JPH0632988A - Nonaqueous colored resin dispersion and its production - Google Patents

Abstract

PURPOSE:To produce a nonaqueous resin dispersion having improved dispersion stability and redispersibility without using a ball mill, etc., by mixing a dispersant and a colorant, converting the mixture into fine particles, and adding a nonaq. solvent to the mixture. CONSTITUTION:A dispersant and a colorant are mixed and converted into fine particles followed by the addition of a nonaq. solvent to the mixture in the process for producing a nonaq. dispersion obtd. by dispersing colored resin particles contg. the dispersant and the colorant in the nonaq. solvent. The dispersant is insol. in the solvent. The dispersion is easily produced without using a milling machine, such as a ball mill or an attrition mill, greatly shortening the production process, and has a remarkably improved dispersion stability even after a long storage.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-aqueous color resin dispersion used in inks, paints and liquid developers for developing electrostatic latent images. More specifically, it has improved dispersion stability and redispersibility. The present invention relates to a non-aqueous colored resin dispersion and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, as a resin used for dispersing a colorant in a non-aqueous solvent, an amphipathic resin such as a block copolymer or a graft copolymer is generally used. However, in order to use these polymers as an amphipathic resin which is a constituent of a liquid developer for electrostatic latent image development, the solvent is an aliphatic hydrocarbon, so it is used to synthesize a block copolymer. There are few living polymers and macromonomers that can be produced, and it is difficult to produce a stable amphiphilic resin because it is difficult to increase the grafting rate when synthesizing a graft copolymer. It is difficult to obtain a good non-aqueous colored resin dispersion. Further, in order to manufacture the non-aqueous color resin dispersion liquid, there is a complicated process of manufacturing using an attritor, a ball mill or the like.

[0003]

The problem to be solved by the present invention is to provide a resin in which a soluble segment and an insoluble segment are highly integrated by a physical interaction with the solvent of the amphipathic resin (hereinafter referred to as a chain-like structure). Polymer) is used as a dispersant to provide a non-aqueous colored resin dispersion having improved dispersion stability and redispersibility, and a method for producing a non-aqueous colored resin dispersion without using a ball mill or the like. To provide.

[0004]

In order to solve the above problems, the present invention provides

In a non-aqueous color resin dispersion liquid obtained by dispersing colored resin particles containing a dispersant and a colorant in a non-aqueous solvent, (1) the dispersant is a non-aqueous resin dispersion liquid insoluble in the non-aqueous solvent. (2) Dispersing agent and colorant are mixed beforehand to form fine particles, and then a non-aqueous solvent is added to produce a colored resin particle dispersion, and a non-aqueous colored resin dispersion and a method for producing the same are provided.

As the dispersant used in the present invention, a known non-aqueous resin dispersion liquid can be used as long as it is a resin insoluble in a non-aqueous solvent. For example, the applicant of the present invention (1) Japanese Patent Publication No. 2-4
No. 1749, a non-gelled graft polymer insoluble in a carrier liquid as a whole, which is proposed as a liquid developer having improved resin elution property, transfer property, cleaning property and dispersion stability of toner particles, (2) Japanese Examined Examination 3-7297
No. 6, a vinyl polymer having an active hydrogen atom capable of reacting with an isocyanate group, which is proposed as a liquid developer capable of maintaining good dispersion stability and good image density even after long-term use or long-term storage. A chain-like polymer composed of a cross-linked polymer which is obtained by crosslinking the polymer with a polyisocyanate compound and a vinyl polymer which is insoluble in the carrier solution and is trapped by the cross-linked polymer due to the mutual entanglement of the molecular chains, (3 ) A cross-linked polymer soluble in a carrier liquid obtained by cross-linking a vinyl polymer having a cross-linking reactive functional group in the molecular side chain proposed in JP-A-63-208866, and a basic nitrogen atom or A vinyl copolymer which is insoluble in the carrier liquid and is obtained by copolymerizing a vinyl monomer having an amide group and a vinyl acetate monomer. Coalescence, 縺鎖 like polymer consisting trapped in the crosslinked polymer by entanglement of molecular chains cross,
(4) Captured by the entanglement of molecular chains formed by polymerizing a vinyl monomer containing a vinyl acetate monomer as a main component in a specific copolymer soluble in a carrier liquid proposed in JP-A-3-9369. Examples include chain-like copolymers insoluble in the carrier liquid.

