WO2023008020A1

WO2023008020A1 - Dispersion composition

Info

Publication number: WO2023008020A1
Application number: PCT/JP2022/025345
Authority: WO
Inventors: 勝神埜; 浩司木村; 泰高渡邊; 俊司関口
Original assignee: 日本製紙株式会社
Priority date: 2021-07-29
Filing date: 2022-06-24
Publication date: 2023-02-02
Also published as: JPWO2023008020A1

Abstract

Provided is a dispersion composition of a chlorinated polyolefin resin, the dispersion composition being obtained using an ultraviolet-curable compound as a dispersion medium and being excellent in terms of adhesiveness and long-term stability. The dispersion composition comprises a dispersion medium comprising an ultraviolet-curable compound and, dispersed in the dispersion medium, a (meth)acrylic-modified chlorinated polyolefin resin which is a chlorinated polyolefin resin modified with at least a (meth)acrylic modifying ingredient, wherein the ultraviolet-curable compound has a solubility parameter (SP value), determined by the Fedors method, of 9.8-13.5 (cal/cm3)1/2, the (meth)acrylic-modified chlorinated polyolefin resin has a weight-average molecular weight of 9,000-180,000, and the (meth)acrylic-modified chlorinated polyolefin resin has a combined chlorine content of 15-45 wt% with respect to the weight of the (meth)acrylic-modified chlorinated polyolefin resin, which is taken as 100 wt%, excluding the weight derived from the (meth)acrylic modifying ingredient.

Description

dispersion composition

The present invention relates to a dispersion composition, and in particular to a dispersion composition containing a chlorinated polyolefin resin and uses thereof.

Until now, volatile organic compounds (VOC) have been used as dispersion media for chlorinated polyolefin resin dispersions used in paints and adhesives. However, since volatile organic compounds (VOCs) have a large impact on the environment, there is a demand to reduce their usage, and there is an increasing need for alternative means with a lower environmental impact.

As one of the alternatives with less environmental impact, the use of ultraviolet curable compounds is being studied. Since the UV-curable compound uses UV rays for curing, it is possible to omit or shorten the baking process, which also leads to a reduction in CO ₂ emissions (Patent Document 1).

JP 2014-196375 A

However, UV-curable compounds have low compatibility with chlorinated polyolefin resins, and there are issues with stability over time and adhesion when used as a dispersion medium.

An object of the present invention is to provide a dispersion composition of a chlorinated polyolefin resin which is obtained by using an ultraviolet curable compound as a dispersion medium and has excellent adhesion and stability over time.

The present invention provides the following.
[1] A dispersion medium containing an ultraviolet curable compound, and a (meth)acrylic-modified chlorinated polyolefin resin, which is a polyolefin resin modified with at least a (meth)acrylic-modified component and chlorinated, dispersed in the dispersion medium. A dispersion composition comprising
The solubility parameter (SP value) of the UV-curable compound according to the Fedors method is 9.8 to 13.5 (cal/cm ³ ) ^1/2 ,
The weight average molecular weight of the (meth)acrylic-modified chlorinated polyolefin resin is 9,000 to 180,000, and the degree of chlorination of the (meth)acrylic-modified chlorinated polyolefin resin is the weight derived from the (meth)acrylic-modified component. When the weight of the (meth)acrylic-modified chlorinated polyolefin resin excluding the (meth)acrylic-modified chlorinated polyolefin resin is 100% by weight, the dispersion composition is 15% by weight to 45% by weight.
[2] The dispersion composition according to [1] above, wherein the UV-curable compound is a (meth)acrylic acid ester.
[3] The dispersion according to [1] or [2] above, wherein the content of the ultraviolet curable compound contained in the dispersion medium is 80% by weight or more when the total amount of the dispersion medium is 100% by weight. Composition.
[4] The (meth)acryl-modified component has the following general formula (I):

(In general formula (I), R ¹ represents a hydrogen atom or a methyl group, R ² represents -C _m H _2m OH, and m represents an integer of 1 to 18.)
The dispersion composition according to any one of [1] to [3] above, comprising a (meth)acrylic acid ester represented by.
[5] The dispersion composition according to any one of [1] to [4] above, wherein the UV-curable compound has a viscosity at 25°C measured with a Brookfield viscometer of 700 mPa·s or less.
[6] The dispersion composition may further contain a (meth)acrylic modified component polymer, and the total content of structures derived from the (meth)acrylic modified component in the dispersion composition is equal to (meth)acrylic When the total amount of the modified chlorinated polyolefin resin and the (meth)acrylic modified component polymer is 100% by weight, it is 5% by weight to 95% by weight, according to any one of [1] to [5] above. dispersion composition.
[7] The dispersion composition according to any one of [1] to [6] above, wherein the (meth)acrylic-modified chlorinated polyolefin resin is further modified with an acid component other than the (meth)acrylic-modified component.
[8] A primer containing the dispersion composition according to any one of [1] to [7] above.
[9] An adhesive comprising the dispersion composition according to any one of [1] to [7] above.
[10] A paint binder comprising the dispersion composition according to any one of [1] to [7] above.
[11] An ink binder containing the dispersion composition according to any one of [1] to [7] above.
[12] A dispersion medium containing an ultraviolet curable compound, and a (meth)acrylic-modified chlorinated polyolefin resin, which is a polyolefin resin modified with at least a (meth)acrylic-modified component and chlorinated, dispersed in the dispersion medium. A cured product obtained by curing a dispersion composition containing
The solubility parameter (SP value) according to the Fedors method of the UV curable compound before curing is 9.8 to 13.5 (cal/cm ³ ) ^1/2 ,
The weight average molecular weight of the (meth)acrylic-modified chlorinated polyolefin resin is 9,000 to 180,000, and the degree of chlorination of the (meth)acrylic-modified chlorinated polyolefin resin is the weight derived from the (meth)acrylic-modified component. When the weight of the (meth)acrylic-modified chlorinated polyolefin resin excluding the (meth)acrylic-modified chlorinated polyolefin resin is 100% by weight, the cured product is 15% by weight to 45% by weight.

According to the present invention, it is possible to obtain a dispersion composition of a chlorinated polyolefin resin that is excellent in adhesion and stability over time despite using an ultraviolet curable compound as a dispersion medium.

The present invention relates to a dispersion medium containing an ultraviolet-curable compound, and a (meth)acrylic-modified chlorinated polyolefin resin, which is a polyolefin resin modified with at least a (meth)acrylic-modified component and chlorinated, dispersed in the dispersion medium. and wherein the solubility parameter (SP value) of the UV-curable compound according to the Fedors method is 9.8 to 13.5 (cal/cm ³ ) ^1/2 , and (meta) The weight average molecular weight of the acrylic-modified chlorinated polyolefin resin is 9,000 to 180,000, and the degree of chlorination of the (meth)acrylic-modified chlorinated polyolefin resin excludes the weight derived from the (meth)acrylic-modified component ( Provided are a dispersion composition in which the weight of the meth)acrylic-modified chlorinated polyolefin resin is 15% by weight to 45% by weight, and a cured product obtained by curing the dispersion composition.

(1. (Meth)acrylic-modified chlorinated polyolefin resin)
The dispersion composition of the present invention contains a (meth)acrylic-modified chlorinated polyolefin resin dispersed in a dispersion medium. The (meth)acrylic-modified chlorinated polyolefin resin is a polyolefin resin modified with at least a (meth)acrylic modifying component and chlorinated.

