JPH0635237A - Wet developer, manufacturing method thereof, and printed matter using the wet developer - Google Patents

Abstract

(57) [Summary] [Structure] The wet developer of the present invention comprises an olefin resin particle having a carboxyl group or an ester group, or an olefin resin particle having a carboxyl group or an ester group in which a colorant is dispersed. In a wet developer composed of a liquid aliphatic hydrocarbon, an infrared absorbent is dispersed in the resin particles. [Effect] The wet developer of the present invention can produce a printed matter such as an OCR readable barcode regardless of the type of the sensor, and in particular, the barcode printing for a silicon type OCR sensor which is currently widely used. Moreover, by improving the sensitivity in the infrared sensitivity region, reading and detection are possible. Further, it is possible to improve the infrared sensitivity of the printed matter by developing and printing on the usual printed matter using the wet type developer of the present invention, and it is also possible to conceal it by using the wet type developer of the present invention. By printing characters, etc., it can be used for maintaining confidentiality and preventing forgery.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a wet developer used for electrophotography, electrostatic printing, and information recording, and a printed matter using the same, and more particularly to a wet type developer having an improved OCR sensor reading sensitivity. The present invention relates to a developer and a printed matter using the developer.

[0002]

2. Description of the Related Art Recently, in product management, quality control, etc.
The CR (optical reading) method has been adopted, and bar code reading is particularly popular. However, in the case of the OCR method, the reading sensitivity depends on the sensor used, and the read object is currently combined with a specific sensor. For example, even if a bar code for a silicon type OCR sensor, which is widely used at present, is printed with a normal wet developer, the reading cannot be detected. When the sensor used in this way is fixed, the reading of the printed matter is limited to the sensor sensitivity range, and there is a problem that the configuration of the ink material and the like is limited. Therefore, it is conceivable to use a plurality of sensors or improve the sensitivity of the sensor itself, but this causes a problem of cost increase.

On the other hand, the bar code is generally printed by printing or the like, but it can also be printed by electrostatic printing. Generally, a wet type developer used as a toner for electrophotography has an electrically insulating liquid and a particle size of 0.1 to 0.1 dispersed therein.
1 μm colorant particles are used, and a resin for the purpose of dispersing, fixing and controlling charge of the colorant particles is dissolved in the electrically insulating liquid.

This type of wet type developer has the advantage that it has excellent resolution due to its small particle size, but since the toner is fixed by drying and fixing the resin dissolved in the solvent, it has poor adhesion to the printing plate substrate. In addition, since the cohesive force of the image area itself is small, the image area of the printing plate is easily removed during printing, and the printing durability is weak.

The present inventor uses an olefinic resin having a carboxyl group or an ester group as a resin, and heat-dissolves it in a solvent having a high temperature dependence in solubility with respect to the resin to prepare a resin solution. The resin particles having a narrow particle size distribution can be formed by precipitating the resin particles by cooling the resin particles to obtain a wet developer, which has excellent printing durability, excellent transferability, and good resolution. The present invention has been found to be a wet type developer, and was filed earlier. However, the present invention aims to obtain a wet type developer suitable for bar code printing, for example, by expanding the light absorption sensitivity of the wet type developer to the infrared region. To aim.

Therefore, the present invention is, firstly, a wet type developer which is excellent in dispersion stability as a wet type developer and is excellent in transferability and resolution, and particularly, the infrared sensitivity range is expanded. An object is to provide a wet type developer.

Secondly, it is an object to provide a wet type developer suitable for bar code printing or color bar code printing in the OCR system or the like.

Thirdly, according to the present invention, a wet development is carried out which is printed on an ordinary printed matter and can be made into a hidden character by adjusting the printing position, which makes it possible to maintain confidentiality and prevent forgery. It is an object to provide an agent and a printed matter using the agent.

[0009]

The wet developer of the present invention comprises:
In a wet developer comprising olefin resin (hereinafter referred to as olefin resin) particles having a carboxyl group or ester group or olefin resin particles in which a colorant is dispersed, and most of liquid aliphatic hydrocarbons, the resin particles It is characterized in that an infrared absorbent is dispersed therein.

The wet developer of the present invention is a wet developer comprising olefin resin particles or olefin resin particles in which a colorant is dispersed, and most of liquid aliphatic hydrocarbons. In the wet developer, infrared rays are contained in the resin particles. The absorbent is dispersed, and a polyhydroxycarboxylic acid ester of a 3- to 10-mer having a hydroxycarboxylic acid ester as a monomer is present in the wet developer.

The method for producing a wet developer of the present invention is
After the olefin resin is heated and dissolved in a solvent having a high temperature dependency in solubility with respect to the resin to form a resin solution,
The resin solution is a liquid aliphatic hydrocarbon in the presence of an infrared absorbing agent or a colorant and an infrared absorbing agent, and in the presence of a polyhydroxycarboxylic acid ester of a 3- to 10-mer containing hydroxycarboxylic acid ester as a monomer. It is characterized in that it is charged and cooled to deposit the resin particles and the solvent is replaced by the aliphatic hydrocarbon.

Further, the printed matter using the wet developer of the present invention comprises olefin resin particles in which an infrared absorbing agent is dispersed or olefin resin particles having a carboxyl group or an ester group in which an infrared absorbing agent and a colorant are added, It is characterized in that the printing is carried out by using a wet type developer composed of most of liquid aliphatic hydrocarbons.

The present invention will be described in detail below.

