CN102344716A - Ink composition, ink set, ink jet recording method, printed matter, forming printed matter and manufacturing method of forming printed matter - Google Patents

Abstract

The invention provides an ink composition, an ink set, an ink jet recording method, printed matter, formed printed matter and manufacturing method of formed printed matter, which are good in curing performance and flexibility and high in film hardness. The ink composition is characterized by containing (component A) aluminum pigments, (component B) free radical polymerizable compound, and (component C) optical free radical polymerization initiator, wherein the free radical polymerizable compound of component B contains 80-99.9 mass% monofunctional monomer and 0.1-20 mass% polyfunctional monomer.

Description

The method of manufacture of ink composite, printing ink group, ink jet recording method, print, shaping print and shaping print

Technical field

The present invention relates to the method for manufacture and the shaping print of ink composite, printing ink group, ink jet recording method, print, shaping print.

Background technology

Image recording process as on printing medium, form image according to viewdata signal has electronic photo mode, subliming type and fusion thermal transfer mode, ink-jetting style etc.Ink-jetting style is owing to use cheap device and only to the image portion ejection printing ink of needs and on printing medium, directly carry out image and form, therefore can use ink composite efficiently, and running cost is low.In addition, noise is little, is excellent as the image recording mode.

As the ink composite that contains metallic pigment, can enumerate out the ink composite of record in patent documentation 1 and 2.

The prior art document

Patent documentation

Patent documentation 1: TOHKEMY 2009-91550 communique

Patent documentation 2: TOHKEMY 2008-88228 communique

Summary of the invention

Invent problem to be solved

The object of the present invention is to provide and to obtain the solidified nature excellence and take into account excellent flexibility and the method for manufacture and the shaping print of the ink composite of the metalluster image of high film hardness, printing ink group, the ink jet recording method that has used this ink composite, print, shaping print.

Be used to solve the means of problem

Above-mentioned problem is able to solve through the means of following record.

< 1>a kind of ink composite; It is characterized in that; Contain (composition A) aluminum metal pigment, (composition B) free-radical polymerised compound and (composition C) optical free radical polymerization starter, and comprise monofunctional monomer 80～99.9 quality % and polyfunctional monomer 0.1～20 quality % in the free-radical polymerised compound of composition B.

< 2>according to < 1>described ink composite, wherein, the content of the composition A in the ink composite is 0.5～20 quality %.

< 3>according to < 1>or < 2>described ink composite, wherein, contain the compound of formula (b-1) expression and/or the compound of formula (b-2) expression as said monofunctional monomer,

(in the formula (b-1), R ¹Expression hydrogen atom or methyl, X represent singly-bound, alkylidene group, oxygen base alkylidene group or the group that said oxygen base alkylidene group is combined more than 2, ester bond, or with the group that combine of these groups more than 2, R ²And R ³Represent hydrogen atom or alkyl independently of one another, R ⁴～R ⁸Represent hydrogen atom, alkyl, alkoxyl group, amino or aminoalkyl group independently of one another, R ⁴～R ⁸In at least 1 be hydrogen atom, R ²～R ⁸In can combine to form ring texture more than 2 arbitrarily.)

(in the formula (b-2), n representes 1～5 integer.)

< 4>according to < 3>described ink composite, wherein, the total content of the compound of said formula (b-1) expression among the composition B and the compound of formula (b-2) expression is 5～99.9 quality % of ink composite.

< 5>a kind of printing ink group is characterized in that, comprise < 1 >～< 4>in each described ink composite and at least a kind of ink composite that contains the tinting material except that composition A.

< 6>a kind of ink jet recording method is characterized in that, comprises following operation: with < 1 >～< 4>thus in each described ink composite be ejected on the printing medium image that forms image and form operation; With, shine active radioactive rays, this ink composite is solidified to the ink composite that sprays, thereby obtain on said printing medium, having the curing process of the print of solidified image.

< 7>a kind of print, it obtains through < 6>described ink jet recording method.

< 8>a kind of method of manufacture of the print that is shaped; It is characterized in that; Comprise following operation: with < 1 >～< 4>thus in each described ink composite be ejected on the printing medium image that forms image and form operation, thereby shine active radioactive rays, this ink composite solidified obtain the curing process of the print that on said printing medium, has the solidified image and said print formed the operation of processing to the ink composite of ejection.

< 9>a kind of shaping print, it is that method of manufacture through < 8>described shaping print obtains.

The effect of invention

According to the present invention, it is excellent and taken into account the method for manufacture and the shaping print of ink composite, the printing ink group of the metalluster image of excellent flexibility and high film hardness, the ink jet recording method that has used this ink composite, print, shaping print to provide that to obtain solidified nature.

Description of drawings

The sketch chart of an example of the mould that uses in the test of Fig. 1 for expression shaping processing.

Embodiment

I. ink composite

Ink composite of the present invention is preferred for ink-vapor recording and uses; It is characterized in that; Contain (composition A) aluminum metal pigment, (composition B) free-radical polymerised compound and (composition C) optical free radical polymerization starter, and the free-radical polymerised compound of composition B comprises monofunctional monomer 80～99.9 quality % and polyfunctional monomer 0.1～20 quality %.

Need to prove that in this specification sheets, the short of special instruction of record of " A～B " of expression numerical range is then with " A is above and B the is following " same meaning of (comprising as the A of lower value with as the B of higher limit).In addition, the same meaning of the record of " (methyl) acrylate " etc. and " methacrylic ester and/or acrylate " etc.

Ink composite of the present invention is can the solidified oil-based ink composition under the effect of active radioactive rays." active radioactive rays " are meant the radioactive rays of the energy that under its irradiation, can give the initiation kind generation that makes in the ink composite, comprise alpha-ray, gamma-rays, X ray, ultraviolet ray, visible rays, electron rays etc.Wherein, from the viewpoint of the easy property of acquisition of solidifying sensitivity and device, preferred ultraviolet ray and electron rays, more preferably ultraviolet.Below, each composition is described.

((composition A) aluminum metal pigment)

Ink composite of the present invention contains (composition A) aluminum metal pigment.

As the aluminium powder that can be suitable as aluminum metal pigment, can suitably select to use known any aluminium powder.

Aluminium powder can be through method of manufacture manufacturing arbitrarily.Method of manufacture as aluminium powder; But for example going out, illustration broken method for processing is carried out in the aluminum substrate cold draw on one side on one side; Aluminium-vapour deposition is become thin film, is made into the method for powder then; Process the method for powder etc., but the present invention is not limited to these the paper tinsel superprecision that photoluminescent is good.

In addition, the aluminium powder of interpolation can be the arbitrary shape in pasty state or the powder.As the aluminium powder of pasty state,, illustration becomes the aluminium powder of pasty state but going out to be distributed in the hydrocarbon system solvent (for example ethyl acetate).

The aluminium powder that uses among the present invention can carry out surface treatment etc.The aluminium powder that obtains but illustration goes out for example to make stearic acid etc. to be adsorbed onto the surface of powder; When using the aluminium powder that obtains through this method processing; Ink pellet surface aluminium powder in ejection has the tendency that is arranged in parallel, and can access the print that is similar to satinizing (minor finish).

In addition, but also illustration goes out the aluminium powder that resin-coated obtains, and can improve adherence, resistance to chemical reagents, weathering resistance etc. thus, and is therefore preferred.But, the tendency of glossy property and disguised variation.

Aluminium powder has commercially available; For example as being distributed to the hydrocarbon system solvent and the aluminium powder of the pasty state that obtains, but illustration goes out ROTOVARIO 500 series (ECART corporate system), ASTROSHINE T-8990, ASTROSHINE T-8765 (being Japanese damp proof Industrial Co., Ltd system).

Among the present invention, the aluminum metal pigment optimization is dispersed in the free-radical polymerised compound.That is, the aluminum metal pigment optimization is not to be dispersed in water or the solvent but to be dispersed in the free-radical polymerised compound.

In the ink composite, the volume average particle size of aluminum metal pigment be preferably 0.05～1.5 μ m, more preferably 0.10～1.3 μ m, further be preferably 0.15～1.0 μ m.When in above-mentioned numerical range, can take into account ejection property and metalluster.

Among the present invention, volume average particle size can be utilized laser diffraction, scattering method particle size distribution device (trade(brand)name: MicroTrack MT3300EX, Nikkiso Company Limited's system) etc. and use the liquid diluting identical with dispersion medium to measure.

Among the present invention, the preferred content of aluminum metal pigment with respect to the total amount (total mass) of ink composite be 0.5～20 quality %, more preferably 3～20 quality %, further be preferably the scope of 5～18 quality %.

When the content of aluminum metal pigment is 0.5 quality % when above, can obtain good radiance sense, therefore preferred.In addition, when the content of aluminum metal pigment when 20 quality % are following, having good stability of ink composite, therefore preferred.

The ink composite that uses among the present invention contains free-radical polymerised compound, optical free radical polymerization starter and aluminum metal pigment, is preferably with non-water system and has carried out the dispersive dispersion liquid.

Ink composite for example can prepare (processing printing ink) through adding free-radical polymerised compound, optical free radical polymerization starter, aluminum metal pigment and various additives as required.

In addition, among the present invention, preferably when the preparation ink composite, use dispersion agent, more preferably use acid dispersion agent as dispersion agent.

In addition, said ink composite also can be like the preparation of getting off: at first make the high dispersion of aluminum metal pigment concentration, to wherein adding said free-radical polymerised compound and various additives etc., dilute then.

Said aluminum metal dispersing of pigments can be used for example ball mill, sand mill, masher, roller mill, airflow milling, homogenizer, coating agitator, kneader, stirrer, Henschel mixing tank, colloidal mill, Soniprep, ball mill, in bulk the putting of wet type airflow milling five equilibrium.

Among the present invention, when disperseing, preferably use bead (dispersion medium) with aluminum metal pigment, free-radical polymerised compound and dispersion agent disperse imperceptibly at least.As diverting device, can use ball mill, stirrer, in bulk the putting of coating agitator five equilibrium.

