JP2002156794A - Printed matter for optical reader - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a printed matter for optical reader which is manufactured by printing image information which drops out, using a proper high chromatic orange toner. SOLUTION: This printed matter for optical reader is one, such that the image information to be dropped out is printed on a medium to be printed, by the electrostatic charge image developing orange toner which contains a mixture of binder resin and orange-type colorant, or yellow-type colorant and red-type colorant, and the reflectivity of printed part for dropout and the same of non-printed part, when irradiating the printed matter with a light of wavelength 620 nm which satisfies the equation (1): 1-(reflectively of printed part for dropout/reflectively of non-printed part)<=0.04.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] 1. Field of the Invention [0002] The present invention relates to a printed matter for an optical reader in which an optical reading unit such as an OCR or OMR is printed in a dropout color, and more particularly to image information dropped out by an orange toner for developing an electrostatic image. Is printed.

[0002]

2. Description of the Related Art OCR such as postal codes and bank transfer forms
(Optical Character Reader) written on a pencil or ballpoint pen, or a mark written on an OMR (Optical Mark Reader) such as a census or examination problem solving paper, using an optical reader to read information to a computer. At the time of input, characters such as character entry frames and precautionary notes are printed with ink called dropout color so that they can be recognized by the naked eye but cannot be detected by an optical reading device, and the time required for reading is lengthened or recognized. This prevents information that should be recognized from being unrecognized or unnecessary information from being erroneously recognized.

[0003] The ink used to print this dropout color is OCR / OMR ink (recently, both inks are collectively referred to as OCR / OMR ink).
The printing is performed mainly by an offset form printing machine or a chrysanthemum half-class printing machine.

[0004] Ink for dropout color is
Like ordinary offset inks, it is used between warm colors such as red and orange to cool colors such as blue and indigo. PCS (Print Contrast) specified from the wavelength range of the reading device
Signal) inks are limited.

[0005] The PCS value represents the degree of relative darkness between a printed color and a printing medium such as paper, and is calculated by the following equation. The smaller this value is, the closer the printing medium is to the printing medium. color,
That is, the suitability as the dropout color is higher. PCS value = 1− (reflectivity of ink / reflectance of printing medium)

Currently, more than 100 types of readers are in operation, and the brands of dropout color inks are limited by checking the read wavelength of each model and the PCS value at that wavelength.

[0007] Naturally, the character entry frames and precautionary notes on the OCR / OMR sheet are printed with dropout color ink before use, and the user writes the amount and mark on the sheet as needed. . In recent years, the amount of money, address, product name, code No. in mail-order sales, various transfer papers, etc. If, for example, the side requesting the transfer is known in advance, they are printed on an OCR / OMR sheet and sent.

At this time, various data are stored in the ink jet,
Non-impact printers such as electrophotography print directly from computer data files to OCR / OMR sheets, but character entry frames and precautionary statements also use paper pre-printed with dropout color ink. .

[0009] In this way, the side requesting the transfer or the investigating side determines in advance the amount or code No. to be transferred. In the case of printing such individual data, the number of OCR / OMR sheets required is relatively small in many cases, and the format It is required to complete the printing in a short period of time from the determination of the printing to the completion of printing.

However, current printing systems requiring pre-printing with dropout color inks require a small number of copies.
It is not possible to cope with a short delivery time, and in particular, when a large number of types of printing (for example, changing only symbols) are required with a small number of copies, the cost becomes considerably high, so that it is not practically possible. Was.

In order to solve such a problem of the prior art, the present applicant has made a printed image on a medium substantially match the reflectance of the medium surface with the reflectance of the printed image in a specific wavelength range. It consists of both a print image consisting of optically unreadable dropout information and a print image consisting of non-dropout information that is optically readable in the same wavelength range.Either print image is made of resin and colorant or We have invented and applied for a patent for a printed material for non-dropout information optical reading, which comprises a resin fixing film developed with an electrostatic image developing toner containing an invisible light absorbing agent. For details, refer to JP-A-11-78208.

As described in Japanese Patent Application Laid-Open No. 11-78208, a conventional printing system using a drop-out color ink is developed by developing this type of optical reading print using an electrostatic image developing toner. Can solve the problem that it is impossible to cope with a small number of copies and a short delivery time. It should be noted that JP-A-11-78
In the printed matter for optical reading described in Japanese Patent Publication No. 208, for example, the dropout information image is produced using magenta toner, the non-dropout information image is produced using black toner, and is used for developing the dropout information image. It does not use a special color toner.

[0013]

SUMMARY OF THE INVENTION The present inventors conducted a panel test using a print sample for the purpose of improving the definition of a dropout information image.
As a color of a print image composed of drop-out information, particularly when developed on a print medium of white or a color close to white, orange is less irritating to eyes than red,
Visually favorable, such as high chroma was obtained.

However, for example, conventional black, red,
A printed matter obtained by developing an orange dropout information image using a color copier using each of blue and yellow color toners is inferior in orange vividness compared to a printed matter printed using orange ink, and still has such a point. There was room for improvement.

[0015]

The present inventors have found that, when obtaining image information of an orange-based dropout using a color toner, the present invention can provide a method which is more effective than a conventional dropout image produced by color copying using a combination of color toners. When developed using a novel orange toner prepared using an orange-based colorant, a vivid orange color without dullness is obtained, and at around 620 nm, which is the main reading wavelength in a generally widely used reading device. It has been found that a very good dropout condition in which the PCS value is close to zero can be obtained, and the present invention has been completed.

The present invention provides a binder resin and an orange colorant,
Alternatively, it is a printed matter for an optical reading device in which image information dropped out by an orange toner for developing an electrostatic image containing a mixture of a yellowish colorant and a redish colorant is printed on a printing medium, and has a wavelength of 620 nm. The reflectance of the printed part for dropout and the non-printed part when irradiating the printed matter with light of the following formula is expressed by the following formula 1: 1− (reflectance of printed part for dropout / reflectance of non-printed part) ≦ 0.04 And a printed matter for an optical reader.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION A printed material for an optical reader according to the present invention is obtained by printing image information to be dropped out on a printing medium with orange toner for developing an electrostatic image. The orange toner for developing an electrostatic image is as described below.

