JPS62143065A - Liquid color developer for electrostatic photography - Google Patents

Abstract

PURPOSE:To obtain a sharp overprinted image by using mica or modified mica for 20-80wt% of a coloring agent for dispersing a toner. CONSTITUTION:The mica or modified mica is used for 20-80wt% of the coloring agent of a liquid color developer for electrostatic photography prepared by dispersing toner particles composed essentially of the coloring agent and a binder resin into an aliphatic hydrocarbon solvent in order to well opecity the toner layer. There are many kinds of mica, such as white mica, golden mica, black mica, and artificial mica, and it is preferred to use, especially, the white mica. When an amount of mica type pigment occupying the pigment component is too small, its hiding power is lowered, and when it is too much, its coloring power is decreased, consequently, it is proper to use it in an amount of 20-80wt%, thus permitting an overprinted image, especially, a color transferred image to be sharp.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a liquid developer for electrostatography, and more particularly to a color liquid developer for electrostatography using mica or a treated mica product as a part of the colorant component. .

[Prior art]

Color liquid developer for electrostatic photography uses a resin (binder) as a coloring agent.
It is made by uniformly dispersing toner coated with a high insulating and low dielectric constant carrier liquid. These color liquid developers generally have high transparency and therefore are highly susceptible to the influence of the underlying color. For this reason,
For example, when an image is formed using green toner on a dark red background, the image does not turn green but appears black due to the influence of the background color (red).

By the way, one way to obtain a clear image is to create a toner image with a specific color by hiding the underlying color on color transfer paper, etc., instead of forming the toner image in natural colors using the subtractive color method. There are often times when it is desired to form a color, in which case the use of conventional color liquid developers is not suitable.

〔the purpose〕

The present invention provides a color liquid developer for electrostatography which contains an n-color agent having excellent opacity (hiding property) as a toner component.

()1-Part of the present invention relates to a color liquid developer for electrostatography comprising toner particles containing a colorant and a binder as main components dispersed in an aliphatic hydrocarbon carrier liquid. 20-80 of us
Incidentally, the present inventor has discovered that by mixing mica or a mica-treated product into the toner as a coloring agent (pigment), the toner can be made more opaque. The present invention has been completed based on these findings.

Micas include natural micas such as muscovite, phlogopite, biotite, and soda mica, and artificial micas such as fluorophlogopite, fluorine tetrasilicon mica, and duolite, and among these, muscovite is particularly suitable for the present invention. It is. Furthermore, titanium mica obtained by processing muscovite may be used. Titanium mica is a mica surface coated with titanium dioxide, and is generally referred to as a "pearl pigment." Table 1 shows commercially available mica and mica-treated products.

(Margins below) Table 1 (1) Silver type (anatase type titanium-coated mica pigment) Note 1) Rutile tinta-coated pigments are also available in various colors.

Note 2) Product name: Upper row: Nihon Koken Kogyo Co., Ltd. Lower row: Merck Japan Co., Ltd. Same as below for iris colored type and colored type.

Note 3) The coating amount of titanium monide indicates the average rate.

(2) Iridescent type (anatase type titanium-coated mica pigment) (3) Colored type (anatase type titanium-coated mica pigment) Products with different colored bodies are also available depending on the manufacturer.

In addition, Table 2 shows examples of the production of colored mica titanium that have been recently announced.

Table 2 The toner according to the present invention is produced by grinding the mica-based pigment as a powder using a wet grinder (attritor, kiddy mill, ball mill, etc.).
You can make one by putting it in a vibrating mill, etc.), but
It is desirable to use a product prepared by kneading this with a coloring pigment, rosin resin, wax, etc. and then flashing it.

If the amount of mica-based pigment in the pigment is small, the hiding power will be small, and if it is too large, the coloring power will be poor.
Approximately 80% by weight is appropriate.

Next, I will explain the flushing process.

