CN102549460B - Coloring composition and color filter - Google Patents

Coloring composition and color filter Download PDF

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Publication number
CN102549460B
CN102549460B CN201080042466.8A CN201080042466A CN102549460B CN 102549460 B CN102549460 B CN 102549460B CN 201080042466 A CN201080042466 A CN 201080042466A CN 102549460 B CN102549460 B CN 102549460B
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acid
pigment
blue
resin
molecular weight
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CN102549460A (en
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中村高士
山崎智己
尾立嘉岳
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Toyocolor Co Ltd
Artience Co Ltd
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Toyo Ink SC Holdings Co Ltd
Toyocolor Co Ltd
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B11/00—Diaryl- or thriarylmethane dyes
    • C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
    • C09B11/10—Amino derivatives of triarylmethanes
    • C09B11/24—Phthaleins containing amino groups ; Phthalanes; Fluoranes; Phthalides; Rhodamine dyes; Phthaleins having heterocyclic aryl rings; Lactone or lactame forms of triarylmethane dyes
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/201—Filters in the form of arrays
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133514—Colour filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical & Material Sciences (AREA)
  • Nonlinear Science (AREA)
  • Organic Chemistry (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Optical Filters (AREA)
  • Materials For Photolithography (AREA)

Abstract

Disclosed are: a color filter having excellent color properties, heat resistance, light resistance and solvent resistance; and a coloring composition for use in the production of the color filter. Specifically disclosed is a coloring composition for a color filter, which comprises a transparent resin and a coloring agent. The coloring agent comprises a salt-forming product of a basic dye and a counter compound that is an anionic component. The counter compound has a molecular weight of 200 to 3500.

Description

Coloured composition and color filter
Technical field
The present invention relates to the coloured composition using in the manufacture of the color filter of color liquid crystal display arrangement and color image pickup apparatus etc.In addition, the invention still further relates to and possess filter section (the filter segment that uses this coloured composition to form; Colour filter section) color filter.
Background technology
Liquid crystal indicator for example has between a pair of polaroid clamping the structure of liquid crystal layer.According to such liquid crystal indicator, utilize the orientation of liquid crystal molecule that the state of the polarized light that sees through one of them polaroid is changed, thus the light quantity that sees through another polaroid is controlled.
The display mode of liquid crystal indicator has VA (vertical orientated, Vertically Aligned) pattern, IPS (switch in face, In-Plane Switching) pattern and TN (twisted nematic, Twisted Nematic) pattern.Wherein TN pattern becomes main flow.
These liquid crystal indicators, by color filter is set between polaroid, can carry out the demonstration of coloured image.Color liquid crystal display arrangement is used in the various devices such as the monitor of kinescope and PC in recent years.For this reason, color filter is required to high-contrast and high brightness, wide color reproduction region and the requirement of height reliability are also uprised.
It should be noted that, color filter has the structure that disposes the filter section of more than two kinds that form and aspect are different on the transparency carriers such as glass.The width of each filter section is the fine degree of several microns～hundreds of microns.In filter section, can be the various shapes such as striped arrangement and triangle arrangement and configuration.No matter be any situation, these filter sections be all every kind of form and aspect with the marshalling of regulation configure.
In addition, utilizing C-MOS (Complementary Metal Oxide Semiconductor, complementary metal oxide semiconductor (CMOS)) or CCD (Charge Coupled Device, charge-coupled image sensor) color image pickup apparatus in, generally on the sensitive surface of imaging apparatus, configure color filter, this color filter be by arrange three primary colors that addition mixes, blue (B), green (G) and red (R) look filter section or form as the filter section of the Huang (Y) of their complementary colors, pinkish red (M) and blue or green (C) look.In recent years, for color filter used in color image pickup apparatus, the requirement of the color characteristics such as high-transmission rate, i.e. high brightness and wide color reproduction region is also improved constantly.
In the manufacture method of color filter, for example have utilize the decoration method of salify color development (also claiming halochromism) and as dyestuff dispersion method, use dyestuff as the method for colorant, use Pigments method, print process and the electrodeposition process of pigment as colorant.
In Pigments method, use colored resist, this colour resist is to obtain by disperse also to mix wherein emulsion and adjuvant etc. as the pigment particles of colorant in transparent resin.Then, utilize the apparatus for coating such as spin coater by this colour resist-coating on substrate, then use and aim at exposer or stepping exposer carries out selectivity exposure to this film across mask.Film after this exposure is supplied successively to alkaline development and heat curing processing, thereby obtain filter section pattern.Repeat above operation by each color, thereby complete color filter.
