JPH03181504A - Nonaqueous resin dispersion - Google Patents

Abstract

PURPOSE:To obtain the subject dispersion containing an insoluble polymer captured with entanglement of mutual molecular chains dispersed therein by copolymerizing a monomer mixture constituting an insoluble copolymer in a nonaqueous solvent containing a copolymer, soluble in the nonaqueous solvent and having carboxyl groups, etc., and a basic nitrogen compound. CONSTITUTION:The objective resin dispersion obtained by copolymerizing 70-95wt.% 6-24C alkyl ester having hydroxyl group of (meth)acrylic acid with 5-30wt.% vinyl monomer having carboxyl group, sulfo group or phosphoric acid group, preparing a vinyl copolymer, soluble in a nonaqueous solvent and having the carboxyl group, sulfo group or phosphoric acid group and copolymerizing a vinyl monomer mixture containing vinyl monomers constituting a vinyl copolymer insoluble in the aforementioned nonaqueous solvent in the above-mentioned nonaqueous solvent containing the resultant soluble vinyl copolymer and a compound having basic nitrogen atom and containing an entangled chain polymer, insoluble in the nonaqueous solvent as a whole, captured by mutual entanglement of the molecular chain and dispersed in the nonaqueous solvent.

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 nonaqueous resin dispersions used in liquid developers for electrostatic latent images, paints, etc., and methods for producing the same. For example, Special Public Interest Publication No. 60-17331
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 (I) CH2=C-C00CゎH2n+1 (wherein R is H or CHa, and n represents an integer of 8 to 20) and a monomer having a glycidyl group, or 1st step of copolymerizing with a specific monomer having a carboxyl group, when the copolymer obtained in the 1st step is used in the 1st step as a monomer having a glycidyl group, the copolymer is copolymerized with a monomer having a carboxyl group, and When a monomer having a carboxyl group is used in the first step, the step of esterifying each monomer with a monomer having a glycidyl group and the resulting esterified copolymer are combined with the general formula (II) CH2''C
A second step of grafting a monomer selected from the group consisting of a compound represented by -C00C1lH211+1 (in the formula, m represents an integer from 1 to 4), vinyl acetate, styrene, vinyltoluene, vinylpyridine, and chlorstyrene. A method of producing a non-aqueous resin dispersion by continuously performing the following steps 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 has been made to solve the above-mentioned problems. (2) a vinyl monomer constituting a vinyl copolymer insoluble in the non-aqueous solvent (hereinafter referred to as a third monomer component);

) is obtained by copolymerizing a vinyl monomer mixture containing: An aqueous resin dispersion is provided.

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

That is, a vinyl copolymer having a carboxyl group, a sulfo group, or a phosphoric acid group that is soluble in (al non-aqueous solvent) and (bl
In the non-aqueous solvent containing a compound having a basic nitrogen atom, a vinyl monomer mixture containing a vinyl monomer constituting a vinyl copolymer insoluble in the non-aqueous solvent is heated in the presence of a polymerization initiator for 60 to By copolymerizing at 130°C, a chain polymer that is captured by the mutual entanglement of molecular chains and is insoluble in the non-aqueous solvent as a whole is produced, and the chain polymer is transferred to the non-aqueous solvent. A method for producing a non-aqueous resin dispersion to be dispersed in a liquid.

The vinyl copolymer having a carboxyl group, a sulfo group, or a phosphoric acid group that is soluble in a non-aqueous solvent used in the present invention includes (a) an alkyl group having 6 to 24 carbon atoms and having a hydroxyl group of acrylic acid and/or methacrylic acid; 70 to 95% by weight of ester (hereinafter referred to as the first monomer component); (b) a vinyl monomer having a carboxyl group, a sulfo group, or a phosphoric acid group (hereinafter referred to as the second monomer component);

)5 to 30% by weight and (C) a vinyl monomer mixture containing other copolymerizable vinyl monomers (hereinafter referred to as the fourth monomer component) as necessary in a non-aqueous solvent in the presence of a polymerization initiator. It can be produced by copolymerizing at 60-130'C.

The compound having a basic nitrogen atom used in the present invention may be mixed before copolymerizing a vinyl copolymer having a carboxyl group, a sulfo group, or a phosphoric acid group that is soluble in a non-aqueous solvent; After the vinyl copolymer is produced, it may be mixed.

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.

When the content of the first monomer component is less than 70% by weight, the resulting vinyl copolymer has poor solubility in non-aqueous solvents, so that the chain polymer obtained by polymerizing the third monomer component This is not preferred because the dispersion stability tends to deteriorate.

In addition, when the content of the first monomer component is more than 95% by weight, the mutual stitching of the molecular chains of the second monomer component and the third and seventh component, which constitute the structural part insoluble in non-aqueous solvents, is reduced. This is not desirable because it tends to

The second monomer component used in the present invention is copolymerized with the first monomer component, and apparent crosslinking occurs due to interaction between acid groups and basic functional groups. When the compound polymerizes, the polymerization occurs while being captured by the pseudo three-dimensional crosslinked structure part that is insoluble in the non-aqueous solvent composed of the second monomer component, so that the three-dimensional mutual stitching of molecular chains occurs. It is something that 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.

