CN108215506B - Cleaning solution, accepting container, ink jet printing method and ink-jet printing apparatus - Google Patents

Abstract

The present invention relates to the external members of cleaning solution, accepting container, ink jet printing method, ink-jet printing apparatus and ink and cleaning solution.Problem of the present invention is that providing even if using the ink occasion for containing specific resin and interfacial agent to improve fixation performance, for cleaning solution being attached to body with excellent cleaning of ink attachment.Cleaning solution of the invention is used to clean the body that is attached to of following ink attachment, and above-mentioned cleaning solution includes water and organic solvent, and the hydrogen bond item of the Hansen solubility parameters for the mixed liquor being made of above-mentioned water and above-mentioned organic solvent is 10.0 (cal/cm³)^1/2Hereinafter, it is 8 polysiloxanes interfacial agents below that ink, which includes water, organic solvent, urethane resin particles and HLB value, the content of above-mentioned urethane resin particles is 5 mass % or more with respect to ink full dose.

Description

Cleaning solution, accepting container, ink jet printing method and ink-jet printing apparatus

Technical field

The present invention relates to cleaning solution, accepting container, ink jet printing method, ink-jet printing apparatus and ink and cleaning solutions External member.

Background technique

In the industrial applications such as advertisement, signboard, in order to enable the durability of light resistance, water resistance, abrasion performance etc. obtains It improves, using the impermeabilities recording medium such as such as plastic film, develops various for above-mentioned impermeability record Jie The ink of matter.

As such ink, the solvent system ink for for example using organic solvent as solvent is widely used, will polymerize Ultraviolet ray hardening type ink etc. of the property monomer as principal component.But above-mentioned solvent system ink is worried because of organic solvent evaporation pair Environment impacts.From a security point of view, used polymerizable monomer selects above-mentioned ultraviolet ray hardening type ink sometimes It is restricted.

Then, propose carrying capacity of environment it is small, can be directly recorded in the water-based ink of impermeability recording medium (for example, referring to Patent Documents 1 to 2).

Above-mentioned ink is in order to ensure containing resin to the fixation performance of impermeability recording medium.But if make in ink Containing resin, in continuous record, sometimes because ink attachment, agglutination and drying are in record head etc., the discharge stability of ink It reduces.Therefore, in order to ensure the discharge stability of ink, it is necessary to which cleaning is attached to the ink of record head etc..

But the ink containing resin is securely attached to record head, therefore, there is cleaning with cleaning solution so far The insufficient problem of power.

Then, propose the cleaning solution comprising polyoxyalkylene hydroxyl monoalky lether, glycerol and water (for example, referring to patent document 3)。

Also, propose the record ink containing resin and the displacement ink containing activator and solvent ink sets (for example, Referring to patent document 4).

Further more, proposing the cleaning constituent for providing solvent-based Hansen (Hansen) solubility parameters (for example, referring to patent text It offers 5).

[patent document]

[patent document 1] Japanese Unexamined Patent Publication 2005-220352 bulletin

[patent document 2] Japanese Unexamined Patent Publication 2011-094082 bulletin

No. 5618250 bulletins of [patent document 3] Japanese Patent No.

[patent document 4] Japanese Unexamined Patent Publication 2014-162819 bulletin

[patent document 5] Japanese Unexamined Patent Application Publication 2013-518138 bulletin

Summary of the invention

Even if the object of the present invention is to provide contain specific resin and interfacial agent using in order to improve fixation performance Ink occasion, being attached to body also there is the cleaning solution of excellent cleaning for ink attachment.

The above subject is solved by the following invention constituted 1).

1) a kind of cleaning solution, for cleaning the body that is attached to of following ink attachment, above-mentioned cleaning solution is comprising water and organic Solvent, the mixed liquor being made of above-mentioned water and above-mentioned organic solvent the hydrogen bond item of Hansen solubility parameters be 10.0 (cal/ cm³)^1/2Cleaning solution below.

Ink: being that 8 polysiloxanes interfaces below are living comprising water, organic solvent, urethane resin particles and HLB value Agent, the content of above-mentioned urethane resin particles are 5 mass % or more with respect to ink full dose.

Illustrate effect of the invention below:

According to the present invention it is possible to provide even if containing specific resin and interfacial agent using in order to improve fixation performance Ink occasion, being attached to body also there is the cleaning solution of excellent cleaning for ink attachment.

Detailed description of the invention

Fig. 1 is the strabismus explanatory diagram for indicating tandem type image forming apparatus an example.

Fig. 2 is the strabismus explanatory diagram for indicating an example of the primary tank of device of Fig. 1.

Fig. 3 is the skeleton diagram for indicating an example of the heating means of device of Fig. 1.

Fig. 4 is the skeleton diagram for indicating an example of the cleaning means in the present invention.

Specific embodiment

In the following, the implementation form that present invention be described in more detail.

< cleaning solution >

What cleaning solution of the invention was used to clean particular ink described below attachment is attached to body, the feature of the cleaning solution It is, includes water and organic solvent, the hydrogen of the Hansen solubility parameters for the mixed liquor being made of above-mentioned water and above-mentioned organic solvent Key item is 10.0 (cal/cm³)^1/2Below.

It is believed that the HLB value in ink described below be 8 polysiloxanes interfacial agents below easily and Hansen The hydrogen bond item of solubility parameters is 10.0 (cal/cm³)^1/2Mixed liquor below mixes, which plays rush The ingredient (mainly urethane resin particles) contained in ink feed water is distributed to the effect of the mixed liquor, improves cleaning.Ink In polysiloxanes interfacial agent and ink attachment be attached to body, such as head nozzle face water-sprinkling film compatibility it is high, promote Ink feed water is to the consolidation of nozzle face, and still, it is 8 or less that the mixed liquor in cleaning solution of the invention, which has as described above with HLB value, Polysiloxanes interfacial agent intermiscibility, therefore, urethane resin particles are distributed in mixed liquor, the above-mentioned body that is attached to Cleaning obtains leap and improves.As a result, it is above-mentioned be attached to body cleaning after, ink be discharged excellent in stability.

" mixed liquor "

Above-mentioned mixed liquor is made of water and solvent, and the hydrogen bond item of Hansen solubility parameters is 10.0 (cal/cm³)^1/2Below.

[the hydrogen bond item of Hansen solubility parameters]

The hydrogen bond item of Hansen solubility parameters (following to be otherwise referred to as " HSP ") as above-mentioned mixed liquor is (below sometimes Also referred to as " δ H "), it is 10.0 (cal/cm³)^1/2Hereinafter, it is preferred that 8.5 (cal/cm³)^1/2Below.If above-mentioned Hansen solubility parameters Hydrogen bond item be 10.0 (cal/cm³)^1/2Hereinafter, can then improve cleaning force.Further more, passing through so that being 8 below containing HLB value The combination of inks of polysiloxanes interfacial agent can obtain excellent discharge reliability.

If the hydrogen bond item of above-mentioned Hansen solubility parameters is 8.5 (cal/cm³)^1/2Hereinafter, can then obtain superior discharge Stability.

Also, according to the invention it is preferred to the hydrogen bond item that mixed liquor includes at least a kind of Hansen solubility parameters is 5.0 (cal/ cm³)^1/2Organic solvent below can obtain superior cleaning under the form.The hydrogen bond item of Hansen solubility parameters is 5.0(cal/cm³)^1/2The content of organic solvent below preferably 10~70 mass %, more preferable 15~60 matter in mixed liquor Measure %.

Above-mentioned Hansen solubility parameters (HSP) is that the solubility parameters (SP) that will be imported by Hildebrand is divided into dispersion item (δ D), polarity item (δ P), hydrogen bond item (δ H) three ingredients are indicated in three-dimensional space.Above-mentioned dispersion item (δ D) is based on Van Der The item of the proximity power of Waals.Above-mentioned polarity item (δ P) is also referred to as split pole item, is because of the item that dipole moment, dielectric constant etc. are cause. At above-mentioned hydrogen bond item (δ H), comprising the molecular separating force based on hydrogen bond, in turn, also comprising other unclassified π-π interactions Deng.In the present invention, using the hydrogen bond item (δ H).

Above-mentioned dispersion item (δ D), polarity item (δ P), hydrogen bond item (δ H) three ingredients are asked by Hansen and its research successions , it is recorded in detail Polymer Handbook (the 4th edition), VII -698~711.Also, the definition and calculating of HSP be recorded in it is following Document: Charles M.Hansen writes, Hansen solubility parameters: A Users Handbook (CRC printing, 2007).

The value that the Hansen solubility parameters about many solvents and resin can be investigated, for example, being recorded in Wesley L.Archer writes, Industrial Splvents Handbook.

The hydrogen bond item (δ H) of Hansen solubility parameters as above-mentioned mixed liquor, can be sought by following formula:

The hydrogen bond item (δ H) of the Hansen solubility parameters of mixed liquor={ [(the δ H of water) × (body of the water in mixed liquor Product %)]/100+{ [(the δ H of solvent) × (the volume % of the organic solvent in mixed liquor)]/100 }

It, can be with the Hansen solubility parameters of suitably selected above-mentioned mixed liquor as the organic solvent in above-mentioned mixed liquor Hydrogen bond item is 10.0 (cal/cm³)^1/2Such organic solvent below, for example, can enumerate 1,2- butanediol (the δ H of HSP: 10.39(cal/cm³)^1/2), the 3-Methoxy-3-methyl-1-butanol (δ H:6.29 (cal/cm of HSP³)^1/2), 2-Pyrrolidone (δ H:4.39 (the cal/cm of HSP³)^1/2), 1, the 2- hexylene glycol (δ H:17.1 (cal/cm of HSP³)^1/2), 1,2-PD be (HSP's δ H:21.3 (cal/cm³)^1/2) etc..Organic solvent in above-mentioned mixed liquor as needed can also be with two or more combination It uses.

It as the water in mixed liquor, is not particularly limited, can be properly selected according to purpose, such as ion can be enumerated Exchanged water, ultrafiltration water, reverse osmosis water, the pure water of distilled water etc., ultrapure water etc..These can be used alone, can also with two kinds or Two kinds or more are used in mixed way.

Cleaning solution of the invention can cooperate the additive of interfacial agent, defoaming agent etc. as needed.

The content of organic solvent in above-mentioned mixed liquor preferably 30 mass % or more, 90 mass % are hereinafter, more preferable 50 matter % or more, 85 mass % are measured hereinafter, particularly preferred 60 mass % or more, 80 mass % or less.

The content of above-mentioned mixed liquor in cleaning solution of the invention preferably 90 mass % or more, more preferable 95 mass % with On.

< accepting container >

Accepting container in the present invention stores above-mentioned cleaning solution of the invention in a reservoir.