All the time, the phthalocyanine colors that use tolerance and tone excellence in blue electric-wave filter joint and cyan filter section more.Phthalocyanine color has the different crystal formations such as α type, β type, δ type and ε type, all has colourity and a high excellent properties of colouring power due to any, is therefore suitable as the colorant that color filter is used.
As phthalocyanine color, known have there is copper, the phthalocyanine color of the various central metals such as zinc, nickel, cobalt and aluminium.Wherein, copper phthalocyanine, because colourity is the highest, is therefore widely used.In addition, the dissimilar metal phthalocyanine color such as metal-free phthalocyanine, ZnPc pigment, aluminium phthalocyanine color and cobalt phthalocyanine color is also practical.
Diketopyrrolo-pyrrole pigment, quinacridone pigment and the anthraquinone pigments etc. that use tolerance and tone excellence in red filter joint and magenta filter section more.Because they all have colourity and the high excellent properties of colouring power, be therefore suitable as the colorant that color filter is used.
In the formation of green filter joint, use the halo phthalocyanine colors of tolerances and tone excellence etc. more.Because they all have chromaticity (saturation) and the high excellent properties of colouring power, be therefore suitable as the colorant that color filter is used.In addition, the same with blue pigment, known have there is copper, the phthalocyanine color of the various central metals such as zinc, nickel, cobalt and aluminium.Wherein, ZnPc pigment and aluminium phthalocyanine color are widely used because chromaticity is the highest.
For the available liquid crystal display device backlight that has used cold-cathode tube type, for example by use copper phthalocyanine in blue electric-wave filter joint or cyan filter section with the combination of dioxazine series pigments, use the combination of anthraquinone pigment and diketopyrrolo-pyrrole pigment in red filter joint or pinkish red filter section, use halo phthalocyanine color in green filter joint, realized thus high brightness and wide color viewing area.But, as previously mentioned, color filter is required to higher brightness and wider color reproduction region.
In No. 6-75375, Japanese kokai publication hei, record and made dyestuff instead of pigment be dissolved in the technology in resin etc. as colorant in order to solve above-mentioned problem.In addition, in No. 2001-81348, TOHKEMY, recorded triarylmethane based dye, rhodamine based dye and azo dyes are formed to color lake and use with colorant these color lakes as color filter.But, for dyestuff, there is the problem of thermotolerance, photostability and poor solvent resistance compared with pigment.
In No. 2008-304766, TOHKEMY, record: in order to improve thermotolerance, photostability and solvent resistance, be that basic-dyeable fibre uses as color filter colorant using the salify product of triarylmethane based dye and aromatic sulphonic acid or triarylmethane.But triarylmethane is that the salify product of basic-dyeable fibre and aromatic series monobasic sulfonic acid has the shortcoming because of the little poor durability of molecular weight.Certainly, even if directly former state is used basic-dyeable fibre, permanance or poor.
Summary of the invention
The object of the present invention is to provide the color filter of color characteristics, thermotolerance, photostability and solvent resistance excellence and the coloured composition for the manufacture of this color filter.
People of the present invention conduct in-depth research repeatedly in order to address the above problem, found that, as the colorant of coloured composition, by the product that uses basic-dyeable fibre and equilibrium compound (counter compound) salify of molecular weight in particular range to form, high brightness and wide color reproduction region become possibility, and also can realize excellent performance to thermotolerance, photostability and solvent resistance.Like this, according to this discovery, completed the invention of following the 1st aspect and the 2nd aspect.
Be that the 1st aspect of the present invention relates to a kind of color composition for color filter, it contains transparent resin and colorant, described colorant contains basic-dyeable fibre and the salify product as the equilibrium compound of negative ion source, and the molecular weight of described equilibrium compound is in 200 to 3500 scope.
The molecular weight of above-mentioned equilibrium compound also can be in 250 to 3500 scope.
Above-mentioned equilibrium compound can be at least a kind that is selected from heteropoly acid, organic sulfonic acid, organic carboxyl acid and acid dyes.
Above-mentioned colorant can further contain the resin with acidic group.The weight-average molecular weight of the above-mentioned resin with acidic group can be in 400 to 12000 scope.The above-mentioned resin with acidic group can be Abietyl modified maleic acid resin.The acid number of the above-mentioned resin with acidic group can be in 100 to 300mgKOH/g scope.
