CN110402404A

CN110402404A - Pigment composition for color filter and colour filter

Info

Publication number: CN110402404A
Application number: CN201880017245.1A
Authority: CN
Inventors: 坂本圭亮; 千叶祐奈; 清水郁马; 木村亮
Original assignee: DIC Corp
Current assignee: DIC Corp
Priority date: 2017-04-03
Filing date: 2018-03-22
Publication date: 2019-11-01
Anticipated expiration: 2038-03-22
Also published as: CN110402404B; TW201843247A; KR102531076B1; JPWO2018186182A1; JP6455748B1; KR20190137072A; WO2018186182A1; TWI745571B

Abstract

The problem to be solved by the present invention is that providing a kind of color compositions of colour filter for obtaining improving brightness without thick-film.The present invention is capable of providing a kind of pigment composition for color filter and has colour filter made of the pigment composition for color filter in pixel portion, the pigment composition for color filter is characterized in that, contains pigment derivative represented by zinc halide phthalocyanine color and the following general formula (1).(in general formula (1), Z¹~Z¹⁶Bromine atom, chlorine atom, hydrogen atom or sulfo group are each independently represented, at least average substitution radix of sulfo group is 0.1~4, and M indicates Al, Si, Sc, Ti, V, Mg, Fe, Co, Ni, Zn, Ga, Ge, Y, Zr, Nb, In, Sn or Pb).

Description

Pigment composition for color filter and colour filter

Technical field

The present invention relates to pigment composition for color filter and colour filter.

Background technique

Colour filter for liquid crystal display is such as lower member: more by regularly configuring on transparent glass substrate A color only makes the light transmission of required wavelength region from the white light by its backlight, to realize the coloured silk of display Color is shown.Wherein used color generally comprises Red Green Blue, in order to adjust separately transmitted spectrum and to being used Colorant, resin, additive etc. improvement has been repeated.From the viewpoint of display image quality raising, to colour filter therein The expansion of high brightness and color reproduction range is required with green colourant.

About high brightness, it is important that the selection pigment high to the transmissivity of backlight light, by using naphthol green 58 Previous pigment green 36 is substituted as main pigments, to be improved.In addition, by highlighted brought by pigment improvement Degreeization can efficiently use the white light of backlight, therefore can be realized the energy-saving of display, manufacturing cost reduction.

About the expansion of color reproduction range, need to improve the chroma of colorant contained in colour filter.In order to make chroma High film, the pigment concentration being improved in film or the method etc. that film film thickness is thickened with same pigment concentration.However, In It is all difficult to ensure all patience of film under either case, therefore, has selected and the previous pigment green 36 for color filter application, face Expect that green 58 compare, the pigment Green 7 of filming can be carried out under the specific hue after mixing colours with yellow colorant as main pigments. It, can not be with 3.5 μm or so of reality although can also expand color reproduction range by the thick-film of pigment green 36, naphthol green 58 NTSC is realized with film thickness than 90% or more, this is the reasons why selecting pigment Green 7.For example, propose using containing pigment Green 7, The green photonasty resin composition of pigment yellow 185 forms green pixel, realizes high color again with 2.2 μm of films below It is existing.But pigment Green 7 transmissivity when compared with pigment green 36, naphthol green 58 is low, therefore has the brightness of obtained display Such problems can be reduced.In addition, can also be made up by improving the light quantity of backlight, but about brightness due to that can generate Power consumption increases such new problem, it is therefore desirable to improve.By upper, it is expected that taking into account the colour filter color of brightness and colorrendering quality Material.

In order to solve these projects, proposes: in the case where main pigments are aluminium phthalocyanine, so that it is contained phthalocyanine sulfonic acids and spread out Biology, it is excellent to make colour saturation and excitation purity, the transparency, heat resistance, light resistance also good colour filter (patent document 1).But It is, sometimes due to heat resistance, the light resistance of the aluminium phthalocyanine color as main pigments are low, to lead to not what satisfaction required in recent years Performance.

Further it is proposed that using halogenated copper phthalocyanine pigment and low halogenated copper phthalocyanine sulfonic acid and primary particle is contained Average grain diameter be 0.01~0.1 μm and green pigment composition that aspect ratio is 1~3, to make the good colour filter of contrast Device (patent document 2).But sometimes due to the brightness of the copper phthalocyanine as main pigments is low, lead to not meet in recent years Come desired performance.

Actual conditions are as a result: in order to form the colour filter for the purpose of high brightness, color reproduction range expansion, this A little prior arts be insufficient for it is rapidly raised in recent years require performance, still cannot achieve purpose.

Patent document 1: Japanese Unexamined Patent Publication 2011-057910 bulletin

Patent document 2: Japanese Unexamined Patent Publication 2005-316244 bulletin

Summary of the invention

Subject to be solved by the invention

The problem to be solved by the present invention is that providing a kind of colour filter for obtaining improving brightness without thick-film The color compositions of device.

The method used for solving the problem

The inventors of the present invention have carried out positive research in view of such situation, as a result, it has been found that: by using halogenation ZnPc face Material is used as main pigments, and it is made to contain specific pigment derivative, and can make can mention without thick-film The colour filter of high brightness.That is, the present invention relates to a kind of pigment composition for color filter and in pixel portion there is the colour filter to use Colour filter made of color compositions, the pigment composition for color filter be characterized in that, containing zinc halide phthalocyanine color and under State pigment derivative represented by general formula (1).

[changing 1]

(in general formula (1), Z¹~Z¹⁶Each independently represent bromine atom, chlorine atom, hydrogen atom or sulfo group, at least sulfo group Averagely replacing radix is 0.1~4, and M indicates Al, Si, Sc, Ti, V, Mg, Fe, Co, Ni, Zn, Ga, Ge, Y, Zr, Nb, In, Sn Or Pb.)

Invention effect

According to the present invention, the colour filter that brightness can be improved without thick-film can be made.

Specific embodiment

Zinc halide phthalocyanine color used in the present invention can be being replaced in addition to halogen in center configuration zinc metal The compound for replacing the halogen atom selected in the slave chlorine, bromine, fluorine and the iodine that have at least one or more on the phthalocyanine ring of substituent group, respectively takes The total number of Dai Ji most 16.The part that substituent group by halogen and in addition to halogen does not replace refers to the portion for hydrogen atom Point.

Wherein, from the viewpoint of the wide colour filter of design colours reproduction range, halogenation ZnPc used in the present invention Pigment preferably has average 10~14 halogen atoms in 1 molecule, and wherein bromine atom number is 8~12 average, amount of chlorine atom For average 2~5 pigment.

Pigment derivative used in the present invention can be indicated by above-mentioned general formula (1).

Wherein, from the viewpoint of keeping the main pigments of green color filter similar with the form and aspect of pigment derivative, above-mentioned face Expect that it is preferable to use following pigment derivatives for derivative: in above-mentioned general formula (1), Z¹~Z¹⁶With bromine atom, chlorine atom, hydrogen atom Or any one of sulfo group, and in terms of being averaged in a molecule, at least from Z¹、Z⁴、Z⁵、Z⁸、Z⁹、Z¹²、Z¹³、Z¹⁶Middle selection is appointed Meaning 2 or more has chlorine atom.

In addition, from the viewpoint of keeping the main pigments of green color filter similar with the form and aspect of pigment derivative, above-mentioned face Expect derivative it is also preferred that using following pigment derivative: in above-mentioned general formula (1), Z¹~Z¹⁶It is former with bromine atom, chlorine atom, hydrogen Son or any one of sulfo group, and in terms of being averaged in a molecule, at least from Z¹、Z⁴、Z⁵、Z⁸、Z⁹、Z¹²、Z¹³、Z¹⁶Middle selection Any 2 or more have bromine atom.

It should be noted that being described in Japanese Unexamined Patent Publication 2010-189528: if chlorine atom or bromine atom enter Z¹、Z⁴、 Z⁵、Z⁸、Z⁹、Z¹²、Z¹³、Z¹⁶Position, then form and aspect are afforested partially.

From the viewpoint of keeping the form and aspect of pigment derivative similar with the form and aspect of main pigments, more preferably with a molecule In average meter, Z¹~Z¹⁶In contain 10~14 halogen atoms, 8~12 bromine atoms, 2~5 chlorine atoms.

Color compositions present invention as described above are not that the pigment of previous such pigment and homologous ray skeleton is derivative The color compositions that object is composed merely, but the present invention is completed based on following thought.

(A) firstly, the conjugated system of height has been integrally formed as molecule for general organic pigment, become planar structure, this It is stable on energy.It is each intermolecular if configured (in parallel) in a manner of planar each molecule is laminated The pi-electron of possessed conjugated system can be overlapped, therefore become more stable state.General formula used in the present invention (1) is represented Pigment derivative due to being planar structure, being easy to generate between the planar structure of organic pigment with phthalocyanine ring Interaction.Further, it is believed that: in the case where main pigments are halogenated phthalocyanines pigment, it is particularly easy in derivative and pi-electron Between generate halogen-π interaction.Think: if making such specific pigment derivative in the dispersion step of organic pigment It coexists, then derivative can efficiently be adsorbed in the active surface of the newly generated halogenated phthalocyanines pigment in dispersion.In addition, utilizing , can be by halogenated phthalocyanines pigment with fine state dispersion stability as the sulfo group of polar group, therefore can be improved brightness.This Place, sulfonated phthalocyanine derivative of the invention can be added in pigmentation, can be played the addition in dispersion good Effect is then able to enter the intermolecular of halogenated phthalocyanines pigment, protects primary particle but if it coexists in pigmentation process It holds fine, accordingly, with respect to sulfonated phthalocyanine derivative of the invention, the case where compared to adding in dispersion, makes it in pigmentation Shi Gongcun can be realized much bigger brightness improvement.

