JPH0641402A - Non-aqueous resin dispersion, method for producing the same, and liquid developer - Google Patents

Abstract

(57) [Summary] [Structure] In the non-aqueous solvent or carrier liquid containing a polyester resin obtained by condensing a polybasic acid and a polyhydric alcohol soluble in a non-aqueous solvent or an electrically insulating carrier liquid, By polymerizing a vinyl monomer mixture in which the combination is insoluble in the non-aqueous solvent or carrier liquid, the non-aqueous solvent or carrier liquid as a whole is captured by the mutual entanglement of the vinyl copolymer and the polyester resin. A non-aqueous resin dispersion comprising an insoluble chain polymer dispersed in the non-aqueous solvent or carrier liquid, and a liquid developer using the chain polymer as a fixing agent (dispersant). [Effect] The non-aqueous resin dispersion liquid of the present invention has excellent dispersion stability, and when used as a fixing agent (dispersant) constituting a liquid developer, it is possible to provide a liquid developer 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]

A non-aqueous resin dispersion (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 ungrafted polymer or insoluble polymer deteriorates dispersibility in a colorant. When the graft polymer was used as a fixing agent (which also functions as a dispersant) as a constituent component of (1), there was a problem that sedimentation occurred during long-term storage.

Further, regarding NAD used in liquid developers for electrostatic latent image development, paints and the like, and the manufacturing method thereof,
Various proposals have been made so far, but NAD using a polyester resin is not well known. This is due to the technical difficulty of stably dispersing the polyester resin in the non-aqueous solvent. To improve the dispersion stability, for example, JP-A-3-263053 and JP-A-3-266 are available.
A polyester resin is proposed as a resin forming the toner particles of the electrophotographic liquid developer described in JP-A No. 854, JP-A-3-271752, JP-A-3-274065, JP-A-3-274066. Has been done.

[0004]

However, although these polyester resins are effective in improving the dispersion stability of the colorant, they are used as the colorant because the solvent in the polyester resin contains a relatively large amount of the soluble segment. Since the amount of the insoluble segment to be adsorbed is limited, it cannot be said that NAD has sufficient dispersion stability.

The problem to be solved by the present invention is to improve the dispersibility in a colorant, thereby maintaining good dispersion stability even after storage for a long time, NAD, a method for producing the same, and the use thereof. It is to provide a liquid developer.

[0006]

In order to solve the above problems, the present invention comprises (1) (a) a polyester resin obtained by condensing a polybasic acid and a polyhydric alcohol soluble in a non-aqueous solvent. In the non-aqueous solvent, (b) by polymerizing a vinyl monomer mixture in which the polymer is insoluble in the non-aqueous solvent, the vinyl copolymer and the polyester resin are trapped as a whole by mutual entanglement. In a liquid developer containing a non-aqueous resin dispersion liquid obtained by dispersing a chain-like polymer insoluble in the non-aqueous solvent in the non-aqueous solvent, and (2) a colorant, a fixing agent and an electrically insulating carrier liquid. In the carrier liquid containing (a) a polyester resin obtained by condensing a polybasic acid soluble in an electrically insulating carrier liquid and a polyhydric alcohol as the fixing agent,
(B) Polymerization of a vinyl monomer mixture in which the polymer becomes insoluble in the carrier liquid, thereby trapping by mutual entanglement of the vinyl copolymer and the polyester resin as a whole, a chain insoluble in the carrier liquid A liquid developer using a linear polymer is provided.

The NAD of the present invention can be manufactured, for example, according to the following manufacturing method. That is, in (a) the non-aqueous solvent containing a polyester resin obtained by condensing a polybasic acid and a polyhydric alcohol soluble in the non-aqueous solvent, (b) the polymer becomes insoluble in the non-aqueous solvent. The vinyl monomer mixture is added in the presence of a polymerization initiator in an amount of 50 to 15
By copolymerizing at a temperature of 0 ° C., a chain-like polymer that is totally insoluble in the non-aqueous solvent and is trapped by the mutual entanglement of the vinyl copolymer and the polyester resin is produced. A method for producing a non-aqueous resin dispersion, which comprises dispersing a polymer in the non-aqueous solvent.

