CN106909034A - Curable liquid developer - Google Patents

Abstract

The present invention relates to a kind of curable liquid developer, it contains toner-particle, polymerization initiator and cationically polymerizable liquid monomer, wherein the cationically polymerizable liquid monomer contains the compound provided by following formula (A)：(R-CH=CH-O -)_n–C_mH_(2m+2–n)[in formula (A), m represents more than 12 and less than 50 integer to formula (A)；N represents more than 2 integer；Hydrogen atom or alkyl with more than 1 and the carbon of less than 3 are represented with R].

Description

Curable liquid developer

Technical field

The present invention relates in the image shape using electrophotographic system such as electrophotography, electrostatic recording and electrostatic printing The liquid developer used in forming apparatus.

Background technology

Electrophotographic system is wherein by making uniformly powered (the powered step of image bearing member such as Electrifier frame, photoreceptor Suddenly), electrostatic latent image (step of exposure) is formed by the exposure on described image bearing carrier surface, with containing colored resin particles Developer make the latent electrostatic image developing (development step) being consequently formed, by the developer image to recording medium such as paper Or plastic foil (transfer step) and the developer image of transfer is fixed to the recording medium (fix steps) is printed The method of material.

Here, developer is broadly divided into dry developer and liquid developer：In the former, by containing resin glue and The colored resin particles that the material of colouring agent such as pigment is formed are used with drying regime, and in the latter, the pigmentary resin Grain is dispersed in electrically insulating liquid.

In recent years, from the image forming apparatus using electrophotographic system, such as duplicator, facsimile machine, printer etc. Color output and the demand of flying print increasing always.In the field of colour print, to high-resolution, high quality image Demand caused to can adapt to flying print while high-resolution, the demand of the developer of high quality image can be formed.

Known liquid developer is to provide the developer of the advantage in terms of color image reproduction.For liquid development The aggregation of the colored resin particles between agent, suppression Storage period in liquid developer occurs, therefore, fine toner can be used Grain.Therefore, using liquid developer, the excellent properties on fine rule image rendition and grayscale reproducibility are readily available.Pass through Using these excellent features, carry out that toner-particle is powered in liquid developer and the developer passes through electrophoretic development And transfer, the development on the high image quality using the Electronic Photographing Technology, high-speed figure printing equipment just becoming quite to live Jump.In view of these situations, there is the demand to liquid developer of the research and development with even better property.

Used as liquid developer, colored resin particles are dispersed in electrically insulating liquid such as hydrocarbon organic solvent, silicone oil etc., are It is known.However, when electrically insulating liquid remains in recording medium such as paper, plastic foil etc. above, image can be significantly reduced Quality, thus must be driven off the electrically insulating liquid.In being generally used for removing the method for electrically insulating liquid, apply heat energy and lead to Pervaporation removes electrically insulating liquid.However, from the viewpoint or energy-conservation viewpoint of environment, being steamed due to releasing organic solvent from described device The possibility of gas and due to big energy requirement, thus the method is not favourable.

In this as countermeasure, it has been suggested that by the method for photopolymerization curing electrically insulating liquid.Photo curable liquid shows Shadow agent uses the monomer with reactive functional groups as electrically insulating liquid, and further contains the Photoepolymerizationinitiater initiater of dissolving. The photo curable liquid developer also can adapt at a high speed, because it passes through the reactive functional groups exposes for example purple to light Reaction under the irradiation of outside line and experience solidification.Proposed in Japanese Patent Application Laid-Open 2003-57883 it is such can light consolidate The liquid developer of change.

In Japanese Patent Application Laid-Open 2003-57883, there is provided acrylate monomer such as urethane acrylate is made It is the example of the monomer with reactive functional groups.

Japanese Patent No. 3442406 proposes the curable liquid medium for use the impedance value with particular range as can The electrically insulating liquid of solidification.Give cationic polymerization type curable developer, for example, epoxide, vinyl ethers, ring Vinyl ethers of shape etc., as the example of curable liquid medium.

Additionally, Japanese Patent Application Laid-Open 2015-127812 provides the reality of ultraviolet solidifiable liquid developer Example, it avoids specific insulation reduction and shows the balance between fixing performance and high image density.This is by using second What alkenyl ether monomer was realized as cationically polymerizable liquid monomer and by being combined with specific aggregation initiator.

The content of the invention

However, foregoing acrylate monomer has low volume resistivity, this promotes the electricity of electrostatic latent image in development step Gesture declines, therefore has been difficult to obtain high image density, and has generated image blurring (image is presented the deterioration of its acutance).

On the other hand, when the liquid developer for using foregoing cationically polymerizable curable, occur what moisture caused Solidification suppresses.Even if in order to also keep the fixing performance of liquid developer in a humid environment, it is believed that preferably mix and use It is at least one that there are at least 2 polyfunctional monomers of vinyl ethers vinyl ether group in each molecule as such liquid The cationically polymerizable liquid monomer of body developer.

The example of such polyfunctional vinyl ether monomers is given in Japanese Patent No. 3442406：1,4- hexamethylenes Dimethanol divinyl ether, diethylene glycol divinyl ether, butanediol divinyl ether, hexylene glycol divinyl ether, ethohexadiol Divinyl ether and decanediol divinyl ether.

As example, trimethylolpropane tris vinyl is also provided in Japanese Patent Application Laid-Open 2015-127812 Ether, 2- ethyl -1,3- hexylene glycols divinyl ether, 2,4- diethyl -1,5- pentanediols divinyl ether, 2- butyl -2- ethyls - 1,3- propane diols divinyl ether, neopentyl glycol divinyl ether, pentaerythrite tetravinyl ether and Decane-1,2-diol divinyl Base ether.

When using these polyfunctional vinyl ether monomers, it is seen that the improvement of fixing performance in wet environment, but these The Typical examples of polyfunctional vinyl ether monomer are respectively provided with low boiling, and actually readily volatilized monomer.

It is described after image formation and printing have been completed in using the image forming apparatus of curable liquid developer Developer roll, intermediate transfer member in equipment etc. keep holding state, in this condition from the curable liquid development The carrier fluid of agent is thinly coated on their surface.

However, in the case of using the liquid developer of conventional liq monomer as described above, carrier fluid experience by Gradually volatilize.Diffusion from described device to the outside can be prevented by the mechanism for providing the composition of the absorption volatilization, but pacified Dress absorber increases the cost and size of the equipment.

On the other hand, it is also possible to which the carrier components for sealing the equipment to prevent the volatilization diffuse to outside, but such as The carrier components of this volatilization finally pollute other components of the device interior.In these components, Charging system is to waving The pollution sensibility of the composition of hair, when it pollutes, the charging uniformity reduction of the Electrifier frame, photoreceptor is produced negative to image quality Influence.By cleaning the component, can to a certain extent recover image quality, but complete cleaning requirement hand labour, this It is heavy and exacerbation operating cost.

The present invention provides the liquid developer for solving the above problems.Therefore, the present invention provides a kind of curable liquid and shows Shadow agent, it is shown for the very little volatilization of the vinyl ether compound of curable liquid developer, thus avoids institute The component pollution of device interior is stated, while high image quality is kept for a long time, even if in a humid environment, also showing that excellent Fixing performance.

The present invention is curable liquid developer, and it contains toner-particle, polymerization initiator and cationically polymerizable Liquid monomer, wherein the cationically polymerizable liquid monomer contains the compound provided by following formula (A)：

(R-CH=CH-O-)_n-C_mH_(2m+2-n)Formula (A)

[in formula (A), m represents more than 12 and less than 50 integer；N represents more than 2 integer；With R represent hydrogen atom or Alkyl with more than 1 and the carbon of less than 3].

Therefore, the present invention can provide a kind of curable liquid developer, and it avoids the component of the device interior from polluting, High image quality is kept for a long time simultaneously, even if in a humid environment, also showing that excellent fixing performance.

From the description (referring to the accompanying drawing) of following illustrative embodiments, further aspect of the present invention will become bright It is aobvious.

Brief description of the drawings

Fig. 1 is the schematic diagram of the major part of image forming apparatus；

Fig. 2 is the sectional view of image formation unit；

Fig. 3 is compound A-13's¹H-NMR spectrum；

Fig. 4 A are the enlarged drawing of Fig. 3；

Fig. 4 B are the enlarged drawing of Fig. 3；

Fig. 4 C are the enlarged drawing of Fig. 3；With

Fig. 5 is the FT-IR spectrograms of compound A-13.

Specific embodiment

It is discussed in more detail below the present invention.

Curable liquid developer (hereinafter also referred to as liquid developer) of the invention contains toner-particle, polymerization Initiator and cationically polymerizable liquid monomer.