The amount of the dispersant used is 0.
A range of 5 to 99 weight is preferred.

The colorant used in the present invention is not particularly limited and various conventionally known dyes and / or pigments can be used, and the amount used is such that the coloring of the non-aqueous color resin dispersion can be visually recognized. It suffices, for example, carbon black, spirit black, aniline black, oil black, nigrosine, wool black, blue black E, alkali blue, phthalocyanine blue, oil blue, acid blue, dianidine blue, pictoria blue, methylene blue, chrysoidine. , Sutan Violet, Crystal Violet, Oil Violet, Methyl Violet, Phthalocyanine Green, Acid Black Green, Malachite Green, Safranine, Brilliant Carmine 6B, Rhodamine 6G, Fast Red, Oh Rureddo, Congo Red, auramine, rhodamine B, barium red 2B, calcium red 2B, strontium red, manganese red 2B, barium sole red, calcium Red 52,
Lake Red C, Holmaroon L-58, Brilliant Carmine 3B, Brilliant Scarlet G, Quinacridone Magenta, Bismarck Brown, Benzidine Yellow, Hansa Yellow, First Yellow G, First Yellow 10G, Disazo Yellow AAA, Disazo Yellow AAMX, Disazo Yellow AAOT, Disazo Yellow AADA and the like can be mentioned. Examples of commercially available products thereof include Kayaset Yellow A manufactured by Nippon Kayaku Co., Ltd.
-G, Kayaset Red B, Kayaset Blue FB, Kayaset Yellow E-5G, Kayaset Yellow E-3
GL, Kayaset Yellow E-HGL, Kayaceron Red E-GL, Kayaceron Red E-BF, Kayaselon Red E-2BL, Kayaselon Blue E-2BL, Kayaselon Blue E-BR, Kayaselon Blue E-BG. , Kayatheron Blue E-5G, Kayatheron Torquay's Blue E
-GL, Kayaseron Navy Blue E-EX, Kayaseron Black E-EX, Kayaron Brilliant Flavin G
L-SF, Kayaron Brilliant Flavin FG-S, Kayaron Light Yellow 5GS, Kayaron Yellow HGL
-SF, Kayaron Yellow YL-SE, Kayaron Yellow 4R-E, Kayaron Yellow PAL-E, Kayaron Red BR-S, Kayaron Red AD-S, Kayaron Red TL-SF, Kayaron Red BL-E4L-SF, Kayaron Red PAL-E. , Kayaron Blue 3R-SF,
Kayaron Blue CR-E200, Kayaron Blue 2R-
SF, Kayaron Blue GR-E, Kayaron Blue EBL
-E, Kayaron Blue PAL-E, Kayaron Brilliant Blue FR-S, Kayaron Brilliant Blue F2B-
S, Kayaron Torquaise Blue GL-S200, Kayaron Navy Blue GX-SF200, Kayaron Black S200, Kayaron Black BR-SF, Kayaron Black EX-SF200; Sumikaron Brilliant Flavin S-10G manufactured by Sumitomo Chemical Co., Ltd. , Sumikaron Yellow SE
-5G, Sumikaron Yellow SE-3GLconc. ,
Sumikaron Yellow SE-RPD, Sumikaron Yellow E-RPD, Sumikaron Yellow SR, Sumikaron Yellow S-RPD, Sumikaron Orange SE-RPD,
Sumikaron Orange SR, Sumikaron Red E-3B
R, Sumikaron Red S-BDF, Sumikaron Red E
-RPD, Sumikaron Red E-FBL, Sumikaron Red S-BLF, Sumikaron Red S-RPD, Sumikaron Red S-BF, Sumikaron Blue S-3RF, Sumikaron Blue E-GRL, Sumikaron Blue SE- R
F, Sumikaron Blue E-R, Sumikaron Blue E-B
L, Sumikaron Blue E-FBL, Sumikaron Blue E
-RPD, Sumikaron Blue S-BG, Sumikaron Blue SE-RPD, Sumikaron Black S-BL, Sumikaron Black EB (N), and the like.