(1-1. Polyolefin resin)
Polyolefin resins are olefin (α-olefin) polymers. Examples of α-olefins include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene and 1-octene.

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

Polyolefin resins include polypropylene (propylene homopolymer), ethylene-propylene copolymer, and propylene-1-butene copolymer from the viewpoint of exhibiting sufficient adhesion to non-polar resin substrates such as polypropylene substrates. , ethylene-propylene-1-butene copolymers are preferred.

Here, "polypropylene" refers to a polymer whose constituent units are propylene-derived constituent units. “Ethylene-propylene copolymer” means a copolymer containing ethylene-derived structural units and propylene-derived structural units as structural units. “Propylene-1-butene copolymer” means a copolymer containing a propylene-derived structural unit and a butene-derived structural unit as structural units. "Ethylene-propylene-1-butene copolymer" represents a copolymer containing, as structural units, ethylene-derived structural units, propylene-derived structural units and butene-derived structural units. These (co)polymers may contain a small amount of structural units derived from other olefins as structural units, as long as the amount does not significantly impair the inherent performance of the resin.

The polyolefin resin preferably contains 50 mol% or more of propylene-derived structural units in 100 mol% of all structural units. When the propylene-derived structural unit is included in the above range, adhesion to non-polar resin substrates such as propylene resin can be maintained.

When the ethylene-propylene copolymer or propylene-1-butene copolymer is a random copolymer, preferably 3 to 50 mol% of ethylene-derived structural units or butene-derived structural units out of 100 mol% of all structural units. and the constituent units derived from propylene are 50 to 97 mol %.

(1-2. Chlorination)
A (meth)acrylic-modified chlorinated polyolefin resin is a chlorinated resin.

The degree of chlorination (chlorine content) of the (meth)acrylic-modified chlorinated polyolefin resin is as follows: It is 45% by weight or less, 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. The lower limit is 15% by weight or more, preferably 17% by weight or more, more preferably 20% by weight or more, and particularly preferably 23% by weight or more. The degree of chlorination is in one embodiment preferably between 17% and 40% by weight, more preferably between 20% and 30% by weight. As a result, the polarity can be suppressed to a certain level or less, and sufficient adhesion to non-polar substrates such as polyolefin substrates can be obtained. The degree of chlorination 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 with water, and quantitatively determined by titration.

(1-3. Modification with (meth)acrylic modification component)
The (meth)acrylic-modified chlorinated polyolefin resin is a resin modified (graft-modified) with a (meth)acryl-modified component. The (meth)acrylic modified component is (meth)acrylic acid and derivatives thereof, and examples of the derivatives include (meth)acrylic anhydride and (meth)acrylic acid ester.

In one embodiment, the (meth)acryl-modified component preferably has the following general formula (I):

(In general formula (I), R ¹ represents a hydrogen atom or a methyl group, R ² represents -C _m H _2m OH, and m represents an integer of 1 to 18.)
(Meth) acrylic acid ester represented by (hereinafter sometimes referred to as "hydroxyl monomer").

R ¹ represents a hydrogen atom or a methyl group, preferably a hydrogen atom. m is an integer of 1 to 18, preferably an integer of 1 to 16, an integer of 1 to 14, an integer of 1 to 12 or an integer of 1 to 10, an integer of 1 to 8, an integer of 1 to 6 or 1 An integer of ˜4 is more preferred, an integer of 2 to 4 or 2 or 3 is more preferred, and 2 is particularly preferred.

Examples of hydroxyl group monomers include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxy-1-methylethyl (meth)acrylate, 2-hydroxy butyl (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-hydroxy Hexyl (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 and the like. Among these, 2-hydroxyethyl (meth)acrylate is preferred.

The content of the structure derived from the hydroxyl group monomer in the (meth)acrylic-modified chlorinated polyolefin resin is preferably relative to the total content of 100 mol% of the structure derived from the (meth)acrylic-modified component in the (meth)acrylic-modified chlorinated polyolefin resin. is 30 mol % or less, preferably 20 mol % or less, more preferably 15 mol % or less, still more preferably 10 mol % or less. 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.

The hydroxyl group monomer may be used singly or in combination of two or more.

In one embodiment, the (meth)acrylic-modified component preferably has the following general formula (II):

(In 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.)
(Meth) acrylic acid ester represented by (hereinafter sometimes referred to as "low polar monomer").

R3 represents a hydrogen atom or a methyl group ^, preferably a methyl group. R ⁴ represents a linear, branched and/or cyclic alkyl group having 4 to 18 carbon atoms. The number of carbon atoms in the alkyl group of R ⁴ is 4-18, preferably 4-16, 4-14, 4-12 or 4-10, more preferably 4-8 or 4-6.

Examples of low-polar monomers include 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. ^R4 is linear alkyl (Meth)acrylic acid ester as a group; isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, isopentyl (meth)acrylate, neopentyl (meth)acrylate, tert-pentyl (meth) (Meth)acrylic acid esters in which ^R4 is a branched chain alkyl group, such as acrylate, isohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate; cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate Examples thereof include (meth)acrylic acid esters such as acrylates in which ^R4 is a cyclic alkyl group. Among these, (meth)acrylate esters in which R ⁴ is a linear alkyl group and (meth)acrylate esters in which R ⁴ is a cyclic alkyl group are preferred, and n-butyl (meth)acrylate and cyclohexyl (meth)acrylate are preferred. ) acrylates are more preferred.

The content of structures derived from low-polar monomers in the (meth)acrylic-modified chlorinated polyolefin resin is 100 mol% of the total content of structures derived from (meth)acrylic-modified components in the (meth)acrylic-modified chlorinated polyolefin resin, It is preferably 25 mol % or more, more preferably 30 mol % or more, still more preferably 40 mol % or more. 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, and particularly preferably 60 mol% or less, or 55 mol% or less. be.

The low-polarity monomer may be used singly or in combination of two or more.

The low-polarity monomer preferably contains a combination of a (meth)acrylic acid ester in which ^R4 is a linear alkyl group and a (meth)acrylic acid ester in which ^R4 is a cyclic alkyl group, n-butyl (meth) ) acrylate and cyclohexyl (meth)acrylate.

The molar ratio of the content of the structure derived from the hydroxyl group monomer and the structure derived from the low-polar monomer in the (meth)acrylic-modified chlorinated polyolefin resin (hydroxyl group monomer/low-polar monomer) is preferably 1/100 to 1/1.5, It is more preferably 1/50 to 1/2, still more preferably 1/50 to 1/4.

The total content of structures derived from hydroxyl group monomers and structures derived from low-polar monomers in the (meth)acrylic-modified chlorinated polyolefin resin is the total content of structures derived from (meth)acrylic-modified components in the (meth)acrylic-modified chlorinated polyolefin resin. It is preferably 30 mol % or more, more preferably 40 mol % or more, and still more preferably 45 mol % or more with respect to the content of 100 mol %. The upper limit is preferably 95 mol% or less, more preferably 90 mol% or less, still more preferably 85 mol% or less.

In one embodiment, the (meth)acryl-modified component preferably has the following general formula (III):

(In general formula (III), R ⁵ represents a hydrogen atom or a methyl group, R ⁶ represents —C _a H _2a OC _b H _2b+1 , and a and b each independently represent 1 to 18 indicates an integer.)
(Meth) acrylic acid ester represented by (hereinafter sometimes referred to as "alkoxy group monomer").

