JPH03152103A - Nonaqueous resin dispersion - Google Patents

Abstract

PURPOSE:To obtain the title dispersion capable of retaining good dispersion stability also after long-term storage in improved dispersibility with pigment, etc., by copolymerizing specific monomers in a nonaqueous solvent in the presence of a specific copolymer soluble in the above-mentioned solvent. CONSTITUTION:The aimed dispersion liquid obtained by copolymerizing (A) a vinyl monomer mixture containing vinyl monomers constituting a vinyl copolymer insoluble in a nonaqueous solvent in the presence of (B) a vinyl copolymer soluble in the above-mentioned solvent and having carboxyl, sulfo or phosphate group and basic N atom together in the same solvent and wholly dispersing a chain polymer caught by mutual tangle of molecular chains and insoluble in the above-mentioned solvent into the same solvent. Furthermore, the polymer B is preferably obtained by copolymerizing 6-24C alkyl ester of (meth)acrylic acid with a vinyl monomer having carboxyl, sulfo or phosphate group and basic N atom-containing vinyl monomer.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a non-aqueous resin dispersion useful for liquid developers for electrostatic latent images, paints, and the like.

[Conventional technology]

Various proposals have been made regarding non-aqueous resin dispersions used in liquid developers for electrostatic latent images, paints, etc., and their manufacturing methods.
In the method for producing a non-aqueous resin dispersion described in the publication,
In a non-aqueous solvent, a monomer represented by the general formula (1) % formula % (wherein R represents H or CH=, and n represents an integer of 8 to 20) and a monomer having a glycidyl group or a carboxyl group. If the copolymer obtained in the first step is copolymerized with a monomer having a carboxyl group, the copolymer obtained in the first step is copolymerized with a monomer having a carboxyl group. When a monomer having a carboxyl group is used, the step of esterifying each monomer with a monomer having a glycidyl group and the resulting esterified copolymer are combined with the general formula (If) CHz=C
-COOC-Hz@ya.

(In the formula, m represents an integer of 1 to 4.) A second step of grafting a monomer selected from the group consisting of vinyl acetate, styrene, vinyltoluene, vinylpyridine, and chlorostyrene is carried out continuously. A method for producing a non-aqueous resin dispersion is known.

However, since this method increases the esterification rate, it is possible to efficiently produce a grafted non-aqueous resin dispersion, but a relatively large amount of grafted resin is produced as a by-product during the production of the graft polymer. Polymers soluble in non-aqueous solvents and polymers insoluble in non-aqueous solvents impair the dispersibility of pigments and dyes, resulting in the problem of sedimentation during long-term storage.

[Problem to be solved by the invention]

The problem to be solved by the present invention is to provide a non-aqueous resin dispersion that can maintain good dispersion stability even after long-term storage by improving dispersibility for pigments and dyes.

[Means to solve the problem]

In order to solve the above-mentioned problems, the present invention provides a non-aqueous solvent containing a vinyl copolymer having a carboxyl group, a sulfo group, or a phosphoric acid group and a basic nitrogen atom, which is soluble in the non-aqueous solvent. As a whole captured by the entanglement of molecular chains obtained by copolymerizing a vinyl monomer mixture containing a vinyl monomer (hereinafter referred to as the fourth monomer component) constituting a vinyl copolymer insoluble in a non-aqueous solvent The present invention provides a non-aqueous resin dispersion characterized in that the stitched polymer insoluble in the non-aqueous solvent is dispersed in the non-aqueous solvent.

The non-aqueous resin dispersion of the present invention can be produced, for example, according to the following production method.

That is, in the non-aqueous solvent containing a vinyl copolymer having a carboxyl group, a sulfo group, or a phosphoric acid group and a basic nitrogen atom, the vinyl copolymer is insoluble in the non-aqueous solvent. In the presence of a polymerization initiator, a vinyl monomer mixture containing vinyl monomers constituting 6
By copolymerizing at 0 to 130°C, a threaded polymer is produced which is trapped by the entanglement of molecular chains and is insoluble in the non-aqueous solvent as a whole, and the threaded polymer is transferred to the non-aqueous solvent. A method for producing a non-aqueous resin dispersion that is dispersed in a solvent.

