CN108070279A - The pigment dispersion and coloured composition of phthalimide and its derivative are used - Google Patents

Abstract

Though the problem of the present invention inhibit with being to provide the species of being capable of phthalocyanine color to prepare the rising of the viscosity after pigment dispersion and inhibiting prepare the film after the coloured composition containing it contrast reduction pigment dispersion and the coloured composition containing it.One kind contains the pigment dispersion selected from least one of the phthalimide shown in following formula (1) and its derivative, phthalocyanine color, dispersant and solvent.(in formula (1), R¹~R⁴For hydrogen atom or halogen atom; Q is that the alkyl of the carbon number 1~4 for the substituent X that (i) hydrogen atom, (ii) can be combined with the carbon atom with end or (iii) can the aryl with the substituent group Y that the carbon atom with aromatic rings is combined; substituent X is acetyl group, carboxyl, phosphate or sulfo group, and substituent group Y is methyl, acetyl group, carboxyl, phosphate or sulfo group.).

Description

The pigment dispersion of phthalimide and its derivative and colour cell are used Close object

Technical field

The present invention relates to the pigment dispersion and coloured composition for having used phthalimide and its derivative, especially Be related to pigment dispersion used in the color-filter element for the flat panel for being for example arranged at display device and containing its colour cell Close object.

Background technology

Color-filter element is widely used as the structure member of liquid crystal display (LCD) etc..LCD be widely used in monitor, The display device of TV, subnotebook PC, plate PC, smart mobile phone etc..The requirement of these display devices is high Image quality.On the other hand, in recent years, from the viewpoint of global environment protection etc., the requirement for the reduction of consumption electric power It becomes higher.Therefore, color-filter element requirement high brightness, high contrast to forming the display device etc..

On color-filter element, usually the colorant of the dyestuff, the pigment that make red, green and blueness etc. is dissolved or dispersed in The coloring photosensitive combination that photoresist obtains is used as coating fluid, forms film by photo-mask process to make.Make To be used to realize the method for the higher image quality of color-filter element as described above, it may be considered that by improving in coloring photosensitive combination Dyestuff, the concentration etc. of pigment make the method that excitation purity improves.But at this point, since the backlight of LCD causes the transmitance of light It reduces, consumption electric power becomes larger.In addition, in order to realize high contrast, it may be considered that the large-size particles of pigment are not present, it will Pigment is scattered in the form of the small size particle below the wavelength of light in coloring photosensitive combination.But pigment has grain size It is smaller more to hold agglutinophilic trend, and there is the trend for being more difficult to be uniformly dispersed in coloring photosensitive combination.It is therefore desirable to Exploitation with not improving the concentration of pigment etc., can show equal lightness with light quantity less than in the past can realize high brightness And the pigment of the color-filter element of high contrast.Then, it is proposed that the color-filter element (patent document formed using such pigment 1)。

For example, by using pigment as disclosed in Patent Document 1, the height of color-filter element can be expected to a certain extent Brightness, high contrast.But, it is however generally that, it is not easy to pigment is made to be uniformly dispersed in coloring photosensitive combination, because This, the general ingredient using for example as composition coloring photosensitive combination uses dispersant, pigment derivative or uses through table The method of the pigment of surface treatment.The characteristic of these ingredients is related to the dispersiveness of pigment, it is therefore contemplated that selecting phase by it It should influence of the ground confirmation to the performance of color-filter element.

Therefore, as described above, color-filter element usually forms film to make by photo-mask process.Therefore, it is proposed to conduct Resist has the anti-corrosion agent composition (patent document 2) of good characteristic.In patent document 2, describe to inhibit against corrosion In film acid diffusion velocity and further improve resolution ratio, inhibit exposure after susceptibility variation etc., preferably comprise alkalization Close object.In addition, as alkali compounds, the imide derivative that can use phthalimide etc. is described.

In addition, imide derivative is occasionally used for ink for inking, recording ink (patent document 3,4).Patent document 3 In, when describing for thermal ink jet printers, in order to possess long stand-by time and long-term discharge stability, use hydroxyl amide Derivative as the concrete example of hydroxyl amide derivatives, describes phthalimide derivative.In patent document 4, describe In the recording ink containing water and polyvinylpyrrolidone, the hydration of water and polyvinylpyrrolidone in order to prevent shows As containing the substance with pyrrolidone ring, as its concrete example, instantiating phthalimide.

Prior art literature

Patent document

【Patent document 1】Japanese Unexamined Patent Publication 2016-38584 publications

【Patent document 2】Japanese Unexamined Patent Publication 2006-251296 publications

【Patent document 3】Japanese Unexamined Patent Publication 10-204359 publications

【Patent document 4】Japanese Unexamined Patent Publication 7-331146 publications

The content of the invention

Problems to be solved by the invention

The present inventor is used as the phthalocyanine system of Dainippon Ink Chemicals of the pigment disclosed in patent document 1 Viridine green C.I.Pigment Green 59 are prepared for the pigment dispersion containing dispersant and solvent and use its coloring Composition forms film using coloured composition, it turns out that, pair of the film of the composition of certain time has been stood after preparation It is reduced than contrast of the degree than the film of the composition just prepared.In addition, it is used instead of C.I.Pigment Green 59 other The pigment of phthalocyanine system equally operated, it turns out that when pigment dispersion has been stood certain time, viscosity rises, hair Life becomes unworkable problem in the preparation of coloured composition.

Therefore, no matter inhibiting it is an object of the invention to provide the species for being capable of phthalocyanine color after preparing pigment dispersion Viscosity rising and inhibit prepare the coloured composition containing it after film contrast reduction pigment dispersion With the coloured composition containing it.

The method used for solving the problem

The present inventor has made intensive studies, it turns out that, by using phthalimide and specifically Phthalimide derivative can solve the above subject, so as to complete the present invention.The main points of the present invention are as described below.

The first aspect of the present invention is related to containing in the phthalimide and its derivative shown in following formula (1) At least one, phthalocyanine color, the pigment dispersion of dispersant and solvent.

(in formula (1), R¹~R⁴For hydrogen atom or halogen atom, Q is that (i) hydrogen atom, (ii) can have carbon with end The alkyl or (iii) of the carbon number 1~5 for the substituent X that atom combines can have to be taken with what the carbon atom of aromatic rings was combined For the aryl of base Y, substituent X is acetyl group, carboxyl, phosphate or sulfo group, and substituent group Y is methyl, acetyl group, carboxyl, phosphoric acid Base or sulfo group.)

In the preferred embodiment of the present invention, above-mentioned phthalocyanine color is metal phthalocyanine pigment.In addition, more preferably ZnPc Pigment or copper phthalocyanine.In addition, the more preferred embodiment of ZnPc pigment is averaged to be contained in one molecule Number of hydrogen atoms is more than 2 zinc halide phthalocyanine color, particularly preferably in one molecule contained average hydrogen atom number for 2 with On zinc halide phthalocyanine color, be most preferably chlorination bromination ZnPc pigment.

In the preferred embodiment of the present invention, the Q in above-mentioned formula (1) has for (ii) to be taken with what the carbon atom of end was combined For the alkyl of the carbon number 2 of base X, substituent X is carboxyl or phosphate.

The second aspect of the present invention is related to the coloured composition containing above-mentioned pigment dispersion and film forming component.This hair In bright preferred embodiment, contain optical polymerism ingredient as above-mentioned film forming component.

The effect of invention

No matter in accordance with the invention it is possible to the species of phthalocyanine color inhibit to prepare viscosity after pigment dispersion rising, And inhibit the reduction of the contrast of the film after coloured composition of the preparation containing it.

Specific embodiment

Hereinafter, embodiments of the present invention will be described.

The embodiment of pigment dispersion according to the present invention is containing selected from the phthalyl shown in following formula (1) At least one of imines and its derivative, phthalocyanine color, dispersant and solvent.

(in formula (1), R¹~R⁴For hydrogen atom or halogen atom, Q is that (i) hydrogen atom, (ii) can have carbon with end The alkyl or (iii) of the carbon number 1~4 for the substituent X that atom combines can have to be taken with what the carbon atom of aromatic rings was combined For the aryl of base Y, substituent X is acetyl group, carboxyl, phosphate or sulfo group, and substituent group Y is methyl, acetyl group, carboxyl, phosphoric acid Base or sulfo group.)

Phthalocyanine color is applied in combination in this way and selected from the phthalimide shown in formula (1) and specific adjacent benzene two At least one of carboximide derivative, although its mechanism of action is not known, no matter but it is possible to the species of phthalocyanine color Ground inhibition prepares the rising of the viscosity after pigment dispersion, and can inhibit to prepare the film after the coloured composition containing it Contrast reduction.

There can be the alkyl of the carbon number 1~5 of the substituent X combined with the carbon atom of end as (ii), not have It is particularly limited to, is the alkyl of carbon number 1~5 or the carbon number 1~5 with the substituent X combined with the carbon atom of end Alkyl.That is, it is methyl (- CH₄), ethyl (- C₂H₅), propyl (- C₃H₇), butyl (- C₄H₉), amyl (- C₅H₁₁)、―CH₂―X、―C₂H₄―X、―(C₂H₄)CH₂―X、―(C₃H₆)CH₂―X、―(C₄H₈)CH₂- X.Butyl and Amyl can be straight-chain or branched.Wherein, inhibition and painting are risen from the further viscosity for playing pigment dispersion From the viewpoint of the reduction inhibition of the contrast of film, the preferred alkyl of carbon number 1~4, more preferable carbon number 1~3 Alkyl, the alkyl of more preferred carbon number 1~2, the alkyl of particularly preferred carbon number 2.

(ii) it is preferably acetyl group, carboxyl, phosphate or sulfo group as substituent X when.Wherein, played from further From the viewpoint of the viscosity of pigment dispersion rises the reduction inhibition of inhibition and the contrast of film, more preferable acetyl Base, carboxyl, phosphate, more preferred carboxyl, phosphate.

(iii) as the aryl that there can be the substituent group Y combined with the carbon atom of aromatic rings, it is not particularly limited, it is excellent Select the aryl of carbon number 6~14, the aryl of more preferable carbon number 6~10.It, can be with as the concrete example for the ring for forming aryl Enumerating phenyl ring, naphthalene nucleus, anthracene nucleus, phenanthrene ring, fluorenes ring, benzo phenanthrene ring, pyrene ring, aphthacene, cyclohexyl biphenyl, (2 phenyl can be with arbitrary Mode of connection links), terphenyl ring (3 phenyl can be linked with arbitrary mode of connection) etc..(iii) when, as substituent group Y is preferably methyl, acetyl group, carboxyl, phosphate or sulfo group.In addition, as substituent group, preferably without the official beyond these It can group.The position of substituent group Y, quantity are not particularly limited.

In embodiment, it can use in the phthalimide and its derivative shown in above-mentioned formula (1) extremely Few one kind.Wherein, the reduction suppression of inhibition and the contrast of film is risen from the further viscosity for playing pigment dispersion From the viewpoint of effect processed, in formula (1), Q preferably (i) hydrogen atom or (ii) can have to be taken with what the carbon atom of end was combined For the alkyl of the carbon number 1~4 of base X, the more preferably carbon atom of (ii) with the substituent X combined with the carbon atom of end The alkyl and substituent X of number 1~4 be carboxyl or phosphate, be more preferably (ii) have taken with what the carbon atom of end was combined Alkyl and substituent X for the carbon number 1~2 of base X are carboxyl or phosphate, and particularly preferably (ii) is with the carbon with end The alkyl and substituent X of the carbon number 2 for the substituent X that atom combines are carboxyl or phosphate.

(ii) it is carboxylic to have the alkyl of the carbon number 1~2 of the substituent X combined with the carbon atom of end and substituent X Concrete example when base or phosphate is-CH₂COOH、―C₂H₄COOH、―CH₂―OPO(OH)₂、―C₂H₄―OPO(OH)₂。

In formula (1), R¹~R⁴As long as the result of study of hydrogen atom or halogen atom, according to the present invention people, according to Q Species, have and preferably combine different trend.For example, there is following trend：Q is-CH₂In the case of COOH, R¹~R⁴For hydrogen Atomic time contributes to the reduction of the contrast of the film of coloured composition to inhibit, and Q is-C₂H₄In the case of COOH, R¹~R⁴For Contribute to the raising of above-mentioned contrast during halogen atom.In addition, R¹~R⁴Any one be halogen atom when, be substituted by halogen original The quantity of son, R¹~R⁴Which be not particularly limited for halogen atom.It as halogen atom, is not particularly limited, from pigment It is preferably chlorine original from the viewpoint of the viscosity of dispersion rises the contrast reduction inhibition of the film of inhibition and coloured composition Son, bromine atoms.Halogen atom is in R¹~R⁴Can be all identical, it can also be arbitrarily a different.

Selected from least one of the phthalimide shown in formula (1) and its derivative containing in pigment dispersion Amount is not particularly limited, and is preferably 2~10 parts by weight compared with 100 parts by weight of phthalocyanine color, more preferably 3~6 parts by weight.

Phthalimide can use commercially available substance.Phthalimide derivative can be with conventionally known Method manufactures.In addition commercially available substance can also be used.

It as above-mentioned phthalocyanine color, is not particularly limited, inhibits from the rising for the viscosity for easily enjoying pigment dispersion From the viewpoint of the effect that reduction with the contrast of coloured composition inhibits, preferred metal phthalocyanine pigment.Metal phthalocyanine pigment There are the ligand of metal ion and its derivative to form by the central part coordination in phthalocyanine.As the metal that can form coordination The metal of ion for metal generally in the art, for example, as the metal for forming stable coordinate bond, can be enumerated Copper, zinc, vanadium, chromium, manganese, iron, cobalt, nickel, platinum etc..Wherein, preferably zinc, copper.That is, as metal phthalocyanine pigment, more preferable ZnPc Pigment, copper phthalocyanine.

Can be that at least one is former by halogen in the hydrogen atom combined with the phenyl ring of phthalocyanine in addition, as above-mentioned phthalocyanine color The halo derivatives of son substitution.As halogen atom, preferably chlorine atom and bromine atoms.Halogen atom can be a kind or 2 Kind or more.It as expected color can suitably select.

It is preferably zinc halide phthalocyanine color as ZnPc pigment.Such zinc halide phthalocyanine color can use for example Substance described in patent document 1.Summary is recorded on its content, as described below.

ZnPc has 16 hydrogen atoms in 1 molecule, by the halogen atom of these hydrogen atom chlorine atom, bromine atoms etc. Substance obtained from substitution is then zinc halide phthalocyanine color.Wherein, preferred chlorination bromination ZnPc pigment.

The content ratio of chlorine atom is preferably more than 3.5 mass % below 30 mass % in zinc halide phthalocyanine color.As Lower limit, more preferably more than 3.8 mass %, be more preferably more than 4.0 mass %, still more preferably for 4.3 mass % with On.As the upper limit, more preferably below 20 mass % are more preferably below 10 mass %, particularly preferably 6 mass % with Under.The content of halogen atom contained by zinc halide phthalocyanine color can by by pigment dissolved after ethyl benzoate, with burning Device burns, and the burning gases is made to be absorbed by hydrogen peroxide absorbing liquid, measure the burning gases of ion in the absorbing liquid-from Sub- chromatography determination.

It is not limited especially containing number there are the chlorine atom in the substituent group of 16 in 1 molecule of zinc halide phthalocyanine color It is fixed, it is preferably less than 1 or more 14.It it is more preferably 3 or more as lower limit, more preferably 2 or more.As the upper limit, More preferably less than 10, be more preferably less than 6, particularly preferably less than 4.Chlorine atom in 1 molecule of pigment contains It is from the average value of the average molecular weight measured by aftermentioned LDI-MS methods and by above-mentioned burning gases-ion to have number The average value that the content ratio for the chlorine atom that coefficients data measured by chromatography obtains calculates.

When zinc halide phthalocyanine color is bromination chlorination ZnPc pigment, compared with rubbing for the bromine atoms in 1 molecule of pigment That content ratio, a mole content ratio for chlorine atom are not particularly limited, and are preferably less than more than 0.1 7.It is more excellent as lower limit It elects more than 0.12 as, is more preferably more than 0.15, is still more preferably more than 0.2.As the upper limit, less than 3 are more preferably, More preferably less than 1, it is still more preferably less than 0.5, particularly preferably less than 0.3.

The content ratio of bromine atoms is preferably more than 30 mass % below 80 mass % in zinc halide phthalocyanine color.As under Limit, more preferably more than 40 mass % are more preferably more than 45 mass %, particularly preferably more than 50 mass %.As upper Limit, more preferably below 70 mass % are more preferably below 60 mass %, particularly preferably below 55 mass %.

It is not limited especially containing number there are the bromine atoms in the substituent group of 16 in 1 molecule of zinc halide phthalocyanine color It is fixed, it is preferably less than 5 or more 15.As lower limit, more preferably 8 or more.As the upper limit, less than 13 are more preferably, More preferably less than 12, be still more preferably less than 11, particularly preferably less than 10.It is flat in 1 molecule of pigment Equal bromine atoms are the average value calculated similary with during above-mentioned chlorine atom containing number.

Contained average hydrogen atom number is not particularly limited in 1 molecule of zinc halide phthalocyanine color, be preferably more than 2 14 with Under.It is more preferably more than 4 as lower limit, more preferably more than 3, particularly preferably more than 5, it is most preferably more than 6.As The upper limit, more preferably less than 12 are more preferably less than 10, and particularly preferably less than 8, it is most preferably less than 7.Halogenation ZnPc Average hydrogen atom number in 1 molecule of pigment is from the average value of the average molecular weight measured by aftermentioned LDI-MS methods and logical Cross the average value that the content ratio of bromine atoms that above-mentioned burning gases-chromatography of ions measures and chlorine atom calculates.In detail and Speech, is obtained by following step.

First, with laser desorption ionization method (Laser Desorption/Ionization, LDI)-mass analysis (Mass Spectrometry, MS) measures average molecular weight.The measure of average molecular weight carries out 4 times, takes 4 measurement results Average value (following, to be simply denoted as " average value of average molecular weight ").

Then, by burning gases-chromatography of ions, the chlorine atom content ratio [quality %] and bromine in pigment are measured Atom content ratio [quality %].It is calculated from the average value of average molecular weight with chlorine atom content ratio and bromine atoms content ratio Average amount of chlorine atom and average bromine atoms number in 1 molecule of pigment.Chlorine atom in ZnPc, bromine atoms, the position shared by hydrogen atom Point is 16, therefore, by calculating the remaining site do not occupied by chlorine atom and bromine atoms, obtains average hydrogen atom number.

Such zinc halide phthalocyanine color can manufacture in a known manner.It in addition, can be used as commercially available pigment The viridine green " G59 " of Dainippon Ink Chemicals.

As copper phthalocyanine, without being particularly limited to use.With color index come when illustrating, as described below.

C.I.Pigment Blue 15,15 ﹕ 1,15 ﹕ 2,15 ﹕ 3,15 ﹕ 4,15 ﹕ 6,17 ﹕ 1,

C.I.Pigment Green 7、36。

The content of contained phthalocyanine color is preferably 8~18 weight % in pigment dispersion, more preferably 10~16 weights Measure %.

In pigment dispersion, other pigment beyond phthalocyanine color can be contained.As such other organic pigments, Represented with color index, for example, can enumerate C.I.Pigment Yellow 1,2,12,13,14,16,17,20,24,31, 32、34、35、36、37、40、41、42、43、48、53、55、61、62、63、65、73、74、75、81、83、108、109、110、 111、120、125、126、129、133、138、139、142、150、151、153、154、155、158、160、162、164、165、 168、169、170、172、174、175、176、180、181、182、183、184、185、189、190、191、192、193、194、 195、196、197、198、199、200、202、203、204、205、206、207、208、C.I.Pigment Blue 1、 C.I.Pigment Violet 23.Alternatively, it is also possible to be added as needed on dyestuff.

The content of pigment beyond phthalocyanine color can suitably be determined according to purpose.Compared with 100 parts by weight of phthalocyanine color About 1~8 parts by weight.

The average grain diameter (average primary particle diameter) of the primary particle of phthalocyanine color can not influence the scope of contrast etc. Interior appropriate adjustment.It is preferably 10~100nm as average primary particle diameter, more preferably 10~50nm, particularly preferably 10~ 30nm.Primary particle size for example can from infiltration type electron microscope with 100,000 times of pictures photographed to pigment of multiplying power It measures.In addition, on average primary particle diameter, for example, 100 particles can be measured, value is averaged as average primary particle diameter.

It,, can be with from considerations such as the viewpoints of adjustment average primary particle diameter according to the species of pigment in embodiments of the present invention (milling) processing is ground in advance.Milled processed can by conventional method be carried out according to species of pigment etc..As Such milled processed, for example, solvent salt milling etc. can be enumerated.

As dispersant, for example, resin type dispersant, surfactant type dispersant etc. can be enumerated.In addition, resin type In dispersant, according to the acid value of resin and the difference of amine value, there is amine value for 0 and dispersant, the acid value of acid value type of the acid value more than 0 It is more than 0 dispersant for dispersant, acid value and the amine value of 0 and amine value type of the amine value more than 0.

As resin type dispersant, such as polyurethane can be enumerated；Polyester；Unsaturated polyamide；Phosphate；Polycarboxylic acids and Its amine salt, ammonium salt, alkylamine salt；Polycarboxylate；Polycarboxylate containing hydroxyl；Polysiloxanes；Modified polyacrylate；Seaweed Acids, polyvinyl alcohol, hydroxypropyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, methylcellulose, polyvinylpyrrolidine The water-soluble high-molecular compound of ketone, Arabic gum etc.；Styrene-acrylic resins, styrene-t resin, Styrene And Chloroalkyl Acrylates-acrylate, styrene-maleic acid resin, styrene-maleic acid ester resin, metering system Acid-methacrylate resin, acrylic acid-acrylic ester resin, isobutylene maleic resin, vinyl -ester resin, The resins containing olefinic double bond such as rosin modified maleic resin；The amine system tree of polyallylamine, polyvinylamine, polyethyleneimine etc. Fat etc..

Among resin type dispersant, rise pair of inhibition and film from the further viscosity for playing pigment dispersion From the viewpoint of the reduction inhibition of degree, the dispersant of tertiary amine groups is preferably had.

Resin type dispersant can use commercially available resin type dispersant.The concrete example of commercially available product is as described below, but not It is defined in these.

Japanese Lubrizol Co. Ltd. systems：SOLSPERSE 3000、9000、13240、17000、20000、24000、 26000、27000、28000、32000、32500、36000、38500、39000、55000、41000、

BYK Japan Co. Ltd. systems：Disperbyk 108、110、112、140、142、145、161、162、163、 164、166、167、171、174、182、190、2000、2001、2050、2070、2150、LPN 6919、LPN22101、 LPN21116

BASF AG's system：EFKA 4401、4403、4406、4330、4340、4010、4015、4046、4047、4050、 4055、4060、4080、5064、5207、5244、

Ajinomoto Fine-Techno Co. Ltd. systems：Ajisper-PB821(F)、PB822、PB880、

Kawaken Fine Chemicals Co. Ltd. systems：ヒノアクトT-8000、

Nanmu this chemical conversion Co. Ltd. system：DISPARLON PW-36、DISPARLON DA-325、375、7301、

Otsuka Chemical Co., Ltd's system：TERPLUS D2015 etc..

The molecular weight of resin type dispersant is not particularly limited, and weight average molecular weight is preferably 1000~100000.

The acid value of resin type dispersant and amine value according to the functional group contained in the resin for forming resin type dispersant and its Content determines.Acid value (being scaled acid value during solid constituent) can for example pass through the method according to DIN EN ISO 2114 It is obtained, amine value (amine value when being scaled solid constituent) for example can be by being obtained according to the method for DIN 16945.Acid value type The acid value of dispersant is not particularly limited, and is preferably 20~150mgKOH/g, and the amine value of the dispersant of amine value type does not limit especially It is fixed, it is preferably 5~30mgKOH/g.When acid value and amine value are more than 0 dispersant, it is not particularly limited, acid value is preferably 5~ 50mgKOH/g, amine value are preferably 5~50mgKOH/g.

As surfactant type dispersant, according to ionic, naphthalene sulfonic acid-formaldehyde condensation product salt, aromatic series sulphur can be enumerated The anion active agent (anionic) of sour formaldehyde condensation products, polyethylene glycol oxide alkyl phosphate etc., polyethylene oxide alkyl ethers Deng tween (non-ionic), alkylamine salt, quaternary ammonium salt etc. cationic active agent (cationic) etc..It lives on surface Property dosage form dispersant also has various commercially available dispersant, and concrete example is as follows, but is not limited to these.

Kao Corp's system：DEMOL N、RN、MS、SN-B、EMULGEN 120、430、ACETAMIN 24、86、 QUARTAMIN24P、

Nikko Chemicals Co., Ltd. systems：NIKKOL BPS-20、BPS-30、DHC-30、BPSH-25、

Di-ichi Kogyo Seiyaku Co., Ltd.'s system：PLYSURF AL、A208F、

Lion Corporation systems：ア ー カ ー De C-50, T-28, T-50, etc..

Dispersant as described above can be a kind, can also combine two or more.During two or more combination, such as it can arrange It lifts：For resin type dispersant when resin different dispersant each other, the combination of acid value type and amine value type；For surfactant type point Ionic different dispersant combination of (for example, anionic and non-ionic etc.) etc., but be not limited to this each other during powder A bit.

The content (solid constituent or active ingredient) of dispersant in pigment dispersion, is examined from the viewpoint of dispersion stabilization Consider, (add up to compared with 100 parts by weight of phthalocyanine color during containing other pigment for it), be preferably 2~20 parts by weight, more preferably 5~10 parts by weight.Wherein, the optimum addition of dispersant suitably adjusts i.e. according to combination of the species of the pigment with using etc. It can.In addition, during using aftermentioned pigment derivative, the content of phthalocyanine color refers to the total amount for including pigment derivative.

In embodiments of the present invention, in addition to above-mentioned dispersant, in order to make phthalocyanine color in pigment dispersion more Steadily disperse, can also be used as dispersing aid and use pigment derivative.During using pigment derivative, import and had with dispersant There are the part of compatibility or the pigment derivative of polar group to be adsorbed in the surface of each pigment, the absorption of dispersant can be become Point.At this point, by pigment derivative dispersant can be made to be present in surface of pigments, therefore, it is possible to which each pigment is formed as fine Particle, be more stably scattered in pigment dispersion.It is aggregated again in addition it is possible to more efficiently prevent from it.

On pigment derivative, specifically, be using pigment as precursor skeleton, side chain by acidic-group, basic group, Compound obtained from aromatic group is imported as substituent group.Pigment as precursor skeleton can specifically enumerate quinoline a word used for translation Pyridine ketone series pigments, phthualocyanine pigment, azo pigment, quinophthalone series pigments, isoindoline series pigments, isoindolinone system face Material, quinoline pigments, diketo-pyrrolo pyrrole pigments, benzimidazolone pigment, dioxazine series pigments etc..In addition, as parent Skeleton, the flaxen aromatic series for generally also including not being known as the naphthalene system of pigment, anthraquinone system, triazine system, quinoline system etc. are multiple ring Close object.

As pigment derivative, Japanese Unexamined Patent Publication 11-49974 publications, Japanese Unexamined Patent Publication 11-189732 can be used Publication, Japanese Unexamined Patent Publication 10-245501 publications, Japanese Unexamined Patent Publication 2006-265528 publications, Japanese Unexamined Patent Publication 8-295810 Publication, Japanese Unexamined Patent Publication 11-199796 publications, Japanese Unexamined Patent Publication 2005-234478 publications, Japanese Unexamined Patent Publication 2003-240938 Pigment derivative described in number publication, Japanese Unexamined Patent Publication 2001-356210 publications etc..

From the viewpoint of dispersion stabilization, total 100 weights of the pigment contained compared with phthalocyanine color and as needed Part is measured, the content (solid constituent) of the pigment derivative in pigment dispersion is preferably 2~15 parts by weight, and more preferably 5~10 Parts by weight.Wherein, the optimum addition of pigment derivative is according to the pigment used and appropriate with the combination of the species of dispersant etc. Adjustment.In addition, total 100 parts by weight of " phthalocyanine color and the pigment contained as needed " refer to that not including pigment derives The total amount of object.

In pigment dispersion, from the dispersiveness of the phthalocyanine color further improved in pigment dispersion and coloured composition etc. From the viewpoint of, except above-mentioned dispersant, dispersion resin is can also use as dispersing aid.Such dispersion resin is special Film forming component suitable for being used in aftermentioned coloured composition contains polymerizable component, is particularly, optical polymerism ingredient When use.As such dispersion resin, aftermentioned alkali soluble resin can be enumerated.Dispersion resin can be and coloring compositions The congener resin types of alkali soluble resin used in object or different types of resin types.Compared with phthalocyanine Pigment (total for it during containing other pigment) 100 parts by weight, the content of dispersion resin is preferably 10~50 parts by weight.In addition, During using pigment derivative, the content of phthalocyanine color (total for it during containing other pigment) refers to the conjunction for including pigment derivative Metering.

As solvent, can suitably be selected according to species of aftermentioned film forming component etc., for example, fragrance can be enumerated The various organic solvents of family, ketone system, ester system, glycol ethers system, alcohol system, fatty family etc..Wherein, from the sight of film formative Point consideration, the organic solvent being preferably selected from aromatic system, ketone system, ester system, glycol ethers system.Organic solvent can be only a kind, Two or more can be combined.

As the organic solvent of aromatic system, for example, the aromatic hydrocarbon of toluene, dimethylbenzene, ethylo benzene etc. can be enumerated.

As the organic solvent of ketone system, for example, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), diisobutyl ketone, levulinic can be enumerated Ketone, isophorone, acetophenone, cyclohexanone etc..

As the organic solvent of ester system, for example, it is different to enumerate ethyl acetate, n-butyl acetate, isobutyl acetate, acetic acid Propyl ester, methyl propionate, acetic acid -3- methoxybutyls, acetic acid glycol ester, propylene glycol methyl ether acetate (PMA), propylene glycol list Ether acetate, 3- methyl -3- methoxybutyls acetic acid esters, monochloro acetic acid methyl esters, monochloro acetic acid ethyl ester, monochloro acetic acid butyl ester, Methyl acetoacetate, ethyl acetoacetate, acetate of butyl carbitol, butyl lactate, ethyl -3- ethoxy-cs acid esters, second two Alcohol monobutyl ether-acetate, ethylene glycol monomethyl ether acetate, propyl acetate, 1,3 butylene glycol diacetate esters etc..

As the organic solvent of glycol ethers system, for example, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol can be enumerated Monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol list positive propyl ether, ethyleneglycol monopropylether, diethylene glycol Single isopropyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol mono-n-butyl ether, the tertiary butyl ether of ethylene glycol list, diethyl The tertiary butyl ether of glycol list, 1- methyl-1s-methoxybutanol, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol t-butyl ether, third Glycol list positive propyl ether, monoisopropyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol list positive propyl ether, two The water-soluble glycol ethers of monoisopropyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol mono-n-butyl ether etc., ethylene glycol list oneself Ether, ethylene glycol -2- ethyls hexyl ether, ethylene glycol phenyl ether, diethylene glycol n-hexyl ether, diethylene glycol -2- ethyls hexyl ether, propyleneglycol monobutyl Water-insoluble glycol ethers of ether, Dipropylene glycol mono-n-butyl Ether, dipropylene glycol propyl ether, propylene glycol monomethyl ether acetate etc. etc..

As the organic solvent of alcohol system, for example, the carbon atom of ethyl alcohol, methanol, butanol, propyl alcohol, isopropanol etc. can be enumerated Alkanols, ethylene glycol, propylene glycol, diethylene glycol, pentamethylene glycol, trimethylene, the 2- butene-1s of number 1~4,4- bis- Alcohol, 2- ethyl -1,3- hexylene glycols, polyethylene glycol, 1,3- of the 2- methyl -2,4-PD, tripropylene glycol, molecular weight below 2000 It is propylene glycol, Isopropanediol, i-butylene glycol, 1,4- butanediols, 1,3 butylene glycol, 1,5- pentanediols, 1,6-HD, glycerine, red Moss sugar alcohol, pentaerythrite etc..

As the organic solvent of fatty family, for example, the aliphatic hydrocarbon of pentane, n-hexane, normal heptane etc. can be enumerated Deng.

The additive amount of solvent, when for the preparation of aftermentioned coloured composition, from the viewpoint of operability, Neng Goutian It adds as that the solid component concentration for including phthalocyanine color etc. is made to become 50~85 weight %.

In pigment dispersion, other additives can also be contained in addition to above-mentioned ingredient.

Pigment dispersion such as can by the way that above-mentioned each ingredient is added to bead mill, sand milling, disperser well known to Disperseed to be obtained in dispersion machine.That is, pigment dispersion is that the solid constituent of phthalocyanine color etc. is dispersed in solvent as particle In obtained from dispersion.Wherein, the primary particle of other pigment that particle refers to above-mentioned phthalocyanine color, contains as needed The second particle formed Deng aggegation.

The average grain diameter of the particle disperseed in obtained pigment dispersion is operated as described above (below, sometimes referred to as " is divided Dissipate average grain diameter ".) be not particularly limited, it can it is preferable to use the about particles of 30~300nm.In addition, from the surface of film From the viewpoint of flatness, scattered average grain diameter is more preferably 30~150nm.In addition, scattered average grain diameter can for example utilize Particle size determination machine is measured.In addition, as particle size determination machine, Otsuka Electronics Co., Ltd.'s system, FPAR-1000 can be enumerated Deng.

＜ coloured compositions ＞

The embodiment of coloured composition according to the present invention contains above-mentioned pigment dispersion and film forming component. By containing above-mentioned pigment dispersion as described above, it can inhibit to prepare the reduction of the contrast of film after coloured composition. Further, since inhibiting the rising of the viscosity after preparing pigment dispersion, the operation of pigment dispersion is easy, can easily into The preparation of row coloured composition.

As film forming component, film component is applied as long as can be formed, is not particularly limited, can be polymerism Ingredient, can be polymer or these mixture.As the ingredient of polymerism, by developing (negative development), hold Easily implement patterning, it is therefore preferable that optical polymerism ingredient.In addition, as polymer, for example, thermoplastic polyurethane can be enumerated It is resin, (methyl) acrylic resin, polyamide series resin, polyimides system resins, styrene-maleic acid system resin, poly- Ester system resin, organic siliconresin, Cardo resins etc..The molecular weight of polymer can be determined suitably.

As the optical polymerism ingredient that can be used, contain photopolymerizable compound and Photoepolymerizationinitiater initiater.Such light Polymerizable compound and Photoepolymerizationinitiater initiater can for example use the substance recorded in Japanese Unexamined Patent Publication 2009-179789 publications. Specifically, such photopolymerizable compound is the polyaddition compound at least one ethylenical unsaturated double bonds, is selected from With at least one, the compound of preferably 2 or more terminal ethylenic unsaturated bonds.Such compound group is extensive in this field Well known compound can be not particularly limited to use in the present invention.Photopolymerizable compound for example with monomer, The chemical form of prepolymer, i.e. 2 aggressiveness, 3 aggressiveness and oligomer or these mixtures and these copolymer etc..

As monomer and its example of copolymer, unsaturated carboxylic acid can be enumerated (for example, acrylic acid, methacrylic acid, clothing Health acid, crotonic acid, methacrylate, maleic acid etc.), its esters, amides, it is preferable to use unsaturated carboxylic acids and aliphatic polyol The amides of the ester of compound, unsaturated carboxylic acid and aliphatic polybasic amine compounds.In addition, it is suitable for use of with hydroxyl, ammonia The esters of unsaturated carboxylic acids or amides and simple function group or many functional group isocyanates' class of the nucleophilic substitution base of base, sulfydryl etc. or The addition reaction of epoxies and with the dehydration condensation object of simple function group or multi-functional carboxylic acid etc..In addition, it also is adapted for For the esters of unsaturated carboxylic acids or amides and simple function group or more of the electrophilicity substituent group with isocyanate group, epoxy group etc. Alcohols, amine, the addition reaction of thio-alcohol and the detachment substitution with halogen, tosyloxy etc. of functional group The esters of unsaturated carboxylic acids or amides of base and simple function group or multi-functional alcohols, amine, the substituted reactant of thio-alcohol.Separately Outside, as other examples, it can also use and replace above-mentioned unsaturated carboxylic acid and be replaced into unsaturated sulfonic acid, styrene, second The compound group of alkene ether etc..

In addition, these concrete example is substantially as described in Japanese Unexamined Patent Publication 2009-179789 publications, as aliphatic polyol The concrete example of the monomer of the ester of compound and unsaturated carboxylic acid as acrylate, there is glycol diacrylate, triethylene glycol Diacrylate, 1,3 butyleneglycol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, season penta Omega-diol diacrylate, trimethylolpropane trimethacrylate, trimethylolpropane tris (acryloxypropyl) ether, three hydroxyl first Base ethane triacrylate, hexanediyl ester, 1,4- cyclohexanediols diacrylate, tetraethylene glycol diacrylate, Pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate Ester, dipentaerythritol hexaacrylate, Dipentaerythritol Pentaacrylate, D-sorbite triacrylate, D-sorbite 4 third It is olefin(e) acid ester, five acrylate of D-sorbite, six acrylate of D-sorbite, three (acryloyl-oxyethyl) isocyanuric acid esters, poly- Ester acrylate oligomer, isocyanuric acid EO modified triacrylates etc..

On these polyaddition compounds, structure, be used alone or and the application method of use, additive amount etc. it is detailed Content can carry out arbitrary setting according to the performance design of final coloured composition.

For example, it is selected according to following viewpoint.In terms of susceptibility, the structure more than the unsaturated group content of preferably every 1 molecule, In most cases preferably more than 2 functional groups.It is preferably chemical combination more than 3 functional groups in addition, in order to improve curing film strength Object, in addition, by and with different functional group number, different polymerizable groups (for example, acrylate, methacrylate, benzene Vinyl compound, vinyl ethers based compound) compound to adjust the method for susceptibility and intensity both sides be also effective.

In addition, for in coloured composition other ingredients (for example, the binder polymer of alkali soluble resin etc., Photoepolymerizationinitiater initiater, colorant (pigment)) compatibility, dispersiveness, the selection of polyaddition compounds, using method be also it is important because Element for example, by using low-purity compound, being used together by two or more types, can improve compatibility sometimes.

In addition, in order to improve the adaptation with base material etc., specific structure can also be selected.Compared in coloured composition Fixedness ingredient, photopolymerizable compound preferably comprises 5~70 weight %, further preferably 10~60 weight %.In addition, These, which can be used alone, to be used together by two or more types.In addition, the use method of photopolymerizable compound is it can be considered that compared with oxygen Size, resolution ratio, sprayability, variations in refractive index, the surface adhesive of Inhibition of polymerization etc. viewpoint arbitrarily select it is appropriate Structure, cooperation, additive amount.

As above-mentioned Photoepolymerizationinitiater initiater, can also the light recorded in Japanese Unexamined Patent Publication 2009-179789 publications be used to gather Close initiator.

Such as have, it is acetophenone system, ketal system, benzophenone series, benzoin system, benzoyl system, thioxanthones system, activated halogenated Close object (triazine Xi, oxadiazoles system, coumarin series), acridine system, double imidazoles systems, oxime ester system etc..

These concrete example, as the concrete example of benzophenone series Photoepolymerizationinitiater initiater, for example, hexichol first can be enumerated Double (dimethylamino) benzophenone of ketone, 4,4'-, 4,4'- double (diethylamino) benzophenone, 4,4'- dichloro benzophenones Deng.

As content of the Photoepolymerizationinitiater initiater in coloured composition, compared with all solids ingredient of coloured composition, Preferably 0.1~10.0 mass %, more preferably 0.5~5.0 mass %.When the content of Photoepolymerizationinitiater initiater is in the scope, Polymerisation is made to carry out well, the good film of intensity can be formed.

When containing optical polymerism ingredient as film forming component in coloured composition, above-mentioned pigment dispersion and light gather Beyond conjunction property ingredient, alkali soluble resin can also be contained.

When containing alkali soluble resin in coloured composition, such as in photo-mask process, apply in the patterning During color composition, patternability can be further improved.

As such alkali soluble resin, the resin recorded in Japanese Unexamined Patent Publication 2009-179789 publications can be used. Briefly, as alkali soluble resin, for example, can from as linear organic high molecular polymer and molecule (preferably with Acrylic acid series copolymer, styrene based copolymer be main chain molecule) in have at least one promote alkali-soluble group (example Such as, carboxyl, phosphate, sulfonic group etc.) alkali soluble resin in suitably select.Wherein, it is more preferably solvable in organic solvent And the resin that can be developed by weak base aqueous solution.

As the suitable example of alkali soluble resin, it can especially enumerate (methyl) acrylic acid and can be copolymerized with it The copolymer of other monomers.Here, (methyl) acrylic acid refers to the general name for including acrylic acid and methacrylic acid, below equally Ground, (methyl) acrylate are the general name of acrylate and methacrylate.

As alkyl (methyl) acrylate, aryl can be enumerated with other monomers of (methyl) acrylic acid copolymer (methyl) acrylate, vinyl compound etc..Wherein, the hydrogen atom of alkyl and aryl can be substituted with a substituent.

As abovementioned alkyl (methyl) acrylate and the concrete example of aryl (methyl) acrylate, can enumerate (methyl) Methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) acrylic acid are different Butyl ester, (methyl) amyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) 2-ethyl hexyl acrylate, (methyl) phenyl acrylate, (first Base) benzyl acrylate, (methyl) toluene toluene, (methyl) acrylic acid naphthalene ester, (methyl) cyclohexyl acrylate etc..

As above-mentioned vinyl compound, for example, styrene, α-methylstyrene, vinyltoluene, methyl can be enumerated Glycidyl acrylate, glycidyl acrylate, acrylonitrile, vinyl acetate, n-vinyl pyrrolidone, metering system Sour tetrahydrochysene chaff ester, Group-capped Polystyrene Macromer, polymethyl methacrylate macromonomer, CH₂=CR⁵R⁶、CH₂=C (R⁵) (COOR⁷) (wherein, R⁵Represent the alkyl of hydrogen atom or carbon number 1~5, R⁶Represent the aromatic series hydrocarbon ring of carbon number 6~10, R⁷Represent the alkyl of carbon number 1~8 or the aralkyl of carbon number 6~12.) etc..

These other monomers that can be copolymerized can be used alone, and can also combine two or more use.

From the viewpoint of developability, the weight average molecular weight of alkali soluble resin is preferably 5000~50000.

As alkali soluble resin, there are various commercially available alkali soluble resins, concrete example is as described below, but does not limit In these.

Showa Highpolymer Co., Ltd's system：RIPOXY SPC-2000、

Mitsubishi's RAYON Co. Ltd. systems：DIANAL NR Series、

Diamond hamrock Co.Ltd., system：Photomer6173 (the polyurethane acroleic acid oligomers containing COOH (Polyurethane acrylic oligomer))、

Osaka Organic Chemical Industry Co., Ltd.'s system：VISCOAT R-264、KS Resist 106、SOP―005、

Daicel chemical industry Co. Ltd. systems：CYCLOMER P Series, PLACCEL CF200 series,

Daicel UCB Co. Ltd. systems：Ebecry1 3800、

Nippon Shokubai Co., Ltd：ACRYCURE (registered trademark) RD-Y-503, RD-Y-702-A etc..

It is excellent in all solids ingredient of coloured composition as content of the alkali soluble resin in coloured composition Elect 1~20 weight % as, more preferably 2~15 weight %, particularly preferably 3~12 weight %.The conduct in pigment dispersion Dispersion resin contains sometimes, is total amount.

When containing optical polymerism ingredient as film forming component in coloured composition, except above-mentioned pigment dispersion and Beyond optical polymerism ingredient, alkali soluble resin, solvent can also be contained.By using solvent, can suitably prepare.

As such solvent, esters, such as ethyl acetate, n-butyl acetate, isobutyl acetate, formic acid penta can be enumerated Ester, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl isobutyrate, ethyl butyrate, butyl butyrate, alkyl esters, lactic acid Methyl esters, ethyl lactate；Oxoacetic acid methyl ester, ethyl, Oxoacetic Acid butyl ester, methoxy menthyl acetate, methoxyl group second Acetoacetic ester, methoxyacetic acid butyl ester, ethoxy acetate, ethoxy ethyl acetate；3- propionic acid methyl esters, 3- oxopropanoic acids The 3- oxopropanoic acid alkyl esters of ethyl ester etc.；3- methoxy methyl propionates, 3- methoxypropionates, 3- ethoxy-propionic acid first Ester, 3- ethoxyl ethyl propionates, Acetylformic acid methyl esters, ethyl 2-oxopropanoate, Acetylformic acid propyl ester, 2- methoxypropionic acids Methyl esters, 2- methoxypropionates, 2- methoxy propyls propyl propionate, 2- ethoxypropanoates, 2- ethoxyl ethyl propionates, 2- oxygen Generation -2 Methylpropionic acid methyl esters, 2- oxos -2 Methylpropionic acid ethyl ester, 2- methoxyl groups -2 Methylpropionic acid methyl esters, 2- ethyoxyl -2- first Base ethyl propionate, methyl pyruvate, ethyl pyruvate, Propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2- oxos Methyl butyrate, 2-Oxobutyric acid ethyl ester etc.；Ethers, such as diethylene glycol dimethyl ether, tetrahydrofuran, glycol monoethyl ether, second two Alcohol list ether, acetic acid methyl cellosolve, acetic cellosolve, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol Monobutyl ether, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol propyl ether acetic acid esters etc.； Ketone, such as methyl ethyl ketone, cyclohexanone, 2-HEPTANONE, 3- heptanone；It is aromatic hydrocarbon, such as toluene, dimethylbenzene.

Solvent can be used alone, and can also combine two or more use.

As content of the solvent in coloured composition, it is considered preferred to species, the content of the solvent in pigment dispersion, with The mode that all solids ingredient (nonvolatile component) content in coloured composition is 15~50 weight % contains.

When using polymer as film forming component, also with using optical polymerism ingredient when it is also possible to use solvent. As such solvent, the solvent that can be used in above-mentioned pigment dispersion can be used, can be with optical polymerism ingredient The solvent being used together.

At this point, the content as solvent in coloured composition, it is also preferred that consider the species of the solvent in pigment dispersion, Content contains in a manner that all solids ingredient (nonvolatile component) content in coloured composition is 15~50 weight %.

In coloured composition, dispersing aid, sensitizer (sensitizing coloring matter), chain movement agent, fluorine can be added as needed on It is series organic compound, thermal polymerization, thermal polymerization ingredient, filler, surfactant, closely sealed accelerating agent, antioxidant, anti- The various additives of agglutinant, surface conditioner (levelling agent) etc..Contain in pigment dispersion sometimes, adjustment additive amount is It can.

Coloured composition by pigment dispersion add film forming component, using disperser be stirred come It arrives.

The film formed using coloured composition can inhibit to prepare the reduction of the contrast after coloured composition.Therefore, Coloured composition containing above-mentioned pigment dispersion is suitable for the formation of color-filter element.

Embodiment

Reagent used in aftermentioned embodiment, comparative example, control etc. is as described below.

(1) pigment

·C.I.Pigment Green 59

Product name " FASTOGEN GREEN C100 " (is known as " C100 " in table.), Dainippon Ink Chemicals's system.For chlorination bromination ZnPc pigment, contained average hydrogen atom number is more than 2 in a molecule.

15 ﹕ 6 of C.I.Pigment Blue

Product name CYANINE BLUE A540, Dainippon Ink Chemicals's system.For copper phthalocyanine.

(2) phthalimide and its derivative

Phthalimide：Tokyo HuaCheng Industry Co., Ltd's system

Phthalimide acetic acid：Tokyo HuaCheng Industry Co., Ltd's system

N- butyl phthalimides：Tokyo HuaCheng Industry Co., Ltd's system

Phthalimide acetone：Tokyo HuaCheng Industry Co., Ltd's system

3- phthalimide propionic acid：Accel Pharmtech company systems

Tetrachloro-phthalimide acetic acid：With reference to Production Example 3.

Tetrabromo phthalimide acetic acid：With reference to Production Example 4.

3- tetrachloro-phthalimide propionic acid：With reference to Production Example 1.

3- tetrabromo phthalimide propionic acid：With reference to Production Example 5.

N- (2- hydroxyethyls) phthalimide：Tokyo HuaCheng Industry Co., Ltd's system

2- tetrachloro-phthalimide ethane phosphoric acid：With reference to Production Example 2.

(3) dispersant

Disperbyk-LPN6919, BYK Japan Co. Ltd. systems, the resin type dispersant with tertiary amino

SOLSPERSE 41000, Japan's Lubrizol Co. Ltd. systems, resin type dispersant (4) solvent

Propylene glycol methyl ether acetate (hereinafter referred to as " PMA ".)

Propylene glycol monomethyl ether (hereinafter referred to as " PM ".)

(5) dispersion resin

ACRYCURE (registered trademark) RD-Y-702-A, Nippon Shokubai Co., Ltd's system.

The manufacture of (Production Example 1) phthalimide derivative (3- tetrachloro-phthalimides propionic acid)

100ml eggplant type flasks are placed in oil bath, add in propylene glycol monomethyl ether (hereinafter referred to as " PM ".) 75g, tetrachloro be adjacent Phthalate anhydride 20.02g (70mmol), beta Alanine 6.24g (70mmol) set cooling tube, while using magnetic stirrer on top It is stirred side oil bath heats up.Start that object is precipitated when temperature reaches 130 DEG C, therefore, maintenance stirs 5 minutes. Hereafter, it is cooled to room temperature, the PM of additional 25g, and then continues stirring 30 minutes.Content is filtered with suction filter, with pure water pair After residue is cleaned, when 100 DEG C of dryings 18 are small.Receipts amount is 18.7g (yield 74%).Using the dried object as O-phthalic Imide derivative, that is, 3- tetrachloro-phthalimide propionic acid, for aftermentioned embodiment.

It is being obtained with MALDI-TOF-MS mass analyzer AXIMA CFR plus (Shimadzu Seisakusho Ltd.'s system), make in matrix In spectrum with the negative mode of 2,5-dihydroxybenzoic acid (2,5-Dihydroxybenzoic acid (DHBA)), confirm To the peak for having object (m/z 355).

The manufacture of (Production Example 2) phthalimide derivative (2- tetrachloro-phthalimide ethane phosphoric acid)

500m1 four-hole boiling flasks are placed in oil bath, add in PM 200g, tetrachlorophthalic tetrachlorophthalic anhydrid 41.95g (150mmol), O- phosphoethanolamines 20.70g (150mmol), 1,4- diazabicylos [2,2,2]-octane 33.65g (300mmol), top set cooling tube, heat when being stirred with magnetic stirrer also flow 6 it is small when.Placement is cooled to room After temperature, content with suction filter is filtered, residue is cleaned with PM.Divide residue redisperse 30 in 1.5L methanol After clock, add 35% hydrochloric acid 300g and stir 30 minutes.Content with suction filter is filtered, residue is carried out with a small amount of methanol After cleaning, make its drying.Receipts amount is 42g (yield 69%).Using the dried object as phthalimide derivative, that is, 2- tetra- Chlorophthalimide ethane phosphoric acid, for aftermentioned embodiment.

It is being obtained with MALDI-TOF-MS mass analyzer AXIMA CFR plus (Shimadzu Seisakusho Ltd.'s system), make in matrix With alpha-cyano -4- hydroxycinnamic acids (α-cyano-4-hydroxycinnamic acid (CHCA)) and 2,5- dihydroxy benzenes first In the spectrum of the negative mode of sour (2,5-Dihydroxybenzoic acid (DHBA)), object (m/z 407) has been confirmed Peak.

The manufacture of (Production Example 3) phthalimide derivative (tetrachloro-phthalimide acetic acid)

In addition to making beta Alanine 70mmol for glycine 70mmol, to be operated with 1 same condition of Production Example, Obtain dried object.Receipts amount is 15.12g (yield 63%).It is adjacent using the dried object as phthalimide derivative, that is, tetrachloro Phthalimide acetic acid, for aftermentioned embodiment.

It is being obtained with MALDI-TOF-MS mass analyzer AXIMA CFR plus (Shimadzu Seisakusho Ltd.'s system), make in matrix With alpha-cyano -4- hydroxycinnamic acids (α-cyano-4-hydroxycinnamic acid (CHCA)) and 2,5- dihydroxy benzenes first In the spectrum of the negative mode of sour (2,5-Dihydroxybenzoic acid (DHBA)), object (m/z 341) has been confirmed Peak.

The manufacture of (Production Example 4) phthalimide derivative (tetrabromo phthalimide acetic acid)

Except beta Alanine 70mmol is made to be glycine 70mmol, tetrachlorophthalic tetrachlorophthalic anhydrid 70mmol is made to be tetrabromo-phthalic Beyond dicarboxylic acid anhydride 70mmol, to be operated with 1 same condition of Production Example, dried object is obtained.Receipts amount is 26.24g (yields 72%).Using the dried object as phthalimide derivative, that is, tetrachloro-phthalimide acetic acid, for aftermentioned reality Apply example.

It is being obtained with MALDI-TOF-MS mass analyzer AXIMA CFR plus (Shimadzu Seisakusho Ltd.'s system), make in matrix With alpha-cyano -4- hydroxycinnamic acids (α-cyano-4-hydroxycinnamic acid (CHCA)) and 2,5- dihydroxy benzenes first In the spectrum of the negative mode of sour (2,5-Dihydroxybenzoic acid (DHBA)), object (m/z 517) has been confirmed Peak.

The manufacture of (Production Example 5) phthalimide derivative (3- tetrabromo phthalimides propionic acid)

Except making tetrachlorophthalic tetrachlorophthalic anhydrid 70mmol in addition to tetrabromophthalic anhydride 70mmol, with Production Example 1 Same condition is operated, and obtains dried object.Receipts amount is 28.08g (yield 75%).Using the dried object as phthalyl Imine derivative, that is, 3- tetrabromo phthalimide propionic acid, for aftermentioned embodiment.

It is being obtained with MALDI-TOF-MS mass analyzer AXIMA CFR plus (Shimadzu Seisakusho Ltd.'s system), make in matrix With alpha-cyano -4- hydroxycinnamic acids (α-cyano-4-hydroxycinnamic acid (CHCA)) and 2,5- dihydroxy benzenes first In the spectrum of the negative mode of sour (2,5-Dihydroxybenzoic acid (DHBA)), object (m/z 531) has been confirmed Peak.

(control 1)

The manufacture ＞ of ＜ pigment dispersions

In sand milling, the C.I.Pigment Green 59 (FASTOGEN GREEN C100) as phthalocyanine color are put into 38.40g, dispersant (Disperbyk-LPN6919) 22.03g, dispersion resin (ACRYCURE (registered trademark) RD-Y-702-A) 23.59g, the PMA 75.98g as solvent.

After being stirred 10 minutes with 2000 turns, Φ 0.8mm Zirconia beads 640g are put into, row decentralized processing is rotated into 2000 30 minutes.

PMA 30.28g, dispersant (SOLSPERSE 41000, Japan are further added in the decentralized processing liquid Lubrizol systems) 1.72g, rotate into row decentralized processing 10 minutes with 2000.The scattered place of Φ 0.8mm Zirconia beads will be eliminated Reason liquid 160g is put into together with Φ 0.lmm Zirconia beads 640g in other basins, and row decentralized processing is rotated into 60 minutes with 2000.

After additional PMA 77.04g, rotate into row decentralized processing 10 minutes with 1500, remove Φ 0.lmm Zirconia beads, Obtain viridine green dispersion.

The manufacture ＞ of ＜ coloured compositions

As the polymer of (methyl) acrylic acid series, prepare containing Nippon Shokubai Co., Ltd's system, ACRYCURE (registrars Mark) 12.0 weight % (pure point) of BX-Y-10, as optical polymerism ingredient polyfunctional acrylate monomer dipentaerythritol (six/five) acrylate (Nippon Kayaku K. K's system, KAYARAD DPHA) 26.0 weight %, as Photoepolymerizationinitiater initiater BASF Japan systems, 4.0 weight % of Irgacure369, as solvent 58.0 weight % of PMA film forming component.

Film forming component is added in obtained viridine green dispersion, is stirred with disperser, obtains coloured composition. Compared with viridine green dispersion 6.0g, the additive amount of film forming component is 4.0g.

(Examples 1 to 9, comparative example 1)

The manufacture ＞ of ＜ pigment dispersions

Except by C.I.Pigment Green 59 (FASTOGEN GREEN C100) and phthalimide or its spread out Beyond the additive amount of biology is set to as described in Table 1, with compareing 1 similary operation, viridine green dispersion is obtained.

<The manufacture of coloured composition>

Using obtained viridine green dispersion, with compareing 1 similary operation, coloured composition is obtained.

(control 2)

The manufacture ＞ of ＜ pigment dispersions

In sand milling, 15 ﹕ 6 (FASTGEN BLUE A540) of C.I.Pigment Blue as phthalocyanine color are put into 30.72g, dispersant (Disperbyk-LPN6919) 21.28g, dispersion resin (ACRYCURE (registered trademark) RD-Y-702-A) 42.44g, the phthalimide derivative 1.28g of Production Example 2, the PMA 38.68g as solvent, PM 25.60g.

After being stirred 10 minutes with 2000 turns, Φ 0.8mm Zirconia beads 640g are put into, row decentralized processing is rotated into 2000 30 minutes.

PMA 28.24g are further added in the decentralized processing liquid, row decentralized processing is rotated into 10 minutes with 2000.

It will be together with decentralized processing liquid 160g and Φ 0.05mm the Zirconia beads 640g that Φ 0.8mm Zirconia beads be eliminated In the other basins of input, row decentralized processing is rotated into 60 minutes with 2000.

After additional PMA 105.0g, rotate into row decentralized processing 10 minutes with 1500, remove Φ 0.05mm Zirconia beads, Obtain blue pigment dispersion.

The manufacture ＞ of ＜ coloured compositions

Using obtained viridine green dispersion, with compareing 1 similary operation, coloured composition is obtained.

(embodiment 10~12)

The manufacture ＞ of ＜ pigment dispersions

Except by 15 ﹕ 6 (FASTGEN BLUE A540) of C.I.Pigment Blue and phthalimide derivative Additive amount be set to as described in Table 1 beyond, with compare 2 equally operate, obtain blue pigment dispersion.

The manufacture ＞ of ＜ coloured compositions

Using obtained viridine green dispersion, with compareing 2 similary operations, coloured composition is obtained.

(evaluation)

The ongoing change ＞ of the viscosity of ＜ pigment dispersions

The face obtained in control, embodiment, comparative example is measured using Dong Ji industry companies system, E types viscosimeter " RE-80L " Expect viscosity of the dispersion after firm manufacture and by its viscosity after being stood 3 days at 40 DEG C.It is represented in table 1 to each envelope photograph, in fact Apply the viscosity (mPas) that the pigment dispersion of example and comparative example measures.

The ongoing change ＞ of the contrast of ＜ coloured compositions

With the following method to viscosity after firm manufacture of the pigment dispersion that is obtained in control, embodiment, comparative example and Its contrast after being stood 3 days at 40 DEG C is evaluated.That is, using spin coater (the Mikasa plants of formula meetings for having adjusted rotating speed Society's system, spin coater MS-150A) it is coated on the glass plate of thickness 1mm, 100mm square so that during green coloring composition Colourity be x=0.550, blue colored composition when colourity be y=0.107.By the coated panel be stored at room temperature 5 minutes it Afterwards, at 80 DEG C (preliminary drying) is dried with air bath 2 minutes.Then, with exposure device (K.K. Minaga Denki Seisakusho's system, business The name of an article：UVE-1001S type exposure light sources device, YSH -100SA types extra-high-pressure mercury vapour lamp) with 60mJ/cm²Exposure intensity pair Coated panel irradiation ultraviolet light (UV), to be toasted 60 minutes when 235 DEG C, green, when blue after the condition implementation of 30 minutes.It is dried by after Coated panel after roasting is in lamp (trade name：HF-LS-100WLCG polarizer (trade name is used on)：POLAX-38S, Co., Ltd. Luceo systems) clip setting.Use chroma-luminance instrument (trade name：LS-100, KONICA MINOLTA SENSING Co., Ltd. System) measure brightness when brightness of polarizer when being located at the position of crossed Nicol is in parallel position with polarizer, calculating This spends (CR) as a comparison than (%).It represents to be measured the pigment dispersion of each control, embodiment and comparative example in table 1 Result.Value is represented with each embodiment and comparative example compared with the ratio of control, is evaluated according to following benchmark.Compared with ◎ is denoted as when the ratio of control is more than 140, be denoted as when the zero, ratio is 0~99 when the ratio is 100~139 be denoted as ×.

【Table 1】

Claims (8)

1. a kind of pigment dispersion, it is characterised in that：

Containing selected from least one of the phthalimide shown in following formula (1) and its derivative, phthalocyanine color, scattered Agent and solvent,

In formula (1), R¹~R⁴For hydrogen atom or halogen atom, Q is that (i) hydrogen atom, (ii) can have carbon atom knot with end The alkyl or (iii) of the carbon number 1~5 of the substituent X of conjunction can be with the substituent group Y's combined with the carbon atom of aromatic rings Aryl, substituent X are acetyl group, carboxyl, phosphate or sulfo group, and substituent group Y is methyl, acetyl group, carboxyl, phosphate or sulphur Base.

2. pigment dispersion as described in claim 1, it is characterised in that：

The phthalocyanine color is metal phthalocyanine pigment.

3. pigment dispersion as claimed in claim 2, it is characterised in that：

The metal phthalocyanine pigment is ZnPc pigment or copper phthalocyanine.

4. pigment dispersion as claimed in claim 3, it is characterised in that：

The ZnPc pigment is the zinc halide phthalocyanine color that contained average hydrogen atom number in one molecule is more than 2.

5. pigment dispersion as claimed in claim 4, it is characterised in that：

The zinc halide phthalocyanine color is chlorination bromination ZnPc pigment.

6. such as pigment dispersion according to any one of claims 1 to 5, it is characterised in that：

Q in the formula (1) is the alkyl for the carbon number 2 that (ii) can have the substituent X combined with the carbon atom of end, Substituent X is carboxyl or phosphate.

7. a kind of coloured composition, it is characterised in that：

Contain pigment dispersion according to any one of claims 1 to 6 and film forming component.

8. coloured composition as claimed in claim 7, it is characterised in that：

Contain optical polymerism ingredient as the film forming component.