The single constituent that curable liquid developer of the invention includes is described below.

[cationically polymerizable liquid monomer]

Cationically polymerizable liquid monomer in the present invention contains the compound provided by following formula (A)：

(R-CH=CH-O-)_n-C_mH_(2m+2-n)Formula (A)

[in formula (A), m represent more than 12 and less than 50 (preferably more than 12 and less than 25, more preferably more than 18 and 25 with Under) integer；N represents more than 2 integer；Hydrogen atom or alkyl with more than 1 and the carbon of less than 3 are represented with R].

(R-CH=CH-O-) in formula (A)_n(being expressed as formula (A1) below) represents vinyl ether group feature, and n tables Show the quantity of the vinyl ether group in a molecule for being present in the compound.

In the present invention, n is more than 2 integer, thus represents the polyfunctional monomer with a plurality of vinyl ether groups. By using polyfunctional monomer, less influence by the polymerization-inhibiting effects that moisture causes and in wet environment is thus obtained Show the liquid developer of excellent fixing performance.

Cationic polymerization is commonly referred to be, wherein by with by exposure cause decompose and from polymerization initiator generate The reaction of acid monomers produces the polymerisation of cationic active material, as long as wherein cationic active material presence, described poly- Reaction is closed with regard to continuously carrying out.

It is thought that in the present invention, being produced with the sour reaction generated by polymerization initiator by the vinyl ether structure Raw cationic active material.When now there is hydrone near the monomer, the cationic active material is captured, therefore It is not polymerized further.

That is, each hydrone stops a chain reaction for vinyl ether structure.In consideration of it, larger n numerical value is aobvious to liquid The fixing of shadow agent is favourable.

On the other hand, as n numerical value increases, it is more difficult to obtain corresponding cationically polymerizable liquid monomer.

Based on these considerations, the n in formula (A1) is preferably more than 2 and less than 6, more preferably more than 2 and less than 4, and even More preferably more than 2 and less than 3.

On the other hand ,-the C in formula (A)_mH_(2m+2-n)(being expressed as formula (A2) below) is alkane chain, and m represents the alkane Carbon number in hydrocarbon chain.The hydrocarbon can be with branched along its direction (course).By having the carbon number of more than 12 in alkane chain, The evaporation of the monomer almost can be completely prevented, and when the carbon number is more than 18, can completely prevent the evaporation of the monomer.

When the upper limit of carbon number in considering the alkane chain, viscosity should be focus.In order to keep the electrophoresis of toner-particle Speed, the liquid developer is preferably more than 0.5mPas and below 100mPas in 25 DEG C of viscosity, more preferably More than 0.5mPas and below 30mPas.

When the viscosity is higher than indicated scope, the electrophoretic velocity of the toner-particle tends to reduce, printing Speed tends to reduce or print density tends to reduce.

The viscosity of the cationically polymerizable liquid monomer in curable liquid developer of the invention can be by containing formula (A) compound is adjusted as main component and addition viscosity modifier, and the viscosity modifier is, for example, oligomeric high viscosity Thing or the low viscosity cationically polymerizable liquid monomer in addition to the compound of formula (A).

In consideration of it, the viscosity of the compound of formula (A) is preferably more than 0.5mPas and below 100mPas, more preferably More than 0.5mPas and below 30mPas.This eliminates the necessity of addition viscosity modifier.

On the other hand, the carbon number in alkane chain on formula (A2), monomer viscosity in itself is with carbon number increase Increase.Consider above-mentioned, the carbon number (that is, the value of m) in the alkane chain of formula (A2) is preferably less than 50, more preferably less than 25.

The instantiation [Compound of Example A-1 to A-31] of the compound of formula (A) given below, but the present invention is not limited to These examples are not limited to these examples.

(the C in the Compound of Example_xH_yPart represents straight-chain hydrocarbons.)

The compound of single type (A) can be used, or two or more combinations can be used.Additionally, the compound of formula (A) is in institute The content stated in cationically polymerizable liquid monomer is preferably, in cationically polymerizable liquid monomer described in 100 mass parts, 60 More than mass parts and below 100 mass parts, and more preferably in cationically polymerizable liquid monomer described in 100 mass parts, 70 matter More than amount part and below 100 mass parts.

In the present invention, from liquid have specific insulation high, for electric insulation and have near room temperature low viscous Viewpoint, selects the cationically polymerizable liquid monomer.

The viewpoint of the resin glue in being present in toner-particle is not dissolved from liquid further preferably, the cation is selected Polymerizable liquid monomer.

In detailed programs, preferably from for cationically polymerizable liquid monomer/resin glue combination, no more than 1 matter Amount part resin glue is dissolved in the viewpoint in cationically polymerizable liquid monomer described in 100 mass parts at 25 DEG C, carries out Selection.

Here, the specific insulation of the cationically polymerizable liquid monomer is preferably from about 1 × 10⁹More than Ω cm and 1 ×10¹⁵Below Ω cm, more preferably from about 1 × 10¹⁰More than Ω cm and 1 × 10¹⁵Below Ω cm.

When the body resistivity is less than 1 × 10⁹During Ω cm, this promotes the potential of electrostatic latent image to decline, so that more Come get over be difficult to obtain optical density (OD) high and increasingly promoting occur it is image blurring.

On the other hand, the cationically polymerizable liquid monomer 25 DEG C of viscosity be preferably from about more than 0.5mPas and Less than 100mPas, more preferably from about 0.5mPas is less than 30mPas.

Cationically polymerizable liquid monomer in curable liquid developer of the invention contains the compound of formula (A). The compound of the formula (A) is that heteroatomic vinyl ethers chemical combination is not contained in addition to the vinyl ether structure (- CH=CH-O-C-) Thing.

Here, " hetero atom " represents the atom beyond carbon atom and hydrogen atom.

When hetero atom is present in the vinyl ether compound in addition to the vinyl ether structure, this not only promote due to Difference between hetero atom and the electronegativity of carbon atom and there is the polarization of electron density intramolecular, and hetero atom occupy not altogether The electron orbit for enjoying electronics pair and/or sky also becomes to conduct the passage in electronics or hole, therefore promotes specific insulation reduction.

Additionally, the compound of formula (A) does not contain the carbon-to-carbon double bond in addition to the compound medium vinyl ether structure.It is described Carbon-to-carbon double bond has the unoccupied molecular orbit for taking molecular orbit and low energy level of high-energy level, and these are easy The passage in electronics and hole is formed, specific insulation reduction is then easily caused.

When carbon-to-carbon double bond is present in the compound except the vinyl ether structure, volume is promoted by the mechanism Resistivity reduction.

The compound of formula (A) does not still contain the structure of cyclic rings.When there are cyclic rings, this tends to lead to higher Solubility parameter (hereafter abbreviated with SP values).In the case of SP values high, the compound easily absorbs moisture in itself, as a result exists In high humidity environment, the hydrone absorbed by the compound promotes the suppression of the solidification mediated to cationic polymerization, therefore The defective fixing of the liquid developer can occur.

Here, SP values are the parameters of compatibility：Assuming that two molecules are (that is, mutual in the absence of such as electrostatic in regular solution The solution of effect, cohesive force (hydrogen bonding), dipolar interaction etc.) in active force there was only molecular separating force, therefore solubility is joined Number is used as to represent measuring for molecular separating force.Although real solution is not limited to regular solution, by rule of thumb, it is known that with two points Difference between the SP values of son becomes smaller, and bigger dissolubility is presented.

The SP values of vinyl ether compound are typically about 7.0 to 10.0 (cal/cm³)^1/2But, containing ring-type ring structure Vinyl ether compound in the case of, they are presented larger (cal/cm of value 8.5 to 10.0³)^1/2.On the other hand, the SP of water It is 23.4 (cal/cm to be worth³)^1/2Even if compared with other solvents, it is also high level, in consideration of it, the vinyl ether compound SP values should be as small as possible, to prevent water point dissolving.

For example, the computational methods according to Hansen or Hoy are estimated according to molecular structure, it is for calculating SP values Known method, but the value is preferred for according to the evaluation method of the relatively convenient of Fedors.

In view of above-mentioned point, the cationically polymerizable liquid monomer does not preferably contain hetero atom in addition to vinyl ether structure Or carbon-to-carbon double bond, and with not containing the alkane chain structure of cyclic rings.

Considered according to SP values, because when the terminal position of alkane chain has methyl, SP values tend to step-down, thus leave Methyl on the terminal position of the alkane chain in the present invention provides the resistance that the bigger solidification caused to moisture suppresses, and from The viewpoint of fixing performance, this is favourable.