1. Resin The binder resin used in the present invention can be used without particular limitation as long as it is generally used as a binder resin in a toner. For example, polystyrene, styrene- (meth) acryl Examples thereof include acid ester copolymers, olefin resins, polyester resins, amide resins, carbonate resins, epoxy resins, and their graft polymers and mixtures thereof.

Among them, polyester resins and styrene resins are considered in consideration of charge stability, storage stability, fixing characteristics, and color reproducibility, transparency, PCS value and the like when an orange organic pigment is used to make an orange toner. A (meth) acrylate copolymer resin can be suitably used.

The polyester resin used in the present invention is:
For example, it is obtained by dehydrating and condensing a dicarboxylic acid and a diol by a usual method. Examples of dicarboxylic acids include phthalic anhydride, terephthalic acid, isophthalic acid, orthophthalic acid,
Naphthalenedicarboxylic acid, adipic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid,
Examples thereof include dicarboxylic acids such as hexahydrophthalic anhydride, tetrahydrophthalic anhydride, cyclohexanedicarboxylic acid, succinic acid, malonic acid, glutaric acid, azelaic acid, and sebacic acid, and derivatives thereof.

As the diol, for example, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butanediol, pentanediol, hexanediol, cyclohexanedimethanol, bisphenol A, polyoxyethylene- (2.0 ) -2,2-Bis (4-hydroxyphenyl) propane and its derivatives, polyoxypropylene- (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene- (2.2) -Polyoxyethylene- (2.0)
-2,2-bis (4-hydroxyphenyl) propane,
Polyoxypropylene- (6) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene-
(2.2) -2,2-bis (4-hydroxyphenyl)
Propane, polyoxypropylene- (2.4) -2,2
-Bis (4-hydroxyphenyl) propane, polyoxypropylene- (3.3) -2.2-bis (4-hydroxyphenyl) propane and derivatives thereof.

Further, for example, polyethylene glycol,
Diols such as polypropylene glycol, ethylene oxide-propylene oxide random copolymer diol, ethylene oxide-propylene oxide block copolymer diol, ethylene oxide-tetrahydrofuran copolymer diol, and polycaprolactone diol can also be used.

If necessary, a trifunctional or higher functional aromatic carboxylic acid such as trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride or a derivative thereof, or sorbitol, 1,2,3 , 6-
Hexanetetraol, 1,4-sorbitan, pentaerythritol, 1,2,4-butanetriol, 1,
Trifunctional such as 2,5-pentanetriol, glycerin, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trimethylolbenzene The above alcohols or ethylene glycol diglycidyl ether, hydroquinone diglycidyl ether, N, N-diglycidyl aniline, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, trimethylolethane triglycidyl ether, pentaerythritol tetraglycidyl ether , Bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, cresol novolak epoxy resin, phenol novolak type Tri- or higher-functional polyepoxy compounds such as epoxy resins, polymers or copolymers of vinyl compounds having epoxy groups, epoxidized resorcinol-acetone condensates, partially epoxidized polybutadienes, and semi-dry or dry fatty acid ester epoxy compounds Can also be used in combination.

By selecting and reacting a dicarboxylic acid and a diol from the above compounds, a linear polyester resin is produced. When a trifunctional or higher polycarboxylic acid or polyhydric alcohol is selected and reacted in addition to the dicarboxylic acid and the diol, a branched polyester resin is obtained. When a linear polyester resin is used as the binder resin of the present invention, the weight average molecular weight of the resin is preferably 2 × 10 ³ to 1 × 10 ⁵ , more preferably 4 × 10 ^{3 to} 3 ×. 10 ⁴ . The linear polyester has good melting properties at the time of fixing and is excellent in transparency. Therefore, when the binder resin of the orange toner used in the present invention is used, the reflectance at a wavelength around 620 nm becomes high, and It becomes easy to set the value to 0.04 or less.

When a branched or cross-linked polyester resin is used in combination with a trivalent or higher polyvalent carboxylic acid or polyhydric alcohol, the offset resistance at high temperatures is improved, which is suitable for an oilless heat roll fixing system.

Further, when a linear polyester resin is used in combination with a branched or crosslinked polyester resin,
A toner having further excellent low-temperature fixability and high-temperature offset resistance can be obtained. The mixing ratio of the linear polyester and the branched or crosslinked polyester is 10/90 to 90 /
10 is preferable, and 30/70 to 70/30 is more preferable.

The polyester resin used in the present invention can be obtained by performing a dehydration condensation reaction or a transesterification reaction using the above-mentioned raw material components in the presence of a catalyst. The reaction temperature and reaction time at this time are not particularly limited, but are usually 150 to 300 ° C. and 2 to 24 hours.

As a catalyst for carrying out the above reaction, for example, tetrabutyl titanate, zinc oxide, stannous oxide, dibutyltin oxide, dibutyltin dilaurate and the like can be appropriately used.

The polyester resin only needs to have appropriate glass transition point and melt viscosity characteristics as a toner, and the temperature at which the viscosity becomes 1 × 10 ⁵ poise is 95%.
C. or higher is preferable because of good fixability, and among them, the temperature at which the viscosity becomes 1 × 10 ⁵ poise is 95 to 170 ° C.
Is more preferable because of its good low-temperature fixability and offset property. Further, those having a temperature at which the viscosity becomes 1 × 10 ⁵ poise at 95 to 160 ° C. are particularly preferable.

The glass transition temperature (Tg) is preferably 40 ° C. or higher, and particularly preferably the glass transition temperature (Tg) is 45 to 85 ° C.

