JP2003192953A - Oil-based ink for electrostatic ink-jet printing - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrostatic ink-jet oil-based ink capable of stable blow out of ink, and clear and intensive image printing on a number of sheet of papers. <P>SOLUTION: The electrostatic ink-jet oil-based ink containing at least copolymerized resin particles prepared by copoplymerization and granulation of non-aqueous carrier solution composed of (A) a monofunctional monomer soluble in a non-aqueous solvent and becomes insoluble by polymerization, (B) a monomer having an amino group and acidic groups having at least each one -PO<SB>3</SB>H<SB>2</SB>and -SO<SB>3</SB>H groups in the same monomer, and (P) a stable resin for dispersion containing a specific component. <P>COPYRIGHT: (C)2003,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] The present invention relates to an electrostatic type (electrostatic attraction).
(Form or electrostatic suction type) form an image by inkjet recording method
Oil-based ink for electrostatic ink jet
Related to the link. [0002] 2. Description of the Related Art Inkjet recording is low noise and high speed printing.
This is a recording method that allows writing, and has recently been spreading rapidly
It is a recording method. Inkjet recording is highly fluid
Liquid ink is ejected from fine nozzles and recorded on recording paper
On-demand (voluntary injection) and conti
There is a method of near (continuous injection). Furthermore, the continuous type is electrostatic.
Method (Sweet type, Hertz type), On-demand type
Piezoelectric method, thermal ink jet method, electrostatic acceleration
A recording method called a mold is known. On-demand ink using electrostatic force
Susumu Ichinose, Yuji Ohba, JET
Journal vol.J66-C (No.1), p47 (1983), Tadayoshi Ohno, Mizuguchi
Mamoru, published in IEICE vol.10, (No.3), p157 (1981), etc.
Electrostatic acceleration type ink jet or slit printer
A method called a network is known.
For example, JP-A Nos. 56-170, 56-4467, 5
7-151374 and the like. This is
From the tank to the inner surface of the slit-shaped ink holder.
Supply ink to slit-like ink chambers with poles
In addition, a high voltage is selectively applied to these electrodes.
To the recording paper close to the slit and near the electrode.
Ink is ejected and recorded. Also, no slit-like recording head is used.
As another method, JP-A-61-211048 discloses
Is a hole in a film-like ink support having a plurality of micropores.
The ink is filled in and voltage is selectively applied by the multi-needle electrode.
And means for moving the ink in the hole to the recording paper is disclosed.
ing. These ink flying principles were arranged
Due to the high voltage applied to the electrode, the ink in contact with the electrode
The charge is injected and the ink near the electrode becomes charged.
Therefore, it is interpreted that the electrostatic force is generated and ink is ejected.
It is. Therefore, ink is usually not charged.
Only when voltage is applied, the ink near the electrode is energized.
The discharge force is obtained by charging more. Used in these methods
The ink used is 10⁶To 10⁸Electrical resistance of about Ω · cm
Those with resistance are used. Low electrical resistance in water
Therefore, in general, a colorant consisting of a dye is added to the oily solvent.
Disperse with a dispersion aid such as a surfactant to adjust the electrical resistance.
An ordered one is used. Further, as an oil-based ink to be used, its viscosity
And a method of controlling the specific resistance (Japanese Patent Publication No. 52-13127)
No.), the relative dielectric constant of the dispersion medium used in the ink and the specific resistance of the ink
Method for controlling resistance (Japanese Patent Laid-Open No. 53-29808), oiliness
Change the type of ink dispersion medium or ink composition
As a method of containing a specific compound (Japanese Patent Laid-Open No. 3-79)
677, JP-A-3-64377, JP-A-4-202
386, JP-A-7-109431) and the like have been proposed
Yes. However, these prior arts preserve oil-based inks
Stability, reproducibility of recorded images during repeated use, ink reception
Ink bleed resistance on the material or nozzle and ink
Clogging resistance in the ink supply path, ink ejection stability, etc.
Is still not fully satisfactory, and more performance-oriented
Top is desired. On the other hand, another electrostatic ink jet technology is
It is disclosed in WO93 / 11866. This person
The method uses charged particles or an electric field charged in an insulating liquid.
The ink in which the particles exhibiting the properties are dispersed is supplied to the ink ejection device.
At the tip of the discharge electrode for discharging and discharging ink.
Particles in the ink meniscus that form a kmeniscus
A recording medium is placed, which is concentrated by electrophoresis.
An electric field is formed between the counter electrode and discharge electrode
It has a series of steps of flying the particles. Unlike the conventional method, the ink nozzle structure is
Unnecessary features of this method include dispersed particles such as pigments
Ink can be ejected in the size of small droplets of about several μm.
The discharged droplets can be concentrated to a high concentration state.
In addition, the droplet size can be changed by controlling the ejection signal.
For example, the dot size of the image can be changed. Follow
Drawing images based on light and water resistant pigments and
High-resolution, high-density, clear image formation of continuous halftone images
Is possible. The oil-based ink used has an electrical resistance value of 1
0⁹Insoluble and chargeable in insulating liquids of Ω · cm or more
A material containing particles and a charge agent is WO95 / 140.
No. 4, WO 96/10058. Further
Specifies the charge amount of charged particles or the average particle size
(Japanese Patent Laid-Open Nos. 9-193389 and 8-291)
No. 267) or the thermal properties of the dried ink composition
A standardized one (Japanese Patent Laid-Open No. 9-137094) is proposed.
It is. However, these oil-based inks are used.
When ink jet recording was performed, anxiety of ink ejection
Qualitative or insufficient concentration of pigment particles in the ink, resulting in shape
Missing images, blurring of images, or
The image density is insufficient (particularly, the solid image portion). Also save
A place where ink that is fresh when used over time
The conditions for discharging and discharging (applied voltage, etc.) fluctuate or concentrate
As a result, the discharge rate changes significantly and the resulting image is
The problem of changing with the storage state of the link occurred. On the other hand, recent development of office equipment and progress of OA
With the exhibition, in the light printing field, images on a water-resistant support
Plate making by various methods to a lithographic printing plate precursor having a receiving layer, that is,
Plate making method to create offset printing plate by image formation
As one of the plate making methods, inkjet
Plate making is also done by the method. Conventional oil-based ink
To actually print a printing plate on which a clear image is formed.
As a result, a clear printed matter was obtained without missing the image area.
The maximum number of copies that can be printed is limited to a few hundred.
It was enough. That is, for offset printing, ink particles
There is a problem that the fixing strength of the image is insufficient. [0012] Accordingly, it is an object of the present invention.
Ink ejection stability, sharp image formation and image strength
Provide oil-based inks for electrostatic inkjet
Is Rukoto. Another object of the present invention is to print clear images.
An electrostatic ink that can form a printing plate that can print a large number of objects.
An oil-based ink for ink jet is provided. Main departure
Other objectives of Ming are excellent in redispersibility and storage stability of dispersed particles.
Ink supply path is not clogged and ink discharge is
To provide electrostatic ink jet ink
It is. [0013] The above object is achieved by the following configuration.
Was found to be achieved. (1) Electric resistance 10⁹Ω · cm or more and dielectric constant 3.5
Disperse at least the chargeable resin particles in the following non-aqueous carrier liquid.
Scattered electrostatic ink jet ink
In the non-aqueous solvent, the dispersed resin particles are
Soluble in non-aqueous solvent and insoluble by polymerization
(B) the following general formula
An amino group represented by (I) and -PO_ThreeH₂Group and -SO
_ThreeThere are few acidic groups selected from H groups in the same molecule.
Copolymerizable with the above monomer (A) containing at least one kind
At least one monofunctional monomer and (P)
Non-water which is a polymer containing a component represented by the formula (PI)
Contains at least one dispersion stabilizing resin that is soluble in the solvent
Copolymer obtained by polymerizing and granulating solution
Electrostatic ink jet characterized by resin particles
Oil-based ink. [0014] [Formula 4] In the general formula (I), R¹And R²Are the same
But it may be different, hydrogen atom or carbon having 1 to 22 carbon atoms
Represents a hydride group or R¹And R²Together with the nitrogen atom
A ring may be formed. [0016] [Chemical formula 5]In general formula (PI), A^1pIs -COO-,-
OCO-,-(CH₂)_aCOO-,-(CH₂)_aOCO
-, -O-, or [0018] [Chemical 6] (Where E is a direct bond, -O-, -OCO
-Or -COO-). a is an integer of 1 to 12
Represents. L is an alkyl group having 8 to 32 carbon atoms or carbon atoms
Represents 8-32 alkenyl groups. p¹And p²Are each other
May be the same as or different from each other.
Child, cyano group, hydrocarbon group having 1 to 7 carbon atoms, -COO-
D¹Or -COO-D via a hydrocarbon group¹Represents
(Where D¹Is a hydrogen atom or a C1-C22 hydrocarbon
Indicates the basis). The following are further preferred embodiments of the present invention.
The (2) The dispersion stabilizing resin (P) is a fragment of the polymer main chain.
In the substituent of the terminal or polymer repeating component, the following general formula
It is formed by bonding a polymerizable double bond group represented by (PII).
(1) for electrostatic ink jets
Oil-based ink. [0021] [Chemical 7] In the general formula (PII), A^2pIs -COO-,-
OCO-,-(CH₂)_bCOO-,-(CH₂)_bOCO
-, -O-, -SO₂-, -CONHCOO-, -CO
NHCONH-, -CON (E^1p)-, -SO₂N (E
^1p)-(Where E^1pIs a hydrogen atom or having 1 to 22 carbon atoms
A hydrocarbon group, b represents an integer of 1 to 4) or [0023] [Chemical 8] (Here E^2pIs a direct bond, -O-, -OCO
-Or -COO-). q¹And q²Are each other
May be the same or different, and each of p in formula (PI)¹,
p²It is synonymous with. (3) The dispersed resin particles are further separated into single particles.
It is represented by the following general formula (IV) that can be copolymerized with the monomer (A).
A solution containing at least one monofunctional monomer (C)
Copolymer resin particles obtained by polymerizing and granulating
The electrostatic method according to (1) or (2), wherein
Oil-based ink for inkjet. [0026] [Chemical 9] In general formula (IV), U¹Is -COO-, -C
ONH-, -CON (E²)-(Where E²Is an aliphatic group
Or a substituent represented by the following general formula (IVa)):
-OCO-, -CONHCOO-, -CH₂COO-,
-(CH₂)_SOCO-, where s is an integer from 1 to 4
-O- or -C₆H_Four-COO- is represented. d¹
And d²Are the same or different and each represents a hydrogen atom,
Alkyl group, halogen atom, cyano group, -COO-E^ThreeMa
Or -CH₂COO-E^Three(Here E^ThreeRepresents an aliphatic group
). E¹Is an aliphatic group with 8 or more carbon atoms or total atoms
Number of children 8 or more (however, directly bonded to carbon atom or nitrogen atom)
Substitution represented by the following general formula (IVa)
Represents a group. Formula (IVa) -(A¹-B¹)_m-(A²-B²)_n-R⁴¹ In general formula (IVa), R⁴¹Is a hydrogen atom or a C1-C1
Represents an aliphatic group of 8; B¹And B²Is the same or different
-O-, -S-, -CO-, -CO, respectively. ₂-,-
OCO-, -SO₂-, -N (R⁴²)-, -CON (R
⁴²)-, -N (R⁴²) CO-, -N (R⁴²) SO₂−,
-SO₂N (R⁴²)-, -NHCO₂-Or -NHCO
NH— (where R⁴²R⁴¹Is synonymous with
) A¹And A²Are the same or different and the following general
Group represented by formula (IVb) and hydrocarbon having 1 to 18 carbon atoms
It represents at least one group selected from the group. m
And n are the same or different and each represents an integer of 0 to 4
Represent. However, the sum of m and n cannot be zero. [0028] Embedded image In the general formula (IVb), B^ThreeAnd B^FourIs the same
Or differently, above B¹, B²Is synonymous with A^FourIs charcoal
Represents a hydrocarbon group having a prime number of 1 to 18, R⁴³Is the above R⁴¹Same as
It is righteousness. p represents an integer of 0 to 4. [0030] BEST MODE FOR CARRYING OUT THE INVENTION The electrostatic ink jet ink of the present invention will be described below.
The oil-based ink for ink jet will be described. Electricity used in the present invention
Qi resistance 10⁹Non-water bearing with Ω · cm or more and dielectric constant of 3.5 or less
The body fluid is preferably linear or branched fat
Aromatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and
These hydrocarbon halogen substitution products, silicone liquids, etc.
Or silicone oil. For example, as the hydrocarbon solvent, penta-
, Isoheptane, octane, isooctane, decane,
Isodecane, decalin, nonane, dodecane, isododeca
, Cyclohexane, cyclooctane, cyclodecane,
Benzene, toluene, xylene, mesitylene, isopa
-E, Isopar G, Isopar H, Isopar L (A
Isopar; trade name of Exxon), Shellsol 70,
Shell sol 71 (shell sol; quotient of Shell Oil Co., Ltd.)
Product name), Amsco OMS, Amsco 460 solvent (Ams
Ko; a brand name of Spirits). Fully used as a halogen-substituted hydrocarbon solvent
There is an orocarbon solvent, for example C₇F₁₆, C₈F₁₈Na
Which C_nF_{2n + 2}Perfluoroalkanes represented by
Tomo 3M “Florinart PF5080”, “Flori
NART PF5070 "(trade name), etc.), fluorine inert
Liquid (Sumitomo 3M “Fluorinert FC Series”
Product name)), fluorocarbons (DuPont Japan
“Crytox GPL Series” manufactured by Mited (product)
Name), etc.), CFCs ("HCF" manufactured by Daikin Industries, Ltd.)
C-141b "(product name), etc.), [F (CF₂)_FourCH₂C
H₂I], [F (CF₂)₆I] etc.