That is, considered according to fixing performance, the compound of formula (A) preferably has the second provided by the following formula (A1) in formula (A) At least one of alkenyl ether groups is bonded to the non-end of the carbon atom to form the alkane chain provided by the following formula (A2) in formula (A) Carbon atom：：

(R-CH=CH-O-)_nFormula (A1)

-C_mH_(2m+2-n)Formula (A2)

[in formula (A1) and formula (A2), m represent more than 12 and less than 50 (preferably more than 12 and less than 25, more preferably 18 with It is upper and less than 25) integer；N represents more than 2 integer；Hydrogen atom is represented with R or with the carbon of more than 1 and less than 3 Alkyl].

The compound of formula (A) can be by with the hydrogen atom on multiple hydroxyls replacement alkane, then carrying out the vinyl of hydroxyl It is etherified to synthesize.

Consideration based on being readily available property, the initial alkane preferably has the carbon of less than 25.

Particularly, it may be advantageous to using having 12 or 18 alkane of carbon, because they can be from natural material such as castor-oil plant Oil is reclaimed.

The hydroxylated alkane is also commercially available：For example, 1,2- dodecanediol (Tokyo Chemical Industry Co., Ltd.), 1,12- dodecanediols (Tokyo Chemical Industry Co., Ltd.), 1,12- it is pungent Glycol (ProductName：HSTOL, KOKURA SYNTHETIC INDUSTRIES, LTD.), and phytantriol (KURARAY CO., LTD. it is) commercially available.

The method for obtaining vinyl ether group from hydroxyl is known：For example, such as the use second in WO 2013/018302 The method of alkynes gas；Such as J.Am.Chem.Soc.9, Vol.124, the use acetic acid second disclosed in No.8,2002,1590-1591 The method of alkene ester and iridium complex；With the method using palladium and bathophenanthroline (bathophenanthroline).

For example, in order to serve as viscosity modifier, the cationically polymerizable liquid monomer in the present invention can contain except formula (A) Various cationically polymerizable liquid monomers beyond compound.

The cationically polymerizable liquid monomer to may include is not limited, as long as not damaging the liquid developer Developing performance and fixing performance, the example are cationically polymerizable liquid monomer such as acrylic monomer, cyclic ether monomers such as ring Oxide and oxetanes, and the vinyl ether compound in addition to the compound of formula (A).

Among foregoing, preferably having specific insulation high and low viscosity in the present invention and can providing high sensitivity to consolidate The vinyl ether compound (in addition to the compound of formula (A)) of the liquid developer of change.

[Compound of Example B-1 is extremely for the instantiation of the vinyl ether compound in addition to the compound of formula (A) given below B-22], but the present invention is not limited to these examples or not limited to these examples.

One kind of these vinyl ether compounds can be used, or two or more combinations can be used.

Among foregoing, based on volatile consideration, there is the carbon of more than 12 and less than 50 preferably in alkane segment Monofunctional vinyl ether compound, for example, dodecyl vinyl (B-1), octadecyl vinyl ether (B-2), different hard Aliphatic radical vinyl ethers (B-3) etc..

These vinyl ether compounds cause the deterioration of the fixing performance in wet environment, because all of which is that have one The monofunctional monomer of individual vinyl ether group.

However, by them being used in conjunction with the compound of formula (A), the fixing performance in wet environment can be kept.

In cationically polymerizable liquid monomer described in 100 mass parts, the content of the vinyl ether compound of the simple function (that is, the compound of formula (A) is more than 60 mass parts) below preferably 40 mass parts, and (that is, formula below more preferably 30 mass parts (A) compound is more than 70 mass parts).

On the other hand, the consideration based on fixing performance, the example of preferred polyfunctional monomer is cyclohexanedimethanol diethyl Alkene ether (B-15), trimethylolpropane tris vinyl ethers (B-16), 2- ethyls -1,3- hexylene glycols divinyl ether (B-17), 2,4- diethyl -1,5- pentanediols divinyl ether (B-18), 2-butyl-2-ethyl-1,3-propanediol divinyl ether (B- 19), pentaerythrite tetravinyl ether (B-20) and 2- decanediols divinyl ether (B-21).

Although these vinyl ether compounds all provide excellent fixing performance in wet environment, they are in alkane Having less than 12 carbon in segment.Therefore, when the cationically polymerizable liquid monomer is only by these vinyl ether compound groups , due to the volatilization of these vinyl ether compounds, thus there is the component pollution in the equipment in Cheng Shi.

However, being used in conjunction with by the compound with formula (A), the pollution of the component in the equipment can be prevented.

It is many having less than 12 carbon in alkane segment in cationically polymerizable liquid monomer described in 100 mass parts The content of functional vinyl ether compound is preferably below 40 mass parts (that is, the compound of formula (A) is more than 60 mass parts), and (that is, the compound of formula (A) is more than 70 mass parts) below more preferably 30 mass parts.

In the present invention, the cationically polymerizable liquid monomer can contain oligomer, to improve the cationic polymerization The viscosity of property liquid monomer.

It is preferred feature to have the vinyl ether oligomers of vinyl ether group in oligomer end position, because they Show the excellent curability by being polymerized together with the cationically polymerizable liquid monomer.

The instantiation [Compound of Example C-1 to C-6] of vinyl ether oligomers presented below, but the present invention is not limited to These examples are not limited to these examples.

(m and n in above-mentioned formula represent that offer weight average molecular weight is more than 1,000 and less than 10,000 independently of one another The integer of Compound of Example.)

These vinyl ether oligomers can be by the hydrogenated polyolefins with terminal position with hydroxyl as raw material carries out hydroxyl Vinyl etherificate prepare.

Consider the compatibility with the compound of formula (A), have the vinyl ethers of vinyl ether group oligomeric in terminal position The weight average molecular weight of thing is preferably less than 10,000.On the other hand, in order to realize the function of thickener, the vinyl ethers is oligomeric The weight average molecular weight of thing is preferably more than 1,000.

In cationically polymerizable liquid monomer described in 100 mass parts, the vinyl ethers for realizing thickener function is low The content of polymers is preferably from about more than 1 mass parts and below 30 mass parts, it is more than more preferably from about 5 mass parts and 20 mass parts with Under.

[polymerization initiator]

In order to trigger the polymerisation of the cationically polymerizable liquid monomer, the reaction of referred to as initiation reaction is necessary 's.Material for the purpose is polymerization initiator.

It is below the example of the polymerization initiator in the present invention.

Cationic polymerization initiators can enumerate salt compound and non-ionic compound such as sulfonyidiazomethanes compound, Oxime sulfonate compounds, iminosulfonate compound and trichloromethyl triaizine compounds；However, being not limited to these.

The salt compound can enumerate iodine compound (for example, the IRGACURE (registration mark) from BASF SE 250 and WPI-113, WPI-116, WPI-169, WPI- from Wako Pure Chemical Industries, Ltd. 170 and WPI-124) and sulfonium compound (triaryl matte salt compound CPI-110P and CPI- from San-Apro Ltd. 210S, and the aromatics sulfonium salt compound Adeka Optomer SP-150 from ADEKA CORPORATION).

The non-ionic compound can enumerate following compounds.

Sulfonyidiazomethanes compound can be enumerated from Wako Pure Chemical Industries, Ltd's WPAG-145 (double (cyclohexylsulfonyl) diazomethanes)), WPAG-170 (double (tert. butylsulfonyl) diazomethanes)) and WPAG-199 (double (p-toluenesulfonyl) diazomethanes)).

Oxime sulfonate compounds can enumerate IRGACURE (registration mark) PAG103 [(5- sulfonyl propyl epoxides imino group- 5H- thiophene -2- pitch base (ylidene))-(2- aminomethyl phenyls) acetonitrile], IRGACURE (registration mark) PAG108 [(5- octyl group sulphurs Acyloxy imino group -5H- thiophene -2- pitches base)-(2- aminomethyl phenyls) acetonitrile] and IRGACURE (registration mark) PAG121 [(5- Tolysulfonyl epoxide imino group -5H- thiophene -2- pitches base)-(2- aminomethyl phenyls) acetonitrile], it all is from BASF SE.

Iminosulfonate compound can enumerate the N- trimethyl fluoride sulfonyl epoxides from Sigma-Aldrich Co.LLC. Succinimide, N- hydroxynaphthylimides triflate and N- hydroxyl -5- ENB -2,3- dicarboximides perfluor - 1- butane sulphonic acid esters.