^R5 represents a hydrogen atom or a methyl group, preferably a hydrogen atom. a is an integer of 1 to 18, preferably an integer of 1 to 16, an integer of 1 to 14, an integer of 1 to 12 or an integer of 1 to 10, an integer of 1 to 8, an integer of 1 to 6 or 1 An integer of ˜4 is more preferred, an integer of 2 to 4 or 2 or 3 is more preferred, and 2 is particularly preferred. b is an integer of 1 to 18, preferably an integer of 1 to 16, an integer of 1 to 14, an integer of 1 to 12 or an integer of 1 to 10, an integer of 1 to 8, an integer of 1 to 6 or 1 An integer from 1 to 4 is more preferred, an integer from 1 to 3 or 1 or 2 is more preferred, and 1 is particularly preferred.

Examples of alkoxy group monomers include 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 and the like. Among these, 2-methoxyethyl (meth)acrylate is preferred.

In one embodiment, the content of structures derived from alkoxy group monomers in the (meth)acrylic-modified chlorinated polyolefin resin is the total content of structures derived from (meth)acrylic-modified components in the (meth)acrylic-modified chlorinated polyolefin resin. It is preferably 50 mol % or less, more preferably 40 mol % or less, relative to 100 mol %. The lower limit is preferably 0.1 mol % or more, more preferably 1 mol % or more.

The alkoxy group monomer may be used singly or in combination of two or more.

In one embodiment, the (meth)acryl-modified component preferably has the following general formula (IV):

(In general formula (IV), R ⁷ represents a hydrogen atom or a methyl group, and R ⁸ represents a linear or branched alkyl group having 1 to 3 carbon atoms.)
Contains a (meth) acrylic acid ester (lower monomer) represented by

^R7 represents a hydrogen atom or a methyl group, preferably a methyl group. R ⁸ represents a linear, branched and/or cyclic alkyl group having 1 to 3 carbon atoms. The number of carbon atoms in the alkyl group of R ⁸ is 1 to 3, preferably 1 or 2, more preferably 1.

Lower monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and isopropyl (meth) acrylate. Among these, methyl (meth)acrylate is preferred.

The content of structures derived from lower monomers in the (meth)acrylic-modified chlorinated polyolefin resin is, in one embodiment, the total content of structures derived from (meth)acrylic-modified components in the (meth)acrylic-modified chlorinated polyolefin resin of 100 mol. %, preferably 1 mol % or more, more preferably 5 mol % or more. The upper limit is preferably 70 mol % or less, more preferably 60 mol % or less.

The lower monomers may be used singly or in combination of two or more.

In one embodiment of the present invention, the (meth)acrylic modifying component preferably contains (meth)acrylic acid. (Meth)acrylic acid is preferably methacrylic acid. (Meth)acrylic acid may be in the form of a free acid or in the form of a salt (sodium salt, potassium salt, etc.).

In one embodiment, the content of structures derived from (meth)acrylic acid in the (meth)acrylic-modified chlorinated polyolefin resin is the total amount of structures derived from (meth)acrylic-modified components in the (meth)acrylic-modified chlorinated polyolefin resin. It is preferably 1 mol % or more, more preferably 5 mol % or more, relative to the content of 100 mol %. The upper limit is preferably 70 mol % or less, more preferably 50 mol % or less.

In one embodiment, the (meth)acrylic-modified component may contain a (meth)acrylic-modified component other than the above-described hydroxyl group monomers, low-polar monomers, alkoxy group monomers, lower monomers, and (meth)acrylic acid. good. Examples of such (meth)acryl-modified components 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)acryloyloxy Ethyl-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.

The total content of structures derived from the (meth)acrylic-modified component in the dispersion composition is, when the total amount of the (meth)acrylic-modified chlorinated polyolefin resin and the (meth)acrylic-modified component polymer is 100% by weight, 1% by weight or more is preferred, 5% by weight or more is more preferred, 10% by weight or more is even more preferred, 20% by weight or more is even more preferred, and 30% by weight or more is particularly preferred. Above 40% by weight is particularly preferred. The upper limit is preferably 98% by weight or less, more preferably 95% by weight or less, even more preferably 90% by weight or less, even more preferably 80% by weight or less, and particularly preferably 70% by weight or less. In one embodiment, the total content of structures derived from the (meth)acrylic-modified component in the dispersion composition is 100 wt. %, it is preferably 1 wt % to 98 wt %, more preferably 5 wt % to 95 wt %, and still more preferably 5 wt % to 90 wt % from the viewpoint of further improving adhesion. The term "(meth)acrylic-modified component polymer" means a polymer having a structure derived from a (meth)acrylic-modified component as a structural unit, and is an arbitrary component that can be contained in the dispersion composition. In embodiments, it may be a by-product formed by polymerization of (meth)acrylic-modified components that did not react with the polyolefin resin during (meth)acrylic modification of the polyolefin resin.

(1-4. Modification with acid component other than (meth)acrylic modification component)
In one embodiment, the (meth)acrylic-modified chlorinated polyolefin resin may be further modified with an acid component other than the (meth)acrylic-modified component. Acid components other than (meth)acrylic modifying components include, for example, α,β-unsaturated carboxylic acids other than (meth)acrylic modifying components and derivatives thereof. Examples of such derivatives include α,β-unsaturated carboxylic acid anhydrides and α,β-unsaturated carboxylic acid esters.

Examples of α,β-unsaturated carboxylic acids and derivatives thereof other than (meth)acrylic-modified components include maleic acid, maleic anhydride, fumaric acid, citraconic acid, citraconic anhydride, mesaconic acid, itaconic acid, and itaconic anhydride. , aconitic acid, aconitic anhydride, and hymic acid anhydride. The (meth)acrylic-modified chlorinated polyolefin resin is preferably further modified with maleic anhydride as an acid component other than the (meth)acrylic-modified component.

The total graft weight (degree of modification) of acid components other than the (meth)acrylic-modified component in the (meth)acrylic-modified chlorinated polyolefin resin is 20% by weight when the weight of the raw unmodified polyolefin resin is 100% by weight. It is preferably 10% by weight or less, more preferably 5% by weight or less. Thereby, the generation of unreacted substances can be suppressed. The lower limit can be, for example, 0% by weight or more and 1% by weight or more. The graft weight (% by weight) can be determined, for example, by alkaline titration or Fourier transform infrared spectroscopy.

(1-5. Characteristics of (meth)acrylic-modified chlorinated polyolefin resin)
The (meth)acrylic-modified chlorinated polyolefin resin has a weight average molecular weight of 9,000 or more, preferably 10,000 or more, more preferably 30,000 or more, and particularly preferably 50,000 or more. The upper limit is 180,000 or less, preferably 150,000 or less, more preferably 100,000 or less, and particularly preferably 70,000 or less. The weight average molecular weight can be measured by GPC using polystyrene as a standard.

(1-6. Method for producing (meth)acrylic-modified chlorinated polyolefin resin)
The (meth)acrylic-modified chlorinated polyolefin resin can be produced by performing modification with a (meth)acrylic modifying component and chlorination in any order.

Therefore, the method for producing a (meth)acrylic-modified chlorinated polyolefin resin includes (a) a step of preparing a polyolefin resin, (b) a step of chlorinating the resin, and (c) modifying the resin with a (meth)acrylic modifying component. The steps may include the order of steps (a), (b), (c) or the order of steps (a), (c), (b). The production of the (meth)acrylic-modified chlorinated polyolefin resin is preferably carried out in the order of steps (a), (b) and (c).

When the (meth)acrylic-modified chlorinated polyolefin resin is further acid-modified with a component other than the (meth)acrylic-modified component, at any time after step (a), the (d) resin is (meth) A step of modifying with an acid component other than the acrylic modifying component may be included.

