Dispersion composition

Abstract

The present invention aims to provide an alcohol-based composition containing an acrylic-modified polyolefin resin, which exhibits good adhesion even at high solids content, inhibits an increase in viscosity, and has good stability such as dispersibility and stability over time. [Solution] The present invention provides a dispersion composition in which at least a modified polyolefin resin is dispersed in a dispersion medium containing an alcohol-based solvent and an aliphatic hydrocarbon-based solvent, wherein the modified polyolefin resin is modified with a (meth)acrylic acid-based component containing at least a (meth)acrylic acid ester represented by the following general formula (I) and a (meth)acrylic acid ester represented by the following general formula (II), the total content of structures derived from the (meth)acrylic acid-based component in the dispersion composition is 3 wt% to 94 wt%, where the total amount of the modified polyolefin resin and the (meth)acrylic acid-based component polymer is 100 wt%, and the solid content of the dispersion composition is 30 wt% to 80 wt%.

Description

Technical Field

[0001] The present invention relates to a dispersion composition, and more particularly to a dispersion composition having good stability such as dispersibility and stability over time, which can have a high solid content and a low viscosity, and uses thereof.

Background Art

[0002] In the movement to reduce volatile organic compounds (VOCs), the shift from solvent-based inks to water-based inks is being promoted, and alcohol-based inks, which are positioned as having a medium environmental load, are becoming more popular. For example, Patent Document 1 describes that a block copolymer having a predetermined α-olefin-based polymer block and an acrylate block can be used as an adhesion component of an alcohol-based ink.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] However, in order for the above-described conventional alcohol-based ink to obtain the same level of adhesion as a solvent-based ink (adhesion component: modified polyolefin resin), it is necessary to contain several times the amount of the adhesion component of the latter. And when a large amount of the adhesion component is added, there is also a problem that the viscosity increases and the dispersibility and stability over time decrease, so that it cannot be put into practical use.

[0005] An object of the present invention is to provide a composition having good adhesion even when highly solidified, suppressed increase in viscosity, and good stability such as dispersibility and stability over time in an alcohol-based composition containing an acrylic-modified polyolefin resin.

Means for Solving the Problems

[0006] The present invention provides the following. 〔1〕At least, Component (A): A modified polyolefin resin is a dispersion composition dispersed in a dispersion medium containing an alcohol-based solvent and an aliphatic hydrocarbon-based solvent, wherein the component (A) contains at least Component (C): The following general formula (I): CH2=C(R 1 )COOR 2 ···(I) (In the general formula (I), R 1 represents a hydrogen atom or a methyl group, and R 2 represents -C m H 2m OH. However, m is an integer of 1 to 18.) represented by a (meth)acrylic acid ester, and Component (D): The following general formula (II): CH2=C(R 3 )COOR 4 ···(II) (In the general formula (II), R 3 represents a hydrogen atom or a methyl group, and R 4 represents a linear, branched, and / or cyclic alkyl group having 4 to 18 carbon atoms.) represented by a (meth)acrylic acid ester and is graft-modified with a (meth)acrylic acid-based component containing the total content of the structure derived from the (meth)acrylic acid-based component in the dispersion composition is 3% by weight to 94% by weight with respect to the total amount of the component (A) and the (meth)acrylic acid-based component polymer being 100% by weight, and the solid content ratio of the dispersion composition satisfies 30% by weight to 80% by weight, a dispersion composition. 〔2〕The content of the structure derived from the component (C) in the component (A) is 20 mol% or less with respect to 100 mol% of the total content of the structure derived from the (meth)acrylic acid-based component, the dispersion composition according to 〔1〕. 〔3〕The content of the structure derived from the component (D) in the component (A) is 25 mol% or more with respect to 100 mol% of the total content of the structure derived from the (meth)acrylic acid-based component, the dispersion composition according to 〔1〕or 〔2〕. 〔4〕The weight average molecular weight of the component (A) is from 5,000 to 400,000, the dispersion composition according to any one of 〔1〕to 〔3〕. 〔5〕The component (A) is further modified with an acid component other than the (meth)acrylic acid-based component, the dispersion composition according to any one of 〔1〕to 〔4〕. 〔6〕The component (A) is further chlorinated, the dispersion composition according to any one of 〔1〕to 〔5〕. 〔7〕The degree of chlorination of the component (A) is 30% by weight or less, taking the weight of the component (A) excluding the weight derived from the (meth)acrylic acid-based component as 100% by weight, the dispersion composition according to 〔6〕. 〔1’〕Component (α): The polyolefin resin is Component (β): The following general formula (I): CH2=C(R 1 )COOR 2 ···(I) (In the general formula (I), R 1 represents a hydrogen atom or a methyl group, and R 2 represents -C m H 2m OH. However, m is an integer from 1 to 18.) And the following general formula (II): CH2=C(R 3 )COOR 4 ···(II) (In the general formula (II), R 3 represents a hydrogen atom or a methyl group, and R 4 represents an aliphatic or alicyclic alkyl group having 4 to 18 carbon atoms.) The component (A): the modified polyolefin resin graft-modified with a modified component containing at least a (meth)acrylate represented by the formula is Dispersed in a mixed solvent of an alcohol-based solvent and an aliphatic solvent, The content ratio of the said components (α) and (β) (component (α) / component (β)) is in the range of 97 / 3 to 6 / 94 (provided that component (α) + component (β) = 100). The solid content is 30 to 80%. A dispersion composition satisfying the above conditions. 〔2’〕The amount of the (meth)acrylic acid ester represented by the general formula (I) is 20 mol / % or less with respect to the total amount of the said component (β). The dispersion composition according to 〔1’〕. 〔3’〕The amount of the (meth)acrylic acid ester represented by the general formula (II) is 25 mol / % or more with respect to the total amount of the said component (β). The dispersion composition according to 〔1’〕 or 〔2’〕. 〔4’〕The said component (A) contains at least a modified polyolefin resin having a weight average molecular weight of 5,000 to 400,000. The dispersion composition according to any one of 〔1’〕 to 〔3’〕. 〔5’〕The said component (α) contains an acid-modified polyolefin resin. The dispersion composition according to any one of 〔1’〕 to 〔4’〕. 〔6’〕The said component (α) contains a chlorinated polyolefin resin. The dispersion composition according to any one of 〔1’〕 to 〔5’〕. 〔7’〕The chlorination degree of the said chlorinated polyolefin resin is more than 0 wt% and 30 wt% or less. The dispersion composition according to 〔6’〕. 〔8〕A primer containing the dispersion composition according to any one of 〔1〕 to 〔7〕 and 〔1’〕 to 〔7’〕. 〔9〕An adhesive containing the dispersion composition according to any one of 〔1〕 to 〔7〕 and 〔1’〕 to 〔7’〕. 〔10〕A binder for paints containing the dispersion composition according to any one of 〔1〕 to 〔7〕 and 〔1’〕 to 〔7’〕. 〔11〕A binder for inks containing the dispersion composition according to any one of 〔1〕 to 〔7〕 and 〔1’〕 to 〔7’〕.

Advantages of the Invention

[0007] According to the present invention, a dispersion composition having good stability such as dispersibility and stability over time, and having a high solid content and a low viscosity is provided. The dispersion composition can exhibit good adhesion to a substrate such as polyolefin, and the coating film formed on the substrate can have gasoline resistance, so it is useful as a binder for paints, a binder for inks, an adhesive, and a primer.

Mode for Carrying Out the Invention

[0008] In a first embodiment, the present invention relates to at least Component (A): A modified polyolefin resin is Component (B): A dispersion medium containing an alcohol-based solvent and an aliphatic hydrocarbon-based solvent, and the dispersion composition is dispersed therein, The component (A) contains at least Component (C): The following general formula (I): CH2=C(R 1 )COOR 2 ···(I) (In the general formula (I), R 1 represents a hydrogen atom or a methyl group, and R 2 represents -C m H 2m OH. However, m is an integer of 1 to 18.) represented by a (meth)acrylic acid ester, and Component (D): The following general formula (II): CH2=C(R 3 )COOR 4 ···(II) (In the general formula (II), R 3 represents a hydrogen atom or a methyl group, and R 4 represents a linear, branched and / or cyclic alkyl group having 4 to 18 carbon atoms.) represented by a (meth)acrylic acid ester modified with a (meth)acrylic acid-based component, The total content of the structure derived from the (meth)acrylic acid-based component in the dispersion composition is 3% by weight to 94% by weight based on the total amount of the component (A) and the (meth)acrylic acid-based component polymer being 100% by weight, and Provided is a dispersion composition satisfying that the solid content fraction of the dispersion composition is 30% by weight to 80% by weight.

[0009] (1. Component (A) Modified polyolefin resin) The dispersion composition of the present invention contains a component (A) modified polyolefin resin in a dispersion medium. The component (A) modified polyolefin resin is a modified product of a polyolefin resin.

[0010] (1-1. Polyolefin resin) The polyolefin resin is usually an olefin (α-olefin) polymer. Examples of the α-olefin include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, and 1-octene.

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

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

[0013] Here, "polypropylene" refers to a polymer whose basic unit is a constitutional unit derived from propylene. "Ethylene-propylene copolymer" refers to a copolymer whose basic unit contains constitutional units derived from ethylene and propylene. "Propylene-1-butene copolymer" refers to a copolymer whose basic unit contains constitutional units derived from propylene and butene. "Ethylene-propylene-1-butene copolymer" refers to a copolymer whose basic unit contains constitutional units derived from ethylene, propylene, and butene. As long as the amount does not significantly impair the original performance of the resin, these (co)polymers may contain a small amount of constitutional units derived from other olefins in addition to the basic units.

[0014] The polyolefin resin preferably contains 50 mol% or more of the constitutional units derived from propylene in 100 mol% of the constitutional units. When the constitutional units derived from propylene are contained within the above range, the adhesiveness to non-polar resin substrates such as propylene resin can be maintained.

[0015] When the ethylene-propylene copolymer or the propylene-1-butene copolymer is a random copolymer, preferably, in 100 mol% of the constitutional units, the constitutional units derived from ethylene or the constitutional units derived from butene are 3 to 50 mol%, and the constitutional units derived from propylene are 50 to 97 mol%.

[0016] (1-2. Modification with (meth)acrylic acid-based components) In the present invention, the modified polyolefin resin of component (A) is modified (graft-modified) with a (meth)acrylic acid-based component. The (meth)acrylic acid-based component means (meth)acrylic acid and its derivatives, and examples of the derivatives include (meth)acrylic anhydride, (meth)acrylic acid ester, and the like.