Trichloromethyl triaizine compounds can enumerate the double (trichlorines of 2- [2- (furans -2- bases) ethylidine (ethenyl)] -4,6- Methyl)-s- triazines, double (the trichloromethyl)-s- triazines of 2- [2- (5- methylfuran -2- bases) ethylidine] -4,6-, 2- (methoxyl groups Phenyl) double (the trichloromethyl)-s- triazines of -4,6- and double (three chloromethanes of 2- [2- (3,4- Dimethoxyphenyls) ethylidine] -4,6- Base)-s- triazines, it all is from Sanwa Chemical Co., Ltd.

Among these cationic polymerization initiators, preferred non-ionic compound such as sulfonyidiazomethanes compound, oxime sulphur Ester compound, iminosulfonate compound and trichloromethyl triaizine compounds.Because, when by these nonionic chemical combination When thing mixes with the cationically polymerizable liquid monomer, the specific insulation of the cationically polymerizable liquid monomer is hardly Reduce.

The instantiation of the iminosulfonate compound is provided and is further described.

The iminosulfonate compound enumerates the compound with following formulas (1).

[in formula (1), R₁And R₂Bond together to form cyclic structure；X represents more than 1 and less than 8 integer；And y Represent more than 3 and less than 17 integer.]

Compound with formula (1) experience light when exposure is to ultraviolet is decomposed, and generates sulfonic acid (it is strong acid).This Outward, it can be applied in combination with sensitizer, in the case the ultraviolet radiation absorption of sensitizer serve as cause polymerization initiator decompose and Produce the triggering agent of sulfonic acid.

By R₁And R₂The ring structure for bonding together to form can enumerate 5- yuan of rings and 6- yuan of rings.By R₁And R₂The ring for bonding together to form The instantiation of structure is succinimide structure, phthalimide structure, ENB dicarboximide structure, the formyl of naphthalene two Asia Amine structure, hexamethylene dicarboximide structure and epoxycyclohexyethylSiOi alkene dicarboximide structure.

These cyclic structures can also have, for example, the conduct such as alkyl, alkoxy, alkylthio group, aryl, aryloxy group, arylthio Substitution base.

C in formula (1)_xF_yStraight chained alkyl (RF1), wherein hydrogen that wherein hydrogen atom has been replaced by fluorine atoms can be enumerated former Branched alkyl (RF2), the cycloalkyl (RF3) that wherein hydrogen atom has been replaced by fluorine atoms and wherein hydrogen that son has been replaced by fluorine atoms The aryl (RF4) that atom has been replaced by fluorine atoms.

The straight chained alkyl (RF1) that wherein hydrogen atom has been replaced by fluorine atoms can enumerate trifluoromethyl (x=1, y=3), five fluorine Ethyl (x=2, y=5), seven fluorine n-propyls (x=3, y=7), perfluoro-n-butyl group (nonafluoro-n-butyl group) (x =4, y=9), perfluor n-hexyl (x=6, y=13) and n-perfluoro-octyl (x=8, y=17).

The branched alkyl (RF2) that wherein hydrogen atom has been replaced by fluorine atoms can enumerate perfluoroisopropyl (x=3, y=7), complete The fluorine tert-butyl group (x=4, y=9) and perfluor -2- ethylhexyls (x=8, y=17).

The cycloalkyl (RF3) that wherein hydrogen atom has been replaced by fluorine atoms can enumerate perfluorocyclobutanearyl (x=4, y=7), perfluor Cyclopenta (x=5, y=9), perfluorocyclohexyl (x=6, y=11) and perfluor (1- cyclohexyl) methyl (x=7, y=13).

The aryl (RF4) that wherein hydrogen atom has been replaced by fluorine atoms can enumerate pentafluorophenyl group (x=6, y=5) and 3- trifluoros Methyl tetrafluoro phenyl (x=7, y=7).

For the C in formula (1)_xF_y, from the being readily available property and the viewpoint of decomposability of sulfonate moiety, preferably straight chain alkane Base (RF1), branched alkyl (RF2) and aryl (RF4).More preferably straight chained alkyl (RF1) and aryl (RF4).Particularly preferred trifluoro Methyl (x=1, y=3), pentafluoroethyl group (x=2, y=5), seven fluorine n-propyls (x=3, y=7), perfluoro-n-butyl group (x=4, y= 9) with pentafluorophenyl group (x=6, y=5).

The instantiation [Compound of Example D-1 to D-27] of the compound with formula (1) given below, but the present invention is not It is confined to these examples or not limited to these examples.

Among foregoing, because being combined with sensitizer, they are easily obtained fixing performance high, thus preferably (D-23), (D- 24), (D-25), (D-26) and (D-27).

A kind of polymerization initiator can be used, or two or more combinations can be used.

The content of the polymerization initiator in the curable liquid developer is not particularly limited, but is expressed as every 100 Cationically polymerizable liquid monomer described in mass parts, it is preferably more than 0.01 mass parts and below 5 mass parts, and more preferably 0.05 More than mass parts and below 1 mass parts, more than even more preferably 0.1 mass parts and below 0.5 mass parts.

[toner-particle]

Curable liquid developer of the invention contains toner-particle.

Additionally, the toner-particle preferably comprises resin glue and colouring agent.

<Resin glue>

Have to adherend such as paper and plastic foil fixing performance and insoluble in the cationically polymerizable liquid monomer Know that resin glue can be used as the resin glue that the toner-particle includes.

Here, the insolubility in the cationically polymerizable liquid monomer is represented, at a temperature of 25 DEG C, it is no more than The resin glue of 1 mass parts is dissolved in cationically polymerizable liquid monomer described in 100 mass parts.

The resin glue is specifically exemplified by, and such as epoxy resin, ester resin, (methyl) acrylic resin, styrene- (methyl) acrylic resin, alkyd resin, polyvinyl resin, ethene-(methyl) acrylic resin and Abietyl modified resin Deng resin.If necessary, can independently using individually a kind of or combined using two or more.

The resin glue content is not particularly limited, but colouring agent described in every 100 mass parts, its preferably 50 mass parts Above and below 1,000 mass parts.

[colouring agent]

The colouring agent that the toner-particle includes is not particularly limited, for example, can be used any generally commercially available The organic pigment of acquisition, organic dyestuff, inorganic pigment are dispersed in for example as the face in the insoluble resin of decentralized medium Material or the pigment with the resin for being grafted to its surface.

These pigment are retouched in can enumerating " the Industrial Organic Pigments " of W.Herbst and K.Hunger. The pigment stated.

Instantiation on these pigment, present yellow pigment can enumerate it is following：

C.I. pigment yellow 1,2,3,4,5,6,7,10,11,12,13,14,15,16,17,23,62,65,73,74,83,93, 94、95、97、109、110、111、120、127、128、129、147、151、154、155、168、174、175、176、180、181 With 185；C.I. Vat Yellow 1,3 and 20.

The pigment of presentation red or magenta can enumerate following：

C.I. paratonere 1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,21,22,23, 30、31、32、37、38、39、40、41、48:2、48:3、48:4、49、50、51、52、53、54、55、57:1、58、60、63、64、 68、81:1、83、87、88、89、90、112、114、122、123、146、147、150、163、184、202、206、207、209、 238 and 269；C.I. pigment violet 19；With C.I. vat reds 1,2,10,13,15,23,29 and 35.

The pigment of presentation blueness or cyan can enumerate following：

C.I. alizarol saphirol 2,3,15:2、15:3、15:4th, 16 and 17；C.I. reductive blue 6；C.I. acid blue 45；Wherein phthalein The copper phthalocyanine that cyanines skeleton is replaced by 1 to 5 phthalimidomethyl.

The pigment of presentation green can enumerate following：

C.I. pigment Green 7,8 and 36.

The orange pigment of presentation can enumerate following：

C.I. pigment orange 66 and 51.

The pigment of presentation black can enumerate following：

Carbon black, titanium be black and nigrosine.

The pigment of presentation white can enumerate following：

Basic lead carbonate, zinc oxide, titanium oxide and strontium titanates.

The dispensing implement for being suitable for toner-particle preparation method can be used to be dispersed in the pigment in toner-particle. Hereinafter can be used as the example of the device of the dispensing implement：Ball mill, sand mill, grinder, roller mill, injector-type mill, Change device, paint shaker, kneader, agitator, Henschel blender, colloid mill, ultrasonic homogenizer, ball mill (pearl mill), wet shotcrete technology formula grinding machine etc..