(B) further, it is conceived to the overlap mode of the absorption spectrum of pigment and derivative also to complete the present invention.In order to It is become clear in the colour filter of green pixel and distinct display, particularly preferably improves the transmissivity of 510nm to 560nm.In order to Design only transmits the colour filter in the narrow wavelength region domain, combines viridine green and yellow uitramarine comes using therefore being preferably formed in The pigment derivative handled in viridine green the combination similar with the transmission peak wavelength of viridine green in 510~560nm.

(C) in addition, being described in Japanese Unexamined Patent Publication 8-240708: if the transmissivity of 430nm to 460nm is high, chromaticity y Value is greatly reduced, and green vividness can be significantly damaged, therefore the transmissivity of the wave-length coverage is preferably lower.It is worth in chromaticity y low In the case where, it is necessary to film thickness is thickened and improves chromaticity y value, but if film thickness is thickened, then brightness can reduce.Therefore, it is necessary to Select the transmissivity of 430nm to 460nm such pigment derivative as low as possible.The green pixel of especially colour filter is usually C.I. pigment yellow 13 8 (Y138) as quinophthalone system yellow uitramarine is combined to viridine green to use.Japanese Unexamined Patent Publication 2015- Describe in 26077: Y138 can be transferred to transmission bands from absorption band before and after 460nm, and therefore, Y138 is able to carry out shorter than The absorption of the wavelength of 460nm, but be not suitable for carrying out the absorption of long wavelength side, therefore the derivative handled in green pigment The transmissivity of 460nm is preferably lower.

From the viewpoint of such above-mentioned (B) and (C), the central metal M in above-mentioned formula (1) is preferably Al, Zn, In, preferably Zn.It is the substance of Al as face with the metal M used in above-mentioned formula (1) if the viewpoint of (C) is described in detail Material derivative is compared, when using substance that metal M in above-mentioned formula (1) is Zn as pigment derivative in 430nm~460nm Transmissivity it is lower, therefore color compositions of high brightness can be made.

Such pigment derivative can for example be obtained by known method below.I.e., it is possible to pass through by Phthalocyanine or halogenated phthalocyanines are dissolved in sulfuric acid and are heated to 100 DEG C or more, or are dissolved in oleum and carry out in low temperature Processing is to obtain.It should be noted that phthalocyanine ring can be because of sulphur if sulfo group is imported phthalocyanine ring under stringent reaction condition Acid or oleum and oxygenolysis, the purity of pigment derivative can reduce.From the sight for using the higher pigment derivative of purity Point considers, in above-mentioned general formula (1), in terms of being averaged in a molecule, the average substitution radix of sulfo group is preferably 0.1~4, more excellent It is selected as 0.5~2.

Sulfo group can be sulfonic acid, be also possible to the state of salt.The example of counter ion as forming salt, may include: ammonium Ion, 1~trivalent metal ion (as concrete example, can enumerate: lithium ion, sodium ion, potassium ion, calcium ion, magnesium ion, strontium Ion, aluminium ion etc.) and organic cation (as concrete example, can enumerate: the monoalkyls ammonium such as ethylammonium ions, butyl ammonium ion Ion；The dialkyl ammoniums ions such as dimethyl ammonium ion, diethyl ammonium ion；Three alkane such as trimethyl ammonium ion, triethyl ammonium ion Base ammonium ion；The alkanols ammonium ions such as monoethanol ammonium ion, diethanol ammonium ion, triethanol ammonium ion；Tetramethyl ammonium, tetramethyl Base guanidinium ion, tetramethyl phosphonium ion etc.).Especially can make manufacture colour filter developing procedure in pigment derivative it is molten The aspect that output reduces, the sulfo group of pigment derivative in the present invention is preferably sulfonic acid or organic cation salt.

In the present invention, the average Number of Halogen Atoms of zinc halide phthalocyanine color can be found out by quality analysis.Quality point Analysis uses Matrix-assisted laser desorption ionization instrument (Jeol Ltd. JMS-S3000) Lai Jinhang, When carrying out the quality analysis for the known compound that molecular weight is Q, each location parameter is set to detect m/z=Q.The present invention In, when carrying out the quality analysis of known compound of molecular weight 1840, the setting of JMS-S3000 is adjusted to detect m/z =l840.It should be noted that using making zinc halide phthalocyanine color 0.5mg be scattered in the resulting 1 μ L of suspension of tetrahydrofuran 1mL To carry out quality analysis.

In the present invention, the average sulphonation rate of pigment derivative can (Shimadzu makes by high performance liquid chromatography mass spectrograph Made LC-MS-8040) it finds out.Constant volume is carried out to pigment derivative with dimethyl sulfoxide, using by 10mmol/L ammonium hydrogen carbonate Aqueous solution/methanol/tetrahydrofuran mixed solvent carries out the resulting curve of gradient elution as mobile phase.Obtained peak is logical It crosses quality analysis (ionization mode: DUIS) and carries out respectively qualitative, sulphonation rate is calculated by peak area ratio.

In addition, in above-mentioned pigment derivative of the invention, Z in above-mentioned general formula (1)¹、Z⁴、Z⁵、Z⁸、Z⁹、Z¹²、Z¹³、Z¹⁶'s Halogenic substituent number m and Z²、Z³、Z⁶、Z⁷、Z¹⁰、Z¹¹、Z¹⁴、Z¹⁵Halogenic substituent number n by with cerous sulfate decompose pigment spread out Biology and after phthalimide class is made, found out with the obtained phthalimide class of liquid-phase chromatographic analysis.In Total molar concentration of the obtained whole phthalimide classes of the result of liquid chromatogram is set as a, it will be at 3 or 6 Total molar concentration of phthalimide class with halogen is set as b, and (phthalyl that halogen is all had at 3,6 is sub- In the case where amine, the molar concentration of the phthalimide class is calculated with 2 times surveyed), will have in 4 or 5 Total molar concentration of the phthalimide class of halogen is set as c and (all has the phthalimide class of halogen at 4,5 In the case where, the molar concentration of the phthalimide class is calculated with 2 times surveyed) in the case where, with m=4 × b/a, n The form calculus of=4 × c/a.It should be noted that, although m, n can be found out by liquid-phase chromatographic analysis, but thrown by control Enter raw material, is free to determine m, n.For example, by using 3- chloro-phthalic anhydride as tetrachloro ZnPc synthesized by raw material into In pigment derivative obtained from row sulfonation, m=4, n=0.In addition, by using 4- chloro-phthalic anhydride as synthesized by raw material Tetrachloro ZnPc carries out in pigment derivative obtained from sulfonation, m=0, n=4.

In addition, in the present invention, the average Number of Halogen Atoms of pigment derivative can be swashed by using above-mentioned Matrix-assisted The quality analysis of photodesorption ionization time-of-flight mass spectrometer is found out.

Pigment derivative of the invention can be added when thick pigment synthesizes, after pigmentation, can also be in pigmentation Pigmentation is carried out together with thick pigment.In addition, colour filter dispersion liquid, colour filter are bright with the dispersibility increase of resist ink Degree improves, therefore can also add pigment derivative in dispersion, when resist production.Pigment derivative used in the present invention It is able to enter the intermolecular of zinc halide phthalocyanine color and primary particle is kept fine, therefore pigment preferably is added in pigmentation Derivative carries out pigmentation together with thick pigment.

The above-mentioned color compositions containing pigment derivative represented by zinc halide phthalocyanine color and above-mentioned formula (1) are according to need Dry type is carried out in the pulverizers such as grater, ball mill, vibrating mill, vibrator to grind, grind followed by lyonium salt Method, solvent boiling process etc. carry out pigmentation, to can be obtained, dispersibility, tinting strength, tinting power are excellent compared with before pigmentation and sending is bright Spend the pigment of high green.

The ratio of pigment derivative represented by zinc halide phthalocyanine color and above-mentioned formula (1) is not particularly limited, with quality Conversion meter contains pigment derivative represented by 0.1~10 part of above-mentioned formula (1), In relative to 100 parts of zinc halide phthalocyanine color When the color compositions are used as colour filter, brightness can be improved without thick-film, therefore preferably.

The pigment of green pigment composition comprising pigment derivative represented by zinc halide phthalocyanine color and above-mentioned formula (1) Change method is not particularly limited, for example, can make containing represented by zinc halide phthalocyanine color and above-mentioned formula (1) before pigmentation The color compositions of pigment derivative are scattered in decentralized medium, while carrying out pigmentation, but are incited somebody to action in a large amount of organic solvents Color compositions comprising pigment derivative represented by zinc halide phthalocyanine color and above-mentioned formula (1) carry out the solvent of heating stirring Processing is compared, and can easily suppress crystalline growth, and the aspect of the pigment particles of large specific surface area can be obtained, it is preferred to use The processing of lyonium salt mill.

