JPH0693105A - Non-aqueous resin dispersion, method for producing the same, and liquid developer - Google Patents

Abstract

(57) [Summary] [Structure] In a solution in which a resin insoluble in the non-aqueous solvent or the carrier liquid is dissolved in a monomer mixture forming a condensate soluble in the non-aqueous solvent or the electrically insulating carrier liquid, the monomer mixture is prepared. By co-condensing the condensate and the non-aqueous solvent or carrier liquid insoluble resin trapped by mutual entanglement as a whole the non-aqueous solvent or carrier liquid insoluble chain polymer A liquid developer using a non-aqueous resin dispersion liquid and a chain-like polymer dispersed in a non-aqueous solvent or carrier liquid as a fixing agent (dispersing agent). The non-aqueous resin dispersion of the present invention has excellent dispersion stability, and when used as a dispersant constituting a liquid developer, it provides a liquid developer for electrostatic latent image development having excellent dispersion stability. It is also useful as a polymer for paints.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-aqueous resin dispersion liquid useful for liquid developers for electrostatic latent image development, paints and the like, and a method for producing the same.

[0002]

2. Description of the Related Art A non-aqueous resin dispersion liquid (hereinafter referred to as NAD) is used for stably dispersing a colorant such as a pigment in a solvent, and an amphipathic resin is generally used.
This amphiphilic resin is derived from a vinyl polymer, and a graft polymer is mainly used. However, when a graft polymer is produced, a relatively large amount of by-produced non-aqueous solvent-soluble non-grafted polymer or insoluble polymer deteriorates dispersibility in a colorant, so that long-term storage There was a problem that sedimentation occurred.

On the other hand, various proposals have been made so far for a non-aqueous resin dispersion liquid used in a liquid developer for electrostatic latent image development, a paint and the like and a method for producing the same. For example,
A resin prepared by reacting a natural resin-modified thermosetting resin in a long-chain alkyl group-containing monomer is proposed as a resin for forming toner particles of a liquid developer for electrophotography, which is described in Japanese Patent Publication No. 62-3859. .

However, although these non-aqueous resin dispersions are effective in improving the dispersion stability of the colorant, they are still not NAD having sufficient dispersion stability.

[0005]

The problem to be solved by the present invention is to improve the dispersibility in a colorant and thereby maintain good dispersion stability even after long-term storage, and NAD and its production. A method and a liquid developer using the method.

[0006]

[Means for Solving the Problems] In order to solve the above-mentioned problems, (1) in a solution in which a resin mixture insoluble in the non-aqueous solvent is dissolved in a monomer mixture constituting a condensate soluble in the non-aqueous solvent. By co-condensing the monomer mixture, the chain-like polymer insoluble in the non-aqueous solvent as a whole is trapped by mutual entanglement of the condensate and the resin insoluble in the non-aqueous solvent. A non-aqueous resin dispersion characterized by being dispersed in an aqueous solvent, (2) in a solution in which a resin mixture insoluble in the non-aqueous solvent is dissolved in a monomer mixture forming a condensate soluble in the non-aqueous solvent , The monomer mixture is co-condensed in the presence of a co-condensation catalyst, whereby the condensate and the resin insoluble in the non-aqueous solvent as a whole are trapped by the mutual entanglement of the non-aqueous solvent insoluble in the non-aqueous solvent. (3) A method for producing a non-aqueous resin dispersion, characterized in that a chain polymer is produced and the chain-like polymer is dispersed in the non-aqueous solvent, and (3) an electrically insulating carrier liquid and coloring In a liquid developer comprising an agent, a fixing agent and a dispersant, a resin mixture insoluble in the carrier liquid is dissolved in a monomer mixture which forms a condensate soluble in the carrier liquid as the fixing agent and the dispersant. Characterized by using a chain-like polymer insoluble in the carrier liquid as a whole captured by mutual entanglement of the condensate and the resin insoluble in the carrier liquid by co-condensing a monomer mixture A liquid developer is provided.