In the pigment dispersion, it is also possible to add pigment dispersing agent.The pigment dispersing agent can be enumerated with hydroxyl The carboxylate of base, the salt of long-chain polyaminoamide and HMW acid esters, the polycarboxylic salt of HMW, HMW are unsaturated It is acid esters, high molecular weight copolymer, modified polyacrylate, aliphatic polycarboxylic acid, naphthalene sulfonic acids/formaline condensates, poly- Ethylene oxide alkyl phosphate and pigment derivative.Further preferably using commercial polymeric dispersant, such as from The The Solsperse series of Lubrizol Corporation.

The synergist for being suitable for specific pigment also is used as pigment dispersion aids.

Every 100 mass parts pigment, preferably adds these pigment dispersing agents and the face more than 1 mass parts and below 50 mass parts Material dispersing aid.

[charge control agent]

If necessary, curable liquid developer of the invention can contain charge control agent.Known electric charge can be used Controlling agent.

The example of particular compound is as follows：

Grease such as Linseed oil and soybean oil；Alkyd resin；Halogenic polymer；Aromatic multi-carboxy acid；Water solubility containing acidic group Dyestuff；The oxidative condensate of aromatic polyamine；Metallic soap for example cobalt naphthenate, nickel naphthenate, iron naphthenate, zinc naphthenate, cobalt octoate, Nickel octoate, zinc octoate, lauric acid/dodecanoic acid cobalt, lauric acid/dodecanoic acid nickel, zinc laurate, aluminum stearate and 2 ethyl hexanoic acid cobalt；Metal sulfonate is such as The slaine of petroleum base metal sulfonate and sulfosuccinate；Phosphatide such as lecithin；Metal salicylate salt such as tert-butyl group bigcatkin willow Acid metal salt complex compound；Polyvinyl pyrrolidone resin；Polyamide；Resin containing sulfonic acid；Hydroxybenzoic acid derivative.

[powered auxiliary agent]

If necessary, in order to adjust the target of the chargeding performance of toner-particle, the toner-particle in the present invention can be wrapped Include powered auxiliary agent.Known powered auxiliary agent can be used.

The example of particular compound is as follows：Metallic soap such as zirconium naphthenate, cobalt naphthenate, nickel naphthenate, iron naphthenate, cycloalkanes Sour zinc, zirconium caprylate, nickel octoate, zinc octoate, lauric acid/dodecanoic acid cobalt, lauric acid/dodecanoic acid nickel, zinc laurate, aluminum stearate, three aluminum foil stearates and 2- Cobalt of ethyl hexanoate；The slaine of metal sulfonate such as petroleum base metal sulfonate and sulfosuccinate；Phosphatide such as lecithin and Hydrolecithin；Metal salicylate salt such as tert-butyl salicylic acid metal salt complex；Polyvinyl pyrrolidone resin；Polyamide resin Fat；Resin containing sulfonic acid；Hydroxybenzoic acid derivative.

[sensitizer]

If necessary, in order to for example improve the sour efficiency of the product of polymerization initiator and photonasty wavelength be extended into longer ripple Target long, can be added to curable liquid developer of the invention by sensitizer.

In addition to the sensitizer should be able to be sensitized polymerization initiator by electron transmission mechanism or energy conversion machine system, It is not particularly limited.

Instantiation be aromatics more than contracting cycle compound such as anthracene, 9,10- dialkoxies anthracene, Bi He perylene；Aromatic keto compounds are such as Acetophenone, Benzophenone, thioxanthones and Michler's keton；With heterocyclic compound such as phenthazine and N- Fang oxazolidinones.

Taken the circumstances into consideration to select sensitizing agent content according to the target, but, polymerization initiator described in every 1 mass parts, sensitizer contains Amount is usually more than 0.1 mass parts and below 10 mass parts, more than preferably 1 mass parts and below 5 mass parts.

In order to improve the target of electron transmission efficiency or energy transfer efficiency between foregoing sensitizer and polymerization initiator, Also sensitizing auxiliary agent can be added to curable liquid developer of the invention.

Instantiation is naphthalene compound such as 1,4- dihydroxy naphthlenes, 1,4- dimethoxy-naphthalenes, 1,4- diethoxies naphthalene, 4- methoxies Base -1- naphthols and 4- ethyoxyl -1- naphthols, and benzene compound such as Isosorbide-5-Nitrae-hydroquinones, Isosorbide-5-Nitrae-dimethoxy benzene, Isosorbide-5-Nitrae-diethoxy Base benzene, 1- methoxyl group -4- phenol and 1- ethyoxyl -4- phenol.

Taken the circumstances into consideration to select sensitizing auxiliary agent content according to the target, but, sensitizer described in every 1 mass parts, sensitizing auxiliary agent contains Amount is usually more than 0.1 mass parts and below 10 mass parts, more than preferably 0.5 mass parts and below 5 mass parts.

[cationic polymerization inhibitor]

Also cationic polymerization inhibitor can be added to curable liquid developer of the invention.

The cationic polymerization inhibitor can enumerate alkali metal compound and/or alkaline earth metal compound and amine.

Amine can enumerate alkanolamine, N, N- dimethyl alkylamines, N, N- dimethyl alkenyl amine and N, N- dimethyl alkynylamine.

Instantiation be triethanolamine, triisopropanolamine, three butanolamines, N- ethyldiethanolamines, Propanolamine, n-butylamine, Sec-butylamine, 2- ethylaminoethanols, 2- methyl amino ethanols, 3- methylamino -1- propyl alcohol, 3- methylamino -1,2- propane diols, 2- second Base ethylaminoethanol, 4- ethylaminos-n-butyl alcohol, 4- (n-butylamino)-n-butyl alcohol, 2- (tert-butylamino) ethanol, N, N- bis- Methylundecane hydramine, N, N- dimethyl dodecyls hydramine, N, N- dimethyltridecanes hydramine, N, N- dimethyl tetradecyl alcohol Amine, N, N- dimethyl pentadecanes hydramine, N, N- dimethyl nonadecyls amine, N, the base amine of N- dimethyl 20 (N, N ,- Dimethylicosylamine), N, N- dimethyl eicosyl amine, N, N- dimethyl heneicosyls amine, N, N- dimethyl two Lauryl amine, N, N- dimethyl tricosyls amine, N, N- dimethyl tetracosyls amine, N, N- dimethyl pentacosyls Amine, N, N- dimethyl-pentens hydramine, N, N- Exxal8s amine, N, N- dimethyl-gs hydramine, N, N- dimethyl-octas hydramine, N, N- bis- Methyl nonyl alcohol amine, N, N- dimethyl decyl alcohol amine, N, N- dimethyl nonyls amine, N, N- dimethyl decyl amines, N, N- dimethyl 11 Alkylamine, N, N- dimethyl dodecylamines, N, N- dimethyltridecane bases amine, N, N- dimethyl tetradecyl amines, N, N- bis- Methyl pentadecyl amine, N, N- dimethyl hexadecyl amines, N, N- dimethyl heptadecyl amine and N, N- dimethyl stearyl Amine.In addition to that, for example, it is also possible to use quaternary ammonium salt.The cationic polymerization inhibitor is particularly preferably secondary amine.

Based on the quality of curable liquid developer, the content of the cationic polymerization inhibitor is preferably more than 1ppm And below 5,000ppm.

[radical polymerization inhibitor]

Radical polymerization inhibitor may be added to that curable liquid developer of the invention.

For example, in the case of the curable liquid developer containing vinyl ether compound, during storing, polymerization Initiator may experience micro decomposition, thus change into free radical compounds, thus may cause to be drawn by the free radical compounds The polymerization for rising.Expect addition radical polymerization inhibitor to prevent such case.

Usable radical polymerization inhibitor can enumerate the compound containing phenolic hydroxyl group；Quinones such as p methoxy phenol (methoquinone) (hydroquinone monomethyl ether), quinhydrones and 4- methoxyl group -1- naphthols；Hindered amine antioxidant；1,1- diphenyl -2- is bitter Diazanyl free radical (picrylhydrazyl free radical)；N- epoxide free radical compounds；Nitrogenous heterocyclic mercapto chemical combination Thing；Thioether antioxidant；Hindered phenol antioxygen；Ascorbic acid；Zinc sulfate；Thiocyanates；Thiourea derivative；Carbohydrate；Phosphatic type resists Oxygen agent；Nitrous acid ester；Sulfite；Thiosulfates；Hydroxylamine derivative；Aromatic amine；Phenylenediamine；Imines；Sulfonamide；Urea derives Thing；Oxime；The condensation polymer of dicyandiamide and polyalkylene polyamine；The compound of sulfur-bearing such as phenthazine；Based on four azaannulenes (TAA) Complexing agent；And hindered amine.

The increased viewpoint of viscosity, the preferably compound of phenolic hydroxy group, N- oxygen are experienced from curable liquid developer is prevented Base free radical compounds, 1,1- diphenyl -2- hardship diazanyls free radical, phenthazine, quinones and hindered amine.More preferably N- epoxides freedom Based compound.