As above-mentioned accepting container, in a reservoir by the storage of above-mentioned cleaning solution, it is appropriate to may further include as needed Other components etc. of selection.

It as said vesse, is not particularly limited, its shape, structure, size, material can be properly selected according to purpose Deng, such as, the container included at least with the ink bags of formation such as aluminium laminated film, resin film etc. can be enumerated.

< ink >

It is suitable for the invention ink (below otherwise referred to as " ink of the invention ") and contains water, organic solvent, poly- ammonia Ester resin particle and HLB value are 8 polysiloxanes interfacial agents below, and the content of above-mentioned urethane resin particles is opposite Ink full dose is 5 mass % or more.Also, ink can contain other ingredients as needed.

Generally, solvent system ink is determined while making impermeability recording medium swelling because of the organic solvent in ink Shadow, it is therefore, excellent for the fixation performance of impermeability recording medium, still, in previous water-based ink, as final entry Object becomes ink film and stays composition on the recording medium, and accordingly, there exist ink films not to fill to the fixation performance of recording medium Divide, the problem of high-speed recording difference.Also, purposes occasion outside house is imagined, even if the Marresistance about record object, it is desirable that house Interior purposes occasion cannot compare the property of the tough Marresistance of degree, image color etc..But in previous water-based ink In, there are problems that the sufficient above-mentioned property that cannot obtain mutually being equal to solvent system ink.

Among ingredient in the ink, the selection left and right ink of interfacial agent records the impermeability of record The fixation performance of medium, therefore, role is very big.The inventors discovered that living by adding polysiloxanes interface to ink HLB value is 8 compounds below among agent, can significantly improve the fixation performance of ink.Although its reason not can determine that, Speculate if HLB value be 8 hereinafter, if hydrophobicity be improved, improve and the compatibilities of various impermeability recording mediums.

Also, the inventors discovered that, by improving fixation performance of the above-mentioned ink to impermeability recording medium, even if high shorthand When record, it can also inhibit the phenomenon that (ink droplet connects (beading)) is shunk in unification after reaching recording medium between adjacent ink droplet, can obtain To high-grade image.Also, it has also been found that improve fixation rate can also improve drying property, adhesion can be improved, therefore, can inhibit remember Transfer when batching recording medium after from record to the paper back side.

In the following, the ink composition is described in detail.

< polysiloxanes interfacial agent >

As above-mentioned polysiloxanes interfacial agent, can enumerate such as dimethyl silicone polymer have poly- silicon oxygen The branch of the compound (silicon systems compound) of alkyl structure has the compound of hydrophilic base or hydrophilic polymer chain, poly- two The end of the compound (silicon systems compound) with polysiloxane structure of methylsiloxane etc. has hydrophilic base or hydrophilic The compound etc. of property polymer chain.Above-mentioned so-called polysiloxanes interfacial agent meaning has polysiloxanes knot in its structure Structure also includes the meaning of polysiloxane series interfacial agent.

As above-mentioned hydrophilic base or above-mentioned hydrophilic polymer chain, can enumerate for example polyether-based (polyethylene oxide, Polypropylene oxide, their copolymer etc.), polyglycereol (C₃H₆O(CH₂CH(OH)CH₂O)_n- H etc.), pyrrolidones, trimethylammonium second Lactone (C₃H₆N⁺(C₂H₄)₂-CH₂COO^-Deng), sulfate (C₃H₆O(C₂H₄O)_n-SO₃Na etc.), phosphate (C₃H₆O(C₂H₄O)_n-P (=O) OHONa etc.), quaternary salt (C₃H₆N⁺(C₂H₄)₃Cl^-Deng) etc..In above-mentioned chemical formula, n indicates 1 or 1 or more integer.Wherein, It is preferred that having polyether-based.

Also, can also suitably enumerate by the way that there is dimethyl silicone polymer of polymerizable vinyl etc. in end and can gather The other monomers (hydrophilic monomer of (methyl) acrylic acid or its salt etc. is preferably used at least part of above-mentioned monomer) closed Polymerization obtain there is the vinyl copolymer etc. of the silicon systems compound chain of dimethyl silicone polymer etc. in branch.

Wherein, preferably with the compound of polysiloxane structure, and the compound with hydrophilic polymer chain, more preferably Containing polyether-based, as above-mentioned hydrophilic polymer chain, particularly preferred polysiloxanes interfacial agent is nonionic interface activation Agent, the structure with methyl polysiloxane as hydrophobic group, polyoxyethylene as hydrophilic group.

It is 8 hereinafter, preferably 4 or less as the HLB value of above-mentioned polysiloxanes interfacial agent.Above-mentioned HLB value is if 8 Hereinafter, for various impermeability recording mediums, even if ink-jet record also ensures that excellent ink fixation performance, if 4 hereinafter, Image gloss can be improved.Polysiloxanes interfacial agent in ink can be used as needed it is a variety of, for example, can be used together HLB value is more than 8 polysiloxanes interfacial agent, and still, such polysiloxanes interfacial agent is with respect to polysiloxanes interface Activator is all, preferably 60 mass % or less.

Here, the hydrophilic group of so-called HLB value meaning interfacial agent and the balance of lipophilic group, above-mentioned HLB value take 0~20 Value, closer to 0, lipophilic higher, closer to 20, hydrophily is higher.Above-mentioned HLB value is defined by following formula (Griffin method):

HLB value=20 × (formula weight summation/molecular weight of hydrophilic portion)

As above-mentioned polysiloxanes interfacial agent, for example polyether-modified silicon can be enumerated, contain polyoxyalkylene hydroxyl silicon Compound etc..

As above-mentioned polysiloxanes interfacial agent, commercially available product can be used, as above-mentioned commercially available product, can enumerate for example (HLB value: 7.0), (HLB value: 7.0) (the above are days to believe chemical industry strain formula meeting to Silface SAG008 to Silface SAG005 Society's system), FZ2110 (HLB value: 1.0), FZ2166 (HLB value: 5.8), SH-3772M (HLB value: 6.0), L7001 (HLB value: 7.4), SH-3773M (HLB value: 8.0) (the above are Dow Toray Co. Ltd. systems), KF-945 (HLB value: 4.0), KF-6017 (HLB value: 4.5) (the above are Shin-Etsu Chemial Co., Ltd's systems), Form Ban MS-575 (Ultra Addives Inc. Corporation, HLB value: 5.0) etc..

As the content of above-mentioned polysiloxanes interfacial agent, opposite ink full dose, preferably 0.1 mass % or more, 4.0 matter % is measured hereinafter, more preferable 1.0 mass % or more, 2.0 mass % or less.Above-mentioned content is if 0.1 mass % or more, 4.0 matter The images product such as gloss can also be improved in turn hereinafter, fixation performance of the ink to various impermeability recording mediums can be improved by measuring % Matter.

" urethane resin particles "

Above-mentioned urethane resin particles can assign high image gloss and Marresistance.Further more, passing through and using above-mentioned Polysiloxanes interfacial agent and urethane resin particles, the Marresistance of the film formed after not only recording, and also it is resistance to molten Agent is also significantly improved.

As above-mentioned urethane resin particles, such as polyether system urethane resin particles can be enumerated, it is polycarbonate-based poly- Urethane resin particle, Polyester urethane resin particles etc..

As above-mentioned urethane resin particles, it is not particularly limited, can be suitably selected according to purpose, example can be enumerated The urethane resin particles for reacting polyalcohol (polyol) and polyisocyanate.

Polyalcohol-

As above-mentioned polyalcohol, can enumerate such as polyether polyol, polycarbonate polyol, polyester polyol.This A little polyalcohols can be used alone, and can also be used in combination with two or more.

-- polyether polyol --

As above-mentioned polyether polyol, can enumerate the compound with two or two or more active hydrogen atoms for example At least one as raw material so that alkylene oxide (alkylene oxide) addition polymerization etc..

As the above-mentioned compound with two or two or more active hydrogen atoms, such as ethylene glycol, diethyl can be enumerated Glycol, triethylene glycol, propylene glycol, 1,3-BDO, 1,4-butanediol, 1,6- hexylene glycol, glycerol, trimethylolethane, three hydroxyls Methylpropane etc..These compounds can be used alone, and can also be used in mixed way with two or more.

As above-mentioned alkylene oxide, such as ethylene oxide, propylene oxide, epoxy butane, Styryl oxide, epoxy can be enumerated Chloropropane, tetrahydrofuran etc..These can be used alone, and can also be used in mixed way with two or more.

As above-mentioned polyether polyol, be not particularly limited, can be properly selected according to purpose, from obtain can assign it is non- The bonding agent angle consideration of the Marresistance ink of Chang Youyi, preferably PEO macromonomer, polyoxypropylene glycol.These can be single It solely uses, can also be used in mixed way with two or more.

-- polycarbonate polyol --

Also, example can be enumerated as the above-mentioned polycarbonate polyol that can be used in manufacturing above-mentioned urethane resin particles Such as make carbonic ester and the polyol reaction person of obtaining, so that reactions person of obtaining such as chlorination carbonyl and bisphenol-A etc..These can be independent It uses, can also be used in mixed way with two or more.

As above-mentioned carbonic ester, such as methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, carbon can be enumerated Sour cyclic ester (cyclo carbonate), diphenyl carbonate etc..These can be used alone, can also be mixed with two or more It closes and uses.

As above-mentioned polyalcohol, such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-PD, 1,3- third can be enumerated Glycol, dipropylene glycol, 1,4-butanediol, 1,3-BDO, 1,2- butanediol, 2,3-butanediol, 1,5-PD, 1,5- oneself two Alcohol, 2,5- hexylene glycol, 1,6- hexylene glycol, 1,7- heptandiol, 1,8- ethohexadiol, 1,9- nonanediol, 1,10- decanediol, 1,11- ten One alkane glycol, 1,12- dodecanediol, Isosorbide-5-Nitrae-cyclohexanediol, Isosorbide-5-Nitrae-cyclohexanedimethanol, quinhydrones, resorcinol, bisphenol-A, bis-phenol F, the dihydroxy compound of the comparison low molecular weight of 4,4'- bis-phenol etc., polyethylene glycol, polypropylene glycol, PEO macromonomer etc. Polyether polyol, the polyester polyol etc. of polyhexamethylene adipate, polyhexamethylene succinate, polycaprolactone etc..These can To be used alone, can also be used in mixed way with two or more.

-- polyester polyol --

As above-mentioned polyester polyol, can enumerate obtained by polyalcohol and the polycarboxylic acid esterification of such as low molecular weight Person, so that the obtained polyester of cyclic ester compounds ring-opening polymerization of 6-caprolactone etc., their polyester copolymerization etc..This It can be used alone, can also be used in mixed way with two or more.