Further, the acid value is from 1 to 30 mg KO.
H / g, more preferably 1 to 20 mgKOH / g
It is. The hydroxyl value is 10 to 100 mg KO.
H / g, more preferably 10 to 60 mgKOH /
g is preferable in that the moisture resistance of the toner is improved.

The styrene monomer used for the styrene- (meth) acrylate copolymer resin used in the present invention includes, for example, styrene, α-methylstyrene, vinyltoluene, p-sulfonestyrene, dimethylaminomethyl There are styrene and the like.

Examples of the (meth) acrylate monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate. Alkyl (meth) acrylates such as (meth) acrylate, tertiary butyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth) acrylate; cyclohexyl (meth) Alicyclic (meth) acrylates such as acrylates; aromatic (meth) acrylates such as benzyl (meth) acrylate; hydroxyl-containing (meth) acrylates such as hydroxyethyl (meth) acrylate; (T) Phosphoric acid group-containing (meth) acrylates such as acryloxyethyl phosphate; such as 2-chloroethyl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate, and 2,3-dibromopropyl (meth) acrylate (Meth) acrylates containing halogen atoms; (meth) acrylates containing epoxy groups such as glycidyl (meth) acrylate; ether groups containing (meth) acrylates such as 2-methoxyethyl (meth) acrylate and 2-ethoxyethyl (meth) acrylate ) Acrylate; dimethylaminoethyl (meth)
(Meth) acrylates containing a basic nitrogen atom or an amide group such as acrylate and diethylaminoethyl (meth) acrylate;

Unsaturated compounds copolymerizable therewith can also be used if necessary. For example, a carboxyl group-containing vinyl monomer such as (meth) acrylic acid, itaconic acid, crotonic acid, maleic acid, and fumaric acid; a sulfo group-containing vinyl monomer such as sulfoethylacrylamide; and a nitrile group such as (meth) acrylonitrile Vinyl monomer; vinyl methyl ketone,
Ketone group-containing vinyl monomers such as vinyl isopropenyl ketone; N-vinylimidazole, 1-vinylpyrrole, 2-vinylquinoline, 4-vinylpyridine, N-vinyl
A basic nitrogen atom or amide group-containing vinyl monomer such as 2-pyrrolidone and N-vinylpiperidone can be used.

The crosslinking agent may be used in the range of 0.1 to 2% by weight based on the vinyl monomer. Examples of the crosslinking agent include divinylbenzene, divinylnaphthalene, divinylether, and ethylene glycol di (meth)
Acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate,
1,3-butylene glycol di (meth) acrylate, 1,6-
Hexane glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate And tetramethylolmethanetetra (meth) acrylate.

Alternatively, in the case of a resin using a styrene- (meth) acrylate copolymer obtained by copolymerizing the carboxyl group-containing vinyl monomer, a crosslinked resin can be formed by using a metal salt. A as the metal salt
1, Ba, Ca, Cd, Co, Cr, Cu, Fe, H
g, Mg, Mn, Ni, Pb, Sn, Sr, Zn, and other halides, hydroxides, oxides, carbonates, carboxylate salts, alkoxylates, chelate compounds, and the like. The crosslinking reaction can be performed by heating and stirring in the presence of a solvent.

As a method for producing the styrene- (meth) acrylic acid ester copolymer, a usual polymerization method can be employed, and the polymerization may be carried out in the presence of a polymerization catalyst such as solution polymerization, suspension polymerization or bulk polymerization. And a method of performing a polymerization reaction.

As the polymerization catalyst, for example, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-yl)
Carbonitrile), benzoyl peroxide, dibutyl peroxide, butyl peroxybenzoate, and the like.
１10.0% by weight is preferred.

The styrene- (meth) acrylate copolymer resin used in the present invention only needs to have appropriate glass transition point and melt viscosity characteristics as a toner for two-component development. Although 1 × 10 ⁵ as poise become temperature is above 95 ° C. preferably a good fixing property, among others, the temperature at which its viscosity is 1 × 10 ⁵ poise 95
A temperature of 170 ° C. is more preferable because the fixability at a low temperature is good, and a temperature at which the viscosity becomes 1 × 10 ⁵ poise is 9 ° C.
Those having a temperature of 5 to 160 ° C are particularly preferred.

On the other hand, the glass transition temperature (Tg) of the styrene- (meth) acrylate copolymer resin is 40
° C or more is preferable, and especially, Tg is 45-85 ° C.
Are particularly preferred. The acid value is desirably 30 or less, particularly desirably 20 or less. If the acid value is too high, the charge amount is reduced, and an initial charge amount cannot be obtained.

In the present invention, in order to produce an orange toner using an orange colorant, it is desirable to use a polyester resin in terms of excellent transparency. Polyester resins are more tough than styrene acrylic resins, can withstand stress in a developing device, and have low melting points, and are suitable as resins for color toners.

2. Wax The release agent used in the present invention is a wax containing a higher fatty acid ester compound and / or an aliphatic alcohol compound as a main component. Such a release agent is preferable because it has good dispersibility in the polyester resin of the present invention, and has good release properties and slidability. When these waxes are added to the toner, better hot offset resistance and fixing strength can be obtained as compared with the same amount of a polyolefin-based wax such as a polypropylene wax or a polyethylene wax.

Further, a wax containing a higher fatty acid ester compound and / or an aliphatic alcohol compound as a main component not only acts as a release agent for preventing an offset phenomenon at the time of heat roll fixing, but also prints a large number of sheets for a long time. Also, for example, when used as a toner for a two-component developer, it gives a stable charge to the toner without adhering to the carrier surface, there is no occurrence of scattered toner, etc. From becoming
It is possible to print high-quality and high-definition images. further,
When an orange toner is used together with the colorant of the present invention, a color toner having excellent transparency as compared with a hydrocarbon wax such as a polypropylene wax can be obtained. The orange toner having such characteristics is transparent and can obtain a good PCS value when printed on the surface of a printing medium such as paper.