The vinyl copolymer having a carboxyl group, a ζ sulfo group, or a phosphoric acid group and a basic nitrogen atom, which is soluble in a non-aqueous solvent used in the present invention, includes (a) a carbon atom having a hydroxyl group of acrylic acid and/or methacrylic acid; 70 to 95% by weight of alkyl esters of numbers 6 to 24 (hereinafter referred to as the first monomer component) (b) Vinyl monomer having a carboxyl group, sulfo group or phosphoric acid group (hereinafter referred to as the second monomer component)
2 to 27% by weight, (C) 3 to 28% by weight of a vinyl monomer having a basic nitrogen atom (hereinafter referred to as the third monomer component), and (B) other copolymerizable vinyl monomers as necessary (
Hereinafter referred to as the fifth monomer component), a vinyl monomer mixture containing
It can be produced by copolymerizing at 0 to 130°C.

The first monomer component used in the present invention is a monomer that constitutes a vinyl copolymer that dissolves in a non-aqueous solvent through polymerization, such as hexyl (meth)acrylate, 2-
Examples include ethylhexyl (meth)acrylate, octyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cetyl (meth)acrylate, and dodecyl (meth)acrylate.

If the content of the first monomer component is less than 70% by weight, the resulting vinyl copolymer will have poor solubility in non-aqueous solvents, so This is not preferred because the dispersion stability of the polymer tends to deteriorate.

In addition, when the content of the first monomer component is more than 95% by weight, the molecular chains of the second monomer component, the third monomer component, and the fourth monomer component that constitute a structural part insoluble in a non-aqueous solvent may be entwined with each other. tends to decrease, which is not preferable.

The second monomer component and the third monomer component used in the present invention are copolymerized with the first monomer component, and apparent crosslinking occurs due to the interaction between the acid group and the basic functional group. When a vinyl monomer mixture containing a 7-monomer component is polymerized, the polymerization occurs while being captured by a pseudo three-dimensional crosslinked structural part that is insoluble in a non-aqueous solvent and is composed of a 2nd 7-monomer component and a 3rd monomer component. As a result, three-dimensional intertwining of molecular chains can be formed.

Examples of such second monomer components include (meth)acrylic acid, itaconic acid, crotonic acid, maleic acid,
Examples include fumaric acid, tetrahydrophthalic anhydride, and polybasic acid monoalkyl esters thereof; acryloxyethyl phosphate, p-sulfostyrene, sulfoethyl acrylamide, and the like.

Examples of the third monomer component include dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminostyrene, dimethylaminomethylstyrene, and the like.

The fourth monomer component is a vinyl monomer that constitutes a vinyl copolymer that is insoluble in non-aqueous solvents through polymerization, and has the general formula (I) CHz=CHOCOR', for example.
......(1) (In the formula, R1 represents an alkyl group having 1 to 5 carbon atoms.) Saturated fatty acid vinyl ester represented by the general formula () % formula % () (in the formula, R1 represents an alkyl group having 1 to 5 carbon atoms.) dialkyl ester of an unsaturated dicarboxylic acid represented by; the second monomer component and the third monomer component; 1-5 alkyl ester; 2 of (meth)acrylic acid
-Halogen atom-containing vinyl monomers such as chloroethyl ester, 2-hydroxy-3-chloropropyl ester, 2,3-dibrumobrobyl ester; glycidyl (
Epoxy group-containing vinyl monomers such as meth)acrylate; 2-methoxyethyl ester, 2-ethoxyethyl ester of (meth)acrylic acid; (meth)acrylonitrile: vinyl methyl ketone, vinyl isopropenyl ketone; styrene, vinyltolulene, α-methyl Styrene; N-vinylimidazole, N-vinyl-2-methylthiazole, l-vinylpyrrole, N-β-acryloxyethylindole, 2-vinylquinoline, 4-vinylpyridine, 5-vinyl-4-methylthiazole, 3-Methyl-5-isopropenylpyrazole, N-vinyl-2-
Examples include vinyl monomers having an amide group in the molecule, such as pyrrolidone, N-vinylpiperidone, N-vinyloxazolidone, and (meth)acrylamide. In particular, a fourth vinyl monomer component containing a vinyl monomer component represented by general formula (1) is preferred.

The fifth monomer component is a saturated monomer component represented by the fourth seventh monomer component; Fatty acid vinyl esters include dialkyl esters of unsaturated dicarboxylic acids represented by the general formula () % formula % (wherein R4 represents an alkyl group having 6 to 18 carbon atoms).

Examples of non-aqueous solvents include n-hexane, n-pentane, n-octane, n-nonane, n-decane, n-undecane, and n-dodecane, as well as commercially available products such as "Isopar G" manufactured by Exxon. , "Isopar H", "Isopar K", "Isopar L", "Isopar M", etc.
It has a boiling point in the temperature range of 68 to 250 °C, and 10'
Various hydrocarbon solvents having a volume resistivity of Ω·cm or less and a dielectric constant of less than 3, and if necessary, ordinary organic solvents can be used.