Lyonium salt mill refers to, will it is freshly synthesized after or be ground after composition without pigmentation comprising halogenation Color compositions, inorganic salts and the organic solvent of pigment derivative represented by ZnPc pigment and above-mentioned formula (1) are kneaded It grinds.As kneading machine at this time, such as kneader, mixing rivet bucker (Mix Muller), ternary mixing machine can be used (Trimix), double screw extruder etc..

As above-mentioned inorganic salts, suitably can use water-soluble inorganic salt, it is preferable to use for example sodium chloride, potassium chloride, The inorganic salts such as sodium sulphate.In addition, more preferably using 0.5~50 μm of average grain diameter of inorganic salts.Such inorganic salts can pass through Common inorganic salts are subjected to Crushing of Ultrafine and are readily derived.

In the present invention, preferably by the average grain diameter of primary particle be 0.01~0.10 μm comprising zinc halide phthalocyanine color and The color compositions of pigment derivative represented by above-mentioned formula (1) are used for color filter application.It is above-mentioned in the present invention in order to obtain Preferable particle size preferably improves the inorganic salts usage amount relative to thick pigment usage amount in lyonium salt mill.That is, the inorganic salts make Dosage is set as 5~20 mass parts preferably with respect to thick 1 mass parts of pigment, is more preferably set as 7~15 mass parts.

It, can as such organic solvent as organic solvent, it is preferable to use being able to suppress the organic solvent of crystalline growth Suitably to use water-miscible organic solvent, the poly- second two of such as diethylene glycol, glycerol, ethylene glycol, propylene glycol, liquid can be used Alcohol, liquid polypropylene glycol, 2- (methoxymethoxy) ethyl alcohol, butoxy ethanol, 2- (isoamoxy) ethyl alcohol, 2- (hexyloxy) Ethyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol list first Base ether, 1- methoxy-2-propanol, 1- ethyoxyl -2- propyl alcohol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl Ether, dipropylene glycol etc..The usage amount of the water-miscible organic solvent is not particularly limited, and is preferably relative to thick 1 mass parts of pigment 0.01~5 mass parts.

It is being manufactured by lyonium salt mill comprising pigment derivative represented by zinc halide phthalocyanine color and above-mentioned formula (1) In the case where color compositions, pigment derivative represented by zinc halide phthalocyanine color and above-mentioned formula (1) can be carried out respectively Lyonium salt mill, is then combined, and can also mix represented by halogenation ZnPc pigment and above-mentioned formula (1) simultaneously in the device Phthalocyanine color derivative, and carry out lyonium salt mill.In the optical characteristics evaluation based on colour filter, no matter any method is in energy The aspect of brightness is enough improved all without too big difference.

As previously mentioned, color compositions of the invention are in the same manner as previous zinc halide phthalocyanine color, in 380~780nm Wavelength (Tmax) when becoming maximum of the transmissivity of spectral transmission spectrum be 500~525nm, the half breadth of transmission curve For 110nm hereinafter, very sharp (wavelength is not influenced by photoresist as described later).

Spectral transmission spectrum in colour filter evaluation is according to the 8722 (measuring method-of color of Japanese Industrial Standards JIS Z Reflection and transparent objects color) the first spectrophotometer and find out, film predetermined is done at above-mentioned on glass substrate etc. The light in the resin coating scanning irradiation predetermined wavelength region comprising color compositions of dry film thickness, describes each transmission under each wavelength Rate value and obtain.

Herein, zinc halide phthalocyanine color shape in such a way that the spectral transmission of very big transmission peak wavelength becomes 70% will used At the integrated value of transmissivity of 510nm~560nm of film be set as D1, pigment represented by above-mentioned general formula (1) will be made Derivative be supported at the obtained derivative of aluminium oxide hold body with the spectral transmission of very big transmission peak wavelength become 70% side When the integrated value of transmissivity of the 510nm~560nm for the film that formula is formed is set as D2, the ratio (D2/D1) with D1 and D2 at For the pigment composition for color filter of 0.7 or more dichroism, due to being capable of the green color as caused by pigment derivative The brightness reduction of device is limited to minimum limit, therefore preferably.In addition, in order to design the higher green color filter of brightness, more preferably Become the pigment composition for color filter of 1.0 or more dichroism for the ratio (D2/D1) with D1 and D2, further preferably Become the pigment composition for color filter of 1.2 or more dichroism for the ratio (D2/D1) with D1 and D2.

Moreover, having makes pigment derivative represented by above-mentioned general formula (1) be supported at the obtained derivative of aluminium oxide The transmissivity that object holds the 460nm for the film that body is formed in such a way that the spectral transmission of very big transmission peak wavelength becomes 70% becomes The pigment composition for color filter of 60% dichroism below, the face that the reduction due to that can make chromaticity y is inhibited The high green color filter of color reproduction, therefore preferably.In addition, for the higher green color filter of design colours reproducibility, it is more excellent It is selected as the pigment composition for color filter that there is the transmissivity of 460nm to become 55% dichroism below, further preferably Transmissivity with 460nm becomes the pigment composition for color filter of 50% dichroism below.

Color compositions of the invention can be only directly used in the green pixel portion of manufacture colour filter, can also basis Need and use other viridine greens etc..

In addition, other than viridine green, sometimes for performance characteristic using yellow uitramarine for mixing colours.As herein Can yellow uitramarine, such as C.I. pigment yellow 83, C.I. pigment yellow 110, pigment Yellow 12 9, C.I. pigment yellow can be enumerated 138, the Huangs such as C.I. pigment yellow 13 9, C.I. pigment yellow 150, C.I. pigment yellow 180, C.I. pigment yellow 185, C.I. pigment yellow 231 Color organic pigment.About zinc halide phthalocyanine pigment composition and yellow uitramarine of the invention and with ratio, relative to above-mentioned halogen Change 100 mass parts of ZnPc color compositions, yellow uitramarine is 1~200 mass parts.

(colour filter)

Green pixel is formed using color compositions of the invention, so as to obtain colour filter.

(manufacturing method of colour filter)

Color compositions of the invention can be used to form the pattern in the green pixel portion of colour filter by well known method. For typical case, it can obtain using comprising this color compositions and photoresist as the colour filter green pixel portion of neccessary composition Photosensitive composite.

As the manufacturing method of colour filter, for example, referred to as photolithographic method etc., the photoetching process can be enumerated are as follows: make this After the pigment composition for color filter of invention is scattered in the decentralized medium comprising photoresist, by spin-coating method, rolling method, Slot coated method, ink-jet method etc. are coated on the transparent substrates such as glass, then carry out utilizing purple to the coated film across photomask After the pattern exposure of outside line, unexposed portion is cleaned with solvent etc. and obtains green pattern.

It as other manufacturing methods, such as can enumerate: by electrodeposition process, transfer printing, micelle electrolysis method, PVED The methods of (Photovoltaic Electrodeposition, photoelectricity electro-deposition) method forms the pattern in green pixel portion, system The method etc. for making colour filter.It should be noted that public affairs also can be used in the pattern in red pixel portion and the pattern in blue pixel portion The pigment known is formed by the same method.

In order to modulate colour filter green pixel portion photosensitive composite, for example, by colour filter of the invention pigment group The organic solvent for closing object, photoresist, Photoepolymerizationinitiater initiater and the above-mentioned resin of dissolution is mixed as neccessary composition.More Specifically, generally following method: using color compositions of the invention, organic solvent and dispersing agent tune as needed After dispersion liquid processed, photoresist etc. is added thereto and is modulated.

It as above-mentioned dispersing agent, such as can enumerate: the DISPERBYK (DISPERBYK, registered trademark) of Bi Ke chemical company 130、DISPERBYK 161、DISPERBYK 162、DISPERBYK 163、DISPERBYK 170、DISPERBYK LPN- 6919, DISPERBYK LPN-21116 etc..In addition it is also possible to and with levelling agent, coupling agent, cationic system surfactant Deng.

As above-mentioned organic solvent, for instance that the aromatic systems solvent such as toluene, dimethylbenzene, methoxybenzene；Ethyl acetate, The acetic acid ester series solvents such as butyl acetate, propylene glycol monomethyl ether, propylene glycol monoethyl acetic acid esters；Propionic acid ethyoxyl second The propionic acid ester series solvent such as ester；The alcohol series solvents such as methanol, ethyl alcohol；Butyl cellosolve, propylene glycol monomethyl ether, diethylene glycol ethyl The ether series solvents such as ether, diethylene glycol dimethyl ether；The ketone series solvents such as methyl ethyl ketone, methyl iso-butyl ketone (MIBK), cyclohexanone；Hexane etc. Aliphatic hydrocarbon series solvent；The nitridation such as N,N-dimethylformamide, butyrolactam, n-methyl-2-pyrrolidone, aniline, pyridine Close object series solvent；Ester series solvent in gamma-butyrolacton etc.；The mixture of the 48:52 of methyl carbamate and urethanes that Carbamate, water of sample etc..As organic solvent, especially propionic ester system, alcohol system, ether system, ketone system, nitride compound, interior Ester system, water isopolarity solvent and water-soluble solvent are suitable.

