JPS5811516A - Preparation of nonaqueous resin dispersion - Google Patents

Abstract

PURPOSE:To obtain the titled dispersion having improved storability and pigment dispersibility, by copolymerizing a specific acrylate or methacrylate with a monomer, soluble in an aliphatic hydrocarbon as solvent, and polymerizable to form an insoluble polymer in a resin solution in the solvent. CONSTITUTION:(A) A monomer of formulaI[R is H or CH3; X is 1-4C alkyl, formula II (Y is OH, OCH3, naphthyl, formula III), etc.], e.g. formula IV, is copolymerized with (B) a monomer, soluble in an aliphatic hydrocarbon, e.g. isooctane, and polymerizable to form an insoluble polymer, e.g. methyl methacrylate, in the solvent to give the aimed copolymer. The weight ratio of the resin/ component (A)/component (B) is suitably (30-80):(1-40):(20-70).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a novel non-aqueous resin dispersion useful for paints, adhesives, electrophotographic liquid developing agents, and the like.

Polymerization of polyfunctional acrylates such as ethylene glycol dimethacrylate and propylene glycol trimethacrylate with polymerizable monomers such as styrene and male nyltoluene in an aromatic hydrocarbon IA solvent such as toluene and xylene in the presence of a polymerization initiator. A method of producing a non-aqueous resin by reaction is known.

The resins obtained in this way have been widely used for paints and adhesives. However, since aromatic hydrocarbon solvents are used in such manufacturing methods for non-aqueous resins (solutions), crosslinking of the resin tends to proceed, resulting in gelation of the resin during the polymerization reaction and solidification of the resin during storage. There were other problems.

In addition, the dispersibility of the pigment was poor, causing agglomeration and solidification.

Furthermore, the aromatic solvents used in this method are highly toxic and I
There is a sanitary problem with the II tomb.

The first object of the present invention is to uniformly carry out the polymerization reaction in a resin solution using an aliphatic hydrocarbon as a solvent, thereby achieving excellent storage stability and dispersibility for pigments, as well as eliminating environmental hygiene problems. It is an object of the present invention to provide a method for producing a non-aqueous resin dispersion liquid with a small amount.

A second object of the present invention is to provide a method for producing a non-aqueous v-lipid dispersion which is colored yellow and can therefore be used as such as a yellow paint or a yellow liquid developer.

A third object of the present invention is to provide a method for producing a non-aqueous resin dispersion that is colored yellow, has excellent transparency and oil sensitivity, and is therefore useful as a liquid developing agent for offset printing or multicolor copying. It is to be.

That is, in the method of the present invention, in a resin solution using an aliphatic hydrocarbon as a solvent, in the presence of a polymerization initiator, the general formula [wherein the wind is -H or -
〇H,,X is a C3-C4 aryl group, (X1F group or pyridyl group is represented by -) Monomer A is soluble in the solvent, but monomer B becomes insolubilized upon polymerization reaction. It is characterized by:

To carry out the method of the present invention, first, a resin solution prepared by dissolving a resin (one that is soluble in an aliphatic hydrocarbon solvent) in the above-mentioned solvent, a 7-mer A having the general formula, and a 7-mer B having the above-mentioned properties are combined. and a 7mer solution consisting of a polymerization initiator,
While the former resin solution is heated and stirred to the reflux temperature of the solvent, the latter 7mer solution is gradually added dropwise into the resin solution. As a result, Nanatsumer A and monomer B undergo random copolymerization in the resin solution to form a yellow copolymer that is insoluble in the solvent, and a part of this copolymer further adsorbs the resin in the resin solution. As a result of forming a three-dimensional repellent layer, a nonaqueous resin dispersion in which these copolymer components are dispersed is obtained.

In the above reaction, the mixing ratio of resin: monomer A: monomer B is 30-80: 1-40: 20-70 (weight) #i
The degree is appropriate.

As the resin used in the resin solution, any resin can be used as long as it is soluble in an aliphatic hydrocarbon solvent, such as linseed oil-modified alkyd resin, higher alkyl acrylic acid or methacrylic acid (e.g. lauryl, dodecyl, octyl, 2- Examples include ethylhexyl, etc.) ester polymers, styrene-citadiene copolymers, and the like.

The monomer is represented by the above general formula, and includes, for example, the following compounds.

compound layer CH3 Oh.

The monomer can be synthesized by a general method as shown in the reaction formula below.

For example, the method for synthesizing compound 41 is as follows, but other compounds can also be obtained by similar methods.

Synthesis of compound 41 p-hydroxybenzaldehyde 244t.

After mixing and dissolving IJum 10F (hydroxide) and water 100%, it is cooled to 5°C or less. Acrylic chloride 16F was added dropwise to the mixture, stirred at the above temperature for 1 hour, and then extracted with ether. The extract was diluted with 5-sodium hydroxide aqueous solution.
After washing twice with water, the ether was distilled off and the residual sound was distilled under reduced pressure to 93°C/2-HP to 95°C/2■H.
Obtain fractions so and st of f. Next, p− obtained in this way
Alcohol 1011j is added to (formylphenyl methacrylate) 17.6F, and phenylhydrazine 1a8F is added while stirring, and the mixture is cooled to 10°C or lower.

