group further has a urea bond.
[3] The modified polyolefin resin composition according to [2], wherein the compound having an isocyanate group and an oxyalkylene group is a reaction product of a compound having an isocyanate group at both ends and an amine compound having a polyoxyalkylene group.
[4] The modified polyolefin resin composition according to any one of [1] to [3], wherein the modified polyolefin contains at least a modified polyolefin represented by the following general formula (1) or (2).

(In general formula (1),
R ¹ is a group containing an oxyalkylene group and a group represented by -NH-COO-,
R ² is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms,
R ³ is a polyolefin resin,
R ⁴ is an alkyl group having 10 or less carbon atoms,
A ¹ O is an oxyalkylene group which may be the same or different,
n1 is an integer of 1 or more,
a is an integer of 1 or more. )

(In general formula (2),
R ⁵ is a hydrogen atom or an alkyl group,
R ¹ , R ² , R ³ , R ⁴ , A ¹ O, n1, and a are the same as in general formula (1). )
[5] The aqueous dispersion composition according to any one of [1] to [4], which is an aqueous dispersion composition.
[6] The aqueous dispersion composition according to [5], further comprising a glycol solvent.
[7] The aqueous dispersion composition according to [5] or [6], further comprising an alkyl ether surfactant.
[8] A paint, binder, adhesive, or ink containing the modified polyolefin resin composition according to any one of [1] to [4].
[9] A paint, binder, adhesive, or ink containing the aqueous dispersion composition according to any one of [5] to [7].
[10] A method for producing a modified polyolefin resin composition, including the following steps.
(A): Step of modifying polyolefin resin with (I) α,β-unsaturated carboxylic acid and its derivative to obtain acid-modified polyolefin resin (B): Process of modifying the obtained acid-modified polyolefin resin with (II) primary or Process of obtaining an amidated modified polyolefin resin by modifying with an amino alcohol having a secondary amino group (c): Reacting the amidated modified polyolefin resin with (III) a compound having an isocyanate group and an oxyalkylene group to graft the resin. Step of obtaining a modified polyolefin resin composition containing resin (IV)

According to the present invention, a modified polyolefin resin composition having good emulsion stability and adhesion can be provided.

<Modified polyolefin resin composition>
The modified polyolefin resin composition according to one embodiment of the present invention includes a graft resin (modified polyolefin resin) (IV).

<Polyolefin resin>
The polyolefin resin as the base of the graft resin (IV) is not particularly limited, and may be a homopolymer of one type of olefin or a copolymer of two or more types of olefins. The copolymer may be a random copolymer or a block copolymer. As the olefin, α-olefin is preferred. Examples of the α-olefin include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, and 1-octene.

As the polyolefin resin, polypropylene (propylene homopolymer), ethylene-propylene copolymer, propylene-1-butene copolymer, or ethylene-propylene-1-butene copolymer is preferable. Thereby, the modified polyolefin resin composition can have good adhesion to non-polar resin substrates such as polypropylene substrates.

In this specification, polypropylene refers to a polymer whose basic unit is a constitutional unit derived from propylene. The ethylene-propylene copolymer refers to a copolymer whose basic units are structural units derived from ethylene and propylene. The propylene-butene copolymer refers to a copolymer whose basic units are constitutional units derived from propylene and butene. These polymers may contain a small amount of other olefin-derived structural units other than the above-mentioned basic units. This content may be any amount that does not significantly impair the inherent performance of the resin. Such structural units derived from other olefins may be mixed in during the manufacturing process of the modified polyolefin resin composition.

The polyolefin resin preferably contains 60 mol% or more of propylene-derived structural units in 100 mol% of the structural units. Thereby, adhesion to non-polar resin substrates such as polypropylene substrates can be maintained.

There is no particular limitation on the method for producing the polyolefin resin, and examples thereof include production methods using polymerization catalysts such as metallocene catalysts and Ziegler-Natta catalysts, but production methods using metallocene catalysts are preferred.

Polyolefin resins obtained using metallocene catalysts have a narrow molecular weight distribution. When the polyolefin resin is a copolymer, it has advantages such as excellent random copolymerizability, narrow composition distribution, and a wide range of comonomers that can be copolymerized.

When the ethylene-propylene copolymer and the propylene-butene copolymer are random copolymers, they contain ethylene-derived structural units or butene-derived structural units in an amount of 5 to 50% by weight based on 100% by weight of the structural units. , it is preferable that the structural unit derived from propylene be contained in an amount of 50 to 95% by weight.

The weight average molecular weight of the polyolefin resin is not particularly limited, but is preferably 10,000 to 500,000, more preferably 30,000 to 400,000. When the weight average molecular weight is 500,000 or more, it may be adjusted to fall within the above range. Examples of the adjustment method include a method of degrading in the presence of heat or radicals. In this specification, the weight average molecular weight is a value measured by gel permeation chromatography (GPC, standard material: polystyrene).

The number of polyolefin resins is usually one type, but a combination of two or more types may be used. In the case of a combination of two or more types, the composition may contain two or more types of modified polyolefin resins derived from each polyolefin resin. In the case of a combination of two or more types, their ratio is not particularly limited.

<(I): α,β-unsaturated carboxylic acid or derivative thereof>
The first component (I) constituting the graft chain of the graft resin (IV) is an α,β-unsaturated carboxylic acid or a derivative thereof. Examples of α,β-unsaturated carboxylic acids include unsaturated dicarboxylic acids such as fumaric acid, maleic acid, itaconic acid, mesaconic acid, citraconic acid, and nadic acid; and unsaturated tricarboxylic acids such as aconitic acid. Among these, unsaturated dicarboxylic acids are preferred. Examples of derivatives of α,β-unsaturated carboxylic acids include acid anhydrides of α,β-unsaturated carboxylic acids (e.g., unsaturated dicarboxylic acids, unsaturated tricarboxylic acids); monomethyl fumarate, monoethyl fumarate, Acid monopropyl, monobutyl fumarate, dimethyl fumarate, diethyl fumarate, dipropyl fumarate, dibutyl fumarate, monomethyl maleate, monoethyl maleate, monopropyl maleate, monobutyl maleate, dimethyl maleate, diethyl maleate, maleic acid Alkyl esters of α,β-unsaturated carboxylic acids (e.g., unsaturated dicarboxylic acids, unsaturated tricarboxylic acids) such as dipropyl acid and dibutyl maleate; of α,β-unsaturated carboxylic acids such as maleimide and N-phenylmaleimide. Examples include imidides.