It can will be 300~1000 matter relative to 100 mass parts of color compositions of the invention in a manner of becoming uniform The dispersing agent of the organic solvent and 0~100 mass parts as needed of measuring part is stirred dispersion and obtains dispersion liquid.Then, Being added into the dispersion liquid relative to 100 mass parts of color compositions of the invention is the photoresists of 3~20 mass parts, phase It is the Photoepolymerizationinitiater initiater of 0.05~3 mass parts for 1 mass parts of photoresist, and it is molten to be further added with machine as needed Agent is stirred dispersion in a manner of becoming uniform, so as to obtain colour filter green pixel portion photosensitive composite.

It as above-mentioned photoresist, can enumerate: such as polyurethane series resin, acrylic resin, polyamic acid system tree The thermoplastic resins such as rouge, polyimides system resins, styrene maleic acid system resin, maleic anhydride of styrene system resin；Such as 1, It is 6- hexanediyl ester, glycol diacrylate, neopentylglycol diacrylate, triethylene glycol diacrylate, double 2 functional monomers as (acryloyloxyethoxy) bisphenol-A, 3- methyl pentanediol diacrylate etc.；Trimethylolpropane Triacrylate, pentaerythritol triacrylate, three (2- ethoxy) isocyanates, dipentaerythritol hexaacrylate, two seasons The photopolymerization monomers such as polyfunctional monomer as penta tetrol, five acrylate etc..

As above-mentioned Photoepolymerizationinitiater initiater, such as acetophenone, benzophenone, benzil dimethyl ketal, peroxide can be enumerated Change benzoyl, 2-chlorothioxanthone, bis- (4 '-nitrine the benzal) -2- propane of 1,3-, bis- (4 '-nitrine the benzal) -2- third of 1,3- Alkane -2 '-sulfonic acid, 4,4 '-two nitrine stilbenes -2,2 '-disulfonic acid etc..

The colour filter green pixel portion modulated can be by carrying out across photomask using ultraviolet with photosensitive composite After the pattern exposure of line, unexposed portion is cleaned with organic solvent, buck etc. to obtain colour filter.

Embodiment

Hereinafter, illustrating the present invention, however, the present invention is not limited thereto based on embodiment.It should be noted that in embodiment and In comparative example, in case of no particular description, " part " and " % " is quality criteria.

In addition, measuring method used in aftermentioned embodiment is as follows.

[evaluation of brightness]

Under the illuminant-C for measuring obtained colour filter with light splitting luminance meter U-3900 (Hitachi Ltd.'s system) Coloration x, y and brightness.The higher brightness the more excellent.

Reference example 1

Sulfonic acid chloride (and Wako Pure Chemical Industries reagent) 90g, aluminium chloride (Northeast chemical reagent) are put into 300ml flask 105g, sodium chloride (Tokyo chemical conversion industry reagent) 14g, Dainippon Ink Chemicals ZnPc 27g, bromine (and Wako Pure Chemical Industries reagent) 55g.130 DEG C are warming up to, after taking out into water, is filtered, washes, dries, to obtain halogenation ZnPc (R1).For halogen Change ZnPc (R1), carries out the quality analysis using Jeol Ltd. JMS-S3000, confirming average chlorination rate is 2.9, average bromination rate is 9.3.It should be noted that the Delay Time (delay time) when quality analysis is 510ns, Laser Intensity (laser intensity) is 40%, the Resolving Power at the peak below m/z=1820 or more 1860 Value (resolution value) is 65086.

Obtained halogenation ZnPc (R1) 40g, the sodium chloride 400g through crushing, diethylene glycol 63g will be operated in this way to throw Enter in dual-arm kneader, is kneaded 8 hours at 80 DEG C.It takes out after mixing into 80 DEG C of water 2kg, after stirring 1 hour, carried out Filter, hot water wash, drying, crushing, to obtain green pigment composition (RG1).Using the zirconium pearl of 0.3~0.4mm, with Japan's essence Machine Co. Ltd. system paint shaker is by green pigment composition (RG1) 2.48g and Bi Ke chemical company BYK-LPN6919 1.24g, Dainippon Ink Chemicals UNIDIC ZL-295 1.86g, that propylene glycol monomethyl ether 10.92g disperses 2 together is small When, obtain coloured composition (RMG1).Coloured composition (RMG1) 4.0g, Dainippon Ink Chemicals UNIDIC ZL-295 is added 0.98g, propylene glycol monomethyl ether 0.22g, are mixed with paint shaker, to obtain evaluation composition (RCG1).The evaluation is spun on soda-lime glass with composition (RCG1), it is public with Hitachi's new and high technology after 90 DEG C are 3 minutes dry It takes charge of U-3900 processed and measures spectral transmission spectrum.It should be noted that being measured by the revolution for adjusting rotation when carrying out spin coating Very big transmissivity becomes 70% spectral transmission spectrum.When measuring transmitted spectrum, base wavelet is carried out using soda-lime glass. The transmissivity that the integrated value of the transmissivity of 510nm~560nm is 2511.6,460nm is 8.79.

Reference example 2

Sulfonic acid chloride (and Wako Pure Chemical Industries reagent) 91g, aluminium chloride (Northeast chemical reagent) are put into 300ml flask 109g, sodium chloride (Tokyo chemical conversion industry reagent) 15g, Dainippon Ink Chemicals ZnPc 30g, bromine (and Wako Pure Chemical Industries reagent) 230g.130 DEG C are warming up to, after taking out into water, is filtered, washes, dries, to obtain halogenation ZnPc (R2).For Halogenation ZnPc (R2), carries out the quality analysis using Jeol Ltd. JMS-S3000, confirms average chlorination rate It is 1.8, average bromination rate is 13.2.It should be noted that the Delay Time (delay time) when quality analysis is 500ns, Laser Intensity (laser intensity) are 44%, the Resolving at the peak below m/z=1820 or more 1860 Power Value (resolution value) is 31804.

Obtained halogenation ZnPc (R2) 40g, the sodium chloride 400g through crushing, diethylene glycol 63g will be operated in this way to throw Enter in dual-arm kneader, is kneaded 8 hours at 80 DEG C.It takes out after mixing into 80 DEG C of water 2kg, after stirring 1 hour, carried out Filter, hot water wash, drying, crushing, to obtain green pigment composition (RG2).Using the zirconium pearl of 0.3~0.4mm, with Japan's essence Machine Co. Ltd. system paint shaker is by green pigment composition (RG2) 2.48g and Bi Ke chemical company BYK-LPN6919 1.24g, Dainippon Ink Chemicals UNIDIC ZL-295 1.86g, that propylene glycol monomethyl ether 10.92g disperses 2 together is small When, obtain coloured composition (RMG2).Coloured composition (RMG2) 4.0g, Dainippon Ink Chemicals UNIDIC ZL-295 is added 0.98g, propylene glycol monomethyl ether 0.22g, are mixed with paint shaker, to obtain evaluation composition (RCG2).The evaluation is spun on soda-lime glass with composition (RCG2), it is public with Hitachi's new and high technology after 90 DEG C are 3 minutes dry It takes charge of U-3900 processed and measures spectral transmission spectrum.It should be noted that being measured by the revolution for adjusting rotation when carrying out spin coating Very big transmissivity becomes 70% spectral transmission spectrum.When measuring transmitted spectrum, base wavelet is carried out using soda-lime glass. The transmissivity that the integrated value of the transmissivity of 510nm~560nm is 2787.8,460nm is 3.07.

Synthesis example 1

98% sulfuric acid 288g and 30% oleum 272g are stirred while being cooled to 10 DEG C, DIC plants of formulas are added Commercial firm ZnPc 70g.Then, it is stirred 3 hours at 60 DEG C.Reaction solution is taken out into water 1750g, after stirring 1 hour, is carried out Filtering, washing, drying, to obtain sulfonation zinc phthalocyanine phthalocyanine derivative (S1).For sulfonation zinc phthalocyanine phthalocyanine derivative (S1), pass through LC- MS measurement, confirming average sulphonation rate is 1.Add in Japanese AEROSIL corporation aluminium oxide (AEROXIDE Alu C) 30g After entering ethyl alcohol 100g and being sufficiently stirred, the slurry of water 2000g production white is added.It is added sulfonation zinc phthalocyanine phthalocyanine derivative (S1) 1.5g is adjusted to pH12 with potassium hydroxide aqueous solution, is stirred at room temperature 2 hours.It is adjusted to pH3 with 10% hydrochloric acid, in room temperature Under futher stir 1 hour after, be filtered, wash, dry, crush, so that obtaining derivative holds body (A1).Use 0.3 Derivative is held body (A1) 2.48g and Bi Ke chemistry with Toyo Seiki Co. Ltd. system paint shaker by the zirconium pearl of~0.4mm Corporation BYK-LPN6919 1.24g, Dainippon Ink Chemicals UNIDIC ZL-295 1.86g, propylene glycol monomethyl ether 10.92g disperses 2 hours together, obtains coloured composition (AMG1).Coloured composition (AMG1) 4.0g, Dainippon Ink Chemicals is added UNIDIC ZL-295 0.98g processed, propylene glycol monomethyl ether 0.22g, are mixed with paint shaker, to obtain Composition (ACG1) is used in evaluation.The evaluation is spun on soda-lime glass with composition (ACG1), after 90 DEG C 3 minutes dry, with day Vertical high and new technology company U-3900 measures spectral transmission spectrum.It should be noted that being rotated by being adjusted when carrying out spin coating Revolution come measure very big transmissivity become 70% spectral transmission spectrum.When measuring transmitted spectrum, carried out using soda-lime glass Base wavelet.The transmissivity that the integrated value of the transmissivity of 510nm~560nm is 1988.8,460nm is 55.27.