[0017] In the present invention, the (meth)acrylic acid-based component is Component (C): The following general formula (I): CH2=C(R 1 )COOR 2 ···(I) (In the general formula (I), R 1represents a hydrogen atom or a methyl group, and R 2 is -C m H 2m OH. However, m is an integer from 1 to 18.) contains a (meth)acrylic acid ester (hydroxyl group monomer) represented by

[0018] R 1 represents a hydrogen atom or a methyl group, and a hydrogen atom is preferred. m is an integer from 1 to 18, preferably 1 to 16, 1 to 14, 1 to 12 or 1 to 10, more preferably 1 to 8, 1 to 6 or 1 to 4, still more preferably 2 to 4 or 2 to 3, and particularly preferably 2.)

[0019] Examples of the hydroxyl group monomer as the component (C) include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxy-1-methylethyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 3-hydroxy-1-methylpropyl (meth)acrylate, 3-hydroxy-2-methylpropyl (meth)acrylate, 2-hydroxy-1-methylpropyl (meth)acrylate, 2-hydroxy-2-methylpropyl (meth)acrylate, 2-hydroxy-1,1-dimethylethyl (meth)acrylate, 2-hydroxypentyl (meth)acrylate, 3-hydroxypentyl (meth)acrylate, 4-hydroxypentyl acrylate (meth)acrylate, 5-hydroxypentyl acrylate (meth)acrylate, 2-hydroxyhexyl (meth)acrylate, 3-hydroxyhexyl (meth)acrylate, 4-hydroxyhexyl (meth)acrylate, 5-hydroxyhexyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 7-hydroxyheptyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 9-hydroxynonyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, etc. Among these, 2-hydroxyethyl (meth)acrylate is preferred.

[0020] The content of the structure derived from the hydroxyl group monomer as the component (C) in the modified polyolefin resin of the component (A) is preferably 30 mol% or less, preferably 20 mol% or less, more preferably 15 mol% or less, still more preferably 10 mol% or less, with respect to 100 mol% of the total content of the structure derived from the (meth)acrylic acid-based component in the modified polyolefin resin of the component (A). The lower limit is preferably 0.1 mol% or more, more preferably 1 mol% or more, still more preferably 2 mol% or more, and particularly preferably 3 mol% or more.

[0021] The carboxylic acid group monomer of component (C) may be a single type or a combination of two or more types.

[0022] In the present invention, the (meth)acrylic acid-based component is Component (D): The following general formula (II): CH2=C(R 3 )COOR 4 ···(II) (In the general formula (II), R 3 represents a hydrogen atom or a methyl group, and R 4 represents a linear, branched, and / or cyclic alkyl group having 4 to 18 carbon atoms.) and includes a (meth)acrylic acid ester (low-polarity monomer) represented by

[0023] R 3 represents a hydrogen atom or a methyl group, and a methyl group is preferred. R 4 represents a linear, branched, and / or cyclic alkyl group having 4 to 18 carbon atoms. The number of carbon atoms is an integer of 4 to 18, preferably 4 to 16, 4 to 14, 4 to 12, or 4 to 10, and more preferably 4 to 8 or 4 to 6.

[0024] Examples of the low-polarity monomer of component (D) include (meth)acrylic acid esters in which R 4 is a linear alkyl group, such as n-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate, n-decyl (meth)acrylate, lauryl (meth)acrylate (n-dodecyl (meth)acrylate), n-tridecyl (meth)acrylate, stearyl (meth)acrylate, etc.; (meth)acrylic acid esters in which R 4(Meth)acrylate ester in which R is a branched alkyl group; R such as cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, etc. 4 Examples include (meth)acrylate esters in which R is a cyclic alkyl group. Among these, R 4 (Meth)acrylate ester in which R is a linear alkyl group, and R 4 (Meth)acrylate ester in which R is a cyclic alkyl group are preferred, and n-butyl (meth)acrylate and cyclohexyl (meth)acrylate are more preferred.

[0025] In component (A) modified polyolefin resin, the content of the structure derived from component (D) low-polarity monomer is preferably 25 mol% or more, more preferably 30 mol% or more, still more preferably 40 mol% or more, based on 100 mol% of the total content of the structure derived from (meth)acrylic acid-based components in component (A) modified polyolefin resin. The upper limit is preferably 90 mol% or less, or 85 mol% or less, more preferably 80 mol% or less, or 75 mol% or less, still more preferably 70 mol% or less, or 65 mol% or less, particularly preferably 60 mol% or less, or 55 mol% or less.

[0026] Component (D) low-polarity monomer may be used alone or in combination of two or more.

[0027] Component (D) low-polarity monomer preferably contains a combination of (meth)acrylate ester in which R 4 is a linear alkyl group and (meth)acrylate ester in which R 4 is a cyclic alkyl group, and more preferably contains a combination of n-butyl (meth)acrylate and cyclohexyl (meth)acrylate.

[0028] In component (A) modified polyolefin resin, the molar ratio of the content of the structure derived from component (C) hydroxyl monomer and the structure derived from component (D) low-polarity monomer (component (C) / component (D)) is preferably 1 / 100 to 1 / 1.5, more preferably 1 / 50 to 1 / 2, still more preferably 1 / 50 to 1 / 4.

[0029] The total content of the structure derived from component (C) hydroxyl group monomer and the structure derived from component (D) low-polarity monomer in the modified polyolefin resin of component (A) is preferably 30 mol% or more, more preferably 40 mol% or more, still more preferably 45 mol% or more, based on 100 mol% of the total content of the structure derived from the (meth)acrylic acid-based component in the modified polyolefin resin of component (A). The upper limit is preferably 95 mol% or less, more preferably 90 mol% or less, still more preferably 85 mol% or less.

[0030] In one embodiment of the present invention, the (meth)acrylic acid-based component further contains, as an optional component, Component (E): The following general formula (III): CH2=C(R 5 )COOR 6 ···(III) (In the general formula (III), R 5 represents a hydrogen atom or a methyl group, and R 6 represents -C a H 2a OC b H 2b+1 . However, a and b are each independently an integer of 1 to 18.) and preferably contains a (meth)acrylic acid ester (alkoxy group monomer) represented by

[0031] R 5 represents a hydrogen atom or a methyl group, and a hydrogen atom is preferred. a is an integer of 1 to 18, preferably 1 to 16, 1 to 14, 1 to 12 or 1 to 10, more preferably 1 to 8, 1 to 6 or 1 to 4, still more preferably 2 to 4 or 2 to 3, and particularly preferably 2. b is an integer of 1 to 18, preferably 1 to 16, 1 to 14, 1 to 12 or 1 to 10, more preferably 1 to 8, 1 to 6 or 1 to 4, still more preferably 1 to 4 or 1 to 3, and particularly preferably 1.

[0032] As the component (E) alkoxy group monomer, for example, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-propoxyethyl (meth) acrylate, 2-(1-methylethoxy)ethyl (meth) acrylate, 2-methoxypropyl (meth) acrylate, 2-ethoxypropyl (meth) acrylate, 2-propoxypropyl (meth) acrylate, 2-(1-methylethoxy)propyl (meth) acrylate, 3-methoxypropyl (meth) acrylate, 3-ethoxypropyl (meth) acrylate, 3-propoxypropyl (meth) acrylate, 3-(1-methylethoxy)propyl (meth) acrylate, 2-methoxy-1-methylethyl (meth) acrylate, 2-ethoxy-1-methylethyl (meth) acrylate, 2-propoxy-1-methylethyl (meth) acrylate, 2-(1-methylethoxy)-1-methylethyl (meth) acrylate, etc. may be mentioned. Among these, 2-methoxyethyl (meth) acrylate is preferable.

[0033] In one embodiment, the content of the structure derived from the component (E) alkoxy group monomer in the component (A) modified polyolefin resin is preferably 50 mol% or less, more preferably 40 mol% or less, based on 100 mol% of the total content of the structure derived from the (meth) acrylic acid-based component in the component (A) modified polyolefin resin. The lower limit is preferably 0.1 mol% or more, more preferably 1 mol% or more.

[0034] The component (E) alkoxy group monomer may be used alone or in combination of two or more.

[0035] In one embodiment of the present invention, the (meth) acrylic acid-based component further includes, as an optional component, Component (F): The following general formula (IV): CH2=C(R 7 )COOR 8 ···(IV) (In the general formula (IV), R 7 represents a hydrogen atom or a methyl group, and R 8represents a linear or branched alkyl group having 1 to 3 carbon atoms.) Preferably contains a (meth)acrylic acid ester (lower monomer) represented by .

[0036] R 7 represents a hydrogen atom or a methyl group, and a methyl group is preferred. R 8 represents a linear, branched and / or cyclic alkyl group having 1 to 3 carbon atoms. The number of carbon atoms is an integer of 1 to 3, preferably 1 or 2, more preferably 1.

[0037] Examples of the component (F) lower monomer include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and isopropyl (meth)acrylate. Among these, methyl (meth)acrylate is preferred.

[0038] In one embodiment, the content of the structure derived from the component (F) lower monomer in the component (A) modified polyolefin resin is preferably 1 mol% or more, more preferably 5 mol% or more, based on 100 mol% of the total content of the structure derived from the (meth)acrylic acid component in the component (A) modified polyolefin resin. The upper limit is preferably 70 mol% or less, more preferably 60 mol% or less.

[0039] The component (F) lower monomer may be used alone or in combination of two or more.

[0040] In one embodiment of the present invention, the (meth)acrylic acid component preferably further contains, as an optional component, component (G) (meth)acrylic acid. Component (G) (meth)acrylic acid is preferably methacrylic acid. Component (G) (meth)acrylic acid may be in the form of a free acid or in the form of a salt (such as a sodium salt or a potassium salt).

[0041] In one embodiment, the content of the structure derived from component (G) (meth)acrylic acid in component (A) modified polyolefin resin is preferably 1 mol% or more, more preferably 5 mol% or more, based on 100 mol% of the total content of the structure derived from (meth)acrylic acid components in component (A) modified polyolefin resin. The upper limit is preferably 70 mol% or less, more preferably 50 mol% or less.

[0042] In one embodiment of the present invention, the (meth)acrylic acid component may further contain, as an optional component, a (meth)acrylic acid component other than components (C) to (G).

[0043] Examples of the (meth)acrylic acid component other than components (C) to (G) include isobornyl (meth)acrylate, glycidyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, phenoxyethyl (meth)acrylate, 4-hydroxycyclohexyl (meth)acrylate, (4-hydroxymethylcyclohexyl)methyl (meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-(meth)acryloyloxyethyl-2-hydroxypropyl phthalate glycerol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, polytetramethylene glycol mono(meth)acrylate, 2-(dimethylamino)ethyl (meth)acrylate, 2-(diethylamino)ethyl (meth)acrylate, acetoacetoxyethyl (meth)acrylate, and the like.