As the polyalcohol of above-mentioned low molecular weight, can enumerate such as ethylene glycol, propylene glycol.These can individually make With can also be used in mixed way with two or more.

As above-mentioned polycarboxylic acid, such as succinic acid can be enumerated, adipic acid, decanedioic acid, dodecanedicarboxylic acid, terephalic acid, Isophathalic acid, phthalandione, above-mentioned acid anhydrides or ester formative derivative etc..These can be used alone, can also be with two or more It is used in mixed way.

Polyisocyanate-

As above-mentioned polyisocyanate, such as phenylene diisocyanate, first phenylene double isocyanates, hexichol first can be enumerated The aromatic diisocyanate of group diisocyanate, naphthalene diisocyanate etc., hexamethylene diisocyanate, two isocyanide of lysine Acid esters, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexyl methane diisocyanate, two methylene of benzene, two isocyanide The aliphatic or alicyclic ring of acid esters, tetramethyl xylylene diisocyanate, 2,2,4- trimethyl hexamethylene diisocyanate etc. Formula diisocyanate etc..These can be used alone, and can also be used in mixed way with two or more.Wherein, in the present invention Ink is also used as the outdoor applications such as poster or signboard to use, and therefore, it is necessary to the films with very high long-term weatherability, from this Angle considers, it is preferable to use ester ring type diisocyanate.

Furtherly, by using at least one ester ring type diisocyanate, easily obtain coating strength as a purpose with And Marresistance.

As above-mentioned ester ring type diisocyanate, such as isophorone diisocyanate, dicyclohexyl-methane two can be enumerated Isocyanates etc..

As the content of above-mentioned ester ring type diisocyanate, opposite isocyanate compound full dose, preferably 60 mass % with On.

[manufacturing methods of urethane resin particles]

Above-mentioned urethane resin particles can be obtained by the manufacturing method generally used in the past, for example, can enumerate with Lower method etc.:

Firstly, making above-mentioned polyalcohol and above-mentioned polyisocyanate under solvent-free state or under organic solvent existence It is reacted with the equivalent proportion of isocyanate group surplus, obtains isocyanates end polyurethane prepolymer.

Secondly, the anionic group in the polyurethane prepolymer of above-mentioned isocyanates end uses in neutralizer as needed With hereafter, react it with chain extender, finally, the organic solvent in removing system obtains product as needed.

As the organic solvent that can be used in the manufacture of above-mentioned urethane resin particles, such as acetone, first can be enumerated The ketone of ethyl ketone etc.；Tetrahydrofuran, the ethers of dioxane etc.；Ethyl acetate, the acetate esters of butyl acetate etc.；Acetonitrile Deng nitrile；Dimethylformamide, N- N-methyl 2-pyrrolidone N, the amides etc. of N- N-ethyl pyrrole N ketone etc..These can individually make With can also be used in mixed way with two or more.

As above-mentioned chain extender, can enumerate such as polyamine or others are containing active hydrogen base compounds.

As above-mentioned polyamine, such as ethylene diamin(e) can be enumerated, 1,2- propanediamine, 1,6- hexamethylene diamine, Piperazine, 2,5- lupetazins, isophorone diamine, 4,4 '-dicyclohexylmethane diamine, Isosorbide-5-Nitrae-cyclohexane diamine etc. Diamines；Diethylentriamine, diallyl triamine, the polynary amine of triethylenetetramine etc.；Hydrazine, N, N '-dimethylhydrazine, 1,6- The hydrazine of hexamethylene bis hydrazine etc.；Amber acid dihydrazide, two isoniazid of adipic acid, two isoniazid of glutaric acid, the different cigarette of decanedioic acid two Hydrazine, two isoniazid classes of two isoniazid of isophathalic acid etc. etc..These can be used alone, and can also be made with two or more mixing With.

As it is above-mentioned it is other contain active hydrogen base compounds, can enumerate ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-PD, 1,3-BDO, 1,4-butanediol, hexylene glycol, sucrose, methylene glycol, glycerine, sorbierite etc. Glycols；Bisphenol-A, 4,4 '-dihydroxy hexichol, 4,4 '-dihydroxy diphenyl ether, 4,4 '-dihydroxy diphenyl sulfones, hydrogenated bisphenol A are right The phenols of benzenediol etc.；Water etc..As long as these substances in the range of the storage stability of black liquid does not reduce, can individually make With can also be used in mixed way with two or more.

As above-mentioned urethane resin particles, because of the high cohesive force of carbonate group, from water resistance, heat resistance, abrasion performance Property, weatherability and image Marresistance angle consider, preferably polycarbonate-based urethane resin particles.Above-mentioned poly- carbonic acid Ester system urethane resin particles occasion can obtain the ink of record object for being suitable for using under the excessively cruel environment as outdoor application Water.

As above-mentioned urethane resin particles, commercially available product can be used, such as YUKOTO UX-485 (poly- carbon can be enumerated Acid esters system urethane resin particles), YUKOTO UWS-145 (Polyester urethane resin particles), PERMARIN UA-368T (polycarbonate-based urethane resin particles), PERMARIN UA-200 (Polyester urethane resin particles) (more than, three foreignize At Industrial Co., Ltd's system) etc..These can be used alone, and can also be used in mixed way with two or more.

Above-mentioned urethane resin particles in the state of the resin emulsion dispersed using water as dispersing agent, preferably with color material The material of material, organic solvent etc. is mixed to get ink.

If considering to cooperate with organic solvent, color material and water, the easiness of the operation of water-based ink is adjusted, and Uniformly dispersing as far as possible medium to above-mentioned ink, preferably urethane resin particles are in the shape steadily dispersed using water as dispersing agent State is added in ink under resin emulsion state.

Above-mentioned urethane resin particles pass through the organic solvent for being dissolved in and adding to ink, are easy film forming, are formed membranaceous Recording layer.With the evaporation of organic solvent and water, promote resin particle film forming.It therefore, also can be into if using ink of the invention The record of capable not heating process.

When so that above-mentioned urethane resin particles being dispersed using water as dispersing agent, as urethane resin particles, Ke Yilie The resin particle of the forced emulsification type using dispersing agent is lifted, in the molecular structure so-called self-emulsifying type containing anionic property base Resin particle etc..Wherein, from improve record object intensity angle consider, preferably in the molecular structure containing anionic property base from The resin particle of emulsifying.

The acid value of the anionic property base of resin particle as above-mentioned self-emulsifying type, from water dispersible, Marresistance and Reagent resistance angle considers that preferably 5mgKOH/g or more, 100mgKOH/g are hereinafter, more preferable 5mgKOH/g or more, 50mgKOH/g Below.

As above-mentioned anionic group, such as carboxyl, carboxylate, sulfonic group, sulfonate group etc. can be enumerated, wherein From maintaining good dispersion stability angle to consider, it is preferable to use part or all is the carboxylic acid of the neutralizations such as alkali compounds Ester group, sulfonate group.In order to import above-mentioned anionic group in resin, the list with above-mentioned anionic group can be used Body.

There is the method for the aqueous dispersion of the resin particle of above-mentioned anionic group as manufacture, can enumerate to water dispersion Body addition can be used for the method etc. of the alkali compounds of anionic group neutralization.

As above-mentioned alkali compounds, such as ammonium hydroxide, triethylamine, pyridine, the organic amine of morpholine etc. can be enumerated；Dan Yi The alkanolamine of hydramine etc.；Containing Na, K, Li, the metal chloride etc. of Ca etc..These can be used alone, can also be with two kinds or two kinds It is used in mixed way above.

As the method for the above-mentioned resin particle manufacture aqueous dispersion using forced emulsification type, such as nonionic can be enumerated Property interfacial agent, the method for the interfacial agent of anionic property interfacial agent etc..These can be used alone, can also be with two It plants or two kinds or more is used in mixed way.Wherein, consider from water resistance angle, it is preferable to use nonionic interfacial agent.

As above-mentioned nonionic interfacial agent, such as polyoxyethylene alkyl ether, polyoxyethylene alkylidene can be enumerated Alkyl ether, polyoxyethylene deriv, polyoxyethylene fatty acid ester, polyoxyethylene multivalence alcohol fatty acid ester, polyoxyethylenepropylene base Polyalcohol, sorbitan fatty acid ester, polyoxyethylene sorbitol aliphatic ester, polyoxyethylene hardened castor oil, polyoxygenated The polycyclic phenyl ether of alkene, polyoxyethylene alkanamine, alkylalkanol amide, ployalkylene glycol (methyl) acrylate etc..Wherein, preferably poly- Ethylene oxide alkyl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitol aliphatic ester, polyoxyethylene alkyl amine.These can To be used alone, can also be used in mixed way with two or more.

As above-mentioned anionic property interfacial agent, such as alkyl sulfate salt, polyoxyethylene alkyl ether sulphur can be enumerated Hydrochlorate, alkylbenzene sulfonate, alpha-alefinically sulphonic acid ester salt, methyidodecanoic acid salt, sulfosuccinate, ether sulfonate, ether carbonic acid Salt, fatty acid salt, naphthalene sulfonic acid-formaldehyde condensation product, alkylamine salt, tetravalence ammonium salt, alkyl betaine, alkyl amine oxide etc..Wherein, It is preferred that polyoxyethylene alkyl ether sulfate salt, sulfosuccinate.

Aqueous dispersion occasion is manufactured using the resin particle of above-mentioned forced emulsification type, as containing for above-mentioned interfacial agent Amount, is not particularly limited, can be properly selected according to purpose, still, the opposite resin particle full dose for forcing emulsifying, and preferably 0.1 mass % or more, 30 mass % are hereinafter, more preferable 5 mass % or more, 20 mass % or less.If above-mentioned content is 0.1 matter % or more, 30 mass % ranges below are measured, then resin particle can suitably form a film, and obtain the ink of adhesion and excellent water resistance Water, record object will not agglomerate, can suitably use.

As the volume average particle size of above-mentioned urethane resin particles, if considering use in ink-jet recording apparatus, volume is flat The preferred 10nm or more of equal partial size, 1000nm are hereinafter, more preferably 10nm or more, 500nm are hereinafter, particularly preferred 10nm or more, 200nm Below.Above-mentioned volume average particle size is if 10nm or more, 1000nm hereinafter, the then contact portion of organic solvent and resin particle surfaces Position increases, and the film forming of resin particle improves, and forms the continuous coating of tough resin, therefore, can obtain high-intensitive record Object.

Such as particle size analyzing device (MICROTRACK UPA type 9340, day machine dress can be used in above-mentioned volume average particle size Co. Ltd. system) it is measured.