The wax containing a higher fatty acid ester compound and / or an aliphatic alcohol compound as a main component is represented by carnauba wax, montan ester wax, rice wax, scale insect wax, lanolin wax or the following general formulas 1 to 5: Compound.

<General formula 1>

Embedded image (In the formula, R1 and R2 are a hydrocarbon group having 1 to 40 carbon atoms, and at least one of them represents a chain hydrocarbon group having 12 or more carbon atoms.)

<General formula 2>

Embedded image (Wherein, R1, R2 and R3 are hydrocarbon groups having 1 to 40 carbon atoms, at least one of which has 1 carbon atom)
(Indicating two or more chain hydrocarbon groups)

<General formula 3>

Embedded image (Wherein, R1, R2 and R3 are hydrocarbon groups having 1 to 40 carbon atoms, at least one of which has 1 carbon atom)
(Indicating two or more chain hydrocarbon groups)

<General formula 4>

Embedded image (Wherein, R1 is a hydrocarbon group having 12 to 40 carbon atoms,
R2 is a hydrocarbon group having 1 to 40 carbon atoms; a + b = 4
Wherein a represents an integer of 1 to 4 and b represents an integer of 0 to 3)

<General formula 5>

Embedded image (Wherein, R1, R2 and R3 are hydrocarbon groups having 1 to 40 carbon atoms, at least one of which is a hydrocarbon group having 12 carbon atoms)
A and c are integers from 0 to 2 and a + c = 2; b is an integer from 1 to 4; d is 1 or 2, and e = d- 1).

The following compounds are specific examples of the wax represented by the above general formula.

<Wax 1>: Specific example of general formula 1

Embedded image

<Wax 2>: Specific example of general formula 2

Embedded image

<Wax 3>: Specific example of general formula 3

Embedded image

<Wax 4>: Specific example of general formula 4

Embedded image

<Wax 5>: Specific example of general formula 5

Embedded image

<Wax 6>: Specific example of general formula 5

Embedded image

As the carnauba wax, it is preferable to use a carnauba wax that has been freed from fatty acids and whose free fatty acids have been removed by purification. The acid value of the free fatty acid type carnauba wax is preferably 8 or less, more preferably 5 or less. The free fatty acid-type carnauba wax becomes finer crystals than the conventional carnauba wax, and the dispersibility in the polyester resin is improved. The montan-based ester wax is refined from a mineral, and becomes fine crystals like the carnauba wax by the purification, so that the dispersibility in the polyester resin is improved.

The acid value of the montan ester wax is preferably 30 or less. Rice wax is obtained by refining rice bran wax and has an acid value of 13%.
The following is preferred.

The scale insect wax is a waxy component secreted by the larva of the scale insect (also known as lobster).
For example, it can be obtained by dissolving in hot water, cooling and solidifying after separating the upper layer, or by repeating the same. The scale insect wax purified by such a means is white in a solid state and has an extremely sharp melting point, and thus is suitable as the toner wax in the present invention. The acid value is reduced to 10 or less by the purification, and is preferably 5 or less for toner.

The lanolin wax is obtained by purifying and dehydrating a waxy substance adhering to wool's wool, and preferably has an acid value of 8 or less, and more preferably has an acid value of 5 or less.
It is as follows.

Examples of the release agent mainly containing an aliphatic alcohol compound include those mainly containing a higher alcohol obtained by an oxidation reaction of paraffin, olefin and the like. Examples of the release agent containing an aliphatic alcohol as a main component include “Unilin 425”, “Unilin 550” (all described above, Petrolite Co., Ltd.), “NPS-9210”,
"PARACOL 5070" (Nippon Seiro Co., Ltd.) and the like.

Among the above specific examples, carnauba wax, acid scale wax and tetrabehenic acid ester of pentaerythritol having an acid value of 8 or less are particularly preferred.
Wax 4> is the most preferred wax that can be used in the present invention.

The wax of the present invention has a melting point of 65.
C. to 130.degree. C. are particularly preferable because they greatly contribute to the offset resistance.

The wax may be used alone or in combination of two or more kinds.
Good fixing offset performance can be obtained by adding 15 parts by weight, preferably 1 to 5 parts by weight. If the amount is less than 0.3 parts by weight, the offset resistance is impaired. If the amount is more than 15 parts by weight, the fluidity of the toner deteriorates. This will adversely affect the charging characteristics of the toner.

Incidentally, synthetic waxes such as polyamide wax, graft polymerization wax, modified polyolefin wax, polypropylene wax and polyethylene wax can be used in combination with the wax of the present invention.

3. Colorant The colorant incorporated in the orange toner for developing an electrostatic image in the present invention is an orange colorant, or an orange mixed color of a yellow colorant and a red colorant.

The orange colorant can be appropriately selected from orange organic pigments well known in the art and used. I. Pigment Orange 1,
2, 5, 13, 15, 16, 17, 18, 19, 31,
At least one selected from the group consisting of 34, 36, 38, 40, 42, 43, 51, 60 and 62 can be used. Among these orange-based colorants, it is preferable to use C in view of factors such as dispersibility, degree of coloration, stability, and the possibility of realizing a low PCS value with light having a wavelength of 620 nm when used as a colorant for a toner. . I. Pi
gment Orange 13 (generic name disazo orange), 16 (dianisidine orange), 36 (benzimidazolone orange HL), 38 (naphthol orange 38) and 43 (perinone orange), most preferably C.I. I. Pigment Orange
ge 16, 43.

The yellow colorant can be appropriately selected from yellow organic pigments well known in the art and used. I. Pigment Yellow
w 1,3,4,5,6,12,13,14,15,1
6, 17, 18, 24, 55, 65, 73, 74, 8
1,83,87,93,94,95,97,98,10
0, 101, 104, 108, 109, 110, 11
3,116,117,120,123,128,12
9,133,138,139,147,151,15
3,154,155,156,168,169,17
At least one selected from the group consisting of 0, 171, 172, 173 and 180 can be used. Among these yellow colorants, dispersibility, degree of coloration, stability, suitability for mixing with a red colorant (including the possibility of achieving a low PCS value with light having a wavelength of 620 nm when a mixed orange colorant is used) )), Preferably C.I.
I. Pigment Yellow 12 (generic name disazo yellow AAA), 13 (disazo yellow AAA)
MX), 17 (Disazo Yellow AAOA), 97
(Fast yellow FGL), 110 (isoindolinone yellow 3RLT), 155 (sandolin yellow 4G) and 180 (benzimidazolone yellow), most preferably C.I. I. Pigmen
t Yellow 17, 155 and 180.