[0044] The total content of the structure derived from the (meth)acrylic acid-based component in the dispersion composition is 3% by weight or more, preferably 5% by weight or more, based on 100% by weight of the total amount of the component (A) modified polyolefin resin and the (meth)acrylic acid-based component polymer. The upper limit is 94% by weight or less, preferably 90% by weight or less, more preferably 80% by weight or less, still more preferably 70% by weight or less, and particularly preferably 60% by weight or less. In one embodiment, the total content of the structure derived from the (meth)acrylic acid-based component in the dispersion composition is 3% to 94% by weight based on 100% by weight of the total amount of the component (A) modified polyolefin resin and the (meth)acrylic acid-based component polymer, and from the viewpoint of further improving the adhesion, it is preferably 5% to 90% by weight. The term "(meth)acrylic acid-based component polymer" means a polymer having a structure derived from the (meth)acrylic acid-based component as a structural unit, and is an arbitrary component that can be contained in the dispersion composition. In one embodiment, it can be a by-product formed by the polymerization of (meth)acrylic acid-based components that did not react with the polyolefin-based resin during the modification of the polyolefin-based resin.

[0045] (1-3. Modification with acid components other than (meth)acrylic acid-based components) In the present invention, the component (A) modified polyolefin resin may be modified with an acid component other than the (meth)acrylic acid-based component. Examples of the acid component other than the (meth)acrylic acid-based component include α,β-unsaturated carboxylic acids and their derivatives other than the (meth)acrylic acid-based component. Examples of the derivatives include α,β-unsaturated carboxylic acid anhydrides, α,β-unsaturated carboxylic acid esters, and the like.

[0046] Examples of the α,β-unsaturated carboxylic acids and their derivatives other than the (meth)acrylic acid-based component include maleic acid, maleic anhydride, fumaric acid, citraconic acid, citraconic anhydride, mesaconic acid, itaconic acid, itaconic anhydride, aconitic acid, aconitic anhydride, hymic anhydride, and the like. Among them, maleic anhydride is preferred in consideration of the graftability to polyolefin.

[0047] (Meta)acrylic acid-based components other than the acid components used for modification by acid components may be used alone or in combination of two or more.

[0048] In the modified polyolefin resin of component (A), the total graft weight (modification degree) of acid components other than (meta)acrylic acid-based components is preferably 20% by weight or less, more preferably 10% by weight or less, and even more preferably 5% by weight or less, with the weight of the modified polyolefin resin of component (A) excluding the weight derived from (meta)acrylic acid-based components being 100% by weight. This can suppress the generation of unreacted substances. The lower limit can be, for example, 0% by weight or more. The graft weight (% by weight) can be determined, for example, by an alkali titration method or a Fourier transform infrared spectroscopy method.

[0049] (1-4. Chlorination) In the present invention, the modified polyolefin resin of component (A) may be chlorinated.

[0050] The chlorination degree (chlorine content) of the modified polyolefin resin of component (A) is preferably 40% by weight or less, more preferably 35% by weight or less, even more preferably 30% by weight or less, and particularly preferably 25% by weight or less, with the weight of component (A) excluding the weight derived from (meta)acrylic acid-based components being 100% by weight. This can improve gasoline resistance. The lower limit is, for example, 0% by weight or more, preferably more than 0% by weight, more preferably 5% by weight or more, even more preferably 10% by weight or more, and even more preferably 14% by weight or more. This can obtain good solvent solubility. In one embodiment, the chlorination degree is preferably 5% to 30% by weight, more preferably 10% to 25% by weight. This can suppress the polarity below a certain level and obtain sufficient adhesiveness to non-polar substrates such as polyolefin substrates. The chlorination degree can be measured according to JIS-K7229. That is, it can be measured using the "oxygen flask combustion method" in which a chlorine-containing resin is burned in an oxygen atmosphere, the generated gaseous chlorine is absorbed by water, and quantified by titration.

[0051] (1-5. Characteristics of Component (A) Modified Polyolefin Resin) The weight average molecular weight of the component (A) modified polyolefin resin is preferably 5,000 or more, more preferably 7,000 or more, still more preferably 9,000 or more, and particularly preferably 10,000 or more. The upper limit is preferably 400,000 or less, more preferably 350,000 or less, and still more preferably 300,000 or less. In one embodiment, the weight average molecular weight of the component (A) modified polyolefin resin is preferably 5,000 to 400,000, more preferably 7,000 to 350,000, and still more preferably 10,000 to 300,000. The weight average molecular weight can be measured by GPC using polystyrene as a standard substance.

[0052] (1-6. Manufacturing Method of Component (A) Modified Polyolefin Resin) The component (A) modified polyolefin resin can be produced by modifying a polyolefin resin.

[0053] Therefore, the manufacturing method of the component (A) modified polyolefin resin is Step (a): A step of preparing a polyolefin resin, Step (b): A step of modifying with a (meth)acrylic acid-based component may be included in this order.

[0054] When the component (A) modified polyolefin resin is modified with an acid component other than the (meth)acrylic acid-based component, after step (a), Step (c): A step of modifying with an acid component other than the (meth)acrylic acid-based component may be included.

[0055] Step (c) may be carried out at a different time from step (b), or may be carried out simultaneously with step (b). It is preferable that step (c) is carried out at a different time from step (b). Step (c) can be carried out at any time after step (a), but it is preferable that it is carried out before step (b).

[0056] When the component (A) modified polyolefin resin is chlorinated, after step (a), Step (d): A chlorination step may be included.

[0057] Step (d) can be carried out at any time after step (a), but it is preferably carried out prior to step (b). When step (c) is included, it is more preferably carried out prior to step (b) and after step (c).

[0058] In one embodiment, the method for producing the component (A) modified polyolefin resin preferably includes each step in the order of steps (a)·(b), steps (a)·(c)·(b), steps (a)·(d)·(b), steps (a)·(c)·(d)·(b), or steps (a)·(d)·(c)·(b), and preferably includes each step in the order of steps (a)·(b), steps (a)·(c)·(b), steps (a)·(d)·(b), or steps (a)·(c)·(d)·(b).

[0059] Step (a) is a step of preparing a polyolefin resin.

[0060] The lower limit of the melting point of the polyolefin resin prepared in step (a) is preferably 50°C or higher, more preferably 60°C or higher. When the melting point of the polyolefin resin prepared in step (a) is 50°C or higher, sufficient coating film strength can be exhibited when the component (A) modified polyolefin resin is used in applications such as inks and paints. Therefore, sufficient adhesion to the substrate can be exhibited. Also, when used as an ink, blocking during printing can be suppressed.

[0061] The upper limit of the melting point of the polyolefin resin prepared in step (a) is preferably 120°C or lower, more preferably 110°C or lower, still more preferably 100°C or lower. When the melting point of the polyolefin resin prepared in step (a) is 120°C or lower, it is possible to suppress the coating film from becoming too hard when the component (A) modified polyolefin resin is used in applications such as inks and paints. Therefore, the coating film can exhibit appropriate flexibility.

[0062] As one embodiment of the melting point of the polyolefin resin prepared in step (a), 50°C to 120°C is preferable, 60°C to 110°C is more preferable, and 60°C to 100°C is even more preferable.

[0063] Step (b) is a step of modifying with a (meth)acrylic acid-based component, and step (c) is a step of modifying with an acid component other than the (meth)acrylic acid-based component (hereinafter may be abbreviated as "acid component").

[0064] Steps (b) and (c) can each be carried out, for example, by a method of introducing a (meth)acrylic acid-based component or an acid component into the polyolefin resin by graft copolymerization. The method of graft copolymerization is not particularly limited, and known methods such as a melting method and a solution method can be used. In the case of the melting method, the operation is simple and the reaction can be carried out in a short time. In the case of the solution method, there are few side reactions and a uniform graft polymer can be obtained.

[0065] In one embodiment, step (b) is preferably carried out by the solution method. In one embodiment, step (c) is preferably carried out by the melting method.

[0066] When step (b) or (c) is carried out by the melting method, for example, the polyolefin is heated and melted (heated to melt) and reacted in the presence of a radical reaction initiator. The temperature of heating and melting may be above the melting point, and it is preferably above the melting point and below 300°C. When heating and melting, equipment such as a Banbury mixer, a kneader, and an extruder can be used.

[0067] As the radical reaction initiator, for example, it can be a thermal polymerization reaction initiator that generates free radicals upon heating. Examples thereof include organic peroxide compounds and azonitriles. Examples of the organic peroxide compounds include di-tert-butyl peroxide, dicumyl peroxide, tert-butyl cumyl peroxide, dibenzoyl peroxide, benzoyl m-tolyl peroxide, di(m-tolyl)benzoyl, dilauryl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, cumene hydroperoxide, tert-butyl hydroperoxide, 1,1-bis(tert-butylperoxy)-3,5,5-trimethylcyclohexane, 1,1-bis(tert-butylperoxy)-cyclohexane, cyclohexanone peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyisobutyrate, tert-butyl peroxy-3,5,5-trimethylhexanoate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxyisopropyl carbonate, cumyl peroxy octoate, and the like. Examples of the azonitriles include 2,2-azobis(2-methylbutyronitrile), 2,2-azobisisobutyronitrile, 2,2-azobis(2,4-dimethylvaleronitrile), 2,2-azobis(4-methoxy-2,4-dimethylvaleronitrile).

[0068] When step (b) or (c) is carried out by a melting method, step (c) is preferably carried out using an extruder (performing extrusion modification). As the method of extrusion modification, for example, raw materials are blended and supplied to the supply part of an extruder (for example, a co-rotating multi-screw extruder, a twin-screw extruder), and each step of raw material mixing, melt kneading, reaction, and devolatilization cooling is sequentially carried out in the extruder, and the resin coming out from the tip die is cooled (for example, immersed in a water tank) to obtain a polyolefin resin modified with a (meth)acrylic acid-based component or an acid component. The progress of the reaction can be adjusted by adjusting the temperature of each part of the barrel and the screw rotation speed.

[0069] When step (b) or (c) is carried out by a solution method, for example, after dissolving a polyolefin in an organic solvent, it is reacted by heating and stirring in the presence of a radical reaction initiator. The temperature during the reaction is preferably 100 to 180 °C. After step (b) or (c), the organic solvent in the system may be distilled off under reduced pressure, or the organic solvent may be removed using an extruder.