Synthesis example 2

3- chloro-phthalic anhydride 55g, phthalic anhydride 45g, zinc chloride 20g, urea 116g, seven are put into 1L flask Molybdic acid six ammonium tetrahydrate 600mg and sulfolane 250g is stirred 5 hours at 190 DEG C.Later, stop heating, it is laggard to place cooling Row filtering, is cleaned using 2- propyl alcohol 780g, 1% sodium hydrate aqueous solution 1000g, 1% hydrochloric acid 1000g.After washing, 90 DEG C by obtained wet cake (wetcake) dry 12 hours, the dichloro ZnPc of blue solid is obtained.On one side by 95% sulphur Sour 20g and 30% oleum 180g is cooled to 10 DEG C and stirs on one side, and dichloro ZnPc 20g is added.Then, 5 are stirred at 80 DEG C Hour.Reaction solution is taken out into water 1000g, after stirring 30 minutes, is filtered, washes, dries, to obtain sulfonated zinc phthalein Cyanines derivative (S2).It for sulfonation zinc phthalocyanine phthalocyanine derivative (S2), is measured by LC-MS, confirming average sulphonation rate is 1, is put down Equal chlorination rate is 2.Ethyl alcohol 100g is added in Japanese AEROSIL corporation aluminium oxide (AEROXIDE Alu C) 30g and fills After dividing stirring, the slurry of water 2000g production white is added.Sulfonation zinc phthalocyanine phthalocyanine derivative (S2) 1.5g is added, uses potassium hydroxide water Solution is adjusted to pH12, is stirred at room temperature 2 hours.It is adjusted to pH3 with 10% hydrochloric acid, is further stirred at room temperature 1 hour Afterwards, it is filtered, washes, dries, crushes, so that obtaining derivative holds body (A2).Using the zirconium pearl of 0.3~0.4mm, with east Derivative is held body (A2) 2.48g and Bi Ke chemical company BYK-LPN6919 by foreign essence machine Co. Ltd. system paint shaker 1.24g, Dainippon Ink Chemicals UNIDIC ZL-295 1.86g, that propylene glycol monomethyl ether 10.92g disperses 2 together is small When, obtain coloured composition (AMG2).Coloured composition (AMG2) 4.0g, Dainippon Ink Chemicals UNIDIC ZL- is added 2950.98g, propylene glycol monomethyl ether 0.22g, are mixed with paint shaker, to obtain evaluation composition (ACG2).The evaluation is spun on soda-lime glass with composition (ACG2), it is public with Hitachi's new and high technology after 90 DEG C are 3 minutes dry It takes charge of U-3900 processed and measures spectral transmission spectrum.It should be noted that being measured by the revolution for adjusting rotation when carrying out spin coating Very big transmissivity becomes 70% spectral transmission spectrum.When measuring transmitted spectrum, base wavelet is carried out using soda-lime glass. The transmissivity that the integrated value of the transmissivity of 510nm~560nm is 3054.6,460nm is 57.47.

Synthesis example 3

3- chloro-phthalic anhydride 111g, zinc chloride 20g, urea 116g, the hydration of seven molybdic acids, six ammonium four are put into 1L flask Object 600mg and sulfolane 250g is stirred 5 hours at 190 DEG C.Later, stop heating, be filtered after placing cooling, use 2- Propyl alcohol 780g, l% sodium hydrate aqueous solution 1000g, 1% hydrochloric acid 1000g are cleaned.It, will be obtained at 90 DEG C after washing Wet cake is 12 hours dry, obtains the tetrachloro ZnPc of blue solid.30% oleum 131g is cooled to 10 DEG C one on one side Side stirring, is added tetrachloro ZnPc 15g.Then, it is stirred 3 hours at 90 DEG C.Reaction solution is taken out into water 750g, stirs 15 points Zhong Hou is filtered, washes, dries, to obtain sulfonation zinc phthalocyanine phthalocyanine derivative (S3).For sulfonation zinc phthalocyanine phthalocyanine derivative (S3), it is measured by LC-MS, confirming average sulphonation rate is 1.6, and average chlorination rate is 4.In Japanese AEROSIL company After ethyl alcohol 100g is added in oxygenerating aluminium (AEROXIDE Alu C) 30g and is sufficiently stirred, the slurry of water 2000g production white is added Material.Sulfonation zinc phthalocyanine phthalocyanine derivative (S3) 1.5g is added, is adjusted to pH12 with potassium hydroxide aqueous solution, is stirred at room temperature 2 hours. It is adjusted to pH3 with 10% hydrochloric acid, after being further stirred at room temperature 1 hour, is filtered, washes, dries, crushes, thus Body (A3) is held to derivative.Using the zirconium pearl of 0.3~0.4mm, will be derived with Toyo Seiki Co. Ltd. system paint shaker Object holds body (A3) 2.48g and Bi Ke chemical company BYK-LPN69191.24g, Dainippon Ink Chemicals UNIDIC ZL-295 1.86g, propylene glycol monomethyl ether 10.92g disperse 2 hours together, obtain coloured composition (AMG3).Colour cell is added Object (AMG3) 4.0g, Dainippon Ink Chemicals UNIDIC ZL-295 0.98g, propylene glycol monomethyl ether 0.22g are closed, is used Paint shaker is mixed, to obtain evaluation composition (ACG3).The evaluation is spun on sodium with composition (ACG3) Glass measures spectral transmission spectrum with high and new technology company, Hitachi U-3900 after 90 DEG C 3 minutes dry.It needs to illustrate It is to become 70% spectral transmission spectrum by adjusting the revolution of rotation when carrying out spin coating to measure very big transmissivity.It is surveying When determining transmitted spectrum, base wavelet is carried out using soda-lime glass.The integrated value of the transmissivity of 510nm~560nm is 3065.8, The transmissivity of 460nm is 53.41.

Synthesis example 4

Into 300ml flask put into sulfonic acid chloride (and Wako Pure Chemical Industries reagent) 54g, aluminium chloride (Northeast chemical reagent) 63g, Sodium chloride (Tokyo chemical conversion industry reagent) 8.6g, sulfonation zinc phthalocyanine phthalocyanine derivative (A) 17g, bromine (and Wako Pure Chemical Industries reagent) 87g. 130 DEG C are warming up to, after taking out into water, is filtered, washes, dries, to obtain sulfonation zinc phthalocyanine phthalocyanine derivative (S4).For Sulfonation zinc phthalocyanine phthalocyanine derivative (S4), carries out the quality analysis using Jeol Ltd. JMS-S3000, confirms average Sulphonation rate is 1, and average chlorination rate is 2.2, and average bromination rate is 10.8.It should be noted that when quality analysis Delay Time (delay time) is 275ns, and Laser Intensity (laser intensity) is 42%, m/z=1820 or more 1860 The Resolving Power Value (resolution value) at peak below is 42559.In Japanese AEROSIL corporation aluminium oxide After ethyl alcohol 100g is added in (AEROXIDE Alu C) 30g and is sufficiently stirred, the slurry of water 2000g production white is added.It is added Sulfonation zinc phthalocyanine phthalocyanine derivative (S4) 1.5g, is adjusted to pH12 with potassium hydroxide aqueous solution, is stirred at room temperature 2 hours.With 10% Hydrochloric acid is adjusted to pH3, after being further stirred at room temperature 1 hour, is filtered, washes, dries, crushes, to be derived Object holds body (A4).Using the zirconium pearl of 0.3~0.4mm, derivative is held with Toyo Seiki Co. Ltd. system paint shaker Body (A4) 2.48g and Bi Ke chemical company BYK-LPN6919 1.24g, Dainippon Ink Chemicals UNIDIC ZL-295 1.86g, propylene glycol monomethyl ether 10.92g disperse 2 hours together, obtain coloured composition (AMG4).Colour cell is added Object (AMG4) 4.0g, Dainippon Ink Chemicals UNIDIC ZL-2950.98g, propylene glycol monomethyl ether 0.22g are closed, with painting Material shaking machine is mixed, to obtain evaluation composition (ACG4).The evaluation is spun on sodium glass with composition (ACG4) Glass measures spectral transmission spectrum with high and new technology company, Hitachi U-3900 after 90 DEG C 3 minutes dry.It should be noted that Become 70% spectral transmission spectrum by adjusting the revolution of rotation when carrying out spin coating to measure very big transmissivity.It is saturating in measurement When penetrating spectrum, base wavelet is carried out using soda-lime glass.The integrated value of the transmissivity of 510nm~560nm is 3273.1,460nm's Transmissivity is 42.89.

Synthesis example 5

Investment phthalonitrile 60g, 1- chloronaphthalene 300g and aluminium chloride 16g into 1L flask, stirred at reflux 6 hours.Later, stop Heating, placement are carried out heat filtering after being cooled to 200 DEG C, are cleaned using hot toluene 600g, acetone 300g.Make obtained wet Filter cake is scattered in toluene 250g, is stirred at reflux 3 hours.Heat filtering is carried out again, is carried out using hot toluene 600g, acetone 300g It after cleaning, is dispersed in the ion exchange water of 1500g, applies 60 minutes heating stirrings at 60 DEG C.After filtering, washing, 50 It DEG C is dried in vacuo, obtains the aluminium phthalocyanine (AlPc-Cl) of blue solid.Make aluminium phthalocyanine while temperature is remained 5 DEG C (AlPc-Cl) 30g is dissolved at leisure in concentrated sulfuric acid 1200g, is stirred 1 hour at such a temperature.With temperature while stirring Mode no more than 5 DEG C is injected into ice water 6000g, is futher stirred 1 hour after terminating injection.After filtering, washing, then It is scattered in the ion exchange water of 6500g, is filtered again.After washing, wet cake is redispersed in 4% ammonium hydroxide 2500g, Stirred at reflux 6 hours.After filtering, after cleaning filter cake with ion exchange water, it is dried in vacuo at 50 DEG C, obtains blue solid Aluminium phthalocyanine (AlPc-OH).It stirs, is added while 98% sulfuric acid 288g and 30% oleum 272g are cooled to 10 DEG C Aluminium phthalocyanine (AlPc-OH) 70g.Then, it is stirred 3 hours at 60 DEG C.Reaction solution is taken out into water 1750g, after stirring 1 hour, It is filtered, washes, dries, to obtain sulphonation aluminum phthalocyanine derivative (S5).For sulphonation aluminum phthalocyanine derivative (S5), pass through LC-MS measurement, confirming average sulphonation rate is 1.In Japanese AEROSIL corporation aluminium oxide (AEROXIDE Alu C) 30g Middle addition ethyl alcohol 100g and after being sufficiently stirred, is added the slurry of water 2000g production white.It is added sulphonation aluminum phthalocyanine derivative (S5) 1.5g is adjusted to pH12 with potassium hydroxide aqueous solution, is stirred at room temperature 2 hours.It is adjusted to pH3 with 10% hydrochloric acid, in room temperature Under futher stir 1 hour after, be filtered, wash, dry, crush, so that obtaining derivative holds body (A5).Use 0.3 Derivative is held body (A5) 2.48g and Bi Ke chemistry with Toyo Seiki Co. Ltd. system paint shaker by the zirconium pearl of~0.4mm Corporation BYK-LPN6919 1.24g, Dainippon Ink Chemicals UNIDIC ZL-295 1.86g, propylene glycol monomethyl ether 10.92g disperses 2 hours together, obtains coloured composition (AMG5).Coloured composition (AMG5) 4.0g, Dainippon Ink Chemicals is added UNIDIC ZL-295 0.98g processed, propylene glycol monomethyl ether 0.22g, are mixed with paint shaker, to obtain Composition (ACG5) is used in evaluation.The evaluation is spun on soda-lime glass with composition (ACG5), after 90 DEG C 3 minutes dry, with day Vertical high and new technology company U-3900 measures spectral transmission spectrum.It should be noted that being rotated by being adjusted when carrying out spin coating Revolution come measure very big transmissivity become 70% spectral transmission spectrum.When measuring transmitted spectrum, carried out using soda-lime glass Base wavelet.The transmissivity that the integrated value of the transmissivity of 510nm~560nm is 2757.5,460nm is 64.24.

Synthesis example 6

Ethyl alcohol 100g is added in Japanese AEROSIL corporation aluminium oxide (AEROXIDE Alu C) 30g and is sufficiently stirred Afterwards, the slurry of water 2000g production white is added.(the Japanese Lubrizol Co. Ltd. system sulfonation copper of Solsperse 12000 is added Phthalocyanine derivates) 1.5g, it is adjusted to pH12 with potassium hydroxide aqueous solution, is stirred at room temperature 2 hours.It is adjusted to 10% hydrochloric acid PH3 after being further stirred at room temperature 1 hour, is filtered, washes, dries, crushes, so that obtaining derivative holds body (A6).Using the zirconium pearl of 0.3~0.4mm, derivative is held into body (A6) with Toyo Seiki Co. Ltd. system paint shaker 2.48g and Bi Ke chemical company BYK-LPN6919 1.24g, Dainippon Ink Chemicals UNIDIC ZL-295 1.86g, the third two Alcohol monomethyl ether acetate 10.92g disperses 2 hours together, obtains coloured composition (AMG6).It is added coloured composition (AMG6) 4.0g, Dainippon Ink Chemicals UNIDIC ZL-295 0.98g, propylene glycol monomethyl ether 0.22g, use paint shaker It is mixed, to obtain evaluation composition (ACG6).The evaluation is spun on soda-lime glass with composition (ACG6), at 90 DEG C After 3 minutes dry, spectral transmission spectrum is measured with high and new technology company, Hitachi U-3900.It should be noted that by into The revolution of adjustment rotation becomes 70% spectral transmission spectrum to measure very big transmissivity when row spin coating.In measurement transmitted spectrum When, base wavelet is carried out using soda-lime glass.The integrated value of the transmissivity of 510nm~560nm is the transmissivity of 1303.8,460nm It is 64.19.

Synthesis example 7

Sulfolane 15g, titanium tetrachloride 10g, repefral 200g, 4- chlore O-phthalic acid are put into 1L flask Urea 150g, copper chloride (I) 9.5g is added after 170 DEG C are heated 30 minutes in acid sodium-salt 100g, 20% oleum 31g.Into one Step heats 1 hour at 150 DEG C, heats 1 hour at 170 DEG C, heats 8 hours at 190 DEG C.After being cooled to 80 DEG C, take out to dissolution Have in the 700g water of 60g sodium hydroxide.After 85 DEG C are stirred 1 hour, it is injected into while stirring in 2300g water, at 80 DEG C It futher stirs 2 hours.It is filtered, after hot water cleaning, is starched again in the 2300g water dissolved with 35% hydrochloric acid of 140g Materialization exists 70 DEG C while stirring and heats 1 hour.It is filtered, after hot water cleaning, it is 17 hours dry at 80 DEG C, thus To the tetrachloro copper phthalocyanine of blue solid.It is stirred while 30% oleum 131g is cooled to 10 DEG C, tetrachloro copper phthalein is added Cyanines 15g.Then, it is stirred 3 hours at 90 DEG C.Reaction solution is taken out into water 750g, after stirring 15 minutes, be filtered, wash, It is dry, to obtain sulfonated copper phthalocyanine derivative (S7).It for sulfonated copper phthalocyanine derivative (S7), is measured, is confirmed by LC-MS It is 1 to average sulphonation rate, average chlorination rate is 4.At Japanese AEROSIL corporation aluminium oxide (AEROXIDE Alu C) After ethyl alcohol 100g is added in 30g and is sufficiently stirred, the slurry of water 2000g production white is added.Sulfonated copper phthalocyanine derivative is added (S7) 1.5g is adjusted to pH12 with potassium hydroxide aqueous solution, is stirred at room temperature 2 hours.PH3, In are adjusted to 10% hydrochloric acid It after futher stirring 1 hour at room temperature, is filtered, washes, dries, crushes, so that obtaining derivative holds body (A7).It uses Derivative is held body (A7) 2.48g and Bi Ke with Toyo Seiki Co. Ltd. system paint shaker by the zirconium pearl of 0.3~0.4mm Chemical company BYK-LPN6919 1.24g, Dainippon Ink Chemicals UNIDIC ZL-295 1.86g, propylene glycol monomethyl ether second Acid esters 10.92g disperses 2 hours together, obtains coloured composition (AMG7).Coloured composition (AMG7) 4.0g, DIC plants of formulas of addition Commercial firm UNIDIC ZL-295 0.98g, propylene glycol monomethyl ether 0.22g, are mixed with paint shaker, thus Obtain evaluation composition (ACG7).The evaluation is spun on soda-lime glass with composition (ACG7), after 90 DEG C are 3 minutes dry, Spectral transmission spectrum is measured with high and new technology company, Hitachi U-3900.It should be noted that passing through the adjustment when carrying out spin coating The revolution of rotation becomes 70% spectral transmission spectrum to measure very big transmissivity.When measuring transmitted spectrum, soda-lime glass is used Carry out base wavelet.The transmissivity that the integrated value of the transmissivity of 510nm~560nm is 1401.9,460nm is 64.60.

Production Example 1

By halogenation ZnPc (R1) 36g, sulfonation zinc phthalocyanine phthalocyanine derivative (S1) 4g, the sodium chloride 400g through crushing, diethyl two Alcohol 63g is put into dual-arm kneader, is kneaded 8 hours at 80 DEG C.It takes out after mixing into 80 DEG C of water 2kg, stirs 1 hour Afterwards, it is filtered, hot water wash, drying, crushing, to obtain green pigment composition (G1).

Production Example 2

Other than sulfonation zinc phthalocyanine phthalocyanine derivative (S1) is replaced with sulfonation zinc phthalocyanine phthalocyanine derivative (S2) in Production Example 1, It operates in the same way, obtains green pigment composition (G2).

Production Example 3

Other than sulfonation zinc phthalocyanine phthalocyanine derivative (S1) is replaced with sulfonation zinc phthalocyanine phthalocyanine derivative (S3) in Production Example 1, It operates in the same way, obtains green pigment composition (G3).

Production Example 4

Other than sulfonation zinc phthalocyanine phthalocyanine derivative (S1) is replaced with sulfonation zinc phthalocyanine phthalocyanine derivative (S4) in Production Example 1, It operates in the same way, obtains green pigment composition (G4).