The α,β-unsaturated carboxylic acid or its derivative is preferably α,β-unsaturated carboxylic acid or its anhydride, more preferably α,β-unsaturated dicarboxylic acid or its anhydride, maleic anhydride, itaconic anhydride, etc. The acid, maleic acid is more preferred, and maleic anhydride is even more preferred. Thereby, a preferable amount of hydroxyl groups can be introduced into the polyolefin resin.

Component (I) may be used alone or in combination of two or more selected from the group consisting of α,β-unsaturated carboxylic acids and derivatives thereof. Examples of the combination of two or more types include a combination of two or more types selected from α,β-unsaturated carboxylic acids; a combination of two or more types selected from α,β-unsaturated carboxylic acid derivatives; and α,β- Examples include a combination of one or more unsaturated carboxylic acids and one or more derivatives thereof. In the case of a combination of two or more types, the respective ratios are not particularly limited.

<(II) Component: Amino alcohol>
The second component (II) constituting the graft chain of the graft resin (IV) is an amino alcohol. Amino alcohol is usually a compound that has an amino group as well as a hydroxyl group. The amino group is usually a primary or secondary amino group, and a primary amino group is preferred. The number of hydroxyl groups and amino groups is not particularly limited, but is usually one each. The number of carbon atoms in the amino alcohol is usually 10 or less, 9 or less, or 8 or less, preferably 7 or less or 6 or less, and more preferably 5 or less. The lower limit is usually 1 or 2 or more, and is not particularly limited.

Examples of amino alcohols include 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) Examples include ethanol. Among these, 2-aminoethanol, 2-(2-aminoethoxy)ethanol, 3-amino-propanol, 4-amino-1-butanol, and 2-amino-2-methyl-1-propanol are preferred; Amino-2-methyl-1-propanol is more preferred.

Component (II) may be one type of amino alcohol alone or a combination of two or more types. In the case of a combination of two or more types, their ratio is not particularly limited.

<Component (III): Compound having an isocyanate group and an oxyalkylene group>
The third component (III) constituting the graft chain of the graft resin (IV) is a compound having an isocyanate group and an oxyalkylene group (hereinafter referred to as compound (iii)). The oxyalkylene group is usually contained in compound (iii) as an ether skeleton. The isocyanate group is usually contained at one end of compound (iii).

-Oxyalkylene group-
Examples of the oxyalkylene group include divalent groups such as oxyethylene group (ethylene glycol), oxypropylene group (propylene glycol), oxybutylene group (butylene glycol), and oxytetramethylene group (tetramethylene glycol). .

Compound (iii) may contain multiple oxyalkylene groups. In that case, each oxyalkylene group may be the same or different. As a combination of different oxyalkylene groups, for example, an embodiment in which two or more oxyalkylene groups selected from the group consisting of oxyethylene group (ethylene glycol), oxypropylene group (propylene glycol), and oxybutylene group (butylene glycol) are mixed. An embodiment in which an oxyethylene group (ethylene glycol) and an oxypropylene group (propylene glycol) are mixed, or an embodiment in which an oxyethylene group (ethylene glycol) and an oxybutylene group (butylene glycol) are mixed is preferable. More preferred is an embodiment in which ethylene groups (ethylene glycol) and oxypropylene groups (propylene glycol) are mixed. When compound (iii) contains different oxyalkylene groups, the bonding order of each oxyalkylene group is not limited and may be added in a block or random manner. Further, a plurality of oxyalkylene groups may be included with an organic group other than an oxyalkylene group (for example, a urethane bond or a urea bond) interposed therebetween.

The number of oxyalkylene groups contained in compound (iii) is usually 1 to 200, preferably 1 to 150, 1 to 100, 1 to 90 or 1 to 80, more preferably 1 to 70. The number of oxyalkylene groups means the average number of moles of oxyalkylene groups added to 1 mole of compound (iii). When compound (iii) contains different oxyalkylene groups, the ratio of each group is not particularly limited; Or when it is included in random addition, the EO:PO (molar ratio) is preferably 1 to 80:1 to 20, more preferably 5 to 50:1 to 10, even more preferably 10 to 30:1 to 5.

-Isocyanate group-
Compound (iii) contains an isocyanate group. The number of isocyanate groups contained in compound (iii) is at least one, and may be two or more, but is usually one. The isocyanate group is preferably located at the end of compound (iii).

- Preferred structure of compound (iii) -
It is more preferable that compound (iii) further has a urea bond (urea bond: -NH-CO-NH-), and in addition, it is even more preferable that it has a urethane bond (-NH-COO-).

-Method for producing compound (iii)-
The method for producing compound (iii) is not particularly limited, but for example, a compound having isocyanate groups at both ends (hereinafter referred to as compound (iii-1)) and an amine compound containing an oxyalkylene group (hereinafter referred to as compound (iii)) -2)) is preferred.