As bead (dispersion medium), but illustration goes out granulated glass sphere, stainless shot, alumina bead, zirconium oxide bead etc., wherein, preferably uses zirconium oxide bead as bead (dispersion medium).Zirconium oxide bead is because intensity and hardness are excellent, the generation of the cutting powder of bead (dispersion medium) is few, and is therefore preferred.

In addition, as stated, preferably when carrying out said aluminum metal dispersing of pigments, add dispersion agent.

Among the present invention, preferably use acid dispersion agent as dispersion agent.Acid dispersion agent is meant through block or Grafting Structure to have the macromolecular compound of acid pigment hydrophilic radical at an end of main chain at least.When using acid dispersion agent, stable disperse object can carried out and obtain to said aluminum metal dispersing of pigments fast, and is therefore preferred.

As the acid pigment hydrophilic radical, but illustration goes out carboxyl, sulfonic group, phosphate.

As polymer, but illustration goes out to gather (methyl) acrylate, urethane, polyester or their modifier.

Such dispersion agent has commercially available article, but illustration goes out DISPERBYK-102, DISPERBYK-110, DISPERBYK-111, DISPERBYK-112, DISPERBYK-180 (above by the BYK corporate system), SOLSPERSE 26000, SOLSPERSE 36000, SOLSPERSE41000 (above by the Lubrizol corporate system).In addition, dispersion agent can a kind of independent use, also can be two or more and use.

In ink composite, the dispersion medium as each compositions such as said aluminum metal pigment can also add solvent.In addition, can use the low molecular weight compositions of no solvent is that free-radical polymerised compound is as dispersion medium.Among the present invention, ink composite is the ink composite of radiation-curing type, and in order after being applied to ink composite on the printing medium, to make its curing, is preferably solvent-free or low solvent.

As the structure of the free-radical polymerised compound that is used as dispersion medium, the structure that contains oxyethane (EO) chain, propylene oxide (PO) chain, phenyl ring can make dispersed the raising especially, and is therefore preferred.In addition, the structure with polymerizable group also is preferred from the viewpoint of solidified nature.

As more preferred example; As the dispersion medium that contains the EO chain, can enumerate out triethylene glycol divinyl ether (RAPI-CURE DVE-3, ISPJapan Co., Ltd. system), polyoxyethylene glycol two (methyl) acrylate, vinylformic acid 2-(2-ethoxy ethoxy) ethyl ester (EOEOEA) and ethoxylated trimethylolpropane triacrylate (EOTMPTA) etc.

As the dispersion medium that contains the PO chain, can enumerate out tripropylene glycol methyl ether, polypropyleneglycol diacrylate, ethoxylated neopentylglycol diacrylate (NPGPODA), propylene glycol diacrylate (DPGDA), tripropylene glycol diacrylate (TPGDA) and alkoxylate vinylformic acid tetrahydrofuran ester (CD611, Sartomer corporate system) etc.

As the dispersion medium that contains phenyl ring, can enumerate out phenoxyethyl acrylate (PEA), vinylformic acid phenoxy group ethyl oxygen base ethyl ester (EBECRYL110, Daicel-Cytec Co., Ltd. system) etc.

((composition B) free-radical polymerised compound)

Ink composite of the present invention contains (composition B) free-radical polymerised compound.The free-radical polymerised compound of composition B comprises monofunctional monomer 80～99.9 quality % and polyfunctional monomer 0.1～20 quality %.

< monofunctional monomer >

Ink composite of the present invention contains monofunctional monomer as free-radical polymerised compound.Monofunctional monomer accounts for 80～99.9 quality % of the total mass of composition B.

When the content of the monofunctional monomer among the composition B was lower than 80 quality %, the flexibility of cured film reduced.From the solidified nature of ink composite, the flexibility of cured film and the viewpoint of film hardness, the content of the monofunctional monomer among the composition B is preferably 82～98.0 quality %.

As monofunctional monomer; Preferably can enumerate out the compound that has 1 free-radical polymerised ethylenic unsaturated group at intramolecularly, more preferably can enumerate out have 1 be selected from that (methyl) is acrylate-based, the monofunctional monomer of the ethylenic unsaturated group of (methyl) acrylamido, vinyl oxygen base and N-vinyl.Through containing these monofunctional monomers, can access the excellent image of solidified nature and flexibility.

As monofunctional monomer, preferably can enumerate out compound and the monofunctional aromatic monomer etc. of compound, formula (b-2) expression of formula (b-1) expression.

< compound of formula (b-1) expression >

Ink composite of the present invention preferably contains the compound of formula (b-1) expression.Through containing the compound of formula (b-1) expression, dispersion stabilization improves, the aluminum ratio on ink film surface raises, can obtain to obtain the ink composite of the high image of solidified nature and film hardness.

(in the formula (b-1), R ¹Expression hydrogen atom or methyl, X represent singly-bound, alkylidene group, oxygen base alkylidene group or the group that said oxygen base alkylidene group is combined more than 2, ester bond or the group that they are combined more than 2, R ²And R ³Represent hydrogen atom or alkyl independently of one another, R ⁴～R ⁸Represent hydrogen atom, alkyl, alkoxyl group, amino or aminoalkyl group independently of one another, R ⁴～R ⁸In at least 1 be hydrogen atom, R ²～R ⁸In wantonlyly can combine to form ring texture more than 2.)

In the formula (b-1), R ¹Expression hydrogen atom or methyl, preferred hydrogen atom.

X representes singly-bound, alkylidene group, oxygen base alkylidene group or the group that said oxygen base alkylidene group is combined more than 2, ester bond or the group that they are combined more than 2.

The preferred carbonatoms of said alkylidene group is 1～10 alkylidene group, more preferably carbonatoms is 1～8 alkylidene group.

Oxygen base alkylidene group or be that the alkylidene group side is combined in the group on the Sauerstoffatom of (methyl) acryloxy in the formula (b-1) with the group that said oxygen base alkylidene group combines more than 2.As contained alkylidene group in the oxygen base alkylidene group, the carbonatoms that preferably has straight or branched is 1～5 alkylidene group, more preferably has the alkylidene group that carbonatoms is 2 or 3 straight or branched, a further preferred isopropylidene.When oxygen base alkylidene group is made up more than 2, preferably will make up below 10, more preferably will make up below 5.

When contain among the X ester bond (COO-or-OCO-) time, X is preferably the group that said alkylidene group and ester bond are combined.That is, be preferably Sauerstoffatom and be combined in R ²And R ³Oxygen base carbonyl alkylen group on institute's bonded carbon atom.

R ²And R ³Represent that independently of one another hydrogen atom or alkyl, preferred hydrogen atom or carbonatoms are 1～3 alkyl, more preferably hydrogen atom or methyl.

R ⁴～R ⁸Represent hydrogen atom, alkyl, alkoxyl group, amino or aminoalkyl group independently of one another.

As said alkyl, the carbonatoms that preferably has straight or branched is 1～10 alkyl.

As said alkoxyl group, the carbonatoms that preferably has straight or branched is 1～5 alkoxyl group, more preferably methoxyl group.

Comprise amino, alkyl monosubstituted amino, dialkyl amido in the said amino, the carbonatoms that this alkyl preferably has a straight or branched is 1～3 alkyl.As amino, preferred dimethylamino, diethylamino, diisopropylaminoethyl.

Amino that is comprised in the aminoalkyl group and above-mentioned amino are same.That is, comprise alkyl monosubstituted amino alkyl, dialkyl aminoalkyl in the aminoalkyl group.It is 1～3 alkyl that the part of the alkyl except that amino of aminoalkyl group is preferably carbonatoms.As aminoalkyl group, preferred dimethylaminomethyl, diethylamino methyl, diisopropylaminoethyl methyl.

R ⁴～R ⁸In at least 1 be hydrogen atom.Pass through R ⁴～R ⁸In at least 1 be hydrogen atom, can access the excellent ink composite of solidified nature.

R ²～R ⁸In wantonlyly also can combine to form ring texture more than 2.When forming ring, form the R of ring ²～R ⁸Be preferably alkyl.Preferred R ⁴Or R ⁵And R ⁶～R ⁸In wantonly 1 ring that combine to form, more preferably form that the ring element number is 4～6 ring-type ether, more preferably the ring element number is 5 ring-type ether, promptly forms tetrahydrofuran base.

In addition, R ²Or R ³And R ⁶～R ⁸In wantonly 1 can combine to form ring texture.At this moment, preferred R ⁶～R ⁸In wantonly 1 be alkoxyl group.

First number that formed ring texture preferably contains the ring of 2 Sauerstoffatoms is 6～8 ring texture, more preferably first number of ring is 6 a ring texture, preferred especially 1,3-diox-5-base.

From the excellent angle of solidified nature, the compound of formula (b-1) expression is preferably compound with tetrahydrofuran base, the more preferably compound of formula (b-1-1) expression.

(in the formula (b-1-1), R ¹Expression hydrogen atom or methyl, X represent singly-bound, alkylidene group, oxygen base alkylidene group perhaps combine said oxygen base alkylidene group more than 2 group, ester bond or the group that they are combined more than 2.)

X is identical with X in the formula (b-1), preferred range is also identical.

Following illustration goes out the object lesson of the compound of formula (b-1) expression, but is not limited to these object lessons.Wherein, in the exemplary compounds, R representes hydrogen atom or methyl.

[chemical formula 5]

[chemical formula 6]

Ink composite of the present invention preferably contains the compound of formula (b-2) expression.

(in the formula (b-2), n representes 1～5 integer.)

In the formula (b-2); N representes 1～5 integer; Flexibility after solidifying from ink composite, with the adherence and the raw-material acquired viewpoint of printing medium, preferred n is 2～4 integer, more preferably n is 2 or 4, preferred especially n 4 is the N-caprolactam.The N-caprolactam is because excellent in safety, general and can obtain, particularly can obtain good ink solidification property and the cured film adherence to printing medium more at an easy rate is therefore preferred.