Further, the red colorant can be appropriately selected from among red organic pigments well-known in the art and used. I. Pigment Red
1,2,3,4,5,6,7,8,9,10,12,1
4,15,17,18,22,23,31,37,3
8,41,42,48: 1,48: 2,48: 3,4
8: 4, 49: 1, 49: 2, 50: 1, 52: 1, 5
2: 2, 53: 1, 54, 57: 1, 58: 4, 60:
1,63: 1,63: 2,64: 1,65,66,6
7, 68, 81, 83, 88, 90, 90: 1, 11
2,114,115,122,123,133,14
4,146,147,149,150,151,16
6,168,170,171,172,174,17
5,176,177,178,179,185,18
7,188,189,190,193,194,20
2,208,209,214,216,220,22
1,224,242,243,243: 1,245,2
At least one selected from the group consisting of 46 and 247 can be used. Among these red colorants, dispersibility, degree of coloration, stability, suitability for mixing with a yellow colorant (including the possibility of achieving a low PCS value with light having a wavelength of 620 nm when a mixed orange colorant is used) )), Preferably C.I. I. Pigment R
ed 48: 1 (generic name Barium Red), 48: 2
(Calcium red), 48: 3 (strontium red), 48: 4 (manganese red), 53: 1 (lake red), 57: 1 (brilliant carmine 6B), 1
22 (quinacridone magenta 122) and 209
(Dichloroquinacridone red), most preferably C.I. I. Pigment Red 57: 1,1
22 and 209.

One of the above-mentioned orange colorants can be used alone, or two or more can be used as a mixture. Further, the yellow-based coloring system and the red-based coloring agent,
The mixture is mixed in a mixing ratio such that the mixture has an orange color. These mixing ratios are not particularly limited as long as the obtained orange mixed colorant can be used as a colorant for orange toner. Each of the yellow colorant and the red colorant is one kind,
Alternatively, two or more kinds can be used.

An orange colorant or a mixed orange colorant comprising a yellow colorant and a red colorant is mixed with the binder resin 10.
The range of 1 to 50 parts by weight per 0 parts by weight is preferable,
A range of 15 parts by weight is particularly preferred.

4. Charge Control Agent As the charge control agent, a conventionally known charge control agent can be used. For example, as a positive charge control agent, a nigrosine dye, a triphenylmethane dye, a quaternary ammonium salt, a resin containing a quaternary ammonium group and / or an amino group, and the like, and as a negative charge control agent, a trimethylethane dye, Metal complex salt of salicylic acid, metal complex salt of benzylic acid, copper phthalocyanine, perylene, quinacridone, azo pigment, metal complex salt azo dye, heavy metal-containing acid dye such as azochrome complex, calixarene-type phenol condensate, cyclic polysaccharide , A resin containing a carboxyl group and / or a sulfonyl group and the like are used as necessary.

In particular, since the toner used in the present invention is an orange toner, it is desirable to use a colorless compound as the charge control agent. Examples of the colorless negative charge control agent include “Bontron E-84” manufactured by Orient Chemical Co., which is a metal (Zn) complex compound of salicylic acid, and “LR-1” manufactured by Nippon Carlit Co., Ltd., which is a metal complex compound of benzylic acid.
47 "," LR-297 "and the like. Further, as a colorless positive charge control agent, TP-30 having a quaternary ammonium salt structure is used.
2, TP-415, TP-610 (manufactured by Hodogaya Chemical Co.);
Bontron P-51 (manufactured by Orient Chemical); Copy Charge PSY (manufactured by Clariant Japan).

5. Others In the present invention, various additives (referred to as external additives) are used to improve the surface of the toner such as improving the fluidity and the charging characteristics of the toner.
Can be used. Examples of the external additives that can be used in the present invention include inorganic fine powders such as silicon dioxide, titanium oxide, aluminum oxide, cerium oxide, zinc oxide, tin oxide, and zirconium oxide, and silicone oils and silane coupling agents. Surface-treated with a hydrophobizing agent, polystyrene, acrylic, styrene acrylic, polyester, polyolefin, cellulose, polyurethane, benzoguanamine, melamine, nylon,
Resin fine powders such as silicone, phenol, polyvinylidene fluoride, and Teflon (registered trademark) are used.

Among these, silicon dioxide (silica) whose surface is hydrophobized with various polyorganosiloxanes or silane coupling agents can be particularly preferably used. As such a product, for example, there is a product commercially available under the following trade names.

AEROSIL R972, R974, R202, R805, R812, RX200, RY200, R809, RX50, RA200HS, RA200H (Nippon Aerosil Co., Ltd.) WACKER HDK H2000, H2050EP HDK H3050EP, HVK2150 (Wacker Chemicals East Asia) Nipsil SS-10, SS-15, SS-20, SS-50, SS-60, SS-100, SS-50B, SS-50F, SS-10F, SS-40, SS-70, SS-72F (Japan Silica Industries Co., Ltd.) CABOSIL TG820F (Cabot Specialty Chemicals, Inc.)

The particle size of the external additive is desirably 1/3 or less of the diameter of the toner, particularly preferably 1/10 or less. In addition, these external additives have different average particle diameters.
More than one species may be used in combination. The usage ratio of the external additive is 0.05 to 5% by weight, preferably 0.1 to 3% by weight, based on 100 parts by weight of the toner.