Compound (iii-1) preferably further has a urethane bond, more preferably further has a urethane bond and an oxyalkylene group, and has the general formula (21): O=C=N-X ¹ -[A ¹ O ] _n1 -X ² -N=C=O is more preferred. In general formula (21), X ¹ and X ² are each independently a single bond or a divalent linking group. "Divalent linking group" includes, for example, an alkylene group that may have a substituent, an alkenylene group that may have a substituent, an alkynylene group that may have a substituent, and an alkylene group that may have a substituent. A divalent hydrocarbon group that may have a substituent, such as an arylene group that may have a substituent; a group represented by -C(=O)O-, a group represented by -C(=O)- group represented by -C(=O)NH-, group represented by -NHC(=O)NH-, group represented by -NHC(=O)O-, -S- Examples include a group represented by the following formula, a group represented by -SO-, a group represented by -NH-, and a group combining two or more of these groups. In addition, substituents include a halogen atom, a cycloalkyloxy group, an aryloxy group, a monovalent heterocyclic group, an amino group, a silyl group, an acyl group, an acyloxy group, a carboxy group, a sulfo group, a cyano group, a nitro group, Examples include hydroxy group, mercapto group and oxo group. As the divalent linking group, a divalent hydrocarbon group which may have a substituent is preferable, and a divalent hydrocarbon group without a substituent is more preferable. At least one or both of X ¹ and X ² preferably contains a group represented by -NH-COO-, and may further contain a group represented by -[A ² O] _n2 -. n1 and n2 represent the number of moles of A ¹ O and A ² O added, respectively, and are each independently an integer of 1 or more. Usually, it is 1 to 100, preferably 1 to 90, 1 to 80, 1 to 70, or 1 to 60, more preferably 1 to 50, even more preferably 1 to 40, 1 to 30, or 5 to 30. A ¹ O and A ² O are each independently an oxyalkylene group, and when n1 and n2 are 2 or more, they may be 2 or more different oxyalkylene groups. Preferred examples of the oxyalkylene group are as described above, but A ¹ O is preferably an oxyethylene group (ethylene glycol), an oxypropylene group (propylene glycol), or a mixture thereof, and A ² O is Preferred embodiments include oxyethylene groups (ethylene glycol), oxypropylene groups (propylene glycol), oxytetramethylene groups (tetramethylene glycol), or a mixture of these.

The method for producing the compound represented by the general formula (21) is not particularly limited, but it can be produced from a compound having an excess amount of isocyanate groups and a polyol according to a conventional method. The polyisocyanate may have two or more isocyanate groups in the molecule, and examples thereof include 4,4-diphenylmethane diisocyanate, toluene diisocyanate, tolylene diisocyanate, toridine diisocyanate, diphenylmethane diisocyanate, and polymethylene polyphenyl. Polyisocyanate, carbodiimidized diphenylmethane polyisocyanate, crude diphenylmethane diisocyanate (crude MDI), xylylene diisocyanate, 1,5-naphthalene diisocyanate, tetramethylxylylene diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, hexamethylene diisocyanate , dimer acid diisocyanate, norbornene diisocyanate, lysine isocyanate, isopropylidene bis-4-cyclohexyl isocyanate, dicyclohexylmethane diisocyanate, methylcyclohexane diisocyanate, and other compounds having two isocyanate groups in the molecule. Examples of polyols include (poly)alkylene glycol (e.g., (poly)ethylene glycol, (poly)propylene glycol, (poly)butylene glycol, (poly)tetramethylene ether glycol), polyester diol (e.g., polycaprolactone diol) , polycarbonate diol, polybutadiene diol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 1,8-nonanediol, neo Examples include pentyl glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, pentaerythritol, glycerin, trimethylolpropane, and polyoxytetramethylene glycol.

Compound (iii-2) is a compound having an oxyalkylene group and at least one amino group. Amino groups are usually primary amines. The position of the amino group is preferably at one or both ends, more preferably at one end. When constructing a polyether skeleton using a plurality of alkylene oxides, the polyether skeleton may have a random shape or a block shape. Examples of the amine compound having an oxyalkylene group include polyether amines having structures represented by the following general formulas (11) to (15).

In the general formula (11), x1 and y1 represent the average number of added moles of ethylene oxide and propylene oxide, respectively. x1 and y1 are the same as the examples and preferred values of the number of oxyalkylene groups described above, but one example is as follows: x1 is preferably an integer of 1 to 70 or 1 to 60; y1 is , preferably an integer of 1 to 50, more preferably an integer of 2 to 40.

In the general formula (12), x2 represents the average number of moles of propylene oxide added. x2 is the same as the example and preferred value of the number of oxyalkylene groups described above, but one example is as follows: x2 is preferably an integer of 1 to 70.

In the general formula (13), x3 and z3 each independently represent the average number of added moles of propylene oxide, and y3 represents the average number of added moles of ethylene oxide. x3, y3, and z3 are the same as the examples and preferred values of the number of oxyalkylene groups described above, but one example is as follows: x3+z3 is preferably an integer of 1 to 6; y3 is preferably is an integer between 2 and 40.

In general formula (14), R ¹⁰ represents a hydrogen atom or an ethyl group, and n is an integer of 0 or 1. Moreover, x4, y4, and z4 each independently represent the average number of added moles of propylene oxide. x4, y4, and z4 are the same as the examples and preferred values of the number of oxyalkylene groups described above, but one example is as follows: x4+y4+z4 is preferably an integer of 5 to 90.

In the general formula (15), x5 represents the average number of moles of propylene oxide added. x5 is the same as the example and preferred value of the number of oxyalkylene groups described above, but one example is as follows: x5 is preferably an integer of 10 to 15.

The average molecular weight of compound (iii-2) is preferably 200 to 7,000, more preferably 220 to 6,000, and even more preferably 500 to 3,000. The average molecular weight of compound (iii) can be calculated from the average number of added moles of ethylene oxide or propylene oxide and the molecular weight of its terminal structure.

Compound (iii-2) can be prepared by a known method. For example, after adding a desired amount of ethylene oxide or propylene oxide to propylene glycol alkyl ether, the terminal hydroxyl group may be aminated.

A commercially available product may be used as compound (iii-2). Such commercially available products include JEFFAMINE M Series (M-600, M-1000, M-2005, M-2070) and JEFFAMINE D Series (D-230, D-400, D-2000, D) manufactured by HUNTSMAN. -4000), JEFFAMINE ED Series (HK-511, ED-600, ED-900, ED-2003), JEFFAMINE T Series (T-403, T-3000, T-5000), and JEFFAMINE XJT-436. Note that JEFFAMINE is a registered trademark.