As the olefin resin forming the resin particles in the wet developer of the present invention, ethylene-vinyl acetate copolymer is preferable. The ethylene-vinyl acetate copolymer is, for example, Ultrasen series manufactured by Toyo Soda Kogyo Co., Ltd., for example, 510X, 515F, 530,537,537.
L, 537S, 525,520F, 540,540F, 541,541L, 625,630,630F, 68
2,627,631,633,680,681,635,634,710,720,722,725,751,
750,760 etc., Sumitomo Chemical Co., Ltd.'s Sumitate series, eg DD-10, HA-20, HC-10, HE-10, KA-10, KA-20, KA-3
1, KC-10, KE-10, MB-11, RB-11 etc., Mitsui DuPont Chemical
Evaflex series manufactured by, for example, 45X, YW, 15
0,210,220,250,260,310,360,410,420,450,460,550,560
Soagoren series manufactured by Nippon Gohsei Co., Ltd., for example
BH, CH, CI, DH etc. Soarex series, eg RB
H, RCH, RDH, etc. Takeda Pharmaceutical Co., Ltd. Dumiran series, for example Dumiran D-219, D-229, D-251S, C-228
0, C-2270, C-1590, C-1570, C-1550 and the like.
Also, Yucaron-Eva manufactured by Mitsubishi Petrochemical Co., Ltd., Elpax manufactured by DuPont, USA and the like can be used.

In addition, a product obtained by modifying a polyolefin resin to introduce a carboxyl group, an example of which is a product name,
Nippon Petrochemical Co., Ltd. N polymer, Tonen Petrochemical Co., Ltd.
Tonen CMP-HA series manufactured by Mitsubishi Yuka Co., Ltd. MOD
IC, Steel Manufacturing Co., Ltd., Saixen, Mitsui Toatsu Chemical
Ronply Co., Ltd., Mitsui Petrochemical Co., Ltd. Admer, etc., and copolymers of ethylene and acrylic acid, Dow EAA copolymers manufactured by Dow Chemical Co.
Mitsubishi Yuka Co., Ltd., Yucaron EAA, Mitsui DuPont Chemical Co., Ltd., Nucrel, Sumitomo Chemical Co., Ltd., Acryft, etc., and a copolymer of ethylene and acrylic acid or methacrylic acid, or a so-called ionomer obtained by crosslinking them. , Trade names such as DuPont's Surlyn, Mitsui Polychemical Co., Ltd., Himilan, Asahi Dow Co., Ltd.'s corbolen latex, etc., BASF Corporation's EVA1 wax addition, and ethylene and vinyl acetate co-weight Partially saponified product of coalesce, trade name is Dumilan manufactured by Takeda Pharmaceutical Co., Ltd., copolymer of ethylene and acrylic ester, trade name is Nippon Unicar Co., Ltd. DPD-
Examples of the resin include 6169 and the like, and a polyolefin resin containing a carboxylic carbonyl group. These resins can be used alone or in combination of two or more.

Next, the solvent for the olefin resin is
A solvent that dissolves a resin when heated and does not dissolve at room temperature, or a solvent that dissolves at room temperature and is insolubilized by cooling, may be any solvent that gives temperature dependence to solubility,
Solubility difference between 25 ℃ and 65 ℃ is 0.01g /
The solvent may be at least ml, preferably at least 0.05 g / ml solvent. Examples of such a solvent include tetrahydrofuran, benzene, toluene, xylene, dimethylformamide (DMF), dimethyl sulfoxide (DMSO), acetone, methyl ethyl ketone (ME).
K) and the like. The amount of the resin dissolved in the total of the solvent and the resin may be arbitrary, but if the resin ratio is too high,
In the precipitation process of resin particles, the resin particles contact each other,
Since it may become a gel-like mass, it is preferable to set it in the range of 1 to 80% by weight. The heating condition for dissolving the resin may be the lowest temperature required for dissolving the resin, and it is not preferable to heat more than necessary. It is preferable to stir according to a usual method during the dissolution.

Next, the infrared absorbent dispersed in the resin particles will be described. Examples of the infrared absorbent include IR-820 and CY-9 manufactured by Nippon Kayaku Co., Ltd., F2GS manufactured by Bayer, and Braun G manufactured by Hoechst.
GL Stab. Braun RG Stab. , R
ot GGF Stab. , Blau FG Sta
b. , Blau R Stab. , Blau 3R S
tab. , Grun B Stab. , Oliv HG
Stab. , Grau BS Stab. , Schwa
rz CL Stab. Etc. Sumitomo Chemical Green
G, OPTOGEN NIR-760S, OPTOG
EN NIR-810, OPTOGENNIR-83
0, OPTOGEN NIR-840S, OPTOGE
N DIR-980, OPTOGEN DIR-100
0 etc. can be used.

The content of the infrared absorber in the resin is
It is preferable to disperse the resin in an amount of 0.001 to 200% by weight, preferably 0.1 to 100% by weight based on the weight of the resin. The infrared absorbing agent may be obtained by heating and melting the resin to mix the infrared absorbing agent so that the resin and the infrared absorbing agent have a predetermined mixing ratio, and then dispersing / dissolving in the solvent. The infrared absorbers may be separately dissolved in a solvent or dispersed by ultrasonic dispersion or the like, and then mixed, or the powder colorant may be dispersed in a resin solution, and the mixture is placed in an electrically insulating liquid. By charging the resin particles to form the resin particles, the infrared absorbent can be dispersed in the resin particles.