Step (d) may be performed at a different time from step (c), or may be performed simultaneously with step (c). Step (d) is preferably performed at a different time than step (c). Step (d) can be carried out at any time after step (a), but is preferably carried out before step (c), especially before steps (b) and (c). preferable.

Step (a) is a step of preparing a polyolefin resin.

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 (meth)acrylic-modified chlorinated polyolefin resin is used for inks, paints, and the like. Therefore, the adhesion to the base material can be sufficiently exhibited. Also, when used as an ink, blocking during printing can be suppressed.

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, and even more preferably 100°C or lower. If the melting point of the polyolefin resin prepared in step (a) is 120° C. or less, the coating film can be prevented from becoming too hard when the (meth)acrylic-modified chlorinated polyolefin resin is used for ink, paint, or the like. . Therefore, the coating film can exhibit appropriate flexibility.

The melting point of the polyolefin resin prepared in step (a) is preferably 50°C to 120°C, more preferably 60°C to 110°C, and even more preferably 60°C to 100°C.

The step (b) is a step of chlorinating the resin.

The chlorination may be performed after dissolving the raw material resin in a chlorinated solvent such as chloroform in advance. Chlorination is performed, for example, by blowing chlorine gas into the reaction system. The pressure at which chlorine gas is blown is not limited, and may be normal pressure or pressurized. Although the temperature at which chlorine gas is blown is not particularly limited, it is, for example, 50 to 140.degree.

Blowing of chlorine gas may be performed under ultraviolet irradiation or in the presence of a radical reaction initiator, but preferably in the presence of a radical reaction initiator.

The radical reaction initiator can be, for example, a thermal polymerization initiator that generates free radicals when heated, and examples thereof include organic peroxide compounds and azonitriles. Examples of organic peroxide compounds include di-tert-butyl peroxide, dicumyl peroxide, tert-butylcumyl peroxide, dibenzoyl peroxide, benzoyl m-tolyl peroxide, di(m-tolyl)benzoyl , dilauryl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, cumene hydroperoxide, tert-butyl hydroperoxide, 1,1-bis(tert-butylperoxy)- 3,5,5-trimethylcyclohexane, 1,1-bis(tert-butylperoxy)-cyclohexane, cyclohexanone peroxide, tert-butylperoxybenzoate, tert-butylperoxyisobutyrate, tert-butylperoxy- 3,5,5-trimethylhexanoate, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxyisopropyl carbonate, cumyl peroxyoctoate and the like. Azonitriles include, for example, 2,2-azobis(2-methylbutyronitrile), 2,2-azobisisobutyronitrile, 2,2-azobis(2,4-dimethylvaleronitrile), 2,2 -azobis(4-methoxy-2,4-dimethylvaleronitrile).

Step (c) is a step of modifying with a (meth)acrylic modifying component.

The step (c) can be performed, for example, by introducing a (meth)acrylic modified component into the polyolefin resin by graft copolymerization. The graft copolymerization method is not particularly limited, and known methods such as a melt method and a solution method can be used. In the melting method, the operation is simple and the reaction can be carried out in a short time. When the solution method is used, a homogeneous graft polymer can be obtained with less side reactions. In one embodiment, step (c) is preferably performed by a melt method.

When the step (c) is performed by a melting method, for example, the polyolefin is heated and melted (heated and melted) in the presence of a radical reaction initiator to react. The temperature for heating and melting may be the melting point or higher, preferably the melting point or higher and 300° C. or lower. Equipment such as a Banbury mixer, a kneader, and an extruder can be used for heating and melting.

When the step (c) is performed by a melting method, it is preferable to use an extruder (extrusion modification). As a method of extrusion modification, for example, the raw material polyolefin resin is blended, supplied to the feed section of an extruder (e.g., co-directional multi-screw extruder, twin-screw extruder), and the raw materials are mixed, melt-kneaded, and mixed in the extruder. A method of obtaining a polyolefin resin modified with a (meth)acrylic modifying component by sequentially performing each step of reaction and devolatilization cooling, and cooling (for example, immersing in a water tank) the resin coming out of the tip die. The progress of the reaction can be adjusted by adjusting the temperature of each part of the barrel and the number of rotations of the screw.

When the step (c) is performed by a solution method, for example, after dissolving the raw material polyolefin resin in an organic solvent, the solution is heated and stirred in the presence of a radical reaction initiator to react. The temperature during the reaction is preferably 100 to 180°C. After step (c), the organic solvent in the system may be distilled off under reduced pressure, or the organic solvent may be removed using an extruder.

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

The content of hydroxyl group monomers, low-polar monomers, alkoxy group monomers, lower monomers, and (meth)acrylic acid in the (meth)acrylic-modified component used in step (c) when the (meth)acrylic-modified component is 100 mol% ( mol%) is the same as the content (mol%) relative to the total content of 100 mol% of the structure derived from the (meth)acrylic-modified component in the (meth)acrylic-modified chlorinated polyolefin resin described above. is.

The weight-average molecular weight of the modified or unmodified polyolefin resin (polyolefin resin) immediately before step (c) is preferably 200,000 or less, more preferably 180,000 or less, and particularly preferably 150,000 or less. The lower limit is preferably 5,000 or more, more preferably 7,000 or more, and particularly preferably 10,000 or more.

The polyolefin-based resin immediately before step (c) may be a single resin or a mixture of two or more resins.

The reaction ratio (weight ratio) (polyolefin resin/(meth)acrylic modified component) of the polyolefin resin and the (meth)acrylic modified component immediately before the step (c) in the step (c) is 99/1 to 5/95. and preferably 95/5 to 10/90.

Step (d) is a step of modifying with an acid component other than the (meth)acrylic modifying component, and for example, the same method as in step (c) can be used. In one embodiment, step (d) is preferably performed by a melt method.

(2. Dispersion medium containing UV curable compound)
The dispersion composition of the present invention contains a dispersion medium containing an ultraviolet curable compound as a dispersion medium for dispersing the (meth)acrylic-modified chlorinated polyolefin resin.

The solubility parameter (SP value) of the UV-curable compound according to the Fedors method is 9.8 to 13.5 (cal/cm ³ ) ^1/2 . The UV curable compound has a solubility parameter (SP value) according to the Fedors method of preferably 9.8 to 13.0 (cal/cm ³ ) ^1/2 , more preferably 9.8 to 12.5 (cal/cm 3 ) 1/2 . ³ ) UV curability of ^1/2 , more preferably 9.9 to 12.2 (cal/cm ³ ) ^1/2 , particularly preferably 10.0 to 12.0 (cal/cm ³ ) ^1/2 is a compound.

The UV-curable compound is preferably a radically polymerizable compound, more preferably an α,β-unsaturated carboxylic acid or a derivative thereof, further preferably a (meth)acrylic acid or a derivative thereof, ( A meth)acrylic acid ester is particularly preferred. Examples of α,β-unsaturated carboxylic acid derivatives include α,β-unsaturated carboxylic acid anhydrides and α,β-unsaturated carboxylic acid esters. (Meth)acrylic acid derivatives include, for example, (meth)acrylic anhydrides and (meth)acrylic acid esters.