Production Example 5

Other than sulfonation zinc phthalocyanine phthalocyanine derivative (S1) is replaced with sulphonation aluminum phthalocyanine derivative (S5) in Production Example 1, It operates in the same way, obtains green pigment composition (G5).

Production Example 6

Other than sulfonation zinc phthalocyanine phthalocyanine derivative (S1) is replaced with sulfonated copper phthalocyanine derivative (S7) in Production Example 1, It operates in the same way, obtains green pigment composition (G6).

Production Example 7

By halogenation ZnPc (R1) 38g, sulfonation zinc phthalocyanine phthalocyanine derivative (S1) 2g, the sodium chloride 400g through crushing, diethyl two Alcohol 63g is put into dual-arm kneader, is kneaded 8 hours at 80 DEG C.It takes out after mixing into 80 DEG C of water 2kg, stirs 1 hour Afterwards, it is filtered, hot water wash, drying, crushing, to obtain green pigment composition (G7).

Production Example 8

Other than sulfonation zinc phthalocyanine phthalocyanine derivative (S1) is replaced with sulfonation zinc phthalocyanine phthalocyanine derivative (S2) in Production Example 7, It operates in the same way, obtains green pigment composition (G8).

Production Example 9

Other than sulfonation zinc phthalocyanine phthalocyanine derivative (S1) is replaced with sulfonation zinc phthalocyanine phthalocyanine derivative (S3) in Production Example 7, It operates in the same way, obtains green pigment composition (G9).

Production Example 10

By halogenation ZnPc (R2) 36g, sulfonation zinc phthalocyanine phthalocyanine derivative (S3) 4g, the sodium chloride 400g through crushing, diethyl two Alcohol 63g is put into dual-arm kneader, is kneaded 8 hours at 80 DEG C.It takes out after mixing into 80 DEG C of water 2kg, stirs 1 hour Afterwards, it is filtered, hot water wash, drying, crushing, to obtain green pigment composition (G10).

Production Example 11

Other than sulfonation zinc phthalocyanine phthalocyanine derivative (S3) is replaced with sulfonation zinc phthalocyanine phthalocyanine derivative (S4) in Production Example 10, It operates in the same way, obtains green pigment composition (G11).

Production Example 12

In addition to sulfonation zinc phthalocyanine phthalocyanine derivative (S3) is replaced with (Japan of Solsperse 12000 in Production Example 10 Lubrizol Co. Ltd. system sulfonated copper phthalocyanine derivative) other than, it operates in the same way, obtains green pigment composition (G12).

Production Example 13

Using the zirconium pearl of 0.3~0.4mm, with Toyo Seiki Co. Ltd. system paint shaker, by pigment yellow 13 8, (big day is smart Change corporation CHROMOFINE Huang 6206EC) 1.65g and DISPERBYK-161 (Bi Ke chemical company system) 3.85g, propylene glycol list Methylether acetate 11.00g disperses 2 hours together, obtains coloured composition (MY1).Addition coloured composition (MY1) 4.0g, UNIDIC ZL-295 0.98g, propylene glycol monomethyl ether 0.22g are carried out being obtained by mixing toning with paint shaker With composition (TY1).

Embodiment 1

Using the zirconium pearl of 0.3~0.4mm, with Toyo Seiki Co. Ltd. system paint shaker by green pigment composition (G1) 2.48g and Bi Ke chemical company BYK-LPN6919 1.24g, Dainippon Ink Chemicals UNIDIC ZL-295 1.86g, Propylene glycol monomethyl ether 10.92g disperses 2 hours together, obtains coloured composition (MG1).Coloured composition is added (MG1) 4.0g, Dainippon Ink Chemicals UNIDIC ZL-295 0.98g, propylene glycol monomethyl ether 0.22g, are shaken with coating Dynamic device is mixed, to obtain being used to form the evaluation in colour filter green pixel portion with composition (CG1).It will be in Production Example The toning made in 13 composition (TY1) and evaluation mix obtained masking liquid with composition (CG1) and are spun on soda-lime glass, In 90 DEG C after drying 3 minutes, coloration (x, y)=(0.250, the 0.615) film under illuminant-C is presented in production.With the high-new skill of Hitachi Art corporation U-3900 measures brightness, measures film thickness with high and new technology company, Hitachi white interference microscope VS1330.

Embodiment 2

Other than green pigment composition (G1) is replaced with green pigment composition (G2) in embodiment 1, equally Ground operation, obtains evaluation composition (CG2).By the toning made in Production Example 13 with composition (TY1) and evaluation group It closes the obtained masking liquid of object (CG2) mixing and is spun on soda-lime glass, after 90 DEG C 3 minutes dry, the coloration under illuminant-C is presented in production The film of (x, y)=(0.250,0.615).Brightness is measured with high and new technology company, Hitachi U-3900, with Hitachi's new and high technology Corporation white interference microscope VS1330 measures film thickness.

Embodiment 3

Other than green pigment composition (G1) is replaced with green pigment composition (G3) in embodiment 1, equally Ground operation, obtains evaluation composition (CG3).By the toning made in Production Example 13 with composition (TY1) and evaluation group It closes the obtained masking liquid of object (CG3) mixing and is spun on soda-lime glass, after 90 DEG C 3 minutes dry, the coloration under illuminant-C is presented in production The film of (x, y)=(0.250,0.615).Brightness is measured with high and new technology company, Hitachi U-3900, with Hitachi's new and high technology Corporation white interference microscope VS1330 measures film thickness.

Embodiment 4

Other than green pigment composition (G1) is replaced with green pigment composition (G4) in embodiment 1, equally Ground operation, obtains evaluation composition (CG4).By the toning made in Production Example 13 with composition (TY1) and evaluation group It closes the obtained masking liquid of object (CG4) mixing and is spun on soda-lime glass, after 90 DEG C 3 minutes dry, the coloration under illuminant-C is presented in production The film of (x, y)=(0.250,0.615).Brightness is measured with high and new technology company, Hitachi U-3900, with Hitachi's new and high technology Corporation white interference microscope VS1330 measures film thickness.

Embodiment 5

Other than green pigment composition (G1) is replaced with green pigment composition (G5) in embodiment 1, equally Ground operation, obtains evaluation composition (CG5).By the toning made in Production Example 13 with composition (TY1) and evaluation group It closes the obtained masking liquid of object (CG5) mixing and is spun on soda-lime glass, after 90 DEG C 3 minutes dry, the coloration under illuminant-C is presented in production The film of (x, y)=(0.250,0.615).Brightness is measured with high and new technology company, Hitachi U-3900, with Hitachi's new and high technology Corporation white interference microscope VS1330 measures film thickness.

Embodiment 6

Other than green pigment composition (G1) is replaced with green pigment composition (G7) in embodiment 1, equally Ground operation, obtains evaluation composition (CG7).By the toning made in Production Example 13 with composition (TY1) and evaluation group It closes the obtained masking liquid of object (CG7) mixing and is spun on soda-lime glass, after 90 DEG C 3 minutes dry, the coloration under illuminant-C is presented in production The film of (x, y)=(0.250,0.615).Brightness is measured with high and new technology company, Hitachi U-3900, with Hitachi's new and high technology Corporation white interference microscope VS1330 measures film thickness.

Embodiment 7

Other than green pigment composition (G1) is replaced with green pigment composition (G8) in embodiment 1, equally Ground operation, obtains evaluation composition (CG8).By the toning made in Production Example 13 with composition (TY1) and evaluation group It closes the obtained masking liquid of object (CG8) mixing and is spun on soda-lime glass, after 90 DEG C 3 minutes dry, the coloration under illuminant-C is presented in production The film of (x, y)=(0.250,0.615).Brightness is measured with high and new technology company, Hitachi U-3900, with Hitachi's new and high technology Corporation white interference microscope VS1330 measures film thickness.

Embodiment 8

Other than green pigment composition (G1) is replaced with green pigment composition (G9) in embodiment 1, equally Ground operation, obtains evaluation composition (CG9).By the toning made in Production Example 13 with composition (TY1) and evaluation group It closes the obtained masking liquid of object (CG9) mixing and is spun on soda-lime glass, after 90 DEG C 3 minutes dry, the coloration under illuminant-C is presented in production The film of (x, y)=(0.250,0.615).Brightness is measured with high and new technology company, Hitachi U-3900, with Hitachi's new and high technology Corporation white Gan Wataru microscope VS1330 measures film thickness.

Embodiment 9

Using the zirconium pearl of 0.3~0.4mm, with Toyo Seiki Co. Ltd. system paint shaker by green pigment composition (RG1) 2.23g, sulfonation zinc phthalocyanine phthalocyanine derivative (S1) 0.25g and Bi Ke chemical company BYK-LPN6919 1.24g, DIC plants of formulas Commercial firm UNIDIC ZL-295 1.86g, propylene glycol monomethyl ether 10.92g disperse 2 hours together, obtain colour cell It closes object (MG10).Coloured composition (MG10) 4.0g, Dainippon Ink Chemicals UNIDIC ZL-295 0.98g, propylene glycol list is added Methylether acetate 0.22g, is mixed with paint shaker, to obtain being used to form commenting for colour filter green pixel portion Valence is with composition (CG10).The toning made in Production Example 13 composition (TY1) and evaluation is mixed with composition (CG10) Close obtained masking liquid and be spun on soda-lime glass, at 90 DEG C after dry 3 minutes, production present the coloration (x, y) under illuminant-C= The film of (0.250,0.615).Brightness is measured with high and new technology company, Hitachi U-3900, it is white with high and new technology company, Hitachi system Color interference microscope VS1330 measures film thickness.