Bons ("D-14 from Daikin Fine Chemical Laboratory"
20 ”,“ I-1600 ”(trade name), etc.). Silicone liquid, silicone oil
Con solvents include dialkylpolysiloxanes (for example,
Hexamethyldisiloxane, tetramethyldisiloxy
Sun, octamethyltrisiloxane, hexamethyltri
Siloxane, heptamethyltrisiloxane, decamethyl
Tetrasiloxane, trifluoropropyl heptamethylate
Lisiloxane, diethyltetramethyldisiloxane
Etc.), cyclic dialkylpolysiloxanes (eg hexa
Methylcyclotrisiloxane, hexamethylcyclotri
Siloxane, octamethylcyclotetrasiloxane, te
Tramethylcyclotetrasiloxane, tetra (trifluoro)
Ropropyl) tetramethylcyclotetrasiloxane,
Etc.), methylphenyl silicone oil (for example, KF5)
6, KF58 (trade name manufactured by Shin-Etsu Silicon Co., Ltd.) etc.
Can be mentioned. In the present invention, these solvents are used alone or as a mixture.
Used together. In addition, the electrical resistance of such a non-aqueous carrier liquid
The upper limit of 10¹⁶The lower limit of dielectric constant is about Ωcm.
It is preferably about 1.80. The most important structure in the oil-based ink of the present invention.
Resin particles (hereinafter referred to as “non-aqueous dispersion resin particles”)
Called "child", "dispersed resin particles" or "latex particles"
In certain cases, certain components (one
Presence of dispersion stabilizing resin (P) containing general formula (PI))
Below, at least one monofunctional monomer (A), amino
Each containing a group and a specific acidic group in the same molecule.
At least one of the functional monomers (B), preferably further
Monofunctional containing a specific substituent represented by the general formula (IV)
By polymerizing at least one of the polymerizable monomers (C)
Is polymerized and granulated. The resin particles of the present invention are used as copolymer components.
Monomers containing a mino group and a specific acidic group in the same molecule
By containing (B), the particles are positively detected, and the particles
The charge amount of the dispersed particles in the ink further increases.
Ratio (charge fraction of particles) increases and environmental conditions
(From low temperature / low humidity to high temperature / high humidity)
Or maintain a stable charge even after long-term storage
it can. This ensures consistently high-quality images.
be able to. As the non-aqueous solvent, basically,
Can be used if it is miscible with non-aqueous carrier liquid of oil-based ink
Noh. That is, when manufacturing dispersed resin particles
The solvent to be used is one that is miscible with the carrier liquid.
Preferably linear or branched aliphatic carbonization
Hydrogen, alicyclic hydrocarbons, aromatic hydrocarbons and these
And halogen-substituted products. For example, octane, iso
Octane, decane, isodecane, decalin, nonane, do
Decane, isododecane, isopar E, isopar G,
Isopar H, Isopar L, Shellsol 70, Chez
Lusol 71, Amsco OMS, Amsco 460 solvent, etc.
Are used alone or in combination. In combination with these organic solvents,
Solvents that can be used include alcohols (eg, ethyl alcohol).
Coal, propyl alcohol, butyl alcohol, ethyl
Lenglycol monomethyl ether, fluorinated alcohol
Etc.), ketones (for example, methyl ethyl ketone, aceto
Phenone, cyclohexanone, etc.), carboxylic acid ester
(E.g., methyl acetate, ethyl acetate, propyl acetate,
Butyl acetate, methyl propionate, ethyl propionate
, Ethylene glycol monomethyl ether acetate
Etc.), ethers (eg, dipropyl ether, ethyl)
Lenglycol dimethyl ether, tetrahydrofura
, Dioxane, etc.), halogenated hydrocarbons (for example,
Chloroform, dichloroethane, methyl chloroform
Etc.). These organic solvents used in combination are heavy.
It is desirable to distill off after heating or under reduced pressure.
However, as a latex particle dispersion,
Ink resistance is 10⁹Ωcm or more, dielectric constant
If it is within a range that can satisfy the condition of 3.5 or less,
Don't be. Usually, the same as the carrier liquid at the stage of manufacturing the resin dispersion.
It is preferable to use such a solvent, and as described above, linear
Or branched aliphatic hydrocarbons, alicyclic hydrocarbons,
Aromatic hydrocarbon, halogenated hydrocarbon, etc.
The The monofunctional monomer (A) in the present invention is:
Soluble in non-aqueous solvent but insolubilized by polymerization
Any monofunctional monomer may be used. Specifically
Is, for example, a monomer represented by the following general formula (V)
It is. [0042] Embedded image In general formula (V), V²Is -COO-, -O
CO-, -CH₂OCO-, -CH₂COO-, -O-,
-CONHCOO-, -CONHOCO-, -SO
₂-, -CON (Q¹)-, -SO₂N (Q¹)-Or Fe
Nylene group (hereinafter, phenylene group is referred to as “-Ph-”)
Sometimes. The phenylene group is 1,2-, 1,3.
Includes-and 1,4-phenylene groups. ).
Where Q¹Is a hydrogen atom or substituted of 1 to 8 carbon atoms
Optionally aliphatic groups (eg methyl, ethyl
Group, propyl group, butyl group, 2-chloroethyl group, 2-
Bromoethyl group, 2-cyanoethyl group, 2-hydroxy
Ethyl, benzyl, chlorobenzyl, methylben
Dil group, methoxybenzyl group, phenethyl group, 3-phen
Nylpropyl group, dimethylbenzyl group, fluorobenzyl
Group, 2-methoxyethyl group, 3-methoxypropyl group
Etc.). T is a hydrogen atom or a substituted group having 1 to 6 carbon atoms.
Aliphatic groups that may be substituted (for example, methyl, ethyl,
Lopyl group, butyl group, 2-chloroethyl group, 2,2-di
Chloroethyl group, 2,2,2-trifluoroethyl group, 2
-Bromoethyl group, 2-hydroxyethyl group, 2-hydride
Loxypropyl group, 2,3-dihydroxypropyl group,
2-hydroxy-3-chloropropyl group, 2-cyanoe
A til group, a 3-cyanopropyl group, a 2-nitroethyl group,
2-methoxyethyl group, 2-methanesulfonylethyl
Group, 2-ethoxyethyl group, trimethoxysilylpropylene
Group, 3-bromopropyl group, 4-hydroxybutyl
Group, 2-furfurylethyl group, 2-thienylethyl group,
2-carboxyethyl group, 3-carboxypropyl group,
4-carboxybutyl group, 2-carboxyamidoethyl
Group, 2-N-methylcarboxamidoethyl group, cyclo
Pentyl group, chlorocyclohexyl group, dichlorohexyl
Group). A¹And a²Are the same or different from each other
Preferably a hydrogen atom or a halogen atom (eg
Chlorine atom, bromine atom, etc.), cyano group, 1 to 3 carbon atoms
Alkyl group (for example, methyl group, ethyl group, propyl group)
Etc.), -COO-Q²Or -CH₂-COO-Q²[This
Q here²Is a hydrogen atom or an optionally substituted carbon atom
0 or less hydrocarbon group (eg, alkyl group, alkenyl group)
Represents a group, an aralkyl group, an aryl group or the like]. As a specific monofunctional monomer (A),
For example, an aliphatic carboxylic acid having 1 to 6 carbon atoms (acetic acid, propylene
On acid, butyric acid, monochloroacetic acid, trifluoropropion
Vinyl esters or allyl esters of acids etc .;
Acrylic acid, methacrylic acid, crotonic acid, itaconic acid,
C1-C4 substitution of unsaturated carboxylic acids such as maleic acid
Alkyl esters or amides (al
Examples of the kill group include a methyl group, an ethyl group, a propyl group,
Butyl group, 2-chloroethyl group, 2-bromoethyl group,
2-fluoroethyl group, trifluoroethyl group, 2-hydro
Xylethyl group, 2-cyanoethyl group, 2-nitroethyl
Group, 2-methoxyethyl group, 2-methanesulfonylethyl
Group, 2-benzenesulfonylethyl group, 2-carboxy
Cyethyl group, 4-carboxybutyl group, 3-chloropro
Pill group, 2-hydroxy-3-chloropropyl group, 2-
Furfurylethyl group, 2-thienylethyl group, 2-cal
Styrene derivatives (eg, boxyamidoethyl group)
Tylene, vinyl toluene, α-methylstyrene, vinyl
Naphthalene, chlorostyrene, dichlorostyrene, bromine
Mostyrene, vinylbenzenecarboxylic acid, chloromethyl
Styrene, hydroxymethyl styrene, methoxymethyl
Styrene, vinyl benzene carboxamide, vinyl base
Senesulfamide, etc.); acrylic acid, methacrylic acid,
Unsaturated carbo such as crotonic acid, maleic acid, itaconic acid
Acid; Maleic acid, Itaconic acid cyclic acid anhydride;
Ronitrile; methacrylonitrile; including polymerizable double bond groups
Heterocyclic compounds (specifically, for example, edited by the Society of Polymer Science
"Polymer Data Handbook-Basics", p175
184, compounds described in Yafu Kaze (1986), for example
N-vinylpyridine, N-vinylimidazole, N
-Vinylpyrrolidone, vinylthiophene, vinyltetra
Hydrofuran, vinyl oxazoline, vinyl thiazole
And N-vinylmorpholine). Monomer
(A) may use 2 or more types together. Next, the monomer (A) used in the present invention and
The copolymerizable monofunctional monomer (B) will be described.
The monomer (B) is an amino represented by the above general formula (I)
Group, and -PO_ThreeH₂Group and -SO_ThreeSelected from the H group
At least in the same molecule (in the monomer)
It is a monomer containing one kind. Monomer (B) is an intramolecular
An amino group and an acidic group form an inner salt, and the amino group is
Ammonium groups and acidic groups as described above are dissociated as follows
Exist as a group. [0048] Embedded image In the formula (I), R¹And R²Are the same
May be different, preferably a hydrogen atom or 1 to 2 carbon atoms
2 optionally substituted alkyl groups (eg, methyl group,
Ethyl, propyl, butyl, heptyl, hex
Group, octyl group, nonyl group, decyl group, dodecyl group,
Tridecyl, tetradecyl, hexadecyl, oct
Tadecyl group, eicosanyl group, docosanyl group, 2-chloro
Roethyl group, 2-bromoethyl group, 2-cyanoethyl
Group, 2-methoxycarbonylethyl group, 2-methoxyethyl
Til group, 3-bromopropyl group, etc.), having 4 to 18 carbon atoms
Optionally substituted alkenyl groups (eg 2-methyl-
1-propenyl group, 2-butenyl group, 2-pentenyl group
Group, 3-methyl-2-pentenyl group, 1-pentenyl
Group, 1-hexenyl group, 2-hexenyl group, 4-methyl
2-hexenyl, decenyl, dodecenyl, tri
Decenyl, hexadecenyl, octadecenyl, lithium
Norrel group, etc.), C 7-12 optionally substituted ara
Alkyl group (for example, benzyl group, phenethyl group, 3-phenyl group)
Enylpropyl group, naphthylmethyl group, 2-naphthyl group
Til, chlorobenzyl, bromobenzyl, methyl
Benzyl group, ethylbenzyl group, methoxybenzyl group,
Dimethylbenzyl group, dimethoxybenzyl group, etc.), carbon
An alicyclic group of 5 to 8 which may be substituted (for example, cyclo
Hexyl group, 2-cyclohexylethyl group, 2-cyclo
Pentylethyl group etc.) or substituted with 6-12 carbon atoms
Aromatic group (for example, phenyl group, naphthyl group,
Tolyl, xylyl, propylphenyl, butylphenyl
An phenyl group, an octylphenyl group, a dodecylphenyl group,
Methoxyphenyl group, ethoxyphenyl group, butoxif
Enyl group, decyloxyphenyl group, chlorophenyl
Group, dichlorophenyl group, bromophenyl group, cyanophenyl group
Enyl group, acetylphenyl group, methoxycarbonyl group
Enyl group, ethoxycarbonylphenyl group, butoxyca
Rubonylphenyl group, acetamidophenyl group, propylene
Oamidophenyl group, dodeciloylamidophenyl group
Etc.). Also, R¹And R²Together with the nitrogen atom
It represents an organic residue that forms a ring. This organic residue is a heterogeneous
Contains children (eg oxygen, nitrogen, sulfur)
May be. Examples of the cyclic group to be formed include morpho
Lino group, piperidino group, pyridinyl group, imidazolyl
Group, quinolinyl group and the like. The amino group of formula (I) and the specific acidic group are
A plurality of monomers (B) may be contained in the molecule.
However, the amino group may not be less than the number of specific acidic groups.
Preferably, particularly preferably the amino group and the specific acidic group are separated.
Each one is contained in the child. Monomer (A) and monomer used in the present invention
(B) If necessary, the monomer (C) described below is polymerized.
It is copolymerized by the reaction and becomes a resin insoluble in a non-aqueous solvent. Monomer
(B) is preferably 1 to 20 with respect to the total amount of all monomers.
It is 2 to 15% by mass, more preferably 2 to 15% by mass. Next, the dispersion stabilizing resin used in the present invention.
(P) will be described. In the present invention, in a non-aqueous solvent
In a non-aqueous solvent insoluble polymer produced by polymerizing monomers
Dispersion stabilization tree used to make a stable resin dispersion
Fat (P) is a repeating unit represented by the general formula (PI).
Polymer soluble in non-aqueous solvent containing at least one kind of position
It is. The component represented by the general formula (PI) is added to a non-aqueous solvent.
It is a component that becomes soluble. In the formula (PI), A^1pIs preferably -CO
O-, -OCO-, -CH₂COO-, -CH₂OCO-
Or -O-, more preferably -COO-, -OC
O-, -CH₂Represents COO-. L is preferably substituted with 8 to 32 carbon atoms.