Examples of the non-aqueous solvent used in the present invention include n-hexane, n-pentane, n-octane and n-hexane.
-Nonane, n-decane, n-undecane, and n-dodecane, as a commercial product, "Isoper G" manufactured by Exxon Co.,
“Isoper H”, “Isoper K”, “Isoper L”, and “Isoper M” have a boiling point in the temperature range of 68 to 250 ° C. and have a volume resistivity of 10 ⁹ Ω · cm or more and less than 3. Electrically insulating carrier liquids such as various hydrocarbon solvents having a dielectric constant; aromatic solvents such as toluene and xylene; methyl ethyl ketone, methyl isobutyl ketone,
Examples thereof include ketone solvents such as soclohexanone; alcohol solvents such as ethanol, propanol and butanol; ester solvents such as ethyl acetate and butyl acetate. Particularly, a solvent having a boiling point in the range of 100 to 200 ° C., for example, “Isoper G” and “Isoper H” is preferable.

As a method for producing a non-aqueous color resin dispersion, first, a colorant and a non-aqueous resin dispersion, and if necessary, an auxiliary agent are added so that the nonvolatile content becomes 20% by weight or more. It can be produced by adjusting and adding a non-aqueous solvent and stirring and mixing at room temperature or at a temperature not higher than the boiling point of the solvent using a dispersion stirrer or the like.

As the auxiliaries, surfactants can be used for improving dispersibility, and for example, various cation type, anion type and nonion type surfactants may be used as necessary. .

The non-aqueous colored resin dispersion thus produced had an average particle diameter of the colored resin in the range of 0.1 to 2.0 μm and was excellent in dispersion stability and redispersibility. .

[0013]

EXAMPLES The present invention will be described more specifically below by showing examples of the present invention. However, the present invention is not limited to these examples as long as the gist thereof is not exceeded. In addition, "part" represents a "weight part" in an Example.

(Production of Dispersant) Dispersant A "Isopar H" (an aliphatic hydrocarbon solvent manufactured by Exxon Chemical Co., Ltd.) 150 parts, methyl methacrylate 15 parts and 2-ethylhexyl methacrylate 85 parts were equipped with a reflux condenser. After charging the contents in a glass container and heating the contents to 80 ° C. with stirring, 0.5 part of benzoyl peroxide was added while maintaining the same temperature, and the reaction was continued for 6 hours, and the reaction was continued at 90 ° C. for 2 hours. . After cooling, the content was taken out to obtain a viscous polymer having a viscosity of 30 Stokes.

131 parts of the above polymer was charged into a reaction vessel similar to the above, and 152 parts of "Isopar G", 40 parts of vinyl acetate, 8 parts of N-vinylpyrrolidone and 0.48 part of azobisisobutyronitrile were further charged. In addition, raise the temperature to 80 ° C,
The mixture was reacted at 80 ° C. for 6 hours to obtain a white dispersion liquid having a nonvolatile content of 30%. The dispersion thus obtained was designated as "dispersant A".

Dispersant B 30.0 parts of lauryl methacrylate, 22.0 parts of butyl methacrylate, 46.6 parts of butyl acrylate, 0.4 parts of hydroxypropyl methacrylate, 1.0 part of methacrylic acid.
Part, "Perbutyl D" (polymerization catalyst manufactured by NOF CORPORATION) 1.0
And 100 parts of "ISOPER G" (aliphatic hydrocarbon solvent manufactured by Exxon Chemical Co., Ltd.) were charged into a reaction vessel equipped with a nitrogen gas introduction tube, a stirrer and a cooling tube, and the temperature was raised to 120 ° C, and 1
The reaction was carried out at 20 ° C. for 8 hours to obtain a polymer having a nonvolatile content of 48.8% and an average molecular weight of 220,000.

Next, the temperature was lowered to 70 ° C., 0.62 part of isophorone diisocyanate and 0.05 stannous octylate were added.
And 0.6 part of "Isopar G" were added, and urethanization reaction was carried out at 70 ° C for 4 hours, followed by cooling to give a nonvolatile content of 4
A solution of an intermediate containing an isocyanate group with 8.6% and an NCO content of 0.6% was obtained.