In producing compound (iii), the ratio of the amount of compound (iii-1) used to the amount of compound (iii-2) used is preferably 90:10 to 30:70 in terms of molar ratio. When the amount of compound (iii-1) used (molar ratio) is 90 or less (the amount of compound (iii-2) used is 10 or more), a sufficient amount of urea bonds can be generated in the polyolefin component. , the adhesion of the modified polyolefin resin composition can be improved. Furthermore, by using the amount of compound (iii-1) of 30 or more (the amount of compound (iii-2) being used of 70 or less), it is possible to avoid a situation where all the isocyanate in the system is reacted (consumed), Compound (iii) having an active isocyanate group capable of forming a graft chain and capable of improving the performance of a modified polyolefin resin composition can be obtained. Note that the above ratio is a ratio when the total amount of compounds (iii-1) and (iii-2) is taken as 100.
Each raw material 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. If necessary, any raw material compounds other than these raw materials may be used. The reaction conditions are not particularly limited, although the reaction may be carried out using an organic solvent (for example, toluene) and stirring the raw materials as necessary.

<Structure of graft resin (IV)>
The graft resin (IV) has a structure in which components (I) to (III) are graft-polymerized to a polyolefin resin. That is, the graft resin (IV) has at least one graft chain containing structural units (I) to (III) derived from components (I) to (III) in the polyolefin skeleton. The order of graft polymerization of each component is preferably (I), (II), and (III). An example of a graft chain is as follows: a structural unit (I) derived from component (I), an amide bond generated by amidation of the carbonyl group of component (I) in the structural unit (I); A structural unit (II) derived from component (II) that is bonded to structural unit (I) via a urea bond, and a structural unit derived from component (III) that is bonded to a hydroxyl group of structural unit (II) via a urea bond. Structure having structural unit (III).

The weight average molecular weight of the graft resin (IV) measured by gel permeation chromatography (GPC) using a polystyrene standard is preferably 10,000 to 200,000, and preferably 30,000 to 150,000. More preferred.

The graft resin (IV) 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.

<Production method of graft resin (IV)>
Graft resin (IV) can be obtained by graft-modifying a polyolefin resin with components (I) to (III). The order of graft modification is preferably that of components (I), (II) and (III). Thereby, a graft resin (IV) is obtained in which a branched structure containing structural units derived from each of components (I), (II), and (III) is added to the skeleton of the polyolefin resin. To give an example of a branched structural part, the amino alcohol of component (II) is amidated and bonded to the acid modification site derived from component (I), and the isocyanate of component (III) is further bonded to the terminal hydroxyl group of the resulting substituent. The groups are combined to obtain a branched structure having a urea bond and an oxyalkylene group.

Examples of such branched structures include structures represented by the following formulas (1) and (2).

(In general formula (1),
R ² is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms,
R ³ is a polyolefin resin,
R ⁴ is an alkyl group having 10 or less, 9 or less or 8 or less carbon atoms, preferably 7 or less or 6 or less, more preferably 5 or less,
a is an integer of 1 or more,
R ¹ , A ¹ O, and n1 are as described above. )

(In general formula (2), R ⁵ is a hydrogen atom or an alkyl group, and other substituents are as described above.)

In general formulas (1) and (2), the graft component only needs to be bonded to at least one carbon constituting the polyolefin resin ^R3 (in general formulas (1) and (2), a=1). ) is usually bonded to a plurality of carbons constituting the polyolefin resin R ³ (a>1 in general formulas (1) and (2)).

The graft resin (IV) may have a site where components (I) and (II) are graft-polymerized to the polyolefin resin, and a site where only component (I) is graft-polymerized.

<Method for producing modified polyolefin resin composition>
The above-mentioned modified polyolefin resin composition can be obtained by a method of graft polymerizing components (I) to (III) to a polyolefin resin, and the components (I), (II), and (III) are graft-polymerized to the polyolefin resin in this order. The method is preferred. Examples of such a method include a method including the following steps (a) to (c).
Step (a): A step of modifying the polyolefin resin with component (I) to obtain an acid-modified polyolefin resin. Step (b): Modifying the obtained acid-modified polyolefin resin with component (II) to obtain an amidation-modified polyolefin resin. Step (c): Step of reacting component (III) with amidated modified polyolefin resin

<Step (A): Acid modification>
In step (a), polyolefin resin is modified with component (I). The conditions for implementing step (a) may be such that component (I) is introduced into the polyolefin resin, and normal graft polymerization may be used. A radical generator may be used during the graft polymerization reaction. Step (A) includes, for example, a solution method in which the polyolefin resin and component (I) are heated and dissolved in a solvent such as toluene, and a radical generator is added; ) and a melt-kneading method in which a radical generator is added and kneaded with a polyolefin resin. The raw material containing component (I) may be added all at once or sequentially. When component (I) is a combination of two or more α,β-unsaturated carboxylic acids and their derivatives and is added sequentially, the order of graft polymerization is not particularly limited.

During the graft polymerization reaction, the amount of component (I) based on 100 parts by mass of the polyolefin resin is usually 0.5 parts by mass or more and 20 parts by mass or less. This makes it easy to adjust the graft amount to an appropriate amount.

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-butylcumyl 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- Butylperoxyisobutyrate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisopropyl carbonate, cumylperoxyoctoate , 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane. Among these, di-t-butyl peroxide, dilauryl peroxide, and 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane are preferred.

The amount of the radical generator added is preferably 1% by mass or more, more preferably 3% by mass or more, based on 100% by mass of component (I). This allows the grafting rate to be maintained. The upper limit of the amount added is preferably 100% by mass or less, more preferably 50% by mass or less, from the viewpoint of economic efficiency.

In step (a), the component (I) that does not graft polymerize to the polyolefin resin, that is, the unreacted material, may be removed, for example, by extraction with a poor solvent.

The amount of grafting of component (I) is not particularly limited, but is preferably 20% by mass or less, more preferably 10% by mass or less, based on 100% by mass of the acid-modified polyolefin resin. Thereby, in step (a), hydroxyl groups can be introduced in a more preferable amount. The lower limit may be 0% or more. The amount of grafting is determined by an alkaline titration method.

The acid-modified polyolefin resin obtained in step (a) preferably has a weight average molecular weight of 10,000 to 200,000, preferably 50,000 to 100, as measured by gel permeation chromatography (GPC) using a polystyrene standard. ,000 is more preferable. Further, the acid-modified polyolefin resin preferably has a melting point of 50 to 150°C, more preferably 50 to 100°C, as measured by a differential scanning calorimeter (DSC). Further, the acid-modified polyolefin resin preferably has an acid value of 5 to 50 mgKOH/g, more preferably 10 to 30 mgKOH/g, as measured by an alkaline titration method.