[0070] As the organic solvent used when step (b) or (c) is carried out by a solution method, preferably, aromatic hydrocarbon solvents such as toluene, o-xylene, m-xylene, p-xylene, ethylbenzene, etc.; or hydrocarbon solvents such as aliphatic hydrocarbon solvents such as n-pentane, cyclopentane, n-hexane, isohexane, cyclohexane, n-heptane, methylcyclohexane, n-octane, ethylcyclohexane, n-nonane, n-decane, etc. can be used.

[0071] The content of component (C) hydroxyl monomer in the (meth)acrylic acid-based component used in step (b) is preferably 20 mol% or less, more preferably 15 mol% or less, still more preferably 10 mol% or less, based on 100 mol% of the (meth)acrylic acid-based component used in step (b). The lower limit is preferably 0.1 mol% or more, more preferably 1 mol% or more, still more preferably 3 mol% or more.

[0072] The content of component (D) low-polarity monomer in the (meth)acrylic acid-based component used in step (b) is preferably 25 mol% or more, more preferably 30 mol% or more, still more preferably 40 mol% or more, based on 100 mol% of the (meth)acrylic acid-based component used in step (b). The upper limit is preferably 90 mol% or less, or 85 mol% or less, more preferably 80 mol% or less, or 75 mol% or less, still more preferably 70 mol% or less, or 65 mol% or less, particularly preferably 60 mol% or less, or 55 mol% or less.

[0073] In one embodiment, the content of component (E) alkoxy group monomer in the (meth)acrylic acid-based component used in step (b) is preferably 50 mol% or less, more preferably 40 mol% or less, based on 100 mol% of the (meth)acrylic acid-based component used in step (b). The lower limit is preferably 0.1 mol% or more, more preferably 1 mol% or more.

[0074] In one embodiment, the content of component (F) lower monomer in the (meth)acrylic acid-based component used in step (b) is preferably 1 mol% or more, more preferably 5 mol% or more, based on 100 mol% of the (meth)acrylic acid-based component used in step (b). The upper limit is preferably 70 mol% or less, more preferably 50 mol% or less.

[0075] The weight average molecular weight of the modified or unmodified polyolefin resin (polyolefin-based resin) immediately before step (b) is preferably 200,000 or less, more preferably 150,000 or less, still more preferably 120,000 or less. The lower limit is preferably 10,000 or more, more preferably 20,000 or more, still more preferably 40,000 or more.

[0076] The chlorination degree (chlorine content) of the polyolefin-based resin immediately before step (b), with the weight of the polyolefin-based resin being 100% by weight, is preferably 40% by weight or less, more preferably 35% by weight or less, still more preferably 30% by weight or less, particularly preferably 25% by weight or less. The lower limit is, for example, 0% by weight or more, preferably more than 0% by weight, more preferably 5% by weight or more, still more preferably 10% by weight or more, even more preferably 14% by weight or more, particularly preferably 16% by weight or more.

[0077] The total graft weight (modification degree) of acid components other than the (meth)acrylic acid-based component of the polyolefin-based resin immediately before step (b) is preferably 20% by weight or less, more preferably 10% by weight or less, with the polyolefin-based resin being 100% by weight. The lower limit can be, for example, 0% by weight or more.

[0078] The polyolefin resin in the immediately preceding step of step (b) may be a single resin or a mixture of two or more resins.

[0079] The reaction ratio (mass ratio) of the polyolefin resin in the immediately preceding step of step (b) to the (meth)acrylic acid component in step (b) (polyolefin resin / (meth)acrylic acid component) is 97 / 3 to 6 / 94, preferably 95 / 5 to 10 / 90.

[0080] Step (d) is a chlorination step.

[0081] Chlorination may be carried out after previously dissolving the raw material resin in a chlorine-based solvent such as chloroform. Chlorination is carried out, for example, by blowing chlorine gas into the reaction system. The blowing of chlorine gas may be carried out under irradiation with ultraviolet rays or in the presence of a radical reaction initiator. The pressure during the blowing of chlorine gas is not limited and may be normal pressure or under pressure. The temperature during the blowing of chlorine gas is not particularly limited, but is, for example, 50 to 140°C.

[0082] (2. Component (B) dispersion medium) The dispersion composition of the present invention contains an alcohol-based solvent and an aliphatic hydrocarbon-based solvent as a dispersion medium for dispersing the component (A) modified polyolefin resin. Thereby, an increase in the viscosity of the dispersion composition can be suppressed, and good dispersibility and stability can be exhibited. The mechanism is presumed as follows. Dispersion particles in which the polyolefin structure derived from the unmodified raw material encloses a low-polarity group and the structure derived from the (meth)acrylic acid component covers the periphery thereof can be dispersed in the solvent. Therefore, the dispersion particles can stably exist in the composition. In addition, since the hydroxyl group derived from the (meth)acrylic acid component can be oriented toward the alcohol-based solvent side and the low-polarity group can be oriented toward the polyolefin structure side, the dispersion particles can take a stable structure in the composition.

[0083] Examples of the alcohol solvents include aliphatic alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, tert-butyl alcohol, 2-ethyl-hexanol, 1-pentanol, etc.; glycol monoethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monoisopropyl ether, propylene glycol monobutyl ether, etc. Although not particularly limited, alcohols having 4 or less carbon atoms are preferred. Examples of the alcohols having 4 or less carbon atoms include aliphatic alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, tert-butyl alcohol, etc. When the number of carbon atoms is 4 or less, since the alcohol is highly polar, dissolution of the resin component into the alcohol is suppressed, and it becomes easy to stably disperse as resin particles.

[0084] Examples of the aliphatic hydrocarbon solvents include n-pentane, cyclopentane, n-hexane, isohexane, cyclohexane, n-heptane, methylcyclohexane, n-octane, ethylcyclohexane, n-nonane, n-decane, etc. Cyclohexane, methylcyclohexane, and ethylcyclohexane are preferred, and methylcyclohexane is more preferred.

[0085] The alcohol solvent and the aliphatic hydrocarbon solvent may each be used alone or in combination of two or more.

[0086] The content ratio (mass ratio) of the alcohol solvent to the aliphatic hydrocarbon solvent (alcohol solvent / aliphatic hydrocarbon solvent) is preferably 99 / 1 to 10 / 90, more preferably 95 / 5 to 50 / 50, and still more preferably 90 / 10 to 70 / 30.

[0087] The total content of the alcohol-based solvent and the aliphatic hydrocarbon-based solvent contained in the dispersion medium is preferably 80% by weight or more, more preferably 90% by weight or more, still more preferably 95% by weight or more, based on 100% by weight of the dispersion medium.

[0088] In addition to the alcohol-based solvent and the aliphatic hydrocarbon-based solvent, the dispersion medium of the dispersion composition of the present invention may further contain other solvents. As the other solvents, a wide range of solvents commonly used in inks and / or paints can be used. For example, aromatic hydrocarbon-based solvents such as toluene, o-xylene, m-xylene, p-xylene, and ethylbenzene; ester-based solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, and n-butyl acetate; ketone-based solvents such as acetone, methyl ethyl ketone, and methyl butyl ketone; glycol-based solvents such as ethylene glycol, ethyl cellosolve, and butyl cellosolve, etc. can be mentioned, but are not limited thereto.

[0089] The dispersion medium in the dispersion composition of the present invention may contain water. The content ratio of water may preferably be 10% by weight or less based on 100% by weight of the total amount of the dispersion medium.

[0090] (3. Dispersion Composition) The dispersion composition of the present invention is a dispersion composition in which at least the component (A) modified polyolefin resin is dispersed in a dispersion medium containing the component (B) alcohol-based solvent and aliphatic hydrocarbon-based solvent.

[0091] The solid content ratio of the dispersion composition of the present invention is 30% by weight or more, preferably 35% by weight. Thereby, an appropriate interaction is generated between the dispersed particles in the composition, and the dispersibility can be improved. The upper limit of the solid content ratio of the dispersion composition is 80% by weight or less, preferably 70% by weight or less, more preferably 60% by weight or less, and even more preferably 50% by weight or less. In one embodiment, the solid content ratio of the dispersion composition is preferably 30% by weight to 70% by weight, more preferably 30% by weight to 60% by weight, and even more preferably 35% by weight to 50% by weight. Thereby, good stability over time can be achieved. The solid content ratio can be adjusted by changing the amount of the dispersion medium used.

[0092] In addition to the component (A) modified polyolefin resin and the component (B) dispersion medium, the dispersion composition of the present invention may contain other components as long as the objects and effects of the present invention are not inhibited. Examples of the other components include resin components such as (meth)acrylic acid resins, which have only a structure derived from (meth)acrylic acid components as constituent units, and (meth)acrylic acid components (monomers); stabilizers, basic substances, emulsifiers, crosslinking agents, diluents, curing agents, etc. It is preferable to contain at least a stabilizer.

[0093] Examples of the stabilizer include compounds containing an epoxy ring such as epoxy-based stabilizers. Examples of the epoxy-based stabilizer include epoxy compounds having an epoxy equivalent of about 100 to 500 and containing one or more epoxy groups in one molecule. More specifically, the following compounds can be mentioned: Epoxidized soybean oil and epoxidized linseed oil obtained by epoxidizing vegetable oils having natural unsaturated groups with peracids such as peracetic acid; Epoxidized fatty acid esters obtained by epoxidizing unsaturated fatty acids such as oleic acid, tall oil fatty acid, and soybean oil fatty acid; Epoxidized alicyclic compounds typified by epoxidized tetrahydrophthalate; Condensates of bisphenol A or polyhydric alcohol and epichlorohydrin, such as bisphenol A glycidyl ether, ethylene glycol glycidyl ether, propylene glycol glycidyl ether, glycerol polyglycidyl ether, sorbitol polyglycidyl ether; Monoepoxy compounds typified by butyl glycidyl ether, 2-ethylhexyl glycidyl ether, decyl glycidyl ether, stearyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, sec-butylphenyl glycidyl ether, tert-butylphenyl glycidyl ether, phenol polyethylene oxide glycidyl ether, etc. The stabilizer may be a compound not containing an epoxy ring, for example, metal soaps such as calcium stearate and lead stearate, which are used as stabilizers for polyvinyl chloride resins; Organometallic compounds such as dibutyltin dilaurate and dibutyl maleate; Hydrotalcite compounds.

[0094] In addition, as the stabilizer, a stabilizer not containing an epoxy ring may be used. For example, metal soaps such as calcium stearate and lead stearate, which are used as stabilizers for polyvinyl chloride resins; Organometallic compounds such as dibutyltin dilaurate and dibutyl maleate; Hydrotalcite compounds.