Based on the quality of curable liquid developer, the content of the radical polymerization inhibitor is preferably more than 1ppm And below 5,000ppm.

[other additives]

In addition to those described above, if necessary, in order to improve compatibility, storage stability, figure with recording medium As storability and the target of other characteristics, various known additives can be used for curable liquid developer of the invention. It is surfactant, lubricant, filler, defoamer, ultra-violet absorber, antioxidant, anti-color fading agent, sterilization in this example Agent, preservative etc., can take the circumstances into consideration to select and use these.

In the present invention, the preparation method of the curable liquid developer is not particularly limited, and can enumerate known Method, for example, coacervation and case of wet attrition method.

The example of customary preparation methods is to mix pigment, resin glue and other additives and decentralized medium；Use For example ball mill (bead mill) is crushed to obtain toner-particle dispersion；Disperse with the toner-particle that will be obtained Body, polymerization initiator, cationically polymerizable liquid monomer etc. mix to obtain the preparation method of liquid developer.

The details of coacervation are described in such as Japanese Patent Application Laid-Open 2003-241439, WO2007/000974 and WO In 2007/000975.

In coacervation, the solvent of pigment, resin, the solvent for dissolving the resin, the insoluble resin is mixed, so The solvent of the dissolving resin is removed from the mixture afterwards, to cause the resin precipitated for having dissolved, embedding is consequently formed Dispersion of the toner-particle of pigment in the solvent for not dissolving the resin.

On the other hand, the details of case of wet attrition method are described in such as WO 2006/126566 and WO2007/108485.

In case of wet attrition method, pigment and resin glue are mediated under the fusing point of resin glue or more than fusing point；So Afterwards, dry grinding is carried out；Case of wet attrition is carried out in electric insulating medium with the material of crushing obtained by making, toning is consequently formed Dispersion of the agent particle in electric insulating medium.

Known method such as these can be used for the present invention.

From from the viewpoint of obtaining high-definition image, the volume average particle size of the toner-particle is preferably 0.05 μm Above and less than 5 μm, more preferably more than 0.05 μm and less than 1 μm.

Can freely be used in the curable liquid developer in the regulation present invention according to the image forming apparatus for using Toner-particle concentration, but expectation be more than about 1 mass % and below 70 mass %.

[characteristic of curable liquid developer]

Preferably use and be formulated to of the invention curable with conventional liq developer identical property value Liquid developer.

From from the viewpoint of the potential decline for avoiding electrostatic latent image, the specific insulation of the curable liquid developer It is preferred that 1 × 10¹⁰More than Ω cm and 1 × 10¹³Below Ω cm.These property values are met the invention enables preparation while also showing Show that the curable liquid developer of high solidification is possibly realized.

[image forming apparatus]

Curable liquid developer of the invention is advantageously used for using the common or conventional of electrophotographic system Image forming apparatus.

The implementation method of property, describes curable liquid developer application of the invention to as liquid below as an example The electrophotographic image-forming apparatus (in the following referred to as image forming apparatus) of image forming apparatus.

Fig. 1 is the schematic diagram of the major part of the image forming apparatus according to present embodiment.

Described image forms equipment by image formation unit 50C, 50M, 50Y, 50K；Primary transfer unit 60C, 60M, 60Y、60K；Secondary transfer unit 30；Constituted with developer solidified cell 90.

Described image forms unit 50C, 50M, 50Y, 50K and works respectively, with cyan (C) liquid developer, magenta Color (M) liquid developer, yellow (Y) liquid developer and black (K) liquid developer make image development.

Described image forms unit 50C, 50M, 50Y, 50K and by Electrifier frame, photoreceptor 52C, 52M, 52Y, 52K and will come from respectively Store the respective liquid developer replenishing developing cell 51C of developer reservoir 10C, 10M, 10Y, 10K of liquid developer, 51M, Liquid developer supply pump 13C, 13M of 51Y, 51K, 13Y, 13K, and Charging system, exposure device, cleaning unit and around every The Xelminator of individual Electrifier frame, photoreceptor configuration is constituted.

Described image forms unit 50C, 50M, 50Y, 50K all with identical structure, therefore refers to image and forms list First 50C continues described below.

Fig. 2 gives the sectional view of image formation unit 50C.Charged elements are configured along Electrifier frame, photoreceptor 52C direction of rotation 57C, exposing unit 56C, developing cell 51C, primary transfer unit 60C (Fig. 1), recovery scraper 59C and static elimination unit 58C.Electrifier frame, photoreceptor 52C has cylindrical substrate and is formed in the photosensitive layer of its neighboring；It is can center rotation on center shaft Turn；It is rotated clockwise in the present embodiment.The surface of Electrifier frame, photoreceptor 52C is formed by non-crystalline silicon (a-Si). For example, organic photoconductor (OPC) etc. can also be used for the material of the Electrifier frame, photoreceptor.

Charged elements 57C is the device for making Electrifier frame, photoreceptor 52C powered.Charger unit Charging system or roller strap electricity can be used Device.

Exposing unit 56C has semiconductor laser, polygon mirror, F- Theta lens etc., by will modulation laser emission to powered Electrifier frame, photoreceptor 52C on form sub-image.Light emitting diode (LED) or Organic Light Emitting Diode (OLED) be can also be configured as laser Source.

Static elimination unit 58C is the device for neutralizing Electrifier frame, photoreceptor 52C.Can be used corona discharge type Charging system or Roller contact-type Charging system.

Scraper 59C is reclaimed by the rubber components such as polyurethane rubber on contact Electrifier frame, photoreceptor 52C surfaces and the supporting rubber Glue component simultaneously scrapes in recovery unit 12C gold to be removed by will remain in the liquid developer on Electrifier frame, photoreceptor 52C The plate of category etc. is constituted.

Developing cell 51C is made up of developer roll 53C, concentration roller 54C, clearer 55C and masking counter electrode 11C.

Developer roll 53C be cylindrical element, and as shown in Fig. 2 along with Electrifier frame, photoreceptor 52C rightabouts on center shaft in The heart rotates.The developer roll 53C equips elastic member, such as polyurethane rubber of conduction, and in the outer of metal such as iron kernel Resin bed or rubber layer on circumference.

The masking counter electrode 11C is configured so as to there is at least 100 μm of gap with developer roll 53C, it is by hardware Constitute.

Concentration roller 54C is cylindrical element, and as shown in Fig. 2 along with developer roll 53C rightabouts center on center shaft Rotation.The concentration roller 54C is made up of metal such as iron.

Clearer 55C is cylindrical element, and as shown in Fig. 2 along with developer roll 53C rightabouts center on center shaft Rotation.

Developer reservoir 10C stores the cyan coloured liquid developer for the image development for making to be formed on Electrifier frame, photoreceptor 52C. From developer reservoir 10C, by wherein configuring the connecting line of liquid developer supply pump 13C, by the liquid of adjusted concentration Developer replenishing is to developing cell 51C, while the connecting line by wherein configuring developer recovery pump 14C, residual is developed Agent is recovered to developer reservoir 10C.By the toner-particle concentration of the liquid developer in developer reservoir 10C at least adjust to 2 mass %.

Liquid developer with adjusted toner-particle concentration is supplied into rotation developer roll 53C to be balanced with masking Between electrode 11C, and by forming bias between developer roll 53C and masking counter electrode 11C, liquid developer is coated on On developer roll 53C.The bias is at least 100V, and the bias of the electric discharge limit can be formed up to.

By the connecting line including recovery pump, the residual fraction of the liquid developer of supply is reclaimed from recovery unit 12C, And be supplied to recycling can (not shown) and reuse.

Primary transfer unit 60C, 60M, 60Y, 60K respectively by intermediate transfer belt 40, primary transfer roller 61C, 61M, 61Y, 61K and Electrifier frame, photoreceptor 52C, 52M, 52Y, 52K are constituted.Intermediate transfer belt 40 is by the annular with driven roller and driven roller stretching Band, and be driven in rotation, while being contacted with Electrifier frame, photoreceptor 52C, 52M, 52Y, 52K.

Full-colour image is existed four kinds of liquid developer color continuously transfer printings by primary transfer unit 60C, 60M, 60Y, 60K Formed on intermediate transfer belt 40, described primary transfer unit 60C, 60M, 60Y, 60K is by intermediate transfer belt 40, primary transfer roller 61C, 61M, 61Y, 61K and Electrifier frame, photoreceptor 52C, 52M, 52Y, 52K are constituted.