<Step (a): Amidation>
In step (a), the acid-modified polyolefin resin obtained in step (a) is amidated with component (II). To give an example of amidation, an acid-modified polyolefin resin is heated and stirred at a temperature equal to or higher than its melting point (for example, 50 to 200° C.), and then component (II) is added. Thereby, an amidated modified polyolefin resin is obtained. Alternatively, it is considered that an ammonium salt of carboxylic acid is produced by component (II) at the graft polymerization site of component (I). Thus, in the graft resin (IV), it is thought that the hydroxyl group derived from component (II) is introduced via the graft polymerization site of component (I).

<Step (c): Urethane modification>
In step (c), component (III) is introduced into the amidated modified polyolefin resin obtained in step (a) to obtain graft resin (IV). An example of step (c) is as follows. The amidated modified polyolefin resin is heated and stirred at a temperature above its melting point (for example, 50 to 200°C), and then component (III) is added. Thereby, the terminal hydroxyl group of the amidated modified polyolefin resin and the isocyanate group of the component (III) form a urethane bond, and a graft resin (IV) can be obtained.

In step (c), the grafting amount of component (III) is not particularly limited, but is preferably 10% by mass or more, more preferably 20% by mass or more, based on 100 parts by mass of the amidated modified polyolefin resin. The upper limit is preferably 80% by mass or less, more preferably 70% by mass or less.

After the reaction, at least a portion of the reaction solvent (eg, toluene, xylene) may be replaced with another solvent (eg, vacuum treatment, concentration), if necessary. Other solvents may be added prior to the substitution reaction. Examples of other solvents include aliphatic solvents (e.g., n-hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, heptane, nonane, decane) and glycol solvents (e.g., ethylene glycol, ethyl cellosolve, butyl cellosolve). , glycol-based solvents are preferred, and butyl cellosolve is more preferred. By adding an aliphatic solvent or a glycol solvent, an aqueous dispersion containing these can be obtained, and emulsion stability and adhesion can be better exhibited. The removal reaction may be performed at a high temperature (eg, 70°C or higher, preferably 80°C or higher). After removing the solvent, water can be added and a dispersion treatment can be performed to obtain an aqueous dispersion. Examples of the dispersion treatment include stirring treatment using stirring equipment such as a stirring blade, a disper, a homogenizer, a sand mill, and a multi-screw extruder. By adjusting the degree of stirring, the particle size of the resin component in the dispersion can be adjusted. In the dispersion treatment, an emulsifier and a neutralizing agent may be added as necessary. On the other hand, after removing the solvent, it may be molded to obtain a solid product.

When obtaining an aqueous dispersion as a modified polyolefin resin composition, a method of replacing the reaction solvent may be used, for example, a dispersion composition in which a modified polyolefin resin is dispersed in a dispersion medium may be used. The dispersion medium may be nonaqueous or aqueous (aqueous dispersion composition).

<Other components of the composition>
The modified polyolefin resin composition only needs to contain the above-mentioned graft resin (IV), and may contain other components as long as the objects and effects of the present invention are not impaired. Other components include, for example, polymers having only modified components as constituent units, monomers of modified components, and resin components such as unmodified polyolefin resins. These are as described above. Further, examples of other components include optional components such as a solvent, a stabilizer, a neutralizing agent, an emulsifier, a crosslinking agent, a diluent, and a curing agent.

(solvent)
Examples of the solvent include aromatic solvents such as toluene and xylene; alicyclic hydrocarbon solvents such as cyclohexane and methylcyclohexane; hydrocarbon solvents such as hexane, heptane, and octane; acetone, methyl ethyl ketone, methyl isobutyl ketone, etc. Ketone solvents; ester solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate; glycol solvents such as ethylene glycol, ethyl cellosolve, butyl cellosolve; water; methanol, ethanol, n- Alcohol solvents such as propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, tert-butyl alcohol, 2-ethyl-hexanol; propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl Examples include glycol ether solvents such as ether, propylene glycol monoisopropyl ether, and propylene glycol monobutyl ether. Among these, aqueous solvents (e.g., water, alcohol-based solvents, glycol-based solvents, ketone-based solvents, ester-based solvents) are preferred, combinations of water and other aqueous solvents are more preferred, and combinations of water and glycol-based solvents are more preferred. More preferred. Examples of the glycol solvent include those mentioned above, and butyl cellosolve is more preferred. Moreover, it is preferable to use a mixed solvent of toluene and butyl cellosolve as the solvent. When using a toluene/butyl cellosolve mixed solvent, the mixing ratio is usually toluene:butyl cellosolve=10:0 to 2:8, preferably 7:3 to 3:7, more preferably 7:3 to 5: It is 5. Note that the above ratio is a ratio when the total of toluene and butyl cellosolve is 10.

(Neutralizer)
When the solvent is an aqueous solvent (eg, water, alcohol solvent, glycol solvent, ketone solvent, ester solvent; the same applies hereinafter), the composition preferably contains a neutralizing agent. Thereby, the dispersibility of the resin in the solvent can be further improved. Examples of the neutralizing agent include sodium hydroxide, potassium hydroxide, ammonia, methylamine, propylamine, hexylamine, octylamine, ethanolamine, propanolamine, diethanolamine, N-methyldiethanolamine, dimethylamine, diethylamine, triethylamine, N , N-dimethylethanolamine, 2-dimethylamino-2-methyl-1-propanol, 2-amino-2-methyl-1-propanol, morpholine, dimethylethanolamine, etc., preferably ammonia, triethylamine, 2-dimethylethanolamine, etc. Examples include basic substances such as amino-2-methyl-1-propanol, morpholine, and dimethylethanolamine. The number of neutralizing agents may be one type or a combination of two or more types.

The content of the neutralizing agent is such that the pH of the modified polyolefin resin composition after addition is usually 5 or more, preferably 6 or more. This allows sufficient neutralization and stable dispersion to be maintained. The upper limit is usually the amount that results in a pH of 11 or less. This allows good compatibility with other components and operational safety to be maintained.