The polyester resin used in the present invention is prepared by using a polybasic acid and a polyhydric alcohol in a known method, for example, using a catalyst such as tetraisopropylorthotitanate.
It can be produced by copolycondensation at a reaction temperature of 50 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. Examples thereof include succinic acid, adipic acid and fumaric acid. , Maleic acid, phthalic acid,
Tetrahydrophthalic acid, tetrabromophthalic acid, tetrachlorophthalic acid, trimellitic acid, aromatic tetracarboxylic acid, benzophenonetetracarboxylic acid and / or its acid anhydride, oxalic acid, sebacic acid, isophthalic acid, terephthalic acid, straconic acid , Het acid, itaconic acid, azelaic acid, dodecanedioic acid, dimer acid, cyclohexane-1,4-dicarboxylic acid, cyclopentane-1,3-
Dicarboxylic acid, 2,6-naphthalenedicarboxylic acid and /
Or the derivative etc. which were substituted by the alkyl group, the aralkyl group, the alkoxy group, etc. can be mentioned.

As the polyhydric alcohol, alkylene glycol, monocyclic and polycyclic polyhydric alcohols can be used. For example, neopentyl glycol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol. , Dipropylene glycol, tripropylene glycol, tetrapropylene glycol, butanediol,
Pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, dodecanediol, glycerin, trimethylolpropane, pentaerythritol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol,
1,4-cyclohexanediethanol, 1,4-benzenedimethanol, 1,4-benzenediethanol, norbornylene glycol, decahydro-2,6-naphthalenedimethanol and / or its alkyl group, aralkyl group or alkoxy group Examples thereof include substituted derivatives, butyl glycidyl ether, phenyl glycidyl ether, lauryl glycidyl ether, and versatic acid glycidyl ester.

In the polyester resin used in the present invention, it is desirable to use, in the polybasic acid and polyhydric alcohol used, a compound containing an alkyl group having 4 or more carbon atoms in an amount of 50% by weight or more based on the total amount of the compound. When it is 50% by weight or less, the solubility in the non-aqueous solvent is deteriorated, which is not preferable.

The vinyl monomer (hereinafter referred to as insolubilizing monomer) constituting the vinyl copolymer insoluble in the non-aqueous solvent by polymerization used in the present invention is, for example, the general formula (I).

[0013]

Embedded image CH ₂ ═CH—OCOR ¹ ... (I)

A saturated fatty acid vinyl ester represented by the formula (wherein R ¹ represents an alkyl group having 1 to 5 carbon atoms); general formula (II)

[0015]

Embedded image R ² OOCCH = CHCOOR ² (II)

(Wherein R ² represents an alkyl group having 1 to 5 carbon atoms), a dialkyl ester of an unsaturated dicarboxylic acid; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) (Meth) acrylic acid alkyl esters such as acrylate and butyl (meth) acrylate; (meth) acrylic acid or itaconic acid, crotonic acid, maleic acid, fumaric acid, tetrahydrophthalic anhydride and monoalkyl esters of these polybasic acids, (Meth) acryloxyethyl phosphate, p
-Carboxyl group-containing vinyl monomers such as sulfostyrene, sulfoethylacrylamide, 2-chloroethyl ester of (meth) acrylic acid, 2-hydroxy-3-chloropropyl ester, 2,3-dibromopropyl ester, phosphoric acid group-containing vinyl Monomers, sulfo group-containing vinyl monomers, halogen atom-containing vinyl monomers; epoxy group-containing vinyl monomers such as glycidyl (meth) acrylate; ether group-containing vinyls such as (meth) acrylic acid 2-methoxyethyl ester and 2-ethoxyethyl ester Monomers; (meth) acrylonitrile; vinyl monomers containing carbonyl groups such as vinyl methyl ketone and vinyl isopropenyl ketone; aromatic vinyl monomers such as styrene, vinyltoluene and α-methylstyrene; dimethylamido Ethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, N- vinylimidazole, N- vinyl-2-methylimidazole, 1
-Vinylpyrrole, N-β-acryloxyethylindole, 2-vinylquinoline, 4-vinylpyridine, 5-
Vinyl-4-methylthiazole, 3-methyl-5-isopropenylpyrazole, N-vinyl-2-pyrrolidone,
Examples thereof include vinyl monomers having a basic nitrogen atom or an amide group in the molecule such as N-vinylpiperidone, N-vinyloxazolidone, dimethylaminostyrene, dimethylaminomethylstyrene and (meth) acrylamide.