The NAD of the present invention can be manufactured, for example, according to the following manufacturing method.

That is, by co-condensing the monomer mixture in the presence of a co-condensation catalyst in a solution in which a resin insoluble in the non-aqueous solvent is dissolved in a monomer mixture constituting a condensate soluble in the non-aqueous solvent. , Producing a chain-insoluble polymer insoluble in the non-aqueous solvent as a whole captured by mutual entanglement of the condensate and a resin insoluble in the non-aqueous solvent, A method for producing a non-aqueous resin dispersion, which comprises dispersing in an aqueous solvent,

The liquid developer of the present invention can be manufactured, for example, according to the following manufacturing method.

That is, the monomer mixture is condensed in the presence of a cocondensation catalyst in a mixed solution prepared by dissolving a resin insoluble in the electrically insulating carrier liquid in a monomer mixture in which the condensate is soluble in the carrier liquid. As a result, while producing a chain-like polymer insoluble in the carrier liquid as a whole, which is captured by entanglement of the co-condensate and the insoluble resin,
It can be produced by dispersing the chain-like polymer in the carrier liquid together with a colorant.

The resin insoluble in the non-aqueous solvent used in the present invention is a non-aqueous solvent such as an acrylic resin, a polyester resin, an alkyd resin or a urethane resin having a solubility parameter (hereinafter referred to as SP) of 8.3 or more. There is no particular limitation as long as it is a resin insoluble in. When a resin having an SP of less than 8.3 is used, the solubility in a non-aqueous solvent is increased, the physical capture with the soluble condensate is weakened, and the adsorptivity to the colorant is lowered, so that the colored NAD is reduced. It is not preferable because the dispersion stability of No. 1 tends to deteriorate.

As the acrylic resin having SP of 8.3 or more used in the present invention, for example, an ester of (meth) acrylic acid and a hydroxyl group-containing alkyl having 4 or less carbon atoms is 50% by weight or more as an insoluble monomer component. It can be produced by polymerizing at a reaction temperature of 50 to 150 ° C. in the presence of a polymerization initiator. When the amount of the insoluble monomer component is less than 50% by weight, the solubility in the non-aqueous solvent tends to be high, which is not preferable.

As the polyester resin having SP of 8.3 or more used in the present invention, for example, polybasic acid containing an aromatic group and an alkyl group having 4 or less carbon atoms and polyhydric alcohol are used as insoluble monomer components. It can be produced by dehydration condensation using 50% by weight or more. When the amount of the insoluble monomer component is less than 50% by weight, the solubility in the non-aqueous solvent tends to be high, which is not preferable.

The alkyd resin having an SP of 8.3 or more used in the present invention is not particularly limited as long as it is an alkyd resin having an oil length of 50% by weight or less.

The urethane resin having an SP of 8.3 or more used in the present invention includes, for example, a polyvalent isocyanate containing an alkyl group having 18 or less carbon atoms and / or a polyhydric alcohol having 4 or less carbon atoms. Can be produced by carrying out a polyaddition reaction using 50% by weight or more as an insoluble monomer component. Insoluble monomer component is 5
If it is less than 0% by weight, the solubility in the non-aqueous solvent tends to be high, which is not preferable.

As the monomer (hereinafter referred to as a solubilizing monomer) constituting the condensate soluble in the non-aqueous solvent by the condensation used in the present invention, a polybasic acid having 4 or more carbon atoms and a polyhydric alcohol are used. It can be produced by using 50% by weight or more of the total polyester and co-condensing with a catalyst such as tetraisopropyl titanate at a reaction temperature of 150 to 250 ° C.

As the polybasic acid, aliphatic, alicyclic and aromatic polyvalent carboxylic acids or their esters, acid anhydrides and acid halogen derivatives can be used, and examples thereof include adipic acid, sebacic acid and azelaic acid. , Dodecanedioic acid, dimer acid and / or a derivative thereof substituted with an alkyl group, an aralkyl group, an alkoxy group or the like can be used as the solubilizing monomer component of the soluble polyester resin.