(emulsifier)
When the solvent is an aqueous solvent, the composition preferably contains an emulsifier. Thereby, the dispersibility of the graft resin (IV) can be stabilized. Examples of the emulsifier include surfactants such as nonionic surfactants and anionic surfactants, with nonionic surfactants being preferred.

Examples of nonionic surfactants include alkyl ether surfactants (e.g., polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether), polyoxyethylene derivatives, polyoxyethylene fatty acid esters, polyoxyethylene polyhydric esters, etc. Alcohol fatty acid ester, polyoxyethylene polyoxypropylene polyol, sorbitan fatty acid ester, polyoxyethylene hydrogenated castor oil, polyoxyalkylene polycyclic phenyl ether, polyoxyethylene alkylamine, alkyl alkanolamide, polyalkylene glycol (meth)acrylate, etc. It will be done. Preferred is an alkyl ether surfactant, more preferred is polyoxyethylene alkyl ether.

Examples of anionic surfactants include alkyl sulfates, polyoxyethylene alkyl ether sulfates, alkylbenzene sulfonates, α-olefin sulfonates, methyl taurates, sulfosuccinates, ether sulfonates, and ether carboxylic acids. Salts, fatty acid salts, naphthalene sulfonic acid formalin condensates, alkyl amine salts, quaternary ammonium salts, alkyl betaines, alkyl amine oxides, and the like. Preferred are polyoxyethylene alkyl ether sulfates and sulfosuccinates.

The amount of the emulsifier is preferably 25% by weight or less, more preferably 23% by weight or less, even more preferably 20% by weight or less, based on 100% by weight of the graft resin (IV). Thereby, the stabilizing effect can be expressed satisfactorily. The lower limit is not particularly limited.

(Crosslinking agent)
When the solvent is an aqueous solvent, the composition preferably contains a crosslinking agent. The crosslinking agent may be any compound that can form a crosslinked structure by reacting with groups such as hydroxyl groups, carboxyl groups, and amino groups present in the composition. (the crosslinking agent is dispersed in water by some method). Examples of the crosslinking agent include blocked isocyanate compounds, aliphatic or aromatic epoxy compounds, amine compounds, and amino resins. The crosslinking agents may be used alone or in combination of two or more. The method of adding the crosslinking agent is not particularly limited, and it may be added during the aqueous conversion process or after the aqueous conversion process.

(diluent)
When the solvent is an organic solvent (for example, an aromatic solvent, an alicyclic hydrocarbon solvent, or a hydrocarbon solvent; the same applies hereinafter), the composition preferably contains a diluent. This can improve storage stability. Examples of the diluent include alcohol and propylene glycol ether. Examples of alcohol include methanol, ethanol, propanol, isopropanol, and butanol. Examples of the propylene glycol ether include propylene glycol methyl ether, propylene glycol ethyl ether, and propylene glycol-tert-butyl ether.

(hardening agent)
Examples of the curing agent include polyisocyanate compounds, epoxy compounds, polyamine compounds, polyol compounds, and crosslinking agents whose functional groups are blocked with protective groups.

(Other optional ingredients)
Optional components are not limited to the above agents, but may include other resins (e.g., alkyd resins, water-based acrylic resins, urethane resins, epoxy resins, acrylic resins, phenolic resins, alkyd resins, polyamide resins, polyimide resins, silicone resins, Nitrified cotton), modified polyolefin resins other than the modified polyolefin resins mentioned above, lower alcohols, lower ketones, lower esters, preservatives, leveling agents, antioxidants, light stabilizers, ultraviolet absorbers, dyes, pigments, metals. Depending on the purpose, form, etc., it may be selected and used from salts, acids, and combinations thereof.

The concentration of the resin composition (resin solid content concentration) may be appropriately selected depending on the application. However, if the concentration of the resin composition is too high or too low, coating workability will be impaired, so it is preferably 15 to 70% by weight.

<Physical properties of modified polyolefin resin>
-pH-
The pH of the modified polyolefin resin composition is preferably 5 or more, more preferably 6 to 11. If the pH is less than 5, neutralization may be insufficient and the modified polyolefin resin may not be dispersed in water. Further, even if dispersed, precipitation and separation tend to occur over time, which may deteriorate storage stability. On the other hand, if the pH exceeds 11, problems may arise in compatibility with other components and operational safety. The pH can be adjusted by adjusting the amount of raw materials used and the amount of neutralizing agent used when preparing the modified polyolefin resin composition.

-Average particle size-
When the modified polyolefin resin composition is an aqueous dispersion composition, the average particle diameter of the resin emulsified and dispersed in water is preferably 300 nm or less, more preferably 200 nm or less. If it exceeds 300 nm, the storage stability of the aqueous dispersion composition and the compatibility with other resins may deteriorate. Further, when a film is formed, the physical properties of the film, such as adhesion to a substrate, solvent resistance, water resistance, and blocking resistance, may deteriorate. Note that by increasing the amount of emulsifier added, the particle size can be made infinitely small. However, in this case, the physical properties of the coating, such as adhesion to the substrate, water resistance, and gas hole resistance, tend to deteriorate. In this specification, the average particle diameter is a value obtained by particle size distribution measurement using a light diffusion method. The particle size can be adjusted by adjusting the amount and type of emulsifier added, the stirring power used when emulsifying the resin in water, and the like.

<Applications of modified polyolefin resin composition>
The modified polyolefin resin composition contains the graft resin (IV) of the present invention and other components as necessary. Specifically, the above composition is suitably used as a paint, a binder, an ink, or an adhesive.

Hereinafter, the present invention will be explained in detail with reference to Examples. The following examples are provided to suitably illustrate the present invention, but are not intended to limit the present invention. In addition, the measurement method of physical property values, etc. is the measurement method described below, unless otherwise stated. Moreover, "parts" indicates parts by mass. Furthermore, in the following description, the temperature condition is normal temperature (25° C.) unless a temperature is specified, and the pressure condition is normal pressure (1 atm) unless a pressure is specified.