Specific examples of the (meth)acrylic acid ester having an SP value of 9.8 to 13.5 (cal/cm ³ ) ^1/2 according to the Fedors method include 2-phenoxyethyl acrylate (SP value 11.0), phenoxy Diethylene glycol acrylate (SP value 10.8), phenoxydiethylene glycol methacrylate (SP value 10.5), ethoxylated-ortho-phenylphenol acrylate (SP value 10.9), ethoxylated-ortho-phenylphenol methacrylate (SP value 10) .6), 2-acryloyloxyethyl succinic acid (SP value 11.7), 2-acryloyloxyethyl hexahydrophthalic acid (SP value 11.7) and other monofunctional (meth)acrylic acid esters; Propylene glycol diacrylate (SP value 10.4), tricyclodecanedimethanol diacrylate (SP value 10.8), tricyclodecanedimethanol dimethacrylate (SP value 10.3), 1,9-nonanediol diacrylate (SP value 10.5), 1,10-decanediol diacrylate (SP value 10.3), 1,10-decanediol dimethacrylate (SP value 10.0), neopentyl glycol diacrylate (SP value 10 .9), polyethylene glycol #200 diacrylate (SP value 10.9), polyethylene glycol #200 dimethacrylate (SP value 10.5), dipropylene glycol diacrylate (SP value 10.9), dipropylene glycol dimecrylate (SP value 9.9), dioxane glycol diacrylate (SP value 10.4), dioxane glycol dimethacrylate (SP value 10.1), 2-hydroxypropyl dimethacrylate (SP value 13.2), etc. (Meth) acrylic acid ester; trifunctional or higher (meth) acrylic acid ester such as ethoxylated dipentaerythritol polymethacrylate (NK Ester M-DPH-12E (manufactured by Shin-Nakamura Chemical Co., Ltd.)) (SP value 10.0) Among them, bifunctional (meth)acrylic acid esters and trifunctional or higher (meth)acrylic acid esters are preferable from the viewpoint of curability of the ultraviolet-curable compound.

The molecular weight of the UV-curable compound is preferably 1,500 or less, more preferably 1,300 or less, even more preferably 1,200 or less, and particularly preferably 1,000 or less.

The viscosity of the UV-curable compound measured with a Brookfield viscometer at 25°C is preferably 700 mPa·s or less, more preferably 500 mPa·s or less, and still more preferably 300 mPa·s or less.

The dispersion medium may further contain an organic solvent in addition to the ultraviolet curable compound. As the organic solvent, a wide range of solvents commonly used in inks and/or paints can be used. Examples include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, tert -Alcoholic solvents such as butyl alcohol, 2-ethyl-hexanol and 1-pentanol; glycols such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monoisopropyl ether and propylene glycol monobutyl ether monoether solvents; glycol solvents such as ethylene glycol, ethyl cellosolve, butyl cellosolve; n-pentane, cyclopentane, n-hexane, isohexane, cyclohexane, n-heptane, methylcyclohexane, n-octane, ethylcyclohexane, n-nonane , n-decane and other aliphatic hydrocarbon solvents; toluene, o-xylene, m-xylene, p-xylene, ethylbenzene and other aromatic hydrocarbon solvents; methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate , ester solvents such as n-butyl acetate; ketone solvents such as acetone, methyl ethyl ketone, and methyl butyl ketone, but are not limited thereto.

The content of the ultraviolet curable compound contained in the dispersion medium is preferably as high as possible, and when the total amount of the dispersion medium is 100% by weight, it is preferably 70% by weight or more, more preferably 80% by weight or more, More preferably 90% by weight or more, particularly preferably 95% by weight or more.

The dispersion medium may contain water. The content of water contained in the dispersion medium is preferably 10% by weight or less, more preferably 5% by weight or less, and even more preferably 1% by weight or less, when the total amount of the dispersion medium is 100% by weight.

(3. Dispersion composition)
The dispersion composition of the present invention contains a dispersion medium containing an ultraviolet curable compound and a (meth)acrylic-modified chlorinated polyolefin resin dispersed in the dispersion medium.

The solid content of the dispersion composition of the present invention is preferably 1% by weight or more, more preferably 5% by weight or more, still more preferably 10% by weight or more, and particularly preferably 15% by weight or more. The upper limit of the solid content of the dispersion composition is preferably 70% by weight or less, more preferably 60% by weight or less, even more preferably 50% by weight or less, and particularly preferably 40% by weight or less. In one embodiment, the solids content of the dispersion composition is preferably 5 wt% to 60 wt%, more preferably 10 wt% to 50 wt%, even more preferably 15 wt% to 40 wt%. This can improve the stability over time. The solid content can be adjusted by changing the amount of dispersion medium used.

The dispersion composition of the present invention may contain other components in addition to the (meth)acrylic-modified chlorinated polyolefin resin and the dispersion medium as long as they do not impair the object and effect of the present invention. Other components include, for example, modified by-products such as (meth)acrylic modified component polymers, stabilizers, basic substances, emulsifiers, cross-linking agents, diluents, curing agents, etc. At least stabilizers are included. preferably included.

Examples of stabilizers include epoxy-based stabilizers (compounds containing epoxy groups). Epoxy-based stabilizers include, for example, epoxy compounds having an epoxy equivalent of about 100 to 500 and containing one or more epoxy groups in one molecule. More specifically, for example, epoxidized soybean oil and epoxidized linseed oil obtained by epoxidizing a vegetable oil having a natural unsaturated group with a peracid such as peracetic acid; Epoxidized fatty acid esters obtained by epoxidizing fatty acids; Epoxidized alicyclic compounds represented by epoxidized tetrahydrophthalate; Condensed bisphenol A or polyhydric alcohol with epichlorohydrin, such as bisphenol A glycidyl ether and ethylene glycol glycidyl ether , propylene glycol glycidyl ether, glycerol polyglycidyl ether, sorbitol polyglycidyl ether; butyl glycidyl ether, 2-ethylhexyl glycidyl ether, decyl glycidyl ether, stearyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, sec-butylphenyl glycidyl ether, tert mono-epoxy compounds such as -butylphenyl glycidyl ether, phenol polyethylene oxide glycidyl ether and the like;

The stabilizer may be a compound that does not contain an epoxy group, for example, metal soaps such as calcium stearate and lead stearate; organometallic compounds such as dibutyltin dilaurate and dibutyl maleate; hydrotalcite compounds; compounds and the like.

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, relative to 100% by weight of the (meth)acrylic-modified chlorinated polyolefin resin. Thereby, a stabilizing effect can be favorably exhibited. The upper limit of the stabilizer content is preferably 15% by weight or less, more preferably 12% by weight or less, and even more preferably 10% by weight or less. As a result, good adhesiveness to a base material such as polyolefin can be developed.

Examples of basic substances 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 of one type or a combination of two or more types.

Examples of emulsifiers include surfactants such as nonionic surfactants and anionic surfactants.

Examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene derivatives, polyoxyethylene fatty acid esters, polyoxyethylene polyhydric alcohol fatty acid esters, polyoxyethylene polyoxypropylene Polyol, sorbitan fatty acid ester, polyoxyethylene hydrogenated castor oil, polyoxyalkylene polycyclic phenyl ether, polyoxyethylene alkylamine, alkyl alkanolamide, polyalkylene glycol (meth)acrylate and the like.

Examples of anionic surfactants include alkyl sulfates, polyoxyethylene alkyl ether sulfates, alkylbenzene sulfonates, α-olefin sulfonates, methyl taurates, sulfosuccinates, ether sulfonates, and ether carboxylic acids. salts, fatty acid salts, naphthalenesulfonic acid formalin condensates, alkylamine salts, quaternary ammonium salts, alkylbetaines, alkylamine oxides, and the like.