As the polyhydric alcohol, alkylene glycol, monocyclic and polycyclic polyhydric alcohols can be used. For example, tetraethylene glycol, tetrapropylene glycol, butanediol, pentanediol, hexanediol, heptanediol. , Octanediol, nonanediol, decanediol, dodecanediol and / or derivatives thereof substituted with an alkyl group, an aralkyl group or an alkoxyl group, butyl glycidyl ether, lauryl glycidyl ether, versatic acid glycidyl ester and the like. .

The amount of the solubilizing monomer component used in the present invention is preferably 10 to 900 parts by weight with respect to 100 parts by weight of the resin which is insoluble in the non-aqueous solvent, and if less than 10 parts by weight, the chain polymer is dissolved. If the amount is more than 900 parts by weight, the solubility of the chain-like polymer becomes too high and the adsorptivity with the colorant decreases. This is not preferable because the chain-like polymer tends to separate from the colorant.

In the solubilizing monomer component used in the present invention, the ester group contained in the resin is insoluble in the non-aqueous solvent, and the terminal and / or side chain hydroxyl group, carboxyl group,
Since SP is similar to ester group or urethane group,
When the solubilizing monomer component is condensed, the condensation occurs while being trapped in the insoluble structural part in the non-aqueous solvent composed of the hydroxyl group, the carboxyl group, the ester group and the urethane group. Is thought to be formed. Further, when a three-dimensional insoluble resin is used, it is considered that the entanglement with the condensate can be formed through this three-dimensional network structure. The thus-prepared chain-like polymer of the present invention is insoluble in the non-aqueous solvent in the temperature range of -30 to 50 ° C.

The polymerization initiator used in the copolymerization reaction is
For example, azobisisobutyronitrile, benzoyl peroxide, diethyl butyl peroxide,
Tertiary butyl peroxybenzoate and the like can be mentioned, and the amount thereof is preferably 0.1 to 10.0% by weight of the monomer component.

Examples of the non-aqueous solvent used in the present invention include n-hexane, n-pentane, n-octane, and n.
-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 hydrocarbon solvents such as toluene and xylene, ketone solvents such as methyl isobutyl ketone and cyclohexanone, and alcohol solvents such as ethyl alcohol and butyl alcohol. Examples of the solvent include 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.

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 include Kayaset Yellow AG, Kayaset Red B, Kayaset Blue FB, and Kayaset Yellow E-5 manufactured by Nippon Kayaku Co., Ltd.
G, Kayaset Yellow E-3GL, Kayaset Yellow E-HGL, Kayatheron Red E-GL, Kayatheron Red E-BF, Kayatheron Red E-2BL, Kayatheron Blue E-2BL, Kayatheron Blue E-BR , Kayaseron Blue E-BG, Kayaseron Blue E-5G,
Kayaceron Torquay's Blue E-GL, Kayacelon Navy Blue E-EX, Kayaceron Black E-EX, Kayaron Brilliant Flavin GL-SF, Kayaron Brilliant Flavin FG-S, Kayaron Light Yellow 5
GS, 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 Torquay's Blue GL-S200, Kayaron Navy. Blue GX-
SF200, Kayaron Black S200, Kayaron Black BR-SF, Kayaron Black EX-SF200;
Sumikaron Brilliant Flavin S-1 manufactured by Sumitomo Chemical Co., Ltd.
0G, 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 S-
R, Sumikaron Red E-3BR, 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- GR
L, Sumikaron Blue SE-RF, Sumikaron Blue E
-R, Sumikaron Blue E-BL, Sumikaron Blue E
-FBL, Sumikaron Blue E-RPD, Sumikaron Blue S-BG, Sumikaron Blue SE-RPD, Sumikaron Black S-BL, Sumikaron Black E-B
(N) and the like.