The infrared absorber may be used alone,
When used in combination with a coupling agent, it is possible to obtain a printed matter that does not have a blur (texture) when used for printing. As such a coupling agent, a functional group having a terminal organic modification and a monofunctional or difunctional reactive group can be used, and a coupling agent having silane, titanium, zircon, aluminum or the like as a constituent element can be used. used.

Specifically, vinyltrichlorosilane, vinyltris (β-methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, β- (3,
4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ
-Glycidoxypropylmethyldiethoxysilane, N-
(Β-Aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane Examples thereof include silane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, methyltrimethoxysilane, and hexamethyldisilazane.

Of these, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane,
γ-glycidoxypropyltrimethoxysilane has excellent image forming properties. Further, when the terminal group is an acid or a base such as γ-aminopropyltriethoxysilane and γ-mercaptopropyltrimethoxysilane, the color tone of the printed matter is changed. The coupling agent is 0.001 to 200% by weight, preferably 0.01 to 5% by weight with respect to the infrared absorber.
0% by weight is used.

Next, as the colorant that can be used in the present invention as necessary, known organic or inorganic colorants can be used. Examples of the black colorant include inorganic carbon black, ferric tetroxide, and organic cyanine black.

Examples of yellow colorants include inorganic yellow lead, cadmium yellow, yellow iron oxide, titanium yellow and ocher. Further, as a acetoacetic acid anilide type monoazo pigment of a hardly soluble metal salt (azo lake), Hansa Yellow G (CINo. Pigment Yellow 1, hereinafter,
The same), Hansa Yellow 10G (pigment Yellow
3), Hansa Yellow RN (pigment Yellow 65),
Hansa Brilliant Yellow 5GX (pigment Yellow
74), Hansa Brilliant Yellow 10GX (pigme
nt Yellow 98), Permanent Yellow FGL (pig
ment Yellow 97), Shimura Lake Fast Yellow 6
G (pigment Yellow 133), Rionol Yellow K
-2R (pigment Yellow 169), and as acetoacetic acid anilide disazo pigment, disazo yellow G (p
igment Yellow 12), Disazo Yellow GR (pigme
nt Yellow 13), Disazo Yellow 5G (pigment Y
ellow 14), Disazo Yellow 8G (pigment Yello
w 17), Disazo Yellow R (pigment Yellow 5
5), Permanent Yellow HR (pigment Yellow 8
3) is mentioned. Examples of condensed azo pigments include Chromophthal Yellow 3G (pigment Yellow 93), Chromophthal Yellow 6G (pigment Yellow 94), and Chromophthal Yellow GR (pigment Yellow 95). Further, as a benzimidazolone-based monoazo pigment, Hosta Palm Yellow H3G (pigment Yellow 1
54), Hosta Palm Yellow H4G (pigment Yello
w 151), Hosta Palm Yellow H2G (pigment Y
ellow 120), Hosta Palm Yellow H6G (pigme
nt Yellow 175), Hosta Palm Yellow HLR (p
igment Yellow 156). Further, as an isoindolinone-based pigment, Irgadine Yellow 3RLT
N (pigment Yellow 110), Irgadine Yellow 2
RLT, Irgadine Yellow 2GLT (pigment Yello
w 109), Fastgen Super Yellow GROH
(Pigment Yellow 137), Fastgen Super Yellow GRO (pigment Yellow 110), and Sandrin Yellow 6GL (pigment Yellow 173), and flavantron (pigment)
ment Yellow 24), anthramylimidine (pigment Y
ellow 108), phthaloylamide type anthraquinone (pigment Yellow 123), Heliofast Yellow E3R (pigment Yellow 99), azo nickel complex pigment (pigment Green 10) which is a metal complex pigment, nitroso type nickel complex pigment (pigment Yell).
ow153), azomethine-based copper complex pigment (pigme
nt Yellow 117) and phthalimide quinophthalone pigment (pigment Yello
w 138) and the like.

Examples of magenta colorants include inorganic cadmium red, red iron oxide, silver vermilion, red lead, and antimony vermilion. As an azo lake type azo pigment, Brilliant Carmine 6B (pigment Red 57:
1), lake red (pigment Red53: 1), permanent red F5R (pigment Red48), resole red (pigment Red49), persia orange (pigme
nt Orange17), Kurosei Orange (pigment Orange
18), Helio Orange TD (pigment Orange1
9), pigment scarlet (pigment Red60:
1), Brilliant Scarlet G (pigment 64:
1), Helio Red RMT (pigment Red51), Bordeaux 10B (pigment Red63), Helio Bordeaux BL
(Pigment Red 54), and as the insoluble azo type (monoazo, disazo type, condensed azo type), Para Red (pigment Red 1), Lake Red 4R (pigment).
Red3), permanent orange (pigment Orange
5), Permanent Red FR2 (pigment Red2),
Permanent Red FRLL (pigment Red9), Permanent Red FGR (pigment Red112), Brilliant Carmine BS (pigment Red114), Permanent Carmine FB (pigment Red5), P.I. V. Carmine HR (pigment Red150), Permanent Carmine FBB (pigment Red146), Nova Palm Red F3
RK-F5RK (pigment Red170), Nova Palm Red HFG (pigment Orange38), Nova Palm Red HF4B (pigment Red187), Nova Palm Orange HL. HL-70 (pigment Orange36), P.I.
V. Carmine HF4C (pigment Red185), Hostabum Brown HFR (pigment Brown25), Vulcan Orange (pigment Orange16), Pyrazolone Orange (pigment Orange13), Pyrazolone Red (pi
gmentRed38), and Chromophtal orange 4R (pigment Orange3) as a condensed azo pigment.
1), Chromophtal Scarlet R (pigment Red1
66), chromophthal red BR (pigment Red14
4) is mentioned.