[0095] The content of the stabilizer is preferably 0.1% by weight or more, more preferably 1% by weight or more, and still more preferably 2% by weight or more, based on 100% by weight of the component (A) modified polyolefin resin. Thereby, the stabilizing effect can be exhibited well. The upper limit of the content of the stabilizer is preferably 15% by weight or less, more preferably 12% by weight or less, and still more preferably 10% by weight or less. Thereby, the adhesiveness to a base material such as polyolefin can be exhibited well.

[0096] Examples of the basic substance 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, 2-amino-2-ethyl-1,3-propanediol, and the like. The basic substance to be used may be one kind or a combination of two or more kinds.

[0097] Examples of the emulsifier include surfactants such as nonionic surfactants and anionic surfactants.

[0098] Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene derivative, polyoxyethylene fatty acid ester, polyoxyethylene polyhydric alcohol fatty acid ester, polyoxyethylene polyoxypropylene polyol, sorbitan fatty acid ester, polyoxyethylene hydrogenated castor oil, polyoxyalkylene polycyclic phenyl ether, polyoxyethylene alkylamine, alkylalkanolamide, polyalkylene glycol (meth)acrylate, and the like.

[0099] Examples of the anionic surfactant include alkyl sulfate salts, polyoxyethylene alkyl ether sulfates, alkylbenzene sulfonates, α-olefin sulfonates, methyl taurates, sulfosuccinates, ether sulfonates, ether carboxylates, fatty acid salts, naphthalene sulfonic acid formalin condensates, alkylamine salts, quaternary ammonium salts, alkyl betaines, alkylamine oxides, and the like.

[0100] The B-type viscosity of the dispersion composition of the present invention is preferably 1200 mPa·s or less, more preferably 1000 mPa·s or less at 25°C.

[0101] The dispersion composition of the present invention has good stability such as dispersibility and stability over time, and is high in solid content and low in viscosity, so it can be used as a primer, an adhesive, a binder for paints, or a binder for inks. When the dispersion composition of the present invention is used for these applications, it may contain components usually contained in various applications, such as preservatives, leveling agents, antioxidants, light stabilizers, ultraviolet absorbers, dyes, pigments, metal salts, acids, etc., as necessary.

[0102] The method for producing the dispersion composition is not particularly limited. For example, a method of adding an alcohol-based solvent, an aliphatic hydrocarbon-based solvent, and optional components as necessary to the component (A) modified polyolefin resin and dispersing them, and a method of adding an alcohol-based solvent and optional components as necessary to the component (A) modified polyolefin resin in the presence of an aliphatic hydrocarbon-based solvent and dispersing them can be mentioned. The dispersion may be carried out by stirring, and temperature adjustment by heating or the like may be performed as necessary.

[0103] In the second embodiment, the present invention Component (α): The polyolefin-based resin is Component (β): The following general formula (I): CH2=C(R 1 )COOR 2 ···(I) (In the general formula (I), R 1 represents a hydrogen atom or a methyl group, and R 2represents -C m H 2m OH. However, m is an integer from 1 to 18.) and the following general formula (II): CH2=C(R 3 )COOR 4 ···(II) (In the general formula (II), R 3 represents a hydrogen atom or a methyl group, and R 4 represents an aliphatic or alicyclic alkyl group having 4 to 18 carbon atoms (linear, branched, and / or cyclic alkyl group).) The component (A): modified polyolefin resin graft-modified with a modified component containing at least a (meth)acrylate represented by the formula is dispersed in a mixed solvent (dispersion medium) of an alcohol-based solvent and an aliphatic solvent (aliphatic hydrocarbon-based solvent), the content ratio (weight ratio) of the component (α) to (β) ((component (α)) / (component (β))) is in the range of 97 / 3 to 6 / 94 (provided that component (α) + component (β) = 100), and the solid content is 30 to 80%, to provide a dispersion composition that satisfies the above conditions.

[0104] Examples of the component (α) polyolefin-based resin include polyolefin resin, acid-modified polyolefin resin, chlorinated polyolefin resin, and chlorinated acid-modified polyolefin resin.

[0105] The acid-modified polyolefin resin is a polyolefin resin modified with an α,β-unsaturated carboxylic acid and its derivatives. Examples of the α,β-unsaturated carboxylic acid and its derivatives include maleic acid, maleic anhydride, fumaric acid, citraconic acid, citraconic anhydride, mesaconic acid, itaconic acid, itaconic anhydride, aconitic acid, aconitic anhydride, hymic anhydride, (meth)acrylic acid, (meth)acrylic acid esters (excluding (meth)acrylic acid esters represented by general formulas (I) and (II)), and the like. Among them, maleic anhydride is preferred in consideration of the graftability to polyolefin. The degree of modification (graft weight) with the α,β-unsaturated carboxylic acid and / or its derivatives is preferably 0 to 20% by weight, more preferably 0 to 10% by weight. As a method for producing the acid-modified polyolefin resin, the same method as in the above step (c) can be used.

[0106] The chlorinated polyolefin resin is a polyolefin resin into which chlorine has been introduced, and may also be a polyolefin resin into which an α,β-unsaturated carboxylic acid or its derivative has been introduced in addition to chlorine (acid-modified chlorinated polyolefin resin). For the introduction of chlorine, the same method as in the above step (d) can be used. In the production of the acid-modified chlorinated polyolefin resin, both acid modification and chlorination may be performed. The order of acid modification and chlorination is not particularly limited, but preferably, chlorination is performed after acid modification. The degree of chlorination of the chlorinated polyolefin resin is preferably 30% by weight or less, more preferably 25% by weight or less. The lower limit is, for example, more than 0% by weight, preferably 5% by weight or more, and more preferably 10% by weight or more. The degree of chlorination is preferably 5 to 30% by weight, more preferably 10 to 25% by weight.

[0107] The weight average molecular weight of the component (α) polyolefin-based resin is preferably 200,000 or less, more preferably 90,000 or less, and still more preferably 70,000 or less. The lower limit is, for example, 10,000 or more, more preferably 20,000 or more.

[0108] Component (α) The polyolefin resin may be a single polyolefin resin or a combination of two or more, but it preferably contains at least one acid-modified chlorinated polyolefin resin.

[0109] Component (β) The modifying component contains (meth)acrylic acid esters (component (C) hydroxyl monomer and component (D) low-polarity monomer) represented by general formulas (I) and (II) respectively. Other modifying components that component (β) may contain include, for example, α,β-unsaturated carboxylic acids and their derivatives, and (meth)acrylic acid esters other than components (C) and (D). These examples are the same as those given in the description of the acid-modified polyolefin resin. Among them, (meth)acrylic acid and (meth)acrylic acid esters other than components (C) and (D) are preferred, and methyl (meth)acrylate and 2-methoxyethyl (meth)acrylate are preferred.

[0110] The content of the (meth)acrylic acid ester represented by general formula (I) is, for example, 20 mol% or less, preferably 15 mol% or less, more preferably 10 mol% or less, based on the total amount of component (β) modifying component. The lower limit is, for example, 0.1 mol% or more, preferably 1 mol% or more, more preferably 3 mol% or more. The content of the (meth)acrylic acid ester represented by general formula (II) is, for example, 25 mol% or more, preferably 30 mol% or more, more preferably 40 mol% or more, based on the total amount of component (β) modifying component. The upper limit is, for example, 90 mol / % or less, preferably 85 mol% or less.

[0111] The molar ratio of the content of the (meth)acrylic acid esters represented by general formulas (I) and (II) in the content of component (β) modifying component is, for example, 30 mol% or more, preferably 40 mol% or more, more preferably 45 mol% or more. The upper limit is 95 mol% or less, preferably 90 mol% or less, more preferably 85 mol% or less.

[0112] The content ratio of component (α) polyolefin resin to component (β) modifying component ((component (α) / component (β))) is from 97 / 3 to 6 / 94, preferably from 95 / 5 to 10 / 90, more preferably from 95 / 5 to 50 / 50, and still more preferably from 95 / 5 to 60 / 40. Thereby, the adhesion can be improved. The above values are the values when component (α) + component (β) = 100.

Examples

[0113] Hereinafter, the present invention will be specifically described using examples, but the present invention is not limited to these examples. In addition, the unit "part" used below means "part by mass". The temperature conditions in the following description are at normal temperature (25 ° C) when the temperature is not specified, and the pressure conditions are at normal pressure (1 atm) when the pressure is not specified.

[0114] [Production Example 1: Production of Acid-Modified Chlorinated Polyolefin Resin (A-1)] 100 parts of a polyolefin resin (propylene-based random copolymer, propylene constituent unit content: 96% by weight, ethylene constituent unit content: 4% by weight) produced using a metallocene catalyst as a polymerization catalyst, 4 parts of maleic anhydride (α,β-unsaturated carboxylic acid anhydride), and 2 parts of di-tert-butyl peroxide (radical reaction initiator) were uniformly mixed and supplied to a twin-screw extruder (L / D = 60, diameter = 15 mm, first barrel to fourteenth barrel).

[0115] The reaction was carried out under the conditions of a residence time of 10 minutes, a rotation speed of 200 rpm, and barrel temperatures of 100 ° C (first and second barrels), 200 ° C (third to eighth barrels), 90 ° C (ninth and tenth barrels), and 110 ° C (eleventh to fourteenth barrels). Then, a vacuum treatment was performed to remove unreacted maleic anhydride, and an acid-modified polyolefin resin modified with maleic anhydride was obtained.

[0116] 100 parts of the acid-modified polyolefin resin was put into a glass-lined reaction kettle. Chloroform was added, and 2 kgf / cm 2Under pressure, after sufficiently dissolving the resin at a temperature of 110 °C, 2 parts of 2,2-azobisisobutyronitrile (radical reaction initiator) were added, and while controlling the pressure inside the kettle to 2 kgf / cm 2 chlorine gas was blown in to carry out chlorination.

[0117] After completion of the reaction, 6 parts of an epoxy compound (Epoxysizer W-100EL, manufactured by DIC Corporation) were added as a stabilizer, and it was supplied to an extruder with a vent equipped with a suction part for solvent removal in the screw shaft part, the solvent was removed, solidified, and an acid-modified chlorinated polyolefin resin (A-1) was obtained. The obtained acid-modified chlorinated polyolefin resin (A-1) had a weight average molecular weight of 60,000, a modification degree with maleic anhydride of 2.5% by weight, and a chlorine content of 15% by weight.

[0118] [Production Example 2: Production of Chlorinated Polyolefin Resin (A-2)] 100 parts of a polyolefin resin (propylene-based random copolymer, propylene constituent unit content: 96% by weight, ethylene constituent unit content: 4% by weight) produced using a metallocene catalyst as a polymerization catalyst were put into a reaction kettle lined with glass. Chloroform was added, and after sufficiently dissolving the resin at a temperature of 110 °C under a pressure of 2 kgf / cm 2 2 parts of 2,2-azobisisobutyronitrile (radical reaction initiator) were added, and while controlling the pressure inside the kettle to 2 kgf / cm 2 chlorine gas was blown in to carry out chlorination.