Above-mentioned basic-dyeable fibre can be at least a kind that is selected from triarylmethane based dye, rhodamine based dye, methylene blue based dye and flavine based dye.
This color composition for color filter can further contain optical polymerism composition and/or Photoepolymerizationinitiater initiater.
In addition, the 2nd aspect of the present invention relates to a kind of color filter, and it possesses the filter section being formed by above-mentioned color composition for color filter.
In addition, what people of the present invention furtherd investigate repeatedly in order to address the above problem found that, by using the salify product being formed by triarylmethane based dye and xanthene based dye, high brightness and wide color reproduction region become possibility, and also can realize excellent performance for tolerance.Like this, according to this discovery, completed the invention of following the 3rd aspect and the 4th aspect.
Be that the 3rd aspect of the present invention relates to a kind of blue coloring composition for color filter, it contains transparent resin and colorant, and above-mentioned colorant contains the salify product being formed by triarylmethane based dye and xanthene based dye.
Above-mentioned triarylmethane based dye can be that basic-dyeable fibre, above-mentioned xanthene based dye can be acid dyes for xanthene for triarylmethane.Or above-mentioned triarylmethane based dye can be that acid dyes, above-mentioned xanthene based dye can be basic-dyeable fibre for xanthene for triarylmethane.
Above-mentioned xanthene based dye can be rhodamine based dye.
Above-mentioned colorant can further contain phthualocyanine pigment.In addition, above-mentioned colorant can further contain dioxazine series pigments.
This blue coloring composition for color filter can further contain photopolymerization monomer and/or Photoepolymerizationinitiater initiater.
In addition, the 4th aspect of the present invention relates to a kind of color filter, and it possesses the blue electric-wave filter being formed by above-mentioned blue coloring composition for color filter and saves.
And then, what people of the present invention furtherd investigate repeatedly in order to address the above problem found that, be that basic-dyeable fibre and xanthene are the salify product that acid dyes forms by using by xanthene, high brightness and wide color reproduction region become possibility, and also can realize excellent performance for tolerance.Like this, according to this discovery, completed the invention of following the 5th aspect and the 6th aspect.
Be that the 5th aspect of the present invention relates to a kind of color composition for color filter, it contains transparent resin and colorant, and it is that basic-dyeable fibre and xanthene are the salify product that acid dyes forms that above-mentioned colorant contains by xanthene.
Above-mentioned xanthene is that basic-dyeable fibre can be basic-dyeable fibre for rhodamine.
Above-mentioned colorant can further contain phthualocyanine pigment.In addition, above-mentioned colorant can further contain dioxazine series pigments.
This color composition for color filter can further contain photopolymerization monomer and/or Photoepolymerizationinitiater initiater.
In addition, the 6th aspect of the present invention relates to a kind of color filter, and it possesses the filter section being formed by above-mentioned color composition for color filter.
Brief description of the drawings
Fig. 1 is the figure that represents the luminescent spectrum backlight using in embodiment and comparative example.
Embodiment
Below form of the present invention is elaborated.
It should be noted that; wherein said " (methyl) acryloyl group ", " (methyl) propenyl ", " (methyl) acrylic acid ", " (methyl) acrylate " and " (methyl) acrylamide " if not otherwise specified, are respectively to represent " acryloyl group and/or methacryl ", " propenyl and/or methylpropenyl ", " acrylic acid and/or methacrylic acid ", " acrylate and/or methacrylate " and " acrylamide and/or Methacrylamide ".In addition, " C.I. " refers to color index (C.I.).
0 the 1st form
First, the 1st form of the present invention is described.
" color composition for color filter "
The color composition for color filter of the 1st form of the present invention contains transparent resin and colorant.This colorant contains basic-dyeable fibre and the salify product as the equilibrium compound of negative ion source.And the molecular weight of this equilibrium compound within the limits prescribed.This colorant counterion that to contain pigment ion be cationic dyestuff replaces with the negative ion with regulation molecular weight the salt forming.Thus, using when this coloured composition, can manufacture and there is high brightness and wide color reproduction region and the color filter of thermotolerance, photostability and solvent resistance excellence.
< colorant >
The salify product that can preferably use in this coloured composition is to present blueness, purple, green, redness, magenta, cyan or yellow salify product.The salify product that can preferably use in this coloured composition is the salify product that the salt-forming reaction of basic-dyeable fibre by being categorized as the alkaline red and C.I. basic yellow of C.I. alkali blue, C.I. alkalescence purple, C.I. Viride Nitens, C.I. etc. and the equilibrium compound of molecular weight in specialized range obtains.