The total content of the compound that the compound of said formula (b-1) among composition B expression and formula (b-2) are represented be preferably 5～99.9 quality %, more preferably 8～80 quality %, further be preferably 10～60 quality %.When in above-mentioned numerical range, solidified nature, film hardness, metalluster are excellent.

< monofunctional aromatic monomer >

Ink composite of the present invention preferably contains the monofunctional aromatic monomer as monofunctional monomer.With the compound of monofunctional aromatic monomer and above-mentioned formula (b-1) expression or the compound of formula (b-2) expression, can access the excellent ink composite of solidified nature through also.

As the monofunctional aromatic monomer; Preferably have 1 the free-radical polymerised ethylenic unsaturated group and the monomer of at least 1 aromatic group, more preferably have the monomer of 1 (methyl) acryloxy or (methyl) acrylamido and at least 1 aromatic hydrocarbyl at intramolecularly at intramolecularly.

As the monomeric object lesson of monofunctional aromatic, preferably can enumerate out the monofunctional aromatic free radical polymerization monomer of putting down in writing in the paragraph 0048～0063 of TOHKEMY 2009-096985 communique.Wherein, as the monofunctional aromatic free radical polymerization monomer, the compound of preferred formula (b-3) expression.

(in the formula (b-3), R ¹Expression hydrogen atom or methyl, X ¹Expression divalent linking group, Ar represent aromatic hydrocarbyl, R ⁵Expression substituting group, u represent 0～5 integer, and u R that exists ⁵Can distinguish identical also can be different.)

In the formula (b-3), R ¹Be preferably hydrogen atom.

X ¹The expression divalent linking group, be preferably ether (O-), ester group (C (O) O-or-OC (O)-), amide group (C (O) NR '-), carbonyl (C (O)-), imino-(NR '-), can have the group that substituent carbonatoms is 1～15 alkylidene group or divalence that they are combined more than 2.Wherein, R ' expression hydrogen atom, carbonatoms are that 1～20 straight chain shape, branched or cyclic alkyl or carbonatoms are 6～20 aryl.

In the formula (b-3), with X ¹Vinyl bonded end be preferably X ¹Carbonyl carbon and ethylenic unsaturated group institute bonded ester group or amide group, ester bond more preferably.Especially preferably has H ₂C=C (R ¹The structure of)-C (O) O-.At this moment, X ¹Other parts can be that singly-bound also can be an optional part from said group.

Contain R ¹And X ¹Part (H ₂C=C (R ¹)-X ¹-can be combined in the optional position on the aromatic hydrocarbyl Ar.

In addition, from the viewpoint of raising, with X with the affinity of tinting material ¹Aromatic hydrocarbyl Ar bonded end be preferably Sauerstoffatom, etheric oxygen atom more preferably, X ¹Be preferably *-C (O) O (LO) _q-or *-C (O) NH (LO) _q-.Here, the X of * expression (A2) ¹With binding site, the q of ethylenic unsaturated group be that 0～10 integer, L represent that carbonatoms is 2～4 alkylidene group.Wherein, X ¹Be preferably *-C (O) O (LO) _q-, q be preferably 0～4 integer, more preferably 0～2 integer, further be preferably 1 or 2.(LO) _qBe preferably ethylene oxide chain or propylene oxide chain.

U R that exists ⁵Being preferably hydroxyl, replacement independently of one another or not having substituted amino, thiol group, siloxanes, perhaps can further have substituent total carbon atom number is alkyl or heterocyclic radical below 30.

U representes 0～5 integer, is preferably 0.

Ar representes aromatic hydrocarbyl.As aromatic hydrocarbyl; Can enumerate out monocycle or Ppolynuclear aromatic alkyl with 1～4 ring; Can enumerate out particularly from the luxuriant and rich with fragrance alkene of benzene, naphthalene, anthracene, 1H-indenes, 9H-fluorenes, 1H-perinaphthene, phenanthrene, triphenylenyl, pyrene, naphthacene, tetraphenylenyl, biphenylene, as-benzo two indenes, s-benzo two indenes, acenaphthylene, fluoranthene, vinegar, aceanthrylene, 1,2-benzophenanthrene, seven days of the week alkene etc. has been removed the hydrogen atom more than 1 and the group that obtains.

Wherein, in the present invention, preferred phenyl, naphthyl, more preferably the monocyclic aromatic alkyl, be phenyl.

In addition, the aromatic hydrocarbyl Ar in the formula (b-3) contains heteroatomic heteroaromatics such as O, N, S, but does not preferably contain heteroatoms.

Among the present invention,, preferably can enumerate out vinylformic acid 2-phenoxy ethyl as the compound of formula (b-3) expression.

< other monofunctional monomer >

Ink composite of the present invention can contain the compound of compound except that above-mentioned formula (b-1) expression, formula (b-2) expression, other the monofunctional monomer the monofunctional aromatic monomer.As other monofunctional monomer, preferred (methyl) acrylic compound.

Comprise in (methyl) acrylic compound have monomer, the compound of chemical form such as oligomer, polymkeric substance.Other (methyl) acrylic compound can only use a kind, also can be in order to improve target property with ratio arbitrarily and with more than 2 kinds.

Particularly, can enumerate out (methyl) methyl acrylate; (methyl) ethyl propenoate; (methyl) 2-EHA; (methyl) vinylformic acid n-octyl; (methyl) vinylformic acid ester in the positive ninth of the ten Heavenly Stems; (methyl) vinylformic acid ester in the positive last of the ten Heavenly stems; (methyl) Isooctyl acrylate monomer; The positive Lauryl Ester of (methyl) vinylformic acid; (methyl) vinylformic acid n-tridecane ester; (methyl) vinylformic acid n-hexadecane ester; (methyl) vinylformic acid Octadecane ester; (methyl) vinylformic acid isooctadecane ester; (methyl) cyclohexyl acrylate; (methyl) IBOA; (methyl) vinylformic acid diamantane ester; (methyl) vinyl acrylate; (methyl) allyl acrylate; (methyl) vinylformic acid 2-hydroxy methacrylate; (methyl) vinylformic acid 2-hydroxy propyl ester; (methyl) vinylformic acid 3-hydroxy propyl ester; (methyl) vinylformic acid 2-hydroxyl butyl ester; (methyl) vinylformic acid 4-hydroxyl butyl ester; (methyl) vinylformic acid 2-methoxyl group ethyl ester; (methyl) vinylformic acid dicyclopentenyl oxygen base ethyl ester; (methyl) vinylformic acid 2-dimethylamino ethyl ester; (methyl) vinylformic acid 2-diethylamino ethyl ester; (gathering) glycol monomethyl (methyl) acrylate; (gathering) terepthaloyl moietie (methyl) methyl acrylate; (gathering) terepthaloyl moietie (methyl) ethyl propenoate; (gathering) Ucar 35 list (methyl) acrylate; (gathering) Ucar 35 (methyl) methyl acrylate; (gathering) Ucar 35 (methyl) ethyl propenoate; The system FANCRYL FA-513A (vinylformic acid two cyclopentenes esters) of Hitachi Chemical Co., Ltd.; FANCRYL FA-513M (methacrylic acid two cyclopentenes esters); FANCRYL FA-711MM (methacrylic acid pentamethyl-piperidines ester); FANCRYL FA-712HM (methacrylic acid tetramethyl piperidine ester); The system functional monomer SR&CD of SartomerJapan Co., Ltd. series; Monofunctional compound such as CN series as the sale of functional oligomerization thing.

More specifically, you can use the foot Shinzo series "bridging AGENT tension nn cloth sleeve boots ku" (1981, Great Society); Kato SD video encoding "U? V · E? B curing tension nn cloth sleeve boots black (raw series)" (198? 5 years, polymer print and publish Council); Getting cloth Te boots ku study will compile "U? V · E? B curing technology Full Applied and Market" 79 (1989, Shin a Eri Rousseau Shin a club); waterfall mountain Sakae Ichiro book "poly Ester resin tension nn cloth sleeve boots ku" (1988, Nikkan Kogyo Shimbun Co.) and other commercially available or described in the industry known radical polymerizable (meth) acrylate monomer.In addition; As free-radical polymerised compound; The polymerizable compound of the light-cured type that uses in the optical polymerism composition of putting down in writing in each communique such as for example known japanese kokai publication hei 7-159983 number, Japan special fair 7-31399 number, japanese kokai publication hei 8-224982 number, japanese kokai publication hei 10-863 number, japanese kokai publication hei 9-134011 number, the special table of Japan 2004-514014 number, (methyl) acrylate of putting down in writing in these documents also is applicable to ink composite of the present invention.

Wherein, (methyl) acrylate that preferably has amino or substituted-amino.Through having amino or substituted-amino, can access the excellent ink composite of aluminum metal dispersing of pigments property.

As the substituting group of substituted-amino, preferred carbonatoms is 1～5 alkyl.As other monofunctional monomer, more preferably has carbonatoms and is (methyl) vinylformic acid substituted-amino alkane ester, further preferred (methyl) vinylformic acid dimethylamino ethyl ester of 1～5 alkyl.

< polyfunctional monomer >

Ink composite of the present invention contains polyfunctional monomer as free-radical polymerised compound.Polyfunctional monomer accounts for 0.1～20 quality % of the total mass of composition B.

When the content of the polyfunctional monomer among the composition B surpassed 20 quality %, the flexibility of cured film, stretchiness reduced.The content of the polyfunctional monomer among the composition B is from the viewpoint of solidified nature, film hardness, flexibility, is preferably 0.5～19.9 quality %, 2～18 quality % more preferably.

As polyfunctional monomer; The polyfunctional monomer that preferably has ethylenic unsaturated group free-radical polymerised more than 2; More preferably have be selected from more than 2 that (methyl) is acrylate-based, the polyfunctional monomer of the ethylenic unsaturated group in (methyl) acrylamido, vinyl oxygen base and the N-vinyl, further preferably have at least 2 polyfunctional monomers that (methyl) is acrylate-based.