It may represent an alkyl group or an alkenyl group. Substituent
As, for example, a halogen atom (for example, a fluorine atom,
Chlorine atom, bromine atom, etc.), -OD², -COO-D²,
-OCO-D²(Where D²Is C 6-22 alk
For example, hexyl, octyl, decyl
Group, dodecyl group, hexadecyl group, octadecyl group, etc.
And the like. More preferably, L is carbon number
10 to 22 alkyl groups or alkenyl groups are represented. Example
For example, decyl, dodecyl, tridecyl, tetradecyl
Sil group, hexadecyl group, octadecyl group, docosyl
Group, eicosyl group, decenyl group, dodecenyl group, tride
Cenyl, tetradecenyl, pentadecenyl, hex
Sadecenyl group, heptadecenyl group, octadecenyl group,
A dococenyl group etc. are mentioned. P¹And p²Are the same or different from each other
Preferably, a hydrogen atom or a halogen atom (for example,
Fluorine atom, chlorine atom, bromine atom, etc.), cyano group,
An alkyl group having 1 to 3 carbon atoms, -COO-D^ThreeOr -C
H₂COO-D^Three(Where D^ThreeIs aliphatic having 1 to 22 carbon atoms
Group, for example, methyl group, ethyl group, propyl group,
Butyl, hexyl, octyl, decyl, dodecyl
Group, tridecyl group, tetradecyl group, hexadecyl group
Group, octadecyl group, docosyl group, pentenyl group, hex
Senyl group, heptenyl group, octenyl group, decenyl group,
Dodecenyl group, tetradecenyl group, hexadecenyl group,
Octadecenyl group, etc., and these aliphatic groups are
Which may have the same substituent as represented by L)
The More preferably, p¹And p²Respectively
A C 1-3 alkyl group (for example, a methyl group, an
Til group, propyl group, etc.), -COO-D^FourOr -CH₂
COO-D ^Four(Where D^FourIs alkyl having 1 to 12 carbons
Group or alkenyl group, for example, methyl group, ethyl
Group, propyl group, butyl group, hexyl group, octyl
Group, decyl group, dodecyl group, pentenyl group, hexenyl
Group, heptenyl group, octenyl group, decenyl group, etc.
These alkyl groups and alkenyl tombs are represented by L above.
Which may have the same substituent as that described above. The dispersion stabilizing resin (P) of the present invention is preferred.
Or equivalent to the repeating unit represented by the above general formula (PI)
And another monomer that can be copolymerized with the monomer.
A copolymer containing copolymer components obtained by copolymerization.
is there. Other monomers that can be copolymerized are polymerizable.
Any one containing a double bond group can be used.
Such as rilic acid, methacrylic acid, crotonic acid, itaconic acid
Saturated carboxylic acid; an ester of an unsaturated carboxylic acid having 6 or less carbon atoms
Steal derivatives or amide derivatives;
Nyl esters or allyl esters; styrene
Methacrylonitrile; acrylonitrile;
Examples thereof include a heterocyclic compound containing a heavy bond group. More specific
Specifically, the same compound as the insoluble monomer (A) described above.
Thing etc. are mentioned. Polymer component in dispersion stabilizing resin (P)
Among them, the component of the repeating unit represented by the general formula (PI) is heavy.
It is preferable that it is at least 50% by mass or more in all combined components.
60% by mass or more, more preferably 70% by mass or more.
Above. In the dispersion stabilizing resin (P), non-water
Copolysynthesis represented by the general formula (PI) that is soluble in a solvent
Other monomers that can copolymerize with the
A polymerization component corresponding to the monomer (A)
Either copolymerization or block copolymerization may be used. Like
Or block copolymerization. The dispersion stability of the present invention
The resin for resin (P) does not have a crosslinked structure between polymer main chains. Further, the dispersion stabilizing resin (P) of the present invention is preferred.
As a preferred embodiment, one end of a polymer main chain or a polymer
In the substituent of the repetitive component constituting the above formula (PI)
It is formed by bonding a polymerizable double bond group represented by I)
(Hereafter, it may be called dispersion stabilizing resin (PG).
This polymerizable double bond group constitutes the dispersed resin particles.
Any functional group that is copolymerizable with the monomer (A) may be used. In the formula (PII), A^2pIs -COO-, -OC
O-,-(CH₂)_bCOO-,-(CH₂)_bOCO-,-
O-, -SO₂-, -CONHCOO-, -CONHC
ONH-, -CON (E^1p)-, -SO₂N (E^1p) −
(Here E^1pIs a hydrogen atom or an alkyl having 1 to 22 carbon atoms.
Or b represents an integer of 1 to 4) or [0062] Embedded image (Here E^2pIs a direct bond, -O-, -OCO
-Or -COO-). Q¹And q²Are the same or different from each other
P in each formula (PI)¹, P²It is synonymous with. q
¹And q²It is preferable that one of these is a hydrogen atom
That's right. In addition, A^2p-CON (E^1p)
-, -SO₂N (E^1pE in the linking group of^1pLike
Or a hydrogen atom or a methyl group, an ethyl group, a propyl group,
Butyl, pentyl, hexyl, heptyl, oct
An alkyl group such as a til group, a decyl group, or a dodecyl group is represented. A polymerizable double bond group is attached to one end of the polymer main chain.
Examples of the bound resin (PG) include, for example, the following general
What is shown by a formula (Pa) is mentioned. [0067] Embedded image In the general formula (Pa), except for G, the formula (PI)
And (PII) is synonymous with each symbol. G is the main polymer
A bond directly linked to one end of the chain, or any linking group
Represents a bonding group. The bonding group is a carbon atom-carbon atom bond.
(Single bond or double bond), carbon atom-heteroatom
Bond (for example, oxygen atom, sulfur atom
Child, nitrogen atom, silicon atom, etc.), heteroatom-heterogen
It is composed of any combination of atomic groups of child bonds
The For example, [0070] Embedded imageZ¹, Z²Are a hydrogen atom and a halogen atom, respectively.
(For example, fluorine atom, chlorine atom, bromine atom, etc.), shear
Group, hydroxyl group, alkyl group (for example, methyl
Group, ethyl group, propyl group, etc.). z^Three, Z^FourEach
A hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms (for example,
Til, ethyl, propyl, butyl, pentyl
Group, hexyl group, benzyl group, phenethyl group, phenyl
Group, tolyl group, etc.) or -Oz^Five(z^FiveIs z^ThreeCharcoal in
Which is synonymous with a hydrogen fluoride group). Bonded to one end of the polymer main chain as described above
About the polymerizable double bond group represented by the general formula (PII),
This is specifically shown below. However, in the following specific examples:
A is -H, -CH_ThreeOr -CH₂COOCH_ThreeRepresents
B is -H or -CH_ThreeRepresents. N is 2 to 10
Represents an integer, m represents 2 or 3, t represents 1, 2 or
3, p represents an integer of 1 to 4, q represents 1 or 2
Represent. [0073] Embedded image [0074] Embedded image[0075] Embedded image [0076] Embedded imageA polymerizable double bond group is attached to one end of the polymer main chain.
The dispersion stabilizing resin (PG) of the present invention formed by bonding is conventionally used.
Known radical polymerization (eg iniferter method), anio
Living by cationic polymerization or cationic polymerization
React reagents containing various double bond groups at the end of the polymer.
Or specially at the end of this living polymer
Certain reactive groups (eg -OH, -COOH, -SO
_ThreeH, -NH₂, -SH, -PO_ThreeH₂, -NCO, -NC
S, [0078] Embedded image -COCl, -SO₂Cl etc.)
After reacting the reagent, polymerizable double bond by polymer reaction
A method of introducing a group (method by ionic polymerization), or
A polymerization initiator containing the specific reactive group in the molecule and
And / or radical polymerization using a chain transfer agent,
Use a specific reactive group attached only to one end of the polymer main chain.
The polymerized double bond group
It can be easily manufactured by a synthesis method such as a method of introduction.
it can. Specifically, Takayuki Otsu, Polymer, 33 (No.
3), 222 (1984), P. Dreyfuss & R.P. Quirk, Encycl. P
olym. Sci. Eng.,7, 551 (1987), Yoshiki Nakajo, Yu Yamashita
"Dye and chemicals",30, 232 (1985), Akira Ueda, Susumu Nagai
"Chemistry and industry",60, 57 (1986), P.F.Rempp & E.Frant
a, Advances in Polymer Science,58, 1 (1984), Italy
Koichi Fuji “polymer processing”,35, 262 (1986), V. Percec, Ap
plied Polymer Science,285, 97 (1984) etc.
And the method described in the literature cited therein.
A heavy bond group can be introduced. Further, i) in general formula (PI)
At least one of the monomers corresponding to the repeat units indicated
Species and chains containing the above specific reactive groups in the molecule
A mixture of transfer agents is converted into a polymerization initiator (for example, an azobis compound).
Ii) the above chain transfer
Contains no specific reactive group in the molecule without using a moving agent
A polymerization method using a polymerization initiator, or iii)
Both the chain transfer agent and the polymerization initiator have the above characteristics in the molecule.
By using a compound containing a specific reactive group, etc.
A heavy chain with a specific reactive group attached only to one end of the polymer main chain.
Synthesize the union and then take advantage of this specific reactive group to
Examples include a method of introducing a polymerizable double bond by a molecular reaction.
It is. The chain transfer agent used is, for example, a specific one.
Contains reactive groups or substituents that can be derivatized to specific reactive groups
Mercapto compounds having {eg, thioglycolic acid,
Thiomalic acid, thiosalicylic acid, 2-mercaptopropi
On acid, 3-mercaptopropionic acid, 3-mercapto
Butyric acid, N- (2-mercaptopropionyl) glycine,
2-mercaptonicotinic acid, 3- [N- (2-mercap
Toethyl) carbamoyl] propionic acid, 3- [N-
(2-Mercaptoethyl) amino] propionic acid, N-
(3-mercaptopropionyl) alanine, 2-merca
Putoethanesulfonic acid, 3-mercaptopropanesulfo
Acid, 4-mercaptobutanesulfonic acid, 2-mercap
Toethanol, 1-mercapto-2-propanol, 3
-Mercapto-2-butanol, mercaptophenol
, 2-mercaptoethylamine, 2-mercaptoimi
Dazole, 2-mercapto-3-pyridinol, etc.}
Or to a specific reactive group or a specific reactive group
Iodinated alkyl compounds containing substituents (e.g.
Acetic acid, iodopropionic acid, 2-iodoethanol
, 2-iodoethanesulfonic acid, 3-iodopropane
Sulfonic acid etc.). Preferably mercaptoized
Compound may be mentioned. Also, a specific reactive group or a specific reactivity
As a polymerization initiator containing a substituent that can be derived from a group,
For example, an azobis compound {eg, 4,4'-azobis
(4-cyanovaleric acid), 4,4'-azobis (4-sia
Novaleric acid chloride), 2,2'-azobis (2-sia
Nopropanol), 2,2'-azobis (2-cyanope)
Tantanol), 2,2'-azobis [2- (5-hydro
Xi-3,4,5,6-tetrahydropyrimidine-2-
Yl) propane], 2,2'-azobis {2-methyl-
N- [1,1-bis (hydroxymethyl) -2-hydro
Xylethyl] propioamide}, 2,2'-azobis
{2-Methyl-N- [1,1-bis (hydroxymethy
L) ethyl] propioamide}, 2,2'-azobis
[2-Methyl-N- (2-hydroxyethyl) -propi
Oamide], 2,2'-azobis (2-amidinopropa
)}, Thiocarbamate compounds {eg benzyl N
-Methyl-N-hydroxyethyldithiocarbamate,
2-carboxyethyl N, N-diethyldithiocarbamate
3-hydroxypropyl N, N-dimethyldithioate
Carbamate} and the like. Use of these chain transfer agents or polymerization initiators
The dose is 0.05 to 100 parts by weight per 100 parts of the total monomer.
10 parts by mass, preferably 0.1 to 5 parts by mass
The In addition, a heavy component is present in the substituent of the polymerization component in the polymer.
Specific embodiment of resin (PG) containing compatible double bond group and
For example, those represented by the following general formula (Pb) are listed.
I can get lost. [0086] Embedded image In the formula (Pb), p¹, P², A^1p, L,
q¹, Q²Is as defined above. x component and y component are resin
You may contain 2 or more types in (P). t¹, T²Each
P ¹, P²It is synonymous with. A^3pAnd A^4pEach
A in formula (PII)^2pIt is synonymous with. G⁰Is a linking group
A^3pAnd linking group A^4pAt least one group
Carbon atom, oxygen atom, sulfur atom, silicon atom or nitrogen
Represents an atom. The bonding group is a carbon atom-carbon atom bond.
(Single bond or double bond), carbon atom-hetero atom bond
Hetero atoms such as oxygen atoms, sulfur atoms
Child, nitrogen atom, silicon atom, etc.), heteroatom-heterogen
Consists of any combination of atomic groups, heterocyclic groups, etc.
It is what is done. For example, in the general formula (Pa)
And those having the same content as the linking group. In the y component in the general formula (Pb), a bond
Group: [-A^4p-G⁰-A^3p-] Connected main chain
Is preferably composed of 8 or more atoms.
Yes. Here, the number of atoms of the connecting main chain is, for example, A^4p-
When COO- or -CONH- is represented, an oxo group (= O
Group) and hydrogen atoms are not included in the number of atoms,
The carbon atom, ether type oxygen atom, and nitrogen atom constituting
Included as the number of atoms. Therefore, -COO- and -C
ONH- is counted as 2 atoms. The following repeats containing a polymerizable double bond group
Although the specific example about a unit (y component) is shown, this invention
It is not limited to these. In the following formula, each symbol is
Indicates the following contents. [0091] Embedded image [0092] Embedded image[0093] Embedded image A polymerizable double bond group is included in the substituent of the polymerization component.