The dispersion composition of the present invention can be used as a primer, an adhesive, a paint binder, an ink binder, and the like. When the dispersion composition of the present invention is used for these uses, antiseptics, leveling agents, antioxidants, light stabilizers, ultraviolet absorbers, dyes, pigments, metal salts, acids, etc. Ingredients commonly used in various applications may also be included.

The viscosity at 25° C. of the dispersion composition of the present invention measured with a Brookfield viscometer is preferably 10,000 mPa·s or less, more preferably 7,000 mPa·s or less, still more preferably 5,000 mPa·s or less, and particularly preferably 4,000 mPa·s. s or less.

The method for producing the dispersion composition is not particularly limited, but examples include a method of adding a dispersion medium to a (meth)acrylic-modified chlorinated polyolefin resin and dispersing it. In the process of dispersing, the mixture may be stirred, and if necessary, the temperature may be adjusted by heating or the like.

The present invention will be specifically described below using examples, but the present invention is not limited to these examples. In addition, the unit "part" used below means "weight part." The temperature conditions in the following description are normal temperature (25° C.) unless otherwise specified, and the pressure conditions are normal pressure (760 mmHg) unless otherwise specified. Below.

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

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

100 parts of the acid-modified polyolefin resin was charged into a glass-lined reactor. Chloroform is added and the resin is 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) is added, and the pressure inside the kettle is increased. Chlorination was performed by blowing chlorine gas while controlling the pressure to 2 kgf/cm ² .

After completion of the reaction, 6 parts of an epoxy compound (Eposizer W-100EL, manufactured by DIC Corporation) was added as a stabilizer, and supplied to a vented extruder equipped with a solvent removal suction part at the screw shaft to remove the solvent. Solvented and solidified to obtain an acid-modified chlorinated polyolefin resin (A-1). The resulting acid-modified chlorinated polyolefin resin (A-1) had a weight average molecular weight of 60,000, a degree of modification with maleic anhydride of 2.5% by weight, and a chlorine content of 24.5% by weight. Met.

[Production Example 2: Production of acid-modified chlorinated polyolefin resin (A-2)]
Acid-modified chlorinated polyolefin resin (A- 2) was obtained. The resulting acid-modified chlorinated polyolefin resin (A-2) had a weight average molecular weight of 10,000, a degree of modification with maleic anhydride of 2.5% by weight, and a chlorine content of 24.5% by weight. Met.

[Production Example 3: Production of acid-modified chlorinated polyolefin resin (A-3)]
The amount of di-tert-butyl peroxide (radical reaction initiator) used during acid modification was changed from 2 parts to 1 part, and the barrel temperature during acid modification was 100 ° C. (first and second barrels), 170 ° C. (3rd to 8th barrels), 90 ° C. (9th and 10th barrels), 110 ° C. (11th to 14th barrels) in the same manner as in Production Example 1, acid-modified chlorinated polyolefin resin (A -3) was obtained. The resulting acid-modified chlorinated polyolefin resin (A-3) had a weight average molecular weight of 150,000, a degree of modification with maleic anhydride of 2.5% by weight, and a chlorine content of 24.5% by weight. Met.

[Production Example 4: Production of acid-modified chlorinated polyolefin resin (A-4)]
Acid-modified chlorinated polyolefin was prepared in the same manner as in Production Example 1, except that the amount of 2,2-azobisisobutyronitrile (radical reaction initiator) used during chlorination was changed from 2 parts to 1.8 parts. A resin (A-4) was obtained. The resulting acid-modified chlorinated polyolefin resin (A-4) had a weight average molecular weight of 60,000, a degree of modification with maleic anhydride of 2.5% by weight, and a chlorine content of 17.0% by weight. Met.

[Production Example 5: Production of acid-modified chlorinated polyolefin resin (A-5)]
Acid-modified chlorinated polyolefin resin ( A-5) was obtained. The resulting acid-modified chlorinated polyolefin resin (A-5) had a weight average molecular weight of 60,000, a degree of modification with maleic anhydride of 2.5% by weight, and a chlorine content of 40.0% by weight. Met.

[Production Example 6: Production of acid-modified chlorinated polyolefin resin (A-6)]
As the polyolefin resin, 100 parts of a polyolefin resin (propylene-based random copolymer, propylene structural unit content: 92% by weight, ethylene structural unit content: 8% by weight) produced using a metallocene catalyst as a polymerization catalyst was used and acid-modified. Acid-modified chlorinated polyolefin resin (A-6) in the same manner as in Production Example 1, except that the amount of di-tert-butyl peroxide (radical reaction initiator) used was changed from 2 parts to 12 parts. got The resulting acid-modified chlorinated polyolefin resin (A-6) had a weight average molecular weight of 8,000, a degree of modification with maleic anhydride of 2.5% by weight, and a chlorine content of 24.5% by weight. Met.

[Production Example 7: Production of acid-modified chlorinated polyolefin resin (A-7)]
The amount of di-tert-butyl peroxide (radical reaction initiator) used during acid modification was changed from 2 parts to 0.7 parts, and the barrel temperature was changed to 100 ° C. (first and second barrels), 170 ° C. 3 to 8 barrels), 90 ° C. (9th and 10th barrels), 110 ° C. (11th to 14th barrels) in the same manner as in Production Example 1, acid-modified chlorinated polyolefin resin (A-7) got The obtained acid-modified chlorinated polyolefin resin (A-7) had a weight average molecular weight of 200,000, a degree of modification with maleic anhydride of 2.5% by weight, and a chlorine content of 24.5% by weight. Met.

[Production Example 8: Production of acid-modified chlorinated polyolefin resin (A-8)]
Acid-modified chlorinated polyolefin was prepared in the same manner as in Production Example 1, except that the amount of 2,2-azobisisobutyronitrile (radical reaction initiator) used during chlorination was changed from 2 parts to 1.5 parts. A resin (A-8) was obtained. The obtained acid-modified chlorinated polyolefin resin (A-8) had a weight average molecular weight of 60,000, a degree of modification with maleic anhydride of 2.5% by weight, and a chlorine content of 10.0% by weight. Met.

[Production Example 9: Production of acid-modified chlorinated polyolefin resin (A-9)]
Acid-modified chlorinated polyolefin resin ( A-9) was obtained. The resulting acid-modified chlorinated polyolefin resin (A-9) had a weight average molecular weight of 60,000, a degree of modification with maleic anhydride of 2.5% by weight, and a chlorine content of 50.0% by weight. Met.

[Example 1: Production of dispersion composition (C-1)]
100 parts of acid-modified chlorinated polyolefin resin (A-1) was dissolved in 264.1 parts of methylcyclohexane (aliphatic hydrocarbon solvent), and 1.5 parts of an epoxy compound (Eposizer W-131, manufactured by DIC Corporation) was added. 0 part (1.0% by weight with respect to 100% by weight of acid-modified chlorinated polyolefin resin (A-1)) was added.

In a nitrogen atmosphere, under stirring at 85 ° C., 5.0 parts of Nyper BMT-K40 (manufactured by NOF Corporation) (radical reaction initiator) (3 per 100% by weight of the (meth)acrylic modifying component addition amount) .2% by weight), and after holding for 1 hour, 3.8 parts of methacrylic acid, 30.0 parts of methyl methacrylate, 28.1 parts of cyclohexyl methacrylate, 46.9 parts of n-butyl methacrylate, and 2-methoxy acrylate. A mixture of 35.6 parts of ethyl and 5.6 parts of 2-hydroxyethyl acrylate ((meth)acrylic modification component) was continuously added over 3 hours, maintained at 85° C. for 6 hours, and (meth)acrylic modification. A chlorinated polyolefin resin was obtained. The weight average molecular weight of the obtained (meth)acrylic-modified chlorinated polyolefin resin was 60,000.