Functional group's number that polyfunctional monomer had is preferably 2～6, more preferably 2～4, further is preferably 2.

As polyfunctional monomer; Can enumerate out 1; 6-hexylene glycol two (methyl) acrylate; 1; 9-nonanediol two (methyl) acrylate; 1; 10-decanediol two (methyl) acrylate; Two (4-(methyl) acryloxy polyethoxye phenyl) propane; Neopentyl glycol two (methyl) acrylate; Ethoxylation neopentyl glycol two (methyl) acrylate; Ethoxylated neopentylglycol two (methyl) acrylate; Hydroxyl trimethylacetic acid neopentyl glycol two (methyl) acrylate; Ethylene glycol bisthioglycolate (methyl) acrylate; Diethylene Glycol two (methyl) acrylate; Triethylene glycol two (methyl) acrylate; TEG two (methyl) acrylate; Polyoxyethylene glycol two (methyl) acrylate; Polypropylene glycol two (methyl) acrylate; Gather tetramethylene glycol two (methyl) acrylate; Tetramethylolmethane three (methyl) acrylate; Oxyethane (EO) modification tetramethylolmethane three (methyl) acrylate; Propylene oxide (PO) modification tetramethylolmethane three (methyl) acrylate; Tetramethylolmethane four (methyl) acrylate; EO modification tetramethylolmethane four (methyl) acrylate; PO modification tetramethylolmethane four (methyl) acrylate; Tetramethylolmethane three (methyl) acrylate toluene support vulcabond polyurethane prepolymer; Tetramethylolmethane three (methyl) acrylate hexamethylene diisocyanate polyurethane prepolymer; Tetramethylolmethane three (methyl) acrylate hexamethylene diisocyanate polyurethane prepolymer; Dipentaerythritol four (methyl) acrylate; EO modification Dipentaerythritol four (methyl) acrylate; PO modification Dipentaerythritol four (methyl) acrylate; Trimethylolethane trimethacrylate (methyl) acrylate; Trimethylolpropane tris (methyl) acrylate; EO modification trimethylolpropane tris (methyl) acrylate; PO modification trimethylolpropane tris (methyl) acrylate; Tetramethylol methane four (methyl) acrylate; EO modification tetramethylol methane four (methyl) acrylate; PO modification tetramethylol methane four (methyl) acrylate; Tetramethylol methane three (methyl) acrylate; Dihydroxymethyl tristane two (methyl) acrylate; Two-TriMethylolPropane(TMP) four (methyl) acrylate; Modified glycerol three (methyl) acrylate; Modified bisphenol A two (methyl) acrylate; PO affixture two (methyl) acrylate of dihydroxyphenyl propane; EO affixture two (methyl) acrylate of dihydroxyphenyl propane; Dipentaerythritol six (methyl) acrylate; Caprolactone modification Dipentaerythritol six (methyl) acrylate; 2, two (4-(methyl) the acryloxy polyethoxye phenyl) propane of 2-; Phthalic acid, diallyl ester; Trimellitic acid triallyl etc.

In addition, as free-radical polymerised compound, can also use the Vinyl Ether compound.

As the Vinyl Ether compound, can enumerate out for example ethylene glycol bisthioglycolate Vinyl Ether; The Diethylene Glycol divinyl ether; Triethylene glycol divinyl ether; The Ucar 35 divinyl ether; The dipropylene glycol divinyl ether; The butyleneglycol divinyl ether; The hexylene glycol divinyl ether; The cyclohexanedimethanol divinyl ether; Two or triethylene ether compound of trimethylolpropane tris Vinyl Ether etc.; The glycol monomethyl Vinyl Ether; Triethylene glycol list Vinyl Ether; Ethyl vinyl ether; The normal-butyl Vinyl Ether; Isobutyl vinyl ether; The octadecyl Vinyl Ether; Hydroxyethyl list Vinyl Ether; The hydroxybutyl Vinyl Ether; Hydroxyl nonyl list Vinyl Ether; 2-ethylhexyl Vinyl Ether; The n-propyl Vinyl Ether; Isopropyl-ethylene ether; The pseudoallyl Vinyl Ether; The dodecyl Vinyl Ether; Diethylene Glycol list Vinyl Ether; Single Vinyl Ether compound such as octadecyl Vinyl Ether etc.

The content of composition B in the ink composite is from the viewpoint of flexibility and metalluster, is preferably 65～95 quality %, 75～92 quality % more preferably.

((composition C) optical free radical polymerization starter)

Ink composite of the present invention contains (composition C) optical free radical polymerization starter (below be also referred to as " polymerization starter ").Polymerization starter is to absorb the external energy of said active radioactive rays etc. and generate the compound that polymerization causes kind.As the polymerization starter that can use among the present invention, can enumerate out aromatic series ketone, acylphosphanes compound, aromatic series salt compound, organo-peroxide, thio-compounds, six aryl di-imidazolium compoundss, ketoxime ester cpds, boric acid ester compound, nitrine (azinium) compound, metallocene compound, active ester compound and have compound of carbon-halogen bond etc.As the object lesson of these polymerization starters, can enumerate out the polymerization starter of putting down in writing in TOHKEMY 2008-208190 communique, the TOHKEMY 2009-096985 communique.Polymerization starter can a kind uses separately, also can more than 2 kinds and use.

Wherein, as polymerization starter, preferred acylphosphanes compound, aromatic series ketone.As the aromatic series ketone, preferred thioxanthone compound.Especially preferably with acylphosphanes compound and thioxanthone compound and usefulness.

< acylphosphanes compound >

As the acylphosphanes compound; Preferably can enumerate out the acylphosphine oxide compound of putting down in writing in the paragraph 0080～0098 of TOHKEMY 2009-096985 communique; Wherein, the compound that preferably in the structure of compound, has the structure of formula (c-1) or formula (c-2) expression.

Especially, as the acylphosphine oxide compound, especially preferably has the compound of the chemical structure of formula (c-3) or formula (c-4).

(in the formula (c-3), R ⁶, R ⁷, R ⁸Expression can have methyl or ethyl as substituent aromatic hydrocarbyl.)

As the monoacyl phosphine oxide compound of formula (c-3) expression, preferred R ⁶～R ⁸For having methyl as substituent phenyl, more preferably R ⁷And R ⁸Be phenyl and R ⁶For having the phenyl of 1～3 methyl.

Wherein, preferred 2,4 as the monoacyl phosphine oxide compound of formula (c-3) expression, 6-Three methyl Benzene formyl diphenyl phosphine oxide (Darocur TPO:Ciba Specialty Chemicals corporate system, Lucirin TPO:BASF corporate system).

(in the formula (c-4), R ⁹, R ¹⁰, R ¹¹Expression can have methyl or ethyl as substituent aromatic hydrocarbyl.)

As two acylphosphine oxide compounds of formula (c-4) expression, preferred R ⁹～R ¹¹For having methyl as substituent phenyl, more preferably R ¹¹Be phenyl and R ⁹And R ¹⁰For having the phenyl of 1～3 methyl.

Wherein, as two acylphosphine oxide compounds of formula (c-4) expression, preferred two (2,4,6-Three methyl Benzene formyl) phenyl phosphine oxides (IRGACURE819, Ciba Specialty Chemicals corporate system).

< thioxanthone compound >

The thioxanthone compound is preferably the compound of formula (c-5) expression.

(in the formula (c-5), R ¹～R ⁸Represent that independently of one another hydrogen atom, alkyl, halogen atom, hydroxyl, cyanic acid, nitro, amino, alkyl sulfenyl, alkylamino (comprise that one replaces and dibasic situation.), alkoxyl group, alkoxy carbonyl, acyloxy, acyl group, carboxyl or sulfonic group.)

The carbonatoms of the moieties in said alkyl, alkyl sulfenyl, alkylamino, alkoxyl group, alkoxy carbonyl, acyloxy and the acyl group is preferably 1～20, more preferably 1～8, further is preferably 1～4.

R ¹～R ⁸2 of each adjacency can be interconnected to form ring.Ring structure when forming ring as their can be enumerated out the aliphatics ring, aromatic ring of 5 or 6 yuan of rings etc., can also in addition, can also further be combined to form for example fused rings of 2 nuclear rings between the formed ring for containing the heterocycle of the element except that carbon atom.These ring structures can also further have substituting group.As substituting group, can enumerate out halogen atom, hydroxyl, cyanic acid, nitro, amino, alkyl sulfenyl, alkylamino, alkoxyl group, alkoxy carbonyl, acyloxy, acyl group, carboxyl and sulfonic group.Heteroatomic example when being heterocycle as formed ring structure can be enumerated out N, O and S.

As the thioxanthone compound; Can enumerate out thioxanthone; The 2-isopropyl thioxanthone; The 2-chloro thioxanthone; 2-dodecyl thioxanthone; 2; The 4-diethyl thioxanthone; 2; 4-dimethyl thioxanthone; 1-methoxycarbonyl thioxanthone; 2-ethoxy carbonyl thioxanthone; 3-(2-methoxy ethoxy carbonyl) thioxanthone; 4-butoxy carbonyl thioxanthone; 3-butoxy carbonyl-7-methyl thioxanthone; 1-cyanic acid-3-chloro thioxanthone; 1-ethoxy carbonyl-3-chloro thioxanthone; 1-ethoxy carbonyl-3-oxyethyl group thioxanthone; The amino thioxanthone of 1-ethoxy carbonyl-3-; 1-ethoxy carbonyl-3-phenyl sulfonyl thioxanthone; 3; 4-two [2-(2-methoxy ethoxy) ethoxy carbonyl] thioxanthone; 1-ethoxy carbonyl-3-(1-methyl isophthalic acid-morpholino ethyl) thioxanthone; 2-methyl-6-dimethoxy-methyl thioxanthone; 2-methyl-6-(1; The 1-dimethoxy-benzyl) thioxanthone; 2-morpholino methyl thioxanthone; 2-methyl-6-morpholino methyl thioxanthone; Positive allyl group thioxanthone-3; 4-dicarboxyl imide; N-octyl thioxanthone-3; 4-dicarboxyl imide; N-(1; 1; 3; The 3-tetramethyl butyl) thioxanthone-3; 4-dicarboxyl imide; 1-phenoxy group thioxanthone; 6-ethoxy carbonyl-2-methoxyl group thioxanthone; 6-ethoxy carbonyl-2-methyl thioxanthone; Thioxanthone-2-macrogol ester; 2-hydroxyl-3-(3; 4-dimethyl-9-oxo-9H-thioxanthone-2-base oxygen base)-N; N, N-trimethylammonium-1-propane ammonia chloride.