Embodiment 10

Other than sulfonation zinc phthalocyanine phthalocyanine derivative (S1) is replaced with sulfonation zinc phthalocyanine phthalocyanine derivative (S2) in embodiment 9, It operates in the same way, obtains evaluation composition (CG11).By the toning made in Production Example 13 composition (TY1) and evaluation Obtained masking liquid is mixed with composition (CG11) and is spun on soda-lime glass, and after 90 DEG C 3 minutes dry, production is presented under illuminant-C Coloration (x, y)=(0.250,0.615) film.Brightness is measured with high and new technology company, Hitachi U-3900, with Hitachi's height New Tech S. R. L. white interference microscope VS1330 measures film thickness.

Embodiment 11

Other than sulfonation zinc phthalocyanine phthalocyanine derivative (S1) is replaced with sulfonation zinc phthalocyanine phthalocyanine derivative (S3) in embodiment 9, It operates in the same way, obtains evaluation composition (CG12).By the toning made in Production Example 13 composition (TY1) and evaluation Obtained masking liquid is mixed with composition (CG12) and is spun on soda-lime glass, and after 90 DEG C 3 minutes dry, production is presented under illuminant-C Coloration (x, y)=(0.250,0.615) film.Brightness is measured with high and new technology company, Hitachi U-3900, with Hitachi's height New Tech S. R. L. white interference microscope VS1330 measures film thickness.

Embodiment 12

Other than green pigment composition (G1) is replaced with green pigment composition (G10) in embodiment 1, equally Ground operation, obtains evaluation composition (CG13).By the toning made in Production Example 13 with composition (TY1) and evaluation group It closes the obtained masking liquid of object (CG13) mixing and is spun on soda-lime glass, after 90 DEG C 3 minutes dry, the color under illuminant-C is presented in production Spend the film of (x, y)=(0.275,0.570).Brightness is measured with high and new technology company, Hitachi U-3900, with the high-new skill of Hitachi Art corporation white interference microscope VS1330 measures film thickness.

Embodiment 13

Other than green pigment composition (G1) is replaced with green pigment composition (G11) in embodiment 1, equally Ground operation, obtains evaluation composition (CG14).By the toning made in Production Example 13 with composition (TY1) and evaluation group It closes the obtained masking liquid of object (CG14) mixing and is spun on soda-lime glass, after 90 DEG C 3 minutes dry, the color under illuminant-C is presented in production Spend the film of (x, y)=(0.275,0.570).Brightness is measured with high and new technology company, Hitachi U-3900, with the high-new skill of Hitachi Art corporation white interference microscope VS1330 measures film thickness.

Comparative example 1

Other than green pigment composition (G1) is replaced with green pigment composition (G6) in embodiment 1, equally Ground operation, obtains evaluation composition (CG6).By the toning made in Production Example 13 with composition (TY1) and evaluation group It closes the obtained masking liquid of object (CG6) mixing and is spun on soda-lime glass, after 90 DEG C 3 minutes dry, the coloration under illuminant-C is presented in production The film of (x, y)=(0.250,0.615).Brightness is measured with high and new technology company, Hitachi U-3900, with Hitachi's new and high technology Corporation white Gan Wataru microscope VS1330 measures film thickness.

Comparative example 2

Other than green pigment composition (G1) is replaced with green pigment composition (G12) in embodiment 1, equally Ground operation, obtains evaluation composition (CG12).By the toning made in Production Example 13 with composition (TY1) and evaluation group It closes the obtained masking liquid of object (CG12) mixing and is spun on soda-lime glass, after 90 DEG C 3 minutes dry, the color under illuminant-C is presented in production Spend the film of (x, y)=(0.275,0.570).Brightness is measured with high and new technology company, Hitachi U-3900, with the high-new skill of Hitachi Art corporation white interference microscope VS1330 measures film thickness.

Table 1

Table 2

As shown in table 1,2, confirm using the case where sulfonation zinc phthalocyanine phthalocyanine derivative, sulphonation aluminum phthalocyanine derivative and using sulphur The case where changing copper phthalocyanine derivative is high compared to brightness.In addition, the film thickness situation thinner than 3.4 μm is determined as ◎, by 3.4 μm or more 3.6 μm or less of situation is determined as 〇, will be determined as than the case where 3.6 μ m-thick ×, as a result use sulfonation zinc phthalocyanine phthalocyanine derivative, sulphur The case where changing aluminium phthalocyanine derivates becomes ◎ or 〇.

The sulfonated copper phthalocyanine for having used with having used in the past is selected in the present invention, and (SOLSPERSE 12000, sulfonated copper phthalocyanine spreads out Biological (S7)) pigment derivative of D2/D1 high is compared, therefore brightness is high.Further, the present invention in, selection used with it is previous The sulfonated copper phthalocyanine (SOLSPERSE 12000, sulfonated copper phthalocyanine derivative (S7)) used the face low compared to the transmissivity of 460nm Expect derivative, therefore film thickness is thin.

Claims

1. a kind of pigment composition for color filter, which is characterized in that contain zinc halide phthalocyanine color and the following general formula (1) institute table The pigment derivative shown,

[changing 1]

In general formula (1), Z¹~Z¹⁶Bromine atom, chlorine atom, hydrogen atom or sulfo group are each independently represented, at least being averaged for sulfo group takes It is 0.1~4 for radix, M indicates Al, Si, Sc, Ti, V, Mg, Fe, Co, Ni, Zn, Ga, Ge, Y, Zr, Nb, In, Sn or Pb.

2. pigment composition for color filter according to claim 1, which is characterized in that

The zinc halide phthalocyanine color will used to be formed in such a way that the spectral transmission of very big transmission peak wavelength becomes 70% The integrated value of the transmissivity of 510nm~560nm of film is set as D1, and use is enabled the pigment to derivative and is supported at aluminium oxide institute Obtained derivative hold body by the spectral transmission of very big transmission peak wavelength become 70% in a manner of formed film 510nm~ When the integrated value of the transmissivity of 560nm is set as D2,

Ratio, that is, D2/D1 with D1 and D2 becomes 0.7 or more dichroism.

3. pigment composition for color filter according to claim 1 or 2, which is characterized in that the pigment derivative is such as Under pigment derivative: in the formula (1), Z¹~Z¹⁶For any one of bromine atom, chlorine atom, hydrogen atom or sulfo group, and with Average meter in one molecule, at least from Z¹、Z⁴、Z⁵、Z⁸、Z⁹、Z¹²、Z¹³、Z¹⁶Any 2 or more of middle selection have chlorine atom.

4. pigment composition for color filter according to claim 1 or 2, which is characterized in that the pigment derivative is such as Under pigment derivative: in the formula (1), Z¹~Z¹⁶With any one of bromine atom, chlorine atom, hydrogen atom or sulfo group, and In terms of being averaged in a molecule, at least from Z¹、Z⁴、Z⁵、Z⁸、Z⁹、Z¹²、Z¹³、Z¹⁶Any 2 or more of middle selection have bromine atom.

5. pigment composition for color filter according to any one of claims 1 to 4, which is characterized in that the pigment spreads out Biology is following pigment derivative: the Z in terms of being averaged in a molecule, in the formula (1)¹~Z¹⁶Contain 10~14 halogen originals Son, 8~12 bromine atoms, 2~5 chlorine atoms.

6. pigment composition for color filter according to any one of claims 1 to 5, which is characterized in that further include Yellow uitramarine.

7. a kind of colour filter, which is characterized in that contain colour filter described in any one of the claims 1~6 in pixel portion Device color compositions.

8. a kind of colour filter, which is characterized in that derivative containing pigment represented by zinc halide phthalocyanine color and the following general formula (1) Object,

[changing 2]

9. colour filter according to claim 8, which is characterized in that

Ratio, that is, D2/D1 with D1 and D2 becomes 0.7 or more dichroism.

10. colour filter according to claim 8 or claim 9, which is characterized in that the pigment derivative is that following pigment is derivative Object: in the formula (1), Z¹~Z¹⁶For any one of bromine atom, chlorine atom, hydrogen atom or sulfo group, and with flat in a molecule It counts, at least from Z¹、Z⁴、Z⁵、Z⁸、Z⁹、Z¹²、Z¹³、Z¹⁶Any 2 or more of middle selection have chlorine atom.

11. colour filter according to claim 8 or claim 9, which is characterized in that the pigment derivative is that following pigment is derivative Object: in the formula (1), Z¹~Z¹⁶With any one of bromine atom, chlorine atom, hydrogen atom or sulfo group, and in a molecule Average meter, at least from Z¹、Z⁴、Z⁵、Z⁸、Z⁹、Z¹²、Z¹³、Z¹⁶Any 2 or more of middle selection have bromine atom.

12. the colour filter according to any one of claim 8~11, which is characterized in that the pigment derivative is as follows Pigment derivative: the Z in terms of being averaged in a molecule, in the formula (1)¹~Z¹⁶Contain 10~14 halogen atoms, 8~12 Bromine atom, 2~5 chlorine atoms.

13. the colour filter according to any one of claim 8~12, which is characterized in that further include yellow uitramarine.