Further, the (meth) acrylic acid has 6 to 2 carbon atoms.
Esterified monomer of hydroxyl group-containing alkyl group of 4; General formula (III)

[0018]

Embedded image CH ₂ ═CH—OCOR ³ (III)

A saturated fatty acid vinyl ester represented by the formula (wherein R ³ represents an alkyl group having 6 to 18 carbon atoms); general formula (IV)

[0020]

Embedded image R ⁴ OOCCH = CHCOOR ⁴ (IV)

(In the formula, R ⁴ represents an alkyl group having 6 to 18 carbon atoms.) A dialkyl ester of an unsaturated dicarboxylic acid or the like can also be used together within a range not impairing the insolubility in a non-aqueous solvent. .

The amount of the insolubilizing monomer component used in the present invention is preferably 10 to 900 parts by weight with respect to 100 parts by weight of the soluble polyester resin, and if it is 10 parts by weight or less, the solubility of the chain-like polymer becomes too high. Therefore, the resin easily separates from the colorant, and when it is 900 parts by weight or more, the dispersion stability of the chain-like polymer is deteriorated, which is not preferable. Further, the insolubilizing monomer component used in the present invention is similar in solubility parameter (hereinafter, referred to as SP) to the hydroxyl group, carboxyl group or ester group of the terminal and / or side chain of the polyester resin soluble in the non-aqueous solvent. Therefore, when the insolubilized monomer component is polymerized, the polymerization occurs while being trapped in the structural part insoluble in the non-aqueous solvent composed of the hydroxyl group and the carboxyl group, so that a three-dimensional entanglement of the molecular chains can be formed. it is conceivable that. Further, when a trifunctional or higher functional alcohol component or basic acid component is used in combination, a three-dimensional soluble polyester resin is produced, and therefore, it is considered that entanglement with the copolymer can be formed through this three-dimensional network structure. The thus produced chain chain polymer of the present invention is insoluble in the non-aqueous solvent in the temperature range of -30 to 50 ° C.

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.

Examples of the non-aqueous solvent used in the present invention include n-hexane, n-pentane, n-octane, 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.

Further, an auxiliary agent or the like can be used if necessary.

As the auxiliaries, charge control agents, waxes, surfactants and the like which are commonly used in liquid developers for electrophotography can be used.

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
Charge control agents such as u, Zn, Cd, Al, Pt, and Cr are mentioned.

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

As the surfactant, for example, various cation type, anion type and nonionic type surfactants can be used as required.

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.

[0032]

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 0.5 mol of ethylene glycol, 0.5 mol of dodecanediol, 0.5 mol of adipic acid, 0.6 mol of dodecanedioic acid and dibutyltin oxide were dehydrated and condensed at 220 ° C. for 15 hours. A soluble polyester resin (A) having an acid value of 15 was produced.

60 parts of soluble polyester resin (A), 30 parts of vinyl acetate, 10 parts of N-vinyl-2-pyrrolidone,
0.8 parts of azobisisobutyronitrile and 150 parts of "Isopar G" are reacted at 80 ° C for 10 hours to give a non-volatile solvent having a nonvolatile content of 39.7% and insoluble in a non-aqueous solvent (A)
Was manufactured.

100 parts of the chain-like polymer (A), 40 parts of carbon black and 660 parts of "Isopar G" were kneaded in a ball mill for 8 hours and further diluted with 7200 parts of "Isopar G" to give a coloring of a nonvolatile content of 1%. NAD (A) was manufactured.

Colored NAD (A) is a colored NAD which has no dispersion 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 "Isopar G" were kneaded in a ball mill for 8 hours and further diluted with 7200 parts of "Isopar G". A liquid developer (A) having a nonvolatile content of about 1% 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.

(Comparative Example 1) Colored NAD (Comparative A) and Comparative Example 1 were prepared in the same manner as in Example 1 except that the soluble polyester resin (A) was used in place of the chain-like polymer (A). A liquid developer (Comparative A) was produced.

The colored NAD (comparative A) had poor dispersion stability after standing for 1 month, and the occurrence of sediment was observed.

The liquid developer (Comparative A) had poor dispersion stability after standing for 1 month, and generation of sediment was observed.