Wherein, from obtaining the viewpoint of easy property and solidified nature, more preferably 2-isopropyl thioxanthone and 4-isopropyl thioxanthone.

Among the present invention, from the viewpoint of solidified nature, preferably with acylphosphanes compound and thioxanthone compound and usefulness.

When with acylphosphanes compound and thioxanthone compound and time spent, the acylphosphanes compound: the thioxanthone compound is preferably 99: 1～1: 99, more preferably 90: 10～50: 50 by quality ratio, further is preferably 80: 20～50: 50 scope.

Among the present invention, total consumption of optical free radical polymerization starter is from the viewpoint of solidified nature, with respect to the total mass of ink composite be preferably 1～20 quality %, more preferably 3～15 quality %, further be preferably 5～10 quality %.

((components D) tinting material except that composition A)

Ink composite of the present invention can also contain (components D) tinting material except that composition A except the aluminum metal pigment of composition A.Through with aluminum metal pigment and tinting material and usefulness except that composition A, can make the metalluster image have various colour-change.

As tinting material, have no particular limits, but preferably have excellent weather resistance and pigment and oil-soluble colourant that color reproduction is abundant, can from known tinting materials such as solvability dyestuff, select to use arbitrarily.The viewpoint that the sensitivity of the curing reaction that active radioactive rays cause is reduced is set out, and tinting material is preferably selected not the compound that can play a role as polymerization retarder.

As operable pigment among the present invention, there is not special qualification, can use the organic or inorganic pigment of the following numbering of putting down in writing among the ColorIndex for example.As redness or magenta pigment; Can use pigment red 3,5,19,22,31,38,42,43,48:1,48:2,48:3,48:4,48:5,49:1,53:1,57:1,57:2,58:4,63:1,81,81:1,81:2,81:3,81:4,88,104,108,112,122,123,144,146,149,166,168,169,170,177,178,179,184,185,208,216,226,257 according to purpose; Pigment violet 3,19,23,29,30,37,50,88, pigment Orange 13,16,20,36; As blueness or green pigment, can use pigment blue 1,15,15:1,15:2,15:3,15:4,15:6,16,17-1,22,27,28,29,36,60 according to purpose; As veridian, can use pigment Green 7,26,36,50 according to purpose; As yellow ultramarine, can use Pigment Yellow 73 1,3,12,13,14,17,34,35,37,55,74,81,83,93,94,95,97,108,109,110,120,137,138,139,153,154,155,157,166,167,168,180,185,193 according to purpose; As black pigment, can use Pigment black 7,28,26 etc. according to purpose.

As white pigment, preferred titanium oxide.

Titanium oxide does not have particular determination, can from the known titanium oxide that is used as white pigment, suitably select to use.Rutile titanium dioxide and anatase titanium dioxide all can use, but the angle low from the catalyst activity sexuality, that ageing stability is excellent is preferably used rutile titanium dioxide.

Titanium oxide has commercially available, but illustration goes out for example Tipaque CR60-2, Tipaque A-220 (being Ishihara Sangyo Kaisha, Ltd.'s system) or KRONOS1001,1014,1071,1074,1075,1077,1078,1080,1171,2044,2047,2056,2063,2080,2081,2084,2087,2160,2190,2211,2220,2222,2225,2230,2233,2257,2300,2310,2450,2500,3000,3025 (being the KRONOS corporate system) etc.

In addition, titanium oxide can also carry out surface treatment as required.Particularly, for example carry out silicon-dioxide, aluminum oxide, zinc, zirconium white, organism processing, also different according to the different weathering resistancies of treatment process with the oleophylic water-based.Among the present invention, preferred aluminum oxide, zinc, zirconium white, alkaline organic are handled the titanium oxide that obtains.

Among the present invention, also can in the scope that can be dissolved into the non-miscibility organic solvent of water, use dispersed dye.Dispersed dye also comprise water miscible dyestuff usually, but preferably in the scope that can be dissolved into the non-miscibility organic solvent of water, use in the present invention.

As the preferred object lesson of dispersed dye, can enumerate out C.I. DISPERSE YELLOW 5,42,54,64,79,82,83,93,99,100,119,122,124,126,160,184:1,186,198,199,201,204,224 and 237; C.I. DISPERSE ORANGE 30 200 13,29,31:1,33,49,54,55,66,73,118,119 and 163; C.I. Disperse Red 54,60,72,73,86,88,91,92,93,111,126,127,134,135,143,145,152,153,154,159,164,167:1,177,181,204,206,207,221,239,240,258,277,278,283,311,323,343,348,356 and 362; C.I. 63 ,DIS,PER,SE ,Vio,let, 63 33; C.I. Disperse Blue-56,60,73,87,113,128,143,148,154,158,165,165:1,165:2,176,183,185,197,198,201,214,224,225,257,266,267,287,354,358,365 and 368; And C.I. Disperse Green 6:1 and 9; Deng.

The dispersion of tinting material can be used for example various diverting devices such as ball mill, sand mill, masher, roller mill, stirrer, Henschel mixing tank, colloidal mill, Soniprep, ball mill, wet type airflow milling, coating agitator.

Tinting material can directly add with each composition when the preparation of ink composite.In addition,, also can add in advance in the dispersion medium such as polymerizable compound that use among solvent or the present invention in order to improve dispersiveness, make its homodisperse or the dissolving after cooperate.

Among the present invention; For fear of the VOC of the deterioration of dissolvent residual solvent resistance when solidifying image and residual solvent (Volatile Organic Compound: problem volatile organic compounds), preferably tinting material is added in advance in the dispersion medium such as polymerizable compound and cooperates.In addition, when only when disperseing adaptive viewpoint to consider, the polymerizable compound that uses in the interpolation of tinting material is preferably selected the minimum monomer of viscosity.Application target according to ink composite also can suitably select to use the tinting material more than a kind or 2 kinds.

In addition; In the ink composite; When using the tinting materials such as pigment of solid form existence; Preferred selected, dispersion condition, the filtration condition that preferably sets tinting material, dispersion agent, dispersion medium so that the volume average particle size of colorant particle reach 0.005～0.5 μ m, more preferably reach 0.01～0.45 μ m, further preferably reach 0.015～0.4 μ m.Through this particle diameter management, can suppress the obstruction of a nozzle, the storage stability of keeping ink composite, the transparency and solidify sensitivity, therefore preferred.

The content of the tinting material in the ink composite can suitably select according to color and application target, and preferably whole with respect to ink composite quality is 0.01～30 quality %.

((composition E) dispersion agent)

Ink composite of the present invention preferably contains dispersion agent.Particularly under the situation of using pigment,, preferably contain dispersion agent in order to make pigment stable dispersion in ink composite.As dispersion agent, preferred macromolecule dispersing agent.

As macromolecule dispersing agent, can enumerate out DISPERBYK (registered trademark)-101,102,103,106,111,161,162,163,164,166,167,168,170,171,174,182 (BYK corporate system); EFKA (registered trademark) 4010,4046,4080,5010,5207,5244,6745,6750,7414,745,7462,7500,7570,7575,7580 (EFKAADDITIVES corporate system); DISPERSE AID 6,8,15,9100 (SAN NOPCO Co., Ltd. system); Various SOLSPERSE dispersion agents (Lubrizol corporate system) such as SOLSPERSE (registered trademark) 2000,3000,5000,9000,12000,13240,13940,17000,22000,24000,26000,28000,32000,36000,39000,41000,71000; ADEKA (registered trademark) PLURONIC L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (Asahi Denka Co., Ltd.'s system), IONET S-20 (Sanyo Chemical Industries, Ltd.'s system); DISPARLON (registered trademark) KS-860,873SN, 874 (macromolecule dispersing agent), #2150 (aliphatics polycarboxylic acid), #7004 (polyether ester type) (nanmu originally changes into Co., Ltd.'s system).

The content of the dispersion agent in the ink composite can suitably select according to application target, and preferably whole with respect to ink composite quality is 0.05～15 quality %.

((composition F) tensio-active agent)

In order to give long-time stable ejection property, can also add tensio-active agent in the operable ink composite among the present invention.As tensio-active agent, can enumerate out the tensio-active agent of putting down in writing in japanese kokai publication sho 62-173463 number, japanese kokai publication sho 62-183457 number each communique.Can enumerate out for example cationic surfactants such as nonionic surfactants such as anionic surfactants such as dialkyl sulfosuccinate Succinic Acid salt, alkyl naphthalene sulfonic acid salt, fatty acid salt, Voranol EP 2001 class, polyxyethylated allyl ether series, acetylenic diols, polyoxyethylene polyoxypropylene block copolymer class, alkylamine salt, quaternary ammonium salt.

(other compositions)

Can also add the sensitizing agent put down in writing in the TOHKEMY 2009-096985 communique, polymerization retarder, UV light absorber, antioxidant, anti-fading agent, electroconductibility salt, solvent, macromolecular compound, basic cpd etc. in the ink composite of the present invention as other compositions.

(printing ink rerum natura)

Among the present invention, consider ejection property, the viscosity of ink composite under 25 ℃ is preferably below the 40mPas.More preferably 5～40mPas, further be preferably 7～30mPas.In addition, the viscosity under ejection temperature (being preferably 25～80 ℃, more preferably 25～50 ℃) is preferably 3～15mPas, 3～13mPas more preferably.The suitable ratio of components of preferred adjustment ink composite of the present invention is so that viscosity reaches above-mentioned scope.Through setting the viscosity under the room temperature higher,, also can avoid ink composite in printing medium, to soak into, reduce uncured monomer even under the situation of the printing medium that uses porous matter.In addition, can also the printing ink of inhibited oil ink composition when drop adheres to spread and sink in and ooze, its resultant image quality improves.

The surface tension of ink composite of the present invention under 25 ℃ is preferably 20～35mN/m, 23～33mN/m more preferably.When recording various printing mediums such as polyolefine, PET, White Board, uncoated paper, blend the viewpoint of soaking into from spreading and sinking in to be preferably more than the 20mN/m, be preferably below the 35mN/m from the angle of wettability.

II. printing ink group

Printing ink group of the present invention is characterised in that and contains ink composite of the present invention and at least a kind of ink composite that contains the tinting material except that composition A.

As the ink composite that contains the tinting material except that composition A, can use known free-radical polymerised ink composite, unqualified, preferably contain ink composite identical with the composition of ink composite of the present invention except that composition A.In addition, as the tinting material except that composition A, preferably can use the tinting material of components D.

When containing the printing ink group of ink composite of the present invention; So long as contain a kind of ink composite of the present invention at least; And printing ink group with ink composite more than 2 kinds that ink composite of the present invention or the ink composite except that ink composite of the present invention are combined; Then have no particular limits, preferably contain at least a kind be selected from cyan, magenta, yellow, black, white, shallow magenta and light blue in the ink composite of color.

In addition, printing ink group of the present invention can be applicable to ink jet recording method of the present invention.

III. ink jet recording method and print

Ink jet recording method of the present invention is characterised in that and comprises following operation: thus with ink composite of the present invention be ejected on the printing medium image that forms image form operation (below be also referred to as (a) operation.Thereby) and to the ink composite of ejection shine active radioactive rays, this ink composite is solidified obtain the curing process that has the print of solidified image on the said printing medium (below be also referred to as (b) operation.)。

Print of the present invention is characterised in that it obtains through ink jet recording method of the present invention.

At first, (a) operation is described.

Among the present invention; As printing medium; There is not special qualification; Known printing medium can be used, for example paper can be enumerated out; Plastics (Vilaterm for example; Polypropylene; Polystyrene etc.) paper that cascades; Metal sheet (aluminium for example; Zinc; Copper etc.); Plastics film (polyvinyl chloride for example; Cellulose diacetate; Cellulosetri-acetate; Cellulose propionate; Cellulose butyrate; Cellulose acetate butyrate; Nitrocellulose; Polyethylene terephthalate; Vilaterm; Polystyrene; Polypropylene; Polycarbonate; Polyvinyl acetal etc.); Above-mentioned metal stacking or vapor deposition and the paper that obtains or plastics film etc.In addition, as the printing medium among the present invention, also be fit to use the nonabsorbable printing medium.

As the ink-jet recording device that uses in the ink jet recording method of the present invention, not special restriction can select to use the known ink-jet recording device that can realize target exploring degree arbitrarily.That is, so long as comprise the known ink-jet recording device of commercially available article, then the ink composite in (a) operation of ink jet recording method that all can embodiment of the present invention is to the ejection of printing medium.

As the ink-jet recording device that can use among the present invention, can enumerate out the device that for example comprises ink supply system, temperature sensor, active radiation source.

The ink gun of the ink composite supplying tank that ink supply system for example is close to by main jar, supplying tubing, ink gun the place ahead of comprising ink composite of the present invention, strainer, piezo-electric type constitutes.The ink gun of piezo-electric type according to can with preferred 1～100pL, more preferably 3～42pL, further many size points of preferred 8～30pL are with preferred 320 * 320～4; 000 * 4; 000dpi, more preferably 400 * 400～1; 600 * 1, the mode of 600dpi, the further exploring degree ejection of preferred 720 * 720dpi drives.Wherein, the dpi described in the present invention representes counting of every 2.54cm.

In order to obtain the excellent image of metalluster, preferably the aluminum metal pigment that coordinating size is big in ink composite.But when the big aluminum metal pigment of coordinating size in ink composite, the nozzle of ink gun stops up sometimes.Therefore, in image forms operation, the diameter of peristome that is used to spray the nozzle of ink composite of the present invention be preferably 20 μ m above, more preferably 21～100 μ m, further be preferably 22～50 μ m.When in above-mentioned numerical range, obtain the excellent image of metalluster under the situation about can not stop up at the nozzle of ink gun, therefore preferred.

About the shape of the peristome of nozzle, can enumerate out circle, ellipse, Polygons etc.Under the round situation of the shape of the peristome of nozzle, the diameter of peristome is meant the circular diameter suitable with the area of peristome.

Among the present invention, preferably the ink composite that will spray maintains steady temperature, can begin partly to carry out thermal insulation and heating to ink gun from the ink composite supplying tank thus.As temperature controlled method, do not have special restriction, but preference is as being provided with a plurality of temperature sensors and adding thermal control according to flow, the envrionment temperature of ink composite at each pipe arrangement position.Temperature sensor can be arranged near the nozzle of ink composite supplying tank and ink gun.In addition, the head unit that heat preferably carries out thermoshield or thermal insulation so that device body can not receive the Influence of Temperature from extraneous air.In order to shorten heating desired printer time of recovery or, preferably to reduce the whole thermal capacity of heating unit simultaneously at the adiabatic that carries out with other positions in order to reduce the loss of thermal energy.

The ink composite isoradial curable ink composition of the present invention generally speaking viscosity than the aqueous ink composition that uses in the common composition for ink jet recording is high, and the viscosity that temperature variation the caused change when therefore spraying is big.The viscosity change of ink composite can produce big influence to the variation of drop size and the variation of drop spouting velocity, and then can cause deterioration in image quality.Therefore, the temperature of the ink composite during ejection need keep constant as far as possible.Therefore, among the present invention, the temperature controlling amplitude of ink composite be preferably design temperature ± 5 ℃, more preferably design temperature ± 2 ℃, further be preferably design temperature ± 1 ℃.

Below, (b) operation is described.

The ink composite that is ejected on the printing medium solidifies through shining active radioactive rays.This is that polymerization initiations such as generation free radical are planted because contained polymerization starter issues estranged separating in the irradiation of active radioactive rays in the ink composite of the present invention, and the polyreaction of polymerizable compound is initiated, promotes under the effect that this initiation is planted.At this moment; When also having sensitizing agent with polymerization starter in the ink composite; Sensitizing agent assimilating activity radioactive rays in the system and become excited state through contact the decomposition that promotes polymerization starter with polymerization starter, can be realized the more curing reaction of high sensitivity.

Here, employed active radioactive rays can use alpha-ray, gamma-rays, electron rays, X ray, ultraviolet ray, visible or infrared light etc.Also the absorption characteristic with sensitizing agent is relevant though the spike of active radioactive rays is long, preference as be 200～600nm, more preferably 300～450nm, further be preferably 350～420nm.

In addition, even the active radioactive rays of the low output rating of the photopolymerization initiator system of ink composite of the present invention also have sufficient sensitivity.Therefore, plane of exposure illumination is fit to preferably with 1,000～3,000mW/cm ², more preferably with 1,200～2,500mW/cm ²Make its curing.

As active radiation source, mainly utilize mercury lamp or gas-solid laser etc., as the solidified light source that is used for ultraviolet photo-curing type composition for ink jet recording, mercury lamp, metal halid lamp are widely known by the people.But, from the viewpoint of present environment protection, expect mercurylessly strongly, replacing with GaN based semiconductor ultra-violet light-emitting device all is being very useful on the industry, on the environment.In addition, LED (UV-LED), LD (UV-LD) therefore expect that it is as light-cured type ink-jet light source owing to small-sized, high life, high-level efficiency, low cost.

In addition, also can use photodiode (LED) and laser diode (LD) as active radiation source.Particularly needing under the situation of ultraviolet source, can use ultraviolet LED and ultraviolet LD.For example the main emmission spectrum of Ri Ya KCC sale has the purple LED of 365nm to the wavelength between the 420nm.In addition, further needing as LED, to number the 6th, 084 under short wavelength's more the situation, disclosed LED that can the active radioactive rays of launching centre between 300nm and 370nm in No. 250 specification sheetss but illustration goes out United States Patent (USP).In addition, other ultraviolet LED also can obtain, can the different radiation of irradiation ultraviolet radiation bandwidth.Preferred active radiation source is UV-LED, especially preferably has the long UV-LED of spike of 350～420nm among the present invention.

Ink composite of the present invention is fit to by so active radiation exposure preferred 0.01～120 second, more preferably 0.01～90 second, further preferred 0.01～10 second.

In addition, in ink jet recording method of the present invention, preferably the ejection ink composite after, with 2,000mW/cm ²Following plane of exposure illumination was shone active radioactive rays 0.01～10 second, so that above-mentioned ink composite solidifies.

The illuminate condition of active radioactive rays and basic illuminating method disclose in japanese kokai publication sho 60-132767 communique.Particularly, through both sides light source is set and carries out with so-called shuttle mode scan head unit and light source at the head unit of the blowoff that comprises ink composite.The constant time (preferred 0.01～0.5 second, more preferably 0.01～0.3 second, further preferred 0.01～0.15 second) carries out at interval in the back of adhering to that is radiated at ink composite of active radioactive rays.So through will being controlled to be the extremely short time from the time that is attached to irradiation of ink composite, thereby can prevent that the ink composite that adheres on the printing medium from spreading and sinking in before curing oozes.In addition,, can be impregnated into light source at ink composite and be beyond one's reach and make public before the deep, thereby can suppress the residual of unreacted monomer even for the printing medium of porous matter, therefore preferred.

In addition, also can utilize without the other light sources that drives and accomplish curing.Disclose as illuminating method in No. 99/54415 brochure of International Publication; Used the method for optical fiber or make through the light source of calibration towards be arranged on the lateral minute surface of head unit, then to the method for record portion irradiation UV light, such curing also can be applicable to ink jet recording method of the present invention.

Through adopting as above-mentioned ink jet recording method,, also the point of the ink composite that adheres to directly can be kept constant, thereby improve picture quality even for the different various printing mediums of wetting of surfaces property.In addition, in order to obtain coloured image, preferably begin to carry out in order overlapping from the low color of lightness.Overlapping through beginning to carry out in order from the low ink composite of lightness, illuminated line can arrive the ink composite of bottom easily, thereby can expect the minimizing of good curing sensitivity, residual monomer, the raising of adherence.In addition, though irradiation can make public after the whole colors of ejection together, from promoting the solidified viewpoint, preferred per a kind of color ground makes public.

Can preferably use the printing ink group of the ink composite of the present invention that comprises more than 1 in the ink jet recording method of the present invention.The order of each colored ink compositions that sprays does not have special qualification, but preferably begins to be imparted on the printing medium from the low colored ink compositions of lightness.When using the ink composite of ink composite of the present invention, yellow, cyan, magenta, black, preferably the order according to ink composite → yellow of the present invention → cyan → magenta → black is imparted on the printing medium.In addition, use under the situation of white when increasing, preferably the order according to white → ink composite → yellow of the present invention → cyan → magenta → black is imparted on the printing medium.In addition; The present invention is not limited thereto; Also can be light blue to comprise at least, the form of the printing ink group of the ink composite of shallow magenta and cyan, magenta, black, white, xanchromatic heavy colour ink composite uses; At this moment, preferably be imparted on the printing medium according to the order of white → ink composite of the present invention → light blue → shallow magenta → yellow → cyan → magenta → black.

IV. the method for manufacture and the shaping print of print are shaped

The method of manufacture of shaping print of the present invention is characterised in that and comprises following operation: thus with ink composite of the present invention be ejected on the printing medium image that forms image form operation (below be also referred to as (a) operation.), thereby to the ink composite of ejection shine active radioactive rays, this ink composite is solidified obtain the curing process that has the print of solidified image on the said printing medium (below be also referred to as (b) operation.) and to said print form processing operation (below be also referred to as (c) operation.)。

In addition, shaping print of the present invention is characterised in that, it is that method of manufacture through said shaping print obtains.

About (a) operation in the method for manufacture of shaping print of the present invention and (b) operation; With (a) operation in the ink jet recording method of the present invention be same with (b) operation, this only to the method for manufacture of shaping print of the present invention in the preferred printing medium that uses describe.

Operable printing medium does not have special qualification in the method for manufacture of shaping print of the present invention, can use the known printing medium of the processing that is suitable for being shaped.Particularly; But illustration goes out Vilaterm; Polypropylene; Polymethylpentene; Polybutene; Polyolefin-based resins such as ethylene series thermoplastic elastomer; Polyethylene terephthalate; Polybutylene terephthalate; PEN; Terephthalic acid-m-phthalic acid-glycol copolymer; Terephthalic acid-terepthaloyl moietie-1; 4 cyclohexanedimethanol multipolymers; Vibrin such as polyester based thermoplastic elastomerics; Nylon 6; Nylon 9; Nylon 6,6 polyamide resins such as grade; Fluorinated ethylene propylene; Poly(vinylidene fluoride); Gather three vinylidene fluorides; Ethylene-tetrafluoroethylene copolymer; Fluorine resins such as tetrafluoroethylene; Acrylic resin; Polyvinyl chloride; Polystyrene; Polycarbonate resin etc.

Aforesaid propylene acid be resin can for example use gather (methyl) methyl acrylate, gather (methyl) ethyl propenoate, gather (methyl) Bing Xisuandingzhi, the monomer or the mixture more than 2 kinds of resin such as (methyl) methyl acrylate-(methyl) butyl acrylate copolymer, (methyl) ethyl propenoate-(methyl) butyl acrylate copolymer, (methyl) methyl acrylate-styrol copolymer.

Wherein, From band printing easily with the excellent angle of each patience of the shaping thing of processing; The preferred resin sheet that uses polyethylene terephthalate, polycarbonate resin or in polycarbonate resin, be mixed with other resins, optimization polycarbonate resin or in polycarbonate resin, be mixed with the resin sheet of other resins.In addition, printing medium can be the range upon range of duplexer that resin sheet more than a kind or 2 kinds is arranged.

Among the present invention; Thickness (being total thickness during duplexer) about printing medium; So long as embossing processing, vacuum forming, and with pressing empty be shaped and vacuum presses the vacuum of the empty principle that is shaped to press the resin sheet of the thickness of the scope that empty shaping can carry out; Then there is not special qualification; Be preferably 50～2; 000 μ m, more preferably 100～1,500 μ m, further be preferably 150～1,000 μ m.

Can also suitably add additive as required in the thermoplastic resin sheet.As additive, so long as, then can add various additives in right amount bringing in the dysgenic scope can not for thermal characteristicss such as surface luster, fusing point.For example can enumerating out, UV light absorber, hindered amines such as benzotriazole system, benzophenone series are lubricants such as photostabilizer, polyorganosiloxane resin, varnish, tinting material, softening agent, thermo-stabilizer, antiseptic-germicide, mould inhibitor, static inhibitor etc. such as radical scavenger.

Shaping print of the present invention is made through thermoplastic resin sheet being implemented shaping processing such as vacuum forming, before being shaped, on printing medium, forms image through ink-jetting style.

Image is imparted into the inner surface side (side for contacting with mould in vacuum forming) of clear sheet usually, but image also can be formed on its opposing face.In addition,, can also only on said opposing face, form image, at this moment, need not be transparent as the thermoplastic resin sheet of base material according to different situations.

Among the present invention,, can use embossing processing, vacuum forming, the empty shaping of pressure or vacuum to press empty the shaping for the processing that is shaped.Device as print being formed processing can use known device, can be that the device with said ink-jet recording device one also can be other device.

Embossing processing is to show relief processing through fitting depressions such as print for arbitrary shapes such as pattern or literal, for example uses roller or press to wait and carries out.As an example of embossing processing, can enumerate out heat, cold pressurization, can be with reference to the method for putting down in writing in the japanese kokai publication hei 10-199360 communique etc.An example of the embossing building mortion that utilizes heat, cold pressurization below is shown.This embossing building mortion can dispose near spaced manner according to lower platform (lower platform) and upper brace (upper mounting plate) each other.And, be fixed with plate-type heater on the lower platform, also be fixed with plate-type heater on the lower surface of upper brace.Can carry out hot pressing while heating printing medium thus.In this hot pressing machine, install on the plate-type heater on its lower platform mould with protuberance consistent with the embossing shape of regulation and according to the lower surface of upper mounting plate on the mode that contacts of fixed well heater the mould that has with the recess of the shape of said protuberance unanimity is installed.And configuration is formed with the printing medium of image, and configuration buffering sheet material is suppressed printing medium and buffer substrate tablet material between upper mounting plate and lower platform through upper mounting plate is descended between this printing medium and recess mould.Plus-pressure in this hot pressing operation for example is 30 tons, and the Heating temperature that plate-type heater produced for example is 170 ℃.And, upper mounting plate is given as security be pressed onto on the lower platform, between mould, hold printing medium and buffer substrate tablet material under the arm pressure, keep this hot pressing restriction 3 minutes.Printing medium by the well heater heating, forms a plurality of protuberances through thermal distortion through mould.Then; This printing medium and buffer substrate tablet material directly are being configured under the state of seizing on both sides by the arms between mould between the internal water cold mould platform that does not possess well heater; At for example plus-pressure is that 30 tons, hold-time are to utilize internal water cold mould platform to give as security pressure under the about 3 minutes condition, carries out cold compaction.Thus, the printing medium convex form that thermal distortion forms through hot pressing is able to keep, thereby has obtained applying the shaping print of embossing processing.Plus-pressure and Heating temperature can be come suitably adjustment according to conditions such as the material of employed print and machining shapes.

Vacuum forming is that the printing medium that will be formed with image in advance is preheating to the temperature that thermal distortion can take place, and is pressing the method that is cooled to form on the mould while utilize decompression that it is attracted to stretch in the mould; Pressing empty the shaping is that the printing medium that will be formed with image in advance is preheating to the temperature that thermal distortion can take place, and pressurizes and is pressing the method that mould forms that is cooled to from the opposition side of mould.Thereby it is to carry out the method that said decompression and pressurization form simultaneously that vacuum is pressed empty the shaping.The document that detailed content can be quoted in " thermoforming " project and this project of record in p.766～768 referring to polymer voluminous dictionary (ball is apt to Co., Ltd.).

Embodiment

Embodiment and comparative example below are shown so that the present invention is illustrated more specifically.But the present invention is not subjected to the qualification of these embodiment.Wherein, " part " in below putting down in writing, short of special instruction is then represented " mass parts ", " % " expression " quality % ".

(preparation of metallic pigment millbase)

Aluminum metal pigment (ROTOVARIO 500022, aluminium powder pigment paste, ECART corporate system)

50 mass parts (solids component)

Vinylformic acid 2-(2-ethoxy ethoxy) ethyl ester 40 mass parts

SOLSPERSE 36000 (Lubrizol corporate system) 10 mass parts

Mentioned component is used ball mill and use diameter to disperse 20 hours, obtain the metallic pigment millbase as 0.2mm zircon bead.

At this moment, with the volume average particle size of laser diffraction, scattering method particle size distribution device (trade(brand)name: MicroTrackMT3300EX, Nikkiso Company Limited's system) mensuration aluminum metal pigment, the result is 0.25 μ m.

With the preparation of metallic pigment millbase likewise, according to the composition shown in the table 1, dispersion condition, preparation cyan millbase, magenta millbase, yellow millbase, black millbase and white millbase.