Basic-dyeable fibre and equilibrium compound for example can generate salify product by both are dissolved in aqueous solution or alcoholic solution.Or also can be by both are heated while melting mixing obtains salify product.
Although basic-dyeable fibre has good dichroism, the same with general dyestuff, extremely lack photostability and thermotolerance.Be the color filter of basic-dyeable fibre for the colour display device for requiring high reliability or color image pickup apparatus, characteristic is inadequate.
Therefore, in this case eliminate the shortcoming of basic-dyeable fibre, by the larger negative ion displacement of molecular weight for the negative ion of basic-dyeable fibre.Specifically, use the salify product of basic-dyeable fibre and the equilibrium compound of molecular weight in specialized range.And the resin that preferably this salify product utilization is had to acidic group carries out modification.
The molecular weight of equilibrium compound is in 200 to 3500 scope.The molecular weight of equilibrium compound preferably in 250 to 3500 scope, more preferably in 300 to 3500 scope.Or the molecular weight of equilibrium compound is preferably in 200 to 750 scope.While using the little equilibrium compound of molecular weight, be difficult to realize sufficient thermotolerance and photostability.While using the large equilibrium compound of molecular weight, be difficult to make salify product to exist with larger molal quantity in unit volume, be difficult to develop the color fully.
[basic-dyeable fibre]
As basic-dyeable fibre, can to enumerate triarylmethane be basic-dyeable fibre, comprise rhodamine be the xanthene of basic-dyeable fibre be basic-dyeable fibre, flavine be basic-dyeable fibre, Chinese scholartree Huang be basic-dyeable fibre, safranine be basic-dyeable fibre, flame red be that basic-dyeable fibre and methylene blue are basic-dyeable fibre etc.
Be basic-dyeable fibre as concrete triarylmethane, for example, can enumerate C.I. alkaline purple 1 (methyl violet), C.I. alkaline purple 3 (crystal violet) and C.I. basic violet 14 (Magenta); C.I. alkali blue 1 (alkaline dark blue 6G), C.I. alkali blue 5 (alkaline dark blue EX), C.I. Blue 7 (Victoria's pure blue B O) and C.I. alkali blue 26 (victoria blue B conc.); And C.I. Viride Nitens 1 (bright green GX) and C.I. Viride Nitens 4 (peacock green).Wherein preferably use C.I. Blue 7, C.I. Viride Nitens 4, C.I. alkaline purple 1 or C.I. alkaline purple 3.
In addition, be basic-dyeable fibre as rhodamine, for example can enumerate C.I. alkali red 1:1 (rhodamine 6G, 6GCP) and C.I. red 8 (rhodamine Gs) of alkalescence and C.I. alkaline purple 10 (rhodamine B).Wherein preferably use C.I. alkali red 1:1 or C.I. alkaline purple 10.
In addition, be basic-dyeable fibre as flavine, for example can enumerate C.I. basic yellow 1.Be basic-dyeable fibre as Chinese scholartree Huang, for example, can enumerate C.I. basic yellow 2 and C.I. basic yellow 3.Be basic-dyeable fibre as safranine, for example, can enumerate C.I. alkalescence red 2.Red as flame is basic-dyeable fibre, for example, can enumerate C.I. alkali red 1:1 2.Be basic-dyeable fibre as methylene blue, for example, can enumerate C.I. alkali blue 9 (methylene blue FZ, methylene blue B), C.I. alkali blue 25 (alkali blue GO) and C.I. alkali blue 24 (new methylene blue NX).
Wherein preferably use C.I. basic yellow 1, C.I. alkali blue 9, C.I. alkali blue 24 or C.I. alkali blue 25.
Wherein, from the good aspect of colour rendering, preferably using triarylmethane is that basic-dyeable fibre, rhodamine are that basic-dyeable fibre or methylene blue are basic-dyeable fibre.In addition, not only form red pixel but also be that basic-dyeable fibre is effective material as the flavine of complementary colors.
Methylene blue basic-dyeable fibre presents distinct blueness, in the time making above-mentioned salify product, is preferred material from the aspect of excellent heat resistance.In addition, flavine is that basic-dyeable fibre presents distinct yellow, in the time making above-mentioned salify product, is preferred material from the aspect of excellent heat resistance.
Be that basic-dyeable fibre and rhodamine are that basic-dyeable fibre describes in detail to triarylmethane below.