[0119] After completion of the reaction, 6 parts of an epoxy compound (Epoxysizer W-100EL, manufactured by DIC) were added as a stabilizer, and it was supplied to an extruder with a vent equipped with a suction part for solvent removal in the screw shaft part, the solvent was removed, solidified, and a chlorinated polyolefin resin (A-2) was obtained. The obtained chlorinated polyolefin resin (A-2) had a weight average molecular weight of 60,000 and a chlorine content of 15% by weight.

[0120] [Production Example 3: Production of Acid-Modified Polyolefin Resin (A-3)] 100 parts of a polyolefin resin (propylene-based random copolymer, propylene constitutional unit content: 96% by weight, ethylene constitutional unit content: 4% by weight) produced using a metallocene catalyst as a polymerization catalyst, 4 parts of maleic anhydride (α,β-unsaturated carboxylic acid anhydride), and 2 parts of di-tert-butyl peroxide (radical reaction initiator) were uniformly mixed and fed into a twin-screw extruder (L / D = 60, diameter = 15 mm, barrel 1 to barrel 14).

[0121] The reaction was carried out under the conditions of a residence time of 10 minutes, a rotation speed of 200 rpm, and barrel temperatures of 100 °C (barrels 1 and 2), 200 °C (barrels 3 to 8), 90 °C (barrels 9 and 10), and 110 °C (barrels 11 to 14). Thereafter, a vacuum treatment was performed to remove unreacted maleic anhydride, and an acid-modified polyolefin resin (A-3) modified with maleic anhydride was obtained.

[0122] The obtained acid-modified polyolefin resin (A-3) had a weight-average molecular weight of 60,000 and a modification degree with maleic anhydride of 2.5% by weight.

[0123] [Production Example 4: Production of Acid-Modified Chlorinated Polyolefin Resin (A-4)] 100 parts of a polyolefin resin (propylene-based random copolymer, propylene constitutional unit content: 96% by weight, ethylene constitutional unit content: 4% by weight) produced using a metallocene catalyst as a polymerization catalyst, 4 parts of maleic anhydride (α,β-unsaturated carboxylic acid anhydride), and 2 parts of di-tert-butyl peroxide (radical reaction initiator) were uniformly mixed and fed into a twin-screw extruder (L / D = 60, diameter = 15 mm, barrel 1 to barrel 14).

[0124] The reaction was carried out under the conditions of a residence time of 10 minutes, a rotation speed of 200 rpm, and barrel temperatures of 100 °C (barrels 1 and 2), 200 °C (barrels 3 to 8), 90 °C (barrels 9 and 10), and 110 °C (barrels 11 to 14). Thereafter, a vacuum treatment was performed to remove unreacted maleic anhydride, and an acid-modified polyolefin resin modified with maleic anhydride was obtained.

[0125] 100 parts of the acid-modified polyolefin resin were charged into a glass-lined reaction kettle. Chloroform was added, and after the resin was sufficiently dissolved at a temperature of 110 °C under a pressure of 2 kgf / cm 2 , 2 parts of 2,2-azobisisobutyronitrile (radical reaction initiator) were added, and while controlling the pressure in the kettle to 3 kgf / cm 2 , chlorine gas was blown in to carry out chlorination.

[0126] After completion of the reaction, 6 parts of an epoxy compound (Epoxysizer W-100EL, manufactured by DIC Corporation) as a stabilizer were added, and the mixture was supplied to an extruder with a vent equipped with a suction part for solvent removal in the screw shaft part, and the solvent was removed and solidified to obtain an acid-modified chlorinated polyolefin resin (A-4). The obtained acid-modified chlorinated polyolefin resin (A-4) had a weight average molecular weight of 60,000, a modification degree with maleic anhydride of 2.5% by weight, and a chlorine content of 25% by weight.

[0127] [Production Example 5: Production of Acid-Modified Chlorinated Polyolefin Resin (A-5)] 100 parts of a polyolefin resin (propylene-based random copolymer, propylene constituent unit content: 96% by weight, ethylene constituent unit content: 4% by weight) produced using a metallocene catalyst as a polymerization catalyst, 4 parts of maleic anhydride (α,β-unsaturated carboxylic acid anhydride), and 2 parts of di-tert-butyl peroxide (radical reaction initiator) were uniformly mixed and supplied to a twin-screw extruder (L / D = 60, diameter = 15 mm, first barrel to fourteenth barrel).

[0128] The reaction was carried out under the conditions of a residence time of 10 minutes, a rotation speed of 200 rpm, and barrel temperatures of 100 °C (first and second barrels), 200 °C (third to eighth barrels), 90 °C (ninth and tenth barrels), and 110 °C (eleventh to fourteenth barrels). Then, a vacuum treatment was carried out to remove unreacted maleic anhydride, and an acid-modified polypropylene resin modified with maleic anhydride was obtained.

[0129] 100 parts of the acid-modified polypropylene resin were charged into a glass-lined reaction kettle. Chloroform was added, and at 2 kgf / cm 2Under pressure, after the resin was sufficiently dissolved at a temperature of 110 °C, 2 parts of 2,2-azobisisobutyronitrile (radical reaction initiator) was added, and chlorine gas was blown in while controlling the pressure in the kettle to 2 kgf / cm 2 to carry out chlorination.

[0130] After completion of the reaction, 6 parts of an epoxy compound (Epoxysizer W-100EL, manufactured by DIC Corporation) was added as a stabilizer, and the mixture was supplied to an extruder with a vent equipped with a suction part for solvent removal in the screw shaft part, and the solvent was removed and solidified to obtain an acid-modified chlorinated polyolefin resin (A-5). The obtained acid-modified chlorinated polyolefin resin (A-5) had a weight average molecular weight of 110,000, a modification degree with maleic anhydride of 2.0% by weight, and a chlorine content of 17% by weight.

[0131] [Production Example 6: Production of acid-modified chlorinated polyolefin resin (A-6)] 100 parts of a polyolefin resin (propylene-based random copolymer, propylene constituent unit content: 96% by weight, ethylene constituent unit content: 4% by weight) produced using a metallocene catalyst as a polymerization catalyst, 4 parts of maleic anhydride (α,β-unsaturated carboxylic acid anhydride), and 2 parts of di-tert-butyl peroxide (radical reaction initiator) were uniformly mixed and supplied to a twin-screw extruder (L / D = 60, diameter = 15 mm, first barrel to fourteenth barrel).

[0132] The reaction was carried out under the conditions of a residence time of 10 minutes, a rotation speed of 200 rpm, and barrel temperatures of 100 °C (first and second barrels), 200 °C (third to eighth barrels), 90 °C (ninth and tenth barrels), and 110 °C (eleventh to fourteenth barrels). Thereafter, a vacuum treatment was carried out to remove unreacted maleic anhydride to obtain an acid-modified polypropylene resin modified with maleic anhydride.

[0133] 100 parts of the acid-modified polypropylene resin was put into a reaction kettle lined with glass. Chloroform was added, and after the resin was sufficiently dissolved at a temperature of 110 °C under a pressure of 2 kgf / cm 2 to 2 kgf / cm2 While controlling to [specific condition], chlorine gas was blown in to conduct chlorination.

[0134] After the reaction was completed, 6 parts of an epoxy compound (Epoxysizer W-100EL, manufactured by DIC Corporation) was added as a stabilizer, and it was supplied to an extruder with a vent equipped with a suction part for solvent removal in the screw shaft part, and the solvent was removed and solidified to obtain an acid-modified chlorinated polyolefin resin (A-6). The obtained acid-modified chlorinated polyolefin resin (A-6) had a weight average molecular weight of 60,000, a modification degree with maleic anhydride of 2.5% by weight, and a chlorine content of 24.5% by weight.

[0135] [Example 1: Production of Dispersion Composition (B-1)] 100 parts of an acid-modified chlorinated polyolefin resin (A-1) was dissolved in 264.1 parts of methylcyclohexane (an aliphatic hydrocarbon solvent), and 1.0 part (1.0% by weight based on the acid-modified chlorinated polyolefin resin (A-1)) of an epoxy compound (Epoxysizer W-131, manufactured by DIC Corporation) was added.

[0136] In a nitrogen atmosphere, under stirring at 85°C, 5.0 parts of Niper BMT-K40 (manufactured by NOF Corporation) (a radical reaction initiator) (3.2% by weight based on the following addition amount of (meth)acrylic acid components) was added, and after holding for 1 hour, a mixed solution of 3.8 parts of methacrylic acid, 28.1 parts of methyl methacrylate, 28.1 parts of cyclohexyl methacrylate, 46.9 parts of n-butyl methacrylate, 35.6 parts of 2-methoxyethyl acrylate, and 7.5 parts of 2-hydroxyethyl acrylate ((meth)acrylic acid components) was continuously added over 3 hours and held at 85°C for 6 hours to obtain a modified polyolefin resin with a molecular weight of 80,000.

[0137] 100 parts of the reaction solution after the reaction was completed was concentrated by distilling off 37.6 parts of methylcyclohexane (an aliphatic hydrocarbon solvent) under reduced pressure with stirring at 90°C, and 57.6 parts of isopropanol (an alcohol solvent) was added over about 2 hours with stirring at 70°C to obtain a dispersion composition (B-1) of the modified polyolefin resin.

[0138] [Example 2: Production of Dispersion Composition (B-2)] The (meth)acrylic acid-based component added to 100 parts of the acid-modified chlorinated polyolefin resin (A-1) was changed to a mixed solution of 3.8 parts of methacrylic acid, 13.1 parts of methyl methacrylate, 28.1 parts of cyclohexyl methacrylate, 46.9 parts of n-butyl methacrylate, 35.6 parts of 2-methoxyethyl acrylate, and 22.5 parts of 2-hydroxyethyl acrylate. Except for this change, modification and dispersion were carried out in the same manner as in Example 1 to obtain a dispersion composition (B-2).

[0139] [Example 3: Production of Dispersion Composition (B-3)] The (meth)acrylic acid-based component added to 100 parts of the acid-modified chlorinated polyolefin resin (A-1) was changed to a mixed solution of 3.8 parts of methacrylic acid, 33.6 parts of methyl methacrylate, 28.1 parts of cyclohexyl methacrylate, 46.9 parts of n-butyl methacrylate, 35.6 parts of 2-methoxyethyl acrylate, and 2.0 parts of 2-hydroxyethyl acrylate. Except for this change, modification and dispersion were carried out in the same manner as in Example 1 to obtain a dispersion composition (B-3).