After stirring at this temperature for 30 minutes, the precipitated yellow crystals were filtered and dried to obtain 19.8 f of Compound AI.

As monomer B, any monomer can be used as long as it is soluble in aliphatic hydrocarbon solvents but becomes insolubilized when polymerized. For example, lower alkyl of acrylic acid or methacrylic acid (
Methyl, ethyl, etc.) esters, acetate, styrene, ethylene, etc.

Examples of aliphatic swelling hydrogen used as a solvent include inoctane, n-octane, n-nonane, isononane,
n-decane, isodecane, n-tridecane, indoridecane, n-tetradecane, intetradecane, n-hexane, n-pentane, n-hebutane, and mixtures thereof (commercially available products include Aitunogu manufactured by Esso Standard Co., Ltd. H, G, L, K: Naphtha/I66, Shell Sol, manufactured by Shell Oil Co., etc.) These solvents are less qualitative than aromatic solvents such as benzene and toluene. Furthermore, the solubility in the non-aqueous resin of the present invention is also lower than in aromatic solvents.

As the polymerization initiator, conventional ones such as azobisisobutyronitrile, penzoyl oxide, lauryl peroxide, etc. can be used.

Examples are shown below.

Example 1 Polylauryl methacrylate 10F as a resin component was dissolved in isooctane 40F4C@, and this was mixed with a stirrer, a cooler,
Place in a four-loaf flask equipped with a temperature needle and dropping funnel.
Heat from the outside with a water path and stir while maintaining the internal temperature at 80°C. On the other hand, compound 2f of AI as Nanatsumer-A and methyl methacrylate 5 as Nanatsumer-B.
and azobisin butyronitrile αlf are dissolved, transferred to a dropping funnel, and this solution is dropped into the flask over about 30 minutes. After the dropwise addition, stirring was continued for 3 hours to carry out polymerization, and a yellow non-aqueous resin dispersion was obtained with a polymerization rate of 98%. This dispersion did not form any precipitates even after being left for 3 months, and had excellent dispersion stability.

Next, after dispersing this dispersion liquid 7f in Isopar H1t, 1O% of nickel dodecylsalicylate (polarity control agent)
An electrophotographic liquid developer was prepared by adding Iso/#-H solution 1-. When this developer was used to develop an electrostatic layer on a zinc oxide photosensitive paper for offset printing formed by a conventional method, a clear yellow positive image was formed.

Example 2 In Example 1, polylauryl methacrylate 10f
Instead of dissolving rosin-modified alkyd resin 15F in Isopar H: 15f instead of dissolving it in isooctane 409, and dissolving methyl methacrylate 5f and azobisisobutyronitrile α1f in compound 2t of A62, Pynyl acetate monomer St The same operation was repeated except that 7g62 of Compound 2f and 0.1f of azo♂sisodecylonitrile were dissolved in the solution to obtain a yellow non-aqueous resin dispersion with a polymerization rate of 9&7*. As in Example 1, this dispersion did not produce any precipitation even after being left for 3 months.Next, this dispersion 7f was dispersed in Isopar H1t, and the same polarity control agent solution as in Example 1 was - was added to prepare an electrophotographic liquid agent. Even if this developer was left open for a month, almost no precipitate was formed. Further, when copying was carried out in the same manner as in Example 1, a copy with no background stain was obtained in the image @@fo, 8B of the peta portion.

Example 3 Based on Example 1, polylauryl methacrylate, /%
The same operation was repeated using octyl methacrylate-hydroxy methacrylate copolymer (copolymerization ratio 9:1 by weight), compound A6 and methyl acrylate in place of compound No. 1 and methyl methacrylate, respectively, and a yellow non-aqueous mixture was obtained. A resin dispersion was prepared. The dispersion stability of this dispersion was almost the same as in Example 1.

Next, this dispersion liquid 15f was dispersed in IsoA-81t to prepare an electrophotographic liquid preparation. Furthermore, this developer was used to develop an electrostatic latent image on zinc oxide photosensitive paper for offset printing formed by a conventional method, and the printing plate thus obtained was desensitized and then subjected to offset printing. The printing start-up was good (clear prints were obtained even in large-volume printing of 1000 sheets, confirming the excellent fixing properties of the non-aqueous resin of the present invention.

Claims (1)

[Claims] L In a resin solution using an aliphatic hydrocarbon as a solvent, in the presence of a polymerization initiator, a compound of the general formula [where -H or -0HhX is a C, ~C4 anaphthyl group, ◇) NH- Production of a non-aqueous resin dispersion, characterized by polymerizing a monomer A represented by ◎ representing a group or a zellidyl group and a monomer B that is soluble in the solvent but becomes insolubilized when polymerized. Method.