(triarylmethane is basic-dyeable fibre)
Triarylmethane is that basic-dyeable fibre passes through with respect to center carbon potential in the NH of contraposition 2or the oxidation of OH base and the structure of getting quinone develop the color thus.
Triarylmethane is that basic-dyeable fibre is according to NH 2and the number of OH base and be divided into following 3 types.Wherein, the basic-dyeable fibre of triaminotriphenyl methylmethane system is preferred from the aspect that blueness, redness and green are developed the color well.
A) diamido triphenyl methane is basic-dyeable fibre
B) triaminotriphenyl methylmethane is basic-dyeable fibre
C) rosolic acid that has an OH base is basic-dyeable fibre
Triaminotriphenyl methylmethane is that basic-dyeable fibre and diamido triphenyl methane are that basic-dyeable fibre is preferred from tone excellence, the aspect more excellent than the daylight fastness of other dyestuff.In addition, diphenyl naphthyl methane basic-dyeable fibre and/or triphenyl methane basic-dyeable fibre are also preferred.
The triarylmethane of blue series is that basic-dyeable fibre has the dichroism high in 400 to 440nm wavelength coverage internal transmission factor.
(rhodamine is basic-dyeable fibre)
Be that basic-dyeable fibre describes to rhodamine below.
The rhodamine that can preferably use in this coloured composition is that basic-dyeable fibre is the basic-dyeable fibre that presents redness or purple.
The basic-dyeable fibre that presents redness or purple for example belongs to the alkaline basic-dyeable fibre such as purple of the red and C.I. of C.I. alkalescence.
Rhodamine is that basic-dyeable fibre has the dichroism high in 400 to 430nm wavelength coverage internal transmission factor.
Rhodamine is that optical transmission rate that basic-dyeable fibre is preferably 650nm to wavelength is that the optical transmission rate that is 600nm more than 90%, to wavelength is more than 75%, is that 500 to 550nm scope internal transmission factors are to be 400nm below 5%, to wavelength optical transmission rate is more than 70% at wavelength.More preferably the optical transmission rate that the optical transmission rate that is 650nm to wavelength is is 600nm more than 95%, to wavelength is more than 80%, be that 500 to 550nm scope internal transmission factors are to be 400nm below 10%, to wavelength optical transmission rate is more than 75% at wavelength.
If gather above-mentioned basic-dyeable fibre by every kind of color, can be for example that triarylmethane is that basic-dyeable fibre or methylene blue are basic-dyeable fibre for the basic-dyeable fibre of blue pixel, for example can enumerate particularly C.I. alkali blue 1 (alkaline dark blue 6G), C.I. alkali blue 5 (alkaline dark blue EX), C.I. Blue 7 (Victoria's pure blue B O), C.I. alkali blue 9 (methylene blue FZ, methylene blue B), C.I. alkali blue 24 (new methylene blue NX), C.I. alkali blue 25 (alkali blue GO) and C.I. alkali blue 26 (victoria blue B conc.).In addition, as the complementary colors of blue pixel, rhodamine be basic-dyeable fibre and described later present red safranine be basic-dyeable fibre and flame red be that basic-dyeable fibre is effective.
For example, by by copper phthalocyanine (C.I. pigment blue 15: 6) with by the salify product the use that present red basic-dyeable fibre and obtain, can obtain the high blue pixel of brightness.Particularly copper phthalocyanine (C.I. pigment blue 15: 6) and the combination that is the salify product that obtains of basic-dyeable fibre by rhodamine can obtain high brightness, thereby preferably.
Can for the basic-dyeable fibre of red pixel be for example rhodamine be basic-dyeable fibre, safranine be basic-dyeable fibre or flame red be basic-dyeable fibre, for example can enumerate particularly red 2 (safranine is basic-dyeable fibre) of C.I. alkali red 1:1 (rhodamine 6G and 6GCP), C.I. alkalescence, red 8 (rhodamine Gs) of C.I. alkalescence, C.I. alkali red 1:1 2 (flame is red is basic-dyeable fibre) and C.I. alkaline purple 10 (rhodamine B).In addition, as the complementary colors of red pixel, presenting yellow flavine is that basic-dyeable fibre is preferred.
Can be for example that triarylmethane is basic-dyeable fibre for the basic-dyeable fibre of green pixel, for example can enumerate particularly C.I. Viride Nitens 1 (bright green GX) and C.I. Viride Nitens 4 (peacock green).