[0140] [Example 4: Production of Dispersion Composition (B-4)] The (meth)acrylic acid-based component added to 100 parts of the acid-modified chlorinated polyolefin resin (A-1) was changed to a mixed solution of 3.8 parts of methacrylic acid, 13.1 parts of methyl methacrylate, 73.1 parts of cyclohexyl methacrylate, 46.9 parts of n-butyl methacrylate, 5.6 parts of 2-methoxyethyl acrylate, and 7.5 parts of 2-hydroxyethyl acrylate. Except for this change, modification and dispersion were carried out in the same manner as in Example 1 to obtain a dispersion composition (B-4).

[0141] [Example 5: Production of Dispersion Composition (B-5)] The (meth)acrylic acid-based component to be added to 100 parts of the acid-modified chlorinated polyolefin resin (A-1) was changed to a mixed solution of 3.8 parts of methacrylic acid, 58.1 parts of methyl methacrylate, 8.1 parts of cyclohexyl methacrylate, 36.9 parts of n-butyl methacrylate, 35.6 parts of 2-methoxyethyl acrylate, and 7.5 parts of 2-hydroxyethyl acrylate. Except for this change, modification and dispersion were carried out in the same manner as in Example 1 to obtain a dispersion composition (B-5).

[0142] [Example 6: Production of Dispersion Composition (B-6)] The (meth)acrylic acid-based component to be added to 100 parts of the acid-modified chlorinated polyolefin resin (A-1) was changed to a mixed solution of 3.8 parts of methacrylic acid, 13.1 parts of methyl methacrylate, 28.1 parts of cyclohexyl methacrylate, 46.9 parts of n-butyl methacrylate, 20.6 parts of 2-methoxyethyl acrylate, and 22.5 parts of 2-hydroxyethyl acrylate. Except for this change, modification and dispersion were carried out in the same manner as in Example 1 to obtain a dispersion composition (B-6).

[0143] [Example 7: Production of Dispersion Composition (B-7)] The amount of the (meth)acrylic acid-based component to be added to the acid-modified chlorinated polyolefin resin (A-1) was changed so that the mass ratio of acid-modified chlorinated polyolefin resin (A-1) / (meth)acrylic acid-based component = 95 / 5. Except for this change, modification and dispersion were carried out in the same manner as in Example 1 to obtain a dispersion composition (B-7).

[0144] [Example 8: Production of Dispersion Composition (B-8)] The amount of the (meth)acrylic acid-based component to be added to the acid-modified chlorinated polyolefin resin (A-1) was changed so that the mass ratio of acid-modified chlorinated polyolefin resin (A-1) / (meth)acrylic acid-based component = 10 / 90. Except for this change, modification and dispersion were carried out in the same manner as in Example 1 to obtain a dispersion composition (B-8).

[0145] [Example 9: Production of Dispersion Composition (B-9)] The amount of the (meth)acrylic acid-based component to be added to the acid-modified chlorinated polyolefin resin (A-1) was changed so that the ratio of acid-modified chlorinated polyolefin resin (A-1) / (meth)acrylic acid-based component = 80 / 20 (mass ratio). Except for this, modification and dispersion were carried out in the same manner as in Example 1 to obtain a dispersion composition (B-9).

[0146] [Example 10: Production of Dispersion Composition (B-10)] The amount of the (meth)acrylic acid-based component to be added to the acid-modified chlorinated polyolefin resin (A-1) was changed so that the ratio of acid-modified chlorinated polyolefin resin (A-1) / (meth)acrylic acid-based component = 60 / 40 (mass ratio). Except for this, modification and dispersion were carried out in the same manner as in Example 1 to obtain a dispersion composition (B-10).

[0147] [Example 11: Production of Dispersion Composition (B-11)] The amount of methylcyclohexane (aliphatic hydrocarbon solvent) to be distilled off under reduced pressure and isopropanol (alcohol solvent) to be added to 100 parts of the reaction solution after the reaction was changed so that the final solid content was 30% by weight while keeping the final solvent ratio the same. Except for this, modification and dispersion were carried out in the same manner as in Example 1 to obtain a dispersion composition (B-11).

[0148] [Example 12: Production of Dispersion Composition (B-12)] Modification and dispersion were carried out in the same manner as in Example 1 except that chlorinated polyolefin resin (A-2) was used instead of the acid-modified chlorinated polyolefin resin (A-1) to obtain a dispersion composition (B-12).

[0149] [Example 13: Production of Dispersion Composition (B-13)] Modification and dispersion were carried out in the same manner as in Example 1 except that acid-modified polyolefin resin (A-3) was used instead of the acid-modified chlorinated polyolefin resin (A-1) to obtain a dispersion composition (B-13).

[0150] [Example 14: Production of Dispersion Composition (B-14)] Denaturation and dispersion were carried out in the same manner as in Example 1, except that the acid-modified chlorinated polyolefin resin (A-4) was used instead of the acid-modified chlorinated polyolefin resin (A-1), to obtain a dispersion composition (B-14).

[0151] [Example 15: Production of Dispersion Composition (B-15)] Denaturation and dispersion were carried out in the same manner as in Example 1, except that the addition amount of the radical reaction initiator (Niper BMT-K40, manufactured by NOF Corporation) was changed to 0.5% by weight based on the addition amount of the (meth)acrylic acid-based component, to obtain a dispersion composition (B-15).

[0152] [Example 16: Production of Dispersion Composition (B-16)] Denaturation and dispersion were carried out in the same manner as in Example 1, except that the addition amount of the radical reaction initiator (Niper BMT-K40, manufactured by NOF Corporation) was changed to 6.4% by weight based on the addition amount of the (meth)acrylic acid-based component, to obtain a dispersion composition (B-16).

[0153] [Example 17: Production of Dispersion Composition (B-17)] The acid-modified chlorinated polyolefin resin (A-5) was used instead of the acid-modified chlorinated polyolefin resin (A-1), and the (meth)acrylic acid-based component added to 100 parts of the acid-modified chlorinated polyolefin resin (A-5) was changed to a mixed solution of 3.8 parts of methacrylic acid, 30.0 parts of methyl methacrylate, 28.1 parts of cyclohexyl methacrylate, 47.0 parts of n-butyl methacrylate, 35.7 parts of 2-methoxyethyl acrylate, and 5.6 parts of 2-hydroxyethyl acrylate. Denaturation and dispersion were carried out in the same manner as in Example 1, except that n-butyl alcohol (alcohol-based solvent) was used instead of isopropanol (alcohol-based solvent), to obtain a dispersion composition (B-17).

[0154] [Example 18: Production of Dispersion Composition (B-18)] Instead of using the acid-modified chlorinated polyolefin resin (A-1), the acid-modified chlorinated polyolefin resin (A-6) was used. The (meth)acrylic acid-based component added to 100 parts of the acid-modified chlorinated polyolefin resin (A-6) was changed to a mixed solution of 3.8 parts of methacrylic acid, 30.0 parts of methyl methacrylate, 28.1 parts of cyclohexyl methacrylate, 47.0 parts of n-butyl methacrylate, 35.7 parts of 2-methoxyethyl acrylate, and 5.6 parts of 2-hydroxyethyl acrylate. Denaturation and dispersion were carried out in the same manner as in Example 1, except that n-butyl alcohol (an alcohol-based solvent) was used instead of isopropanol (an alcohol-based solvent), and a dispersion composition (B-18) was obtained.

[0155] [Example 19: Production of Dispersion Composition (B-19)] Instead of using the acid-modified chlorinated polyolefin resin (A-1), the acid-modified chlorinated polyolefin resin (A-5) was used. The (meth)acrylic acid-based component added to 100 parts of the acid-modified chlorinated polyolefin resin (A-5) was changed to a mixed solution of 3.8 parts of methacrylic acid, 30.0 parts of methyl methacrylate, 28.1 parts of cyclohexyl methacrylate, 47.0 parts of n-butyl methacrylate, 35.7 parts of 2-methoxyethyl acrylate, and 5.6 parts of 2-hydroxyethyl acrylate. Denaturation and dispersion were carried out in the same manner as in Example 1, except that neoethanol PIP (a mixed solution of ethanol, isopropyl alcohol, and n-propyl alcohol) (an alcohol-based solvent) was used instead of isopropanol (an alcohol-based solvent), and a dispersion composition (B-19) was obtained.

[0156] [Example 20: Production of Dispersion Composition (B-20)] Instead of using the acid-modified chlorinated polyolefin resin (A-1), the acid-modified chlorinated polyolefin resin (A-6) was used. The (meth)acrylic acid-based component added to 100 parts of the acid-modified chlorinated polyolefin resin (A-6) was changed to a mixed solution of 3.8 parts of methacrylic acid, 30.0 parts of methyl methacrylate, 28.1 parts of cyclohexyl methacrylate, 47.0 parts of n-butyl methacrylate, 35.7 parts of 2-methoxyethyl acrylate, and 5.6 parts of 2-hydroxyethyl acrylate. Except for using neoethanol PIP (an alcohol-based solvent) instead of isopropanol (an alcohol-based solvent), modification and dispersion were carried out in the same manner as in Example 1 to obtain a dispersion composition (B-20).

[0157] [Comparative Example 1: Production of Dispersion Composition (B-1’)] 100 parts of the acid-modified chlorinated polyolefin resin (A-1) was dissolved in 108 parts of methylcyclohexane (an aliphatic hydrocarbon-based solvent), and 1.0 part of an epoxy compound (Epoxysizer W-131, manufactured by DIC Corporation) was added so as to be 1.0% by weight based on the polyolefin resin (A).

[0158] 37.6 parts of methylcyclohexane (an aliphatic hydrocarbon-based solvent) was removed by distillation under reduced pressure with stirring at 90°C from 100 parts of the above resin solution and concentrated. 57.6 parts of isopropanol (an alcohol-based solvent) was added with stirring at 70°C over about 2 hours, but the resin component did not disperse, and the dispersion composition (B-1’) was not obtained.

[0159] [Comparative Example 2: Production of Dispersion Composition (B-2’)] Modification and dispersion were carried out in the same manner as in Example 1, except that the (meth)acrylic acid-based component added to 100 parts of the acid-modified chlorinated polyolefin resin (A-1) was changed to a mixed solution of 3.8 parts of methacrylic acid, 35.6 parts of methyl methacrylate, 28.1 parts of cyclohexyl methacrylate, 46.9 parts of n-butyl methacrylate, and 35.6 parts of 2-methoxyethyl acrylate. However, the resin component did not disperse, and the dispersion composition (B-2’) was not obtained.