The liquid developer of the present invention comprises the above-mentioned non-aqueous resin dispersion of the present invention using an electrically insulating carrier liquid as a non-aqueous solvent, and further, if necessary, a charge control agent, wax, surfactant and the like. A liquid having an average particle diameter of 0.1 to 5.0 μm by adding the auxiliary agent described above, diluting with an electrically insulating carrier liquid to a nonvolatile content of about 0.1 to 2% by weight, and mixing and stirring. The developer can be easily manufactured.

Examples of the charge control agent include metal salts of naphthenic acid, metal salts of stearic acid, metal salts of dodecylbenzenesulfonic acid and metal salts of dioctylsulfosuccinic acid,
Metals are Li, Ca, Ba, Zr, Mn, Co, Ni, C
Examples include u, Zn, Cd, Al, Pt, and Cr.

Examples of the wax include paraffin wax, polyethylene wax, polypropylene wax, ethylene copolymer, propylene copolymer and the like.

Examples of the surfactant include various cation type, anion type and nonionic type surfactants.

[0029]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. In the examples,
“Parts” and “%” represent “parts by weight” and “% by weight”, respectively.

(Example 1) Methyl methacrylate 60
Part, butyl acrylate 40 parts, azobisisobutyronitrile 1 part and toluene 150 parts are reacted at 82 ° C. for 10 hours to produce an acrylic resin having a nonvolatile content of 39.8%, and then toluene is distilled off to insoluble. Acrylic resin (A) was manufactured.

30 parts of the insoluble acrylic resin (A), 50 parts of dodecanedioic acid, 20 parts of butanediol and 0.7 part of dibutyltin oxide were dehydrated and condensed at 220 ° C. for 16 hours and then cooled, and then “Isopar G” was added. Diluted with 150 parts to produce a chain-like polymer (A).

100 parts of the chain-like polymer (A), 40 parts of carbon black and 660 parts of "Isopar G" were kneaded for 12 hours in a ball mill, and further diluted with 7200 parts of "Isopar G" to give a coloring of a nonvolatile content of 1%. NAD (A) was manufactured.

The colored NAD (A) is a colored NAD which does not cause sedimentation even when left standing for one month and has good dispersion stability.
Met.

100 parts of the chain-like polymer (A), 38 parts of carbon black, 2 parts of cobalt naphthenate and 660 parts of "Isoper G" were kneaded in a ball mill for 12 hours and further diluted with 7200 parts of "Isoper G". Nonvolatile content about 1%
A liquid developer (A) was produced.

The liquid developer (A) was a liquid developer having no dispersion even when left standing for one month and having good dispersion stability.

(Example 2) In Example 1, instead of the insoluble acrylic resin (A), ethylene glycol 0.5
Mole, dodecanediol 0.5 mole, adipic acid 0.2
Mol, 0.9 mol of phthalic anhydride and dibutyltin oxide were dehydrated and condensed at 220 ° C. for 15 hours, and an insoluble polyester resin (B) having an acid value of 15 was used, in the same manner as in Example 1, Colored NAD with good dispersion stability
(B) and a liquid developer (B) were produced.

(Example 3) In Example 1, 1 mol of dehydrated castor oil fatty acid, 3 mol of glycerin and 4 mol of phthalic anhydride were used in place of the insoluble acrylic resin (A).
Colored NAD (C) and liquid developer having good dispersion stability in the same manner as in Example 1 except that the insoluble alkyd resin (C) having an acid value of 12 obtained by dehydration condensation at 15 ° C. for 15 hours was used. (B) was produced.

Example 4 In Example 1, 1 mol of tolylene diisocyanate, 0.3 mol of dodecanediol and 0.8 mol of diethylene glycol were used in place of the insoluble acrylic resin (A) and reacted at 80 ° C. for 15 hours. The colored NAD (D) and the liquid developer (D) having good dispersion stability were obtained in the same manner as in Example 1 except that the insoluble urethane resin (D) having a residual isocyanate content of 0.1% was used. Was manufactured.