100 parts of the reaction solution after the completion of the reaction was concentrated by removing 43.0 parts of methylcyclohexane (aliphatic hydrocarbon solvent) under reduced pressure while stirring at 90°C. Next, 100 parts of the concentrated reaction solution was stirred at 50° C., and NK Ester APG-200 (Shin-Nakamura Chemical Co., Ltd. acrylate; tripropylene glycol diacrylate) 225 was used as the UV-curable compound (B-1). 0 part was added over about 1 hour to obtain a (meth)acrylic-modified chlorinated polyolefin resin dispersion composition (C-1).

[Example 2: Production of dispersion composition (C-2)]
NK Ester M-DPH-12E (manufactured by Shin-Nakamura Chemical Co., Ltd. methacrylate; ethoxylated di- Modification, concentration and dispersion were carried out in the same manner as in Example 1 except that 225.0 parts of pentaerythritol polymethacrylate) was used to obtain a dispersion composition (C-2).

[Example 3: Production of dispersion composition (C-3)]
Modification, concentration and dispersion were carried out in the same manner as in Example 1, except that the acid-modified chlorinated polyolefin resin (A-2) was used instead of the acid-modified chlorinated polyolefin resin (A-1), and the dispersion composition was obtained. A product (C-3) was obtained. The weight average molecular weight of the (meth)acrylic-modified chlorinated polyolefin resin as the dispersion was 10,000.

[Example 4: Production of dispersion composition (C-4)]
Modification, concentration and dispersion were carried out in the same manner as in Example 1 except that the acid-modified chlorinated polyolefin resin (A-3) was used instead of the acid-modified chlorinated polyolefin resin (A-1) to obtain a dispersion composition. A product (C-4) was obtained. The weight average molecular weight of the (meth)acrylic-modified chlorinated polyolefin resin as the dispersion was 150,000.

[Example 5: Production of dispersion composition (C-5)]
Modification, concentration 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). A product (C-5) was obtained. The weight average molecular weight of the (meth)acrylic-modified chlorinated polyolefin resin as the dispersion was 60,000.

[Example 6: Production of dispersion composition (C-6)]
Modification, concentration and dispersion were carried out in the same manner as in Example 1, except that the acid-modified chlorinated polyolefin resin (A-5) was used instead of the acid-modified chlorinated polyolefin resin (A-1). A product (C-6) was obtained. The weight average molecular weight of the (meth)acrylic-modified chlorinated polyolefin resin as the dispersion was 60,000.

[Example 7: Production of dispersion composition (C-7)]
Except that the UV-curable compound (B-3), 225.0 parts of 1,9-nonanediol diacrylate (NDDA), was added to 100 parts of the reaction solution after concentration. Denaturation, concentration and dispersion were carried out in the same manner as in Example 1 to obtain a dispersion composition (C-7).

[Example 8: Production of dispersion composition (C-8)]
The same as in Example 1, except that the UV-curable compound added to 100 parts of the reaction solution after concentration was 225.0 parts of phenoxyethyl acrylate (PEA) as the UV-curable compound (B-4). Then, denaturation, concentration and dispersion were carried out to obtain a dispersion composition (C-8).

[Comparative Example 1: Production of dispersion composition (C-9)]
In the same manner as in Example 1, except that 225.0 parts of isobornyl acrylate as the UV-curable compound (B-5) was added to 100 parts of the reaction solution after concentration. , denaturation, concentration and dispersion to obtain a dispersion composition (C-9).

[Comparative Example 2: Production of dispersion composition (C-10)]
NK Ester A-TMM-3LM-N (Shin-Nakamura Chemical Co., Ltd. methacrylate; tetra Modification, concentration and dispersion were carried out in the same manner as in Example 1 except that the mixture of methylolmethane triacrylate and tetramethylolmethane tetraacrylate) was 225.0 parts to obtain a dispersion composition (C-10). .

[Comparative Example 3: Production of dispersion composition (C-11)]
Modification, concentration and dispersion were carried out in the same manner as in Example 1, except that the acid-modified chlorinated polyolefin resin (A-6) was used instead of the acid-modified chlorinated polyolefin resin (A-1). A product (C-11) was obtained. The weight average molecular weight of the (meth)acrylic-modified chlorinated polyolefin resin as the dispersion was 8,000.

[Comparative Example 4: Production of dispersion composition (C-12)]
Modification, concentration and dispersion were carried out in the same manner as in Example 1, except that the acid-modified chlorinated polyolefin resin (A-7) was used instead of the acid-modified chlorinated polyolefin resin (A-1). It became defective, and dispersion composition (C-12) was not obtained. The (meth)acrylic-modified chlorinated polyolefin resin had a weight average molecular weight of 200,000.

[Comparative Example 5: Production of dispersion composition (C-13)]
Modification, concentration and dispersion were carried out in the same manner as in Example 1, except that the acid-modified chlorinated polyolefin resin (A-8) was used instead of the acid-modified chlorinated polyolefin resin (A-1). It became defective, and dispersion composition (C-13) was not obtained. The (meth)acrylic-modified chlorinated polyolefin resin had a weight average molecular weight of 60,000.

[Comparative Example 6: Production of dispersion composition (C-14)]
Modification, concentration and dispersion were carried out in the same manner as in Example 1 except that the acid-modified chlorinated polyolefin resin (A-9) was used instead of the acid-modified chlorinated polyolefin resin (A-1), and the dispersion composition was obtained. A product (C-14) was obtained. The (meth)acrylic-modified chlorinated polyolefin resin had a weight average molecular weight of 60,000.

[Comparative Example 7: Production of dispersion composition (C-15)]
264.1 parts of methylcyclohexane (aliphatic hydrocarbon solvent), 1.0 parts of an epoxy compound (Eposizer W-131, manufactured by DIC Corporation), in a nitrogen atmosphere with stirring at 85 ° C., Nyper BMT-K40 ( NOF Corp.) (radical reaction initiator) was added in an amount of 5.0 parts (3.2% by weight based on the amount of the (meth)acrylic modifying component added below), and after holding for 1 hour, 3.8 parts of methacrylic acid was added. parts, 30.0 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 5.6 parts of 2-hydroxyethyl acrylate. The mixed solution ((meth)acrylic-modified component) was continuously added over 3 hours and kept at 85° C. for 6 hours to obtain a resin solution of the (meth)acrylic-modified component.

100 parts of the reaction solution after the completion of the reaction was concentrated by removing 43.0 parts of methylcyclohexane (aliphatic hydrocarbon solvent) under reduced pressure while stirring at 90°C. Next, 100 parts of the concentrated reaction solution was stirred at 50° C., and NK Ester APG-200 (Shin-Nakamura Chemical Co., Ltd. acrylate; tripropylene glycol diacrylate) 225 was used as the UV-curable compound (B-1). 0 part was added over about 1 hour to obtain a polymer resin dispersion composition (C-15) of a (meth)acrylic-modified component.

[Comparative Example 8: Production of dispersion composition (C-16)]
100 parts of acid-modified chlorinated polyolefin resin (A-1) was dissolved in 264.1 parts of methylcyclohexane (aliphatic hydrocarbon solvent), and 1.5 parts of an epoxy compound (Eposizer W-131, manufactured by DIC Corporation) was added. 0 part (1.0% by weight with respect to the acid-modified chlorinated polyolefin resin (A-1)) was added.