Further, pyranthrone orange (pigment Orange) is used as an anthraquinone pigment which is a condensed polycyclic pigment.
40), Antoanthrone Orange (pigment Orange
168), dianthraquinonyl red (pigment Red1
77), thioindigo magenta (pigment Violet38), thioindigo violet (pigment Violet36), thioindigo red (pigment Red88), and perinone orange (pigment Orange43). In addition, as perylene pigments, perylene red (pigment Red190), perylene vermillion (pig
ment Red123), Perylene Maroon (pigment Red1)
79), perilence scarlet (pigment Red14
9) and perylene red (pigment Red 178), and as a quinacridone-based pigment, quinacridone red (p
igment Violet19), quinacridone magenta (pigme
nt Red122), quinacridone maroon (pigment Red
206), quinacridone scarlet (pigment Red2
07), and other condensed polycyclic pigments include pyrocholine pigments, red fluorbin pigments, and dyed lake pigments (water-soluble dye + precipitating agent → lake fixing).

As the cyan colorant, an inorganic ultramarine blue,
Navy blue, cobalt blue, cerulean blue, etc. are mentioned, and as the phthalocyanine type, Fast Gemble-BB (pigment Blue 15), Sumiton cyanine.
Blue HB (pigment Blue 15), cyanine blue 5
020 (pigment Blue 15: 1), Sumika print
Cyanine Blue GN-O (pigment Blue 15), Fast Sky Blue A-612 (pigment Blue 1
7), cyanine green GB (pigment Green7),
Cyanine Green S537-2Y (pigment green3
6), Sumiton Fast Violet RL (pigment
Violet 23), and indanthrone blue (PB-60P, PB-22, P) which is a slene-based pigment.
B-21, PB-64), a basic dye lake pigment, methyl violet / phosphorus / molybdic acid lake (PV
-3) and the like. In addition, a colorant called a so-called processed pigment in which the surface of the colorant is coated with a resin can be similarly used.

Further, sublimation printing dyes can be preferably used.
Generally, the sublimation printing dye is a dye that melts, diffuses or sublimes by heat to migrate, and a disperse dye is particularly preferably used. These dyes are about 150-55
It has a molecular weight of about 0 and is selected in consideration of sublimation (melting) temperature, hue, light resistance, resin, solubility in a toner solution, and the like.

Generally, for example, diaryl methane series,
Triarylmethane-based, thiazole-based, methine-based, azomethine-based, xanthine-based, oxazine-based, azo and azo-based derivatives, anthraquinone derivatives, quinophthalone derivatives, spirodipyran-based, isodolinosspiropyran-based, fluoran-based, rhodamine-lactam-based dyes are preferred And C.I. I. (Color Index, omitted below) Yellow 51, 3, 54, 79, 60, 23,
7, 141, and C.I. I. Disperse Blue 24, 5
6, 14, 301, 334, 165, 19, 72, 8
7, 287, 154, 26, and C.I. I. Disperse Thread 135, 146, 59, 1, 73, 60, 16
7, C.I. I. Disperse Violet 4, 13,
26, 36, 56, 31, and C.I. I. Solvent Violet 13, also C.I. I. Solvent Black 3, C.I. I. Solvent Green 3, also C.I. I. Solvent Yellow 56, 14, 16, 29, C.I. I. Solvent Blue 70, 35, 63, 36, 50, 49,
111, 105, 97, 11, and C.I. I. Solvent Red 135, 81, 18, 25, 19, 23, 24,
143, 146, 182, etc.

Specifically, for example, 3,3-diethyloxacyanine iodide, Astrazone Pink FG
(Bayer Co., CI48015), 2,2-carbocyanine (CI808), Astrafiloxin FF (CI148070), Astrazone Yellow 7GLL (CI Basic Yellow) 21), Aizen carotene yellow 3GLH (Hodogaya Chemical Co., C.I.
48055), Aizen carotene red 6BH (C.
I. 48020) and the like, methine (cyanine) -based basic dyes such as dimethine-based or trimethine-based basic dyes, diphenylmethane-based basic dyes such as auramine (CI.655), and malachite green (CI. 420).
00), brilliant grain (C.I. 4204)
0), magenta (C.I. 42510), methyl violet (C.I. 42535), crystal violet (C.I. 42555), methyl green (C.I. 42555).
I. 684), Victorian Blue B (C.I. 440)
45) and other basic triphenylmethane dyes, Pyronin G (C.I.739), Rhodamine B (C.I.451)
70), xanthene basic dyes such as Rhodamine 6G (C.I. 45160), Acridine Yellow G (C.I.
I. 785), Leonin AL (CI.46075),
Benzoflavin (C.I. 791), affine (C.I.
I. 46045) and other acridine-based basic dyes, neutral red (CI.50040), astrazone blue BGE / X125% (CI.51005), methylene blue (CI.52015) and other quinoneimine-based basic dyes. , And other basic dyes such as anthraquinone basic dyes having a quaternary amine. These dyes can be used in the form as they are, or in the form obtained by subjecting these dyes to alkali treatment, and the counter ion exchanger or leuco form of these dyes can also be used. When a colorless or light-colored leuco dye or the like is used in a normal state, a developer may be included on the image forming sheet side. Furthermore, these disperse dyes may not be used alone (one component) but may be used as a mixture of two or more kinds.