The orange toner of the present invention may contain additives other than the above-described materials inside the toner particles. As an example, a metal soap, a lubricant such as zinc stearate, an abrasive such as cerium oxide or silicon carbide, or the like can be used.

The toner composition of the present invention can be obtained by a very general manufacturing method without depending on a specific manufacturing method. For example, a resin, a colorant, and a charge controlling agent may be obtained by melting the resin at the melting point ( (Softening point), and can be obtained by pulverizing and classifying after melt-kneading. Specifically, for example,
The resin and the colorant are mixed by a kneading means such as a two-roll, three-roll, pressure kneader, or a twin-screw extruder. At this time, the colorant or the like may be uniformly dispersed in the resin, and the conditions for the melt-kneading are not particularly limited, but are generally at 80 to 180 ° C. for 30 seconds to 2 hours. As the colorant, a flashing treatment may be used in advance so as to be uniformly dispersed in the resin, or a master batch melt-kneaded with the resin at a high concentration may be used. Then, after cooling it,
A method of finely pulverizing with a pulverizer such as a jet mill and classifying with a pneumatic classifier is used.

The average particle size of the particles constituting the toner is not particularly limited, but is usually adjusted to be 5 to 15 μm. Usually, fine particles (hereinafter, referred to as an external additive) having a smaller particle size than the toner base are mixed with the toner base obtained in this manner using a mixer such as a Henschel mixer.

The toner of the present invention can be used as a two-component developer by mixing with a magnetic carrier. In this case, the surface of the magnetic carrier is desirably coated with a resin. The charged state of the developer is stabilized by coating the surface with the resin.

As a carrier for preparing a two-component developer using the toner of the present invention, an iron powder carrier, a magnetite carrier, and a ferrite carrier used in a usual two-component developing system can be used. Ferrite or magnetite carriers having good fluidity are preferably used because they have high resistance, are excellent in environmental stability, and are easy to be spherical. The shape of the carrier can be spherical or irregular, and any of them can be used without any trouble. The average particle size of the carrier is generally 10 to 500 μm,
Particularly, for printing high-resolution images, 30 to 100 μm
Is preferred.

Further, a coated carrier obtained by coating these carriers with a resin can also be suitably used. As the coating resin, for example, polyethylene, polypropylene, polystyrene, polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral,
Polyvinyl chloride, polyvinyl carbazole, polyvinyl ether polyvinyl ketone, vinyl chloride / vinyl acetate copolymer, styrene / acrylic copolymer, straight silicone resin comprising organosiloxane bond or its modified product, fluororesin, (meth) acrylic resin, Polyester, polyurethane, polycarbonate, phenol resin, amino resin, melamine resin, benzoguanamine resin, urea resin, amide resin, epoxy resin and the like can be used. Among these, silicone resin, fluororesin, and (meth) acrylic resin are particularly excellent in charge stability and coating strength, and can be more preferably used. That is, in the present invention, the magnetic carrier is desirably a resin-coated magnetic carrier coated with at least one resin selected from a silicone resin, a fluororesin, and a (meth) acrylic resin.

The method for coating the resin on the surface of the carrier core material is as follows.
Although it is not necessary to particularly limit the means, preferred coating methods include a dipping method of dipping the core material in a solution of the coating resin, a spray method of spraying the coating resin solution onto the carrier core material surface,
Alternatively, a fluidized bed method in which a carrier is sprayed in a state of being floated by flowing air, a kneader coater method in which a carrier core material and a coating resin solution are mixed in a kneader coater to remove a solvent, and the like can be mentioned. The solvent used in the coating resin solution is not particularly limited as long as it dissolves the coating resin. For example, toluene, xylene, acetone, methyl ethyl ketone, tetrahydrofuran, dioxane and the like can be used. The thickness of the coating layer on the carrier surface is usually 0.1 to 3.0 μm.

The weight ratio of the toner of the present invention to the magnetic carrier is not particularly limited, but is usually 0.5 to 10 parts by weight of the toner per 100 parts by weight of the carrier.

The thus-obtained orange toner for developing an electrostatic image of the present invention and the developer using the same are developed and fixed on a printing medium by a known and commonly used method. It is preferable to use a fixing method. As the heat roll, a roll in which the surface of a cylindrical body that can be heated to a temperature at which the toner can be melted and fixed is coated with a coating resin having both releasability and heat resistance, such as a silicone resin or a fluororesin, is used. In the heat roll fixing method, the toner is fixed by passing the printing medium between two rolls having at least one heat roll and pressed at an appropriate pressure as described above. The remarkable technical effect of the toner for developing an electrostatic image according to the present invention is exhibited in a developing / fixing device in which development is performed at a higher speed and heat roll fixing is performed.

As the recording medium in the present invention, any of those known and used can be used.
Examples include papers such as resin-coated paper, synthetic resin films and sheets such as PET films and OHP sheets. These print media can be used not only in plain colors,
Partially printed media may also be used, including image portions printed in colors that do not drop out.

The printed matter for an optical reader according to the present invention comprises:
In a printing apparatus such as an electrophotographic copying machine, a printer, a facsimile, or a toner jet printer, it can be easily manufactured using the above-described orange toner for developing an electrostatic image. When an orange-based dropout information image is obtained using the above-described orange toner, a vivid orange color without dullness is obtained, compared to a dropout information image produced by color copying using a combination of conventional color toners, and in general, An extremely good dropout condition in which the PCS value near 620 nm, which is the main reading wavelength in a widely used reading device, is close to zero is obtained.

The printed matter for an optical reader according to the present invention comprises:
As described above, an arbitrary dropout information image is printed on the printing medium using the orange toner dedicated to the dropout printing section, so that the dropout printing when irradiating the print with light having a wavelength of 620 nm is performed. The reflectance of the print portion and the non-print portion satisfies the following expression 1: 1− (reflectance of print portion for dropout / reflectance of non-print portion) ≦ 0.04 The PCS value calculated by “1− (reflectance of printed portion for dropout / reflectance of non-printed portion)” is:
The smaller the value is, the higher the suitability as a dropout color is. According to the present invention, a bright orange color without dullness is obtained, so that the PCS value for light having a wavelength of 620 nm is 0.04 or less, Preferably 0.03
In the following, it can most preferably be close to zero.