First, a pigment or a water-containing paste of the pigment is placed in a kneader called a flasher together with oil, wax, or a solution thereof, and mixed well. In this process, the water present around the pigment is replaced by the resin solution and/or wax.

This was taken out from the kneader, the aqueous phase was discarded, and the pigment dispersed in the resin solution and/or wax was dried.
After removing M, the resulting agglomerate is ground. In the present invention, this material will be referred to as a "flushing-treated colorant." Note that it is also possible to use a method of removing water and solvent under reduced pressure while kneading with a kneader.

Flushing treatment is known to be very good in one dispersion because it can use a water-containing paste as a material and can be treated while kneading with a kneader.

Pigments used in the present invention other than mica-based pigments include phthalocyanine blue, phthalocyanine green, sky blue, rhodamine lake, malachite green lake, methyl violet lake, peacock blue lake, naphthol green B, naphthol green Y, and naphthol yellow S. , Resol Fast Yellow 2G,
Permanent Red 4R, Brilliant 1 Fast Scarlet, Hansa Yellow, Benzidine Yellow, Resole Red, Lake Red C, Lake Red D, Brilliant Carmino 6B, Permanent Red F5R, Victory Scarlet 3B, and Bordeaux 10B.

In the present invention, these pigments may be used alone or in combination of several types. In addition, the resins used for flushing treatment include natural resin-modified coal resin, natural resin-modified maleic acid resin, dammar, copal,
Sheratsk.

Resins such as gum rosin, hardened rosin, ester gum, glycerin ester-modified maleic acid resin, styrene-butadiene copolymer, etc. Specifically, the following resins and waxes can be used. These resins and waxes may be used singly or in combination.

(Example of Fi4 fat) Tenranhouhadahensakuヱsmall inm silicone MRG, MRG 411. MRG-S, MRG-H
, MRP, MRA-L, MRM-42, MRM-',
+3 (more than Tokushima essential oil layer), Hekkasai l-1110° same 111. F23], J811. Same +120. same page
-720゜J-896 (manufactured by Inu Nippon Ink Chemical)
1. Sebo-denatured phenol 2. U. PRG, PRP, SPRN, SPRA.

5PR-H (manufactured by Tokushima Essential Oils) Veracasite +100. 1123. Same 112G, Same F
-171 (manufactured by Dainippon Ink Chemical Co., Ltd.) F E &44uM 2υKai±S Kyuzo Lithri I--Le resin Pentasite I) -406, same P-423 (manufactured by Dainippon Ink Chemical Co., Ltd.) Su ILIIL change 4fr; RU King Noj Sosu Sniff 1-RM-1
000, RM-1300, RM-4090, RM-41
00 (Tokushima essential oil layer) Ester gum EG-8000, EG-9000, HG-H, PE.

PE-H (Tokushima essential oil layer above) Glycated rosin TLR-21, TLR-57 (Tokushima essential oil layer above) (Hereafter blank) (Example of wax) Manufacturer name Product name "Sihi Q Engineering X Lee Eastman Chemical N -10111N-11108 N-12113 N-14106 N-34103 N-45118 C-10104 C-13110 C-15102 C-16106 E-10106 E 11 10 [i E -12112 E -14104 E -15100 Mitsui petrochemical t to pto.