Secondary transfer unit 30 from band driven roller, secondary transfer roller 31, pre-wetted roller 20 and pre-wetted to being constituted to roller 21, Its monochromatic liquid developer image or panchromatic liquid developer image that will be formed on intermediate transfer belt 40 is transferred to record and is situated between On such as paper of matter 80.

Pre-wetted roller 20 is cylindrical element, and as shown in figure 1, along with the rightabout of intermediate transfer belt 40 on center shaft Central rotation.

Carrier fluid is being delivered to pre-wetted roller 20 from carrier tank (not shown) and is being formed in its surface no more than 1.0 μm After carrier fluid film, by making monochromatic liquid developer image or panchromatic liquid in pre-wetted roller 20 and transfer belt formed between 40 Body developer image is contacted, and adjusts the liquid film amount of the monochromatic liquid developer image or panchromatic liquid developer image.

Light, such as ultraviolet are radiated the monochromatic liquid being transferred in recording medium 80 by developer solidified cell 90 Developer image or panchromatic liquid developer image, cause reactive functional groups to react, so as to implement solidification.The solidified cell It is made up of LED, but LED is not limited, as long as described device can radiate ultraviolet, it is possible to use heater, EB spoke Injection device etc..

[light source]

By applying energy to curable liquid developer of the invention immediately after recording medium is transferred to, consolidate it Change to be fixed image.

It is not particularly limited for energy source of the invention, but advantageously uses ultraviolet.For example, mercury lamp, metal halide Thing lamp, excimer laser, ultraviolet laser, cold-cathode tube, thermionic-cathode tube, black light or light emitting diode (LED) can be used as It is used herein to carry out the light source of ultraviolet irradiation, preferably stripe shape metal halide lamp, cold-cathode tube, thermionic-cathode tube, mercury lamp, black light Or LED.

Ultraviolet dosage is preferably 0.1mJ/cm²Above and 1,000mJ/cm²Below.

It is given below for measuring method of the invention.

<Viscosity Measurement Methods>

Rotation viscometer commercial measurement viscosity is used in the present invention.

Specifically, viscoelasticity measuring apparatus (Physica MCR300, Anton Paar GmbH) are used as described below to be surveyed Amount.

About 2mL samples are filled into and are equipped with the measuring apparatus of cone plate measured material (75mm diameters, 1 °), and It is adjusted to 25 DEG C.Measurement viscosity, while from 1,000s^-1To 10s^-1It is continuous to change shear rate, and use 10s^-1Under value As viscosity.

<Structural analysis>

Using nuclear magnetic resonance equipment (¹) and FT-IR spectrum determine compound structure H-NMR.

Test equipment and measuring method for the measurement is as follows.

(i)¹H-NMR

Measuring apparatus：JNM ECA400FT-NMR equipment (JEOL Ltd.)

Measurement frequency：500MHz

Impulsive condition：10μs

Frequency range：10,330Hz

Integral number of times (number of integrations)：16

Measurement temperature：25℃

By 50mg Sample introductions internal diameter in the coupon of 5mm；Addition deuterochloroform (CDCl₃) as solvent；With pass through Dissolved at 25 DEG C and prepare measurement sample.Using the measurement sample, measure under these conditions.

(ii) FT-IR spectrum

Measuring apparatus：Spectrum One(PerkinElmer Co.,Ltd.)

Measuring method：Single reflection ATR

Scope starting：4,000cm^-1

Terminal：400cm^-1(KRS-5ATR crystal)

Scanning times：40

Resolution ratio：4.00cm^-1

In advance：Carry out CO₂/H₂O is corrected

The correct amount 0.01g samples on atr crystal, and extrude the sample using compression arm.Surveyed using above-mentioned condition Sample obtained by amount.

[embodiment]

Embodiment and comparative example is used below and more specifically describes curable liquid developer, but the present invention does not limit to In these or it is not limited thereto.

Unless otherwise explicitly indicated, " part " and " % " in otherwise following description represents " mass parts " and " matter respectively Amount % ".

<Cationically polymerizable liquid monomer synthesis example>

(synthesis of Compound of Example A-13)

To add as 1, the 12- ethohexadiols (6.73g, 24.7mmol) and vinylacetate (16g, 186mmol) of raw material 1 Add to two-μ-chlorine two (1,5- cyclo-octadiene) two iridium (I) [Ir (cod) Cl]₂(0.15mg, 0.2mmol) and potassium carbonate (13.5g, Toluene (40.0mL) mixture 98mmol), and at 100 DEG C, under an argon, be stirred for 6 hours.The reaction solution Gas chromatographic analysis display raw material 1 conversion ratio be 93%, be denoted as difunctional vinyl's base ether list of compound A-13 The yield for preparing of body is 55%.Using separatory funnel, by organic phase and aqueous phase separation, and the organic phase is set to carry out post purifying, It is concentrated under reduced pressure, and dry, obtain compound A-13 (weight average molecular weight：338.6).Resulting compound is viscous for micro- amber transparent Property liquid.The FT-IR measurements of compound A-13 confirm that the peak produced by hydroxyl disappears.

<Embodiment 1>

(toner-particle preparation)

By 25 parts of Nucrel N1525 (ethylene-methyl methacrylate resin, DU PONT-MITSUI POLYCHEMICALS CO., LTD.) and 75 parts of dodecyl vinyls (Compound of Example B-1) import separable flask, while using Three- One motors, stir at 200 rpm, in oil bath, temperature are increased into 130 DEG C through 1 hour.In the case where being kept for 130 DEG C 1 hour Afterwards, Slow cooling is carried out with 15 DEG C/h of cooldown rate, resin glue dispersion liquid is obtained.Resulting resin glue Dispersion liquid is white paste.

Using 59.40 parts of the resin glue dispersion liquids, the pigment blue 15s as pigment:3 (4.95 parts), 0.20 part used as band Three aluminum foil stearates of electric auxiliary agent and 35.45 parts of dodecyl vinyls are filled into together with the zirconium oxide bead of a diameter of 0.5mm In planetary ball mill (Classic Line P-6, Fritsch GmbH), and at room temperature, crushing 4 is carried out at 200 rpm Hour, obtain containing 80.00 parts of toner-particle dispersions of dodecyl vinyl (Compound of Example B-1) (solid level Divide=20 mass %).

The toner-particle in toner-particle dispersion obtained by being present in has 0.85 μm of volume average particle size [measured using the Size Distribution Analyzer based on dynamic light scattering (DLS), name of product：Nanotrac 150, NIKKISO CO.,LTD.]。

(preparation of curable liquid developer)

Using 10.00 parts of foregoing toner-particle dispersions, 0.10 part of hydrolecithin as charge control agent (Lecinol S-10, Nikko Chemicals Co., Ltd.s), 80.00 parts be synthesized as above as cationically polymerizable liquid The compound A-13 of monomer and it is other 12.00 parts toner-particle dispersion preparation in be used as viscosity adjust monomer instantiation Compound B-1 mixes, then by mixing Compound of Example D-26 (0.30 part) as polymerization initiator, 0.50 part used as sensitizing 2, the 4- diethyl thioxanthones of agent and 0.50 part of Isosorbide-5-Nitrae-diethoxy naphthalene as sensitizing auxiliary agent, obtain curable liquid development Agent.Altogether containing 20.00 parts of Compound of Example B-1,8.00 parts come from toner to resulting curable liquid developer Prepared by grain dispersion and 12.00 parts are adjusted for viscosity.

<Evaluate>

The curable liquid developer is evaluated using following evaluation methods.The result is given in table 1.

(image is formed)

Using the image forming apparatus shown in Fig. 1 and 2 and resulting curable liquid developer, in poly- terephthaldehyde Image is formed on sour glycol ester (PET) piece, and checks the quality of resulting image.

Comprise the following steps that.

(1) developer roll 53, Electrifier frame, photoreceptor 52 and primary transfer roller 61 are separated from each other, and the direction of arrow exists along Fig. 1 Under contactless state, these components are driven with different rotary.Rotating speed now is 250mm/ seconds.

(2) under the squeeze pressure of 5N/cm, developer roll 53 is made to be contacted with Electrifier frame, photoreceptor 52, and formed using dc source Bias.Because developing bias are expected in the range of 100 to 400V, thus use 200V.

(3) under the squeeze pressure of regulation, Electrifier frame, photoreceptor 52 is contacted with primary transfer roller 61, and use dc source shape Into bias.Transfer bias are made to be 1,000V.

(4) under the squeeze pressure of regulation, secondary transfer unit 30 is made to be contacted with secondary transfer roller 31, and use direct current Source forms bias.Transfer bias are made to be 1,000V.