As described above, the printed matter for an optical reader according to the present invention is an orange toner for developing an electrostatic image containing a binder resin and an orange colorant or a mixture of a yellow colorant and a red colorant. Is printed on the print-receiving medium at 620 nm
The reflectance of the printed portion for dropout and the non-printed portion when the printed material is irradiated with light having a wavelength of is expressed by the following formula 1: 1− (reflectance of printed portion for dropout / reflectance of non-printed portion) ≦ 0. .04, the production cost and production time for producing a small number of copies and many types of printed materials are significantly greater than when producing printed materials for optical readers by the conventional printing method using ink. Can be reduced. In addition, since a special orange toner is used for the image information to be dropped out, a high saturation orange dropout image can be obtained with less saturation compared to printed matter prepared using a normal full-color toner. Since the user can obtain a good feeling of use such that the dropout image can be clearly recognized, and at the same time, the value obtained by the above equation 1 can be made close to zero, a reading wavelength of about 620 nm is used. In the reading device, the dropout characteristics are improved, and the occurrence of reading errors can be reduced. Hereinafter, the effects of the present invention will be demonstrated by examples.

[0091]

Examples <Resin Synthesis Example> (Resin (1); Synthesis of linear polyester) Terephthalic acid: 664 parts by weight Polyoxypropylene- (2.2) -2.2-bis (4-hydroxyphenyl) ) Propane: 688 parts by weight ・ Ethylene glycol: 150 parts by weight

The above materials were placed in a two-liter four-necked flask equipped with a stirrer, a condenser and a thermometer, and 4 parts by weight of tetrabutyl titanate was added under a nitrogen gas stream to remove water generated by dehydration condensation. While 240
The reaction was carried out at normal temperature for 15 hours. Then reduce the pressure sequentially 5
The reaction was continued at mmHg. The reaction is ASTM E28-
The reaction was followed by a softening point according to 517, and the reaction was terminated when the softening point reached 85 ° C. The obtained polyester had a softening point: 95 ° C., an acid value: 9.8, and a T
g: 59 ° C.

(Resin (2); Synthesis of Branched Polyester) Terephthalic acid: 664 parts by weight Ethylene glycol: 150 parts by weight Neopentyl glycol: 166 parts by weight Trimethylolpropane: 80 parts by weight

The above materials were placed in a two-liter four-necked flask equipped with a stirrer, a condenser and a thermometer. Under a nitrogen gas stream, 4 parts by weight of tetrabutyl titanate was added to remove water generated by dehydration condensation. While 240
The reaction was carried out at a normal pressure for 10 hours. Then reduce the pressure sequentially 5
The reaction was continued at mmHg. The reaction is ASTM E28-
Traced by softening point according to 517, softening point is 145 ° C
When the reaction reached, the reaction was terminated. The obtained branched polyester had a softening point of 141 ° C., an acid value of 3.3 and a Tg in DSC measurement of 61 ° C.

Example 1 Production of Toner A In the following,% is% by weight unless otherwise specified. Resin (1) 40% Resin (2) 60% Symuler Fast Orange V (manufactured by Dainippon Ink and Chemicals, Inc .: Pigment orange 16) 3% Charge control agent TP-415 (manufactured by Hodogaya Chemical) 1% Purified carnauba Wax No. 13% (Acid value 5, Carnauba wax manufactured by Celerica NODA Co., Ltd.)

Each of the above-mentioned materials was preliminarily mixed with a Henschel mixer, melted and kneaded with a twin-screw kneader PCM30 made by Ikegai, and then ground and classified by a usual method to obtain an average particle size of 10.0 μm.
(Measured by a Coulter counter) was obtained.

To 100 parts by weight of the toner particles, 0.3 part by weight of RA200HS silica manufactured by Aerosil Co. was added.
The mixture was mixed with a Henschel mixer to obtain toner A.

Example 2 Preparation of Toner B Purified carnauba wax No. 1 in Example 1 A toner B was obtained in the same manner as in Example 1 except that wax 4 was used instead of 1.

Example 3 Production of Toner C Toner C was obtained in the same manner as in Example 1 except that the resin of Example 1 was changed to resin (1) only.

Example 4 Production of Toner D A toner D was obtained in the same manner as in Example 1 except that the resin of Example 1 was changed to only the resin (2).

Example 5 Preparation of Toner E Purified carnauba wax No. 1 of Example 1 Change to 1,
A toner E was obtained in the same manner as in Example 1, except that the polypropylene wax 550P was used. Example 6 Production of Toner F Toner F was obtained in the same manner as in Example 1, except that the pigment of Example 1 was changed to Hostaperm Orange GR (Pigmentorange 43, manufactured by Clariant Japan).

Preparation of Developer Each of the toners of Examples 1 to 6 was mixed with a carrier according to the following formulation to prepare a developer. (Blending) Toner (each of Examples 1 to 6) 7% Silicone-coated ferrite carrier 93% (Mixing method) Put each of the above toners and carriers in a polypropylene bottle having a diameter of 5 cm and a height of 6 cm, and place them at 285 rpm
For 10 minutes. Developer A using toner A,
Developer B using toner B, developer C using toner C, developer D using toner D, developer E using toner E, developer F using toner F, Each was produced.

Preparation of Print Sample Each developer described above was charged into a commercially available copying machine (XC-810, a copy machine manufactured by Xerox Co., Ltd.), and a print sample was printed on white plain paper.

[Evaluation 1]: Measurement of PCS value at 620 nm 620 nm using a color difference meter SE-2000 manufactured by Nippon Denshoku Co., Ltd.
, The reflectance of the printed portion and the blank portion were measured, and the PCS value was calculated. Example 1: 0.02 Example 2: 0.02 Example 3: 0.01 Example 4: 0.03 Example 5: 0.04 Example 6: 0.01 As described above, Examples 1 to Each of the print samples prepared using the toner No. 6 satisfies Expression 1 and has a low PC
It was found that the S value could be realized.