The dispersion stabilizing resin (PG) contained is a conventionally known synthesis method.
It can be easily synthesized by the method. That is, the tree
Polymerization component containing a polymerizable double bond group in fat (y component
As a method for introducing a minute), a specific reactive group (for example,
For example, —OH, —COOH, —SO_ThreeH, -NH₂, -S
H, -PO_ThreeH₂, -NCO, -NCS, -COCl,-
SO₂Cl, epoxy groups, etc.)
Polymerized with monomers corresponding to x component in (Pb)
After reacting, a reactive test containing a polymerizable double bond group
Reacting the drug, polymerizing double bond group by polymer reaction
The method to introduce is mentioned. Specifically, at the end of the polymer main chain piece described above,
Review of examples of resin (PG) containing a polymerizable double bond group
And the method described in the literature cited therein.
A heavy bond group can be introduced. Another method is a radical polymerization reaction.
Using bifunctional monomers with different polymerization reactivity in
A gel is reacted with a monomer corresponding to the x component to form a gel.
Copolymer represented by the general formula (Pb) without causing a reaction
A method described in JP-A-60-185962 for synthesizing coalescence
Etc. In the resin represented by the general formula (Pb),
The ratio of x and y components is 90/10 to 99/1
The ratio is preferably 92/8 to 98/2 mass ratio.
The Within this range, the reaction during polymerization granulation reaction
Gelation of the reaction mixture or coarse particle size of the resulting resin particles
There is no fear of causing The dispersion stabilizing resin used in the present invention
(PG) represents each repeating unit of the general formulas (Pa) and (Pb).
Contains other repeating units as a copolymerization component
May be. Other copolymer components include those represented by the general formula (P
Monomer corresponding to each repeating unit of a) and (Pb)
As long as it consists of a monomer copolymerizable with
A compound may be used. However, good dispersion stability of dispersed resin particles
In order to obtain the properties, at most in 100 parts by mass of all polymer components
It is preferably used in a range not exceeding 20 parts by mass of
Yes. The mass average of the dispersion stabilizing resin (P) of the present invention
Molecular weight (Mw) is 2 × 10^Four~ 1x10⁶Is preferred,
More preferably 3 × 10^Four~ 2x10^FiveIt is. As described above, it can be represented by the general formula (PI).
Dispersion consisting of block copolymer of soluble and insoluble components
It is preferable to use a stabilizing resin (P). In this case
Insoluble resin particles (P) are insoluble in insoluble resin particles.
The block part of the component is sufficiently adsorbed. In addition, polymerizable double
Using a dispersion stabilizing resin (PG) containing a linking group
Is preferred. In this case, the resin (PG) is insoluble.
Chemically bonds with fat particles. As a result, the dispersed resin particles are filled.
Of dispersion stabilizing resin (P) adsorbed or chemically bonded to
By improving the affinity of soluble components to the dispersion medium,
It is thought to bring about a body rebound effect and further improve dispersibility
It is. Next, in the present invention, resin particles are co-polymerized.
Copolymerizable with monomer (A), preferably used as a component
A specific substituent represented by the general formula (IV)
The monofunctional monomer (C) will be described. U¹Is preferably -COO-, -CON
H-, -CON (E²)-{Where E ²Preferably charcoal
An aliphatic group having a prime number of 1 to 32 (as the aliphatic group,
An alkyl group, an alkenyl group, an aralkyl group, etc.
Or a substituent represented by the general formula (IVa)
}, -OCO-, -CH₂Table of OCO- or -O-
The D¹And d²Are the same or different
Preferably, hydrogen atom, fluorine atom, chlorine atom, bromine
Atom, cyano group, methyl group, -COO-E^ThreeOr -C
H₂COO-E^Three(However, E^ThreePreferably has 3 carbon atoms
2 or less alkyl group, alkenyl group, aralkyl group
Or a cycloalkyl group). In the formula (IV), U¹-COO-, -CON
H- or -CON (E²)-, D¹And d
²Are the same or different, hydrogen atom, fluorine atom, salt
More preferably it represents an elementary atom, a cyano group or a methyl group.
That's right. Next, in the general formula (IV), E¹Is charcoal
A case where an aliphatic group having a prime number of 8 or more is represented will be described. E
¹As the aliphatic group having 8 or more carbon atoms, preferably total carbon
Several tens or more of optionally substituted alkyl groups or total carbons
List several tens or more alkenyl groups that may be substituted.
You can. E¹Where represents an aliphatic group having 8 or more carbon atoms
In this case, specific examples of the monomer (C) include a total carbon number of 10
~ 32 aliphatic groups (aliphatic groups are halogen atoms, hydroxyl groups
Contains substituents such as syl group, amino group, alkoxy group
Or oxygen atom, sulfur atom, nitrogen atom
The main chain carbon atom-carbon atom bond is a heteroatom such as
Acrylic acid, which may be
Crylic acid, α-chloroacrylic acid, α-cyanoacrylic
Acid, methacrylic acid, crotonic acid, maleic acid, itacone
Esters of unsaturated carboxylic acids such as acids (with aliphatic groups)
For example, decyl group, dodecyl group, tridecyl group, teto
Ladecyl group, hexadecyl group, octadecyl group, dokoshi
Group, dodecenyl group, hexadecenyl group, oleyl group,
Linoleyl group, dococenyl group, etc.);
Amide of Japanese carboxylic acid (as aliphatic group,
And higher fatty acids).
Vinyl esters or allyl esters (high-grade fats)
Examples of fatty acids include lauric acid, myristic acid, and stearic acid.
Listed are Aric acid, Oleic acid, Linoleic acid, Behenic acid, etc.
Or an aliphatic group having a total carbon number of 10 to 32 is oxygen
Vinyl ethers bonded to atoms (as aliphatic groups,
Aliphatic groups exemplified in the above unsaturated carboxylic acid esters
The same thing can be mentioned). Next, a monomer represented by the general formula (IV)
In (C), E¹Is more than 8 atoms in total (however, carbon
Excluding hydrogen atoms directly bonded to nitrogen atoms)
Details on the case of representing the substituent represented by formula (IVa)
I will explain. A¹And A²Are the same or different,
A group represented by the general formula (IVb) and a group having 1 to 18 carbon atoms;
At least one group selected from among hydrocarbon groups;
Represent. Here, if more than one group is selected, this
Represents a group in which two or more groups are bonded. Explain in detail
And A¹And A²Is, for example, -C (R⁴⁴) (R⁴⁵) −
(Where R⁴⁴, R⁴⁵Are the same or different,
Represents hydrogen atom, alkyl group, halogen atom, etc.),-
(CH = CH)-, a cyclohexylene group (hereinafter, cyclo
The hexylene group is represented by “-C₆H_Ten-"And" -C₆H_Ten
-"Represents 1,2-cyclohexylene group, 1,3-cyclohexyl
Including xylene group and 1,4-cyclohexylene group
And assignment of atomic groups such as the group represented by the general formula (IVb)
It is composed of any combination. E¹Is the general formula (IVa) where the total number of atoms is 8 or more
In the formula (IV), the bonding group (—U¹
-(A¹-B¹)_m-(A²-B²)_n-R⁴¹)
U¹To R⁴¹(Ie U¹, A¹, B¹, A², B²as well as
R⁴¹) Is composed of the connected main chain.
The total number of atoms formed is preferably 8 or more. Here, the number of atoms constituting the “linking main chain” and
For example, U¹Where represents -COO- or -CONH-
The oxo group (= O group) and hydrogen atom
Not included, carbon atoms constituting the connecting main chain, ether type acid
Elemental and nitrogen atoms are included as the number of atoms.
Taste. Therefore, -COO- or -CONH- has 2 atoms.
Counted as. At the same time, R⁴¹-C₉H₁₉Place to represent
The hydrogen atom is not included as the number of atoms, and the carbon atom is
included. Therefore, in this case, it is counted as 9 atoms.
The Note that U¹-CON (E²) −
One E²Is a substituent represented by the general formula (IVa),
(-(A¹-B¹)_m-(A²-B²)_n-R⁴¹)
E²The linking main chain composed of
included. A¹, A²Is represented by the general formula (IVb)
In the case of having a group (-B^Three-(A^Four-B^Fourp-R
⁴³) Groups are also included in the “linking backbone”. A single monomer represented by the above general formula (IV)
In the body (C), E¹Is represented by the general formula (IVa)
As specific examples of the substituents represented by
Can be mentioned. The following formulas (C-1) to (C-19)
Each symbol represents the following contents. r₁: -H, -CH_Three, -Cl or -CN, r₂: -H or -CH_Three l: an integer of 2 to 10, p: an integer of 2 to 6, q: an integer of 2 to 4, m: an integer from 1 to 12, n: an integer from 4 to 18, [0114] Embedded image [0115] Embedded image[0116] Embedded imageBy using the monomer (C), the dispersion tree
The dispersion stability and redispersibility of the fat particles are further improved. this is
The copolymer component corresponding to the monomer (C) is a lyophilic medium with the dispersion medium.
Orientation to the particle surface due to its high compatibility,
The particles become more amphiphilic with the dispersion medium on the surface of the child.
It is presumed to suppress aggregation and precipitation. Monomer
The amount used when (C) is used is preferably among all monomers.
Is 0.5 to 20 mass%, more preferably 1 to 15 mass%
It is. Production of dispersed resin particles used in the present invention
In general, the dispersion stabilizing resin (P) as described above,
Monomer (A) and monomer (B), and if necessary, monomer
(C) and benzoyl peroxide, azobisi in a non-aqueous solvent
Presence of polymerization initiators such as sobutyronitrile and butyllithium
What is necessary is just to heat-polymerize in the presence. Specifically, dispersion stability
Resin (P), monomer (A) and monomer (B) are further required
Depending on the condition, a polymerization initiator is added to the mixed solution with the monomer (C).
Or the dispersion stabilizing resin (P) is dissolved.
Monomer (A) and monomer (B) in the solution
When the monomer (C) is dropped together with the polymerization initiator
Can be manufactured using either method.
Yes. Monomer (A) and monomer (B) Further necessary
Accordingly, the total amount of monomer (C) is 100 parts by mass of the non-aqueous solvent.
On the other hand, it is preferably about 10 to 100 parts by mass.
More preferably, it is 10-80 mass parts. Dispersion stabilizing resin
(P) is equivalent to 100 parts by mass of all monomers used above.
And preferably 3 to 25 parts by mass, more preferably
Is 5 to 20 parts by mass. The amount of the polymerization initiator is completely
0.1 to 10% by weight of the monomer is suitable. The polymerization temperature is 4
It is preferably about 0 to 180 ° C, more preferably 50 to 1
20 ° C. The reaction time is preferably 3 to 15 hours. In the non-aqueous solvent used in the reaction, the above-mentioned al
Polarity of coals, ketones, ethers, esters, etc.
When a solvent is used in combination,
If the reactant remains, polar solvent or monomer
Evaporate by heating above the boiling point or evaporate under reduced pressure
It is preferable to remove them. The non-manufactured as described above is manufactured according to the present invention.
Water-based dispersed resin particles are fine and have a uniform particle size distribution
Exists as. The average particle size is preferably 0.05.
~ 5μm, more preferably 0.08 ~ 1.5μm
The This particle size is CAPA-700 (Horiba, Ltd.)
Manufactured). Quality of the resin constituting the dispersed resin particles of the present invention
Weight average molecular weight (Mw) (polystyrene conversion by GPC method
(Calculated value) is preferably 5 × 10^Three~ 1x10⁶Yes
More preferably 8 × 10^Three~ 5x10^FiveIt is. Also that
As the thermophysical properties, the glass transition point is 0 to 80 ° C or soft.
The conversion point is preferably 35 ° C to 120 ° C, more preferably
The lath transition point is 10 ° C to 70 ° C, or the softening point is 38 ° C to 9 ° C.
0 ° C. The oil-based ink of the present invention has a load of dispersed resin particles.
Excellent electrical characteristics, dispersion stability, redispersibility, storage stability, and
In addition, it has good fast fixability after image formation and can be used during printing.
A sufficient strength is maintained and high printing durability is exhibited. That is, very stable
Shows dispersibility, especially in recording devices
Dispersibility is good even when used, and redispersion is easy,
It is completely unacceptable to adhere to parts of the device and cause contamination.
Yes. Furthermore, because of the good fixability, the ink image
If fixed by rapid processing such as heating after image formation, it is easily lithographic
A strong film is formed on the surface of the printing plate precursor. this thing
Because of this, even in offset printing,
Printing durability). Books that have the above effects
The oil-based ink of the invention is a non-aqueous ink provided by the present invention.
Made possible by Tex. The above dispersion in the oil-based ink used in the present invention.
Resin particles exhibit positive chargeability. Charge the positive charge of these particles.
In order to maintain a sufficient amount of wet electrophotographic developer technology.
It can be achieved by using it. Specifically, “Recent
Development and commercialization of electrophotographic development systems and toner materials ”13
Pages 9-148, edited by the Society of Electrophotography,
497-505 (Corona, 1988), Yuji Harasaki “Den”
Electrophotographic materials described in "Child Photograph" 16 (N0.2), p. 44 (1977), etc.
By using additives and other additives. For example, as a metal soap, the number of carbon atoms is 6
To 24 fatty acids (eg 2-ethylhexanoic acid, 2-ethyl
Tilcaproic acid, lauric acid, palmitic acid, Eleiji
Acid, linolenic acid, ricinoleic acid, oleic acid,
Aric acid, enanthic acid, naphthenic acid, ethylenediamine
Tetraacetic acid), resin acid, dialkyl succinic acid, alkylphenol
Metal salts such as taric acid and alkylsalicylic acid (metal ion
Na, K, Li, B, Al, Ti, Ca, P as metals
b, Mn, Co, Zn, Mg, Cl, Ag, Cd, Z
r, Cu, Fe, Ba, etc.). Specific example is rice
Japanese Patents 3,411,936 and 3,900,412
No. 49, 27-27707, JP-A 51-3765
No. 1, No. 52-38937, No. 52-107837
No. 53-123138, and the like. [0127] 3 carbon atoms as organophosphoric acid or its salts
Mono-, di- or trial consisting of ~ 18 alkyl groups
Kill phosphoric acid or dialkyldithiophosphoric acid etc.