The third monomer component used in the present invention is a vinyl monomer that constitutes a vinyl copolymer that is insoluble in non-aqueous solvents through polymerization, and has, for example, the general formula (1) % formula % (1) (wherein, R1 represents an alkyl group having 1 to 5 carbon atoms.) Saturated fatty acid vinyl ester represented by the general formula () % formula % () (wherein R2 represents an alkyl group having 1 to 5 carbon atoms. ) dialkyl ester of unsaturated dicarboxylic acid represented by; the second monomer component; alkyl ester of acrylic acid or methacrylic acid having 1 to 5 carbon atoms having a hydroxyl group; 2-chloroethyl ester of (meth)acrylic acid;
2-hydroxy-3-chloropropyl ester, 2.3
- Vinyl monomers containing halogen atoms such as dibrumopropyl ester; vinyl monomers containing epoxy groups such as glycidyl (meth)acrylate; 2-hydroxyethyl ester, 2-ethoxyethyl ester of (meth)acrylic acid; (meth)acrylonitrile; vinyl Methyl ketone, vinyl isopropenyl ketone; styrene, vinyltoluene, α-methylstyrene; dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, N-vinylimidazole, N-vinyl-2-methylimidazole, l-vinyl Pyrrole, N-
β-acryloxyethylindole, 2-vinylquinoline, 4-vinylpyridine, 5-vinyl-4-methylthiazole, 3-methyl-5-isopropenylpyrazole,
N-vinyl-2-pyrrolidone, N-vinylpiperidone,
N-vinyloxazolidone, dimethylaminostyrene,
Examples include vinyl monomers having a basic nitrogen atom or an amide group in the molecule, such as dimethylaminomethylstyrene and (meth)acrylamide. In particular, the general formula (
A third vinyl monomer component containing the vinyl monomer component represented by 1) is preferred.

The fourth monomer component is a saturated fatty acid represented by the third monomer component; Vinyl esters; dialkyl esters of unsaturated dicarboxylic acids represented by the general formula () % formula % (wherein R4 represents an alkyl group having 6 to 18 carbon atoms) and the like can be mentioned.

Examples of the compound having a basic nitrogen atom used in the present invention include alkylamines such as propylamine and 2-ethylhexylamine; aromatic amines such as benzylamine; and alkanolamines such as hydroxyethylaminopropylamine. I can list many things.

The amount of the compound having a basic nitrogen atom to be used is determined from the amount of the vinyl monomer mixture containing a vinyl copolymer having a carboxyl group, sulfo group, or phosphoric acid group that is soluble in a non-aqueous solvent and the amount of the compound having a basic nitrogen atom (having a basic nitrogen atom). 3 to 28 of the total amount of things
A weight percent range is preferred.

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 LJ", "Isopar M", etc.
has a boiling point in the temperature range of 68 to 250 °C, and 109
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.

Examples of the ordinary organic solvent include organic solvents having a solubility parameter (hereinafter referred to as SP) of 9.0 or less, for example,
Cyclohexane, xylene, toluene, etc. can be used as necessary.

Examples of the polymerization initiator used in the copolymerization reaction include azobisisobityronitrile, benzoyl peroxide,
Di-tertiary butyl peroxide, tertiary
Examples include butyl peroxybenzoate, and the amount thereof used is preferably in the range of 1 to 10.0% by weight of O, based on 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.
range 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 chain 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 chain polymer of the present invention produced in this manner is -3
It is insoluble in non-aqueous solvents in the temperature range of 0-500C.

〔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, "part J" and "%" represent "part by weight" and "% by weight", respectively.

Examples 1 to 6 and Comparative Examples Production of Soluble Copolymers Copolymers soluble in non-aqueous solvents were produced using the formulations and synthesis methods listed in Table 1.

For comparison, a polymer was also produced without using the second monomer component.

/ / 7/ Manufacture of chain polymer By polymerizing the 3rd seventh component in a non-aqueous solvent containing a copolymer soluble in the non-aqueous solvent listed in Table 2, the non-aqueous solvent is A chain polymer was produced which was insoluble in .

For comparison, the third 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 constitutes a non-aqueous solvent-insoluble vinyl copolymer among specific vinyl copolymers soluble in non-aqueous solvents. By copolymerizing a vinyl monomer mixture containing vinyl monomer as the main component, the copolymers soluble and insoluble in non-aqueous solvents are captured by the mutual entanglement of molecular chains, so that the copolymers soluble and insoluble in non-aqueous solvents are integrated into each other. Since the combined non-aqueous resin dispersion is formed, it is stably dispersed in the non-aqueous solvent.

The chain 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. (1) (a) A vinyl copolymer having a carboxyl group, a sulfo group or a phosphoric acid group that is soluble in a non-aqueous solvent, and (
b) In the non-aqueous solvent containing a compound having a basic nitrogen atom, (2) a vinyl monomer mixture containing a vinyl monomer constituting a vinyl copolymer insoluble in the non-aqueous solvent is copolymerized. 1. A non-aqueous resin dispersion, characterized in that a chain polymer, which is insoluble in the non-aqueous solvent as a whole, is dispersed in the non-aqueous solvent, and is captured by entanglement of molecular chains. 2. The vinyl copolymer having a carboxyl group, a sulfo group, or a phosphoric acid group that is soluble in a non-aqueous solvent is (a) an alkyl ester of acrylic acid and/or methacrylic acid having 6 to 24 carbon atoms and having a hydroxyl group; The non-aqueous system according to claim 1, which is a vinyl polymer obtained by copolymerizing a vinyl monomer mixture containing 95% by weight and (b) 5 to 30% by weight of a vinyl monomer having a carboxyl group, a sulfo group, or a phosphoric acid group. Resin dispersion. 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.