As the qualitative of above-mentioned resin particle and quantitatively, it is referred to such as " test method(s) of each dynamic characteristic of plastic material And evaluation result (22), a peace field man of great physical prowess write, and plastics: Japan Plastics Industry Federation's magazine/" plastics " editorial board compiles " that is described in detail The sequence of sample confirms.Specifically, infrared spectroscopic analysis (IR), heat analysis (DSC, TG/DTA), thermal decomposition gas can be passed through The analysis such as chromatography (PyGC) nuclear magnetic resonance method (NMR), is confirmed.

As the vitreous transition temperature of above-mentioned resin particle, differential scanning calorimetry (Seiko can be used Instruments Co. Ltd. system, DSC6200) it is measured.Specifically, in the item of continuous temperature program 1~4 below It is measured under part, using the value measured in temperature program(me) 3 as vitreous transition temperature.Why carried out in above-mentioned temperature program(me) Measurement, the measured value using temperature program(me) 3 is the reproducibility in order to ensure measured value.

Temperature program(me):

1.30 DEG C or more, 250 DEG C or less: 30 DEG C/min of heating rate, the retention time 1 minute

2.250 DEG C or more, -100 DEG C or less: 30 DEG C/min of cooling velocity, the retention time 30 minutes

3.-100 DEG C or more, 250 DEG C or less: 5 DEG C/min of heating rate, the retention time 1 minute

4.250 DEG C or more, 30 DEG C or less: 30 DEG C/min of cooling velocity, the retention time 2 minutes

If ink of the invention is heated, residual solvent is reduced, and can improve caking property.In particular, when resin particle Minimum film formation temperature (hereinafter, otherwise referred to as " MFT ") more than 80 DEG C occasions, the film forming for eliminating resin is bad, from can improve figure As preferably being heated from the point of view of fastness.Also, being carried out after reordering after heating preferably assigns ink to recording medium.

Ink of the invention in order to obtain, adjusts the minimum film formation temperature occasion of resin emulsion, for example, can pass through control The vitreous transition temperature (hereinafter, otherwise referred to as " Tg ") of resin particle is adjusted, can when resin particle is copolymer occasion To be adjusted by the ratio for changing the monomer for forming above-mentioned copolymer.Above-mentioned so-called minimum film formation temperature refers to so that resin Particle thinly extends on the metal plates such as aluminium, and temperature forms the minimum temperature of transparent continuous film when increasing, it is above-mentioned not In the temperature field of sufficient minimum film formation temperature, latex is white powder.Above-mentioned minimum film formation temperature can be for example, by " film forming Temperature testing device " (well member production made), " TP-801MFT testing machine " (TESTER industry companies system) etc. it is commercially available it is minimum at Film temperature measurement device is measured.

Also, above-mentioned minimum film formation temperature changes because of the volume average particle size of resin particle, therefore, resin can be passed through The minimum film formation temperature of resin particle is set as desired value by the controlling elements of the volume average particle size of grain.

< organic solvent >

It as above-mentioned organic solvent, is not particularly limited, can suitably be selected according to purpose, can be enumerated water-soluble organic Solvent etc..So-called water-soluble meaning for example dissolves 5g or more in 25 DEG C of water 100g.

As above-mentioned water-miscible organic solvent, such as ethylene glycol can be enumerated, diethylene glycol (DEG), 1,2-PD, 1,3- the third two Alcohol, 1,2- butanediol, 1,3-BDO, 2,3-butanediol, 3- methyl-1,3- butanediol, 3- methoxyl group -3- methyl butanol, three Glycol, polyethylene glycol, polypropylene glycol, 1,5-PD, 2- methyl -2,4- pentanediol, 1,6- hexylene glycol, glycerol, 1,2,6- oneself Triol, 2- ethyl -1,3- hexylene glycol, ethyl -1,2,4-butanetriol, 1,2,3- butane triol, gasoline (petriol) etc. it is polynary Alcohols；Such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, four Glycol monomethyl ether, dihydroxypropane single-ether, the polyol alkyl ether class of dipropylene glycol monomethyl ether etc.；Such as ethylene glycol list phenyl ether, The polyhydric alcohol aryl ethers of ethylene glycol monobenzyl ether etc.；Such as 2-Pyrrolidone, n-methyl-2-pyrrolidone, N- ethoxy -2- pyrroles Alkanone, 1,3- methylimidazole alkanone, epsilon-caprolactams, the nitrogen-containing heterocycle compound of gamma butyrolactone etc.；Such as formamide, N- first Base formamide, the amides of n,N-Dimethylformamide etc.；Such as monoethanolamine, diethanol amine, the amine of triethanolamine etc.；Example Such as dimethyl sulfoxide, sulfolane, the sulfur-bearing Huang compound of thiodiethanol etc.；Acrylic ester；Ethylene carbonate etc..These substances both may be used To be used alone, a variety of can also be used in combination.

As the content of above-mentioned organic solvent, consider from the drying property and discharge reliability perspectives of ink, opposite ink Total amount, preferably 10 mass % or more, 60 mass % are hereinafter, more preferable 20 mass % or more, 60 mass % or less.

< water >

It as above-mentioned water, is not particularly limited, can suitably be selected according to purpose, such as ion exchange water can be enumerated, Ultrafiltration water, reverse osmosis water, the pure water of distilled water etc., ultrapure water etc..These can be used alone, can also be with two or more It is used in mixed way.

The content of above-mentioned water is with respect to ink total amount, and preferably 15 mass % or more, 60 mass % are hereinafter, more preferable 20 mass % Above, 40 mass % or less.It if above-mentioned content is 15 mass % or more, can prevent from becoming high viscosity, discharge stability can be improved, It is if 60 mass % hereinafter, then very suitable to the wetability of impermeability recording medium, image grade can be improved.

The other ingredient > of <

As above-mentioned other ingredients, such as color material can be enumerated, the interfacial agent other than polysiloxanes interfacial agent, Rubber as Antisepticize and mildew preventive, inhibitor, pH regulator, hindered phenol or hindered phenol amine and the colourless age resister of plastics Deng.

< color material >

It as above-mentioned color material, is not particularly limited, can suitably be selected according to purpose, pigment, dyestuff etc. can be enumerated.Its In, preferred pigments.

As above-mentioned pigment, such as inorganic pigment, organic pigment etc. can be enumerated.

As above-mentioned inorganic pigment, such as titanium oxide, iron oxide, calcium carbonate, barium sulfate, aluminium hydroxide, barium can be enumerated The carbon black of the manufacture of method well known to Huang, cadmium red, chrome yellow, also useful contact method, blast furnace process, thermal energy method etc..These can individually make With can also be used in mixed way with two or more.

As above-mentioned organic pigment, azo pigments (including such as azo lake, insoluble azo colour, contracting can be enumerated Close azo pigments, chelate azo pigment etc.), polycyclic pigment (such as phthalocyanine color, pigment, purple cyclic ketones pigment, anthraquinone face Material, quinacridone pigment, dioxazines pigment, indigo pigments, thioindigo color, isoindolinone pigments, quinophthalone pigments etc.), dyestuff Chelating (such as basic dye type chelating, acidic dye type chelating etc.), nitrifies pigment, nitrosation pigment, nigrosine etc..These can To be used alone, can also be used in mixed way with two or more.

In addition it is also possible to using hollow resin particles, inorganic hollow particle.

, it is preferable to use the pigment good with solvent compatibility in these pigment.

The carbon black of such as furnace black, lampblack, acetylene black, channel black can be enumerated as black pigment as above-mentioned pigment (C.I. pigment black 7) class, such as the metal class of copper, iron (C.I. pigment black 11), titanium oxide, such as nigrosine (C.I. pigment black 1) Deng organic pigment etc..These can be used alone, and can also be used in mixed way with two or more.

Also, it is (yellow that C.I. pigment yellow 1,3,12,13,14,17,24,34,35,37,42 can be enumerated as colored pigment Color iron oxide), 53,55,81,83,95,97,98,100,101,104,408,109,110,117,120,138,150,153, 155；C.I. pigment orange 5,13,16,17,36,43,51；C.I. paratonere 1,2,3,5,17,22,23,31,38,48:2,48:2 (permanent red 2B (Ca)), 48:3,48:4,49:1,52:2,53:1,57:1 (carmine 6B), 60:1,63:1,63:2,64:1, 81,83,88,101 (colcothers), 104,105,106,108 (cadmium reds), 112,114,122 (quinacridone magentas), 123,146, 149,166,168,170,172,177,178,179,185,190,193,209,219；C.I. pigment violet 1 (rhodamine color lake), 3,5:1,16,19,23,38；C.I. pigment blue 1,2,15 (phthalocyanine blues), 15:1,15:2,15:3 (phthalocyanine blue), 16,17:1,56, 60,63；C.I. naphthol green Isosorbide-5-Nitrae, 7,8,10,17,18,36 etc..These can be used alone, can also be mixed with two or more It closes and uses.

As above-mentioned dyestuff, C.I. Indian yellow 17,23,42,44,79,142 can be enumerated；C.I. acid red 52,80,82, 249,254,289；C.I. acid blue 9,45,249；C.I. acid black 1,2,24,94；C.I. food black 1,2；C.I. directly Huang 1, 12,24,33,50,55,58,86,132,142,144,173；C.I. directly red 1,4,9,80,81,225,227；C.I. directly blue 1,2,15,71,86,87,98,165,199,202；C.I. directly black 19,38,51,71,154,168,171,195；C.I. it reacts Red 14,32,55,79,249；C.I. black 3,4,35 etc. are reacted.These can be used alone, can also be mixed with two or more It closes and uses.

In order to enable pigment is distributed in ink, it can enumerate and hydrophilic functional group is imported into pigment as self-dispersing face The method of material, the method for dispersing it with resin coated pigment surface, the method etc. for dispersing it using dispersing agent.

Import pigment as the method for self-dispersing pigment as using hydrophilic functional group, can be used for example by sulfo group or The functional group of carboxyl etc. is attached to pigment (such as carbon), is distributed in water, becomes self-dispersing pigment etc..

As the method for dispersing it with resin coated pigment surface, can be used so that pigment is contained in microcapsules, energy It distributes it in water.In other words, this is it may be said that resin coated pigment.The occasion cooperates pigment in the ink must not It all to be coated by resin, in the range for not damaging effect of the present invention, the pigment not being wrapped by or the pigment being locally wrapped by It can be distributed in ink.

As the method for using dispersing agent to disperse it, use can be enumerated using interfacial agent to be low well known to representative The method of the dispersing agent dispersion of the dispersing agent, polymer electrolyte of molecule-type.

As dispersing agent, such as anionic activator, cationic interfacial agent, both sexes can be used according to pigment Interfacial agent, nonionic interfacial agent etc..