As a wet type developer suitable for color bar code printing, in order to secure long-term dispersion stability, a colorant having a specific gravity of 5 or less and a small specific gravity may be used. Examples of such colorants include aniline black-based, carbon black-based for black, benzidine yellow-based, sproin yellow-based for yellow, quinacridone-based for magenta-based, radaramine-based, and phthalocyanine-based for cyan (mainly It is preferable to use oil blue, which includes different metals but titanium, nickel and the like can be in the infrared absorption region).

The content of the colorant in the resin can be arbitrarily selected in the range of 0.0001 to 2000% by weight with respect to the weight of the resin, but in order to reproduce a continuous multi-tone tone similar to that of offset printing. The optical reflection density after the transfer of the toner of each color to the transfer target needs to be 0.7 or more, and particularly preferably 1.0 or more for cyan and black. In order to obtain an optical reflection density of 0.7 or more for each color, in the case of black and cyan, it is 10 to 150% by weight based on the same weight as above, and in the case of magenta, 40.
˜150 wt%, and in the case of yellow 10 to 100 wt%.

The colorant has a particle size of 30 to 15 in the secondary aggregation state.
Even if the resin and the colorant are heated and melted to mix the colorant together with the infrared absorbing agent so that the resin and the colorant have a predetermined mixing ratio, the powder and the colorant are dispersed and dissolved in a solvent. Good, or after the resin and the colorant, the infrared absorber is separately dissolved in a solvent or dispersed by ultrasonic dispersion,
They may be mixed, or a powder colorant and an infrared absorber may be dispersed in the resin solution.

Next, the liquid aliphatic hydrocarbon, which is an electrically insulating liquid, has a volume resistance of 10 ¹⁰ Ω · cm or more and is used for the purpose of enhancing the electrical insulating property in the wet type developer. In addition, it is required that the dissolving power for the wet developer component is relatively small, which prevents deterioration as a wet developer.

Examples of liquid aliphatic hydrocarbons include n
-Paraffinic hydrocarbons, iso-paraffinic hydrocarbons, or mixtures thereof, halogenated aliphatic hydrocarbons and the like. Branched-chain aliphatic hydrocarbons are particularly preferable, and for example, Isopar G, Isopar H, Isopar K, Isopar L, Isopar M, Isopar V manufactured by Exxon Co. are preferably used. These have almost no solubility in an olefin resin having a carboxyl group or an ester group. For example, the solubility of the resin in Isopar H is 0.001 g / Solvent is less than ml.

Next, the polyhydroxycarboxylic acid ester will be described.

The polyhydroxycarboxylic acid ester is soluble in the electrically insulating liquid, and when it is added to the granulation step, resin particles obtained have a uniform particle size distribution. In addition, it has been found that it also has a function as a dispersant because it has an affinity with the resin particles in the wet developer.

The hydroxycarboxylic acid ester as a raw material for polymerization is a derivative such as an ester of the formula HO-X-COOH, wherein X is a divalent saturated or unsaturated aliphatic hydrocarbon containing at least 12 carbon atoms. , Or a divalent aromatic hydrocarbon containing at least 6 carbon atoms and there are at least 4 carbon atoms between the hydroxy and carboxyl groups. Preferred examples of such hydroxycarboxylic acid derivatives include hydroxycarboxylic alkyl esters such as 12-hydroxystearic acid methyl ester and 12-hydroxystearic acid ethyl ester, 12-hydroxycarboxylic acid lithium and 12-hydroxycarboxylic acid aluminum. Examples thereof include metal salts of hydroxycarboxylic acids, amides of hydroxycarboxylic acids, hydrogenated castor oil, and the like.

The polyhydroxycarboxylic acid ester is obtained by partially saponifying the hydroxycarboxylic acid ester in the presence of a small amount of amines or a catalyst to be polymerized, and its polymerized form is intermolecular esterification. In addition, it contains various forms such as those obtained by esterification in the molecule. The polyhydroxycarboxylic acid ester in the present invention is preferably a hydroxycarboxylic acid ester 3- to 10-mer, and is a light gray brown wax-like substance. When the degree of polymerization of the polyhydroxycarboxylic acid ester is less than 3 or more than 10, the polyhydroxycarboxylic acid ester is not compatible with the electrically insulating liquid, and even if it is used in the granulation step, the particle size distribution of the obtained resin particles is not good You can't get the one you want. The addition amount of the polyhydroxycarboxylic acid ester is not particularly limited, but per resin weight,
It is used in a proportion of 0.01% by weight to 200% by weight. The polyhydroxycarboxylic acid ester may be added in the granulation step, but may be added to the resin solution or the pigment dispersion liquid.

The granulation step of the present invention is carried out by mixing the resin solution and the infrared absorbent dispersion and then introducing the mixture into an electrically insulating liquid, preferably by a dispersing means such as stirring and / or ultrasonic irradiation. Therefore, it is desirable to improve the dispersion of the precipitated resin particles.

The cooling rate may be rapid cooling using dry ice, liquid nitrogen, etc., the mixed liquid may be added to the cooled electrically insulating liquid, or natural cooling may be performed. When the resin solution is poured into the electrically insulating liquid, the resin particles are precipitated due to the temperature difference of the resin solution, and at the same time, the resin particles are precipitated due to the difference in solubility between the resin insulating solution and the electrically insulating liquid which is a poor solvent. is there.

In this granulation step, since the polyhydroxycarboxylic acid ester has compatibility with the electrically insulating liquid and has a strong affinity with the resin particles, the resin particles to be precipitated have a particle size of submicron unit. It is considered that the above-mentioned product can be obtained and the one having a narrow particle size distribution can be obtained. That is, the particle size of the obtained particles is in the range of 0.1 to 10 μm,
Further, D ₅₀ showing the average particle diameter shows a single peak of 0.6 to 0.8 μm, and the ball milling operation and classification of the resin particles which are required by the conventional method are not required. However, it goes without saying that fine pulverization may be carried out with a pulverizer such as a ball mill, pin pill or jet mill, if necessary.

Next, after depositing the resin particles, it is desirable to replace the solvent with an electrically insulating liquid. As a method thereof, the precipitated resin particles may be separated and washed by a means such as standing or centrifugation to remove the solvent to increase the concentration of the electrically insulating liquid.

In the wet developer of the present invention, as a charge control agent, a metal salt of dialkylsulfosuccinate, manganese naphthenate, calcium naphthenate, zirconium naphthenate,
Cobalt naphthenate, iron naphthenate, lead naphthenate, nickel naphthenate, chromium naphthenate, zinc naphthenate, magnesium naphthenate, manganese octylate, calcium octylate, zirconium octylate, iron octylate, lead octylate, octylate Cobalt, chromium octylate, zinc octylate, magnesium octylate,
Metallic soaps such as manganese dodecylate, calcium dodecylate, zirconium dodecylate, iron dodecylate, lead dodecylate, cobalt dodecylate, nickel dodecylate, chromium dodecylate, zinc dodecylate, magnesium dodecylate, calcium dodecylbenzenesulfonate, Alkylbenzenesulfonates such as sodium dodecylbenzenesulfonate and barium dodecylbenzenesulfonate,
Phospholipids such as lecithin and sehalin, organic amines such as n-decylamine and the like can be preferably added. In particular, transition metal salts of dialkyl sulfosuccinic acids (cobalt, manganese,
It is desirable to use zirconium, yttrium, nickel, etc.). Particularly, it is preferable to use a metal salt of dialkylsulfosuccinic acid having compatibility with an electrically insulating liquid,
The addition amount may be the minimum amount showing the charge control effect, but is usually 0.01 wt% to 50 wt% in the electrically insulating liquid.

The resin particles in the liquid developer thus obtained are positively or negatively charged. For example, those which are positively charged are those which give a positive image on an electrophotographic photosensitive member used for negative charging, for example, a zinc oxide / resin photosensitive member.

The charge control agent is a resin solution, a colorant dispersion,
It may be added at any stage in the mixed solution thereof, the granulation step, and the final wet developer, but it is preferably added to the resin solution. This has the advantage that the charge control agents that can be used are not limited by the electrically insulating liquid. That is, since the charge control agent dissolved in the solvent remarkably lowers the electric resistance of the electrically insulating liquid, it is desirable that the amount present in the electrically insulating liquid is as small as possible. In order to be adsorbed, it is desirable that the concentration of the charge control agent in the electrically insulating liquid is high, and both conditions are contradictory. However, according to the production method of the present invention, after the charge control agent is added to the resin solution to sufficiently perform the adsorption on the toner particles, the unnecessary charge control agent not involved in the toner particle adsorption can be removed by solvent replacement. This is because the above conditions can be satisfied.

In the wet developer obtained in the present invention, other fixing agents such as various resins soluble in an electrically insulating liquid, for example, modified or unmodified alkyd resin, ordinary acrylic resin, synthetic rubber, poly Alkylene oxide, polyvinyl acetal (including butyral), vinyl acetate resin and the like can be added.

Further, the wet type developer obtained in the present invention includes
Many anionic, cationic, amphoteric or nonionic surfactants can be added as a dispersant. In addition to these, aliphatic acid salts used as the charge control agent and synthetic resins used as the fixing agent. And the like can be used as a dispersant.

When the wet developer according to the present invention is used for electrophotography or electrostatic printing, a usual transfer method, that is, electric field transfer such as corona transfer is performed on an insulating transfer target such as paper. Of course, it is possible, but it is possible to efficiently transfer from the surface of the electrophotographic photoreceptor to the electrically conductive transfer object such as metal by the pressure transfer method.

[0049]

According to the wet type developer of the present invention,
Regardless of the type of sensor, it is possible to produce OCR-readable barcodes and other printed matter. In particular, even in the case of silicon-type OCR sensor barcodes that are widely used at present, the sensitivity in the infrared sensitivity range is required. By improving it, reading detection is possible.

The wet developer of the present invention is used alone for printing, or on a printed matter using a usual printing ink or sublimation dye, the wet developer of the present invention is used for development / printing. As a result, the infrared sensitivity of the printed matter can be improved. Further, by using the wet developer of the present invention on a printed matter or a non-printed portion to print a hidden character or the like, it can be used for confidentiality protection and prevention of forgery, etc. It is useful for printing barcodes on cards, product tags, etc., and can also be used for printing personal information such as identification.

Further, the wet developer of the present invention uses olefin resin particles as resin particles and has an infrared absorber or an infrared absorber and a colorant dispersed therein. By using olefin resin particles, Further, it is excellent in transferability, has flexibility even at room temperature, and does not damage the surface of the photoreceptor even during pressure transfer.

Further, the presence of the polyhydroxycarboxylic acid ester in the manufacturing process exhibits a granulation adjusting function, and the detailed reason thereof is unknown, but the particle size of the resin particles precipitated during the manufacturing process is sub- It is possible to obtain a wet developer with a very narrow particle size distribution in micron units, without the need for ball milling operations, etc., and to be a wet developer with excellent resolution. Is. Further, the polyhydroxycarboxylic acid ester has not only a granulation adjusting function, but also has a function of stably dispersing the resin particles in the electrically insulating liquid due to the affinity with the resin particles. Thus, the resin particles can stably maintain the dispersed state, can be a wet type developer without deterioration, and can be made into a contact toner.

Examples of the present invention will be shown below.

[0054]

Example 1 Partially saponified ethylene-vinyl acetate copolymer (Takeda Pharmaceutical Co., Ltd.) in a 200 ml round bottom flask.
Manufactured by Dumiran 2270, saponification degree 70%) 2.7 g, cobalt diisooctylsulfosuccinate 60 mg, and tetrahydrofuran 50 ml were mixed, and the mixture was heated and stirred at 60 to 80 ° C. for 1 hour to dissolve the resin to prepare a resin solution.

On the other hand, in another container, Macrolex Yellow 6G
(Sand Co., Ltd.) 0.2 g, infrared absorber IR-82
0 (manufactured by Nippon Kayaku Co., Ltd.) 0.5 g, methyltrimethoxysilane (manufactured by Toshiba Silicone Co., Ltd.) 0.8 parts, poly-12-hydroxystearic acid methyl ester [ITO Oil Co., Ltd.]
Made, trimer, acid value 40.8 to 42.8, saponification value 196.
9 to 197.7, weight average molecular weight 1200, hue (Gardner-Heliger) 6 to 7, light gray brown wax] 60
Using 50 ml of tetrahydrofuran and 50 ml of an ultrasonic homogenizer (UHS- manufactured by Nippon Seiki Seisakusho Co., Ltd.),
A pigment dispersion was prepared by mixing and dispersing for 0 minutes.

Isopar G (manufactured by Exxon Co.) cooled to 5 to 10 ° C. was prepared in a 500 ml beaker, and the pigment dispersion previously prepared was charged into the beaker while using an ultrasonic homogenizer, and resin particles were formed. It was deposited.

Next, a centrifuge (Sakuma Seisakusho Co., Ltd.)
(Manufactured by Autobalance System Model 90-4 large capacity multicentrifuge) was used to separate the resin particles, and the resin particles were washed with Isopar G and further dispersed in Isopar G.

When the particle size of the resin particles after solvent substitution was analyzed in the same manner, the resin particles were 0.17 to 1.57 μm.
It had a sharp and single-peak distribution spectrum with a particle size width of m and an average particle size D ₅₀ of 0.95 μm.

Further, it was confirmed by infrared absorption spectrum that the polyhydroxycarboxylic acid ester was attached to the resin particles, that is, the OH group stretching vibration region at 3800 to 3200 cm ^-1 was quantified and the carbonyl group of the carboxylic acid ester was 1760. ~ 17
It was confirmed by the change in the peak position at 70 cm ^-1 .

This wet developer was diluted with Isopar G,
The print density was adjusted to 1%. The obtained wet type developer exhibits negatively chargeable developing characteristics.

The developing process is carried out by using electrostatic recording paper (DSscan Seiko Denshi KK, electrostatic plotter, EP-4010).
A surface latent image (about 100V) was formed by a corona charging device using a mask having a commercially available bar code pattern. The print development was performed by a roller developing machine. The processor speed is 2.6 m / min and 10.0 m /
I went at min. Macbeth RD for photometric and colorimetric evaluation of printed matter
914 (manufactured by Macbeth Co., Ltd.) was used to measure the optical reflection density (OD value).

For this printed matter, a bar code reader (manufactured by DSscan Co., main body; Codascane 3600, recording unit; Codascane Printer, used sensor; Si type photointerrupter method (sensitivity range about 580-720 nm) was used. As a result of OCR reading, OD value was 0.32
Reading and detection were possible within the above range, and reading sensitivity was improved.

In preparing the above-mentioned wet developer, Ma
A wet developer was similarly prepared by using Macrolex Red Violet R (manufactured by Sand Co., Ltd.) in the same amount instead of crolex Yellow 6G. When the barcode was similarly read using this wet type developer, it became possible to read and detect in the range of OD value of 0.32 or more, and the reading sensitivity was improved.

Further, in preparing the above-mentioned wet developer, Ma
A wet developer was similarly prepared by using Baymicron SN VP2670 (manufactured by Bayer) in the same amount instead of crolex Yellow 6G. When the barcode was similarly read using this wet type developer, it became possible to read and detect in the range of OD value 0.14 to 1.6, and the reading sensitivity was improved.

In preparing the above-mentioned wet developer, Ma
A wet developer was similarly prepared by using D07-18 (manufactured by Orient Chemical Co., Ltd.) in the same amount in place of crolex Yellow 6G. When the barcode was similarly read using this wet type developer, it became possible to read and detect the OD value in the range of 0.7 to 1.6, and the reading sensitivity was improved.

Further, in preparing the above-mentioned wet type developer, Ma
A wet developer was similarly prepared by using D07-15 (manufactured by Orient Chemical Co., Ltd.) in the same amount instead of crolex Yellow 6G. When the bar code was similarly read using this wet type developer, it became possible to read and detect in the range of the OD value of 0.38 or more, and the reading sensitivity was improved.

In preparing the above-mentioned wet developer, Ma
DH-C2 (Nippon Kayaku Co., Ltd.) in place of crolex Yellow 6G
Was used in the same manner to prepare a wet type developer. When the barcode was similarly read using this wet type developer, it became possible to read and detect in the range of OD value of 0.3 or more, and the reading sensitivity was improved.

[0068]

Example 2 Instead of the infrared absorber in Example 1,
A wet type developer was prepared in the same manner by using OPTOGEN NIR-840S (manufactured by Sumitomo Chemical Co., Ltd.) in the same amount.

When this bar code was similarly read using this wet developer, it became possible to read and detect in the range of OD value of 0.38 or more, and the reading sensitivity was improved.

[0070]

Example 3 The same amount of DH-C2 (manufactured by Nippon Kayaku Co., Ltd.) was used instead of Macrolex Yellow 6G in Example 1, and OPTOGEN NIR-840S (manufactured by Sumitomo Chemical Co., Ltd.) was used instead of the infrared absorber. Was used in the same manner to prepare a wet developer. When the bar code was similarly read using this wet type developer, it became possible to read and detect in the range of the OD value of 0.21 to 1.24, and the reading sensitivity was improved.

[0071]

[Example 4] In Example 1, CY-9 (manufactured by Nippon Kayaku Co., Ltd.) was used as an infrared absorber without using a coloring agent.
g, methyltrimethoxysilane (manufactured by Toshiba Silicone Co.)
A wet type developer was prepared in the same manner except that the amount was 1.8 g.

When this bar code was similarly read using this wet type developer, the bar code could be read and detected in the range of OD value of 0.32 or more.

[0073]

[Example 5] In Example 4, the infrared absorber was replaced with OPTOGE.
N NIR-840S (manufactured by Sumitomo Chemical Co., Ltd.) and used in the same amount to prepare a wet developer in the same manner. When the barcode was similarly read using this wet type developer, it was possible to read and detect it in the range of OD value of 0.19 or more.

[0074]

Sixth Embodiment In the first embodiment, Macrolex Yellow 6G
(Sand Co., Ltd.) 0.2 g, infrared absorber IR-82
0g (manufactured by Nippon Kayaku Co., Ltd.) and 0.8 parts of methyltrimethoxysilane (manufactured by Toshiba Silicone Co., Ltd.), 2.5g of Seika Fast Yellow 2400B (Dainichi Seika Co., Ltd.) as a coloring agent. A wet type developer was prepared in the same manner except that it was used. Printing was performed in the same manner using this wet type developer, and the bar code was read in the same manner.

Then, a wet developer was prepared in the same manner as in Example 4 except that 0.8 g of methyltrimethoxysilane (manufactured by Toshiba Silicone Co., Ltd.) was used. When overcoat printing was performed on the code pattern, it was possible to read and detect the OD value in the range of 0.14 to 1.6.

[0076]

Example 7 In the wet type developer having the infrared absorbing agent prepared in Example 6, OPTOGE was used as the infrared absorbing agent.
A wet type developer was prepared in the same manner except that N NIR-840S (manufactured by Sumitomo Chemical Co., Ltd.) was used in the same amount.

When this wet type developer was used to perform overcoat printing in the same manner as in Example 6, the wet type developer containing the infrared absorber was colorless and did not change the hue of the bar code of Seika First Yellow 2400B. O
It became possible to read and detect in the range of D value 0.9 to 1.5.

Claims (7)

[Claims] 1. An olefin resin particle having a carboxyl group or an ester group, or an olefin resin particle having a carboxyl group or an ester group in which a colorant is dispersed,
A wet developer comprising most of liquid aliphatic hydrocarbons, wherein an infrared absorbent is dispersed in the resin particles. 2. The wet developer according to claim 1, wherein the colorant has a specific gravity of 5 or less. 3. The wet developer according to claim 1, wherein a coupling agent is dispersed together with a colorant in the resin particles. 4. Olefin resin particles having a carboxyl group or an ester group or olefin resin particles having a carboxyl group or an ester group in which a colorant is dispersed,
In a wet developer composed of most liquid aliphatic hydrocarbons, an infrared absorber is dispersed in the resin particles, and a polyhydroxycarboxylic acid of 3 to 10 mer containing hydroxycarboxylic acid ester as a monomer in the wet developer is used. A wet type developer characterized by containing an acid ester. 5. An olefin resin having a carboxyl group or an ester group is heated and dissolved in a solvent having a high temperature dependency in solubility with respect to the resin to prepare a resin solution,
The resin solution is a liquid aliphatic hydrocarbon in the presence of an infrared absorbing agent or a colorant and an infrared absorbing agent, and in the presence of a polyhydroxycarboxylic acid ester of a 3- to 10-mer containing hydroxycarboxylic acid ester as a monomer. A method for producing a wet developer, which comprises charging and cooling the solution to precipitate resin particles and replacing the solvent with the aliphatic hydrocarbon. 6. Olefin resin particles having a carboxyl group or an ester group dispersed with an infrared absorber or olefin resin particles having a carboxyl group or an ester group added with an infrared absorber and a colorant, and most of the liquid fat. Printed matter printed using a wet type developer containing a group hydrocarbon. 7. An olefin resin particle having a carboxyl group or an ester group having an infrared absorber dispersed therein, or an olefin resin particle having a carboxyl group or an ester group having an infrared absorber and a colorant dispersed therein, and most of the liquid fat. A printed matter obtained by superimposing a print on a printed matter having absorption sensitivity in the visible region by using a wet type developer containing a group hydrocarbon.