To permit 1,411,739, 1,276,363, etc.
Illustrated. As organic sulfonic acid or its salts,
Long chain aliphatic sulfonic acid, long chain alkylbenzene sulfone
Acid, dialkylsulfosuccinic acid, etc. or metal salts thereof
JP-B-47-37128, JP-A-53-12313
No. 8, No. 51-47437, No. 50-79640,
No. 53-30340. As amphoteric surfactant compounds, lecithin,
Phospholipids such as farin (for example, JP-B 51-47046)
Etc.), β-alanine containing an alkyl group having 8 or more carbon atoms
(Japanese Patent Laid-Open Nos. 50-17642 and 49-17774)
Etc.), etc., metal complexes of β-diketones (Japanese Patent Publication No. 49-27)
No. 707) and the like. These charge control agents (CD) may be used alone or
Can be used in combination of two or more. Above
Such a charge adjusting agent is a dispersion medium 1000 that is a carrier liquid.
It is preferable to use 0.001 to 1.0 parts by mass with respect to parts by mass.
Good. The oil-based ink of the present invention contains at least amino.
Monomer containing a group and a specific acidic group in the same molecule
Dispersing resin particles containing (B) and charge adjustment as described above
Dispersed with positively charged particles consisting of an agent (CD)
It is. The oil-based ink of the present invention is referred to the above-mentioned WO 93/11.
Electrostatic with particle concentration or aggregation disclosed in Japanese Patent No. 866
For image forming method using the inkjet recording method
Even when discharging small dots and at high printing speeds.
Missing printed ink dots and deformed dot shapes
High-definition images were formed and printed without
The film thickness of the dot image is sufficiently maintained at 1 μm or more.
This is because the positively charged resin particles in the oil-based ink are discharged.
In the ink meniscus formed on the pole surface,
The particles are concentrated by electrophoresis as soon as
Discharge completely corresponding to the pulse voltage applied with the signal.
It is thought to be for this purpose. In the electrostatic ink jet recording system of the present invention,
If the electric field strength during image formation is too low,
Since good dischargeability may not be obtained, about 1 × 10
^FiveV / cm or more is suitable. On the other hand, too expensive
Dot breaks and satellites occur, resulting in poor image quality
About 1 x 10^ThreeV / cm or less is preferred
That's right. More preferably 2 × 10^FiveTo 5 × 10⁷V / cm
Range. Also, the oil-based ink used in this method is
Percentage of charge of dispersed particles in ink (particle charge
Rate) is preferably high. If the charge fraction of the particles is low,
The required image quality thickness cannot be obtained, and printing durability as a printing plate
It tends to decrease and is not preferable. Specifically, particle charging
The fraction is suitably about 10% or more, preferably 30% or more,
More preferably, it is 40% or more. The charge fraction of the particles and
The calculation method will be described later. The surface tension of the oil-based ink of the present invention is too low.
If this happens, ink will spill out of the head and the stability will be poor.
About 15 dyn / cm to 30 d
The range is yn / cm. The viscosity of oil-based ink is
If it is too low, ink will spill out of the head and be stable.
About 0.4 cP or more is appropriate.
It is. On the other hand, if it is too high, the discharge performance will decrease.
About 15 cP or less. More preferably 0.5
The range is from cP to 10 cP. Furthermore, the oil-based ink of the present invention is stored for a long time.
After, or high temperature and high humidity (eg 40 ° C / 80RH%)
Even if ink-jet recording is performed after storage under the ink,
It shows the same performance as a fresh product just after production.
This is due to the charging characteristics of the oil-based ink of the present invention, particularly positively charged particles.
This is thought to be due to the stable chargeability of the
The The oil-based ink of the present invention may further include various types as desired.
Seed additives may be added and the total amount of these additives is oily
The upper limit is regulated by the electrical resistance of the ink. Immediately
That is, the electric resistance of the ink with the dispersed particles removed is 10
⁹If it is lower than Ωcm, it is difficult to obtain a good quality continuous tone image.
Therefore, the amount of each additive must be controlled within this limit.
Need to be installed. In the oil-based ink used in the present invention, the above-mentioned
The plate after plate making is inspected together with the dispersed resin particles.
Therefore, it is preferable to contain a coloring material as a coloring component.
As the coloring material, an oil-based ink composition or an electrostatic copy has been conventionally used.
What are the pigments and dyes used in true liquid developers?
Any of them can be used. As the pigment, any inorganic pigment or organic pigment can be used.
Use what is commonly used in the technical field of printing
can do. Specifically, for example, carbon bra
, Cadmium red, molybdenum red, chrome
Yellow, cadmium yellow, titanium yellow, oxide
Rom, Pyridian, Cobalt Green, Ultramarine
Blue, Prussian blue, cobalt blue, azo face
Materials, phthalocyanine pigments, quinacridone pigments, iso
Indolinone pigment, dioxazine pigment, selenium face
, Perylene pigment, perinone pigment, thioindigo
Pigments, quinophthalone pigments, metal complex pigments, etc.
Known pigments can be used without any particular limitation. As dyes, azo dyes, metal complex dyes,
Naphthol dye, anthraquinone dye, indigo dye,
Carbonium dye, quinone imine dye, xanthene dye
Material, cyanine dye, quinoline dye, nitro dye, nitro
So dye, benzoquinone dye, naphthoquinone dye, phthalo
Oil-soluble dyes such as cyanine dyes and metal phthalocyanine dyes
A charge is preferred. These pigments and dyes are used alone.
It is also possible to use in combination as appropriate
Is contained in the range of 0.05 to 5% by mass with respect to the whole ink.
It is desirable to have it. These color materials are colored separately from the dispersed resin particles.
The material itself may be dispersed in a non-aqueous solvent as dispersed particles.
And may be contained in the dispersed resin particles. Place to contain
As one of the methods, JP-A-57-48738 is known.
As described in US Pat.
There is a method of staining with. Alternatively, as another method,
As disclosed in Kaisho 53-54029, etc.
There is a method of chemically combining powder resin and dye
Or, it is described in Japanese Examined Patent Publication No. 44-22955 etc.
As it is, when producing by the polymerization granulation method, it contains a pigment in advance.
There is a method to make a dye-containing copolymer using the selected monomer.
The Next, an electrostatic method using the oil-based ink of the present invention.
An image forming method using an inkjet method will be described.
The Here, printing is performed using an original printing plate as an ink receiving material.
An example of image forming (plate making) and printing plate will be described.
The The printing original plate is a hydrophilic surface capable of lithographic printing.
Is divided into two types: one with a surface and one with a hydrophobic surface
Any of these can be used. Sign of the former
In the printing original plate, the support itself has a hydrophilic surface and supports.
The thing which provided the layer which has a hydrophilic surface on a support body is included. Water resistance having a hydrophilic surface capable of lithographic printing
The support provides a hydrophilic surface suitable for lithographic printing
The support used for the conventional offset printing plate
Can be used as they are. Specifically, alumini
Um plate, zinc plate, copper-aluminum plate, copper-stainless steel
Plate, bimetal plate such as chrome-copper plate, chrome-copper-a
Luminium plate, chrome-lead-iron plate, chrome-copper-stainless steel
Substrate having a hydrophilic surface such as a trimetal plate such as a loess plate
Is used. Its thickness is 0.1-3 mm, especially 0.1
˜1 mm is preferred. In the case of a support having an aluminum surface
For graining, sodium silicate, zircon fluoride
Immersion treatment in aqueous solution of potassium nitrate, phosphate, etc.
Is preferably surface-treated such as anodizing
That's right. Also described in US Pat. No. 2,714,066.
As you can see, sodium silicate aqueous solution after graining
Aluminum plate immersed in liquid, JP-B-47-51
As described in No. 25, the aluminum plate is
After oxidation treatment, soak in an aqueous solution of alkali metal silicate.
A pickled product is also preferably used. The above anodic oxidation treatment can be performed by, for example, phosphoric acid, chlorine, etc.
Inorganic acids such as humic acid, sulfur, boric acid, or oxalic acid, soot
An aqueous solution or non-organic organic acid such as sulfamic acid or a salt thereof
In an electrolytic solution containing a single aqueous solution or a combination of two or more aqueous solutions
Implemented by flowing current with a luminium plate as the anode
It is. Also described in US Pat. No. 3,658,662.
Silicate electrodeposition is also effective. West German Patent Authority
Polyvinylsulfonic acid described in Kaikai 1,621,478
The processing by is also appropriate. For the combination of ink and recording method of the present invention
Therefore, even in the image formation on the metal surface,
Printed when the particles are printed in a sufficiently concentrated state
On the surface, ink does not bleed and image bleed does not occur.
Yes. These surface treatments make the surface of the support hydrophilic.
In addition to being applied to the
It is applied to improve the adhesion to the image. Ma
To adjust the adhesion between the support and the ink image
For this purpose, a surface layer may be provided on the support surface. A plastic sheet or paper is used as a support.
In some cases, the area other than the ink image area must be hydrophilic.
For this reason, a surface layer having hydrophilicity is provided.
It is. Specifically, a known direct-drawing lithographic printing original plate or
Use a plate material having the same layer as the image receiving layer of the original
be able to. For example, as the image receiving layer, a water-soluble binder is used.
It is composed mainly of a binder, an inorganic pigment and a water resistant agent.
There is something. As binder, PVA, carboxy
Modified PVA such as PVA, starch and its derivatives, CM
C, hydroxyethyl cellulose, casein, gelatin
, Polyvinylpyrrolidone, vinyl acetate-crotonic acid
Water-soluble resin such as polymer, styrene-maleic acid copolymer
Is used. As water-proofing agents, glyoxal, melami
Formaldehyde resin, urea formaldehyde resin, etc.
Amino blast initial condensate, methylolated polyamid
Modified polyamide resin such as polyamide resin, polyamide poly
Amine / epichlorohydrin adduct, polyamide epic
Lorhydrin resin, modified polyamide polyimide resin, etc.
Can be mentioned. Inorganic pigments include kaolin, clay, and carbonic acid
Calcium, silica, titanium oxide, zinc oxide, sulfuric acid burr
Among them, silica and alumina are preferable. In addition, ammonium chloride is contained in the image receiving layer.
A crosslinking agent such as a silane coupling agent can be used in combination. On the other hand, an image receiving layer comprising a hydrophobic surface is provided.
The original printing plate is used to desensitize non-image areas after image formation.
Desensitization (ie printing ink repellent hydrophilic property)
To make a printing plate. These printing originals include zinc oxide and
A mark having an image receiving layer containing at least a binder resin
Printing plate, desensitizing treatment (treatment liquid, light irradiation, heat treatment)
Etc.) and the hydrophobic binder resin reacts chemically to become a hydrophilic binder resin.
Has an image receiving layer containing at least the binder resin to be converted
Printing original plate (for example, JP-A-1-226394,
(Japanese Patent Publication No. 7-94191). Contains at least zinc oxide and binder resin
A lithographic printing plate having an image receiving layer
The The zinc oxide used is, for example, Nippon Pigment Technology.
319 pages of "New Pigment Manual", Sebundo Co., Ltd.
(1968), zinc oxide, zinc white,
Also commercially available as wet zinc or activated zinc
Either of these may be used. That is, zinc oxide is a starting material and
Depending on the manufacturing method and the French method (indirect
Act), American method (direct method) and wet method
For example, Shodo Chemical Co., Ltd., Sakai Chemical Co., Ltd., White
Sugi Chemical Co., Ltd., Honjo Chemical Co., Ltd., Toho Zinc Co., Ltd.
Those that are commercially available from companies such as Mitsui Kinzoku Co., Ltd.
Can be mentioned. The content of zinc oxide in the image receiving layer is 7
5 to 90% by mass, and further 78 to 88% by mass
Is preferred. If the amount of zinc oxide is too small, it can be used for desensitizing treatment.
As a result, the hydrophilicity of the surface of the image receiving layer becomes insufficient.
If the number increases, the required image receiving layer strength cannot be secured.
It is not preferable. The binder resin used for the image receiving layer is the same as described above.
As shown, the hydrophobic layer that forms the image receiving layer together with zinc oxide
The molecular weight of the resin is a mass average molecular weight Mw,
Preferably 10^Three-10⁶, More preferably 5 × 10^Three~
5 × 10^FiveIt is. The glass transition point of this resin is favorable.
Preferably 0 ° C to 120 ° C, more preferably 10 ° C to 90 ° C.
° C. Specifically, styrene copolymer, methacrylate.
Rate copolymer, acrylate copolymer, vinyl acetate copolymer
Polymer, polyvinyl butyral, alkyd resin, epoxy
Resin, epoxy ester resin, polyester resin, polyester
Examples thereof include a urethane resin. These resins alone
You may use and may use 2 or more types together. In the image receiving layer, together with the above components,
You may contain another structural component. May be contained
The other ingredients are zinc oxide and other inorganic pigments,
Examples of inorganic pigments include kaolin, clay, and carbonic acid.
Calcium, Barium carbonate, Calcium sulfate, Bali sulfate
Um, magnesium carbonate, titanium oxide, silica, aluminum
Na. When using these other inorganic pigments together
Is 20 parts by mass per 100 parts by mass of zinc oxide.
It is desirable to use within the range. Furthermore, for improving the desensitization of the image receiving layer.
JP-A-4-2013387 and 4-223196.
No. 4-319491, No. 5-58071, No. 4
-353495, 5-119545, etc.