220P 113 220M P 113 320M P 114 210M P 120 4202E 108 4053E 111 Manufacturer name Product name Softening point (°C) B
A S F OA wax 93~
96 Petrolite [3ARECO50086BA
RECO655102 BARECO1000113 E 730 93 E2018 1.17 E2020 117 E 1040 105 PETRONABA C90,5 PETRONABA C-3690,5P[ETRON
AllA C-400104,5PETRONABA
C-750097,8 Hoechst PE520
118~120PED121 113~1113
PED136 107~112 PED153 115~120 PED521 103~108PED5
22 100~105P E D534
98-105 Allied Chemical AC-Polyethylene 6
&6A 102AC-Polyethylene 615 10
5 Sanyo Chemical Sunwax 131-P 108 Sunwax 151-P 107 Sunwax 161-P 111 Sunwax 165-P 107 Sunwax 171-P 105 Two ε two left:! 1 ULULiL” light mouth ■Nil Union Carbide D Y N I 10
2D YN F 102 DYN H102 DYN J 102 DYN K 102 Monsanto 0RLIZON 805 1160R
LIZON 705 116 PHILLIPS MAR
LEX 1005 92 Dupont ALAT
IION 3 103ALATHON 10
96 ALATIION 12 84ALATIIO
N 14 80ALATHON 16
95 ALATHON 20 86 ALATIION 22 84ALATHON
25 96 In addition to the above, polyethylene resins include Sunwax E200, E250P (manufactured by Sanyo Chemical Co., Ltd.), 2000
．． 2500.3000.4000.4100.8000
B, 5000, 6000, 7000 (made by Chubu Polyethylene Co., Ltd., Viscol 500P, 660P (made by Sanyo Chemical Co., Ltd.) as polypropylene resin, Denga Vinyl 5S-100, 5S-1 as vinyl chloride resin)
30, DSS-130, 5S-140, ss-ao,
SS-70, SS-Y, 5ll-250,511
-170, M-70, M-120, MM-90, IEM
-140゜VP-30, 5E-130, ME-120,
ME-180, MIIE-100, PA-100, P-
80 (manufactured by Denki Kagaku Kogyo Co., Ltd.), paraffin wax (
Examples include beeswax (softening point: about 60°C), natural wax (softening point: about 51°C).

Pigments, resins and/or
Or the ratio with wax is 0.1 to 6.0 parts by weight of resin or wax, preferably 0.1 to 0 parts by weight of dye and pigment.
．． 6 parts by weight is suitable.

To prepare a liquid developer using the "flushed colorant" thus obtained, the colorant and binder are mixed with a small amount of carrier liquid in an attritor, a ball mill,
A concentrated toner may be prepared by cross-dispersing the toner using a kitty mill or the like, and if necessary, this may be diluted approximately 5 to 10 times with a similar carrier liquid. The ratio of colorant to binder is 1:1 to 10 (weight-k
) is appropriate. It goes without saying that it is advantageous for the general pigment and the mica-based pigment (mica, treated mica) in the coloring agent to be of the same color system in order to make the image clearer.

As the binder here, alkyd resin, rosin-modified phenol formaldehyde resin, polyhydric alcohol ester of hydrogenated rosin, polyacrylic or polymethacrylic ester resin, styrene resin, chlorinated rubber, etc. are used, but in particular, the following general formula (I) R" CH2= C... (I) [However, R1 is hydrogen or methyl group R2 is -COOC
, H21114□ or -0COCIIIH2□1 (m is an integer from 6 to 20). ] A monomer represented by acrylic acid, methacrylic acid, vinylpyridine, the following general formula (II) CH2=C...
(n) [However, R3 is hydrogen or methyl group, R4 is C00C
m Hz m −x or -OCOCff1H,,,
(m is an integer of 1 to 5). [However, R5 is hydrogen or a methyl group, RG is N (CH
3) z, N(C2H4)2 or -OH. ] It is effective to use a copolymer (including a block copolymer) of a monomer represented by the following and one or more monomers selected from ethylene glycol dimethacrylate. The appropriate proportion of the vinyl heptamer component represented by formula (II) in the copolymer is about 30 to 95% by weight.

As a binder, natural resins such as ester gum, softened rosin, natural resin-modified maleic acid resin, and natural resin-modified phenol resin are used as binders.

Natural resin-modified thermosetting resins such as natural resin-modified polyester resins, natural resin-modified pentaerythritol resins, and epoxy resins may be added.

The carrier liquid may be paraffinic or isoparaffinic hydrocarbon (Isopar H-Isopar G manufactured by Esso).
, Isopar L, Isopar K, naphtha Nα6 sorbetso 1OO, etc.), ligroin, n-hexane, n-hebutane, 1so-octane, n-octane, carbon tetrachloride,
1-cyclotrifluoroethane, cyclohexane, etc. may be used alone or in combination of two or more.

Examples are shown below. All parts herein are parts by weight.

Example 1 Copper phthalocyanine blue (manufactured by Dainichiseika Chemical Co., Ltd.) 70 parts (solid content equivalent) (solid content equivalent) Wax (manufactured by Mitsui Petrochemical Co., Ltd. 110P)
100 parts rosin modified resin (MRP manufactured by Arayo Kagaku Co., Ltd.)
Pigment A is obtained by kneading and flashing 100 parts. Next, Pigment A 100 parts 20% dispersion 22
Part 0 Isopar G (Exxon Inc.)
Disperse the too much part in a ball mill for 20 hours.
Add 0.00 parts of Isopar G and disperse for 30 minutes. Take 200 parts of this as a concentrated toner and use Isopar 0100.
A liquid developer diluted with 0 parts was used as a liquid developer (product 1 of the present invention).

For comparison, a liquid developer (comparative product 1) was manufactured using exactly the same amount of liquid developer except for the muscovite.

Example 2 Copper phthalocyanine green (Dainichiseika Chemical Corporation)
70 parts (solid content equivalent) Pier Glaze ML100 (manufactured by Nippon Selling Co., Ltd.) 50 parts Wax (manufactured by Sanyo Chemical Co., Ltd. 161P) 1
00 parts rosin modified resin (Tokushima Oil Co., Ltd.'mIIM100O
) After flashing the kneaded product consisting of 100 parts, a liquid developer (inventive product 2
) was created.

Liquid developer (comparative product 2) was prepared in exactly the same manner except that mica (Pia Glaze L'11100) was removed for comparison.
was manufactured.

Example 3 Seiryoku Fast Red 8040 (manufactured by Dainichiseika Chemical Co., Ltd.) 5
0 part mica (Pier Glaze MBR100 manufactured by Nippon Sales Industry Co., Ltd.)
70 parts OA wax (manufactured by BASF) 120 parts polyethylene (Arayo Kagakusha ill PE6351)
After flushing the mixed material consisting of 80 parts, a liquid developer (product 3 of the present invention) was prepared in the same manner as in Example 1. For comparison, except for mica (Pia Glaze MBR100), general pigment A liquid developer (comparative product 3) was produced in exactly the same manner except that 70 parts of Fast Red 8040) was changed from 50 parts.

These developers are applied to a commercially available electrophotographic copying machine (Ricoh Rei D).
Images were taken using a T5700). As a result, good blue images were obtained for both Inventive Product 1 and Comparative Product 1 on white and light-colored transfer paper, but when dark red transfer paper was used, Comparative Product 1 produced black images. was obtained, whereas
For product 1 of the present invention, an image that could be distinguished as blue was obtained.

Good green images were obtained with both the inventive product 2 and the comparison product 2, but the comparison product 2 also showed good results for the dark red transfer paper.
becomes a black image.

Good red images were obtained with both Inventive Product 3 and Comparative Product 3, but Comparative Product 3 gave a blackish image on dark green transfer paper.

In addition, when overprinting was performed with Comparison Products 1, 2, and 3, the area where the two colors overlapped became almost blackish, whereas in the case of Inventive Products 1, 2, and 3, the color copied later was darker than the Comparison It was confirmed that the copy was more vivid than the copy made with .

〔effect〕

As is clear from the description of the Examples, by using the liquid developer of the present invention, overprinted images become clearer, and especially clearer images can be obtained on color transfer paper.

Claims (1)

[Claims] 1. In a liquid developer formed by dispersing a toner mainly composed of a colorant and a binder in an aliphatic hydrocarbon carrier liquid, 20 to 80% by weight of the colorant is mica or a mica-treated product. A color liquid developer for electrostatic photography characterized by: