CN102344716B - 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 manufacture method of ink composite, ink group, ink jet recording method, print, molded printed matter and molded printed matter

Technical field

The present invention relates to ink composite, ink group, ink jet recording method, print, the manufacture method of molded printed matter and molded printed matter.

Background technology

As the image recording process forming image according to viewdata signal on printing medium, there are electronic photo mode, subliming type and fusion thermal transfer mode, ink-jetting style etc.Ink-jetting style is owing to using cheap device and only spray ink to the image portion needed and directly carry out image formation on printing medium, therefore, it is possible to use ink composite efficiently, running cost is low.In addition, noise is little, is excellent as image recording mode.

As the ink composite containing metallic pigment, the ink composite recorded in patent documentation 1 and 2 can be listed.

Prior art document

Patent documentation

Patent documentation 1: Japanese Unexamined Patent Publication 2009-91550 publication

Patent documentation 2: Japanese Unexamined Patent Publication 2008-88228 publication

Summary of the invention

Invent problem to be solved

The object of the present invention is to provide and can obtain solidified nature excellence and take into account the ink composite of the metalluster image of excellent flexibility and high film hardness, ink group, the ink jet recording method employing this ink composite, print, the manufacture method of molded printed matter and molded printed matter.

For solving the means of problem

Above-mentioned problem is solved by the means of following record.

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

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

The ink composite of <3> according to <1> or <2>, wherein, compound that formula (b-1) represents and/or the compound that formula (b-2) represents is contained as described monofunctional monomer

(in formula (b-1), R ¹represent hydrogen atom or methyl, group, ester bond or the group combined by these groups more than 2 that X represents singly-bound, alkylidene group, oxygen base alkylidene group or combined by described oxygen base alkylidene group 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 any more than 2 can in conjunction with formation ring texture.)

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

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

<5> ink group, it is characterized in that, comprise the ink composite according to any one of <1> ~ <4> and at least a kind of ink composite containing the tinting material except composition A.

<6> ink jet recording method, it is characterized in that, comprise following operation: the ink composite according to any one of <1> ~ <4> to be ejected on printing medium thus to form the image formation process of image; With, the ink composite to ejection irradiates active radioactive rays, this ink composite is solidified, thus obtains the curing process of the print of the image on described printing medium with solidification.

<7> print, it is obtained by the ink jet recording method described in <6>.

The manufacture method of a <8> molded printed matter, it is characterized in that, comprise following operation: to be ejected into by the ink composite according to any one of <1> ~ <4> on printing medium thus to form the image formation process of image, ink composite to ejection irradiates active radioactive rays, this ink composite is solidified, thus obtain the curing process of the print of the image on described printing medium with solidification, with the operation described print being formed to processing.

<9> molded printed matter, it is obtained by the manufacture method of the molded printed matter described in <8>.

The effect of invention

According to the present invention, that can be provided to obtain solidified nature excellent and taken into account the ink composite of the metalluster image of excellent flexibility and high film hardness, ink group, the ink jet recording method employing this ink composite, print, the manufacture method of molded printed matter and molded printed matter.

Accompanying drawing explanation

Fig. 1 is the sketch chart of the example representing the mould used in the test of formed machining.

Embodiment

I. ink composite

Ink composite of the present invention is preferred for ink-vapor recording and uses, it is characterized in that, containing (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 %.

It should be noted that, in this specification sheets, represent the record of " A ~ B " of numerical range unless otherwise specified, then with the same meaning of " more than A and below B " (comprising the A as lower value and the B as higher limit).In addition, the record of " (methyl) acrylate " etc. and the same meaning of " methacrylic ester and/or acrylate " etc.

Ink composite of the present invention is the oil-based ink composition that can solidify under the effect of active radioactive rays." active radioactive rays " refer to the radioactive rays can giving the energy that the initiation kind in ink composite is produced under it irradiates, and comprise alpha-ray, gamma-rays, X-ray, ultraviolet, visible rays, electron rays etc.Wherein, from the view point of solidification sensitivity and device obtain easiness, preferred ultraviolet 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 the suitable known any aluminium powder of choice for use.

Aluminium powder can be manufactured by arbitrary manufacture method.As the manufacture method of aluminium powder, can exemplify such as while by aluminum substrate cold draw while carry out the method for broken processing, aluminium-vapour deposition become thin film, be then made into the method for powder, paper tinsel superprecision good for photoluminescent is made the method etc. of powder, but the present invention is not limited to these.

In addition, the aluminium powder of interpolation can be the arbitrary shape in pasty state or powder.As the aluminium powder of pasty state, the aluminium powder being distributed to and becoming pasty state in hydrocarbon system solvent (such as ethyl acetate) can be exemplified.

The aluminium powder used in the present invention can carry out surface treatment etc.Can exemplify and such as make stearic acid etc. be adsorbed onto the surface of powder and the aluminium powder obtained, when using the aluminium powder obtained by the method process, there is tendency arranged in parallel at the ink pellet surface aluminium powder of ejection, the print being similar to satinizing (minor finish) can be obtained.

In addition, also can exemplify the aluminium powder that resin-coated obtains, adherence, resistance to chemical reagents, weathering resistance etc. can be improved thus, therefore preferably.But, glossy property and the disguised tendency be deteriorated.

Aluminium powder has commercially available, the aluminium powder of the pasty state such as obtained as being distributed to hydrocarbon system solvent, can exemplify ROTOVARIO 500 series (ECART Inc.), ASTROSHINE T-8990, ASTROSHINE T-8765 (being Japanese damp proof Industrial Co., Ltd system).

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

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

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

In the present invention, the preferred content of aluminum metal pigment is 0.5 ~ 20 quality % relative to the total amount (total mass) of ink composite, is more preferably the scope of 3 ~ 20 quality %, more preferably 5 ~ 18 quality %.

When the content of aluminum metal pigment is more than 0.5 quality %, good radiance sense can be obtained, therefore preferably.In addition, when the content of aluminum metal pigment is at below 20 quality %, having good stability of ink composite, therefore preferably.

The ink composite used in the present invention contains free-radical polymerised compound, optical free radical polymerization starter and aluminum metal pigment, the dispersion liquid preferably disperseed by non-water system.

Ink composite such as can be prepared (making ink) by adding free-radical polymerised compound, optical free radical polymerization starter, aluminum metal pigment and various additives as required.

In addition, in the present invention, preferably using dispersion agent when preparing ink composite, more preferably using acid dispersion agent as dispersion agent.

In addition, described ink composite also can be prepared as follows: first make the high dispersion of aluminum metal pigment concentration, add described free-radical polymerised compound and various additives etc. wherein, then dilute.

The dispersion of described aluminum metal pigment can use the diverting devices such as such as ball mill, sand mill, masher, roller mill, airflow milling, homogenizer, paint mixer, kneader, stirrer, Henschel mixing tank, colloidal mill, Soniprep, ball mill, wet type airflow milling.

In the present invention, preferably use bead (dispersion medium) by least aluminum metal pigment, free-radical polymerised compound and dispersion agent disperse imperceptibly when disperseing.As diverting device, the diverting devices such as ball mill, stirrer, paint mixer can be used.

As bead (dispersion medium), granulated glass sphere, stainless shot, alumina bead, zirconium oxide bead etc. can be exemplified, wherein, preferably use zirconium oxide bead as bead (dispersion medium).Zirconium oxide bead is due to intensity and hardness is excellent, the generation of the cutting powder of bead (dispersion medium) is few, therefore preferably.

In addition, as mentioned above, preferably dispersion agent is added when carrying out the dispersion of described aluminum metal pigment.

In the present invention, preferably use acid dispersion agent as dispersion agent.Acid dispersion agent refers to the macromolecular compound at an end of at least main chain by block or Grafting Structure with acid pigment hydrophilic radical.When using acid dispersion agent, the dispersion of described aluminum metal pigment can be carried out fast and obtain stable dispersion, therefore preferably.

As acid pigment hydrophilic radical, carboxyl, sulfonic group, phosphate can be exemplified.

As polymer, poly-(methyl) acrylate, urethane, polyester or their modifier can be exemplified.

Such dispersion agent has commercially available product, can exemplify DISPERBYK-102, DISPERBYK-110, DISPERBYK-111, DISPERBYK-112, DISPERBYK-180 (above by BYK Inc.), SOLSPERSE 26000, SOLSPERSE 36000, SOLSPERSE41000 (above by Lubrizol Inc.).In addition, dispersion agent can one be used alone, also can be two or more and use.

In ink composite, as the dispersion medium of each compositions such as described aluminum metal pigment, solvent can also be added.In addition, can use without the low molecular weight compositions of solvent and free-radical polymerised compound as dispersion medium.In the present invention, ink composite is the ink composite of radiation-curing type, and in order to make it solidify being applied to by ink composite after on printing medium, is preferably solvent-free or low solvent.

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

As more preferred example, as the dispersion medium containing EO chain, 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. can be listed.

As the dispersion medium containing PO chain, 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 Inc.) etc. can be listed.

As the dispersion medium containing phenyl ring, phenoxyethyl acrylate (PEA), vinylformic acid Phenoxyethyl oxygen base ethyl ester (EBECRYL110, Daicel-Cytec Co., Ltd. system) etc. can be listed.

((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 in composition B is lower than 80 quality %, the flexibility of cured film reduces.From the view point of flexibility and the film hardness of the solidified nature of ink composite, cured film, the content of the monofunctional monomer in composition B is preferably 82 ~ 98.0 quality %.

As monofunctional monomer, preferably can list the compound in molecule with 1 free-radical polymerised ethylenic unsaturated group, more preferably can list and there is 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.By containing these monofunctional monomers, the image of solidified nature and flexibility excellence can be obtained.

As monofunctional monomer, compound that formula (b-1) represents preferably can be listed, compound and monofunctional aromatic monomer etc. that formula (b-2) represents.

The compound > that < formula (b-1) represents

Ink composite of the present invention is preferably containing the compound that formula (b-1) represents.By the compound represented containing formula (b-1), dispersion stabilization improves, the aluminum ratio on ink film surface raises, can obtain the ink composite that can obtain solidified nature and the high image of film hardness.

(in formula (b-1), R ¹represent hydrogen atom or methyl, X represent singly-bound, alkylidene group, oxygen base alkylidene group or the group combined by described oxygen base alkylidene group more than 2, ester bond or by they more than 2 groups combined, 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 wantonly more than 2 can in conjunction with formation ring texture.)

In formula (b-1), R ¹represent hydrogen atom or methyl, preferably hydrogen atom.

X represents singly-bound, alkylidene group, oxygen base alkylidene group or the group combined by described oxygen base alkylidene group more than 2, ester bond or by they more than 2 groups combined.

The preferred carbonatoms of described alkylidene group be 1 ~ 10 alkylidene group, more preferably carbonatoms be the alkylidene group of 1 ~ 8.

Oxygen base alkylidene group or are groups that alkylidene group side is combined on the Sauerstoffatom of (methyl) acryloxy in formula (b-1) by described oxygen base alkylidene group more than 2 groups combined.As alkylidene group contained in oxygen base alkylidene group, the carbonatoms preferably with straight or branched is the alkylidene group of 1 ~ 5, more preferably has alkylidene group, the further preferred isopropylidene that carbonatoms is the straight or branched of 2 or 3.When oxygen base alkylidene group more than 2 is combined, preferably by less than 10 combinations, more preferably by less than 5 combinations.

When containing ester bond (-COO-or-OCO-) in X, the group that described alkylidene group and ester bond preferably combine by X.That is, be preferably Sauerstoffatom and be combined in R ²and R ³in conjunction with carbon atom on oxygen base carbonyl alkylen group.

R ²and R ³represent that hydrogen atom or alkyl, preferably hydrogen atom or carbonatoms are alkyl, more preferably hydrogen atom or the methyl of 1 ~ 3 independently of one another.

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

As described alkyl, the carbonatoms preferably with straight or branched is the alkyl of 1 ~ 10.

As described alkoxyl group, the carbonatoms preferably with straight or branched is alkoxyl group, the more preferably methoxyl group of 1 ~ 5.

Described amino comprises amino, alkyl monosubstituted amino, dialkyl amido, and the carbonatoms that this alkyl preferably has straight or branched is the alkyl of 1 ~ 3.As amino, preferred dimethylamino, diethylamino, diisopropylaminoethyl.

The amino comprised in aminoalkyl group is same with above-mentioned amino.That is, aminoalkyl group comprises Mono-alkylaminoalkyl, dialkyl aminoalkyl.The part of the alkyl except amino of aminoalkyl group is preferably the alkyl that carbonatoms is 1 ~ 3.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, the ink composite of solidified nature excellence can be obtained.

R ²~ R ⁸in wantonly more than 2 also can in conjunction with formation ring texture.When forming ring, form the R of ring ²~ R ⁸be preferably alkyl.Preferred R ⁴or R ⁵and R ⁶~ R ⁸in wantonly 1 combine formed ring, more preferably formed ring element number be 4 ~ 6 cyclic ether group, more preferably ring element number be 5 cyclic ether group, namely form tetrahydrofuran base.

In addition, R ²or R ³and R ⁶~ R ⁸in wantonly 1 can in conjunction with formation ring texture.Now, preferred R ⁶~ R ⁸in wantonly 1 be alkoxyl group.

The first number of ring of the ring texture formed preferably containing 2 Sauerstoffatoms to be first number of ring texture, the more preferably ring of 6 ~ 8 be 6 ring texture, particularly preferably 1,3-diox-5-base.

From the angle of solidified nature excellence, the compound that compound, more preferably formula (b-1-1) that the compound that formula (b-1) represents preferably has tetrahydrofuran base represent.

(in formula (b-1-1), R ¹represent hydrogen atom or methyl, X represent singly-bound, alkylidene group, oxygen base alkylidene group or the group combined by described oxygen base alkylidene group more than 2, ester bond or by they more than 2 groups combined.)

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

Below exemplify the object lesson of the compound that formula (b-1) represents, but be not limited to these object lessons.Wherein, in exemplary compounds, R represents hydrogen atom or methyl.

[chemical formula 5]

[chemical formula 6]

Ink composite of the present invention is preferably containing the compound that formula (b-2) represents.

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

In formula (b-2), n represents the integer of 1 ~ 5, from the view point of the flexibility after ink composite solidification, with the adherence of printing medium and raw-material acquired, preferred n be 2 ~ 4 integer, more preferably n be 2 or 4, particularly preferably n 4 be N-caprolactam.N-caprolactam is due to excellent in safety, general and can obtain more at an easy rate, particularly can obtain good ink solidification and cured film to the adherence of printing medium, therefore preferably.

The total content of the compound that the described formula (b-1) in composition B represents and the compound that formula (b-2) represents is preferably 5 ~ 99.9 quality %, is more preferably 8 ~ 80 quality %, more 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 monofunctional aromatic monomer as monofunctional monomer.By and the compound that represents of the compound represented by monofunctional aromatic monomer and above-mentioned formula (b-1) or formula (b-2), the ink composite of solidified nature excellence can be obtained.

As monofunctional aromatic monomer, preferably there is the monomer of 1 free-radical polymerised ethylenic unsaturated group and at least 1 aromatic group in molecule, more preferably there is the monomer of 1 (methyl) acryloxy or (methyl) acrylamido and at least 1 aromatic hydrocarbyl in molecule.

As the object lesson of monofunctional aromatic monomer, the monofunctional aromatic free radical polymerization monomer recorded in the paragraph 0048 ~ 0063 of Japanese Unexamined Patent Publication 2009-096985 publication preferably can be listed.Wherein, as monofunctional aromatic free radical polymerization monomer, the compound that preferred formula (b-3) represents.

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

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

X ¹represent the linking group of divalence, be preferably ether (-O-), ester group (-C (O) O-or-OC (O)-), amide group (-C (O) NR '-), carbonyl (-C (O)-), imino-(-NR '-), can have substituent carbonatoms be 1 ~ 15 alkylidene group or by the group of their more than 2 divalence combined.Wherein, R ' represent hydrogen atom, carbonatoms be 1 ~ 20 straight-chain, branched or cyclic alkyl or carbonatoms be the aryl of 6 ~ 20.

In formula (b-3), with X ¹vinyl combine end be preferably X ¹carbonyl carbon and ethylenic unsaturated group combine ester group or amide group, be more preferably ester bond.Particularly preferably there is H ₂c=C (R ¹) structure of-C (O) O-.Now, X ¹other parts can be singly-bound also can be optional part from described group.

Containing R ¹and X ¹part (H ₂c=C (R ¹)-X ¹-optional position on aromatic hydrocarbyl Ar can be combined in.

In addition, from the view point of improving the affinity with tinting material, with X ¹aromatic hydrocarbyl Ar combine end be preferably Sauerstoffatom, be more preferably etheric oxygen atom, X ¹be preferably *-C (O) O (LO) _q-or *-C (O) NH (LO) _q-.Here, the X of * expression (A2) ¹the integer, the L that are 0 ~ 10 with the binding site of ethylenic unsaturated group, q represent that carbonatoms is the alkylidene group of 2 ~ 4.Wherein, X ¹be preferably *-C (O) O (LO) _q-, q is preferably the integer of 0 ~ 4, is more preferably the integer, more preferably 1 or 2 of 0 ~ 2.(LO) _qbe preferably ethylene oxide chain or propylene oxide chain.

U the R existed ⁵independently of one another be preferably hydroxyl, replacement or without replace amino, thiol group, siloxanes or alkyl or the heterocyclic radical that substituent total carbon atom number is less than 30 can be had further.

U represent 0 ~ 5 integer, be preferably 0.

Ar represents aromatic hydrocarbyl.As aromatic hydrocarbyl, the monocycle or Ppolynuclear aromatic alkyl with 1 ~ 4 ring can be listed, can list particularly and eliminate the hydrogen atom of more than 1 and the group that obtains from 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 luxuriant and rich with fragrance alkene, aceanthrylene, 1,2-benzophenanthrene, seven days of the week alkene etc.

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

In addition, the aromatic hydrocarbyl Ar in formula (b-3) also can be containing the heteroatomic heteroaromatic such as O, N, S, but preferably not containing heteroatoms.

In the present invention, as the compound that formula (b-3) represents, vinylformic acid 2-phenoxy ethyl preferably can be listed.

Other monofunctional monomer > of <

Other monofunctional monomer except the compound that ink composite of the present invention can represent containing the compound represented except above-mentioned formula (b-1), formula (b-2), monofunctional aromatic monomer.As other monofunctional monomer, preferably (methyl) acrylic compound.

(methyl) acrylic compound comprises the compound with chemical forms such as monomer, oligomer, polymkeric substance.Other (methyl) acrylic compound only can using a kind, also can use two or more in order to improve target property with arbitrary ratio.

Particularly, (methyl) methyl acrylate can be listed, (methyl) ethyl propenoate, (methyl) 2-EHA, (methyl) 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) isobornyl acrylate, (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-hydroxybutyl, (methyl) vinylformic acid 4-hydroxybutyl, (methyl) vinylformic acid 2-methoxy acrylate, (methyl) vinylformic acid dicyclopentenyl oxygen base ethyl ester, (methyl) vinylformic acid 2-dimethylamino ethyl ester, (methyl) vinylformic acid 2-diethylamino ethyl ester, (gathering) ethylene glycol list (methyl) acrylate, (gathering) ethylene glycol (methyl) methyl acrylate, (gathering) ethylene glycol (methyl) ethyl propenoate, (gathering) propylene glycol list (methyl) acrylate, (gathering) propylene glycol (methyl) methyl acrylate, (gathering) propylene glycol (methyl) ethyl propenoate, Hitachi Chemical Co., Ltd. FANCRYL FA-513A (vinylformic acid dicyclopentenyl ester), FANCRYL FA-513M (methacrylic acid dicyclopentenyl ester), FANCRYL FA-711MM (methacrylic acid pentamethvl ester), FANCRYL FA-712HM (methacrylic acid tetramethyl piperidine ester), SartomerJapan Co., Ltd. functional monomer SR & CD series, as monofunctional compound such as the CN series that functional oligomerization thing is sold.

More specifically, Shanxi three Knitting " frame Bridge drug Ha Application De Block Star Network " (, great achievement society in 1981) under mountain can be used; Add the clear Visual Knitting of rattan " U VE B solidifies Ha Application De Block Star Network (raw material Knitting) " (, the meeting of polymer publication in 1985); ラ ドテツク research association Knitting " U VE B solidifies skill Intraoperative AppliedYong と city Games " 79 Page (, シ mono-エ system シ mono-society in 1989); Known free-radical polymerised (methyl) acrylate monomer in the commercially available product recorded in waterfall mountain Sakae mono-youth work " Port リ エ ス テ Le Trees fat Ha Application De Block Star Network " (, the new Wen society of daily magazine industry in 1988) etc. or industry.In addition, as free-radical polymerised compound, the polymerizable compound of the light-cured type used in the optical polymerism composition such as, recorded in each publications such as No. 7-159983, known Japanese Unexamined Patent Publication, No. 7-31399, Japanese Patent Publication, No. 8-224982, Japanese Unexamined Patent Publication, No. 10-863, Japanese Unexamined Patent Publication, No. 9-134011, Japanese Unexamined Patent Publication, No. 2004-514014, Japanese Unexamined Patent Application Publication, (methyl) acrylate recorded in these documents is also applicable to ink composite of the present invention.

Wherein, preferably there is (methyl) acrylate of amino or substituted-amino.By having amino or substituted-amino, the ink composite of the excellent dispersion of aluminum metal pigment can be obtained.

Alternatively amino substituting group, preferred carbonatoms is the alkyl of 1 ~ 5.As other monofunctional monomer, more preferably there is (methyl) vinylformic acid substituted-amino alkane ester, further preferred (methyl) acrylate that carbonatoms is the alkyl of 1 ~ 5.

< 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 in composition B is more than 20 quality %, flexibility, the stretchiness of cured film reduce.The content of the polyfunctional monomer in composition B, from the view point of solidified nature, film hardness, flexibility, is preferably 0.5 ~ 19.9 quality %, is more preferably 2 ~ 18 quality %.

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

The functional group number that polyfunctional monomer has is preferably 2 ~ 6, is more preferably 2 ~ 4, more preferably 2.

As polyfunctional monomer, 1,6-hexylene glycol two (methyl) acrylate can be listed, 1,9-nonanediol two (methyl) acrylate, decamethylene-glycol two (methyl) acrylate, two (4-(methyl) acryloxypolyethoxyphenyl) 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, poly-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 diisocyanate 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, two (4-(methyl) acryloxypolyethoxyphenyl) propane of 2,2-, Phthalic acid, diallyl ester, triallyltrimelitate etc.

In addition, as free-radical polymerised compound, vinyl ether compound can also be used.

As vinyl ether compound, such as ethylene glycol divinyl ether can be listed, diethylene glycol divinyl ether, triethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, butyleneglycol divinyl ether, hexylene glycol divinyl ether, cyclohexanedimethanol divinyl ether, two or triethylene ether compound of trimethylolpropane tris Vinyl Ether etc., ethylene glycol list Vinyl Ether, triethylene glycol list Vinyl Ether, ethyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, octadecyl vinyl ether, hydroxyethyl list Vinyl Ether, hydroxybutyl vinyl ether, hydroxynonyl list Vinyl Ether, 2-ethylhexyl vinyl ether, n-propyl Vinyl Ether, isopropyl-ethylene ether, pseudoallyl Vinyl Ether, dodecyl vinyl ether, diethylene glycol monovinyl ether, single vinyl ether compound such as octadecyl vinyl ether etc.

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

((composition C) optical free radical polymerization starter)

Ink composite of the present invention contains (composition C) optical free radical polymerization starter (hereinafter also referred to " polymerization starter ").Polymerization starter is the external energy of the described active radioactive rays of absorption etc. and generates the compound being polymerized and causing and plant.As the polymerization starter that can use in the present invention, aromatic series ketone, acylphosphine compounds, aromatic series salt compound, organo-peroxide, thio-compounds, six aryl di-imidazolium compoundss, ketooxime ester compounds, boric acid ester compound, nitrine (azinium) compound, metallocene compound, active ester compound can be listed and there is the compound etc. of carbon-halogen bond.As the object lesson of these polymerization starters, the polymerization starter recorded in Japanese Unexamined Patent Publication 2008-208190 publication, Japanese Unexamined Patent Publication 2009-096985 publication can be listed.Polymerization starter can a kind be used alone, also can two or more also use.

Wherein, as polymerization starter, preferred acylphosphine compounds, aromatic series ketone.As aromatic series ketone, preferred thioxanthone compounds.Particularly preferably acylphosphine compounds and thioxanthone compounds are used.

< acylphosphine compounds >

As acylphosphine compounds; preferably can list the acylphosphine oxide compound recorded in the paragraph 0080 ~ 0098 of Japanese Unexamined Patent Publication 2009-096985 publication; wherein, preferably there is the compound of the structure that formula (c-1) or formula (c-2) represent in the structure of compound.

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

(in formula (c-3), R ⁶, R ⁷, R ⁸expression can have the aromatic hydrocarbyl of methyl or ethyl alternatively base.)

As the monoacylphosphine oxide phosphine compound that formula (c-3) represents, preferred R ⁶~ R ⁸for the phenyl of methyl alternatively base can be had, more preferably R ⁷and R ⁸for phenyl and R ⁶for having the phenyl of 1 ~ 3 methyl.

Wherein, as the monoacylphosphine oxide phosphine compound that formula (c-3) represents; preferably 2,4,6-trimethylbenzoyl diphenyl phosphine oxides (Darocur TPO:Ciba Specialty Chemicals Inc., Lucirin TPO:BASF Inc.).

(in formula (c-4), R ⁹, R ¹⁰, R ¹¹expression can have the aromatic hydrocarbyl of methyl or ethyl alternatively base.)

As two acylphosphine oxide compounds that formula (c-4) represents, preferred R ⁹~ R ¹¹for the phenyl of methyl alternatively base can be had, more preferably R ¹¹for phenyl and R ⁹and R ¹⁰for having the phenyl of 1 ~ 3 methyl.

Wherein, as two acylphosphine oxide compounds that formula (c-4) represents, preferably two (2,4,6-trimethylbenzoyl) phenyl phosphine oxide (IRGACURE819, Ciba Specialty Chemicals Inc.).

< thioxanthone compounds >

Thioxanthone compounds is preferably the compound that formula (c-5) represents.

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

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

R ¹~ R ⁸each adjacent 2 can be interconnected to form ring.As ring structure during their formation rings, the aliphatics ring, aromatic ring etc. of 5 or 6 rings can be listed, for the heterocycle containing the element beyond carbon atom, in addition, between the ring formed, can also can also be combined to form 2 nuclear rings such as fused rings further.These ring structures can also have substituting group further.Alternatively base, can list halogen atom, hydroxyl, cyano group, 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 list N, O and S.

As thioxanthone compounds, thioxanthone can be listed, ITX, 2-chloro thioxanthone, 2-dodecyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dimethyl thioxanthone, 1-methoxycarbonyl thioxanthone, 2-ethoxy carbonyl thioxanthone, 3-(2-methoxyethoxycarbonyl) thioxanthone, 4-butoxy carbonyl thioxanthone, 3-butoxy carbonyl-7-methyl thioxanthone, 1-cyano group-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-bis-[2-(2-methoxy ethoxy) ethoxy carbonyl] thioxanthone, 1-ethoxy carbonyl-3-(1-methyl isophthalic acid-morpholinoethyl) thioxanthone, 2-methyl-6-dimethoxy-methyl thioxanthone, 2-methyl-6-(1,1-dimethoxy-benzyl) thioxanthone, 2-morpholinomethyl thioxanthone, 2-methyl-6-morpholinomethyl thioxanthone, positive allyl group thioxanthone-3,4-dicarboximide, n-octyl thioxanthone-3,4-dicarboximide, N-(1,1,3,3-tetramethyl butyl) thioxanthone-3,4-dicarboximide, 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 the view point of obtaining easiness and solidified nature, more preferably ITX and ITX.

In the present invention, from the view point of solidified nature, preferably acylphosphine compounds and thioxanthone compounds are used.

When by acylphosphine compounds and thioxanthone compounds and the used time, acylphosphine compounds: thioxanthone compounds is preferably 99: 1 ~ 1: 99 by quality ratio, is more preferably the scope of 90: 10 ~ 50: 50, more preferably 80: 20 ~ 50: 50.

In the present invention, total consumption of optical free radical polymerization starter, from the view point of solidified nature, is preferably 1 ~ 20 quality % relative to the total mass of ink composite, is more preferably 3 ~ 15 quality %, more preferably 5 ~ 10 quality %.

((components D) tinting material except composition A)

Ink composite of the present invention can also contain (components D) tinting material except composition A except the aluminum metal pigment of composition A.By by aluminum metal pigment with tinting material except composition A and use, metalluster image can be made to have various colour-change.

As tinting material, have no particular limits, but preferably have excellent weather resistance and the abundant pigment of color reproduction and oil-soluble colourant, can select to use arbitrarily from the known tinting materials such as solvability dyestuff.The viewpoint that the sensitivity of the curing reaction never making active radioactive rays cause reduces is set out, and the compound that can not play a role as polymerization retarder preferably selected by tinting material.

As pigment operable in the present invention, there is no particular limitation, can use in such as ColorIndex the organic or inorganic pigment of the following numbering recorded.As red or magenta pigment, can according to object 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, pigment violet 3,19,23,29,30,37,50,88, pigment Orange 13,16,20,36; As blue or green pigment, can according to object use pigment blue 1,15,15:1,15:2,15:3,15:4,15:6,16,17-1,22,27,28,29,36,60; As veridian, pigment Green 7,26,36,50 can be used according to object; As yellow ultramarine, 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 can be used according to object; As black pigment, Pigment black 7,28,26 etc. can be used according to object.

As white pigment, preferential oxidation titanium.

Titanium oxide is not particularly limited, can from the known titanium oxide being used as white pigment suitable choice for use.Rutile titanium dioxide and anatase titanium dioxide all can use, but low from catalyst activity sexuality, that ageing stability is excellent angle, preferably use rutile titanium dioxide.

Titanium oxide has commercially available, can exemplify such as 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 KRONOS Inc.) etc.

In addition, titanium oxide can also carry out surface treatment as required.Particularly, such as, carry out silicon-dioxide, aluminum oxide, zinc, zirconium white, organism process, also different with oleophylic water-based according to the different weathering resistance for the treatment of process.In the present invention, the titanium oxide that preferential oxidation aluminium, zinc, zirconium white, alkaline organic process obtain.

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

As the preferred object lesson of dispersed dye, can list 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 use the various diverting devices such as such as ball mill, sand mill, masher, roller mill, stirrer, Henschel mixing tank, colloidal mill, Soniprep, ball mill, wet type airflow milling, paint mixer.

Tinting material directly can add when the preparation of ink composite together with each composition.In addition, in order to improve dispersiveness, also can add in advance in the dispersion medium such as the polymerizable compound used in solvent or the present invention, make its dispersed or dissolve after coordinate.

In the present invention, in order to avoid deterioration and the problem of the VOC (Volatile Organic Compound: volatile organic compounds) of residual solvent of dissolvent residual solvent resistance when solidifying image, preferably tinting material being added in the dispersion medium such as polymerizable compound in advance and coordinating.In addition, when only from the viewpoint of Bet-hedging, the polymerizable compound used in the interpolation of tinting material preferably selects the monomer that viscosity is minimum.Also can tinting material that suitably choice for use is one kind or two or more according to the application target of ink composite.

In addition, in ink composite, when tinting materials such as the pigment using solid form to exist, selected, dispersion condition, the filtration condition of preferred preferred settings tinting material, dispersion agent, dispersion medium, with make the volume average particle size of colorant particle reach 0.005 ~ 0.5 μm, more preferably reach 0.01 ~ 0.45 μm, preferably reach 0.015 ~ 0.4 μm further.Managed by this particle diameter, the blocking of a nozzle, the storage stability maintaining ink composite, the transparency and solidification sensitivity can be suppressed, therefore preferably.

The content of the tinting material in ink composite suitably can be selected according to color and application target, is preferably 0.01 ~ 30 quality % relative to the quality of ink composite entirety.

((composition E) dispersion agent)

Ink composite of the present invention is preferably containing dispersion agent.Particularly when using pigment, in order to make pigment stable dispersion in ink composite, preferably containing dispersion agent.As dispersion agent, preferred macromolecule dispersing agent.

As macromolecule dispersing agent, DISPERBYK (registered trademark)-101,102,103,106,111,161,162,163,164,166,167,168,170,171,174,182 (BYK Inc.) can be listed; EFKA (registered trademark) 4010,4046,4080,5010,5207,5244,6745,6750,7414,745,7462,7500,7570,7575,7580 (EFKAADDITIVES Inc.); DISPERSE AID 6,8,15,9100 (SAN NOPCO Co., Ltd. system); The various SOLSPERSE dispersion agents (Lubrizol Inc.) 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 agents), #2150 (aliphatic polycarboxylic acid), #7004 (polyether ester type) (nanmu originally changes into Co., Ltd.'s system).

The content of the dispersion agent in ink composite suitably can be selected according to application target, is preferably 0.05 ~ 15 quality % relative to the quality of ink composite entirety.

((composition F) tensio-active agent)

In order to give the ejection of long-time stable, in the present invention, in operable ink composite, tensio-active agent can also be added.As tensio-active agent, the tensio-active agent recorded in No. 62-173463, Japanese Laid-Open Patent Publication, Japanese Laid-Open Patent Publication No. 62-183457 each publication can be listed.The cationic surfactants such as nonionic surfactant, alkylamine salt, quaternary ammonium salt such as the anionic surfactants such as such as dialkyl sulfosuccinate class, alkyl naphthalene sulfonic acid salt, fatty acid salt, Voranol EP 2001 class, polyoxyethylene alkylallyl base ethers, acetylenic diols, polyoxyethylene polyoxypropylene block copolymer class can be listed.

(other compositions)

The sensitizing agent, polymerization retarder, UV light absorber, antioxidant, anti-fading agent, electroconductibility salt, solvent, macromolecular compound, basic cpd etc. recorded in Japanese Unexamined Patent Publication 2009-096985 publication can also be added as other compositions in ink composite of the present invention.

(ink physical property)

In the present invention, consider ejection, the viscosity of ink composite at 25 DEG C is preferably below 40mPas.Be more preferably 5 ~ 40mPas, more preferably 7 ~ 30mPas.In addition, the viscosity sprayed at temperature (be preferably 25 ~ 80 DEG C, be more preferably 25 ~ 50 DEG C) is preferably 3 ~ 15mPas, is more preferably 3 ~ 13mPas.The suitable ratio of components of preferred adjustment ink composite of the present invention reaches above-mentioned scope to make viscosity.By the viscosity under room temperature is set higher, even if when using the printing medium of Porous, ink composite also can be avoided to soaking in printing medium, reduce uncured monomer.In addition, the ink of ink composite when drop adheres to can also be suppressed to spread and sink in and ooze, its resultant image quality improves.

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

II. ink group

The feature of ink group of the present invention is containing ink composite of the present invention and at least a kind of ink composite containing the tinting material except composition A.

As the ink composite containing the tinting material except composition A, known free-radical polymerised ink composite can be used, not limit, preferably containing ink composite identical with the composition of ink composite of the present invention except composition A.In addition, as the tinting material except composition A, the tinting material of components D preferably can be used.

When being used as the ink group containing ink composite of the present invention, as long as at least containing a kind of ink composite of the present invention, and there is the ink group of the ink composite of more than two kinds ink composite of the present invention or the ink composite except ink composite of the present invention combined, then have no particular limits, preferably containing 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, 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

The feature of ink jet recording method of the present invention is to comprise following operation: ink composite of the present invention to be ejected on printing medium thus the image formation process forming image (hereinafter also referred to (a) operation.) and irradiate active radioactive rays to the ink composite of ejection, this ink composite is solidified thus the curing process obtaining the print of the image on described printing medium with solidification (hereinafter also referred to (b) operation.)。

The feature of print of the present invention is, it is obtained by ink jet recording method of the present invention.

First, (a) operation is described.

In the present invention, as printing medium, there is no particular limitation, known printing medium can be used, such as paper can be listed, plastics (such as polyethylene, polypropylene, polystyrene etc.) paper that is laminated, metal sheet (such as aluminium, zinc, copper etc.), plastics film (such as polyvinyl chloride, Cellulose diacetate, cellulosetri-acetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, nitrocellulose, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal etc.), above-mentioned metal stacking or evaporation and the paper obtained or plastics film etc.In addition, as the printing medium in the present invention, be also applicable to using nonabsorbable printing medium.

As the ink-jet recording device used in ink jet recording method of the present invention, be not particularly limited, can choice for use can the known ink-jet recording device of realize target exploring degree arbitrarily.That is, as long as comprise the known ink-jet recording device of commercially available product, then the ejection of the ink composite in (a) operation of ink jet recording method of the present invention to printing medium can all be implemented.

As the ink-jet recording device that can use in the present invention, the device such as comprising ink supply system, temperature sensor, active radiation source can be listed.

Ink supply system is such as made up of the ink gun of the ink composite supplying tank comprising the main tank of ink composite of the present invention, supplying tubing, ink gun front are close to, strainer, piezo-electric type.The ink gun of piezo-electric type according to can by preferably 1 ~ 100pL, more preferably 3 ~ 42pL, further preferably many sizes point of 8 ~ 30pL with preferably 320 × 320 ~ 4,000 × 4,000dpi, more preferably 400 × 400 ~ 1, the mode of 600 × 1,600dpi, the preferably exploring degree ejection of 720 × 720dpi further drives.Wherein, the dpi described in the present invention represents counting of every 2.54cm.

In order to obtain the image of metalluster excellence, the aluminum metal pigment that preferably coordinating size is large in ink composite.But when the aluminum metal pigment that coordinating size in ink composite is large, the nozzle of ink gun blocks sometimes.Therefore, in image formation process, the diameter for the opening portion spraying the nozzle of ink composite of the present invention is preferably more than 20 μm, is more preferably 21 ~ 100 μm, more preferably 22 ~ 50 μm.When in above-mentioned numerical range, the image of metalluster excellence can be obtained when the nozzle of ink gun can not block, therefore preferably.

About the shape of the opening portion of nozzle, circle, ellipse, Polygons etc. can be listed.When the shape of the opening portion of nozzle is not justified, the diameter of opening portion refers to the circular diameter suitable with the area of opening portion.

In the present invention, the ink composite that preferably will spray maintains steady temperature, can divide thus carry out thermal insulation and heating from ink composite supplying tank to ink jet head section.As temperature controlled method, do not restrict especially, but preference is as arranged multiple temperature sensor at each pipe arrangement position and carrying out computer heating control according to the flow of ink composite, envrionment temperature.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 with the impact making device body can not be subject to the temperature from extraneous air.In order to shorten the printer time of recovery required by heating or the loss in order to reduce thermal energy, while carrying out the thermal insulation with other positions, preferably reduce the thermal capacity of heating unit entirety.

The radiation-curing type ink composites such as ink composite of the present invention are generally speaking high than the viscosity of the aqueous ink composition used in usual composition for ink jet recording, and the viscosity variation that temperature variation when therefore spraying causes is large.The viscosity variation of ink composite can produce large impact to the change of drop size and the change of drop spouting velocity, and then can cause deterioration in image quality.Therefore, the temperature of ink composite during ejection needs to keep constant as far as possible.Therefore, in the present invention, the span of control limit of control of the temperature of ink composite be preferably design temperature ± 5 DEG C, be more preferably design temperature ± 2 DEG C, more preferably design temperature ± 1 DEG C.

Below, (b) operation is described.

The ink composite be ejected on printing medium solidifies by irradiating active radioactive rays.This is because polymerization starter contained in ink composite of the present invention issues solution estranged in the irradiation of active radioactive rays, produce the polymerization initiations kind such as free radical, under the effect that this initiation is planted, the polyreaction of polymerizable compound is initiated, promotes.Now, when also there is sensitizing agent in ink composite together with polymerization starter, sensitizing agent assimilating activity radioactive rays in system and become excited state, promoting the decomposition of polymerization starter by contacting with polymerization starter, can realize the curing reaction of more high sensitivity.

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

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

As active radiation source, mainly utilize mercury lamp or gas-solid laser etc., as the light source of the solidification for ultraviolet photo-curing type composition for ink jet recording, mercury lamp, metal halid lamp are widely known by the people.But from the view point of present environment protection, strong expectation is mercuryless, and replacing with GaN semi-conductor ultraviolet light emitting device is industrially, environmentally all very useful.In addition, LED (UV-LED), LD (UV-LD), due to small-sized, high life, high-level efficiency, low cost, therefore expect that it is as light-cured type ink-jet light source.

In addition, photodiode (LED) and laser diode (LD) also can be used as active radiation source.Particularly when needs ultraviolet source, ultraviolet LED and ultraviolet LD can be used.The main emmission spectrum that such as Ya KCC sells has the purple LED of the wavelength between 365nm to 420nm.In addition, when need further more short wavelength, as LED, US patent number the 6th can be exemplified, can the LED of the active radioactive rays of launching centre between 300nm and 370nm disclosed in 084, No. 250 specification sheetss.In addition, other ultraviolet LED also can obtain, can the different radiation of irradiation ultraviolet radiation bandwidth.In the present invention, preferred active radiation source is the UV-LED of UV-LED, the length of the spike particularly preferably with 350 ~ 420nm.

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

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

Illuminate condition and the basic illuminating method of active radioactive rays disclose in Japanese Laid-Open Patent Publication 60-132767 publication.Particularly, by arranging light source in the both sides of head unit of the blowoff comprising ink composite and carry out with so-called shuttle mode scan head unit and light source.The irradiation of the active radioactive rays alternate constant time (preferably 0.01 ~ 0.5 second, more preferably 0.01 ~ 0.3 second, further preferably 0.01 ~ 0.15 second) after the attachment of ink composite carries out.So by being the extremely short time by the time controling being attached to irradiation from ink composite, thus can prevent from the ink composite that printing medium adheres to from spreading and sinking in before curing oozing.In addition, even if for the printing medium of Porous, light source can be impregnated at ink composite and be beyond one's reach before deep and expose, thus the residual of unreacted monomer can be suppressed, therefore preferably.

In addition, also can utilize without the other light sources driven to complete solidification.Disclose as illuminating method in International Publication No. 99/54415 brochure, employ the method for optical fiber or make the light source through calibrating towards being arranged on the minute surface of head unit side, then irradiating the method for UV light to recording unit, such curing also can be applicable to ink jet recording method of the present invention.

By adopting ink jet recording method described above, even if for the different various printing mediums of wettability of the surface, also the some footpath of the ink composite of attachment can be kept constant, thus improving picture quality.In addition, in order to obtain coloured image, preferably from the color that lightness is low, carry out overlap in order.By carrying out overlap in order the ink composite low from lightness, illuminated line easily can arrive the ink composite of bottom, thus can expect good solidification sensitivity, the minimizing of residual monomer, the raising of adherence.In addition, can expose together although irradiate after the whole color of ejection, from the view point of promotion solidification, preferably every a kind of color ground exposes.

The ink group of the ink composite of the present invention comprising more than 1 preferably can be used in ink jet recording method of the present invention.There is no particular limitation for the order of each colored ink compositions sprayed, but be preferably imparted on printing medium from the colored ink compositions that lightness is low.When using the ink composite of ink composite of the present invention, yellow, cyan, magenta, black, preferably according to the sequential delivery of ink composite → yellow → cyan → magenta → black of the present invention on printing medium.In addition, when when increase use white, preferably according to the sequential delivery of white → ink composite → yellow → cyan → magenta → black of the present invention on printing medium.In addition, the present invention is not limited thereto, also can with at least comprise the ink composite of light blue, shallow magenta and cyan, magenta, black, white, yellow heavy colour ink composite the form of ink group use, now, preferably according to the sequential delivery of white → ink composite of the present invention → light blue → shallow magenta → yellow → cyan → magenta → black on printing medium.

IV. the manufacture method of molded printed matter and molded printed matter

The feature of the manufacture method of molded printed matter of the present invention is to comprise following operation: ink composite of the present invention to be ejected on printing medium thus the image formation process forming image (hereinafter also referred to (a) operation.), irradiate active radioactive rays to the ink composite of ejection, this ink composite is solidified thus the curing process obtaining the print of the image on described printing medium with solidification (hereinafter also referred to (b) operation.), and the operation of processing is formed (hereinafter also referred to (c) operation to described print.)。

In addition, the feature of molded printed matter of the present invention is, it is obtained by the manufacture method of described molded printed matter.

About (a) operation in the manufacture method of molded printed matter of the present invention and (b) operation, be same with (a) operation in ink jet recording method of the present invention and (b) operation, the printing medium preferably used in this is only to the manufacture method of molded printed matter of the present invention is described.

In the manufacture method of molded printed matter of the present invention, there is no particular limitation for operable printing medium, can use the known printing medium being suitable for formed machining.Particularly, polyethylene can be exemplified, polypropylene, polymethylpentene, polybutene, the polyolefin-based resins such as olefin series thermoplastic elastomer, polyethylene terephthalate, polybutylene terephthalate, PEN, terephthalic acid-m-phthalic acid-glycol copolymer, terephthalic acid-ethylene glycol-1, 4 cyclohexanedimethanol multipolymers, the vibrin such as Polyester thermoplastic elastomer, nylon 6, nylon 9, nylon 6, 6 polyamide resins such as grade, fluorinated ethylene propylene, poly(vinylidene fluoride), poly-three vinylidene fluorides, ethylene-tetrafluoroethylene copolymer, the fluorine resins such as tetrafluoroethylene, acrylic resin, polyvinyl chloride, polystyrene, polycarbonate resin etc.

Aforesaid propylene acid is that resin can use the monomer of the such as resin such as poly-(methyl) methyl acrylate, poly-(methyl) ethyl propenoate, poly-(methyl) butyl acrylate, (methyl) methyl acrylate-(methyl) butyl acrylate copolymer, (methyl) ethyl propenoate-(methyl) butyl acrylate copolymer, (methyl) acrylate-styrene multipolymer or mixture of more than two kinds.

Wherein, print easily and the angle of each patience excellence of the molding made from banding, preferred use polyethylene terephthalate, polycarbonate resin or in polycarbonate resin, be mixed with the resin sheet of other resins, optimization polycarbonate resin or be mixed with the resin sheet of other resins in polycarbonate resin.In addition, printing medium can be the duplexer being laminated with one kind or two or more resin sheet.

In the present invention, about the thickness (being total thickness during duplexer) of printing medium, as long as embossing processing, vacuum forming being shaped and the Vacuum Pressure sky of principle that Vacuum Pressure sky is shaped is shaped the resin sheet of thickness of the scope that can carry out with pressure is empty, then there is no particular limitation, be preferably 50 ~ 2,000 μm, be more preferably 100 ~ 1,500 μm, more preferably 150 ~ 1,000 μm.

Suitably additive can also be added as required in thermoplastic resin sheet.As additive, as long as bring in dysgenic scope can not to the thermal characteristics such as surface luster, fusing point, then various additive can be added in right amount.The lubricants such as photostabilizer, polyorganosiloxane resin, varnish, tinting material, softening agent, thermo-stabilizer, antiseptic-germicide, mould inhibitor, the static inhibitor etc. such as the UV light absorber such as such as benzotriazole system, benzophenone series, hindered amine system radical scavenger can be listed.

Molded printed matter of the present invention makes by implementing the formed machining such as vacuum forming to thermoplastic resin sheet, forms image before formation by ink-jetting style on printing medium.

Image is imparted into the inner surface side (being the side with contacting dies in vacuum forming) of clear sheet usually, but image also can be formed on its opposing face.In addition, according to different situations, only can also form image on described opposing face, now, the thermoplastic resin sheet as base material needs not be transparent.

In the present invention, for formed machining, embossing processing, vacuum forming can be used, pressure sky is shaped or Vacuum Pressure sky is shaped.As device print being formed to processing, can use known device, can be also can be other device with the device of described ink-jet recording device one.

Embossing processing is the arbitrary shape such as pattern or word and show relief processing by the depression such as suitable print, such as, use roller or press etc. to carry out.As an example of embossing processing, heat, cold pressurization can be listed, can with reference to the method etc. recorded in Japanese Unexamined Patent Publication 10-199360 publication.An example of the embossing building mortion utilizing heat, cold pressurization is below shown.This embossing building mortion can configure close to the mode of separating mutually according to lower platform (lower platform) and upper brace (upper mounting plate).Further, lower platform is fixed with plate-type heater, the lower surface of upper brace is also fixed with plate-type heater.Printing medium can be heated thus while carry out hot pressing.In this hot pressing machine, the plate-type heater on its lower platform is installed and has with the mould of the consistent protuberance of embossed shape of regulation and according to the mode of fixing heater contacts on the lower surface of upper mounting plate, the mould of the recess with the shape consistent with described protuberance be installed.Further, configuration is formed with the printing medium of image, configures and cushion sheet material between this printing medium and recess mould, suppresses between upper mounting plate and lower platform by making upper mounting plate decline to printing medium and buffer substrate tablet material.Plus-pressure in this hot pressing operation is such as 30 tons, and the Heating temperature that plate-type heater produces is such as 170 DEG C.Further, upper mounting plate is given as security and is pressed onto on lower platform, between mould, hold printing medium and buffer substrate tablet material under the arm pressure, keep this hot pressing to restrict 3 minutes.Printing medium by heater heats, forms multiple protuberance by mould by thermal distortion.Then, directly are configured under the state that this printing medium and buffer substrate tablet material are seized on both sides by the arms between mould between the internal water cold mould platform not possessing well heater, such as plus-pressure be 30 tons, the hold-time be the condition of about 3 minutes under utilize internal water cold mould platform carry out signature pressure, carry out cold compaction.Thus, the printing medium convex form that thermal distortion is formed by hot pressing is kept, thus obtains the molded printed matter being applied with embossing processing.Plus-pressure and Heating temperature suitably can adjust according to conditions such as the material of used print and machining shapes.

Vacuum forming in advance the printing medium being formed with image is preheating to the temperature that thermal distortion can occur, and utilization decompression is attracted in mould to carry out stretching press against the method being cooled to mould forms; The empty shaping of pressure in advance the printing medium being formed with image is preheating to the temperature that thermal distortion can occur, and carries out pressurizeing and press against the method being cooled to mould to form from the opposition side of mould.It is carry out described decompression and pressurization thus the method formed that Vacuum Pressure sky is shaped simultaneously.Detailed content can see the document quoted in " thermoforming " project recorded in polymer voluminous dictionary (Wan Shan Co., Ltd.) p.766 ~ 768 and this project.

Embodiment

Below illustrate that embodiment and comparative example are to carry out more specific description to the present invention.But the present invention is not by the restriction of these embodiments.Wherein, " part " in below recording, then represents " mass parts ", " % " expression " quality % " unless otherwise specified.

(preparation of metallic pigment millbase)

Aluminum metal pigment (ROTOVARIO 500022, aluminium powder pigment paste, ECART Inc.)

50 mass parts (solids component)

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

SOLSPERSE 36000 (Lubrizol Inc.) 10 mass parts

Use diameter to be that 0.2mm zircon bead disperses 20 hours on mentioned component ball mill, obtain metallic pigment millbase.

Now, measure the volume average particle size of aluminum metal pigment with laser diffraction, scattering method particle size distribution device (trade(brand)name: MicroTrackMT3300EX, Nikkiso Company Limited's system), result is 0.25 μm.

In the same manner as the preparation of metallic pigment millbase, according to the composition shown in table 1, dispersion condition, prepare Cyan Millbase, magenta millbase, yellow millbase, black millbase and white millbase.

Table 1

(pigment)

Green pigment: IRGALITE BLUE GLVO (Ciba Specialty Chemicals Inc.)

Magenta pigment: CINQUASIA MAGENTA RT-355D (Ciba SpecialtyChemicals Inc.)

Yellow ultramarine: NOVOPERM YELLOW H2G (Clariant Inc.)

Black pigment: SPECIAL BLACK 250 (Ciba Specialty Chemicals Inc.)

White pigment: alumina treatment titanium oxide

(monofunctional monomer)

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

(dispersion agent)

SOLSPERSE 2000 (Lubrizol Inc.)

SOLSPERSE 32000 (Lubrizol Inc.)

SOLSPERSE 5000 (Lubrizol Inc.)

SOLSPERSE 36000 (Lubrizol Inc.)

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

The making method > of < ink composite

By the raw material mixing recorded in table 2, stir, obtain the ink composite of embodiment 1 ~ 16 and comparative example 1 and 2.Wherein, the use level (mass parts) of each composition of the numeric representation in table.

< ink jet image record >

Then, the record that the ink-jet recording device with piezoelectric type ink-jet nozzle carries out to printing medium is used.The ink gun (diameter of the opening portion of nozzle is 25 μm) of the inking tank that ink supply system is close to by main tank, supplying tubing, ink gun front, strainer, piezo-electric type is formed, and carries out from inking tank to the thermal insulation of ink gun part and heating.Temperature sensor is separately positioned near the nozzle of inking tank and ink gun, carries out temperature and controls to make nozzle segment be usually 40 DEG C ± 2 DEG C.The ink gun of piezo-electric type is driven to make it with 4, many sizes point of the exploring degree injection 1 ~ 10pl of 800 × 4,800dpi.After attachment by UV light with plane of exposure illumination 700mW/cm ²carry out light harvesting, adjustment exposure system, main-scanning speed and injection frequency are to make to irradiate beginning after ink composite is attached to printing medium upper 0.1 second.In addition, the time shutter is set as variable, irradiates exposure energy.UV-lamp uses HAN250NL height solidification (high cure) mercury lamp (Co., Ltd. GS Yuasa corporation system).Wherein, the dpi described in the present invention represents counting of every 2.54cm.As printing medium, use ester film E5000 (thickness is 125 μm, Toyo Boseki K.K's system).

< ink evaluation >

(evaluation of solidified nature)

According to described ink jet recording method, the thickness that is averaged is the description of whole the image of 12 μm, image surface after uv irradiation, will become the amount (mJ/cm of the exposure energy of sense of not adhering ²) be defined as solidification sensitivity.The less expression of numerical value high sensitivity.

In addition, solidify sensitivity to evaluate according to following benchmark.

5: lower than 3,500mJ/cm ²

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

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

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

1:5,000mJ/cm ²more than individual

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

The evaluation of < flexibility: the resistance to tortuosity of cured film evaluates >

For each ink composite, become there is no adhesive exposure with minimum energy, be the description of whole the image of 4 μm according to described ink jet recording method to transparent substrate (ester film E5000) thickness that is averaged, by this image 23 DEG C, relative humidity be the condition of 60% under keeping 1 day after, observe cured film with hand by tortuous for picture middle body 180 ° and have flawless, evaluate as follows.

When more than 5:20 time, cured film 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: when being less than 5 times, cured film cracks.

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

The evaluation > of < film hardness

To each ink composite with excessive exposure (30,000mJ/cm ²), be the description of whole the image of 12 μm according to described ink jet recording method to transparent substrate (polycarbonate) thickness that is averaged, its image is carried out determination of pencil hardness according to JIS K5600-5-4 at 25 DEG C.

More than 8:4H

7：3H

6：2H

5：H

4：F

3：HB

2：B

Below 1:2B

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

The evaluation > of < metalluster

To each ink composite with excessive exposure (15,000mJ/cm ²), be the description of whole the image of 12 μm according to described ink jet recording method to transparent substrate (polycarbonate) thickness that is averaged, be that image by following visual valuation.

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

4: directly over vertical direction, observing image can be judged as metal tone when departing from level 30 degree

3: directly over vertical direction, observing image can be judged as metal tone when departing from level 60 degree

2: directly over vertical direction, observing image can be judged as metal tone when departing from horizontal 90-degree

1: be grey substantially

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

Writing a Chinese character in simplified form of recording in table 2 is as described below.

(monofunctional monomer)

PEA; Vinylformic acid 2-phenoxy ethyl (following compound, SR339, SARTOMER Inc.)

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-trimethylbenzoyl) phenylacyl phosphine oxide (IRGACURE819, Ciba Specialty Chemicals Inc.)

The mixture (FIRSTCUREITX, ALBEMARLE Inc.) of ITX:2-isopropyl thioxanthone and ITX

(embodiment 17 ~ 32)

By the raw material mixing recorded in table 3, stir, obtain the ink composite of the yellow shown in experimental example 1 ~ 5, magenta, cyan, black, white.

The ink group making embodiment 17 ~ 32 is combined by containing the wantonly a kind of ink composite of metallic pigment recorded in embodiment 1 ~ 16 and the ink composite of experimental example 1 ~ 5.

In described ink jet image record, for the ink composite of embodiment 1 ~ 16, the ink gun (diameter of the opening portion of nozzle is 25 μm) of piezo-electric type is used to spray, for the ink composite of experimental example 1 ~ 5, use the ink gun (diameter of the opening portion of nozzle is 20 μm) of piezo-electric type to spray, form image under identical condition in addition.

Even if when using the multicolor ink group of the ink composite containing embodiment 1 ~ 16, the image of solidified nature, flexibility, film hardness, metalluster excellence also can be obtained.

Table 3

(embodiment 35)

Suction former Forming 300X (Cheng Guang Industry Co., Ltd system) is used to carry out vacuum forming.In above-mentioned ink jet recording method, except adopting Panlite sheet PC-1151 (Teijin Chemicals, Ltd.'s system) as except printing medium, make print by condition similarly to Example 1.

The temperature of setting well heater reaches 90 DEG C to make the temperature of supporter, arranges the wooden die shown in Fig. 1 carry out vacuum forming at the center of vaccum bench.Visual observation is shaped the print that obtains with or without crackle of chapping, pin hole (pinhole).In addition, visual observation processes rear surface with or without scar in vacuum forming.Result has no crackle of chapping, pin hole completely.

Claims (8)

1. an ink composite, is characterized in that, contains

Composition A: aluminum metal pigment,

Composition B: free-radical polymerised compound, and

Composition C: optical free radical polymerization starter,

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

Compound that formula (b-1) represents and/or the compound that formula (b-2) represents is contained as described monofunctional monomer,

In formula (b-1), R ¹represent hydrogen atom or methyl, X represents singly-bound, alkylidene group, oxygen base alkylidene group or the group combined by described oxygen base alkylidene group more than 2, ester bond or by these groups more than 2 groups combined, 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 any more than 2 can in conjunction with formation ring texture;

In formula (b-2), n represents the integer of 1 ~ 5;

In ink composite, the volume average particle size of described aluminum metal pigment is more than 0.05 μm and is less than 1.0 μm.

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

3. ink composite according to claim 1, wherein, the total content of the compound that the described formula (b-1) in composition B represents and the compound that formula (b-2) represents is 5 ~ 99.9 quality % of described ink composite.

4. an ink group, is characterized in that, comprises the ink composite according to any one of claims 1 to 3 and at least a kind of ink composite containing the tinting material except composition A.

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

Ink composite according to any one of claims 1 to 3 to be ejected on printing medium thus to form the image formation process of image, and

Ink composite to ejection irradiates active radioactive rays, this ink composite is solidified, thus obtains the curing process of the print of the image on described printing medium with solidification.

6. a print, it is obtained by ink jet recording method according to claim 5.

7. a manufacture method for molded printed matter, is characterized in that, comprises following operation:

Ink composite according to any one of claims 1 to 3 to be ejected on printing medium thus to form the image formation process of image,

Ink composite to ejection irradiates active radioactive rays, this ink composite is solidified thus obtains the curing process of the print of the image on described printing medium with solidification, and

Described print is formed to the operation of processing.

8. a molded printed matter, it is obtained by the manufacture method of molded printed matter according to claim 7.