Resin particles such as acrylic resin particles containing certain functional groups
May be included. These resin particles are usually spherical.
The average particle size is preferably 0.1 to 2 μm.
Yes. The resin particle content is 20% by mass or more of the image receiving layer component.
Below is preferred. These other inorganic pigments or resin particles are used.
Desensitizing non-image area by desensitizing treatment
(Hydrophilicity) is sufficiently made, and soiling of printed matter is suppressed.
In addition, the image area is in close contact with the image receiving layer and the number of printed sheets
Sufficient printing durability without causing image loss
Sex can be obtained. In addition, in the image receiving layer, the film strength is further improved.
A cross-linking agent may be added to increase the amount. As the binder resin, an image receiving layer composition was applied.
Thereafter, it is preferably light and / or heat cured. heat
For curing, for example, the drying conditions can
Stricter than the drying conditions at the time of receiving layer preparation. For example, dry
Condition is high temperature and / or long time, or
It is preferable to further heat-treat after drying the coating solvent.
For example, the treatment is performed at 60 to 150 ° C. for 5 to 120 minutes. Anti
When used together with response promoters, it can be processed under milder conditions.
You can. Further, as a method of curing by light irradiation, a tree is used.
Light a specific functional group in fat with chemically active light
Yes. Chemically active light includes visible light, ultraviolet light, and deep purple
Any of external line, electron beam, X-ray, γ-ray, α-ray, etc.
Is preferably ultraviolet light, more preferably at a wavelength of 310 nm.
In the range of 500 nm. Generally low pressure, high
Pressure or ultra-high pressure mercury lamp, halogen lamp, etc.
Used. Is the light irradiation treatment usually a distance of 5cm to 50cm?
It can be performed sufficiently by irradiation for 10 seconds to 10 minutes.
The The thickness of the image receiving layer is 1 m for printing original plate.²This
The amount of the image receiving layer composition applied (after drying) is 3 to 3.
It is preferably about 30 g. Also accept this image
The layer is usually 3-50 vol%, preferably 10-40 vol%
Those having a degree of porosity are preferred. The image receiving layer is provided on a water resistant support.
The Water-resistant supports include water-resistant paper and paper.
Paper laminated with plastic film or metal foil
Alternatively, a plastic film or the like can be used. The support preferably has a highly smooth surface.
Good. That is, the smoothness of the surface adjacent to the image receiving layer
However, Beck smoothness of 300 (sec / 10ml) or more is preferable.
It is adjusted to 900-3000 (second / 10ml)
Preferably 1000 to 300.
It is preferably 0 (second / 10 ml). The surface of the support adjacent to the image receiving layer
Smoothness is over 300 (sec / 10ml) in Beck smoothness
Regulating further increases image reproducibility and printing durability.
Can be improved. This improvement effect is
Even if the image receiving layer surface itself has the same smoothness
As the smoothness of the support surface increases, the image area and image
This is thought to be due to the improved adhesion to the image receiving layer. Here, the Beck smoothness is the Beck smoothness test.
It can be measured by a testing machine. Beck smoothness tester
Is a highly smooth circular shape with a hole in the center
Place a test piece on a glass plate at a constant pressure (1 kg / cm²)
A certain amount (10 ml) of air under reduced pressure
Measuring the time required to pass between specimens
It is. A highly smooth surface of such a water-resistant support and
Refers to the surface to which the image-receiving layer is directly applied, for example
For example, an under layer and an overcoat layer described later are formed on the support.
If provided, the under layer and overcoat layer
It refers to the surface. As a result, unevenness on the surface of the support is received.
Without receiving the image with the surface condition adjusted as above.
The physical layer is sufficiently retained, enabling further improvement in image quality.
The As a method for setting the above smoothness range,
Various conventionally known methods can be used. concrete
Includes a method of melt-bonding the substrate surface with a resin, high smoothness
By a method such as a calendar strengthening method using a heat roller
Examples include a method for adjusting the Beck smoothness of the surface of the support.
be able to. As a method of melt-bonding the above resin, extrusion is used.
It is preferably coated by a laminating method. this
By coating by extrusion lamination method, the desired
A support with adjusted smoothness can be produced. Extrusion Lami
The Nate method melts the resin and turns it into a film.
Immediately press the base paper, then cool and laminate.
Various devices are known. In this way Lamine
The thickness of the coated resin layer is 10 μm from the viewpoint of manufacturing stability.
That's it. Preferably they are 10 micrometers-30 micrometers. Also, as described above, the support and the image receiving layer
For the purpose of improving water resistance and interlayer adhesion
-The anti-curl layer on the opposite side of the substrate from the image-receiving layer
Provide a back coat layer (back layer) for the purpose of stopping
The back coat layer has a smoothness of 150 to
The range is preferably 700 (seconds / 10 ml).
In this way, when printing plates are fed to an offset printing machine
In addition, the printing plate can be printed accurately without misalignment or slippage.
Set in the machine. Such an underlayer and back coat of the support
When adjusting the smoothness of the gate layer, for example,
After the under layer is formed, perform calendar processing once to
The calendar process is performed again after forming the quart layer.
In addition, the calendar process can be performed multiple times,
Examples of under and back coat layers as described below
Adjustment of the composition of the pigment ratio and particle size and calendar treatment
Control smoothness by combining with adjustment of conditions
It is desirable. For example, the substrate used for the printing original plate is
Wood pulp paper, synthetic pulp paper, wood pulp and synthetic pulp
Mixed paper, non-woven fabric, plastic film, cloth, metal
Sheets, substrates such as these composite sheets can be used as they are
Can be. Also, to obtain a specific smoothness,
In order to adjust the water resistance and other properties, the above substrate
Sparsely used for the under layer and back coat layer described below
Made of water-based resin, water-dispersible or water-soluble resin, pigment, etc.
The paint may be impregnated. For example, a recording feature required for an original for lithographic printing
In addition to satisfying printability such as water resistance, water resistance and durability,
As described above, the substrate is unloaded on the substrate to adjust to the desired smoothness.
Use a support provided with a ladder layer and a backcoat layer.
Are preferred. Such under layer and back coat
Apply a coating solution containing resin, pigment, etc. on the support.
-It is formed by drying or laminating.
Various resins are selected as appropriate for the resin used here.
Used. Specifically, examples of hydrophobic resins include
For example, acrylic resin, vinyl chloride resin, styrene resin
Fat, urethane resin, vinylidene chloride resin, vinyl acetate
Examples of hydrophilic resins include poly resins.
Vinyl alcohol resin, cellulose derivative, starch
And its derivatives, polyacrylamide resins, steel
Examples include lene maleic anhydride copolymers. Further, as the pigment, clay, kaolin, ta
Lux, diatomaceous earth, calcium carbonate, aluminum hydroxide
, Magnesium hydroxide, titanium oxide, mica, etc.
It is done. These pigments are used to achieve the desired smoothness.
It is preferable to select and use the particle size as appropriate, for example
Relatively high smoothness is required in the under layer
Therefore, cut small and large particles to be concrete
Has a particle size of 8 μm or less, preferably about 0.5 to 5 μm.
Pigments are preferably used. In addition, back coat layer
Therefore, lower smoothness is required compared to the under layer.
From the above, those having a larger particle size, specifically 0.5 to 10
A pigment having a particle size of about μm is preferably used. Above
Such pigment is in the under layer with respect to 100 parts by mass of resin.
80 to 150 parts by weight in the back coat layer
Is preferably used at a rate of 80 to 200 parts by mass.
Yes. The under layer and back coat layer have excellent resistance.
In order to obtain aqueous properties, for example, melamine resin, polyamide
Containing water-proofing agents such as epichlorohydrin resins
Is effective. In addition, the above particle size is a scanning electron microscope.
It can be measured by (SEM) photography. Also grain
If the child is not spherical, the projected area is converted to a circle.
Is the diameter. In order to prepare an original plate for lithographic printing, a support is generally used.
If necessary, apply a solution containing the underlayer component to one side of
Apply and dry to form an under layer, and other if necessary
Apply and dry the solution containing the backcoat layer component on the other side.
After forming the backcoat layer, paint containing the image receiving layer component
The image receiving layer may be formed by applying and drying the cloth liquid. Na
Application amount of image receiving layer, under layer and back coat layer
1 to 30 g / m², Especially 6-20g / m²But
Is appropriate. Preferably, the under layer or back cover
As the film thickness of the water-resistant support provided with the coat layer, 90-1
In the range of 30 μm, more preferably 100-120 μm
It is a range. Next, the above-described lithographic printing original plate (hereinafter referred to as “ma
A method of forming an image on the top)
The As an apparatus system for carrying out such a method, for example, FIG.
There is one shown in 1. The apparatus system shown in FIG.
Having an inkjet recording apparatus 1 using
The As shown in FIG. 1, first, a master 2 is formed.
The pattern information of the images (figures and sentences)
Communication means such as bus 4 from an information supply source such as
Ink jet recording apparatus using oil-based ink
1 is supplied. Ink jet recording head of the recording apparatus 1
The storage 10 stores oil-based ink in the recording device 1
When the master 2 passes, the ink
A minute droplet is sprayed on the master 2. As a result,
Ink adheres to the star 2 in the pattern. Thus
Finish forming the image on Master 2 and make the master
Obtain a printing plate). The ink jet as in the apparatus system of FIG.
2 and 3 show examples of the configuration of the G recording apparatus. 2 is this
Shows a part of the head of an ink jet recording apparatus such as
FIG. 3 is a diagram for further explaining the structure.
is there. Provided in the ink jet recording apparatus
As shown in FIG. 2, the inkjet recording head 10
Made from insulating materials such as plastic and ceramic
Head body 14 and meniscus regulating plates 15 and 16
The In the figure, reference numeral 17 denotes discharge for applying a voltage to perform discharge.
Electrode. Further, the restriction plate is removed from the head as shown in FIG.
The head body will be described in detail. The head body 14 is attached to the edge of the head body.
Multiple ink grooves 18 for circulating ink vertically
The discharge electrode 17 is provided in the inside.
Two adjacent ink grooves form one cell, in which
Discharge parts 20 and 20 'are provided at the tip of the partition wall 19 at the center.
Have In the discharge units 20 and 20 ', the partition wall is another partition wall part.
It is thinner than 25 and sharpened. Discharge part
The tip may be slightly chamfered like 20 '
Yes. Only two cells are shown in the figure, but between cells
Is partitioned by a partition wall 21, and its distal end portion 22 is a discharge portion 20.
It is chamfered to retract more than 20 '. An ink supply (not shown) is applied to this head.
Ink flows through the ink groove from the I direction by the feeding means.
Then, ink is supplied to the ejection unit. Further not shown
Excess ink is collected in the O direction by the ink collecting means,
As a result, fresh ink is always supplied to the ejection unit.
The In this state, it is provided in a form that opposes the discharge part.
A counter electrode (not shown) holding the printing original on the surface
By applying voltage to the discharge electrode,
Ink is ejected to form an image on the printing original. As described above, on the lithographic printing original plate,
Images are formed by inkjet method using oil-based ink.
Plate making is performed. The lithographic printing plate used is a hydrophilic surface layer
If it consists of
Used for printing. On the other hand, in the case of a lithographic printing original plate with desensitization
In this case, the non-image area is insensitive by surface treatment with a desensitizing solution.
A printing plate is made by oiling. Desensitization of zinc oxide
Conventionally, this kind of desensitizing treatment liquid is ferrocyan
Cyanide-containing treatment mainly composed of salt and ferricyan salt
Chemical fluid, ammine cobalt complex, phytic acid and its derivatives
Cyan-free treatment based on conductors and guanidine derivatives
Chemical liquid, inorganic acid that forms chelate with zinc ion or
Treatment liquid based on organic acid or water-soluble polymer
There are known treatment solutions and the like. For example, as a cyanide-containing treatment solution,
JP-B Nos. 44-9045 and 46-39403, JP
Sho 52-76101, 57-107889, 5
4-117201 etc. are mentioned. Phi
JP-A-53-83 discloses a treatment liquid containing a tinic acid compound.
807, 53-83805, 53-10210
2, 53-109701, 53-127003
No., 54-2803, 54-44901, etc.
Listed. [0189] Treatments containing metal complex compounds such as cobalt complexes
As the chemical liquid, JP-A-53-104301, 53-
140103, 54-18304, 43-
The thing of 28404 is mentioned. Inorganic or
As the machine acid-containing treatment liquid, JP-B-39-13702,
40-10308, 43-28408, 40
-26124, Japanese Patent Laid-Open No. 51-118501, etc.
Can be mentioned. As the guanidine compound-containing treatment liquid,
And those described in Kaisho 56-111695 etc.
The As a treatment solution containing a water-soluble polymer, JP-A 52
-126302, 52-134501, 53-
49506, 53-59502, 53-104
No. 302, No. 38-9665, No. 39-2226
No. 3, No. 40-763, No. 40-2202, JP
49-36402 etc. are mentioned. In any of the above desensitizing treatments,
Zinc oxide in the surface layer is ionized into zinc ions,
This ion forms a chelate in the desensitizing solution.
Generates chelation reaction with compound to form zinc chelate
This is considered to be deposited in the surface layer and become hydrophilic.
It has been. The desensitizing treatment is usually performed at room temperature (15 ° C. to 35 ° C.
About 2 to 60 seconds. Wet with this printing plate
Thousands of sheets can be printed using water.
The [0193] The resin particles (lattes) used in the present invention are described below.
The present invention is further illustrated by the following preparation examples and examples.
However, the present invention is not limited to these.
is not. Production Example 1 of Resin Particle (L): Resin Particle (L
-1) The following dispersion stabilizing resin (P-1) 12 g and Isopar
While stirring a mixture of H and 250 g under a nitrogen stream, temperature
Warmed to 70 ° C. To this, methyl methacrylate 30
g, methyl acrylate 60 g, the following monomer (B-1)
10 g, ethanol 50 g and 2,2′-azobis (I
Sovaleronitrile) (abbreviation AIVN) 1.5 g
Was added dropwise over 1.5 hours and stirred as such for 2 hours.
It was. Next, A. I. V. N. Is added at a temperature of 75 ° C.
And stirred for 3 hours. I. B. N. 0.
8 g was added, and the mixture was heated to 80 ° C. and stirred for 3 hours.
Next, the temperature is raised to 100 ° C., and the degree of vacuum is 200 mmHg.
The mixture was stirred for 2 hours to distill off unreacted monomers. 2 after cooling
Pass through a 00 mesh nylon cloth and obtain white dispersion
Is a latex with a polymerization rate of 99% and an average particle size of 0.45 μm
there were. The particle size is CAPA-500 (Horiba, Ltd.)
(Same below). Part of the white dispersion
Centrifuge (rotation speed 1 × 10^Fourr.p.m., Rotation time 1 o'clock
And the precipitated resin particles are collected, dried, and
Mass average molecular weight (Mw) of fat particles and glass transition point (T
g) was measured, Mw was 1 × 10^Five, Tg is 40
° C. [0195] Embedded image[0196] Embedded image Production Examples 2-6 of Resin Particles (L): Resin Particles
(L-2) to (L-6) In Production Example 1 for resin particles (L), a dispersion stabilizing resin
For dispersion stabilization described in Table-G below instead of (P-1)
Other than using the resin (P), the same as in Production Example 1 above.
Resin particles (L) were produced. Each obtained resin particle (L)
The polymerization rate is 99% or more, and the average particle size is 0.40 to 0.4.
The monodispersibility was also good within the range of 5 μm. Also,
Mw for each resin particle is 1 × 10^Five~ 2x10^Five, Tg
40-42 ° C Range. [0198] [Table 1] Production Example 7 of Resin Particles (L): Resin Particles (L
-7) The following dispersion stabilizing resin (P-7) 12g and Isopar
H, while stirring 340 g of mixture under nitrogen stream, temperature 7
Warmed to 0 ° C. Benzyl methacrylate 40
g, 46 g of methyl acrylate, monomer having the following structure (B
-2) 10 g, octadecyl acrylate 4 g, isop
60 g of propyl alcohol and A.I. I. V. N. 1.2
g of the mixture was added dropwise over 2 hours and stirred for 2 hours.
It was. Next, A. I. V. N. Is added at a temperature of 75 ° C.
And stirred for 3 hours. I. B. N. The
0.8 g was added, and the mixture was heated to 80 ° C. and stirred for 3 hours.
The temperature is then raised to 100 ° C. and reduced under a reduced pressure of 200 mmHg.
Stir for hours to distill off ethanol and unreacted monomer.
It was. Pass through a 200 mesh nylon cloth after cooling.
The white dispersion had a polymerization rate of 99% and an average particle size of 0.48 μm.
It was latex. Mw of resin particles is 2 × 10^Five,
Tg was 42 ° C. [0200] Embedded image[0201] Embedded image Production Examples 8-15 of Resin Particles (L): Resin Particles
Child (L-8) to (L-15) In Production Example 7 of resin particle (L), a dispersion stabilizing resin
(P-7) and octadecyl acrylate as monomer (C)
Instead of relate, the dispersion stabilization tree described in Table H below
Fat (P) and monomer (C) listed in Table I below
Resin particles were used in the same manner as in Production Example 7 except that they were used.
(L) was produced. Polymerization rate of each resin particle (L) obtained
Is 98-100%, average particle size is 0.45-0.50 μm
And the monodispersibility was also good. For each resin particle
Mw of 1 × 10^Five~ 3x10^Five, Tg is 40-43 ° C
Range. [0203] [Table 2] [0204] [Table 3]Production Example 16 of Resin Particle (L): Resin Particle
(L-16) The following dispersion stabilizing resin (P-16) 8g and Isopar
While stirring a mixture of H and 335 g under a nitrogen stream, the temperature was 7
Warmed to 0 ° C. 20g methyl methacrylate,
27g ethyl acrylate, octadecyl methacrylate
3 g, monomer (B-3) 13 g having the following structure, A. I.
V. N. , 1.0 g and 65 g of ethyl alcohol
Each of them is added dropwise at the same time in 1 hour and stirred as it is for 2 hours.
Stir. Next, A. I. V. N. 1.0g and temperature 7
The mixture was heated to 5 ° C. and stirred for 3 hours. I. B. N.
0.8g was added, heated to 80 ° C and stirred for 3 hours.
It was. The temperature is then raised to 100 ° C and the degree of vacuum is 200mmHg
And stirred for 2 hours to distill off the ethanol. 200 after cooling
The resulting white dispersion is polymerized.
It was a latex with an average particle size of 0.45 μm at a rate of 99%.
It was. Mw of resin particles is 2 × 10^Five, Tg is 42 ° C
It was. [0206] Embedded image [0207] Embedded image Production Example 17 of Resin Particles (L): Resin Particles
(L-17) The following dispersion stabilizing resin (P-17) 8g and Isopar
G While stirring 284 g of mixture under nitrogen stream, temperature 7
Warmed to 0 ° C. To this, 35 g of methyl methacrylate,
47 g of methyl acrylate, hexadecyl methacrylate
4 g, monomer (B-4) 12 g having the following structure, A. I.
V. N. , 1.5 g and ethanol 60 g
The solution was added dropwise over 1 hour and stirred for 2 hours. Next, A.
I. V. N. 1.0g and warm to 75 ° C to 3
Stir for hours, and I. B. N. Add 0.8g
The mixture was heated to 80 ° C. and stirred for 3 hours. Then set the temperature to 1
Raise to 00 ° C and stir for 2 hours under reduced pressure of 200mmHg.
Knoll and unreacted monomers were distilled off. 200 after cooling
Through a nylon mesh cloth, the resulting white dispersion is heavy
It is a latex with a total ratio of 99% and an average particle size of 0.45 μm.
It was. Mw for resin particles is 1 × 10^Five, Tg at 43 ° C
there were. [0209] Embedded image [0210] Embedded image Production Examples 18-23 of Resin Particles (L): Resin
Particles (L-18) to (L-23) In Production Example 17 of resin particle (L), monomer (B-
4) and the substitution of hexadecyl methacrylate (monomer C)
Instead, 12 g of monomer (B) and monomer in Table-J below
(C) Other than using 4 g, production example of the resin particle (L)
In the same manner as in Example 17, each resin particle (L) was produced. Obtained
The average particle size of each particle (L) is 0.40 to 0.45 μm.
The range was latex. Mx for resin particles is 1 × 1
0^Five~ 3x10^Five, Tg was in the range of 40-45 ° C. [0212] [Table 4] Comparative resin particle production example 1: Resin particles (L
R-1) In Production Example 1 of the resin particle (L), a single amount to be polymerized
As a body, 35 g of methyl methacrylate and methyl acrylate
The ratio was the same as in Production Example 1 except that a rate of 65 g was used.
Comparative resin particles (LR-1) were produced. White content obtained
The powder had a polymerization rate of 96% and an average particle size of 0.42 μm.
It was. Mw of resin particles is 2 × 10^Five, Tg is 39 ° C
It was. Example 1 <Preparation of an original plate for lithographic printing>
Paint shaker with beads (Toyo Seiki Co., Ltd.)
And then dispersed for 60 minutes, and then the glass beads are filtered off.
To obtain a dispersion. [0215] ・ 8g gelatin ・ Alkoxysilane-modified polyvinyl alcohol R1130 (manufactured by Kuraray Co., Ltd.)                                                               4g Silica: Silicia 310 (Fuji Silysia Chemical Co., Ltd.) 8g ・ Colloidal silica 20% solution: Snowtech C 38g (Nissan Chemical Industry Co., Ltd.) ・ Fluorinated alkyl ester FC430 (manufactured by 3M) 0.8g ・ Hardenous compound 0.24g           CH₂= CHSO₂CH₂CONH (CH₂)_ThreeNHCOCH₂SO₂CH = CH₂ ・ Water 54g Known as an electrophotographic lithographic printing original plate
ELP-1X master (Fuji Photo Film Co., Ltd.)
The above composition is placed on the wire bar.
Apply using-and dry at 100 ° C. for 10 minutes to apply
8g / m² An image-receiving layer of lithographic printing plate
Obtained. The surface smoothness of the obtained image receiving layer is Beck smooth
10ml air capacity using a temperature tester (manufactured by Kumagaya Riko Co., Ltd.)
Measure the smoothness (sec / 10ml) under the conditions of 250
(Sec / 10ml). Also, steam on the surface of the image receiving layer.
Place 2 μl of retained water and show the surface contact angle (degrees) after 30 seconds.
Measured using a surface contact meter CA-D (Kyowa Interface Science Co., Ltd.)
Set. The contact angle of the image receiving layer surface with water was 0 degrees.
It was. <Preparation of oil-based ink (IK-1)> Polyd
10 g of decyl methacrylate, 10 g of alkali blue
And Shellsol 71 with 30g glass beads
Put in a paint shaker (manufactured by Toyo Seiki Co., Ltd.), 4 o'clock
And disperse the glass beads to form a fine blue dispersion.
Obtained. Resin particles produced in Production Example 1 of the resin particles (L)
Child (L-1) 50 g (as solid content), the above alkali
18 g of the blue dispersion and cobalt octenoate
By diluting 09g to 1 liter of Isopar G
A blue oil-based ink (IK-1) was prepared. Comparative Example A In Example 1, instead of oil-based ink (IK-1)
And other oil-based ink (IKR-1) with the following contents
Was performed in the same manner as in Example 1. <Preparation of comparative oil-based ink (IKR-1)>
> In preparation of oil-based ink (IK-1), resin particles
Instead of (L-1), use comparative resin particles (LR-1)
Other than that, the oil property for comparison was the same as ink (IK-1).
An ink (IKR-1) was prepared. These oil-based inks have charging characteristics, ejection properties,
Check the dot shape, image reproducibility, printing durability, etc.
The results are shown in Table-K. [0221] [Table 5] The evaluation items described in Table-K are as follows.
I did it. Note 1) Charging characteristics (AC electrical conductivity) AC electrical conductivity as ink charge
The degree (pS / cm) was measured. AC electrical conductivity of ink
Is an LCR meter (AG-431 manufactured by Ando Electric Co., Ltd.)
It was measured in 1). When measuring, test the LCR meter.
Via Toledo (AG-4912, manufactured by Ando Electric Co., Ltd.)
Put 2.3 ml of ink to be measured and make it by yourself
Electrode for liquid (Kawaguchi Electric)
Connect to LP-05 manufactured by Co., Ltd.
Conductance measurement at 5V voltage and 1kHz measurement frequency
Electrical conductivity by dividing the value by the electrode constant.
Converted to degrees. During the measurement, the measurement parameters of the LCR meter
Meter settings are capacitance, circuit mode
The setting was parallel mode. (Charge fraction of particles) Dispersed particles in ink
Represents the ratio of the amount of charge. [0224] [Expression 1] Here, the charge amount of the supernatant is far from the ink.
Heart separation method (Condition: 1 × 10^Four r.p.m., 1 hour)
AC of transparent liquid which is the supernatant obtained by sedimentation
Represents conductivity. Furthermore, the conditions I and II are those after the ink production.
The condition is changed, and condition I is the total composition.
The resulting ink is allowed to stand for 1 week (normal temperature, normal humidity)
On the other hand, Condition II is
Fresh products with high temperature and high humidity (35 ℃, 85% RH)
Stored for 1 month under the conditions and forced aging (aging product)
It is. Note 2) Dischargeability As for the discharge performance, an injection needle as shown in FIG.
It was measured with the equipment. The injection needle is made of stainless steel and has an inner diameter of 36
0 μm, outer diameter 615 μm, tip cutting angle 19 degrees, curved
The rate radius is 13 μm, and the ink tank 36 is provided at the tip of the needle.
From the inside of the needle by the liquid feed pump 35
Always supply, and surplus ink is naturally transferred to the needle surface to waste liquid
Collected in the tank 37. The ink flow rate at this time is 0.75.
ml / min. This injection needle is placed on the drum-shaped counter electrode 31.
The surface of the plate as the recording medium 32 attached to the
200 μm apart from each other, and bias power is supplied by the power source 33.
700V as discharge voltage to 700V, 100μSec width
Is applied with a pulse voltage of 5.0 kHz at a frequency of 5.0 kHz.
Was printed. Bias and pulse voltage poles
Sex was determined so that the ink was repelled from the needle. Vomiting
The output rate is the number of dots actually printed with respect to the number of applied pulses.
Calculated from the number (%). Conditions I and II are in the case of Note 1)
Is the same. Note 3) Print dot shape (Film thickness) Discharge experiments were conducted for the above discharge property evaluation items.
The thickness of the printed dots on the sample was measured using a scanning electron microscope (S
EM) Measured from photographs. As the film thickness is printed thicker,
This means that the particles in the tank are concentrated and discharged. (Shape) Similarly, an optical microscope using the above sample.
Dot bleeding and distortion by microscopic and SEM photo observation
Etc. were examined. [4] Image reproducibility Using the planographic printing original plate created as described above,
Servo Prota made by Graphtec that can draw the output
-DA8400 is modified and the Ben Plotter part is shown in Fig. 2.
Attach the indicated ink ejection head and keep the interval of 300 μm.
The lithographic printing plate placed on the counter electrode
Printing was performed using oil-based ink. Mark at this time
Characters are bias voltage 650V, discharge voltage 750V, 10
A pulse voltage with a width of 0 μsec is called a frequency of 2.0 kHz
Performed under conditions. Continue, RICOHFUSER model 5
92 (Ricoh Co., Ltd.)
Adjust the temperature to be 100 ° C and heat for 30 seconds.
The part was sufficiently fixed. Of the obtained plate-making product (ie, printing plate)
Visual observation of copied images with an optical microscope at 200x magnification
I guessed. Note 5) Printing durability Using the printing plate obtained according to the method of note 4) above, soaking
As water, SLM-OD (Mitsubishi Paper Co., Ltd.) with water 3
Oliver 9 was used as a printing machine using a solution diluted 0 times.
For offset printing using type 4 (manufactured by Sakurai Seisakusho Co., Ltd.)
Printed with black ink. No dirt, lack of fine lines, letters, etc.
The number of prints that produce clear, clear images
Represent. As shown in Table-K, Example 1 shows the charge characteristics.
Shows good results and changes over time
Is small and practically acceptable. On the other hand, comparative example
A has a small charge amount and a low charge fraction of particles.
there were. Furthermore, due to changes over time, the change in chargeability is large,
In particular, the charge fraction of the particles was significantly reduced. Next, the ejection properties and the dots on the printed plate material
From the result of the shape of the product, fresh product (Condition I)
(Condition II) Both show good performance in Example 1.
It was. That is, Comparative Example A has a thin film thickness, and the dot shape is also blurred.
Only occurred. The actual plate-making images are fresh and
Only Example 1 shows good performance for both timed products.
It was. Furthermore, Example 1 was printed using this printing plate.
The printing durability was 3,000 sheets or more. Comparative Example A starts from printing
The image is missing and cannot be used practically.
The image area was lost after printing about 1,000 sheets. From the above results, the ink of the present invention is in the storage state.
Even if the state changes, the charge amount of the entire ink is large and the particles
The charge fraction of the particles is as high as 85% or more, and even after aging, the particles
Has good dispersibility and does not cause aggregation or precipitation. These things
By the electrostatic ink jet ink discharge
To stably form an ink meniscus on the discharge electrode, and
Electrophoresed charged particles in ink quickly under voltage suppression
The particles are concentrated and in that state are ink receiving materials
Printed on the original printing plate. Therefore, the printing dock on the plate material
The film thickness is as thick as 1.0 μm, and the dots are also circular in shape.
No distortion is observed. In addition, as a printing plate
When printing at the time, the thickness of the image part is enough,
The printing durability was as good as 3,000 sheets or more. On the other hand, Comparative Example A has a small amount of ink charge.
In addition, the charge fraction of the particles is as small as 50% or less.
Formability and particle concentration are insufficient and formed
The platemaking image was unsatisfactory. Further charged over time
Sex deteriorated. From the above, only the oil-based ink of the present invention
However, stable and good performance was exhibited over time. Examples 2 to 15 In Example 1, resin particles in oil-based ink (IK-1)
Each resin particle of the following table-L instead of child (L-1) 50g
Other than using 50 g (as solid content), oil-based ink
Prepare and implement each oil-based ink in the same manner as (IK-1)
Evaluation was performed in the same manner as in Example 1. [0237] [Table 6] Oil-based inks (IK-2) to (IK-1)
5) All are equivalent to or better than oil-based ink (IK-1)
AC characteristics are shown, and the AC conductivity is 320 even in the sample of Condition II.
~ 340 (pS / cm), particle charge fraction 85 ~ 93%
It was in range. Actual ejection performance, dot shape, image reproducibility
Both the printing durability and the printing durability are the same as or better than Example 1.
Obtained. In addition, there is no aggregation or precipitation of particles over time,
Dispersibility was good. Example 16 <Preparation of an original plate for lithographic printing>
Place in a paint shaker with beads for 80 minutes
After the dispersion, the glass beads were separated by filtration to obtain a dispersion. [0240] Silica: Silicia 445 (Fuji Silysia Chemical Co., Ltd.) 40g ・ Colloidal silica 20% solution: Snowtech C 200g   (Nissan Chemical Industry Co., Ltd.) ・ Clay 50% dispersion 40g Polyvinyl alcohol: PVA-117, 10% solution 120 g (Kuraray Co., Ltd.) ・ Melamine resin 2.0g ・ Ammonium chloride 0.2g ・ Water 50g Known as an electrophotographic planographic printing original plate
ELP-2X Master (Fuji Photo Film Co., Ltd.)
The above composition is placed on the wire bar.
Apply by using, and heat at 110 ° C for 10 minutes to apply
Amount 6 g / m²An image-receiving layer of lithographic printing plate
Obtained. The surface smoothness of the obtained image receiving layer is Beck smooth
300 degrees (sec / 10ml), the contact angle with the surface water is 0 degrees
there were. Making this printing original plate in the same manner as in Example 1
did. However, the oil-based ink (IK-1) used in Example 1
Use the following oil-based ink (IK-16) instead of
It was. <Preparation of oil-based ink (IK-16)>
Resin particles (L-) obtained in Production Example 17 of resin particles (L)
17) 60 g (as solid content) and Sumikaron Navy B
A mixture of 3 g lue (manufactured by Sumitomo Chemical Co., Ltd.)
The mixture was heated to 0 ° C. and stirred with heating for 3 hours. After standing overnight at room temperature
Pass the 200 mesh nylon cloth to remove the remaining dye.
Leaving a blue resin dispersion with an average particle size of 0.48 μm
I got a thing. 25 g of the above blue resin dispersion (as solid content)
) Zirconium naphthenate as a charge control agent 0.
02 g of hexamethyldisiloxane / Isopar G (2
/ 3 mass ratio) to a total volume of 1 liter
As a result, a blue oil-based ink (IK-16) was prepared. The characteristics of the obtained ink are the same as in Example 1.
To obtain the results shown in Table-M below. load
Electricity, ejection properties, and dot shape are good over time.
It was. [0244] [Table 7] Next, after making the plate in the same manner as in Example 1,
Printing was done. The obtained printed matter is the same as the printed matter of Example 1.
Similarly, the non-image area is clean and clear.
The printing durability was as good as 10,000 sheets or more. Also high
Performance using ink (Condition II) that has been stored under high temperature and high humidity
As a result of the investigation, no aggregation or precipitation of particles was observed and the dispersibility was good.
Actual plate-making and printing results are as good as fresh products
It was a good result. Examples 17-29 In Example 16, instead of oil-based ink (IK-16)
In addition, Example 1 except that each oil-based ink shown in Table-N below was used.
Plate making was carried out in the same manner as in No. 6. The oil-based ink used
In the oil-based ink (IK-16) in Example 16,
In place of the resin particles (L-17)
Other than using 50 g of each resin particle shown in (as solid content)
Was created in the same way. [0247] [Table 8] Ink characteristics were evaluated in the same manner as in Example 16.
As a matter of fact, each ink has an AC electrical conductivity of 38 for each ink.
0-410 (pS / cm), particle charge fraction is 85-9
The range was 5%. The image reproducibility is completely the same as in Example 16.
The performance was equivalent and good. In addition, as a printing plate
The plates printed and all the plates exhibited printing durability of 10,000 sheets or more. Ma
In addition, with respect to the aged ink (condition II), Example 16
Image reproducibility and printing durability equivalent to fresh products
Indicated. Example 30 <Preparation of water-resistant support> Weighing 100 g / m as substrate²
Using high-quality paper, the underside of the following composition on one side of the substrate
Apply the layer paint using a wire bar and dry coating amount
10 g / m²An under layer was provided. Under layer surface
Smoothness is 150 seconds / 10ml.
The smoothness was adjusted to 1500 (second / 10 ml). [0250] <Under layer paint> ・ Silica gel 10 parts by mass ・ 92 parts by mass of SBR latex (50 mass% aqueous dispersion, Tg: 25 ° C.) ・ Clay (45% by mass aqueous dispersion) 110 parts by mass ・ 5 parts by weight of melamine (80% by weight aqueous solution) ・ 191 parts by weight of water Further, a battery having the following composition is formed on the other surface of the substrate.
Apply the coating for the quart layer using a wire bar and dry it.
Dry coating amount 12g / m²After providing the back coat layer,
The smoothness of the back coat layer is about 50 (seconds / 10ml)
Set the calendar conditions to
It was. [0252] <Paint for back coat layer> ・ 200 parts kaolin (50% aqueous dispersion) ・ 60 parts of polyvinyl alcohol aqueous solution (10%) ・ 100 parts of SBR latex (solid content 49%, Tg: 0 ° C.) ・ Melamine resin initial condensate 5 parts (Solid content 80%, Sumirez resin SR-613) <Preparation of planographic printing original plate> Zinc oxide 100
g, 16 g of binder resin (E-1) having the following structure, binder resin
(E-2) 2 g, benzoic acid 0.15 g and toluene 1
55 g of the mixture was mixed with a wet disperser homogenizer (Nippon Seiki)
Rotational speed 6 × 10 using^ThreeDisperse for 8 minutes at rpm
did. [0254] Embedded image This dispersion is coated on the above water-resistant support.
Application amount 10g / m using ear bar²So that
When applied and dried, the surface smoothness is 250 (seconds / 10ml)
An original for lithographic printing was prepared. The surface contact angle with water is 10
It was twice. <Preparation of oil-based ink (IK-30)>
10 g of dispersion stabilizing resin (P-1), black pigment (Microlit
h Black CT (Ciba Geigy) 10g and Isopar
E, 113g paint shaker with glass beads
And disperse for 6 hours.
I got a splinter. 60 g of the above resin particles (L-23) (solid content
66 g of the above black dispersion and naphthenic acid
Total amount of 0.08 g of konium with hexamethyldisiloxane
Diluted to 1 liter to obtain black oil-based ink (IK
-30). AC electrical conductivity of the ink obtained
Is 390 (pS / cm) and the particle charge fraction is 92%
It was. The above printing original plate and oil-based ink (IK-3)
0) was used in the same manner as in Example 1 to make a plate.
A plate-making product with a clear image without missing lines and characters was obtained. Do
The thickness of the tablet is 2.3μm, and there is no blur or distortion
It was good. Sample of condition II shown in Example 1
However, the dispersibility is good and the change in chargeability is slight.
It was. [0258] Next, the oil-in
Each of the plate making products made using
All of the solution (ELP-E2, manufactured by Fuji Photo Film Co., Ltd.)
Automatic printing machine (AM-2850, AM Co., Ltd.)
Put it in the catcher section, and use it as a dampening solution for desensitizing treatment liquid (E
A solution obtained by diluting LP-E2) 4 times with distilled water is used as a dampening solution.
Place in the tray and print using black ink for offset printing
I did it. As a result, a clear image with no smudges
More than 3,000 prints were obtained. [0259] The oil-based ink of the present invention is used.
In the electrostatic ink jet recording system,
An image with excellent ejection stability, clear image formability and image strength
Along with being able to form an image, a large number of prints of clear images
A printing plate that can be printed can be provided.
In addition, the electrostatic ink jet oil-based ink of the present invention
Excellent dispersibility and storage stability of the dispersed particles.
There is no clogging in the supply path, and ink ejection is stable.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic configuration diagram showing an example of an apparatus system to which the oil-based ink of the present invention can be applied. FIG. 2 is a diagram showing a part of a head of an ink jet recording apparatus to which the oil-based ink of the present invention can be applied. FIG. 3 is a diagram in which a meniscus regulating plate is removed from the head shown in FIG. 2; FIG. 4 is a diagram showing a discharge experiment apparatus used in Examples. DESCRIPTION OF SYMBOLS 1 Inkjet recording apparatus 2 Master for lithographic printing (master) 3 Computer 4 Bus 10 Inkjet recording head 13 Inkjet recording head 14 Head body 15, 16 Meniscus regulating plate 17 Discharge electrode 18 Ink groove 19, 21 Partition 20, 20 'discharge part 22 tip part 31 drum-shaped counter electrode 32 recording medium 33 power supply 34 recording head 35 liquid feed pump 36 ink tank 37 waste liquid tank

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 2C056 EA05 EA06 FA07 FB04 FB08                       FC01                 2H084 AA25 AE03 BB02 BB13 CC05                 2H086 BA01 BA54 BA59 BA60                 4J039 AD01 AD03 AD06 AD08 AD09                       AD10 AD12 AD22 AE11 CA04                       CA07 EA41 EA44 EA46 GA24

Claims (1)

[Claims] [Claims] [Claim 1] Oiliness for electrostatic ink jets comprising at least charged resin particles dispersed in a non-aqueous carrier liquid having an electric resistance of 10 ⁹ Ω · cm or more and a dielectric constant of 3.5 or less In the ink, the dispersed resin particles are in a non-aqueous solvent, (A) at least one monofunctional monomer that is soluble in the non-aqueous solvent and becomes insoluble by polymerization, (B) An amino group represented by the following general formula (I);
An acidic group selected from a PO ₃ H ₂ group and a —SO ₃ H group,
At least one monofunctional monomer copolymerizable with the monomer (A), each containing at least one kind in the same molecule, and (P) a weight containing a component represented by the following general formula (PI) An oil-based ink for electrostatic inkjets, characterized in that it is copolymer resin particles obtained by polymerizing and granulating a solution containing at least one kind of dispersion-stabilizing resin soluble in a non-aqueous solvent as a coalescence. [Chemical 1] In general formula (I), R ¹ and R ² may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms, or R ¹ and R ² are bonded together with a nitrogen atom. A ring may be formed. [Chemical 2] In the general formula (PI), A ^1p represents —COO—, —OCO—, —
(CH ₂ ) _a COO—, — (CH ₂ ) _a OCO—, —O—,
Or [Chemical Formula 3] (Where E is a direct bond, -O-, -OCO- or -CO
Represents O-). a represents an integer of 1 to 12. L represents an alkyl group having 8 to 32 carbon atoms or an alkenyl group having 8 to 32 carbon atoms. p ¹ and p ² may be the same or different from each other, and each represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group having 1 to 7 carbon atoms, —COO—D ¹ , or —COO via a hydrocarbon group. -D ¹ (where D ¹
Represents a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms).