CN105824191A - Photo-curable coloring composition, solidification object and article - Google Patents

Abstract

The invention provides a photo-curable coloring composition, a solidification object and an article, wherein, under usage of a pigment with large light reflection and light absorption, the photo-curable coloring composition has excellent solidification performance. In addition, the invention can provide the photo-curable coloring composition, which also has excellent solidification performance even under condition that ultraviolet light-emitting diodes can be taken as a light source. The photo-curable coloring composition is characterized in that the photo-curable coloring composition is the resin composition of an organic compound (A) capable of lightening by absorbing ultraviolet ray, a light polymerization compound (B), a photo polymerization initiator (C), and a pigment (D), for the organic compound (A) capable of lightening by absorbing ultraviolet ray, maximum wavelength of absorption spectrum measured in tetrahydrofuran is in a range of 250-400 nm, and the maximum wavelength of emission spectrum is in a range of 300-500 nm.

Description

Light solidification pigmentation composition, solidfied material and article

Technical field

The present invention relates to the light solidification pigmentation composition that curable is excellent.

Background technology

The light such as an irradiation ultraviolet radiation i.e. light solidification pigmentation composition of instantaneous solidification is used to be used for spraying, hectographic printing, silk screen printing, flexographic printing, ink jet printing etc. as the printing process of ink, reduce and the advantage such as solvent volatile quantity reduction of reply environmental requirement owing to simplifying the cost of drying process, be widely spread in recent years.

About light solidification pigmentation composition, the Photoepolymerizationinitiater initiater in compositions absorbs ultraviolet, thus produces spike (free radical or cation), and monomer is polymerized by this spike, thus compositions solidifies.Therefore, in the case of using light solidification pigmentation composition as the printing process of ink, in order to make ink fully solidify, it is important that ultraviolet arrives the inside of ink.But, the ink of the photo-curable containing colorant due to colorant light absorb, luminous reflectance, compared with transparent ink, the ink of the photo-curable containing colorant have curable difference tendency.Particularly, the ultra-violet absorption of black ink is big, it addition, the ultraviolet reflection of white ink is big, and the problem compared with other color with curable significance difference.

On the other hand, in recent years, developing the irradiation unit with ultraviolet LED as light source, compared with existing high voltage mercury lamp, metal halide lamp, xenon lamp etc., light source life is long, and energy saving is excellent, thus starts in UV Printing field universal.

But, as the shortcoming of ultraviolet light emitting diode light source, compared with existing lamp, the problem that the curable of light solidification pigmentation resin is excessively poor can be enumerated.Its reason can be enumerated: the emission wavelength region of ultraviolet light emitting diode light source is limited to 350nm～420nm, compared with the existing lamp of the ultraviolet sending wide area wavelength, the total amount of ultraviolet energy is little, therefore enough energy cannot be made to arrive Photoepolymerizationinitiater initiater, it is impossible to generate the spike of solidification desired concn.

As the technology of raising curable, Patent Document 1 discloses a kind of technology about the black ink containing specific compound.But, when using light emitting diode to solidify, the problem that there is curable difference.It addition, Patent Document 2 discloses the technology of a kind of ultraviolet-curing resin composition with ultraviolet LED as light source.But, in the resin combination containing colorant, there is the problem that the solidification of internal ink cannot be carried out.

Therefore, wish to develop a kind of light solidification pigmentation composition, even if in the case of making to use up the colorant that absorption, luminous reflectance are big, even and if in the case of with ultraviolet LED as light source, this light solidification pigmentation composition also has the curable of excellence.

Prior art literature

Patent documentation

Patent documentation 1: Japanese Unexamined Patent Publication 2011-116874 publication

Patent documentation 2: Japanese Unexamined Patent Publication 2011-1449 publication

Summary of the invention

The problem that invention is to be solved

The present invention allows for these problems of prior art and carries out, and its object is to provide a kind of light solidification pigmentation composition, and in the case of making to use up the colorant that absorptions, luminous reflectance are big, this light solidification pigmentation composition has excellent curable.Furthermore it is possible to provide a kind of light solidification pigmentation composition, even if in the case of using ultraviolet LED as light source, this light solidification pigmentation composition also has the curable of excellence.

For solving the scheme of problem

The present inventor conducts in-depth research to solve above-mentioned problem, and result completes the present invention.That is, the present invention relates to following (1)～(8).

(1) a kind of light solidification pigmentation composition, it is the organic compound (A) of luminescence, photopolymerizable compound (B), Photoepolymerizationinitiater initiater (C) and the resin combination of colorant (D) containing absorption ultraviolet, it is characterized in that, absorb the scope of a length of 250nm～400nm of maximum wave of the absorption spectrum that the organic compound (A) of ultraviolet and luminescence records in oxolane, and the scope of a length of 300nm～500nm of maximum wave of emission spectrum.

(2) light solidification pigmentation composition as described in (1), it is characterized in that, absorb the scope of a length of 250nm～390nm of maximum wave of the absorption spectrum that the organic compound (A) of ultraviolet and luminescence records in oxolane, and the scope of a length of 330nm～480nm of maximum wave of emission spectrum.

(3) light solidification pigmentation composition as described in (1) or (2), it is characterized in that, Photoepolymerizationinitiater initiater (C) has absorption at absorption ultraviolet under the wavelength of the light that the organic compound (A) of luminescence is sent.

(4) light solidification pigmentation composition as described in (3), it is characterized in that, the specific absorbance of the Unit Weight at 365nm that described Photoepolymerizationinitiater initiater (C) records in acetonitrile is 85ml/ (g cm)～10000ml/ (g cm).

(5) light solidification pigmentation composition as described in (3), it is characterized in that, the specific absorbance of the Unit Weight at 365nm that the Photoepolymerizationinitiater initiater (C) described in (3) records in acetonitrile is 400ml/ (g cm)～10000ml/ (g cm).

(6) light solidification pigmentation composition as according to any one of (1)～(5), it is characterized in that, as photopolymerizable compound (B), it is made up of more than a kind in the group being selected from (methyl) acrylate compounds (B-1), oxetane compound (B-2), epoxide (B-3), vinyl ether compound (B-4).

(7) a kind of solidfied material, it is the light solidification pigmentation composition according to any one of (1)～(6) to be irradiated active energy beam and obtains.

(8) a kind of solidfied material, it is characterized in that, it is to obtain the light solidification pigmentation composition irradiation ultraviolet radiation according to any one of (1)～(6) with ultraviolet light emitting diode light source, and described ultraviolet light emitting diode light source has peak wavelength at 350nm～420nm.

The effect of invention

According to the present invention, a kind of light solidification pigmentation composition can be provided, even if in the case of making to use up the colorant that absorption, luminous reflectance are big, even if in the case of using ultraviolet LED as light source, this light solidification pigmentation composition can also fully carry out the solidification of resin.

Detailed description of the invention

The light solidification pigmentation composition of the present invention is characterised by, its contain absorption ultraviolet and the organic compound (A) of luminescence, photopolymerizable compound (B), Photoepolymerizationinitiater initiater (C) and colorant (D).As long as it should be noted that following not special declaration, then content ratio i.e. weight % of each composition in light solidification pigmentation composition is weight % on the basis of the gross weight of light solidification pigmentation composition.

The light solidification pigmentation composition of the present invention contain absorption ultraviolet and the organic compound (A) of luminescence.

The organic compound (A) of luminescence as absorption ultraviolet, as long as the organic compound of the scope of a length of 300nm～500nm of maximum wave of the scope of a length of 250nm～400nm of the maximum wave of the absorption spectrum recorded in oxolane and emission spectrum, it is possible to be not particularly limited to use.As concrete example, anthracene compound class, coumarin compound class, carbazole compound class, benzoxazole compound class, naphthalene compound class, stilbene compounds, benzidine compound class, diazole compounds class, pyrene compound class, perylene compounds, naphthalimide compounds class, benzotriazole cpd class etc. can be enumerated.

Wherein, from the aspect of light shielding part curable, preferably anthracene compound class, carbazole compound class, benzoxazole compound class, diazole compounds class.

It addition, the compound of the scope of a length of 330nm～480nm of maximum wave of the scope of a length of 250nm～390nm of maximum wave of absorption spectrum that more preferably records in oxolane of the organic compound (A) absorbing ultraviolet and luminescence and emission spectrum.

This is because, if within the above range, then solidfied material absorbs exterior light and colours, and the probability that the tone of the ink after solidification changes is little, and curable is the most excellent.Further, by making emission spectrum within the above range, it is difficult to depending on recognizing luminescence, it is possible to act on the Photoepolymerizationinitiater initiater that absorbing wavelength is 350nm～400nm that solidification is excellent, thus preferably.

In the mensuration of above-mentioned absorption spectrum and emission spectrum, such as, preparation absorbs the tetrahydrofuran solution (concentration 0.002wt%) of the organic compound (A) of ultraviolet and luminescence, the spectrophotometer " UV-3150 " that (strain) Shimadzu Seisakusho Ltd. can be utilized to manufacture measures absorption spectrum, it is possible to use the fluorophotometer " F-7000 " that HitachiHigh-Technologies society manufactures measures emission spectrum.

By making light solidification pigmentation composition contain this absorption ultraviolet and the organic compound (A) of luminescence, it is possible to achieve excellent curable.

Additionally, in the present application, absorb ultraviolet and the organic compound (A) of luminescence preferably mixes in light solidification pigmentation composition and exists.Existing by mixing, compositions becomes uniform, it is thus possible to make it solidify equably.Then, in order to make to mix easily, ultraviolet is absorbed and organic compound (A) the preferably fusing point of luminescence is 0 DEG C～500 DEG C, more preferably 25 DEG C～400 DEG C, particularly preferably 25 DEG C～300 DEG C.Further, from this aspect, preferably obtained light solidification pigmentation composition is the state of mixing (can make organic compound (A) dissolving of absorption ultraviolet and luminescence) room temperature (25 DEG C)～80 DEG C.

The organic compound (A) absorbing ultraviolet and luminescence can be at the material absorbing ultraviolet and decompose after luminescence.By decomposing and the afunction of luminescence, the tone variations of the printed article that exterior light causes disappears, thus preferably.

These organic compound (A) absorbing ultraviolet and luminescence can use a kind or two or more are used in mixed way with arbitrary ratio.Absorb the organic compound (A) of ultraviolet and the luminescence part by weight in the light solidification pigmentation composition of the present invention to be usually 0.001 weight %～5 weight %, be preferably 0.001 weight %～1 weight %.

Below, the preferred skeleton of anthracene compound class, coumarin compound class, carbazole compound class, benzoxazole compound class, stilbene compounds, diazole compounds class, benzidine compound class is exemplified.

As anthracene compound class, it may be preferred to use the compound with following skeleton.It should be noted that in structural formula, * symbol represents and being bonded of each main framing.

(in formula, R₁Representing hydrogen atom, phenyl, phenylmethylene, phenyl-ethylene, phenylpropylene independently of one another, X represents hydrogen atom or halogen atom independently of one another, and n represents the integer of 1～4.)

Phenyl can illustrate following structure specifically, and phenylmethylene, phenyl-ethylene, phenylpropylene can enumerate the group on phenyl ring without substituent group or the group of alkyl alternatively base with carbon number 1～3 specifically.

Phenyl:

(in formula, R₁₁Representing hydrogen atom or the alkyl that carbon number is 1～3 independently of one another, k1 represents the integer of 1～5.)

Herein, R₁Representing and be preferably phenyl, X is preferably hydrogen atom.

As coumarin compound class, it may be preferred to use the compound with following skeleton.It should be noted that in structural formula, * symbol represents and being bonded of each main framing.

(in formula, R₂Represent alkyl, benzimidazolyl or benzothiazolyl, R that hydrogen atom, carbon number are 1～3 independently of one another₃Representing hydrogen atom or the alkyl that carbon number is 1～3, k represents the integer of 1～2.)

Benzimidazolyl, benzothiazolyl can have substituent group, can illustrate following structure specifically.

Benzimidazolyl:

(in formula, R₂₁Representing hydrogen atom or the alkyl that carbon number is 1～3 independently of one another, q1 represents the integer of 1～4.)

Benzothiazolyl:

(in formula, R₂₂Representing hydrogen atom or the alkyl that carbon number is 1～3 independently of one another, q2 represents the integer of 1～4.)

Herein, R₂、R₃Preferably carbon number is the alkyl of 1～3.

As carbazole compound class, it may be preferred to use the compound with following skeleton.It should be noted that in structural formula, * symbol represents and being bonded of each main framing.

(in formula, R₄Represent alkoxyl, phenyl, xenyl, biphenyl diyl or following formula (4) that carbon number is 1～3

The group represented, R₅Represent hydrogen atom or the alkyl that carbon number is 1～3 independently of one another.L represents the integer of 1～3.)

Phenyl, xenyl, biphenyl diyl can have substituent group, can illustrate following structure specifically.

Phenyl:

(in formula, R₄₁Representing hydrogen atom or the alkyl that carbon number is 1～3 independently of one another, k1 represents the integer of 1～5.)

Xenyl:

(in formula, R₄₂Representing hydrogen atom or the alkyl that carbon number is 1～3 independently of one another, k2 represents the integer of 1～4.)

Biphenyl diyl:

(in formula, R₄₃Representing hydrogen atom or the alkyl that carbon number is 1～3 independently of one another, k3 represents the integer of 1～4.)

Above-mentioned carbazoles is excellent due to the curable of light shielding part, therefore can be preferably used.

Herein, R₄It is preferably biphenyl diyl, R₅It is preferably hydrogen atom.

It should be noted that the observability of carbazole compound class is high, it is seen that weak or visible ray the extinction of the luminescence of light is weak, thus may insure that the high transparency when depending on recognizing solidfied material, thus can be preferably used.

As benzoxazole compound class, it may be preferred to use the compound with following skeleton.It should be noted that in structural formula, * symbol represents and being bonded of each main framing.

(in formula, R₆Represent hydrogen atom or the alkyl that carbon number is 1～6, R independently of one another₇Represent alkylidene or following formula (6) that carbon number is 1～3

P represents the integer of 1～4.)

Herein, R₆Preferably carbon number is the alkyl of 1～6, particularly preferably has the alkyl of the side chain that carbon number is 4～6.

It addition, R₇It is preferably above-mentioned formula (6).

Herein, as stilbene compounds, it may be preferred to use the compound with following skeleton.

(in formula, R₈Representing hydrogen atom or the alkyl that carbon number is 1～3 independently of one another, r represents the integer of 1～5.)

Herein, R₈It is preferably hydrogen atom.

It should be noted that the observability of stilbene compounds is high, it is seen that weak or visible ray the extinction of the luminescence of light is weak, thus may insure that high transparent when depending on recognizing solidfied material, thus can be preferably used.

As benzidine compound class, it may be preferred to use the compound with following skeleton.It should be noted that in structural formula, * symbol represents and being bonded of each main framing.

(in formula, R₉Represent hydrogen atom, phenyl or naphthyl, R independently of one another₁₀Representing hydrogen atom or the alkyl that carbon number is 1～3 independently of one another, s represents the integer of 1～4.)

Phenyl, naphthyl can illustrate following structure specifically.

Phenyl:

(in formula, R₁₀₁Representing hydrogen atom or the alkyl that carbon number is 1～6, k1 represents the integer of 1～5.)

Naphthyl:

(in formula, R₁₀₂Representing hydrogen atom or the alkyl that carbon number is 1～3, k4 represents the integer of 1～3.)

Herein, R₉It is preferably phenyl or naphthyl, particularly preferred molecule together has phenyl and naphthyl.

It should be noted that the observability of benzidine compound class is high, it is seen that weak or visible ray the extinction of the luminescence of light is weak, thus may insure that the high transparency when depending on recognizing solidfied material, thus can be preferably used.

As diazole compounds class, it may be preferred to use the compound with following skeleton.

(in formula, R₂₀₁Representing the alkyl that carbon number is 1～4, W represents Direct Bonding or following formula (10)

The linking group represented, Y represents carbon atom or nitrogen-atoms, and Z represents phenylene, bipyridyl residue or fluorenes residue.T3, t4 represent the integer of 0～2, are 0 when t3 with t4 is different.It should be noted that, * linking portion is represented, linking portion in formula (9) and the carbon atom bonding of diazole skeleton, the linking portion left end in formula (10) is bonded with diazole skeleton, and the linking portion right-hand member in formula (10) is combined with benzene skeleton or pyridine skeleton.)

Herein, phenylene, bipyridyl residue, fluorenes residue are the most as follows.

Phenylene:

(in formula, R₂₀₂Representing hydrogen atom or the alkyl that carbon number is 1～3 independently of one another, k5 represents the integer of 1～4.)

Herein, R₂₀₂It is preferably hydrogen atom.

Bipyridyl residue:

(in formula, R₂₀₃Representing hydrogen atom or the alkyl that carbon number is 1～3 independently of one another, k6 represents the integer of 1～3.)

Herein, R₂₀₃It is preferably hydrogen atom.

Fluorenes residue:

(in formula, R₂₀₄Representing hydrogen atom or the alkyl that carbon number is 1～3 independently of one another, k7 represents the integer of 1～3.)

Herein, R₂₀₄It is preferably hydrogen atom.

In the compound that above-mentioned formula (9) represents, when the linking group of the above-mentioned formula (10) that W is Direct Bonding or Z is phenylene, fusing point can be reduced, from the linking group of the above-mentioned formula (10) that the preferred W of this respect is Direct Bonding or Z is phenylene.

It addition, in t3 and t4, preferably t3 Yu t4 adds up to 2, and particularly preferred t3 and t4 is 1.About Y, preferably carbon atom.

As R₂₀₁, as the alkyl that carbon number is 1～4, methyl, ethyl, propyl group, isopropyl, the tert-butyl group can be enumerated specifically, preferably there is the alkyl of side chain, the particularly preferred tert-butyl group.

It addition, in the case of having the linking group that above-mentioned formula (10) represents, any one in preferably t3 or t4 is 2, another one is the compound of 0.

Wherein it is possible to particularly preferably use the compound that following formula (11) represents.

It should be noted that weak or visible ray the extinction of the luminescence of the visible ray of diazole compounds class is weak, thus when depending on recognizing solidfied material, may insure that the high transparency, thus can be preferably used.

It addition, the light solidification pigmentation composition of the present invention contains photopolymerizable compound (B).

As photopolymerizable compound (B), as long as by the compound of polymerizable ultraviolet, it is possible to it is not particularly limited to use, (methyl) acrylate compounds, epoxide, oxetane compound etc. can be enumerated such as.

The light solidification pigmentation composition of the present invention can use (methyl) acrylate compounds (B-1) as photopolymerizable compound (B).

As (methyl) acrylate compounds (B-1) of the light solidification pigmentation composition that can act as the present invention, such as carbamate (methyl) acrylate oligomer can be enumerated, there is (methyl) acrylate oligomer (B-1-1) of polyisoprene, polybutadiene skeleton.They can use one or more.

Herein, the light solidification pigmentation composition of the present invention is by using these photopolymerizable compound as photopolymerizable compound, and the flexibility that can obtain solidfied material is excellent, for the good light solidification pigmentation composition of the adaptation of base material, thus preferably.

As carbamate (methyl) acrylate contained in the compositions of the present invention, it is not particularly limited, carbamate (methyl) acrylate obtained by making (methyl) acrylate these three composition of polyhydric alcohol, organic multiple isocyanate and hydroxyl react can be illustrated；And by making (methyl) acrylate both compositions of organic multiple isocyanate and hydroxyl react and carbamate (methyl) acrylate etc. that obtains.

As polyhydric alcohol, such as neopentyl glycol, 3-methyl isophthalic acid can be enumerated, 5-pentanediol, ethylene glycol, propylene glycol, BDO, 1, the alkylene glycol that carbon number is 1～10 such as 6-hexanediol；The triol such as trimethylolpropane, tetramethylolmethane；Tricyclodecane Dimethanol, double [hydroxymethyl]-hexamethylene etc. have the alcohol etc. of cyclic skeleton；The PEPA obtained by the reaction of these polyhydric alcohol Yu polyprotic acid (such as, succinic acid, phthalic acid, hexahydrophthalic anhydride, p-phthalic acid, adipic acid, Azelaic Acid, tetrabydrophthalic anhydride etc.)；The caprolactone alcohol obtained by the reaction of polyhydric alcohol Yu 6-caprolactone；Polycarbonate polyol (PCDL etc. such as obtained by the reaction of 1,6-HD Yu diphenyl carbonate) or polyether polyol (such as Polyethylene Glycol, polypropylene glycol, polytetramethylene glycol, ethylene-oxide-modified bisphenol-A etc.) etc..Wherein, from giving and the adaptation of base material, the aspect of flexibility, particularly preferred molecular weight is the polypropylene glycol of more than 2000.

As organic multiple isocyanate, such as isophorone diisocyanate, hexamethylene diisocyanate, toluene di-isocyanate(TDI), XDI, diphenyl methane-4,4 '-diisocyanate or bicyclopentyl isocyanates etc. can be enumerated.

Additionally, (methyl) acrylate as hydroxyl, it is possible to use such as (methyl) the dihydroxypropyl C2 such as (methyl) 2-(Acryloyloxy)ethanol, (methyl) Hydroxypropyl acrylate, (methyl) hy-droxybutyl～C4 Arrcostab, dihydroxymethyl cyclohexyl list (methyl) acrylate, hydroxyl caprolactone (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, dipentaerythritol five (methyl) acrylate etc..

The reaction of carbamate (methyl) acrylate obtained by making (methyl) acrylate these three composition of polyhydric alcohol, organic multiple isocyanate and hydroxyl react such as is carried out as follows.I.e., organic multiple isocyanate is mixed in polyhydric alcohol, hydroxyl 1 equivalent relative to polyhydric alcohol, the NCO of mixed organic multiple isocyanate is preferably 1.1 equivalents～2.0 equivalents, more preferably 1.1 equivalents～1.5 equivalents, preferably make reaction temperature be 70 DEG C～90 DEG C to react, synthesis of carbamates oligomer.Next, NCO 1 equivalent relative to oligourethane, hydroxyl (methyl) acrylate compounds is mixed in the way of the hydroxyl of hydroxyl (methyl) acrylate compounds is preferably 1 equivalent～1.5 equivalents, make it in 70 DEG C～90 DEG C reactions, desired carbamate (methyl) acrylate can be obtained.

The reaction of carbamate (methyl) acrylate obtained by making (methyl) acrylate both compositions of organic multiple isocyanate and hydroxyl react such as is carried out as follows.I.e., NCO 1 equivalent relative to organic multiple isocyanate, (methyl) acrylate of hydroxyl is mixed in the way of the hydroxyl of (methyl) acrylate of hydroxyl is preferably 1 equivalent～1.5 equivalents, make it in 70 DEG C～90 DEG C reactions, desired carbamate (methyl) acrylate can be obtained.

As the weight average molecular weight of carbamate (methyl) acrylate, preferably 1000～about 25000, more preferably 4000～20000.If weight average molecular weight is less than 1000, then shrinks and become big, if weight average molecular weight is more than 25000, then lack curable.

In the light solidification pigmentation composition of the present invention, these carbamates (methyl) acrylate can use a kind or two or more is used in mixed way with arbitrary ratio.Carbamate (methyl) acrylate part by weight in the light solidification pigmentation composition of the present invention is usually 0 weight %～90 weight %, is preferably 1 weight %～80 weight %, more preferably 1 weight %～70 weight %.

As (methyl) acrylate oligomer with polyisoprene, polybutadiene skeleton contained in the light solidification pigmentation composition of the present invention, as long as known material, it is possible to it is not particularly limited to use.

As above-mentioned (methyl) acrylate oligomer with polyisoprene, polybutadiene skeleton, preferably can use following oligomer: (a) first synthesizes isoprene copolymer, butadiene polymer or their copolymer, then make these polymer and unsaturated acids anhydride reactant, make thereafter part or all of oligomer reacting with hydroxyl (methyl) acrylate compounds and obtaining in obtained polymer；Or (b) makes the oligomer that C-terminal isoprene copolymer, C-terminal butadiene polymer or their copolymer react with unsaturated carboxylic acid or derivatives thereof and obtain.

First, to (a) oligomer, i.e., first isoprene copolymer, butadiene polymer or their copolymer are synthesized, then making these polymer and unsaturated acids anhydride reactant, the oligomer making thereafter part or all in obtained polymer react and obtain with hydroxyl (methyl) acrylate compounds illustrates.

As above-mentioned isoprene copolymer, butadiene polymer, the isoprene copolymer or butadiene polymer obtained by a kind of homopolymerization by isoprene or butadiene can be used, it is possible to use the isoprene-butadiene copolymer obtained by the mixture copolymerization by isoprene and butadiene.

As the method for polymerization, isoprene and/or butadiene can be made to carry out anionic polymerisation and obtain using lithium alkylide, sodium naphthalene complex such as lithium methide, ethyl-lithium, s-butyl lithium, n-BuLi, amyl group lithiums as initiator；Can also be by the azo dinitrile compounds such as peroxide, azodiisobutyronitrile such as benzoyl peroxide be carried out the incompatible manufacture of radical polymerization as initiator.

It should be noted that these polyreactions can be carried out in-100 DEG C～200 DEG C reactions in the presence of hexane, heptane, toluene, dimethylbenzene equal solvent for 0.5 hour～100 hours.

Then, polymer and the unsaturated acids anhydride reactant utilizing said method to obtain is made.This reaction such as can be carried out as follows: at hexane, heptane, toluene, dimethylbenzene equal solvent etc. to reaction in the presence of inert solvent or under condition of no solvent, makes above-mentioned polymer and unsaturated acid anhydride generally react 0.5 hour～100 hours room temperature～300 DEG C.

As anhydride, it is possible to use such as maleic anhydride, phthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride etc..

Relative to polymer 100 weight portion, the consumption of anhydride is preferably generally in the range of 0.1 weight portion～the scope of 200 weight portions, more preferably 0.1 weight portion～100 weight portions.

About anhydride group and the addition caused by the reaction of above-mentioned polymer, by reacting under these conditions, generally, the adduct number of every 1 molecule is 1～the scope of 30, preferably 2～the scope of 20.

Then, part or all making the anhydride group in the above-mentioned polymer of importing is reacted with hydroxyl (methyl) acrylate compounds, such that it is able to obtain having (methyl) acrylate oligomer of polyisoprene skeleton, have (methyl) acrylate oligomer of polybutadiene skeleton.

In reaction, under hexane, heptane equal solvent or condition of no solvent, generally it is preferably the mode of 1 equivalent～1.5 equivalents according to the hydroxyl of hydroxyl (methyl) acrylate compounds and mixes hydroxyl (methyl) acrylate compounds, it is made to react 0.1 hour～100 hours in 20 DEG C～200 DEG C, such that it is able to obtain having (methyl) acrylate oligomer of polyisoprene skeleton, have (methyl) acrylate oligomer of polybutadiene skeleton.

As hydroxyl (methyl) acrylate compounds, it is possible to use such as (methyl) the dihydroxypropyl C2 such as (methyl) 2-(Acryloyloxy)ethanol, (methyl) Hydroxypropyl acrylate, (methyl) hy-droxybutyl～C4 Arrcostab, dihydroxymethyl cyclohexyl list (methyl) acrylate, hydroxyl caprolactone (methyl) acrylate etc..

Then, to obtaining (b) oligomer, i.e. make the method for the oligomer that the isoprene copolymer containing hydroxyl, butadiene polymer or their copolymer react with unsaturated carboxylic acid or derivatives thereof and obtain illustrate.

By make C-terminal isoprene copolymer, C-terminal butadiene polymer part or all react with unsaturated carboxylic acid or derivatives thereof, can obtain there is (methyl) acrylate oligomer of polyisoprene skeleton, there is (methyl) acrylate oligomer of polybutadiene skeleton.

In reaction, under hexane, heptane equal solvent or condition of no solvent, unsaturated carboxylic acid or derivatives thereof is generally made to react 0.1 hour～100 hours at 20 DEG C～200 DEG C, such that it is able to obtain.

As unsaturated carboxylic acid or derivatives thereof, it is possible to use the derivant such as unsaturated carboxylic acid and their etheride, amide, acid imide, anhydride, ester such as such as acrylic acid, methacrylic acid, maleic acid, α-ethylacrylate, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, methyl tetrahydrophthalic acid.

As the concrete example of so obtained compound, can illustrate that KURARAY society manufactures the UC-203 carboxylate oligomer of 2-hydroxyethyl methacry-late (maleic anhydride adduct of isoprene copolymer with), NISSO-PBTE-2000 that Cao Da society of Japan manufactures (two terminal methacrylate modified butadiene system oligomer) etc..

In the light solidification pigmentation composition of the present invention, these have polyisoprene, (methyl) acrylate oligomer of polybutadiene skeleton can use a kind or two or more is used in mixed way with arbitrary ratio.Have polyisoprene, (methyl) acrylate oligomer part by weight in the light solidification pigmentation composition of the present invention of polybutadiene skeleton is usually 0 weight %～90 weight %, be preferably 1 weight %～50 weight %, more preferably 1 weight %～20 weight %.

The light solidification pigmentation composition of the present invention can use (methyl) acrylate monomer (B-1-2) as (methyl) acrylate compounds (B-1).

nullAs (methyl) acrylate monomer (B-1-2) contained in the light solidification pigmentation composition of the present invention，It is not particularly limited，Such as (methyl) Isooctyl acrylate monomer can be enumerated、(methyl) isoamyl acrylate、(methyl) lauryl acrylate、(methyl) isodecyl acrylate、(methyl) stearyl acrylate ester、(methyl) aliphatic acrylate、(methyl) acrylic acid different myristyl ester、The Arrcostab of (methyl) the acrylic acid carbon numbers 5～20 such as (methyl) tridecyl acrylate、(methyl) benzyl acrylate、(methyl) acrylic acid tetrahydro furfuryl ester、Acryloyl morpholine、(methyl) phenylethyl ethylene oxidic ester、Tristane (methyl) acrylate、Acrylic acid dicyclopentenyloxyethyl methacrylate、Dicyclo amylene epoxide ethyl (methyl) acrylate、(methyl) isobornyl acrylate、(methyl) acrylic acid dicyclopentenyloxyethyl methacrylate、Acrylic acid-1-adamantane esters、Acrylic acid-2-methyl-2-adamantane esters、Acrylic acid-2-ethyl-2-adamantane esters、Methacrylic acid-1-adamantane esters、Polypropylene oxide (methyl) nonylphenol acrylate phenyl ester、Dicyclopentadiene epoxide ethyl (methyl) acrylate etc. has (methyl) acrylate of cyclic skeleton；(methyl) 2-hydroxypropyl acrylate, (methyl) acrylic acid-4-hydroxy butyl ester etc. have the alkyl that carbon number is 1～5 (methyl) acrylate of hydroxyl；Ployalkylene glycol (methyl) acrylate such as ethoxydiglycol (methyl) acrylate, polypropylene glycol (methyl) acrylate, polypropylene oxide (methyl) nonylphenol acrylate phenyl ester；Ethylene oxide denatured phenoxylation phosphoric acid (methyl) acrylate, ethylene oxide denatured butoxylated phosphoric acid (methyl) acrylate and ethylene oxide denatured octyloxy phosphoric acid (methyl) acrylate, tristane dihydroxymethyl two (methyl) acrylate, dioxane glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, polytetramethylene glycol two (methyl) acrylate, alkylene oxide modified bisphenol A type two (methyl) acrylate, caprolactone modification 3-hydroxypivalic acid neopentyl glycol two (methyl) acrylate and ethylene oxide denatured di(2-ethylhexyl)phosphate (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, trihydroxy methyl C2～C10 alkane three (methyl) acrylate such as trihydroxy methyl octane three (methyl) acrylate；Trimethylolpropane polyethoxy three (methyl) acrylate, the poly-propoxyl group of trimethylolpropane three (methyl) acrylate, trihydroxy methyl C2～the poly-alkoxyl of C10 alkane three (methyl) acrylate such as the poly-propoxyl group of trimethylolpropane polyethoxy three (methyl) acrylate, three [(methyl) acryloyl-oxyethyl] isocyanuric acid ester, tetramethylolmethane three (methyl) acrylate, ethylene-oxide-modified trimethylolpropane tris (methyl) acrylate, alkylene oxide modification trimethylolpropane tris (methyl) acrylate such as epoxy pronane modification trimethylolpropane tris (methyl) acrylate；Tetramethylolmethane polyethoxy four (methyl) acrylate, the poly-propoxyl group of tetramethylolmethane four (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, double trimethylolpropane four (methyl) acrylate, dipentaerythritol four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate etc..

From (methyl) acrylate compounds that the aspect of curable, preferably (methyl) acryloyl group are more than 2.

In the range of the characteristic not damaging the present invention, epoxy (methyl) acrylate can be used in the light solidification pigmentation composition of the present invention.Epoxy (methyl) acrylate has the function that curable improves and makes the hardness of solidfied material, curing rate improve.nullAdditionally，As epoxy (methyl) acrylate，As long as the material making glycidyl ether type epoxide and (methyl) acrylic acid react and obtain can use，As for obtaining the glycidyl ether type epoxide of epoxy (methyl) acrylate being preferably used，Bisphenol-A or the diglycidyl ether of its alkylene oxide addition product can be enumerated、Bisphenol F or the diglycidyl ether of its alkylene oxide addition product、Hydrogenated bisphenol A or the diglycidyl ether of its alkylene oxide addition product、A Hydrogenated Bisphenol A F or the diglycidyl ether of its alkylene oxide addition product、Ethylene glycol diglycidyl base ether、Propylene glycol diglycidyl ether、Neopentyl glycol diglycidyl ether、Butanediol diglycidyl ether、Hexanediol diglycidyl ether、Cyclohexanedimethanol diglycidyl ether、Polypropylene glycol diglycidyl ether etc..

Epoxy (methyl) acrylate obtains by making these glycidyl ether type epoxides react under conditions of following with (methyl) acrylic acid.

Relative to epoxy radicals 1 equivalent of glycidyl ether type epoxide, (methyl) acrylic acid is made to react with the ratio of 0.9 mole～1.5 moles, more preferably 0.95 mole～1.1 moles.Reaction temperature is preferably 80 DEG C～120 DEG C, and the response time is 10 hours～about 35 hours.In order to promote reaction, the catalyst such as such as triphenylphosphine, TAP, triethanolamine, tetraethylammonium chloride is preferably used.It addition, in order to prevent polymerization in Fan Ying, it is possible to use such as p methoxy phenol, methylnaphthohydroquinone etc. are as polymerization inhibitor.

Epoxy (methyl) acrylate can being preferably used in the present invention is bisphenol type epoxy (methyl) acrylate obtained by the epoxide of bisphenol A-type.In the present invention, as the weight average molecular weight of epoxy (methyl) acrylate, preferably 500～10000.

In the light solidification pigmentation composition of the present invention, (methyl) acrylate compounds can use a kind or two or more is used in mixed way with arbitrary ratio.

It addition, as photopolymerizable compound, it is possible to use epoxide (B-2).

As the concrete example of epoxide, the condensation polymer of bisphenols (bisphenol-A, Bisphenol F, bisphenol S, xenol, bisphenol-A D etc.) or phenol (phenol, alkyl substituted phenol, aromatic series fortified phenol, naphthols, alkyl-substituted naphthaline phenol, dihydroxy benzenes, alkyl replace dihydroxy benzenes, dihydroxy naphthlene etc.) and various aldehyde (formaldehyde, acetaldehyde, alkyl aldehydes, benzaldehyde, alkyl substituted benzene formaldehyde, hydroxy benzaldehyde, naphthaldehyde, glutaraldehyde, o-phthalaldehyde(OPA), crotonic aldehyde, cinnamic aldehyde etc.) can be enumerated；Above-mentioned phenol and the polymer of various diolefin compounds (dicyclopentadiene, terpenes, VCH, norbornadiene, vinyl norbornene, tetrahydroindene, divinylbenzene, divinyl biphenyls, diisopropenyl biphenyl, butadiene, isoprene etc.)；Above-mentioned phenol and the condensation polymer of ketone (acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), 1-Phenylethanone., benzophenone etc.)；Above-mentioned phenol and the condensation polymer of aromatic series diformazan alcohols (benzene dimethanol, biphenyl dimethanol etc.)；The condensation polymer of above-mentioned phenol and aromatic series dichloromethane base class (α, α '-xylene dichloride, dichloride methyl biphenyl etc.)；Above-mentioned phenol and the condensation polymer of aromatic series bis-alkoxy methyl class (bi-methoxy methylbenzene, bi-methoxy methyl biphenyl, double phenoxymethyl biphenyl etc.)；Glycidyl ether system epoxy resin that the Glycidyl such as the condensation polymer of above-mentioned bisphenols and various aldehyde or alcohols are obtained, alicyclic epoxy resin, glycidyl group amine system epoxy resin, glycidyl esters system epoxy resin etc., as long as normally used epoxy resin, it is not limited to these.They can be used alone, it is possible to use two or more.

In the light solidification pigmentation composition of the present invention, these epoxides can use a kind or two or more are used in mixed way with arbitrary ratio.Epoxide part by weight in the light solidification pigmentation composition of the present invention is usually 5 weight %～70 weight %, is preferably 5 weight %～50 weight %.

Further, it is possible to use oxetane compound (B-3) is as photopolymerizable compound.

Concrete example as oxetane compound, can enumerate such as, double [(3-ethyl-3-oxetanylmethoxy) methyl] benzene of 4-, double [(3-methyl-3-oxetanylmethoxy) methyl] benzene of 4-, 3-methyl-3-glycidyl oxetanes, 3-ethyl-3-hydroxymethyl oxetane, 3-methyl-3-hydroxymethyl oxetane, two (1-ethyl (3-oxetanyl)) methyl ether, 3-ethyl-3-(phenoxymethyl) oxetanes, 3-(cyclohexyloxy) methyl-3-Ethyloxetane, xylylene dioxygen azetidine, line style phenolic aldehyde oxetanes etc., as long as normally used oxetane compound, it is not limited to these.They can be used alone, it is possible to use two or more.

In the light solidification pigmentation composition of the present invention, these oxetane compounds can use a kind or two or more are used in mixed way with arbitrary ratio.Oxetane compound part by weight in the light solidification pigmentation composition of the present invention is usually 5 weight %～70 weight %, is preferably 5 weight %～50 weight %.

Further, it is possible to use vinyl ether compound (B-4) is as photopolymerizable compound.

As the concrete example of vinyl ether compound, divinyl ether compounds or the trivinyl ether compounds such as such as ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethyleneglycol divinylether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, butanediol divinyl ether, hexanediol divinyl ether, cyclohexanedimethanol divinyl base ether, trimethylolpropane tris vinyl ethers can be enumerated；Ethyl vinyl ether, n-butyl vinyl ether, IVE, octadecyl vinyl ether, cyclohexyl vinyl ether, hydroxy butyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexane dimethanol monovinyl ether, n-propyl vinyl ether, isopropyl-ethylene base ether, isopropenyl ethers-o-propylene carbonate, dodecyl vinyl, diethylene glycol monovinyl base ether, octadecyl vinyl ether etc., as long as normally used vinyl ether compound, it is not limited to these.They can be used alone, it is possible to use two or more.

In the light solidification pigmentation composition of the present invention, these vinyl ether compounds can use a kind or two or more are used in mixed way with arbitrary ratio.Vinyl ether compound part by weight in the light solidification pigmentation composition of the present invention is usually 5 weight %～70 weight %, is preferably 5 weight %～50 weight %.

The light solidification pigmentation composition of the present invention contains Photoepolymerizationinitiater initiater (C).

As the Photoepolymerizationinitiater initiater (C) contained in the compositions of the present invention, it is not particularly limited, as radical polymerization initiator, such as 1-hydroxycyclohexylphenylketone (Irgacure184 can be enumerated；BASF society manufacture), 2-hydroxy-2-methyl-[4-(1-methyl ethylene) phenyl] propanol oligomer (エ サ キ ュ ア ONE；ラ Application バ Le テ ィ manufacture), 1-[4-(2-hydroxyl-oxethyl)-phenyl]-2-hydroxy-2-methyl-1-propane-1-ketone (Irgacure2959；BASF society manufacture), 2-hydroxyl-1-{4-[4-(2-hydroxy-2-methyl-propiono)-benzyl]-phenyl-2-methyl-propan-1-ketone (Irgacure127；BASF manufacture), 2,2-dimethoxy-2-phenyl acetophenone (Irgacure651；BASF society manufacture), 2-hydroxy-2-methyl-1-phenyl-propan-1-ketone (Darocure1173；BASF society manufacture), 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholino propane-1-ketone (Irgacure907；BASF society manufactures), epoxide-phenyl-acetic acid 2-[2-oxo-2-phenyl-acetoxy-ethyoxyl]-ethyl ester and epoxide-phenyl-acetic acid 2-[2-Hydroxy-ethoxy]-ethyl ester mixture (Irgacure754；BASF society manufacture), 2-benzyl-2-dimethylamino-1-(4-morphlinophenyl)-butane-1-ketone (Irgacure369；BASF society manufacture), CTX, 2; 4-dimethyl thioxanthone, 2; 4-diisopropylthioxanthone, isopropyl thioxanthone, 2; 4; 6-trimethyl benzoyl diphenyl base phosphine oxide, double (2; 4; 6-trimethylbenzoyl)-phenyl phosphine oxide, double (2,6-Dimethoxybenzoyl)-2,4; 4-trimethylpentylphosphine oxide, 1; 2-acetyl caproyl, 1-[4-(thiophenyl)-, 2-(O-benzoyl oximes)], ethyl ketone; 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base]-, 1-(O-acetyl group oxime) etc..As cation system polymerization initiator, the most double (4-tert-butyl-phenyl) iodine hexafluorophosphate can be enumerated, double (4-tert-butyl-phenyl) iodine fluoroform sulphonate, 2-(3, 4-dimethoxy-styryl)-4, double (trichloromethyl)-1 of 6-, 3, 5-triazine, diphenyl iodine hexafluoro arsenate, diphenyliodonium triflate, 2-[2-(furan-2-base) vinyl]-4, double (trichloromethyl)-1 of 6-, 3, 5-triazine, triphenylsulfonium tetrafluoroborate, three p-methylphenyl sulfonium hexafluorophosphates, three p-methylphenyl sulfonium fluoroform sulphonates, 4-isopropyl-4'-methyldiphenyl base iodine four (pentafluorophenyl group) borate etc..It addition, the Photoepolymerizationinitiater initiater contained in the compositions of the present invention (C) preferably has absorption at absorption ultraviolet under the wavelength of the light that the organic compound (A) of luminescence is sent.

From the aspect of curable, preferably TMDPO (SpeedcureTPO；LAMBSON society manufacture), double (2,4,6-trimethylbenzoyl) phenyl phosphine oxide (Irgacure819；BASF manufacture), 1; 2-acetyl caproyl, 1-[4-(thiophenyl)-, 2-(O-benzoyl oximes)], ethyl ketone; 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base]-, 1-(O-acetyl group oxime).It addition, they can use one or more.

Herein, in above-mentioned Photoepolymerizationinitiater initiater, the specific absorbance of the Unit Weight at 365nm recorded in acetonitrile is preferably 85ml/ (g cm)～10000ml/ (g cm), more preferably 150ml/ (g cm)～10000ml/ (g cm), particularly preferably 400ml/ (g cm)～10000ml/ (g cm).It addition, the specific absorbance of the Unit Weight at the 405nm recorded in acetonitrile is preferably 5ml/ (g cm)～3000ml/ (g cm), particularly preferably 200ml/ (g cm)～3000ml/ (g cm).Further, extremely preferred the two condition is met.It is also preferable to the molar absorption coefficient at the 400nm recorded in acetonitrile is 200M^-1·cm^-1～100,000 M^-1·cm^-1Photoepolymerizationinitiater initiater.

If within the range, the Photoepolymerizationinitiater initiater that has absorption under the wavelength of light that sent at the compound absorbing ultraviolet and luminescence, then can promote the solidification of the ultraviolet-curing resin composition in the region that light is difficult to arrive further.This is because, the character of the ultraviolet generation diffraction of this long wavelength of 350nm～410nm is big.Thus, it is possible to roundabout entrance is by the inner side in the region (lightproof area) of colorant shading, even if in the case of there is the lightproof area hindering ultraviolet irradiation, by this roundabout entrance, the light of long wavelength can also arrive lightproof area.

Therefore, if the Photoepolymerizationinitiater initiater of above-mentioned scope, then the light that the organic compound (A) absorbing ultraviolet and luminescence is sent can be absorbed, the light being irradiated the also long wavelength of diffraction by ultraviolet is absorbed simultaneously, by its multiplier effect, the reaction of Photoepolymerizationinitiater initiater can be promoted, even if in the case of lightproof area is wide scope, it is possible to so that ultraviolet-curing resin composition fully solidifies.

In addition, if the very big wavelength of the absorption spectrum recorded in oxolane above-mentioned preferably in the range of absorb ultraviolet and the combination of the organic compound (A) of luminescence and the Photoepolymerizationinitiater initiater in the range of above-mentioned preferred specific absorbance, then can promote the solidification of lightproof area further, thus particularly preferably.

As meeting the Photoepolymerizationinitiater initiater of above-mentioned condition, BASF society can be enumerated and manufacture the SpeedcureTPO etc. that Irgacure819, LAMBSON society manufactures.

In the light solidification pigmentation composition of the present invention, these Photoepolymerizationinitiater initiaters can use a kind or two or more are used in mixed way with arbitrary ratio.Photoepolymerizationinitiater initiater part by weight in the light solidification pigmentation composition of the present invention is usually 0.01 weight %～15 weight %, is preferably 0.2 weight %～10 weight %.

Further, it is also possible to share the amine etc. that can become photopolymerization initiation auxiliary agent with above-mentioned Photoepolymerizationinitiater initiater.As spendable amine etc., benzoic acid-2-dimethylaminoethyl, dimethylamino 1-Phenylethanone., (dimethylamino)-ethyl benzoate or IADB etc. can be enumerated.In the case of using the photopolymerization such as this amine to cause auxiliary agent, the content in the light solidification pigmentation composition of the present invention is usually 0.005～5 weight %, is preferably 0.01～3 weight %.

The light solidification pigmentation composition of the present invention contains colorant (D).As colorant (D), it is possible to use dyestuff or pigment, from the aspect of the patience of printed article, it may be preferred to use pigment.As pigment, typically can use the pigment used in the ink composite printing purposes, coating applications, can select according to photism, sunproof necessary purposes.As pigment composition, it is possible to use the pigment of the netrual colours such as white carbon black, titanium dioxide, calcium carbonate or coloured organic pigment.

In colorant (D), to can being not particularly limited as the pigment that coloured organic pigment uses, following pigment can be enumerated.

Specifically can enumerate the azoic dyes insoluble azo dyess such as toluidine red, toluidines chestnut palm fibre, Hansa yellow, benzidine yellow, pyrazolone red；The solubility AZOpigments such as lithol red, HelioBordeaux, the most pink, permanent bordeaux 2B；Alizarin, indanthrene, thioindigo Li Zong etc. are from the derivant of dyestuff；The phthalocyanine such as phthalocyanine blue, phthalocyanine green system organic pigment；The organic pigment of the quinacridones such as quinacridone is red, quinacridone magenta；The perylene system organic pigments such as perylene is red, scarlet；The isoindolinone system organic pigments such as isoindolinone is yellow, isoindolinone orange；The pyranthrone system organic pigments such as pyranthrone is red, pyranthrone orange；Thioindigo system organic pigment；Condensation azo system organic pigment；Benzimidazolone system organic pigment；The isoindoline system organic pigments such as isoindoline is yellow；Naphthols system organic pigment；As the flavanthrone Huang of other pigment, amido yellow, nickel azo yellow, copper azomethine cyclic ketones yellow, purple orange, anthrone orange, the pigment such as DIANTHRAQUINONE base is red, diazine is purple.

About the coloured organic pigment that can use as the colorant (D) contained in the compositions of the present invention, if illustrating by color index (C.I.) value, such as, following pigment can be enumerated.

As yellow pigment, can enumerate:

C.I pigment yellow-1,3,12,13,14,17,20,24,42,74,81,83,86,87,93,95,109,110,117,120,125,128,129,137,138,139,147,148,150,151,153,154,155,166,180,185.

As magenta pigment, can enumerate:

C.I pigment orange-16,36,38,43,51,55,59,61

C.I paratonere-5,9,22,38,48:1,48:2,48:4,49:1,53:1,57:1,63:1,101,122,144,146,177,185,192,202,206,215,216,217,220,223,224,226,227,228,238,240,269

C.I pigment violet-19,23,29,30,37,40,50.

As aeruginous pigment, can enumerate:

C.I alizarol saphirol-15:1,15:3,15:4,15:6,18,22,60,27,29,64

C.I naphthol green-7,36

C.I Pigment white-6,18,21.

In addition, C.I pigment brown-23,25,26 etc. can be enumerated.

In colorant (D), to can being not particularly limited as the pigment that the organic pigment of netrual colour uses, following pigment can be enumerated.

As black pigment, white carbon black, nigrosine etc. can be enumerated.

nullAs ProductName，" the SpecialBlack350 that Degussa society manufactures can be enumerated、250、100、550、5、4、4A、6”、“PrintexU、V、140U、140V、95、90、85、80、75、55、45、40、P、60、L6、L、300、3、35、25、A、G”、" the REGAL400R that Cabot society manufactures、660R、330R、250R”、“MOGULE、L”、" the MA7 that society of Mitsubishi Chemical manufactures、8、11、77、100、100R、100S、220、230”“#2700、#2650、#2600、#200、#2350、#2300、#2200、#2000、#990、#980、#970、#960、#950、#900、#850、#750、#650、#52、#47、#45、#45L、#44、#40、#33、#332、#30、#25、#20、#10、#5、CF9、#95、#260 " etc..

As white pigment, titanium dioxide, calcium carbonate, barium sulfate, micropowder silicic acid, silica-based, calcium silicates, aluminium oxide, hydrated alumina, zinc oxide, Talcum, clay etc. can be enumerated.Preferably can enumerate titanium dioxide.

nullAs ProductName，Stone can be enumerated and originate in " the TaipakeCR-50 that industry society manufactures、50-2、57、80、90、93、95、953、97、60、60-2、63、67、58、58-2、85”、“TaipakeR-820、830、930、550、630、680、670、580、780、780-2、850、855”、“TaipakeA-100、220”、“TaipakeW-10”、“TaipakePF-740、744”、“TTO-55(A)、55(B)、55(C)、55(D)、55(S)、55(N)、51(A)、51(C)”、“TTOS-1、2”、“TTOM-1、2”、" the TITANIXJR-301 that TAYCA society manufactures、403、405、600A、605、600E、603、805、806、701、800、808”、“TITANIXJA-1、C、3、4、5”、" the Ti-PureR-900 that society of Du Pont manufactures、902、960、706、931 " etc..

As showing the pigment of metallic luster, metallic pigments can be contained.As metallic pigments, flakey aluminium powder, copper powders, nickel by powder, powder of stainless steel, coloring mica powder, micaceous iron oxide etc. can be enumerated.It addition, employ the metallic pigments of the long-chain fatty acid such as stearic acid, oleic acid when being additionally included in pulverizing as lubricant.

In above-mentioned pigment, quinacridone organic pigment, phthalocyanine system organic pigment, benzimidazolone system organic pigment, isoindolinone system organic pigment, condensation azo system organic pigment, quinophthalone system organic pigment, isoindoline system organic pigment etc. are preferred due to excellent in light-resistance.

Preferably, the measured value obtained based on laser light scattering, mean diameter is the micro pigment of 5nm～210nm to organic pigment.Such micro pigment can be by obtaining above-mentioned organic pigment miniaturization.In the case of the mean diameter of pigment is more than 5nm, it is possible to prevent because the diminish light resistance that causes of particle diameter reduces.On the other hand, by making mean diameter be below 210nm, easily maintain dispersity, the precipitation of pigment can be suppressed.

The miniaturization of organic pigment can utilize following method to carry out.That is, the mixture being made up of at least 3 kinds of compositions of organic pigment, water miscible inorganic salt and water miscible solvent is made claylike mixture, the most mixing with kneader etc., put into after miniaturization in water, make pulp-like with stirrings such as super mixers.It follows that filtration and the washing of slurry is repeated, remove water miscible inorganic salt and water miscible solvent.In miniaturization operation, resin, pigment dispersing agent etc. can be added.

As water miscible organic salt, sodium chloride, potassium chloride etc. can be enumerated.These inorganic salts can use in the scope of the 3 of organic pigment times weight～20 times of weight.

As water miscible solvent, 2-(methoxymethoxy) ethanol, butoxy ethanol, 2-(isoamoxy) ethanol, 2-(hexyloxy) ethanol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid macrogol, 1-methoxy-2-propanol, 1-ethyoxyl-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, DPE, molecular weight polypropylene glycol etc. can be enumerated.

In the present invention, in order to obtain sufficient concentration and sufficient light resistance, on the basis of the gross weight of light solidification pigmentation composition, the preferably scope in 0.1 weight %～30 weight % contains pigment.

In colorant (D), the dyestuff that can use is not particularly limited, following dyestuff can be enumerated.Specifically, it is possible to use the acid staiies such as the direct dyess such as azo based dye, thiazole based dye, anthraquinone based dye, piperazine based dye, phthalocyanine based dye, azo based dye, ton based dye, phthalocyanine based dye, quinoline based dye, azine based dye, indigo based dye；The basic stains such as azo based dye, ton based dye, azine based dye, acridine system dye, methine based dye, thiazole based dye, thiazine based dye, piperazine based dye, anthraquinone based dye, rhodamine based dye, triarylmethane based dye.Hereinafter, spendable dyestuff is illustrated by color index (C.I.) value.

As azo based dye, can enumerate such as:

C.I. direct Huang 2,33,34,35,39,50,69,70,71,86,93,94,95,98,102,109,129,136,141；

C.I. direct orange 41,46,56,61,64,70,96,97,106,107；

The reddest 79,82,83,84,97,98,99,106,107,172,173,176,177,179,181,182,204,207,211,213,218,221,222,232,233,243,246,250；

C.I. direct purple 47,52,54,60,65,66,79,80,81,82,84,89,90,93,95,96,103,104；

C.I. sun blue 51,57,71,81,84,85,90,93,94,95,98,100,101,113,149,150,153,160,162,163,164,166,167,170,172,188,192,193,194,196,198,200,207,209,210,212,213,214,222,228,229,237,238,242,243,244,245,247,248,250,251,252,256,257,259,260,268,274,275；

C.I. direct green 27,34,37,65,67,68,69,72,77,79,82 etc..As thiazole based dye, C.I. directly Huang 54 can be enumerated.

As piperazine based dye, C.I. sun blue 97,99,106,107,108,109,190,293 etc. can be enumerated.

As anthraquinone based dye, C.I. sun blue 77 can be enumerated.

As phthalocyanine based dye, C.I. sun blue 86,87,189,199 etc. can be enumerated.

As other direct dyes, C.I. directly Huang 38,43,47,58,68,108,138 can be enumerated；C.I. direct orange 34,39,50,52,57,65,68；The reddest 91,92,96,105,184,220,234,241；C.I. direct purple 59；C.I. sun blue 80,114,115,117,119,137,155,156,158,159,161,171,173；C.I. direct green 25,31,32,63,66 etc..

As azo based dye, can enumerate such as C.I. azogeramine, 3,4,6,8,11,12,14,18,26,27,33,37,53,57,88,106,108,111,114,131,137,138,151,154,158,159,173,184,186,215,257,266,296,337；

C.I. acid orange 7,10,12,19,20,22,28,30,52,56,74,127；

C.I. acid violet 11,56,58；

C.I. Indian yellow 1,17,18,23,25,36,38,42,44,54,59,72,78,151；

C.I. acid brown 2,4,13,248；

C.I. acid blue 92,102,113,117 etc..

As ton based dye, C.I. Xylene Red 50,51,52,87 etc. can be enumerated.

As phthalocyanine based dye, C.I. acid blue 249 can be enumerated.

As anthraquinone based dye, C.I. Xylene Red 82,92 can be enumerated；C.I. acid violet 41,42,43；C.I. Blue VRS 4,22,25,40,45,78,80,127:1,129,145,167,230；C.I. ACID GREEN 25,27 etc..

As quinoline based dye, C.I. quinoline yellow can be enumerated.

As azine based dye, C.I. acid blue 59,102 etc. can be enumerated.

As indigo based dye, C.I. Acid Blue 74 can be enumerated.

As other acid stain, C.I. acid violet 49 can be enumerated；C.I. acid brown 19；C.I. Acid Blue 7,9,74,112,126,167；C.I. acid green 9；C.I. Food Green 3 etc..

As azo based dye, can enumerate such as C.I. alkali red 1:1 7,22,23,25,29,30,38,39,46,46:1,82；C.I. alkaline orange 2,24,25；C.I. alkaline purple 18；C.I. basic yellow 15,24,25,32,36,41,73,80；C.I. bismarck brown 1；C.I. alkali blue 41,54,64,66,67,129 etc..

As ton based dye, can enumerate C.I. alkali red 1:1,2；C.I. alkaline purple 10,11 etc..

As azine based dye, C.I. alkali red 1:1 2,27 etc. can be enumerated.

As acridine system dye, C.I. Basic Orange 14 etc. can be enumerated.

As methine based dye, can enumerate C.I. Basic Red 13,14；C.I. alkaline orange 21；C.I. Basic Violet16,39；C.I. basic yellow 11,13,21,23,28 etc..

As thiazole based dye, C.I. basic yellow 1 can be enumerated.

As thiazine based dye, C.I. alkali blue 9 can be enumerated.

As piperazine based dye, C.I. alkali blue 3 can be enumerated.

As anthraquinone based dye, C.I. alkali blue 22,35,45,47 etc. can be enumerated.

As rhodamine based dye, C.I. alkaline purple 10 can be enumerated.

As triarylmethane based dye, can enumerate C.I. alkaline purple 1,2,3,4,13,14,23；C.I. alkali blue 1,5,7,8,11,15,18,21,24,26；C.I. Viride Nitens 1,4；Deng.

As other basic stain, C.I. basic yellow 2 can be enumerated；C.I. alkali blue 1,67 etc..

In order to improve the storage stability of dispersibility, resin combination, in the case of using colorant (particularly pigment), preferably add dispersant.nullAs dispersant，Carboxylate and the modifier thereof of hydroxyl can be used、Long-chain polyaminoamide and the salt of high-molecular weight ester、Salt (the ammonium salt of (high molecular) polybasic carboxylic acid、Alkylamine salt etc.)、Long-chain polyaminoamide phosphate、Long-chain polyaminoamide and the salt of polar acid ester、High molecular unsaturated acid ester、High molecular weight copolymer、Modified polyurethane、Modified polyacrylate、Polyether ester type anion system activating agent、Naphthalene sulfonic acid-formaldehyde condensation product salt、Aromatic sulphonic acid formaldehyde condensation products salt、Polyoxyethylene alkyl phosphate、Ethylene nonyl phenyl ether、Stearylamine acetas、The multi-carboxylates such as polyacrylate、Unsaturated polyester amide、Polysiloxanes、The oiliness dispersant such as the amide formed by the reaction of poly-(low alkyl group imines) and the polyester with free carboxy or its salt、(methyl) acrylic-styrene copolymer、(methyl) acrylic acid-(methyl) acrylate copolymer、Styrene-maleic acid copolymer、Polyvinyl alcohol、The water-soluble resins such as polyvinyl pyrrolidone or water-soluble high-molecular compound、Polyester、Modified polyacrylate system、Ethylene oxide/propylene oxide addition product、Phosphate ester system etc..

nullConcrete example as dispersant，" the Anti-TerraU that Bi Ke chemistry society manufactures can be enumerated、AntiTerra-203/204、Disperbyk-101、107、110、111、130、161、162、163、164、165、166、170、400、Bykumen、BYK-P104、P105、P104S、240S、2000、Lactimon”、" the Efka44 that EfkaCHEMICALS society manufactures、46、47、48、49、54、63、64、65、66、71、701、764、766、EfkaPolymer100、150、400、401、402、403、450、451、452、453、745”、" the FlowlenTG-710 that chemistry society of common prosperity society manufactures、FLOWNONSH290、SP-1000、POLYFLOWNo.50E、No.300”、" the DisparlonKS-860 that nanmu this chemical conversion society manufactures、873SN、874、#2150、#7004”、" the DEMOLRN that Hua Wangshe manufactures、N、MS、C、SN-B、EP、HOMOGENOLL-18、EMULGEN920、930、931、935、950、985、ACETAMIN24、86”、" the Solsperse5000 that Lu Borun society manufactures、13940、17000、24000GR、32000、33000、35000、39000、53000、J-100”、" the NikkolT106 that daylight chemistry society manufactures、MYS-IEX、Hexagline4-0”、" the AJISPERPB821 that AJINOMOTOFINETECHNO society manufactures、822、824、711”、" TEGODisper685 " that TegoChemieService society manufactures etc..

The pigment dispersing agent excellent especially as stability, discharge property is excellent especially, basic dye dispersant can be enumerated, specifically, can enumerate Solsperse17000,24000GR, 32000,33000,35000,39000,53000, J-100, AJISPERPB821,822,824,827,711 etc..

On the basis of the gross weight of above-mentioned light solidification pigmentation composition, dispersant preferably comprises 0.01 weight %～10 weight %.

Additionally, the photo-curable of the present invention can contain solvent in compositions.nullAs solvent，Such as 1 can be enumerated,2,3-trichloropropane、1,3-butanediol、1,3-butanediol、1,3-butanediol diacetate esters、1,4-dioxane、2-heptanone、2-methyl isophthalic acid,Ammediol、3,5,5-trimethyl-2-cyclohexene-1-ketone、3,3,5-trimethylcyclohexanone、3-ethoxyl ethyl propionate、3-methyl isophthalic acid,3-butanediol、MMB、3-methoxyl group-3-Methylbutyl acetate、3-methoxybutanol、3-methoxybutyl acetas、Dipropyl ketone、Meta-xylene、NSC 62102、M-dichlorobenzene、N,N-dimethyl acetylamide、N,Dinethylformamide、N-butyl alcohol、N-butyl benzene、N-propyl acetate、N-Methyl pyrrolidone、O-Dimethylbenzene、Ortho-chlorotolu'ene、Adjacent diethylbenzene、O-dichlorohenzene、Parachlorotoluene、P-Diethylbenzene、2-phenylbutane.、2-methyl-2-phenylpropane、Gamma-butyrolacton、Isobutanol、Isophorone、Ethylene glycol diethyl ether、Butyl cellosolve、Ethyleneglycol monopropylether、Ethylene glycol monoethyl ether、Ethylene glycol monoethylether acetate、The tertiary butyl ether of ethylene glycol list、Ethylene glycol monobutyl ether、Ethylene glycol monomethyl ether acetate、Ethylene glycol ether、Ethylene glycol monohexylether、Glycol monoethyl ether、Ethylene glycol monomethyl ether acetate、Diisobutyl ketone、Diethylene glycol diethyl ether、Diethylene glycol dimethyl ether、Diethylene glycol list diisopropyl ether、Diethylene glycol monoethyl ether acetas、Diethylene glycol monobutyl ether、Butyl carbitol acetate、Diethylene glycol monomethyl ether、Hexalin、Adnoral acetate、Ketohexamethylene、Dimethyl ether、Dipropylene glycol methyl ether acetas、DPE、Dipropylene glycol mono-n-butyl Ether、Dipropylene glycol monopropyl ether、Dipropylene glycol monomethyl ether、Diacetone alcohol、Glycerol triacetate、Tri(propylene glycol)butyl ether,mixture of isomers、Tripropylene glycol monomethyl Ether、Propylene-glycol diacetate、Propylene glycol phenylate、Dihydroxypropane single-ether、Propylene glycol monoethyl ether acetate、Propylene glycol monobutyl ether、Propylene glycol monopropyl ether、Propylene glycol monomethyl ether、Propylene glycol methyl ether acetate、Propylene glycol monomethyl ether propionate、Benzyl alcohol、Methyl iso-butyl ketone (MIBK)、Methyl ethyl ketone、Methyl cyclohexanol、N-amyl acetate、N-butyl acetate、Isoamyl acetate、Isobutyl acetate、Propyl acetate、Dibasic acid ester etc.，They can be used alone or as a mixture.

In the present invention, on the basis of the gross weight of light solidification pigmentation composition, the generally scope in 0.1 weight %～90 weight % contains solvent.

Additionally, in the present invention, it is possible to use black particle is as colorant.As black particle, such as, contain copper-ferrum system, copper-black composite oxide such as chromium system, cobalt oxide system；Comprise a kind of or two or more black pigment constituted as the metal-oxide of main component in Fe, Co, Cu, Cr, Mn, Al.Furthermore it is possible to preferably select containing more than a kind in the aggregates such as aluminium oxide, cordierite, zircon.Additionally, in order to improve stability, each glass paste can also add the acid such as mineral acid, organic acid, phosphate cpd (inorganic phosphate, organic phosphoric acid).

Further, in the case of using black particle, organic binder bond is preferably used.

As organic binder bond, it is possible to use have carboxyl resin, specifically itself have ethylenic unsaturated double-bond containing carboxyl photoresist and do not have ethylenic unsaturated double-bond containing any one in carboxy resin.As the resin (can be any one in oligomer and polymer) that can be preferably used, following resin can be enumerated.

(1) by making (a) unsaturated carboxylic acid and (b) has the compound copolymerization of unsaturated double-bond and obtain containing carboxy resin

(2) by make ethylenic unsaturated group as side base add to obtain on the copolymer of the compound that (a) unsaturated carboxylic acid and (b) have unsaturated double-bond containing carboxyl photoresist

(3) copolymer making (c) to have the compound that the compound of epoxy radicals and unsaturated double-bond has unsaturated double-bond with (b) reacts with (a) unsaturated carboxylic acid, make the secondary hydroxyl of (d) multi-anhydride and generation react and obtain containing carboxyl photoresist

(4) copolymer and (f) making (e) to have the compound that the anhydride of unsaturated double-bond and (b) have unsaturated double-bond have the compound of hydroxyl and unsaturated double-bond react and obtain containing carboxyl photoresist

(5) make (g) epoxide and (h) unsaturated monocarboxylic acid react, make (d) multi-anhydride and react with the secondary hydroxyl generated and obtain containing carboxyl photoresist

(6) epoxy radicals making (b) to have the compound of unsaturated double-bond and the copolymer of (methyl) glycidyl acrylate has 1 carboxyl and does not have the organic acid reaction of ethylenic unsaturated bond in (i) 1 molecule, make (d) multi-anhydride and react with the secondary hydroxyl generated and obtain containing carboxy resin

(7) make (j) hydroxyl polymer-containing react with (d) multi-anhydride and obtain containing carboxy resin

(8) make (j) hydroxyl polymer-containing and (d) multi-anhydride react and obtain containing carboxy resin, make this contain carboxy resin and (c) have the compound of epoxy radicals and unsaturated double-bond react further and obtain containing carboxyl photoresist.

As required, can make in the light solidification pigmentation composition of the present invention containing soft softening ingredient.As the concrete example of spendable soft softening ingredient, high polymer, oligomer, phthalate, phosphoric acid ester, ethylene glycol esters, glycol ethers, aliphatic dibasic acid ester, fatty acid ester, citric acid ester type, epoxy plasticizer, Semen Ricini oils, terpenic series hydrogenated resin etc. can be enumerated.As oligomer, the example of high polymer, the polyisoprene system of polyisoprene system, polybutadiene system or the oligomer of diformazan benzene series, high polymer or hydroxyl, the oligomer of polybutadiene system of hydroxyl, high polymer can be illustrated.

This soft softening ingredient part by weight in light solidification pigmentation composition is usually 10 weight %～80 weight %, is preferably 10 weight %～70 weight %.

It addition, as soft softening ingredient, it is possible to use (methyl) acrylate copolymer.

(methyl) acrylate copolymer can enumerate the copolymer being polymerized other polymerizable monomer beyond the polymer obtained or this monomer and this monomer with acrylic acid series or methacrylic monomers as raw material, it is possible to use the usual ways such as polymerisation in solution, suspension polymerisation, polymerisation in bulk manufacture.

As particularly preferred manufacture method, the most at high temperature it is carried out continuously the incompatible manufacture of radical polymerization.Specifically, for by (methyl) acrylate copolymer manufactured by following technique.First, acrylic acid series or methacrylic monomers mix the polymerization initiator of trace and the solvent of trace.Then, more than 10 minutes are under high pressure reacted at a temperature of more than 150 DEG C.Thereafter, utilize seperator to be separated into and react with unreacted component and obtain (methyl) acrylate copolymer, such that it is able to obtain.

Herein, if being mixed into polymerization initiator, then storage stability is likely deteriorated, and therefore preferably solvent is distilled off and reacts, or is distilled off by solvent after isolated (methyl) acrylate copolymer.

As acrylic acid series or the methacrylic monomers of the raw material as (methyl) acrylate copolymer, (methyl) acrylic acid, α-ethylacrylate can be enumerated；null(methyl) acrylic acid methyl ester.、(methyl) n-propyl、(methyl) isopropyl acrylate、(methyl) n-butyl acrylate、(methyl) sec-butyl acrylate、(methyl) tert-butyl acrylate、(methyl) acrylic acid-2-ethyl butyl ester、(methyl) acrylic acid-1,3-dimethyl butyl ester、(methyl) Hexyl 2-propenoate、(methyl) acrylic acid-2-ethyl caproite、(methyl) 1-Octyl acrylate、(methyl) acrylic acid-3-ethyoxyl propyl ester、(methyl) acrylic acid-3-Ethoxybutyl、(methyl) dimethylaminoethyl acrylate、(methyl) acrylic acid-2-hydroxyl ethyl ester、(methyl) hy-droxybutyl、(methyl) acrylic acid-α-(methylol) ethyl ester、(methyl) phenyl acrylate、(methyl) benzyl acrylate、Ester system (methyl) acrylate etc. such as (methyl) phenylethyl，Can use in them is one kind or two or more.

As can be with other polymerizable monomer of copolymerization, it is possible to use there is the known compound of unsaturated double-bond, such as styrene, 3-nitrostyrolene, 4-methoxy styrene can be enumerated；The ring-alkylated styrenes classes such as α-methyl styrene, Beta-methyl styrene, 2,4-dimethyl styrene, vinyltoluene, α-ethyl styrene, α-butylstyrene, α-hexyl benzene ethylene；The halogenated styrenes classes such as 4-chlorostyrene, 3-chlorostyrene, 3-bromstyrol；Butenoic acid, Alpha-Methyl butenoic acid, α-ethyl butenoic acid, methacrylate, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, glutaconates etc. have the carboxylic acids of unsaturated double-bond.

As required, the additives such as organic solvent, silane coupler, polymerization inhibitor, levelling agent, antistatic additive, surface lubricant, light stabilizer (such as hindered amine compound etc.) can be added in the light solidification pigmentation composition of the present invention.

As the concrete example of diluent, the such as alcohols such as methanol, ethanol, isopropanol, dimethyl sulfone, dimethyl sulfoxide, oxolane, dioxane, toluene, dimethylbenzene, methyl ethyl ketone, water etc. can be enumerated.

nullConcrete example as silane coupler，Such as 3-glycidoxypropyltrime,hoxysilane can be enumerated、3-glycidoxypropyl dimethoxysilane、3-glycidoxypropyl dimethoxysilane、2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane、N-(2-amino-ethyl)-3-amino propyl methyl dimethoxysilane、γ mercaptopropyitrimethoxy silane、N-(2-amino-ethyl)-3-amino propyl methyl trimethoxy silane、APTES、3-mercaptopropyi trimethoxy silane、Vinyltrimethoxy silane、N-(2-(vinyl-benzylamino) ethyl) 3-TSL 8330 hydrochlorate、3-methacryloxypropyl trimethoxy silane、3-chloropropylmethyldimethoxysilane、The silane series coupling agents such as 3-r-chloropropyl trimethoxyl silane；The titanium system coupling agents such as isopropyl (N-ethylaminoethyl amino) titanate esters (salt), isopropyl three isostearoyl titanate esters (salt), two (dioctylphyrophosphoric acid ester) ethoxyacetic acid titanium (チ タ ニ ウ system ジ (ジ オ Network チ Le ピ ロ Off ォ ス Off ェ ト) オ キ シ ア セ テ ト), tetra isopropyl two (dioctyl phosphate ester) titanate esters (salt), new alkoxyl three (p-N-(beta-aminoethyl) aminophenyl) titanate esters (salt)；Zr-acetylacetonate, Zr-methacrylate (salt), Zr-propionic ester (salt), new alkoxy zirconates (ester), the new new capryl zirconates (ester) of alkoxyl three, new alkoxyl three (dodecanoyl) benzenesulfonyl zirconates (ester), new alkoxyl three (ethylenediamine base ethyl) zirconates (ester), new alkoxyl three (m-aminophenyl base) zirconates (ester), zirconium carbonate ammonium, Al-acetylacetonate, Al-methacrylate (salt), the zirconiums such as Al-propionic ester (salt) or aluminum system coupling agent etc..

As the concrete example of polymerization inhibitor, p methoxy phenol, methylnaphthohydroquinone etc. can be enumerated.

nullConcrete example as light stabilizer，Such as 1 can be enumerated,2,2,6,6-pentamethyl-4-piperidine alcohols、2,2,6,6-tetramethyl-4-piperidine alcohols、(methyl) acrylic acid-1,2,2,6,(ADEKA Corp. manufactures 6-pentamethyl-4-piperidine ester、LA-82)、Four (1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butane tetracarboxylic acid esters、Four (2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane tetracarboxylic acid esters、1,2,3,4-BTCA and 1,2,2,6,6-pentamethyl-4-piperidine alcohols and 3,Double (the 2-hydroxyl-1 of 9-,1-dimethyl ethyl)-2,4,8,10-tetra-oxa-volution [5.5] undecanoic mixed ester compound、Decanedioic acid double (2,2,6,6-tetramethyl-4-piperidyl) sebacate、Double (1-hendecane epoxides-2,2,6,6-tetramethyl piperidine-4-base) carbonic ester、Methacrylic acid-2,2,6,6,-tetramethyl-4-piperidine ester、Double (2,2,6,6-tetramethyl-4-piperidyl) sebacate、Double (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate、4-benzoyl epoxide-2,2,6,6-tetramethyl piperidine、1-[2-[3-(3,5-di-tert-butyl-hydroxy phenyl) propiono epoxide] ethyl]-4-[3-(3,5-di-tert-butyl-hydroxy phenyl) propiono epoxide]-2,2,6,6-tetramethyl piperidine、1,2,2,6,6-pentamethyl-4-piperidinyl-methacrylate、Double (1,2,2,6,6-pentamethyl-4-piperidinyl) [[3,5-double (1,1-dimethyl ethyl)-4-hydroxy phenyl] methyl] butylmalonic acid ester、Decanedioic acid double (2,2,6,6-tetramethyl-1 (octyloxy)-4-piperidinyl) ester、1,1-dimethyl ethyl hydrogen peroxide and the product of octane、N,N’,N″,N " '-four-(4,6-pair-(butyl-(N-methyl-2,2,6,6-tetramethyl piperidine-4-base) amino)-triazine-2-base)-4,7-diaza decane-1,10-diamidogen、Dibutyl amine 1,3,5-triazine N,N '-bis-(2,2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylene diamine and N-(2,2,6,6-tetramethyl-4-piperidyl) condensation polymer of butylamine、Poly-[[6-(1,1,3,3-tetramethyl butyl) amino-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino group] hexa-methylene [(2,2,6,6-tetramethyl-4-piperidyl) imino group]]、Dimethyl succinate and 4-hydroxyl-2,2,6,The polymer of 6-tetramethyl-1-piperidine ethanol、2,2,4,4-tetramethyl-20-(β-lauryl epoxide carbonyl) ethyl-7-oxa--3,20-diaza two volution [5 1 11 2] heneicosane-20-ketone、Beta-alanine,N,-(2,2,6,6-tetramethyl-4-piperidinyl)-dodecyl ester/myristyl ester、N-acetyl group-3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidinyl) pyrrolidine-2,5-diketone、2,2,4,4-tetramethyl-7-oxa--3,20-diaza two volution [5,1,11,2] heneicosane-20-ketone、2,2,4,4-tetramethyl-21-oxa--3,20-diazabicylo-[5,1,11,2]-heneicosane-20-propanoic acid dodecyl ester/myristyl ester、Malonic acid,[(4-methoxyphenyl)-methylene]-bis-(1,2,2,6,6-pentamethyl-4-piperidinyl) ester (プ ロ パ Application ジ オ イ ッ Network ア シ ッ De,[(4-メトキシフェニル)-メチレン]-ビス(1,2,2,6,6-ペンタメチル-4-ピペリジニル)エステル)、2,2,6,The high-grade aliphatic ester of 6-tetramethyl-4-piperidine alcohols、N,N '-bis-(2,2,6,6-tetramethyl-4-piperidinyl)-1,3-benzenedicarboxamide (1,3-ベンゼンジカルボキシアミド,N,N’-ビス(2,2,6,6-テ ト ラ メ チ Le-4-ピ ペ リ ジ ニ Le)) etc. hindered amine system；The benzophenone based compounds such as octabenzone；2-(2H-benzotriazole-2-base)-4-(1, 1, 3, 3-tetramethyl butyl) phenol, 2-(2-hydroxy-5-methyl base phenyl) benzotriazole, 2-[2-hydroxyl-3-(3, 4, 5, 6-tetrahydric phthalimide-methyl)-5-aminomethyl phenyl] benzotriazole, 2-(the 3-tert-butyl group-2-hydroxy-5-methyl base phenyl)-5-chlorobenzotriazole, 2-(2-hydroxyl-3, 5-bis--tertiary pentyl phenyl) benzotriazole, methyl-3-(3-(2H-benzotriazole-2-base)-5-tert-butyl-hydroxy phenyl) propionic ester and the product of Polyethylene Glycol, the benzotriazole based compounds such as 2-(2H-benzotriazole-2-base)-6-dodecyl-4-methylphenol；2,4-di-tert-butyl-phenyl-3, benzoate system, the 2-(4 such as 5-di-tert-butyl-4-hydroxybenzoic acid ester, 6-diphenyl-1,3,5-triazine-2-bases) the triazine based compound etc. such as-5-[(hexyl) epoxide] phenol, particularly preferably hindered amine based compound.

In the case of there is various additive in light solidification pigmentation composition, various additives part by weight in light solidification pigmentation composition is 0.01 weight %～3 weight %, is preferably 0.01 weight %～1 weight %, more preferably 0.02 weight %～0.5 weight %.

The light solidification pigmentation composition of the present invention can be by obtaining above-mentioned each composition, as required at room temperature (25 DEG C)～80 DEG C of mixed dissolutions, it is possible to use the operation removal of inclusions such as filtration.In view of coating, the viscosity that the light solidification pigmentation composition of the present invention is preferably 25 DEG C is 5mPa s～100Pa s, and the most suitably the mix ratio of modifying ingredients is to reach 5mPa s～the scope of 50000mPa s.

From the standpoint of the discharge guaranteeing excellence, it is preferably regulated as 5mPa s～the scope of 14mPa s.

In the process for dispersing of colorant, dispersant can be utilized, it is possible to use the dispersion machines such as paint mixing unit (PaintConditioner), three-roll mill, two roller mills, kneader, ball mill, sand mill, attritor, ball mill (pearlmill), CoBallMill, homomixer, homogenizer, wet shotcrete technology formula pulverizer, small ball mill, coating rocker.In the case of dispersion machine uses medium, bead, zirconium oxide bead, alumina bead, magnetic beads, styrene pearl etc. are preferably used.About dispersion, two or more dispersion machines or the different two or more medium of size can be used respectively, periodically use.

The form that light solidification pigmentation composition contains dispersant is adjusted preferably by following method.First, after the colorants such as pigment, dispersant, solvent are carried out mixture (carrying out premixing as required), utilize medium as required, use dispersion machine fully to disperse, adjust the concentrated solution containing colorant with high concentration.Then, in obtained pigment dispersion, add photopolymerizable compound, polymerizing initiator, various additive, thus obtain light solidification pigmentation composition.Herein, the light solidification pigmentation resin combination comprising two or more pigment can manufacture as follows: is scattered in the most imperceptibly in photopolymerizable compound, solvent by each pigment, by obtained material mixing, such that it is able to manufacture.

According to the method, the dispersion even with common dispersion machine processes, it is also possible to obtain sufficient dispersibility.In addition, it is not necessary that the energy dispersive of excess, it is not necessary to a lot of jitter times, when therefore can manufacture dispersion colorant do not go bad, the light solidification pigmentation composition of excellent in stability.

Additionally, the light solidification pigmentation composition of the present invention removes certain above big particle preferably by unit such as centrifugation, sintered filter, film filters.

For the light solidification pigmentation composition of the present invention, generally arbitrary method, such as spraying process, spin-coating method, 2P method, rolling method, silk screen print method, ink jet printing method etc. is utilized compositions to be applied on substrate according to the mode that thickness is 5 μm～50 μm of cured coating film.

As active energy beam, as long as irradiate the lamp of the light of ultraviolet～near ultraviolet (near wavelength 200nm～400nm), light source is not limited, such as low pressure, high pressure or ultrahigh pressure mercury lamp, metal halide lamp, (pulse) xenon lamp, electrodeless lamp or light emitting diode (LED) etc. can be enumerated.

The light solidification pigmentation composition of the present invention can be preferred for the purposes of ink jet printing.Specifically, first, the light solidification pigmentation composition of the present invention is supplied the print head to ink-jet recording, this print head is expelled on base material, irradiates thereafter active energy beam.Thus, the ink composite on printing element can solidify rapidly, forms cured coating film, such that it is able to form printing surface.

The printing element that can use in the present invention is not particularly limited, the such as plastic basis material such as Merlon, RPVC, polystyrene, foamed styrene, PMMA, polypropylene, polyethylene, PET or the metal base etc. such as combinations thereof or modifier, free sheet, art printing paper, art paper, cast coated paper, glass, rustless steel can be enumerated.

The light solidification pigmentation composition of the present invention can also be applied to black matrix layer.In the case of making black matrix layer, formed the most as follows.

For the light solidification pigmentation composition of the present invention, be shaped in advance membranaceous in the case of, as long as carrying out lamination, but in the case of thickener shape compositions, on the glass substrate of whole substrate utilize the suitable coating processes such as silk screen printing, bar coater, scraper-type coating machine to be applied to substrate, such as becoming PDP, next utilize heated air circulation type drying oven, far infrared drying stove etc. to be dried 5 minutes～40 minutes at e.g., from about 60 DEG C～120 DEG C to obtain dry to touch, make organic solvent evaporation, obtain noncohesive film.Thereafter, optionally expose, develop, fire, form specific black pattern.

As exposure process, can carry out utilizing the contact exposure of the negative mask with particular exposure pattern and noncontact exposure.As exposure light source, use Halogen light, high voltage mercury lamp, laser, metal halide lamp, black light lamp, electrodeless lamp etc..As light exposure, preferably 50mJ/cm²～1000mJ/cm²Left and right.

As developing procedure, use nebulization, infusion process etc..As developer solution, the metal alkaline aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium silicate is preferably used；Or amine aqueous solution, the particularly concentration such as monoethanolamine, diethanolamine, triethanolamine are about the dilute alkali aqueous solution of below 1.5 mass %, as long as the carboxyl containing carboxy resin in compositions is saponified, uncured portion (unexposed portion) is removed, then it is not limited to above-mentioned developer solution.It addition, for developer solution unwanted after removing development, preferably carry out washing or acid neutralization.

In ablating work procedure, the substrate after development in atmosphere or is carried out about 400 DEG C～the heat treated of 600 DEG C under nitrogen atmosphere, forms desired conductive pattern.It should be noted that programming rate now is preferably set to less than 15 DEG C/min.

Embodiment

Below, further illustrate the present invention by embodiment, but the present invention is not by any restriction of these embodiments.

The raw material used in embodiment is as follows.

It should be noted that the absorbing wavelength of organic compound (A), emission wavelength assay method are as follows.

Preparation absorbs the tetrahydrofuran solution (concentration 0.002wt%) of the organic compound (A) of ultraviolet and luminescence, and the spectrophotometer " UV-3150 " utilizing (strain) Shimadzu Seisakusho Ltd. to manufacture determines absorption spectrum.The fluorophotometer " F-7000 " that emission spectrum uses HitachiHigh-Technologies society to manufacture is measured.

<use raw material>

UA-1: polytetramethylene glycol (molecular weight 850), isophorone diisocyanate, the reactant of mol ratio 1:1.5:2 of acrylic acid-2-these 3 kinds of compositions of hydroxyl ethyl ester

UA-2: hexamethylene diisocyanate, the reactant of mol ratio 1:2 of pentaerythritol triacrylate both compositions

UA-3: hexamethylene diisocyanate, the reactant of mol ratio 1:2 of Dipentaerythritol Pentaacrylate both compositions

Photomer4226: propylene glycol diacrylate, Cognis society manufacture

Irgacure819: double (2,4,6-trimethylbenzoyl) phenyl phosphine oxide, BASF society manufacture

SpeedcureTPO:2,4,6-trimethyl benzoyl diphenyl base phosphine oxide, LAMBSON society manufacture

IrgacureOXE01:1,2-acetyl caproyl, 1-[4-(thiophenyl)-, 2-(O-benzoyl oximes)]

IrgacureOXE02: ethyl ketone, 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base]-, 1-(O-acetyl group oxime)

TINOPALOB:2,5-thiophene diyl double (the 5-tert-butyl group-1,3-benzothiazole), BASF society manufacture, absorb very big wavelength 375nm, luminous greatly wavelength 438nm

PBD:2-(4-biphenyl)-5-(4-tert-butyl-phenyl)-1,3,4-diazole and Wako Pure Chemical Industries (strain) society manufacture, absorb very big wavelength 272nm, luminous greatly wavelength 364nm

CBP:4,4 '-bis-(9H-carbazole-9-base) biphenyl, Tokyo chemical conversion industry (strain) society manufacture, absorb very big wavelength 302nm, luminous greatly wavelength 369nm

NPB:N, N'-bis-(1-naphthyl)-N,N' diphenyl benzidine, (strain) colleague chemistry institute society manufacture, absorb very big wavelength 339nm, luminous greatly wavelength 450nm

KAYALIGHTB:7-diethylamino-4-methylcoumarin, Nippon Kayaku (strain) Club manufacture, absorb very big wavelength 364nm, luminous greatly wavelength 416nm

(preparation of black pigment dispersion liquid)

Mixture white carbon black 20 parts, macromolecule dispersing agent (manufacture of Bi Ke chemistry, BYK-2000) 5 parts, methyl ethyl ketone 80 parts, after premixing, utilize the zirconium oxide bead of 0.3mm, paint agitator dispersion 60 minutes.From obtained dispersion liquid, remove zirconium oxide bead, be prepared for the black pigment dispersion liquid that solid component concentration is 25 weight %.

(preparation of the light solidification pigmentation composition of the present invention)

Dispersion liquid obtained by utilization, stirs following raw material and adds successively.After stirring 2 hours, utilize film filter to filter, prepare light solidification pigmentation composition.

Black pigment dispersion liquid

·UA-1

·Photomer4226

·Irgacure819

·TINOPALOB

The light solidification pigmentation composition that preparation composition (embodiment 1～7, comparative example 1～4) as shown in Table 1 is constituted.

It should be noted that about embodiment 2, in addition to white carbon black is changed to titanium dioxide, same as in Example 1.

The light solidification pigmentation composition using the obtained present invention carries out following evaluation.

(utilizing the curable of high voltage mercury lamp)

By ink-jet coating apparatus, obtained compositions is discharged on vinyl chloride sheet, heats 1 minute at 90 DEG C, solvent is removed and is dried.Thereafter, high voltage mercury lamp (80W/cm, ozone free) irradiation ultraviolet radiation is utilized.Cover blank sheet of paper in compositions after irradiation ultraviolet radiation, the color of compositions the conveyor speed not being transferred on blank sheet of paper evaluates curable.

More than ◎ 20m/min

Zero 10m/min～20m/min

△ 5m/min～10m/min

× below 5m/min

(utilizing the curable of ultraviolet light emitting diode light source)

By ink-jet coating apparatus, obtained compositions is discharged on vinyl chloride sheet, heats 1 minute at 90 DEG C, solvent is removed and is dried.Thereafter, utilization has ultraviolet LED irradiation unit (manufacture of MicroSquare society, the UVL150-365) irradiation ultraviolet radiation of emission wavelength peak at 365nm.Cover blank sheet of paper in compositions after irradiation ultraviolet radiation, the color of compositions the conveyor speed not being transferred on blank sheet of paper evaluates curable.

More than ◎ 20m/min

Zero 10m/min～20m/min

△ 5m/min～10m/min

× below 5m/min

May validate that by the result of table 1 light solidification pigmentation composition of the present invention comprising the embodiment 1～7 absorbing ultraviolet and the organic compound (A) of luminescence, photopolymerizable compound (B), Photoepolymerizationinitiater initiater (C) and colorant (D) has excellent curable.Even if additionally may validate that using light emitting diode as in the case of light source, it is possible to obtain the light solidification pigmentation composition with excellent curable.

Claims (9)

1. a light solidification pigmentation composition, it is the organic compound (A) of luminescence, photopolymerizable compound (B), Photoepolymerizationinitiater initiater (C) and the resin combination of colorant (D) containing absorption ultraviolet, it is characterized in that, absorb the scope of a length of 250nm～400nm of maximum wave of the absorption spectrum that the organic compound (A) of ultraviolet and luminescence records in oxolane, and the scope of a length of 300nm～500nm of maximum wave of emission spectrum.

2. light solidification pigmentation composition as claimed in claim 1, it is characterized in that, absorb the scope of a length of 250nm～390nm of maximum wave of the absorption spectrum that the organic compound (A) of ultraviolet and luminescence records in oxolane, and the scope of a length of 330nm～480nm of maximum wave of emission spectrum.

3. light solidification pigmentation composition as claimed in claim 1 or 2, it is characterised in that Photoepolymerizationinitiater initiater (C) has absorption at absorption ultraviolet under the wavelength of the light that the organic compound (A) of luminescence is sent.

4. light solidification pigmentation composition as claimed in claim 3, it is characterized in that, the specific absorbance of the Unit Weight at 365nm that the Photoepolymerizationinitiater initiater (C) described in claim 3 records in acetonitrile is 85ml/ (g cm)～10000ml/ (g cm).

5. light solidification pigmentation composition as claimed in claim 3, it is characterized in that, the specific absorbance of the Unit Weight at 365nm that the Photoepolymerizationinitiater initiater (C) described in claim 3 records in acetonitrile is 400ml/ (g cm)～10000ml/ (g cm).

6. the light solidification pigmentation composition as according to any one of Claims 1 to 5, it is characterized in that, as photopolymerizable compound (B), including more than a kind in the group being selected from (methyl) acrylate compounds (B-1), oxetane compound (B-2), epoxide (B-3), vinyl ether compound (B-4).

7. the light solidification pigmentation composition as according to any one of Claims 1 to 5, it is characterized in that, (methyl) acrylate compounds (B-1) is carbamate (methyl) acrylate obtained by (methyl) acrylate reactions making organic multiple isocyanate and hydroxyl.

8. a solidfied material, it is the light solidification pigmentation composition according to any one of claim 1～7 to be irradiated active energy beam and obtains.

9. a solidfied material, it is characterized in that, it is to obtain the light solidification pigmentation composition irradiation ultraviolet radiation according to any one of claim 1～7 with ultraviolet light emitting diode light source, and described ultraviolet light emitting diode light source has peak wavelength at 350nm～420nm.