[equilibrium compound]
The equilibrium compound using in this coloured composition is the anionic property compound of molecular weight in 200 to 3500 scope.The molecular weight of equilibrium compound preferably in 250 to 3500 scope, more preferably in 300 to 3500 scope.Or the molecular weight of equilibrium compound is preferably in 200 to 750 scope.In addition, the molecular weight of the negative ion of this equilibrium compound preferably in 199 to 3499 scope, more preferably in 249 to 3499 scope or in 199 to 749 scope.Concrete equilibrium compound is for example organic carboxyl acid or the acid dyess such as the organic sulfonic acid such as heteropoly acid, aromatic sulphonic acid, aromatic carboxylic acid and fatty acid.
Equilibrium compound is preferably organic sulfonic acid or acid dyes.Now, the molecular weight of equilibrium compound is preferably in 200 to 750 scope.
It should be noted that, the molecular weight of regulation and mean molecular weight are by the 1st value that rounds up and obtain of radix point to the theoretical value calculating according to molecular structure and atomic weight here.In addition, in the time that equilibrium compound is sodium salt, the molecular weight of regulation and mean molecular weight refer to the value of the molecule that changes sodium into hydrogen and obtain here.
(heteropoly acid)
As heteropoly acid, for example, can enumerate phosphotungstic acid H 3(PW 12o 40) nH 2o (n ≈ 30; ≈ represents to approximate) (molecular weight is 3421), silico-tungstic acid H 4(SiW 12o 40) nH 2o (n ≈ 30) (molecular weight is 3418), phosphomolybdic acid H 3(PMo 12o 40) nH 2o (n ≈ 30) (molecular weight is 2205), silicomolybdic acid H 3(SiMo 12o 40) nH 2o (n ≈ 30) (molecular weight is 2202), phosphotungstomolybdic acid H 3(PW 12-xmo xo 40) nH 2o (n ≈ 30) (6 < x < 12) and phosphovanadomolybdic acid H 15-x(PV 12-xmo xo 40) nH 2o (n ≈ 30).
For phosphotungstomolybdic acid, phosphovanadomolybdic acid and silicon tungsten molybdic acid, by changing the content of the constituents such as phosphotungstic acid, phosphomolybdic acid, silico-tungstic acid and silicomolybdic acid, molecular weight can be adjusted to 2202 to 3421 scope.
Using heteropoly acid, when equilibrium compound uses, its mean molecular weight is preferably in 2820 to 3421 scope.This is because in the time that equilibrium compound contains molybdenum and tungsten, preferably the ratio of tungsten exceedes 50%.In the time being phosphotungstomolybdic acid, by reducing the content of Mo and more containing W, can obtain the look material of transmittance excellence.
(organic acid: organic sulfonic acid and organic carboxyl acid)
As organic sulfonic acid, for example, can use aromatic sulphonic acid.As aromatic sulphonic acid, preferred compound for example can be enumerated naphthalidine-4,8-disulfonic acid (molecular weight is 303), naphthalidine-3,8-disulfonic acid (molecular weight is 303), naphthalidine-5,7-disulfonic acid (molecular weight is 303), naphthalidine-3,6-disulfonic acid (molecular weight is 303), naphthalidine-3,6,8-trisulfonic acid (Koch's acid) (molecular weight is 383), 2-naphthylamines-6,8-disulfonic acid (molecular weight is 303), 2-naphthylamines-1,6-disulfonic acid (molecular weight is 303), 2-naphthylamines-4,8-disulfonic acid (molecular weight is 303), 2-naphthylamines-3,6-disulfonic acid (amino-R acid) (molecular weight is 303), 2-naphthylamines-5,7-disulfonic acid (amido-J-acid) (molecular weight is 303), 1-naphthols-4,8-disulfonic acid (molecular weight is 304), 1-naphthols-3,8-disulfonic acid (ε acid) (molecular weight is 304), 1-naphthols-3,6-disulfonic acid (molecular weight is 304), 1-naphthols-3,6,8-trisulfonic acid (molecular weight is 384), beta naphthal-6,8-disulfonic acid (molecular weight is 304), beta naphthal-3,6-disulfonic acid (R acid) (molecular weight is 304), beta naphthal-3,6,8-trisulfonic acid (molecular weight is 384), N-phenyl-peri acid (molecular weight is 299), N-p-methylphenyl-naphthalidine-8-sulfonic acid (molecular weight is 313), N-phenyl-1-naphthylamine-5-sulfonic acid (molecular weight is 299), N-phenyl-2-naphthylamine-6-sulfonic acid (molecular weight is 299), N-acetyl group-7-amino-1-naphthols-3-sulfonic acid (molecular weight is 281), N-phenyl-7-amino-1-naphthols-3-sulfonic acid (molecular weight is 315), N-acetyl group-6-amino-1-naphthols-3-sulfonic acid (molecular weight is 281), N-phenyl-6-amino-1-naphthols-3-sulfonic acid (molecular weight is 315), 1,8-dihydro-3,6-disulfonic acid (chromotropic acid) (molecular weight is 320), 8-amino-1-naphthols-3,6-disulfonic acid (molecular weight is 319), 8-amino-1-naphthols-5,7-disulfonic acid (molecular weight is 319), 1,6-diamido-beta naphthal-4-sulfonic acid (molecular weight is 254), 1-amino-beta naphthal-6,8-disulfonic acid (molecular weight is 319), 1-amino-beta naphthal-3,6-disulfonic acid (molecular weight is 319), 2,8-diaminostilbene-naphthols-5,7-disulfonic acid (molecular weight is 334), 2,7-diaminostilbene-naphthols-3-sulfonic acid (molecular weight is 254), 2,6-diaminostilbene-naphthols-3-sulfonic acid (molecular weight is 254), 2,8-diaminostilbene-naphthols-3,6-disulfonic acid (molecular weight is 334) and 2-amino-7-phenyl amino-1-naphthols-3-sulfonic acid (molecular weight is 330).
In addition, also preferably use rylnthracene sulfonin (molecular weight is 258), anthraquinone-2-sulfonic acid or anthraquinone-1-sulfonic acid (molecular weight is 288).
There is 1 amino and 1 sulfonic naphthylamine sulfonic acid if used, can realize excellent thermotolerance and photostability.As naphthylamine sulfonic acid, for example can enumerate 2-amino-1-naphthalene sulfonic aicd (tobias acid, molecular weight is 223), 4-amino-1-naphthalene sulfonic aicd (naphthonic acid, molecular weight is 223), 8-amino-1-naphthalene sulfonic aicd (peri acid, molecular weight is 223), 2-amino-6-naphthalene sulfonic acids (Bronner acid, molecular weight is 223), (the Laurent's acid of 1-amino-5-naphthalene sulfonic acids, molecular weight is 223), 5-amino-2-naphthalene sulfonic acids (molecular weight is 223), 1-amino-6-naphthalene sulfonic acids (molecular weight is 223), 6-amino-1-naphthalene sulfonic aicd (molecular weight is 223) and 3-amino-1-naphthalene sulfonic aicd (molecular weight is 223).Wherein 2-amino-1-naphthalene sulfonic aicd (tobias acid) particularly preferably.
Also preferably use and there is 1 hydroxyl and 1 sulfonic croceine acid.As croceine acid, for example, can enumerate 2-hydroxyl-6-naphthalene sulfonic acids (Schaffer's acid, molecular weight are 224), 1-hydroxyl-4-naphthalene sulfonic acids (Neville and Winther acid: NW acid, molecular weight are 224), 1-hydroxyl-5-naphthalene sulfonic acids (L acid, molecular weight are 224) and 2-hydroxyl-8-naphthalene sulfonic acids (crocetin, molecular weight are 224).
Wherein, good from colour rendering, can to realize high brightness aspect, preferably has 2 to 3 sulfonic organic sulfonic acids.If there are 4 above sulfonic acid, environmental stability variation, easily causes rheological parameters' change with time, and if 1 sulfonic acid, because basic-dyeable fibre and equilibrium compound reacted with 1: 1, therefore in the time forming mass-tone, colour rendering is understood variation sometimes.
But, if the organic sulfonic acid of molecular weight in 200 to 250 scope, because the molecular weight of equilibrium compound is little, even if therefore the sulfonic group of per molecule is 1, can not damage colour rendering yet.
As organic carboxyl acid, for example, can use aromatic carboxylic acid or fatty acid.As concrete organic carboxyl acid, for example can enumerate tetrachlorophthalic acid (molecular weight is 304), palmitic acid (molecular weight is 257), stearic acid (molecular weight is 285), arachidic acid (molecular weight is 313), behenic acid (molecular weight is 341), carnaubic acid (molecular weight is 369), oleic acid (molecular weight is 282), elaidic acid (molecular weight is 282), erucic acid (molecular weight is 339), nervonic acid (molecular weight is 367), linoleic acid (molecular weight is 280), gamma-Linolenic acid (molecular weight is 278), arachidonic acid (molecular weight is 305), alpha-linolenic acid (molecular weight is 278), parinaric acid (molecular weight is 276), eicosapentaenoic acid (molecular weight is 302) and DHA (molecular weight is 328).