(Example 5) In Example 1, instead of the chain polymer (A) insoluble in the non-aqueous solvent, 30 parts of insoluble acrylic resin (A), 60 parts of dimer acid, 9 parts of tetraethylene glycol were used. And 1 part of glycerin at 240 ℃
Colored NAD (E) and liquid developer having good dispersion stability in the same manner as in Example 1 except that the chain-like polymer (E) insoluble in the non-aqueous solvent obtained by dehydration condensation for 8 hours was used. (E) was produced.

[0040]

The chain-like polymer insoluble in the non-aqueous solvent of the present invention is obtained by dissolving and mixing a soluble monomer component constituting a specific polyester resin soluble in the non-aqueous solvent and a specific resin insoluble in the non-aqueous solvent. After that, since the soluble monomer component is co-condensed and trapped by the mutual entanglement of the molecular chains, the non-aqueous resin dispersion in which the co-condensate soluble in the non-aqueous solvent and the insoluble resin are integrally bonded to each other Since it forms a liquid, it is stably dispersed in the non-aqueous solvent.

The chain-like polymer of the present invention having such excellent dispersion stability as described above is used as a fixing agent and a dispersant constituting a liquid developer, whereby an electrostatic latent image excellent in dispersion stability is obtained. It can provide a liquid developer for development and is also useful as a polymer for paints.

Continuation of front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location C08L 75/04 NFX 8620-4J G03G 9/13 // C08L 101/00 LSY 7242-4J

Claims (9)

[Claims] 1. A condensate that is soluble in a non-aqueous solvent is mixed with a monomer mixture that forms a condensate that is soluble in the non-aqueous solvent in a solution in which a resin that is insoluble in the non-aqueous solvent is dissolved. A non-aqueous resin dispersion characterized in that the chain-like polymer insoluble in the non-aqueous solvent as a whole captured by mutual entanglement with a resin insoluble in an aqueous solvent is dispersed in the non-aqueous solvent. . 2. The non-aqueous resin dispersion according to claim 1, wherein the resin insoluble in the non-aqueous solvent is an acrylic resin, a polyester resin, an alkyd resin or a urethane resin having a solubility parameter of 8.3 or more. 3. The non-aqueous resin dispersion liquid according to claim 1, wherein the condensate soluble in the non-aqueous solvent is a polyester resin having a solubility parameter of less than 8.3. 4. By co-condensing the monomer mixture in a solution in which a resin insoluble in the non-aqueous solvent is dissolved in a monomer mixture constituting a condensate soluble in the non-aqueous solvent, in the presence of a co-condensation catalyst. , Producing a chain-insoluble polymer insoluble in the non-aqueous solvent as a whole captured by mutual entanglement of the condensate and a resin insoluble in the non-aqueous solvent, A method for producing a non-aqueous resin dispersion, which comprises dispersing in an aqueous solvent. 5. The non-aqueous resin dispersion according to claim 4, wherein the resin insoluble in the non-aqueous solvent is an acrylic resin, a polyester resin, an alkyd resin or a urethane resin having a solubility parameter of 8.3 or more. Production method. 6. The method for producing a non-aqueous resin dispersion according to claim 4, wherein the condensate soluble in the non-aqueous solvent is a polyester resin having a solubility parameter of less than 8.3. 7. A liquid developer comprising an electrically insulating carrier liquid, a colorant, a fixing agent and a dispersant, wherein the carrier liquid is added to the monomer mixture constituting a condensate soluble in the carrier liquid as the fixing agent and the dispersant. In a solution in which an insoluble resin is dissolved in the solution, the monomer mixture is co-condensed to trap the condensate and the resin insoluble in the carrier solution as a whole, which is insoluble in the carrier solution. A liquid developer characterized by using a chain polymer. 8. The liquid developer according to claim 7, wherein the resin insoluble in the electrically insulating carrier liquid is an acrylic resin, a polyester resin, an alkyd resin or a urethane resin having a solubility parameter of 8.3 or more. 9. The liquid developer according to claim 7, wherein the condensate soluble in the electrically insulating carrier liquid is a polyester resin having a solubility parameter of less than 8.3.