As the usual organic solvent, an organic solvent having an SP of 9.0 or less, such as cyclohexane, xylene, toluene, etc., can be used as necessary.

Examples of the polymerization initiator used in the copolymerization reaction include azobisisobutyronitrile, benzoyl peroxide,
Di-tertiary butyl peroxide, tertiary
Examples include butyl peroxybenzoate, and the amount used is preferably in the range of 0.1 to 10.0% by weight of the monomer component.

The ratio of the non-aqueous solvent-soluble vinyl copolymer to the third monomer component is 20=80 to 90:10 by weight.
A range of is preferred. The usage ratio of the third monomer component is 10
If it is less than % by weight, the amount of pigment or dye adsorbed to the threaded polymer will be reduced, and as a result, when a liquid developer or paint is prepared using the non-aqueous resin dispersion of the present invention, the dispersion stability will be reduced. (Also, if the proportion of the third monomer component used is more than 80% by weight, the solubility of the chain polymer in non-aqueous solvents will deteriorate, and as a result, the This is not preferred because it tends to result in poor dispersion stability when preparing a liquid developer or paint.

The stitched chain polymer of the present invention produced in this way is -3
It is insoluble in non-aqueous solvents in the temperature range of 0 to 50°C.

〔Example〕

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the following Examples unless it exceeds the spirit thereof. In the examples, "parts" and "%" represent "parts by weight" and "% by weight," respectively.

Examples 1 to 5 and Comparative Examples Copolymers soluble in non-aqueous solvents were produced using the formulations and synthesis methods listed in Table 1.

Also, for comparison, a polymer was produced without using the second monomer component and the third monomer component.

' Containing 9' In a non-aqueous solvent containing a copolymer soluble in the non-aqueous solvent listed in Table 2, the y1 chain polymer becomes insoluble in the non-aqueous solvent by polymerizing the fourth monomer component. produced a combination.

For comparison, the fourth monomer component was polymerized in a non-aqueous solvent containing a polymer soluble in the non-aqueous solvent of Comparative Example, and a milky white emulsion was obtained. that time,
The formulation composition and synthesis method described in the same table were set.

As is clear from these results, each of the chain polymers of Examples had good dispersion stability after standing for one month.

However, in the copolymer of the comparative example, since the molecular chains were not mixed together, the dispersion stability after standing for one month was poor, and the occurrence of sediment was observed.

〔Effect of the invention〕

The non-aqueous solvent-insoluble chain polymer of the present invention is mainly composed of vinyl monomers constituting the non-aqueous solvent-insoluble vinyl copolymer among specific vinyl copolymers soluble in non-aqueous solvents. By copolymerizing a vinyl monomer mixture, a non-aqueous resin in which a copolymer soluble in a non-aqueous solvent and a copolymer insoluble in a non-aqueous solvent are integrally bonded to each other, are captured by the entanglement of molecular chains. Since it forms a dispersion, it is stably dispersed in a non-aqueous solvent.

The threaded polymer of the present invention having such excellent dispersion stability is useful as a polymer used in various liquid developers or paints for electrostatic latent images.

Claims (1)

[Scope of Claims] 1. In the non-aqueous solvent containing a vinyl copolymer having a carboxyl group, a sulfo group, or a phosphoric acid group and a basic nitrogen atom, which is soluble in the non-aqueous solvent, The chain polymer, which is insoluble in the non-aqueous solvent as a whole, is captured by the entanglement of the molecular chains obtained by copolymerizing the vinyl monomer mixture containing the vinyl monomers constituting the insoluble vinyl copolymer. A non-aqueous resin dispersion characterized by being dispersed in an aqueous solvent. 2. A vinyl copolymer having a carboxyl group, a sulfo group, or a phosphoric acid group and a basic nitrogen atom, which is soluble in a non-aqueous solvent, has (a) acrylic acid and/or methacrylic acid hydroxyl group having 6 to 6 carbon atoms; 24 alkyl ester 70-95
(b) 2-27% by weight of a vinyl monomer having a carboxyl group, sulfo group or phosphoric acid group; and (c) 3-28% by weight of a vinyl monomer having a basic nitrogen atom.
The non-aqueous resin dispersion according to claim 1, which is a vinyl polymer obtained by copolymerizing a vinyl monomer mixture containing % by weight. 3. The vinyl monomer constituting the vinyl copolymer that is insoluble in non-aqueous solvents has the general formula CH_2=CH-OCOR^1 (wherein, R^1 represents an alkyl group having 1 to 5 carbon atoms). Claim 1 or 2 containing the vinyl monomer represented by
Non-aqueous resin dispersion as described.