(5) curable liquid developer is supplied to developer reservoir 10C；Using by by poly terephthalic acid second two Alcohol ester (PET) piece (TEIJIN LIMITED, Panlite：PC-2151, thickness=0.3mm) adhere to a part of OK Topcoat The recording medium 80 that (Oji Paper Co., Ltd.s) obtains, forms the solid image of full page printing on the PET sheet；Then Evaluated.

After cleaned described image forms equipment and has been loaded into curable liquid developer, most elementary Section, after 1 day and after 3 days, be imaged, in the interim, the unclean device interior.Visual inspection image quality.

(evaluation criterion)

5：Obtain high density, uniform solid image

4：Density inhomogeneity and image blurring is not observed, excellent image is obtained

3：See some Density inhomogeneities or some are image blurring, but obtain general excellent image

2：Serious Density inhomogeneity and/or image blurring is produced, it was observed that unsatisfied position is, it is necessary to clean described The inside of equipment

1：Can hardly be developed, it is necessary to be cleaned the inside of the equipment

(fixing performance)

In 25 DEG C of room temperature/50% humidity environments, curable liquid developer is dropped in into polyethylene terephthalate Ester film (TEIJIN LIMITED, Panlite：PC-2151, thickness=0.3mm) on, and use bar (No. 6) [supplier： MATSUO SANGYO CO., LTD.] rod coating (forming the film that thickness is 8.0 μm) is carried out, and using with 120mW/cm²'s The high-pressure sodium lamp of light output, by exposing to the light of 365nm wavelength, forms cured film.In no surfaces of tacky (viscosity) and hair The point being fully cured has been given birth to, the amount of radiant light has been measured；It is evaluated using following standards.

5：100mJ/cm²

4：200mJ/cm²

3：400mJ/cm²

2：1,000mJ/cm²

1：In 2,000mJ/cm²Under do not solidify

Under any circumstance, for the image quality and fixing performance behind starting stage, 1 day and after 3 days, 3 or higher Grade is considered as and passes through.Evaluation result is given in table 1.

<Embodiment 2>

Replace dodecyl vinyl (example using compound A-13 in (the toner-particle preparation) of embodiment 1 Compound B-1), prepare toner-particle dispersion.Additionally, also using compound in (prepared by curable liquid developer) A-13 replaces Compound of Example B-1, prepares curable liquid developer.In example 2, all cationically polymerizable liquid Monomer is compound A-13.

<Embodiment 3 to 12 and comparative example 1 to 4>

Using the toner-particle dispersion used in embodiment 1, as embodiment 1 is carried out, curable liquid is obtained Developer, but the polymerization initiator and cationically polymerizable liquid monomer is blended, with the composition for obtaining being given in table 1.

In embodiment 7 to 12 and comparative example, (triarylsulfonium salt polymerization initiator, referred to as D-28, come from CPI-210S San-Apro Ltd.) it is used as polymerization initiator, and 1.00 parts are used as its addition.

Using so obtained curable liquid developer, evaluation in the same manner as in Example 1 is carried out.Evaluation result is given Go out in table 1.

[table 1]

As shown in embodiment in table 1, even if in a humid environment, by using the compound by formula (A) as sun The curable liquid developer of the main component of photopolymerizable liquid monomer, also obtains no Density inhomogeneity and has The excellent image of excellent fixing performance.Additionally, after 1 day with 3 days after, the image quality for forming image is seldom reduced.This table Show the pollution of the component for having already prevented from the device interior.

Embodiment 7 is contrasted with embodiment 8, the change with large content of formula (A) in cationically polymerizable liquid monomer The embodiment 7 of compound has better image quality after 3 days.

Additionally, the carbon number in the alkane chain of the compound of the formula (A) used in embodiment 8 is 18, with embodiment 9 and implementation Carbon number in the alkane chain of the compound used in example 10 is 12 contrasts, and the embodiment 8 with bigger carbon number is than embodiment 9 and in fact Apply example 10 has smaller image quality reduction after 1 day.

In embodiment 11 and embodiment 12, the carbon number in the alkane chain of the compound of the formula (A) for using is about 50, due to Somewhat poor image density in starting stage, 3 are given as in image is formed and evaluated.

It is thought that this is due to the high viscosity of curable liquid developer, this causes the electrophoretic velocity of toner-particle The toner-particle quantity for reducing and being attached to charged roller is reduced.

With liquid developer curable in other embodiments viscosity for compared with 5 to 20mPas, embodiment 11 and real The viscosity for applying the curable liquid developer in example 12 is 100mPas.It is therefore contemplated that the alkane chain of the compound of formula (A) In the upper limit of carbon number be about 50.

The compound of the formula (A) used in embodiment 9 and embodiment 10 has the carbon number in identical alkane chain, also has Identical molecular weight.

The compound of the formula (A) used in embodiment 9 is compound A-1, and it has at least one to be bonded to the formula of being formed (A) Vinyl ether group in the formula (A) of the non-end carbon atom of the carbon atom of middle alkane chain.

With this contrast, the compound used in embodiment 10 is compound A-2, and it has the alkane chain in the formula that formed (A) Carbon atom two vinyl ether groups of end.

Embodiment 9 uses the vinyl ether group also with the non-end position among the carbon atom for forming the alkane chain Compound, with more preferable fixing performance.It is thought that this is SP of the SP values less than compound A-2 due to compound A-1 Value, thus preferably suppress water adsorption.SP values are calculated by Fedors methods of estimation, the SP values for drawing compound A-1 are The SP values of 8.27, compound A-2 are 8.36.

In comparative example 1, there are 10 difunctional vinyls's base ether (Compound of Example B-21) of carbon to use in alkane chain Make the main component of the cationically polymerizable liquid monomer.On the other hand, in comparative example 2, there are 8 carbon in alkane chain Difunctional vinyl's base ether (Compound of Example B-15) be used as the cationically polymerizable liquid monomer main component.Although The fixing performance of comparative example 1 and 2 is not very poor compared with embodiment, but the image quality of the image formed after 1 day is aobvious Writing reduces.The component of the device interior is contaminated, and the state in that must clean.Cleaning the component of the device interior Afterwards, image becomes excellent immediately.

The carbon number of alkane chain is more than 12 in the compound used in comparative example 3 and comparative example 4, but these are simple functions Vinyl ether compound, thus significantly reduce fixing performance.

Therefore, the present invention can provide a kind of curable liquid developer, and it is shown for curable liquid development The very little volatilization of the vinyl ether compound of agent, thus avoid the component of the device interior from polluting, while protecting for a long time High image quality is held, even if in a humid environment, also showing that excellent fixing performance.

Although describing the present invention with reference to exemplary, it will be appreciated that showing the invention is not restricted to disclosed Example property embodiment.Scope of the following claims should meet broadest explanation to cover all such change and equivalent knot Structure and function.

Claims (6)

1. a kind of curable liquid developer, it is characterised in that comprising toner-particle, polymerization initiator and cationic polymerization Property liquid monomer,

Wherein

The cationically polymerizable liquid monomer contains the compound provided by following formula (A)：

(R-CH=CH-O -)_n–C_mH_(2m+2–n)Formula (A)

In formula (A), m represents more than 12 and less than 50 integer；N represents more than 2 integer；Hydrogen atom is represented with R or with 1 The alkyl of the individual above and the carbon of less than 3.

2. curable liquid developer according to claim 1, wherein, the second be given by the following formula (A1) in formula (A) At least one of alkenyl ether groups is bonded to the non-end of the carbon atom to form the alkane chain provided by the following formula (A2) in formula (A) Carbon atom：

(R-CH=CH-O-)_nFormula (A1)

–C_mH_(2m+2–n)Formula (A2)

In formula (A1) and formula (A2), m represents more than 12 and less than 50 integer；N represents more than 2 integer；Represent that hydrogen is former with R Son or the alkyl with more than 1 and the carbon of less than 3.

3. curable liquid developer according to claim 1 and 2, wherein, the m in formula (A) represents more than 12 and 25 Following integer.

4. curable liquid developer according to claim 1 and 2, wherein, the m in formula (A) represents more than 18 and 25 Following integer.

5. curable liquid developer according to claim 1 and 2, wherein, in cationic polymerization described in 100 mass parts Property liquid monomer in, the content of the compound represented by formula (A) is for more than 70 mass parts and below 100 mass parts.

6. curable liquid developer according to claim 1 and 2, wherein, the polymerization initiator contains by following The compound that formula (1) is given：

In formula (1), R₁And R₂Bond together to form cyclic structure；X represents more than 1 and less than 8 integer；3 are represented with y Above and less than 17 integer.