[0160] [Comparative Example 3: Production of Dispersion Composition (B-3')] The (meth)acrylic acid-based component added to 100 parts of the acid-modified chlorinated polyolefin resin (A-1) was changed to a mixed solution of 3.8 parts of methacrylic acid, 56.2 parts of methyl methacrylate, 82.5 parts of 2-methoxyethyl acrylate, and 7.5 parts of 2-hydroxyethyl acrylate. Modification and dispersion were carried out in the same manner as in Example 1, but the resin component did not disperse, and the dispersion composition (B-3') could not be obtained.

[0161] [Comparative Example 4: Production of Dispersion Composition (B-4')] The (meth)acrylic acid-based component added to 100 parts of the acid-modified chlorinated polyolefin resin (A-1) was changed so that the acid-modified chlorinated polyolefin resin (A-1) / (meth)acrylic acid-based component = 5 / 95 (mass ratio). Modification and dispersion were carried out in the same manner as in Example 1 to obtain a dispersion composition (B-4').

[0162] [Comparative Example 5: Production of Dispersion Composition (B-5')] The resin solution modified with the (meth)acrylic acid-based component in the same manner as in Example 1 was solidified with an extruder. To 100 parts of the solid resin, 150 parts of isopropanol (alcohol-based solvent) was added with stirring at 90°C over 2 hours, but the resin component did not disperse, and the dispersion composition (B-5') could not be obtained.

[0163] [Comparative Example 6: Production of Dispersion Composition (B-6')] The methylcyclohexane (aliphatic hydrocarbon-based solvent) added to 100 parts of the acid-modified chlorinated polyolefin resin (A-1) was changed to n-butyl acetate. Modification and dispersion were carried out in the same manner as in Example 1, but the once-dispersed resin component settled, and the dispersion composition (B-6') could not be obtained.

[0164] [Comparative Example 7: Production of Dispersion Composition (B-7')] The amount of methylcyclohexane (aliphatic hydrocarbon solvent) to be distilled off under reduced pressure and isopropanol (alcohol solvent) to be added with respect to 100 parts of the reaction solution after the reaction was changed in the same manner as in Example 1 except that the final solid content was changed to 29% by weight while keeping the final solvent ratio as it was, and modification and dispersion were carried out to obtain a dispersion composition (B-7’).

[0165] [Evaluation Method] (Weight-average molecular weight (Mw)) It was measured by GPC according to the following conditions. Apparatus: HLC-8320GPC (manufactured by Tosoh Corporation) Columns: TSK-gel G-6000 HXL, G-5000 HXL, G-4000 HXL, G-3000 HXL, G-2000 HXL (manufactured by Tosoh Corporation) Eluent: THF Flow rate: 1 mL / min Temperature: Pump oven, column oven 40 °C Injection volume: 100 μL Standard substance: Polystyrene EasiCal PS-1 (manufactured by Agilent Technology)

[0166] (Graft weight of maleic anhydride (modification degree) (% by weight)) Measurement was carried out by an alkali titration method according to the method conforming to JIS K 0070.

[0167] (Degree of chlorination (chlorine content) (% by weight)) It was measured based on JIS-K7229.

[0168] (Dispersibility) It was evaluated from the viscosity at the time of preparing the dispersion and the appearance of the solution. Regarding the viscosity, the dispersion placed in a glass bottle was immersed in a constant temperature bath at 25 °C for 6 hours or more for temperature adjustment, and then the viscosity was measured with a B-type viscometer. A: The dispersion is uniformly milky white, and the B-type viscosity of the dispersion is 400 mPa·s or less. B: The dispersion liquid is uniformly milky white, and the B-type viscosity of the dispersion is within the range of more than 400 mPa·s and 700 mPa·s or less. C: The dispersion liquid is uniformly milky white, and the B-type viscosity of the dispersion is within the range of more than 700 mPa·s and 1200 mPa·s or less. D: A precipitate occurs immediately after preparing the dispersion, or the resin component does not disperse in the dispersion medium, or the B-type viscosity of the obtained dispersion is more than 1200 mPa·s.

[0169] (Stability over time) 150 g of the resin dispersion was placed in a 250 ml glass container, allowed to stand at room temperature for a predetermined period, and then the stability of the resin dispersion was evaluated visually. A: Even after standing for 3 months or more, there is no precipitate and it has excellent stability. B: Even after standing for 3 months or more, there is no precipitate and it slightly thickens, but it is within the practical range. C: Some precipitate is observed within 1 to 2 months, but it is within the practical range. D: Precipitate is observed within 1 month and it is not suitable for practical use.

[0170] (Adhesion test) Linear scratches reaching the substrate at 1 mm intervals were made vertically and horizontally on the coating film of the test piece to create 100 compartments (checkerboard pattern), and then cellophane adhesive tape was adhered to it and peeled off in the 180° direction. The operation of adhering and peeling off the cellophane adhesive tape was performed 10 times for the same 100 compartments, and the adhesion (adhesiveness) was evaluated according to the criteria shown below. If the number of compartments of the peeled coating film is 50 or less (evaluation A to C), there is usually no problem in practical use. A: There is no peeling of the coating film. B: The number of compartments of the peeled coating film is 1 or more and 10 or less. C: The number of compartments of the peeled coating film is more than 10 and 50 or less. D: The number of compartments of the peeled coating film is more than 50.

[0171] (Gasohol resistance test) The test piece was immersed in regular gasoline / ethanol = 9 / 1 (v / v) for 120 minutes, the state of the coating film was observed, and the gasoline hole resistance was evaluated according to the criteria shown below. If there is no peeling on the coating film surface (Evaluation A - C), there is usually no problem in practical use. A: There is no change on the coating film surface. B: Slight changes can be seen on the coating film surface, but no peeling is observed. C: Changes can be seen on the coating film surface, but no peeling has occurred. D: Peeling has occurred on the coating film surface.

[0172] For the examples and comparative examples, the weight average molecular weight of the modified polyolefin resin, the solvent contained in the dispersion medium, the total content of the structure derived from the (meth)acrylic acid - based component, the solid content ratio, as well as the evaluation results and viscosities of each test are summarized in Table 1 below.

[0173]

Table 1

[0174] (Footnote to Table 1) IPA: Isopropyl alcohol PIP: Neo - ethanol PIP MCH: Methylcyclohexane BuOH: n - Butyl alcohol BuOAc: n - Butyl acetate

[0175] From the above results, the following can be understood. In Comparative Example 5 where an aliphatic hydrocarbon solvent was used as the dispersion medium but no alcohol-based solvent was added, the resin component did not disperse and a dispersion composition could not be obtained. Also, in Comparative Example 6 where butyl acetate was used instead of the aliphatic hydrocarbon solvent, the once-dispersed resin component sedimented and an alcohol dispersion could not be obtained. On the other hand, in Examples 1 to 20 where a predetermined modified polyolefin resin was adjusted to a predetermined solid content rate using an aliphatic hydrocarbon solvent and an alcohol-based solvent as the solvent, a dispersion composition with a well-balanced evaluation result was obtained compared to each comparative example. From the above results, it became clear that the dispersion composition of the present invention exhibits an appropriate viscosity even as a high solid content and can exhibit good stability and adhesiveness.

Claims

1. At least, Component (A): A modified polyolefin resin, Component (B): A dispersion composition in which a modified polyolefin resin is dispersed in a dispersion medium containing an alcohol solvent having 4 or less carbon atoms and an aliphatic hydrocarbon solvent, Said component (A) is at least, Component (C): The following general formula (I): CH ２ =C(R １ )COOR ２ ...(I) (In the general formula (I), R １ represents a hydrogen atom or a methyl group, and R ２ represents -C ｍ H ２ｍ OH. However, m is an integer from 1 to 18.) (Meth)acrylate represented by, and Component (D): The following general formula (II): CH ２ =C(R ３ )COOR ４ ... (II) (In the general formula (II), R ３ represents a hydrogen atom or a methyl group, and R ４ represents a linear, branched and / or cyclic alkyl group having 4 to 18 carbon atoms.) A modified polyolefin resin obtained by graft-modifying an acid-modified polyolefin resin or a chlorinated polyolefin resin with a (meth)acrylic acid-based component containing a (meth)acrylate represented by The total content of the structure derived from the (meth)acrylic acid-based component in the dispersion composition is 3% by weight to 94% by weight with respect to 100% by weight of the total amount of the component (A) and the (meth)acrylic acid-based component polymer, and the solid content ratio of the dispersion composition is 30% by weight to 80% by weight, The content of the structure derived from the component (C) in the component (A) is 30 mol% or less with respect to 100 mol% of the total content of the structure derived from the (meth)acrylic acid-based component, The content of the structure derived from the component (D) in the component (A) is 25 mol% or more with respect to 100 mol% of the total content of the structure derived from the (meth)acrylic acid-based component, and, The total content of the alcohol solvent having 4 or less carbon atoms and the aliphatic hydrocarbon solvent in the component (B) is 80% by weight or more with respect to 100% by weight of the dispersion medium, and the content ratio (mass ratio) of the alcohol solvent having 4 or less carbon atoms to the aliphatic hydrocarbon solvent (alcohol solvent having 4 or less carbon atoms / aliphatic hydrocarbon solvent) is 95 / 5 to 50 / 50 Satisfying, A dispersion composition.

2. The content of the structure derived from the component (C) in the component (A) is 20 mol% or less with respect to 100 mol% of the total content of the structure derived from the (meth)acrylic acid-based component, and the dispersion composition according to claim 1.

3. The content of the structure derived from the component (D) in the component (A) is 30 mol% or more with respect to 100 mol% of the total content of the structure derived from the (meth)acrylic acid-based component, and the dispersion composition according to claim 1 or 2.

4. The weight average molecular weight of the component (A) is 5,000 to 400,000, and the dispersion composition according to any one of claims 1 to 3.

5. ​ The dispersion composition according to any one of claims 1 to 4, wherein the component (A) is further modified with an acid component other than the (meth)acrylic acid-based component.

6. The dispersion composition according to any one of claims 1 to 5, wherein the component (A) is further chlorinated.

7. The dispersion composition according to claim 6, wherein the degree of chlorination of the component (A) is 30% by weight or less, with the weight of the component (A) excluding the weight derived from the (meth)acrylic acid-based component being 100% by weight.

8. A primer comprising the dispersion composition according to any one of claims 1 to 7.

9. An adhesive comprising the dispersion composition according to any one of claims 1 to 7.

10. A paint binder comprising the dispersion composition according to any one of claims 1 to 7.

11. An ink binder comprising the dispersion composition according to any one of claims 1 to 7.

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