Table 1

(pigment)

Green pigment: IRGALITE BLUE GLVO (Ciba Specialty Chemicals corporate system)

Magenta pigment: CINQUASIA MAGENTA RT-355D (Ciba SpecialtyChemicals corporate system)

Yellow ultramarine: NOVOPERM YELLOW H2G (Clariant corporate system)

Black pigment: SPECIAL BLACK 250 (Ciba Specialty Chemicals corporate system)

White pigment: alumina treatment titanium oxide

(monofunctional monomer)

EOEOEA (vinylformic acid 2-(2-ethoxy ethoxy) ethyl ester)

(dispersion agent)

SOLSPERSE 2000 (Lubrizol corporate system)

SOLSPERSE 32000 (Lubrizol corporate system)

SOLSPERSE 5000 (Lubrizol corporate system)

SOLSPERSE 36000 (Lubrizol corporate system)

(embodiment 1～16, comparative example 1 and 2)

< making method of ink composite >

With raw materials mix, the stirring of record in the table 2, obtain the ink composite of embodiment 1～16 and comparative example 1 and 2.Wherein, the use level (mass parts) of each composition of numeric representation in the table.

< ink jet image record >

Then, use ink-jet recording device to carry out record to printing medium with piezo-electric type inkjet nozzle.The ink gun (diameter of the peristome of nozzle is 25 μ m) of the inking jar that ink supply system is close to by main jar, supplying tubing, ink gun the place ahead, strainer, piezo-electric type constitutes, and carries out the adiabatic and heating of the part from the inking jar to ink gun.Temperature sensor is separately positioned near the nozzle of inking jar and ink gun, carries out temperature control so that nozzle segment usually is 40 ℃ ± 2 ℃.The ink gun that drives piezo-electric type makes it with 4,800 * 4, and the exploring degree of 800dpi penetrates many sizes point of 1～10pl.After adhering to UV light with plane of exposure illumination 700mW/cm ²Carry out light harvesting, adjustment exposure system, main-scanning speed and ejaculation frequency are shone beginning so that be attached to printing medium at ink composite after last 0.1 second.In addition, will be set at the time shutter variable, the irradiation exposure energy.UV-lamp is used high (high cure) mercury lamp (the GS Yuasa corporation of Co., Ltd. system) that solidifies of HAN250NL.Wherein, the dpi described in the present invention representes counting of every 2.54cm.As printing medium, use ester film E5000 (thickness is 125 μ m, Toyo Boseki K.K's system).

< ink evaluation >

(evaluation of solidified nature)

According to said ink jet recording method, average thickness and be the describing of whole image of 12 μ m, the image surface after uviolizing is with the not amount (mJ/cm of the exposure energy of adhesion sense that becomes ²) be defined as the curing sensitivity.The more little expression of numerical value is high sensitivity.

In addition, solidifying sensitivity estimates according to following benchmark.

5: be lower than 3,500mJ/cm ²

4:3,500mJ/cm ²Individual above and be lower than 4,000mJ/cm ²

3:4,000mJ/cm ²Individual above and be lower than 4,500mJ/cm ²

2:4,500mJ/cm ²Individual above and be lower than 5,000mJ/cm ²

1:5,000mJ/cm ²More than individual

As long as it is in the scope of benchmark 3～5, then no problem in practicality.

< evaluation of flexibility: the anti-tortuosity evaluation of cured film >

For each ink composite; With minimum energy and become and do not have adhesive exposure; According to said ink jet recording method transparent substrate (ester film E5000) is averaged the describing of whole image that thickness is 4 μ m; Keeping after 1 day under 60% the condition with this image at 23 ℃, relative humidity; With hand the tortuous 180 ° of observation cured film of picture middle body there is flawless, is done as follows evaluation.

5:20 time cured film when above cracks.

4:15 time above and when being less than 20 times cured film crack.

3:10 time above and when being less than 15 times cured film crack.

2:5 time above and when being less than 10 times cured film crack.

1: cured film cracks when being less than 5 times.

As long as it is in the scope of benchmark 3～5, then no problem in practicality.

< evaluation of film hardness >

To each ink composite with excessive exposure (30,000mJ/cm ²), according to said ink jet recording method transparent substrate (polycarbonate) is averaged the describing of whole image that thickness is 12 μ m, its image is carried out determination of pencil hardness according to JIS K5600-5-4 under 25 ℃.

More than the 8:4H

7：3H

6：2H

5：H

4：F

3：HB

2：B

Below the 1:2B

As long as it is in the scope of benchmark 4～8, then no problem in practicality.

< evaluation of metalluster property >

To each ink composite with excessive exposure (15,000mJ/cm ²), according to said ink jet recording method transparent substrate (polycarbonate) is averaged the describing of whole image that thickness is 12 μ m, be the sort of image through following visual valuation.

5: observe directly over the vertical direction of horizontal image and can be judged as the metal tone

4: observe image directly over the vertical direction and can be judged as the metal tone when level 30 is spent departing from

3: observe image directly over the vertical direction and can be judged as the metal tone when level 60 is spent departing from

2: observe image directly over the vertical direction and can be judged as the metal tone when level 90 is spent departing from

1: be grey basically

As long as it is in the scope of benchmark 3～5, then no problem in practicality.

Writing a Chinese character in simplified form of putting down in writing in the table 2 is as described below.

(monofunctional monomer)

PEA; Vinylformic acid 2-phenoxy ethyl (following compound, SR339, SARTOMER corporate system)

Viscoat#150; Following compound (Osaka Organic Chemical Industry Co., Ltd.'s system)

CTFA; Cyclic trimethylolpropane methylal acrylate, following compound

NVC; N-caprolactam (V-CAP, ISPJapan Co., Ltd. system) (polyfunctional monomer)

NPGPODA; Ethoxylated neopentylglycol diacrylate (following compound)

(polymerization starter)

Irg 819: two (2,4,6-Three methyl Benzene formyl) phenyl acylphosphine oxide (IRGACURE819, Ciba Specialty Chemicals corporate system)

The mixture of ITX:2-isopropyl thioxanthone and 4-isopropyl thioxanthone (FIRSTCUREITX, ALBEMARLE corporate system)

(embodiment 17～32)

With raw materials mix, the stirring of record in the table 3, obtain the ink composite of the yellow shown in the experimental example 1～5, magenta, cyan, black, white.

To contain the wantonly a kind of ink composite of the metallic pigment of record among the embodiment 1～16 and the ink composite of experimental example 1～5 and make up the printing ink group of making embodiment 17～32.

In said ink jet image record; Ink composite for embodiment 1～16; Use the ink gun (diameter of the peristome of nozzle is 25 μ m) of piezo-electric type to spray; Ink composite for experimental example 1～5; Use the ink gun (diameter of the peristome of nozzle is 20 μ m) of piezo-electric type to spray, under same condition, form image in addition.

Even contain in use under the situation of polychrome printing ink group of ink composite of embodiment 1～16, also can access solidified nature, flexibility, film hardness, image that metalluster property is excellent.

Table 3

(embodiment 35)

Use suction former Forming 300X (becoming light Industry Co., Ltd system) to carry out vacuum forming.In above-mentioned ink jet recording method,, use with embodiment 1 same condition and process print except adopting Panlite sheet PC-1151 (Teijin Chemicals, Ltd.'s system) as the printing medium.

The temperature of setting well heater is provided with wooden die shown in Figure 1 at the center of vaccum bench and carries out vacuum forming so that the temperature of supporter reaches 90 ℃.The print that the visual observation shaping obtains has or not the crackle of chapping, pin hole (pinhole).In addition, visual observation has or not scar in vacuum forming processing rear surface.The result does not see the crackle of chapping, pin hole fully.

Claims (9)

1. an ink composite is characterized in that, contains

Composition A: aluminum metal pigment,

Composition B: free-radical polymerised compound and

Composition C: the optical free radical polymerization starter,

And the free-radical polymerised compound of composition B comprises monofunctional monomer 80～99.9 quality % and polyfunctional monomer 0.1～20 quality %.

2. ink composite according to claim 1, wherein, the content of the composition A in the ink composite is 0.5～20 quality %.

3. ink composite according to claim 1 and 2 wherein, contains the compound of formula (b-1) expression and/or the compound of formula (b-2) expression as said monofunctional monomer,

In the formula (b-1), R ¹Expression hydrogen atom or methyl, X are represented singly-bound, alkylidene group, oxygen base alkylidene group or the group that said oxygen base alkylidene group is combined more than 2, ester bond, or group that these groups are combined more than 2, R ²And R ³Represent hydrogen atom or alkyl independently of one another, R ⁴～R ⁸Represent hydrogen atom, alkyl, alkoxyl group, amino or aminoalkyl group independently of one another, R ⁴～R ⁸In at least 1 be hydrogen atom, R ²～R ⁸In can combine to form ring texture more than 2 arbitrarily;

In the formula (b-2), n representes 1～5 integer.

4. ink composite according to claim 3, wherein, the total content of the compound of said formula (b-1) expression among the composition B and the compound of formula (b-2) expression is 5～99.9 quality % of ink composite.

5. a printing ink group is characterized in that, comprises claim 1 or 2 described ink composites and at least a kind of ink composite that contains the tinting material except that composition A.

6. an ink jet recording method is characterized in that, comprises following operation:

Thereby claim 1 or 2 described ink composites are ejected into the image formation operation that forms image on the printing medium; With,

Ink composite to ejection shines active radioactive rays, this ink composite is solidified, thereby obtains on said printing medium, having the curing process of the print of solidified image.

7. print, it obtains through the described ink jet recording method of claim 6.

8. the method for manufacture of the print that is shaped is characterized in that, comprises following operation:

Thereby claim 1 or 2 described ink composites are ejected into the image formation operation that forms image on the printing medium,

Thereby the ink composite to ejection shines active radioactive rays, this ink composite is solidified obtain on said printing medium, having the solidified image print curing process and

Said print is formed the operation of processing.

9. shaping print, it is that method of manufacture through the described shaping print of claim 8 obtains.

Images