Bamboo this grease corporation RT-100 (nonionic interfacial agent), naphthalene sulfonic acid-formaldehyde condensation product can also be used as dispersion Agent suitably uses.

Dispersing agent can be used alone, and can also be used in mixed way with two or more.

< pigment dispersion >

The materials such as water and organic solvent can be mixed into color material and obtain ink.Also, can also be by pigment and other water And dispersing agent etc. is mixed to get pigment dispersion, then the materials such as water and organic solvent is made to be mixed into above-mentioned pigment dispersion, system Make ink.

Above-mentioned pigment dispersion makes water, pigment, pigment dispersing agent and other ingredients dispersion as needed, can adjust Whole grain diameter.Dispersion machine can be used in dispersion.

About the partial size of the pigment in pigment dispersion, be not particularly limited, from the dispersion stabilization of pigment become it is good, Be discharged stability, the image qualities such as image color it is also high from the point of view of, be preferably 20nm with the maximum number maximum frequency that converts Above, 500nm is hereinafter, more preferable 20nm or more, 150nm or less.Particle size analyzing device can be used in the partial size of pigment (NANOTRACK Wave-UT151, Microtrac BEL corporation) measurement.

The content of pigment in above-mentioned pigment dispersion, is not particularly limited, and can be properly selected according to purpose, from energy Obtain good discharge stability, again improve image color from the point of view of, preferably 0.1 mass % or more, 50 mass % hereinafter, More preferable 0.1 mass % or more, 30 mass % or less.

Above-mentioned pigment dispersion preferably filters big particle, degasification with filter, centrifugal separating device etc. as needed.

It as the number average bead diameter of above-mentioned pigment, is not particularly limited, can suitably be selected according to purpose, preferably with maximum Number converts maximum frequency as 20nm or more, 150nm or less.If above-mentioned number average bead diameter is 20nm or more, scatter operation, classification behaviour It is easy, if 150nm hereinafter, the pigment dispersion stability for then serving not only as ink is good, moreover, discharge stability is also excellent Different, the image qualities such as image color are also high, therefore preferably.

Particle size analyzing device can be used in the number average bead diameter of above-mentioned pigment, and (MICROTRACK UPA type 9340, day machine fill strain Formula commercial firm system) it is measured.

As the content of above-mentioned color material, consider from image color, fixation performance and discharge stability angle, opposite ink Total amount, preferably 0.1 mass % or more, 15 mass % are hereinafter, more preferable 1 mass % or more, 10 mass % or less.If above-mentioned content For 0.1 mass % or more, 15 mass % hereinafter, discharge high reliablity, can obtain the image of high colorfulness.

As the content of above-mentioned pigment, opposite ink total amount, preferably 0.1 mass % or more, 15 mass % are hereinafter, more preferably 0.1 mass % or more, 10 mass % are hereinafter, particularly preferred 1 mass % or more, 10 mass % or less.If above-mentioned content is 0.1 matter Amount % or more, 15 mass % are hereinafter, can then improve image color, fixation performance and discharge stability.

Interfacial agent > other than < polysiloxanes interfacial agent

Polysiloxanes interface also can be used together from the wetability angle consideration ensured to recording medium in ink in the present invention Interfacial agent other than activator.

As the interfacial agent other than above-mentioned polysiloxanes interfacial agent, it is not particularly limited, it can be according to purpose Appropriate selection, can enumerate such as both sexes interfacial agent, nonionic interfacial agent, anionic activator etc..This It can be used alone, can also be used in mixed way with two or more.Wherein, from dispersion stabilization and image quality angle Consider, preferred anionic interfacial agent.

Also, it is different according to composition, it also can be used together or be used alone fluorine system interfacial agent or silicon systems interfacial agent.

As above-mentioned nonionic interfacial agent, such as polyoxyethylene alkyl phenyl ether, polyoxyethylene alkane can be enumerated Base ester, polyoxyethylene alkyl amine, polyoxyethylene alkylamide, polyoxyethylenepropylene block polymer, sorbitan fatty acid ester, Polyoxyethylene sorbitol aliphatic ester, the ethylene oxide adduct etc. of acetylene alcohol.These can be used alone, can also be with two kinds Or two kinds or more be used in mixed way.

As the content of the above-mentioned interfacial agent other than above-mentioned polysiloxanes interfacial agent, preferably 0.1 mass % with Upper, 5 mass % or less.If above-mentioned content is 0.1 mass % or more, the wetability to impermeability recording medium can ensure that, Image quality can be improved, if 5 mass % hereinafter, then ink is difficult to blister, excellent discharge stability can be obtained.

< defoaming agent >

It as above-mentioned defoaming agent, is not particularly limited, such as silicon systems defoaming agent, polyether system defoaming agent, fat can be enumerated Acid esters system defoaming agent etc..These can be used alone, and can also be used in mixed way with two or more.Wherein, from effect of breaking bubble Excellent angle consideration, preferably silicon systems defoaming agent.

< Antisepticize and mildew preventive >

It as Antisepticize and mildew preventive, is not particularly limited, such as 1,2- benzothiazepine -3- ketone etc. can be enumerated.

< antirust agent >

It as antirust agent, is not particularly limited, such as acid accumulator sulfite, sodium thiosulfate etc. can be enumerated.

< pH regulator >

It as pH regulator, as long as pH to 7 or more can be adjusted, is not particularly limited, diethanol amine, three second can be enumerated The amine etc. of hydramine etc..

[ink manufacturing method]

It, can be by will for example above-mentioned water, above-mentioned organic solvent, above-mentioned polysiloxanes circle as the manufacturing method of above-mentioned ink Face activator, above-mentioned urethane resin particles and above-mentioned other ingredients as needed are stirred and are manufactured.As upper State and be stirred, can be used for example sand mill, homogenizer, ball mill, paint shaker, ultrasonic dispersing machine, using usually stirring Mix the progress such as blender, magnetic stirrer, high speed disperser of paddle.

It as the physical property of ink, is not particularly limited, can be properly selected according to purpose, for example, it is preferable to viscosity, Surface tension, pH etc. are in following range:

Above-mentioned ink in 25 DEG C of viscosity from can improve gradation of drop-out colour and text grade and good discharge can be obtained From the point of view of, preferably 5mPas or more, 30mPas are hereinafter, more preferable 5mPas or more, 25mPas or less.Herein, Such as rotary viscosimeter (Toki Sangyo Co., Ltd.'s system, RE-80L) can be used in viscosity.As determination condition, 25 DEG C, Under the conditions of standard cone rotor (1 ° of 34' × R24), sample liquid measure 1.2mL, revolving speed 50rpm, measure within 3 minutes.

As the surface tension of ink, can suitably be leveled from ink on the recording medium, ink drying time shortens angle Degree considers, at 25 DEG C, preferably 35mN/m is hereinafter, more preferably 32mN/m or less.

As the pH of ink, consider from the corrosion angle for the metal parts for preventing contact liq, preferably 7~12, more preferable 8 ~11.

Ink in the present invention can be suitably used for ink-jet record.

< recording medium >

It as recording medium, is not particularly limited, plain paper, glossy paper, special paper, cloth etc. can be used, even if using Impermeability basis material can also form good image.

So-called impermeability basis material, refers to the basis material on the low surface of water permeability, absorbability, also includes Even if it is internal there are many cavity, not to the material of external opening, more quantitatively say, in Bristol (Bristow) method, from Contact start is to 30msec^1/2Water uptake be 10mL/m²Basis material below.

As above-mentioned impermeability recording medium, such as vinyl chloride resin film can be suitably used, polyethylene is to benzene Dicarboxylic acid esters (PET) film, polypropylene, polyethylene, the plastic film of polycarbonate film etc..

Also, before color inks, making recording medium coloring (colour record to be situated between by being coated with white ink when colored record Matter), can make recording medium color be it is white, the color development of color inks can be improved.

As above-mentioned coloring recording medium, the paper of coloring, above-mentioned film, cloth, clothes, ceramics etc. are representative examples.

< ink accepting container >

Above-mentioned ink accepting container stores above-mentioned ink of the invention in a reservoir.

As above-mentioned ink accepting container, in a reservoir by the storage of above-mentioned ink, in turn, there is appropriate selection as needed Other components etc..

It as said vesse, is not particularly limited, its shape, structure, size, material can be properly selected according to purpose Deng, such as, the ink bag etc. included at least with formation such as aluminium laminated film, resin films can be enumerated.

Ink jet printing method of the invention is characterised by comprising so that ink is discharged, is printed onto the ink of recording medium Process is discharged, and cleans the cleaning process for remaining in the ink of ink flow path or record head by cleaning solution, cleaning solution is upper State cleaning solution of the invention.

Also, ink-jet printing apparatus of the invention is characterised by comprising so that ink is discharged, is printed onto the ink of recording medium Water discharge means, and the cleaning means for remaining in the ink of ink flow path or record head are cleaned by cleaning solution, cleaning solution is The cleaning solution of aforementioned present invention.

Hereinafter, illustrating ink jet printing method of the invention (recording method) and printing equipment (recording device).

< recording device, recording method >

Ink of the invention can suitably be used in the various recording devices of ink-jet recording, such as, printer passes True device, copy device, printing/fax/duplicating multi-function peripheral, three-dimensional contouring device etc..

In the present invention, so-called recording device, recording method are energy relative record medium discharge ink or various treatment fluids Deng device, the method recorded using the device.So-called recording medium meaning ink or various treatment fluids are even if for the moment It can attachment person.

In the recording device, the head not only comprising discharge ink is divided, and includes the feed for being related to recording medium, removes It send, the means of paper discharge, in addition, the device etc. also comprising referred to as pretreating device, after-treatment device.

Recording device, recording method also may include the heating means for heating process, the drying for drying process Means.Including, for example, heating, drying the printing surface of recording medium or the means at the back side in heating means, drying means.As Heating means, drying means, are not particularly limited, and can be used for example, storage heater, infrared heater.Heating, drying It can carry out before printing, in printing, after printing etc..

Again, recording device, recording method are not limited to form the visual image of text, figure etc. by ink.Also it wraps Containing persons, moulding three-dimensional image person such as the patterns for for example forming geometry decorative pattern.

Again, it in recording device, as long as no being particularly limited to, also may include so that the mobile tandem type device of head is discharged Or that the mobile line style device of head is discharged.

Additionally not only desktop, also includes the wide cut note that can be printed to the medium of AO size in the recording device Recording device, or the continuous book ticket printer that the continuous paper batched as roller shape can be used as recording medium.