106 parts of the above intermediate solution was charged into the same reaction vessel as described above, and 180 parts of "Isopar G" was added,
Hydroxypropyl methacrylate (0.4 parts), methyl methacrylate (46.1 parts) and azobisisobutyronitrile (0.25 parts) were added, the temperature was raised to 80 ° C, and the mixture was reacted at 80 ° C for 5 hours to give a nonvolatile content of 29. A solution of a graft polymer having 2% and an NCO content of 0% was obtained. This graft polymer was a white latex in which the first polymer chain and the second polymer chain were bound by about 6 urethane bonds per molecule. The white latex thus obtained was designated as "dispersant B".
And

Dispersant C 80 parts of lauryl methacrylate, 10 parts of 2-hydroxyethyl methacrylate, 10 parts of N-vinylpyrrolidone, 1 part of di-tert-butyl peroxide and 148 parts of "Isopar G" are introduced into a nitrogen gas. Charge to a reaction vessel equipped with a tube, stirrer and cooling tube, heat to 130 ° C,
Was reacted for 6 hours to obtain a solution of the first polymer. next,
The temperature was lowered to 80 ° C. and isophorone diisocyanate was added.
5 parts, 0.03 part of di-n-butyltin dilaurylate and 2 parts of "Isopar G" were added, and a urethanization reaction was carried out at 80 ° C for 2 hours, followed by cooling to obtain a crosslinking weight of a non-volatile content of 38.2%. A combined solution was obtained.

131 parts of the cross-linked polymer was charged in the same reaction vessel as described above, and 152 parts of "Isopar G", 5 parts of 2-hydroxypropyl methacrylate, 40 parts of methyl methacrylate, 40 parts of phthalic acid-β-methacryloxy group. After adding 5 parts of ethyl and 0.25 part of azobisisobutyronitrile, the temperature was raised to 80 ° C. and the mixture was reacted at 80 ° C. for 6 hours to obtain a white dispersion liquid having a nonvolatile content of 30%. The dispersion thus obtained was designated as "dispersant C".

(Example 1) Carbon black (50 parts) and "Dispersant A" (167 parts) were placed in a 500 ml beaker, and a dispersion stirrer (TK Auto Homo Mixer; manufactured by Tokushu Kika Kogyo Co., Ltd.) was operated at 1500 rpm. Mix for 10 minutes. Furthermore, 33 parts of "Isopar G" are used at the same rotation speed of 30
It was gradually added over a period of time to produce a black dispersion liquid having a nonvolatile content of 40% and an average particle size of 0.28 micron.

The black dispersion liquid was diluted with "Isopar G" so that the non-volatile content was 1% and allowed to stand for 1 month.
There was almost no sediment, and the dispersion stability was excellent.

(Example 2) 40 parts of phthalocyanine blue and 200 parts of "dispersant B" were mixed in the same manner as in Example 1 to obtain a blue dispersion liquid having an average particle diameter of 0.18 micron.
When the dispersion stability was examined in the same manner as in Example 1, almost no sediment was observed.

Example 3 Brilliant Carmine 6B
60 parts and 133 parts of "dispersant C" were mixed in the same manner as in Example 1 to obtain a red dispersion liquid having an average particle diameter of 0.42 micron. The obtained red dispersion liquid was excellent in dispersion stability.

Example 4 First Yellow G 70
Parts and 100 parts of "Dispersant A" were mixed in the same manner as in Example 1 to obtain a yellow dispersion liquid having an average particle size of 0.59 micron. The obtained yellow dispersion was excellent in dispersion stability.

[0026]

The non-aqueous coloring resin dispersion of the present invention can be easily manufactured without using a kneading machine such as a usual ball mill or attritor, and therefore the conventional manufacturing process can be greatly shortened. . Furthermore, since a specific dispersant is used, the dispersion stability of the non-aqueous colored resin dispersion after production is remarkably improved even after long-term storage.

Therefore, the dispersion stability and redispersibility can be improved by using the non-aqueous coloring resin dispersion of the present invention in a paint or a liquid developer for developing an electrostatic latent image.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location C09C 3/10 PBN 6904-4J G03G 9/13

Claims (2)

[Claims] 1. A non-aqueous color resin dispersion liquid comprising a colored resin particle containing a dispersant and a colorant dispersed in a non-aqueous solvent, wherein the dispersant is a non-aqueous resin dispersion liquid insoluble in the non-aqueous solvent. A non-aqueous colored resin dispersion liquid comprising: 2. In a non-aqueous color resin dispersion liquid, which comprises dispersing colored resin particles containing a dispersant and a colorant in a non-aqueous solvent, the dispersant and the colorant are mixed in advance to form fine particles, and then the non-aqueous solvent is added. In addition, a method for producing a non-aqueous colored resin dispersion, which comprises producing a colored resin particle dispersion.