Example 2 Neopentyl glycol 0.
5 mol, 0.5 mol of butyl glycidyl ether, 0.5 mol of isophthalic acid and 0.6 mol of dimer acid were dehydrated and condensed in the same manner as in Example 1 to give a soluble polyester resin (B) having an acid value of 12. A colored NAD (B) and a liquid developer (B) having good dispersion stability were produced in the same manner as in Example 1 except that the above was produced.

Example 3 0.6 mol of hexanediol, 0.5 mol of 1,4-cyclohexanediethanol,
Dodecanedioic acid 0.5 mol, cyclohexane-1,4-dicarboxylic acid 0.5 mol and trimellitic anhydride 0.01
Colored NAD (C) having good dispersion stability as in Example 1 except that a soluble polyester resin (C) having an acid value of 18 was produced by dehydration condensation in the same manner as in Example 1 to produce a soluble polyester resin (C).
And a liquid developer (C) were produced.

(Example 4) Same as Example 1 using 0.5 mol of tetraethylene glycol, 0.5 mol of dodecanediol, 0.02 mol of glycerin, 0.5 mol of azelaic acid and 0.5 mol of dimer acid. Dehydration condensation to
Colored NAD having good dispersion stability as in Example 1 except that a soluble polyester resin (D) having an acid value of 8 was produced.
(D) and a liquid developer (D) were produced.

(Example 5) 60 parts of the soluble polyester resin (A), 40 parts of ethyl methacrylate, 1 part of benzoyl peroxide and 150 parts of "Isopar G" were reacted at 85 ° C for 8 hours to give a nonvolatile content of 39.5%. Colored NAD (E) having good dispersion stability as in Example 1 except that the chain-like polymer (E) insoluble in the non-aqueous solvent was produced.
And a liquid developer (E) was produced.

[0046]

The chain-like polymer insoluble in the non-aqueous solvent or electrically insulating carrier liquid of the present invention is a polyester resin soluble in the non-aqueous solvent or carrier liquid, and the non-aqueous solvent or carrier liquid By copolymerizing a vinyl monomer mixture that constitutes an insoluble vinyl copolymer, the polyester resin and the insoluble vinyl copolymer soluble in the non-aqueous solvent or carrier liquid are trapped by the entanglement of the molecular chains. Form a non-aqueous resin dispersion liquid that is integrally bonded to each other, and thus is stably dispersed in the non-aqueous solvent or carrier liquid.

As described above, the chain-like polymer of the present invention having excellent dispersion stability is used as a fixing agent (dispersant) constituting a liquid developer to provide a liquid developer having excellent dispersion stability. It is also useful as a polymer for paints.

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Claims (3)

[Claims] 1. In (a) the non-aqueous solvent containing a polyester resin obtained by condensing a polybasic acid and a polyhydric alcohol soluble in the non-aqueous solvent, (b) the polymer is added to the non-aqueous solvent. By polymerizing an insoluble vinyl monomer mixture, a chain-like polymer insoluble in the non-aqueous solvent as a whole captured by mutual entanglement of the vinyl copolymer and the polyester resin is in the non-aqueous solvent. A non-aqueous resin dispersion, characterized by being dispersed in. 2. In the non-aqueous solvent containing (a) a polyester resin obtained by condensing a polybasic acid and a polyhydric alcohol soluble in the non-aqueous solvent, (b) the polymer is added to the non-aqueous solvent. By polymerizing a vinyl monomer mixture which becomes insoluble in the presence of a polymerization initiator, a chain-like heavy chain insoluble in the non-aqueous solvent as a whole captured by mutual entanglement of the vinyl copolymer and the polyester resin is obtained. A method for producing a non-aqueous resin dispersion, which comprises producing a polymer and dispersing the chain-like polymer in the non-aqueous solvent. 3. A liquid developer containing a colorant, a fixing agent and an electrically insulating carrier liquid, wherein (a) is used as the fixing agent.
In the carrier liquid containing a polyester resin obtained by condensing a soluble polybasic acid and a polyhydric alcohol in an electrically insulating carrier liquid, (b) polymerizing a vinyl monomer mixture in which the polymer becomes insoluble in the carrier liquid. A liquid developer characterized by using a chain-like polymer insoluble in the carrier liquid as a whole, which is captured by mutual entanglement of the vinyl copolymer and the polyester resin.