Illustrate recording device an example referring to FIG. 1 and FIG. 2.Fig. 1 is the perspective illustration of the device.Fig. 2 is the solid of main tank Explanatory diagram.Image forming apparatus 400 as recording device an example is tandem type image forming apparatus.In image forming apparatus Mechanism part 420 is equipped in 400 outline border 401.Black (K), cyan (C), magenta (M), the assorted main tank of yellow (Y) Each ink incorporating section 411 of 410 (410k, 410c, 410m, 410y) is formed by the package member of such as aluminium laminated film etc..Ink Water incorporating section 411 is accommodated in plastic accommodating container shell 414.Thus, main tank 410 is used as assorted print cartridge.

On the other hand, as the lid 401c of device for opening ontology, in the depth side of opening, it is equipped with ink container holder 404.Main tank 410 are detachably mounted on ink container holder 404.Thus, pass through assorted supply pipe 436, each ink row of connection main tank 410 Ink can be discharged in outlet 413 and assorted discharge head 434 from discharge head 434 to recording medium.

Ink jet printing method in the present invention includes that process is discharged in ink, preferably comprises heating process, as needed, includes Other process.

Ink-jet printing apparatus in the present invention has ink discharge means, preferably there is heating means to have as needed Other means.

Ink jet printing method in the present invention can be suitably carried out by above-mentioned ink-jet printing apparatus, and process is discharged in above-mentioned ink Means can be discharged by above-mentioned ink suitably to carry out.Above-mentioned heating process can suitably be carried out by above-mentioned heating means.Also, above-mentioned Other process can suitably be carried out by above-mentioned other means.

" process and ink discharge means are discharged in ink "

Above-mentioned ink discharge process is the process to form image so that ink of the invention circles in the air, and means can be discharged by ink Implement.

It as above-mentioned ink discharge means, is not particularly limited, can enumerate such as ink gun.

As above-mentioned ink gun, can enumerate so-called piezoelectric type ink-jet head (referring to Japanese Unexamined Patent Publication 2-51734 bulletin), Heat type ink gun (referring to Japanese Unexamined Patent Application 61-59911 bulletin), electrostatic type ink-jet head are (referring to Japanese Unexamined Patent Publication 6-71882 Bulletin) etc..Above-mentioned piezoelectric type ink-jet head uses piezoelectric element to generate means as the pressure to the ink pressurization in ink flow path, The oscillating plate for the wall surface to form ink flow path is deformed, the variation of ink flow path internal volume is changed so that ink droplet discharge；Above-mentioned heat type Ink gun uses heating resistor, and ink is heated in ink flow path, it is made to generate bubble；Above-mentioned electrostatic type ink-jet head makes shape It is oppositely disposed at the oscillating plate and electrode of the wall surface of ink flow path, because the electrostatic force occurred between oscillating plate and electrode to shake Movable plate deformation changes the variation of ink flow path internal volume, drop is discharged.

Circling in the air for ink can be carried out by for example applying stimulation to ink, and above-mentioned stimulation can be for example by stimulation generation means It generates, as the stimulation, is not particularly limited, can be properly selected according to purpose, for example hot (temperature), pressure can be enumerated Power, vibration, light etc..These can be used alone, and can also be used in combination with two or more.Wherein, heat, pressure are very suitable.

As the form of above-mentioned ink discharge, it is not particularly limited, is changed according to above-mentioned stimulation type etc., for example, on Stating stimulation is " heat " occasion, can enumerate following methods etc.: for the above-mentioned ink in record head, for example hot first-class imparting of use Thermal energy corresponding with tracer signal, due to the thermal energy so that bubble is generated in above-mentioned ink, because of the pressure of the bubble, from upper The nozzle bore for stating record head makes the ink that injection be discharged as drop.In addition, above-mentioned stimulation is " pressure " occasion, can enumerate Such as following methods etc.: pressure chamber is located in the ink via in record head, and piezoelectric element is bonded in the position of above-mentioned pressure chamber, By applying voltage, piezoelectric element flexure to piezoelectric element, pressure chamber's volume reduces, makes from the nozzle bore of above-mentioned record head It states ink and is discharged as drop and sprayed.

The drop of the above-mentioned above-mentioned ink that it is discharged, as its size, preferably such as 3pL or more, 40pL are hereinafter, conduct Its speed sprayed, preferably such as 5m/s or more, 20m/s are hereinafter, as its driving frequency, preferably such as 1kHz or more, as Its resolution ratio, preferably such as 300dpi or more.

" heating process and heating means "

Above-mentioned heating process is the process for the recording medium that heating record has image, can be implemented by heating means.

As above-mentioned ink jet printing method, high figure can be carried out in the impermeability recording medium as aforementioned recording medium As the record of quality, in order to form high and high to the recording medium adhesion image of Marresistance with higher-definition, also, Can be corresponding with the record condition of high speed, above-mentioned impermeability recording medium is preferably heated after reordering.If after reordering comprising adding Thermal process then promotes the film forming of the resin particle contained in ink, therefore, can improve the image hardness of record object.

As above-mentioned heating temperature, consider from drying property and film-forming temperature angle, preferably high temperature, more preferable 40 DEG C Above, 120 DEG C hereinafter, particularly preferred 50 DEG C or more, 90 DEG C or less.Above-mentioned heating temperature if 40 DEG C or more, 120 DEG C hereinafter, Can then prevent impermeability recording medium because of thermally-induced damage, black head can be inhibited to generate because of temperature and be not discharged.

Fig. 3 is the skeleton diagram for indicating heating means an example of Fig. 1 device.As shown in figure 3, make balladeur train 133 mobile on one side, Record head is driven according to picture signal on one side, ink droplet is discharged to the recording medium 142 of stopping, recording image.Guiding parts 153 Recording medium is supportted, band 151 is transported and is erected between transport roller 157 and jockey pulley 158, recording medium 142 obtains on transporting band 151 To transport, heated fan 201 is used as hot wind generating unit, to the image blowing hot air 202 for being formed in recording medium 142, keeps it dry It is dry.

In the opposite side with recording medium 142 for transporting band 151, it is equipped with heater group 203, the note of image can be thermally formed Recording medium 142.

< other process and other means >

As above-mentioned other process, can enumerate such as occurring process, control process for stimulation.

As above-mentioned other means, can enumerate such as stimulation generation means, control means.

Means occur as above-mentioned stimulation, such as heating device, pressurizing device, piezoelectric element, vibration generation can be enumerated Device, ultrasonic oscillator, lamp etc..Specifically, for example, can enumerate using the piezoelectric actuator with piezoelectric element etc., The thermal actuator for using phase change caused by film boiling of the electrothermal conversioning element of heating resistor etc. using liquid, utilizes temperature The shape memory alloy actuator of the variation of metal phase caused by changing, utilizes the electrostatic actuator etc. of electrostatic force.

As above-mentioned control means, as long as can control the movement of above-mentioned each means, it is not particularly limited, it can be according to purpose It properly selects, such as, sequencer, the equipment such as computer can be enumerated.

As an example of the ink jet printing method in the present invention, also can be set to including white (white) pigment will be contained Ink (white ink) be coated on the process of recording medium and using the record work that there is the ink of colored color material to be recorded The printing process of sequence, the above-mentioned ink for containing white pigment is as the transparent ink or color material for being free of pigment.At this moment, transparent ink Or white ink can also be coated in recording medium entire surface, or can also be coated on the part of recording medium.It is coated on The local occasion of recording medium both can for example be coated on and carry out identical place at record, or can also be coated on Carry out a part of identical place at record.

It is also effective using recording method below using above-mentioned white ink occasion.White ink is coated on recording medium, On it with the ink-mist recording of color other than white.According to this method, for example, even if using transparent membrane occasion, due to making Above-mentioned white ink is attached to recording medium surface, can ensure that the visibility of record.Ink in the present invention is even for impermeable Property recording medium also there is good drying property, high glaze, Marresistance etc., therefore, in order to enable visibility improve, Ke Yi White ink is coated in the impermeability recording medium of transparent membrane etc..

Also, being coated with white ink after being recorded on transparent membrane, the same excellent image of visibility can be also obtained.If White ink is replaced using transparent ink, can also play the function as protective layer.

Ink in the present invention is not limited to ink jet recording method, can be widely used.In addition to ink jet recording method, may be used also To enumerate such as scraper coating method, gravure coating process, intaglio plate hectograph rubbing method, rod coating method, print roll coating method, cutter painting cloth It is method, air knife coating method, comma coating (comma coating) method, U comma rubbing method, AKKU rubbing method, smooth rubbing method, micro- Gravure coating process, reverse roll coating method, four-roller or five roller coating methods, Dipcoat method, curtain coating processes, sliding rubbing method, mould Coating, spray coating method etc..

As implementation form an example, following form can be enumerated: above-mentioned white ink is coated in recording medium entire surface Occasion is coated with the coating method other than ink jet recording method, with the ink-mist recording occasion of the color other than white, can use ink-jet Recording method record.

As another implementation form, following form can be enumerated: either using the record of white ink, or use chalk The record of the ink of color other than water can be recorded with ink jet recording method.

Replace white ink occasion also the same using transparent ink.

< cleaning process and cleaning means >

Above-mentioned cleaning process be by cleaning solution cleaning remain in as ink attachment be attached to body, such as ink flow path or The process of the ink of record head, above-mentioned cleaning means are to be remained in be attached to body, example as ink attachment by cleaning solution cleaning Such as the means of ink flow path or the ink of record head.

It as the cleaning process and cleaning means of ink flow path, is not particularly limited, for example following form can be enumerated: peace The cartridge of dress filling cleaning solution supplies cleaning solution to ink flow path, is discharged, repeatedly the form of above-mentioned operation instead of print cartridge； From outside by the form of cleaning solution forced feed to ink flow path；Pump outside discharge head side use, attracts the shape of cleaning solution State etc..

The cleaning process and cleaning means for remaining in record head as cleaning, can enumerate for example following form:

Firstly, for example, wiper member is arranged in push part, to wiper member imparting cleaning solution.It is pushed away as above-mentioned Splenium part is not particularly limited as long as the component of such as nozzle face of above-mentioned record head can be pushed by above-mentioned wiper member, It can be properly selected according to purpose, for example, pushing roller can be enumerated, push roller and push the combination of band, polishing piece, scraper plate Deng.Wherein, roller is preferably pushed.

It as above-mentioned wiper member, is not particularly limited, can be properly selected according to purpose, for example, nothing can be enumerated Woven fabric, cloth etc..Above-mentioned component is preferably wound into roll, from the point of view of being difficult to dust accumulation, high reliablity, preferred roll nonwoven Cloth.

The imparting amount of above-mentioned cleaning solution is according to the control of record time.The occasion, the imparting amount of preferably above-mentioned cleaning solution is from more A setting value selection.As above-mentioned multiple setting values, can enumerate such as cleaning solution adding method (such as " pressure ", " assign Number ", " assigning nozzle number ") etc..

The imparting amount of above-mentioned cleaning solution preferably assigns what nozzle applied according to the cleaning solution for assigning means as cleaning solution Pressure control.Also, assign occasion when above-mentioned cleaning solution assigns nozzle from multiple cleaning solutions, preferably above-mentioned cleaning solution to above-mentioned wiping The imparting amount for wiping component assigns nozzle number control according to above-mentioned cleaning solution.Also, the tax to above-mentioned wiper member of above-mentioned cleaning solution The amount of giving preferably assigns number control according to the cleaning solution for assigning nozzle from above-mentioned cleaning solution.

Means are assigned as above-mentioned cleaning solution, as long as it is a certain amount of to assign cleaning solution, are not particularly limited, it can be according to mesh Properly select, for example, nozzle, injector, distributor, apparatus for coating etc. can be enumerated.

Fig. 4 is the skeleton diagram for indicating cleaning means an example in the present invention.The cleaning means 300 of the Fig. 4 are cleaning inks The means of the nozzle face 301a of the ink discharge side of the nozzle plate 301 of head are discharged.

Cleaning means 300 include the non-woven fabrics 303 as wiper member, and the cleaning solution for assigning means as cleaning solution assigns Nozzle 302 as the pushing roller 305 of push part, and batches the work beam 304 of wiping treated non-woven fabrics.

Cleaning solution is supplied from cleaning fluid tank (cleaning solution accepting container) by not shown cleaning solution supplying pipe.Pass through drive The dynamic pump for being located at above-mentioned cleaning solution supplying pipe midway, cleaning solution assign nozzle 302 to the nonwoven as wiper member from cleaning solution Cloth 303 assigns the imparting amount of the corresponding cleaning solution according to the record time.Non-woven fabrics 303 is wound into roll.

Also, as shown in figure 4, the non-woven fabrics 303 for being endowed cleaning solution is pushed by the pushing roller 305 as push part, And abutted with the nozzle face 301a of ink discharge head 301, nozzle face 301a is cleaned.Wipe after treatment, non-woven fabrics 303 It is batched by work beam 304.

(printed article)

On the recording medium using ink printing of the invention, printed article can be obtained.

Printed article can be made using ink-jet printing apparatus.

Also, printed article includes recording medium, and the printing layer in aforementioned recording medium, above-mentioned printing layer contains poly- silicon Oxygen alkane interfacial agent and urethane resin particles are 8 or less containing HLB value as above-mentioned polysiloxanes interfacial agent Polysiloxanes interfacial agent.

Also, the image in term of the present invention forms, records, prints, prints etc. and being all set as synonym.

[embodiment]

In the following, indicating embodiment, the present invention is further illustrated, but the invention is not limited to these embodiments.

(preparation example of pigment dispersion)

The preparation > of < black pigment dispersion

After the premixing of formula as below mixture, with disc type ball mill (Shinmaru-enterprises corporation, KDL Medium: type uses the zirconium oxide bead of diameter 0.3mm), circulation dispersion in 7 hours is carried out, self-dispersion type black pigment dispersion is obtained (pigment solids fraction concentration: 15 mass %).

Carbon black pigment (trade name: Monarch 800, Cabot corporation) 5 mass parts

Anionic property interfacial agent (trade name: PioninA-51-B, this grease of bamboo corporation) 2 mass parts

83 mass parts of ion exchange water

The preparation > of < polyurethane resin latex

In the reaction vessel of the capacity 2L with blender, thermometer, nitrogen-sealed pipe and cooler, it is added following Material, with 60 DEG C of uniform mixing:

100 mass parts of methyl ethyl ketone

(1) 345 mass parts of polyester polyol

9.92 mass parts of 2,2- dihydromethyl propionic acid DMPA

Above-mentioned polyester polyol (1) system is obtained by iPA/AA=6/4 (molar ratio) and EG/NPG=1/9 (molar ratio) Polyester polyol number-average molecular weight=3000, average functional group number=2.

Wherein, iPA is isophathalic acid, and AA is adipic acid, and EG is ethylene glycol, and NPG is neopentyl glycol.

Hereafter, following material is added, reacts it 3 hours with 72 DEG C, obtains polyurethane solutions:

45.1 mass parts of triethylene glycol diisocyanate TEGDI

0.08 mass parts of tin dilaurate dioctyl tin DOTDL

IPA80 mass parts, MEK220 mass parts, TEA3.74 mass parts, 596 mass parts of water are added to the polyurethane solutions After making its phase inversion, MEK and IPA is removed with rotary evaporator, obtains polyurethane resin latex 1.

After obtained water based emulsion is cooled to room temperature, ion exchange water and sodium hydrate aqueous solution are added, is adjusted to Solids fraction 30 mass %, pH8.

Using the latex 1, the vitreous branchpoint (=Tg) measured with " Thermo plus EV02 " (Rigaku corporation) It is -10 DEG C.

(ink preparation example 1)

Following material is added, is mixed:

20 mass % of self-dispersion type black pigment dispersion

Contain 1.0 mass % of polyoxyalkylene hydroxyl silicon compound

(polysiloxanes interfacial agent: Dow Toray Co. Ltd. system, trade name: FZ2110, HLB value: 1.0)

Trade name: Proxel LV (as preservative, Avecia corporation) 0.1 mass %

High purity water residual

With 0.2 μm of average pore size of polypropylene filter (trade name: Betafine polypropylene pleated filter PPG series, 3M corporation) it is filtered, make ink 1.

(ink preparation example 2~9)

In ink preparation example 1, it is changed to composition and content documented by following table 1, is prepared in addition to this with ink Example 1 is identical, makes ink 2~9.

Table 1

In table 1, the trade name of ingredient and manufacturing company's name are as follows:

Polysiloxanes interfacial agent 1:Dow Toray Co. Ltd. system, contains polyoxyalkylene hydroxyl silicon compound, commodity Name: FZ2110, HLB value: 1.0

Polysiloxanes interfacial agent 2: Shin-Etsu Chemial Co., Ltd's system, polyester modification silicon, trade name: KF-945, HLB value: 4.0

Polysiloxanes interfacial agent 3: Shin-Etsu Chemial Co., Ltd's system, polyester modification silicon, trade name: KF-6017, HLB value: 4.5

Polysiloxanes interfacial agent 4:Dow Toray Co. Ltd. system, polyester modification silicon, trade name: SH-3773M, HLB value: 8.0

Polysiloxanes interfacial agent 5: Shin-Etsu Chemial Co., Ltd's system, polyester modification silicon, trade name: KF-353, HLB value: 10.0

1.2- propylene glycol: Asahi Denka Co., Ltd.'s system

2.3- butanediol: Tokyo Chemical Industry Co., Ltd's system

3- methoxyl group -3- methyl butanol: Co., Ltd.'s KURARAY system

2- methyl -2,4- pentanediol: Wako Pure Chemical Industries, Ltd.'s system

Preservative: Avecia corporation, trade name: Proxel LV

(cleaning solution preparation example 1)

Following material is added, stir within 1 hour, cleaning solution 1 is obtained:

1.2- propylene glycol (δ H:10.39 (the cal/cm of HSP³)^1/2, specific gravity: 1.04) 5.0 mass %

3-Methoxy-3-methyl-1-butanol (δ H:6.29 (the cal/cm of HSP³)^1/2, specific gravity: 0.927) 15 mass %

2-Pyrrolidone (δ H:4.39 (the cal/cm of HSP³)^1/2, specific gravity: 1.10) 60 mass %

Fluorine system surfactant (trade name: ZONYL (logging in trade mark) FSO-100, Du Pont corporation) 1.0 mass %

Defoaming agent (2,4,7,9- tetramethyl -4,7- decanediols, Nishin Chemical Industry Co. Lt's system) 0.10 mass %

Ion exchange water residual

(cleaning solution preparation example 2~5)

The preparation > of < cleaning solution 2~5

In cleaning solution preparation example 1, be changed to composition and content documented by following table 2, in addition to this with cleaning solution Preparation example 1 is identical, obtains cleaning solution 2~5.

Table 2

In table 2, the trade name of ingredient and manufacturing company's name are as follows:

1.2- propylene glycol: Asahi Denka Co., Ltd.'s system

1.2- butanediol: Tokyo Chemical Industry Co., Ltd's system

1.3- butanediol: Tokyo Chemical Industry Co., Ltd's system

1.2- hexylene glycol: Tokyo Chemical Industry Co., Ltd's system

3-Methoxy-3-methyl-1-butanol: Co., Ltd.'s KURARAY system

2-Pyrrolidone: Tokyo Chemical Industry Co., Ltd's system

Fluorine system surfactant: Du Pont corporation, trade name: ZONYL (logging in trade mark) FSO-100

Defoaming agent: 2,4,7,9- tetramethyl -4,7- decanediols, Nishin Chemical Industry Co. Lt's system

(embodiment 1)

So that above-mentioned ink 1 and above-mentioned cleaning solution 1 combine, it is set as the external member of ink and cleaning solution

(embodiment 2~11 and comparative example 1~2)

In embodiment 1, ink and cleaning solution are changed to combination documented by following table 3, in addition to this with embodiment 1 It is identical, prepare the external member of ink and cleaning solution.

Using the external member of obtained ink and cleaning solution, evaluate by the following method " Marresistance ", " solvent resistance ", " fixation performance (ink droplet connects) ", " image gloss ", " adhesion ", " discharge stability " and " cleaning ".As a result it indicates Table 3.

Consider that outdoor application utilizes, about the evaluation of " fixation performance (ink droplet connects) " and " Marresistance ", and is recorded in General paper occasion is compared, using the evaluation criteria of rather severe.

[formation of solid image]

Ink 1~9 is filled to ink-jet printer (5500 transformation apparatus of Ricoh corporation IPSiO GXe), for polychlorostyrene second Alkene film (CPPVWP1300, Sakurai Co., Ltd.'s system, hereinafter, otherwise referred to as " PVC film ") recording medium, is adhered to ink Measure 0.6g/cm²Record solid image.After record, by above-mentioned solid image, it is being set as 80 DEG C of hot plate (NINOS ND-1, AS ONE corporation) on carry out drying in 1 hour.

Above-mentioned 5500 transformation apparatus of IPSiO GXe is transformed to 5500 machine of IPSiO GXe, is made it possible to A4 size again Now with the print span of 150cm, be equivalent to 30m²The record of the writing speed of/hr, in addition, above-mentioned hot plate can be arranged by transforming as, be changed Heating condition (heating temperature, heating time) after becoming record.

< Marresistance >

Apply 400g weight load scratching with dry kapok (Kanakin#3) to be formed in PVC film recording medium Solid image, detect by an unaided eye image state, according to following evaluation criteria, evaluates Marresistance, be evaluated as B or more be can be practical The grade used.

[evaluation criteria]

AA: even if scratching 50 times or more, image does not also change.

A: 50 stages are being scratched, how much image generates scratch, but does not influence on image.

B: even if scratch 31 times or more, 49 times hereinafter, image do not change.

C: even if scratching 30 times hereinafter, image does not change.

< solvent resistance >

It is small in 60 mass % ethanol waters 24 with normal temperature dipping that the solid image in PVC film recording medium will be formed in When, then, makes it after room temperature (25 DEG C) lower 24 hours spontaneously dry, use X-Rite 938 (X-Rite corporation) measurement chart As concentration, the reduction amount of the image color of the initial concentration of the image before image color versus dip after calculating dipping, according to Following evaluation criteria evaluates solvent resistance.Being evaluated as B or more is the grade that can be actually used.

[evaluation criteria]

AA: the reduction of image color value is less than 10%.

A: image color value is reduced to 10% or more, less than 20%.

B: image color value is reduced to 20% or more, less than 30%.

C: image color value is reduced to 30% or more.

< fixation performance (ink droplet connects) >

The recording for the solid image being formed in PVC film recording medium that detect by an unaided eye is irregular, according to following evaluation base Quasi- evaluation fixation performance (ink droplet connects).Being evaluated as B or more is the grade that can be actually used.

[evaluation criteria]

A: very good (absolutely not generation ink droplet connects).

B: good (observing that ink droplet, which slightly occurs, to connect).

C: common (ink droplet occurs to connect).

D: bad (apparent ink droplet occurs to connect).

< image gloss >

It is measured four times and is formed in PVC film recording medium with Grossmeters (BYK Gardener corporation, 4501) 60 ° of glossiness of solid image, seek its average value, evaluate image gloss according to following evaluation criteria.Being evaluated as B or more is The grade that can be actually used.

[evaluation criteria]

AA: gloss value is 100 or more.

A: gloss value is 90 or more, less than 100.

B: gloss value is 80 or more, less than 90.

C: gloss value is less than 80.

< adhesion >

It is identical as above-mentioned solid image forming method, for being formed on PP thin film recording medium (Japan spins, P2161) Solid image, by using the gridiron pattern disbonded test of cloth adhesive tape (123LW-50, NICHIBAN corporation), by right The remaining grid number of 100 test grids is counted, according to the evaluation of following evaluation criteria for the adhesion of recording medium.It comments Valence is that B or more is the grade that can be actually used.

[evaluation criteria]

AA: remaining grid number 98 or more.

A: remaining grid number 90 or more, less than 98.

B: remaining grid number 70 or more, less than 90.

C: remaining grid number is less than 70.

(discharge stability)

Using printer (device name: IPSiO GXe 3300, Ricoh's corporation), so that ink is continuously discharged 45 minutes, Discharge makes record head dry tack free in 30 minutes after stopping.Hereafter, cleaning solution 3mL is assigned to the nozzle of record head with blotting water pipe Behind face, implement wiping, carry out discharge ink again, discharge stability is evaluated according to following evaluation criteria.Be evaluated as B or more be can The grade of actual use.

[evaluation criteria]

A: absolutely not discharge is chaotic or is not discharged.

B: 5 nozzles appear below discharge confusion or be not discharged.

C: 5 nozzles are had more than and discharge confusion occurs or is not discharged.

(cleaning)

By SUS316 plate (3cm × 4cm) dipping 60 minutes in the ink.Hereafter, in an atmosphere, the pressurized conditions of 0.1MPa Under, 2 hours are stood under room temperature (25 DEG C) and is made it dry, and the SUS316 plate for being attached with black dry substance is obtained.

The obtained SUS316 plate for being attached with black dry substance clean repeatedly within 3 minutes using cleaning solution 3mL.Cleaning After, detect by an unaided eye SUS316 plate, evaluates cleaning according to following evaluation criteria.Being evaluated as B or more is that can actually use Grade.

[evaluation criteria]

A: black dry substance is not can confirm that completely in cleaning initial stage (within 1 minute) repeatedly.

B: after cleaning repeatedly, black dry substance is not can confirm that completely.

C: confirm that black dry substance is remaining slightly.

D: it after before cleaning, does not see black dry substance and generates variation.

Table 3

From embodiment 1,2,8 it is found that being the suitable form of the present invention, the adhesion of opposite PP thin film recording medium is excellent, When can also obtain high image gloss in the printing of impermeability recording medium, meanwhile, Marresistance and resistance to molten can be obtained The image of agent, cleaning and discharge stability are also excellent.

Embodiment 3 is the hydrogen bond item of the Hansen solubility parameters in the mixed liquor in cleaning solution example high slightly, with reality It applies example 1,2,8 to compare, becomes the result of discharge stability difference.

Embodiment 4 and embodiment 5 are the HLB value of the polysiloxanes interfacial agent in ink examples high slightly, with reality It applies example 1,2,8 to compare, becomes the result of image gloss difference.

Embodiment 6 is the additive amount of the polysiloxanes interfacial agent in ink example few slightly, with embodiment 1,2,8 It compares, becomes the result of fixation performance and poor solvent resistance.

Embodiment 7 is the additive amount of the polysiloxanes interfacial agent in ink example more slightly, with embodiment 1,2,8 It compares, becomes the result of discharge stability difference.

Embodiment 9 is the additive amount of the polyurethane resin in ink example more slightly, is compared with embodiment 1,2,8, at For discharge stability and the poor several result of cleaning.

Embodiment 10 and embodiment 11 are that the hydrogen bond item in cleaning solution without containing Hansen solubility parameters is 5.0 (cal/ cm³)^1/2The example of solvent below is compared with embodiment 1,2,8, becomes several result of cleaning difference.

Comparative example 1 is the example for the polysiloxanes interfacial agent for the use of HLB value being in the ink 8 or more, with embodiment It compares, becomes the result of fixation performance, image gloss, discharge stability and cleaning difference.

Comparative example 2 is that the hydrogen bond item of the Hansen solubility parameters in the mixed liquor in cleaning solution is more than 10.0 (cal/cm³)^1/2 Example, compared to the examples, become discharge stability and cleaning difference result.

From above-mentioned 3 result of table it is found that the ink in the present invention is suitable for outdoor application.Also, the ink set of Examples 1 to 9 Part is very excellent on Marresistance, solvent resistance, fixation performance, image gloss, adhesion, discharge stability and cleaning.

Above with reference to Detailed description of the invention implementation form of the invention, but the invention is not limited to above-mentioned implementation forms.? It can make various changes within the scope of technical thought of the invention, they belong to protection scope of the present invention.

Claims (13)

1. a kind of cleaning solution, body is attached to for clean following ink attachment, it is characterised in that:

Above-mentioned cleaning solution includes water and organic solvent, by the Hansen solubility for the mixed liquor that above-mentioned water and above-mentioned organic solvent form The hydrogen bond item of parameter is 10.0 (cal/cm³)^1/2Below；

Ink includes that water, organic solvent, urethane resin particles and HLB value are 8 polysiloxanes interfacial agents below, The content of above-mentioned urethane resin particles is 5 mass % or more with respect to ink full dose.

2. cleaning solution as described in claim 1, which is characterized in that the hydrogen bond item of the Hansen solubility parameters of above-mentioned mixed liquor is 8.5(cal/cm³)^1/2Below.

3. cleaning solution as claimed in claim 1 or 2, which is characterized in that above-mentioned ink includes that HLB value is 4 poly- silicon oxygen below Alkane interfacial agent.

4. cleaning solution as claimed in claim 1 or 2, which is characterized in that polysiloxanes interfacial agent in above-mentioned ink Content is 1.0 mass % or more, 2.0 mass % or less with respect to ink total amount.

5. cleaning solution as claimed in claim 3, which is characterized in that the content of the polysiloxanes interfacial agent in above-mentioned ink Opposite ink total amount is 1.0 mass % or more, 2.0 mass % or less.

6. cleaning solution as claimed in claim 1 or 2, which is characterized in that above-mentioned mixed liquor includes at least a kind of Hansen solubility The hydrogen bond item of parameter is 5.0 (cal/cm³)^1/2Organic solvent below.

7. cleaning solution as claimed in claim 3, which is characterized in that above-mentioned mixed liquor includes at least a kind of Hansen solubility parameters Hydrogen bond item be 5.0 (cal/cm³)^1/2Organic solvent below.

8. cleaning solution as claimed in claim 4, which is characterized in that above-mentioned mixed liquor includes at least a kind of Hansen solubility parameters Hydrogen bond item be 5.0 (cal/cm³)^1/2Organic solvent below.

9. cleaning solution as claimed in claim 5, which is characterized in that above-mentioned mixed liquor includes at least a kind of Hansen solubility parameters Hydrogen bond item be 5.0 (cal/cm³)^1/2Organic solvent below.

10. a kind of accepting container includes the cleaning solution for being attached to body for cleaning following ink attachment, it is characterised in that:

Above-mentioned cleaning solution includes water and organic solvent, by the Hansen solubility for the mixed liquor that above-mentioned water and above-mentioned organic solvent form The hydrogen bond item of parameter is 10.0 (cal/cm³)^1/2Below；

Ink includes that water, organic solvent, urethane resin particles and HLB value are 8 polysiloxanes interfacial agents below, The content of above-mentioned urethane resin particles is 5 mass % or more with respect to ink full dose.

11. a kind of ink jet printing method, comprising:

Process is discharged in ink, so that ink is discharged, is printed on recording medium；And

Cleaning process remains in the ink of ink flow path or record head by cleaning solution cleaning；

Above-mentioned ink jet printing method is characterized in that above-mentioned cleaning solution is cleaning solution described in any one of claim 1 to 9.

12. a kind of ink-jet printing apparatus, comprising:

Ink output mechanism is printed on recording medium so that ink is discharged；And

Wiper mechanism remains in the ink of ink flow path or record head by cleaning solution cleaning；

Above-mentioned ink-jet printing apparatus is characterized in that above-mentioned cleaning solution is cleaning solution described in any one of claim 1 to 9.

13. the external member of a kind of ink and cleaning solution, it is characterised in that:

Above-mentioned ink includes that water, organic solvent, urethane resin particles and HLB value are 8 polysiloxanes interface activations below Agent, the content of above-mentioned urethane resin particles are 5 mass % or more with respect to ink full dose；

Above-mentioned cleaning solution includes water and organic solvent, by the Hansen solubility parameters for the mixed liquor that above-mentioned water and organic solvent form Hydrogen bond item be 10.0 (cal/cm³)^1/2Below.