<Test conditions>
[Evaluation method of emulsion stability of emulsion]
The sample was placed in a sealed glass bottle and stored at 25° C. for 30 days, after which the appearance was visually evaluated.
○: Liquidity is maintained.
Δ: Fluidity is slightly decreased, but there is no practical problem.
×: Fluidity is decreased.

[Adhesion evaluation method]
The surface of the polypropylene plate was degreased with isopropyl alcohol, the sample was spray-coated so that the dry coating film was 5 μm or more and 20 μm or less, and preheated at 80° C. for 30 minutes. Next, a base paint was sprayed and left to stand for 30 minutes, then a clear paint was applied and left to stand for 30 minutes. Thereafter, a baking treatment was performed at 120° C. for 30 minutes to prepare a test piece. After leaving the test piece at room temperature for 2 days, use a cutter knife to make 100 incisions in a grid pattern reaching the substrate at 2 mm intervals on the coating film, and place adhesive cellophane tape on top of the incisions at a 180° angle. The coating was peeled off 10 times and the remaining coating film was determined. Specifically, we counted the number of squares remaining.

<Example 1> Production of urethane-modified polyolefin resin aqueous dispersion composition (C-1) [Step (a): Acid modification with maleic anhydride]
100 parts of a polyolefin resin produced using a metallocene catalyst as a polymerization catalyst (propylene-butene-based random copolymer, propylene constitutional unit content: 90% by weight, butene constitutional unit content: 10% by weight, weight average molecular weight 300,000), and 4 parts of maleic anhydride (α,β-unsaturated carboxylic acid anhydride) and 4 parts of di-tert-butyl peroxide (radical reaction initiator) were mixed uniformly, and a twin-screw extruder (first barrel to 14th barrel).

Residence time is 10 minutes, rotation speed is 200 rpm, barrel temperature is 100°C (1st and 2nd barrels), 200°C (3rd to 8th barrels), 90°C (9th and 10th barrels), 110°C (11th to 14th barrels). The reaction was carried out under the following conditions (barrel). Thereafter, unreacted maleic anhydride was removed by vacuum treatment to obtain an acid-modified polyolefin resin (A') modified with maleic anhydride.

[Step (a): Amidation with hydrophilic amine]
In a four-necked flask equipped with a stirrer, cooling tube, dropping funnel, and nitrogen supply tube, 100 parts of acid-modified polyolefin resin (A') was dissolved in 185.7 parts of toluene, and AMP-90 (Dow. 4.5 parts of a 90% aqueous solution of 2-amino-2-methyl-1-propanol (manufactured by Chemical Co., Ltd.) was added, and the mixture was stirred for 60 minutes at a flask internal temperature of 100° C. and a rotational speed of 200 rpm in a nitrogen atmosphere. Thereby, an amidated modified polyolefin resin (A) was obtained.

[Production of isocyanate compound (B) having urea bond and oxyalkylene group]
As the urethane resin, Samplen P-6090 (urethane prepolymer manufactured by Sanyo Kasei Co., Ltd., PTMG (polyoxytetramethylene glycol)/MDI (4,4'-diphenylmethane diisocyanate type, NCO content 7.7%) weight average molecular weight 6,000) was dissolved in 95.2 parts of toluene, and while stirring at room temperature in a nitrogen atmosphere at a rotation speed of 200 rpm, JEFFAMINE M-1000 (registered trademark: HUNTSMAN Co., Ltd. polyoxy 35.4 parts of alkylamine, weight average molecular weight approximately 1,000) and 141.4 parts of toluene were added, stirring was continued for 60 minutes, and the urea bond and oxyalkylene having an isocyanate group at the end and a solid content of 20% were added. An isocyanate compound (B) having a group was obtained.

[Step (c): Urethane modification]
-Production of aqueous dispersion composition (C-1) of urethane-modified polyolefin resin-
100 parts of the amidated modified polyolefin resin (A) obtained in step (a) was dissolved in 185.7 parts of toluene, and while stirring at 100°C in a nitrogen atmosphere, an isocyanate compound having a urea bond and an oxyalkylene group ( B) 29.6 parts were added and stirred while heating for 120 minutes to obtain a urethane-modified polyolefin solution.

40.5 parts of n-butyl cellosolve was added to 100 parts of the above urethane-modified polyolefin, 65.5 parts of toluene was removed by vacuum distillation, and the mixture was concentrated to a solid content of 50% to obtain a concentrated solution of the urethane-modified polyolefin.

120 parts of the above concentrated solution of urethane-modified polyolefin was heated and stirred at 100°C, and 1.8 parts of Reox CL-90 (alkyl ether emulsifier manufactured by Lion Corporation, HLB value 13.4) was added as an emulsifier. 2.7 parts of AMP-90 was added as a neutralizing agent, hot water was added, and part of toluene and n-butyl cellosolve was distilled off under reduced pressure to form an aqueous dispersion composition with a solid content of 30%. (C-1) was obtained.

[Example 2: Production of urethane-modified polyolefin resin aqueous dispersion composition (C-2)]
Example 1 was carried out in the same manner as in Example 1, except that the amount of Rheox CL-90 was changed to 12 parts, to obtain a urethane-modified polyolefin resin aqueous dispersion composition (C-2) with a solid content of 30%. Ta.

[Example 3: Production of urethane-modified polyolefin resin aqueous dispersion composition (C-3)]
Example 1 was carried out in the same manner as in Example 1, except that the amount of the isocyanate compound (B) having a urea bond and an oxyalkylene group was changed to 58.7 parts per 100 parts of the resin (A). A 30% urethane-modified polyolefin resin aqueous dispersion composition (C-3) was obtained.

[Example 4: Production of urethane-modified polyolefin resin aqueous dispersion composition (C-4)]
Example 1 was carried out in the same manner as in Example 1, except that Rheox CL-90 was not used, to obtain a urethane-modified polyolefin resin aqueous dispersion composition (C-4) with a solid content of 30%.

[Example 5: Production of urethane-modified polyolefin resin water dispersion composition (C-5)]
Example 1 was carried out in the same manner as in Example 1, except that n-butyl cellosolve was not used, to obtain a urethane-modified polyolefin resin aqueous dispersion composition (C-5) with a solid content of 30%.