In a nitrogen atmosphere, under stirring at 85 ° C., 5.0 parts of Nyper BMT-K40 (manufactured by NOF Corporation) (radical reaction initiator) (3.2 parts relative to the amount of (meth)acrylic modifying component added below % by weight) and held at 85° C. for 6 hours.

100 parts of the reaction solution after the completion of the reaction was concentrated by removing 43.0 parts of methylcyclohexane (aliphatic hydrocarbon solvent) under reduced pressure while stirring at 90°C. Next, 100 parts of the concentrated reaction solution was stirred at 50° C., and NK Ester APG-200 (Shin-Nakamura Chemical Co., Ltd. acrylate; tripropylene glycol diacrylate) 225 was used as the UV-curable compound (B-1). 0 part was added over about 1 hour to obtain a (meth)acrylic-modified chlorinated polyolefin resin dispersion composition (C-16).

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

(Graft weight of maleic anhydride (degree of modification) (% by weight))
It was measured by a method according to JIS K 0070 using an alkaline titration method. It is a numerical value when the weight of the unmodified polyolefin resin as a raw material is taken as 100% by weight.

(Degree of chlorination (chlorine content) (% by weight))
Measured based on JIS-K7229. It is a numerical value when the weight of the acid-modified chlorinated polyolefin resin (polyolefin-based resin) immediately before (meth)acrylic modification is 100% by weight.

(viscosity)
The dispersion or UV-curable compound placed in a glass bottle was immersed in a constant temperature bath at 25° C. for 6 hours or more to adjust the temperature, and then the viscosity was measured with a Brookfield viscometer.

(Adhesion)
Adhesive cellophane tape was adhered to the coating film of the test piece and peeled off in the 180° direction, and adhesion (adhesiveness) was evaluated according to the following criteria according to the peeled area of the coating film. If the area of the peeled coating film is 50% or less (evaluation A to C), there is usually no practical problem.
A: No peeling of coating film.
B: The area of the peeled coating film is 25% or less.
C: The area of the peeled coating film is 50% or less.
D: The area of the peeled coating film is greater than 50%.

(Stability over time)
150 g of the resin dispersion was placed in a 250 ml glass container and allowed to stand at room temperature for a predetermined period, and the stability of the resin dispersion was visually evaluated.
A: Excellent stability with no sediment even after standing for 3 months or longer.
B: There is no sediment even after standing for 3 months or more, and the viscosity increases slightly, but is within the practical range.
C: A slight amount of precipitate is observed after 1 to 2 months, but it is within the range of practical use.
D: Precipitation or solidification is observed within 1 month, not suitable for practical use.

For each example and comparative example, the weight-average molecular weight (Mw) of the (meth)acrylic-modified chlorinated polyolefin resin, the weight-average molecular weight (Mw) of the raw material, the degree of chlorination, the SP value of the UV-curable compound, the viscosity, and the dispersion The solids content, viscosity, and test results of the compositions are summarized in Table 1 below.

From the above results, a dispersion medium containing an ultraviolet-curable compound and a (meth)acrylic-modified chlorinated polyolefin, which is a polyolefin resin modified with at least a (meth)acrylic-modified component and chlorinated, dispersed in the dispersion medium A dispersion composition containing a resin, wherein the solubility parameter (SP value) of the UV-curable compound according to the Fedors method is 9.8 to 13.5 (cal/cm ³ ) ^1/2 , and (meta ) The weight average molecular weight of the acrylic-modified chlorinated polyolefin resin is 9,000 to 180,000, and the degree of chlorination of the (meth)acrylic-modified chlorinated polyolefin resin excludes the weight derived from the (meth)acrylic-modified component Assuming that the weight of the (meth)acrylic-modified chlorinated polyolefin resin is 100% by weight, it can be seen that when a dispersion composition containing 15% to 45% by weight is used, adhesion and stability over time are excellent.

This application is based on Japanese Patent Application No. 2021-124729 (filed on July 29, 2021) filed with the Japan Patent Office, the entire contents of which are incorporated herein.

Claims

A dispersion medium containing an ultraviolet curable compound, and a (meth)acrylic-modified chlorinated polyolefin resin, which is a polyolefin resin modified with at least a (meth)acrylic-modified component and chlorinated, dispersed in the dispersion medium. A dispersion composition comprising:
The solubility parameter (SP value) of the UV-curable compound according to the Fedors method is 9.8 to 13.5 (cal/cm 3 ) 1/2 ,
The weight average molecular weight of the (meth)acrylic-modified chlorinated polyolefin resin is 9,000 to 180,000, and the degree of chlorination of the (meth)acrylic-modified chlorinated polyolefin resin is the weight derived from the (meth)acrylic-modified component. When the weight of the (meth)acrylic-modified chlorinated polyolefin resin excluding the (meth)acrylic-modified chlorinated polyolefin resin is 100% by weight, the dispersion composition is 15% by weight to 45% by weight.
The dispersion composition according to claim 1, wherein the ultraviolet curable compound is a (meth)acrylic acid ester.
The dispersion composition according to claim 1, wherein the content of the ultraviolet curable compound contained in the dispersion medium is 80% by weight or more when the total amount of the dispersion medium is 100% by weight.
The (meth)acrylic-modified component has the following general formula (I):

(In general formula (I), R 1 represents a hydrogen atom or a methyl group, R 2 represents -C m H 2m OH, and m represents an integer of 1 to 18.)
2. The dispersion composition according to claim 1, comprising a (meth)acrylic acid ester represented by.
The dispersion composition according to claim 1, wherein the ultraviolet curable compound has a viscosity at 25°C measured with a Brookfield viscometer of 700 mPa·s or less.
The dispersion composition may further contain a (meth)acrylic-modified component polymer, and the total content of structures derived from the (meth)acrylic-modified component in the dispersion composition is the (meth)acrylic-modified chlorinated 2. The dispersion composition according to claim 1, wherein the total amount of the polyolefin resin and the (meth)acrylic modified component polymer is 5% to 95% by weight when the total amount is 100% by weight.
The dispersion composition according to claim 1, wherein the (meth)acrylic-modified chlorinated polyolefin resin is further modified with an acid component other than the (meth)acrylic-modified component.
A primer containing the dispersion composition according to any one of claims 1 to 7.
An adhesive containing the dispersion composition according to any one of claims 1 to 7.
A paint binder containing the dispersion composition according to any one of claims 1 to 7.
A binder for ink containing the dispersion composition according to any one of claims 1 to 7.
A dispersion medium containing an ultraviolet curable compound, and a (meth)acrylic-modified chlorinated polyolefin resin, which is a polyolefin resin modified with at least a (meth)acrylic-modified component and chlorinated, dispersed in the dispersion medium. A cured product obtained by curing the dispersion composition,
The solubility parameter (SP value) according to the Fedors method of the UV curable compound before curing is 9.8 to 13.5 (cal/cm 3 ) 1/2 ,
The weight average molecular weight of the (meth)acrylic-modified chlorinated polyolefin resin is 9,000 to 180,000, and the degree of chlorination of the (meth)acrylic-modified chlorinated polyolefin resin is the weight derived from the (meth)acrylic-modified component. When the weight of the (meth)acrylic-modified chlorinated polyolefin resin excluding the (meth)acrylic-modified chlorinated polyolefin resin is 100% by weight, the cured product is 15% by weight to 45% by weight.