[Evaluation 2] Offset evaluation Commercially available copying machine (copier XC-810 manufactured by Xerox Corporation)
, An unfixed print image was prepared before passing through a fixing heat heat roll. The image is passed through a fixing heat roll (remodeled from a commercially available device) with a paper feed speed of 9 cm / sec, and there is an offset at that time (the heat roll is stained with toner, and the toner adhered to the roll adheres to the paper again). phenomenon)
While changing the temperature of the heat roll, the developer A, B,
Evaluation was performed using each of the toners C, D, E and F. The temperature range where no offset occurs was as follows. Example 1: 108-200 ° C Example 2: 108-210 ° C Example 3: 90-125 ° C Example 4: 120-210 ° C Example 5: 120-165 ° C Example 6: 108-200 ° C

[0106]

As described above, the printed matter for an optical reader according to the present invention is used for developing an electrostatic image containing a binder resin and an orange colorant or a mixture of a yellow colorant and a red colorant. The image information to be dropped out by the orange toner is printed on the print-receiving medium.
The reflectance of the printed part for dropout and the non-printed part when the printed matter is irradiated with light having a wavelength of m is expressed by the following formula 1: 1− (reflectance of printed part for dropout / reflectance of non-printed part) ≦ 0.04, so the production cost and production time for producing a small number of copies and many types of printed materials are reduced compared to the case of producing printed materials for optical readers by a printing method using a conventional ink. Can be significantly reduced. In addition, since a special orange toner is used for the image information to be dropped out, a high saturation orange dropout image can be obtained with less saturation compared to printed matter prepared using a normal full-color toner. Since the user can obtain a good feeling of use such that the dropout image can be clearly recognized, and at the same time, the value obtained by the above equation 1 can be made close to zero, a reading wavelength of about 620 nm is used. In the reading device, the dropout characteristics are improved, and the occurrence of reading errors can be reduced.

Claims (6)

[Claims] An image information to be dropped out is printed on a printing medium by an orange toner for developing an electrostatic image containing a binder resin and an orange colorant, or a mixture of a yellow colorant and a red colorant. In the printed matter for an optical reading device, the reflectance of the printed part for dropout and the non-printed part when the printed matter is irradiated with light having a wavelength of 620 nm is represented by the following formula 1: 1- ( (Reflectance / reflectance of non-printed portion) ≦ 0.04. 2. The method according to claim 1, wherein the orange colorant is C.I. I. Pigm
ent Orange 1,2,5,13,15,1
6, 17, 18, 19, 31, 34, 36, 38, 4
The printed matter for an optical reader according to claim 1, wherein the printed matter is at least one selected from the group consisting of 0, 42, 43, 51, 60, and 62. 3. The method according to claim 1, wherein the yellow colorant is C.I. I. Pigm
ent Yellow 1,3,4,5,6,12,1
3,14,15,16,17,18,24,55,6
5,73,74,81,83,87,93,94,9
5,97,98,100,101,104,108,1
09, 110, 113, 116, 117, 120, 12
3,128,129,133,138,139,14
7,151,153,154,155,156,16
8, 169, 170, 171, 172, 173 and 1
80, which is at least one pigment selected from the group consisting of: I. Pigment
Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10,
12, 14, 15, 17, 18, 22, 23, 31, 3
7, 38, 41, 42, 48: 1, 48: 2, 48:
3,48: 4,49: 1,49: 2,50: 1,52:
1,52: 2,53: 1,54,57: 1,58: 4
60: 1, 63: 1, 63: 2, 64: 1, 65,6
6, 67, 68, 81, 83, 88, 90, 90: 1,
112, 114, 115, 122, 123, 133, 1
44,146,147,149,150,151,16
6,168,170,171,172,174,17
5,176,177,178,179,185,18
7,188,189,190,193,194,20
2,208,209,214,216,220,22
1,224,242,243,243: 1,245,2
The printed matter for an optical reader according to claim 1, wherein the printed matter is at least one pigment selected from the group consisting of 46 and 247. 4. The printed matter for an optical reader according to claim 1, wherein the binder resin is a polyester resin. 5. The orange toner for developing an electrostatic image,
The printed matter for an optical reader according to any one of claims 1 to 4, further comprising a wax containing a higher fatty acid ester compound and / or an aliphatic alcohol compound as a main component as a release agent. 6. The release agent is at least one selected from the group consisting of carnauba wax, montan ester wax, rice wax, scale insect wax and compounds represented by the following general formulas 1 to 5. The printed matter for an optical reader according to claim 5, wherein: <General formula 1> (In the formula, R1 and R2 are a hydrocarbon group having 1 to 40 carbon atoms, and at least one of them represents a chain hydrocarbon group having 12 or more carbon atoms.) <General formula 2> (Wherein, R1, R2 and R3 are hydrocarbon groups having 1 to 40 carbon atoms, at least one of which has 1 carbon atom)
(Indicating two or more chain hydrocarbon groups.) <General formula 3> (Wherein, R1, R2 and R3 are hydrocarbon groups having 1 to 40 carbon atoms, at least one of which has 1 carbon atom)
(Indicating two or more chain hydrocarbon groups) <General Formula 4> (Wherein, R1 is a hydrocarbon group having 12 to 40 carbon atoms,
R2 is a hydrocarbon group having 1 to 40 carbon atoms; a + b = 4
Wherein a represents an integer of 1 to 4 and b represents an integer of 0 to 3) <General formula 5> (Wherein, R1, R2 and R3 are hydrocarbon groups having 1 to 40 carbon atoms, at least one of which is a hydrocarbon group having 12 carbon atoms)
A and c are integers from 0 to 2 and a + c = 2; b is an integer from 1 to 4; d is 1 or 2, and e = d- 1).