[Comparative Example 1: Production of urethane-modified polyolefin water dispersion composition (E) using urethane-modified polyolefin resin water dispersion composition (using acrylic monomer)]
(i') Modification with hydroxyethyl methacrylate 100 g of acid-modified polyolefin resin (A') and 185.7 g of toluene were charged into a flask equipped with a stirrer, a thermometer, and a cooling tube for refluxing the monomer, and the temperature was increased to 100 g. Warmed to ℃. Next, 1.5 g of 2-hydroxyethyl methacrylate (HEMA) and 23.8 g of Samplen P-665 (urethane prepolymer manufactured by Sanyo Chemical Industries, Ltd.) were added, and the flask was rotated at a temperature of 85°C in a nitrogen atmosphere. The mixture was stirred at several 200 rpm for 120 minutes. Furthermore, 5 g of BMT-K40 (polymerization reaction initiator manufactured by NOF Corporation, benzoyl peroxide) was added and stirred for 30 minutes, followed by a graft copolymerization reaction for 360 minutes to obtain a urethane-modified polyolefin resin (urethane-modified polyolefin resin with a solid content of 30%). D) was obtained.

(ii') Production of aqueous dispersion composition (E) of urethane-modified polyolefin resin 40.5 parts of n-butyl cellosolve was added to 100 parts of the above urethane-modified polyolefin (D), and 65.5 parts of toluene was distilled under reduced pressure. was removed and concentrated to a solid content of 50% to obtain a concentrated solution of urethane-modified polyolefin.

To 120 parts of the above concentrated solution of urethane-modified polyolefin was heated and stirred at 100°C, 12 parts of Rheox CL-90 was added as an emulsifier, 2.7 parts of AMP-90 was added as a neutralizer, and hot water was added. was added, and a portion of toluene and n-butyl cellosolve was distilled off under reduced pressure to obtain a urethane-modified polyolefin resin aqueous dispersion composition (E) with a solid content of 30%.

The results of Examples 1 to 5 and Comparative Example 1 are shown in Table 1 below.

From Table 1, the aqueous dispersion composition of the modified polyolefin resin of each Example has stable fluidity compared to the aqueous dispersion composition of the urethane-modified polyolefin resin of Comparative Example 1. On the other hand, it can be seen that in Comparative Example 1, the fluidity decreased and the emulsion stability was poor, making it difficult to control the fluidity in practical use. Therefore, the aqueous dispersion composition of the modified polyolefin resin of the present invention maintains fluidity and has excellent emulsion stability.

[Example 6: Application of urethane-modified polyolefin resin composition]
As Example 6, 58.7 parts of an isocyanate compound (B) having a urea bond and an oxyalkylene group was added to 100 parts of the resin (A), and the mixture was heated and stirred for 120 minutes to obtain a urethane-modified polyolefin solution. An adhesion test was conducted using this urethane-modified polyolefin solution as a sample.

[Comparative Example 2: Application of unmodified polyolefin resin composition]
As Comparative Example 2, an adhesion test was conducted using a polyolefin resin (propylene-butene random copolymer, propylene constituent unit content: 90% by weight, butene constituent unit content: 10% by weight) as a sample.

The results of Example 6 and Comparative Example 2 are shown in Table 2 below.

From Table 2, the modified polyolefin resin composition of Example 6 has excellent adhesion compared to the unmodified polyolefin resin composition of Comparative Example 2. On the other hand, in Comparative Example 2, several squares of the coating were peeled off, and it was found that the adhesion was poor. Therefore, the modified polyolefin resin composition of the present invention has excellent adhesion without peeling of the coating film.

These results indicate that the present invention provides a modified polyolefin resin composition with good emulsion stability and adhesion.

Claims (10)

(I) structural units derived from α,β-unsaturated carboxylic acids and derivatives thereof;
(II) a structural unit derived from an amino alcohol having a primary or secondary amino group; and (III) a graft resin (IV) having a graft chain containing a structural unit derived from a compound having an isocyanate group and an oxyalkylene group. A modified polyolefin resin composition comprising. The modified polyolefin resin composition according to claim 1, wherein the compound having an isocyanate group and an oxyalkylene group further has a urea bond. The modified polyolefin resin composition according to claim 2, wherein the compound having an isocyanate group and an oxyalkylene group is a reaction product of a compound having an isocyanate group at both ends and an amine compound having a polyoxyalkylene group. The modified polyolefin resin composition according to any one of claims 1 to 3, wherein the modified polyolefin contains at least a modified polyolefin represented by the following general formula (1) or (2).

(In general formula (1),
R ¹ is a group containing an oxyalkylene group and a group represented by -NH-COO-,
R ² is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms,
R ³ is a polyolefin resin,
R ⁴ is an alkyl group having 10 or less carbon atoms,
A ¹ O is an oxyalkylene group which may be the same or different,
n1 is an integer of 1 or more,
a is an integer of 1 or more. )

(In general formula (2),
R ⁵ is a hydrogen atom or an alkyl group,
R ¹ , R ² , R ³ , R ⁴ , A ¹ O, n1, and a are the same as in general formula (1). ) The aqueous dispersion composition according to any one of claims 1 to 4, which is an aqueous dispersion composition. The aqueous dispersion composition according to claim 5, further comprising a glycol solvent. The aqueous dispersion composition according to claim 5 or 6, further comprising an alkyl ether surfactant. Paints, binders, adhesives, and inks comprising the modified polyolefin resin composition according to any one of claims 1 to 4. A paint, binder, adhesive, or ink comprising the aqueous dispersion composition according to any one of claims 5 to 7. A method for producing a modified polyolefin resin composition, including the following steps.
(A): Step of modifying polyolefin resin with (I) α,β-unsaturated carboxylic acid and its derivative to obtain acid-modified polyolefin resin (B): Process of modifying the obtained acid-modified polyolefin resin with (II) primary or Process of obtaining an amidated modified polyolefin resin by modifying with an amino alcohol having a secondary amino group (c): Reacting the amidated modified polyolefin resin with (III) a compound having an isocyanate group and an oxyalkylene group to graft the resin. Step of obtaining a modified polyolefin resin composition containing resin (IV)