In the time being organic acid, the scope of molecular weight is preferably 200 to 400, more preferably 250 to 400.By making molecular weight within the scope of this, can make the colorant of tolerance and painted equilibrium of forces excellence.It should be noted that, in the time being organic acid, the scope of molecular weight can be also 300 to 400.
(acid dyes)
By acid dyes is used as equilibrium compound, can also control form and aspect.
For red pixel, as mentioned above, for example can use by rhodamine be basic-dyeable fibre, safranine be basic-dyeable fibre or flame red be the salify product that basic-dyeable fibre obtains.Now, be for example C.I. acid yellow 11 (molecular weight is 380), C.I. acid yellow 23 (molecular weight is 534), C.I. acid red 52 (acid rhodamine B) (molecular weight is 580), C.I. acid red 87 (eosin G) (molecular weight is 691.6) and C.I. acid red 289 (molecular weight is 676.7) as the preferred acid dyes of equilibrium compound.
For blue pixel, for example can use by triarylmethane is that basic-dyeable fibre or methylene blue are the salify product that basic-dyeable fibre obtains.Now, be for example C.I. acid red 52 (acid rhodamine B) (molecular weight is 580), C.I. acid red 87 (eosin G) (molecular weight is 691.6) and C.I. acid red 289 (molecular weight is 676.7) as the preferred acid dyes of equilibrium compound.
For green pixel, for example can use by triarylmethanes such as C.I. Viride Nitens 1 (bright green GX) and C.I. Viride Nitenses 4 (peacock green) is the salify product that basic-dyeable fibre obtains.Now, be for example C.I. acid green 3 (edible green No. 1) (molecular weight is 690), C.I. acid green 5 (edible green No. 2) (molecular weight is 761), C.I. acid green 9 (molecular weight is 724), C.I. acid green 16 (molecular weight is 560), C.I. acid green 19 (molecular weight is 625) and C.I. ACID GREEN 25 (molecular weight is 622) as the preferred acid dyes of equilibrium compound.
In the time being acid dyes, the scope of molecular weight is preferably 300 to 750, more preferably 350 to 700.If make molecular weight within the scope of this, can obtain the colorant of weatherability and painted equilibrium of forces excellence.
Particularly rhodamine is that the salify product of basic-dyeable fibre and yellow acid dyes is preferred material from obtaining the aspect of red pigments.
The salify product of basic-dyeable fibre and equilibrium compound can synthesize by known method in the past.Concrete method for example has open in No. 2003-215850, TOHKEMY.
If enumerating and using triarylmethane is the example of basic-dyeable fibre, can, by being add organic sulfonic acid solutions after basic-dyeable fibre is dissolved in water and stir in this solution making triarylmethane, make thus it that salt-forming reaction occurs.Be the amino (NHC of basic-dyeable fibre thereby can obtain triarylmethane 2h 5) with the sulfonic group (SO of organic sulfonic acid 3h) the salify product being combined into.
Organic sulfonic acid also can be dissolved in the alkaline solutions such as NaOH before salt-forming reaction.For example organic sulfonic acid can be with sodium sulfonate (SO 3na) form is used.Be that sulfonic acid solutions comprises sulfonic group (SO 3the replaced compound of the solution of the not replaced compound of hydrogen atom H) and sulfonic hydrogen atom, the solution of for example sodium sulfonate.
[thering is the resin of acidic group]
Have if added in salify product the styrene acrylic copolymer etc. that the resin of acidic group, such as Abietyl modified maleic acid resin and Abietyl modified fumaric resin etc. have resin, rosin ester, the vibrin of acidic group or have acid number, the compatibility in adhesive resin, dispersiveness and the dispersiveness in solvent significantly improve.Consequently, can realize more excellent colour rendering, thermotolerance and photostability.Here, as acidic group, preferably carboxyl (COOH) or sulfonic group (for example-SO 3h or-SO 3na).
In addition, have acidic group resin weight-average molecular weight preferably in 400 to 12000 scope, more preferably in 400 to 6000 scope, further preferably in 400 to 2000 scope.The compatibility excellence of such resin and salify product, if therefore use such resin, the dispersion of salify product in adhesive resin becomes good.
It should be noted that, the weight-average molecular weight with the resin of acidic group is measured as follows.
In body to be measured, add tetrahydrofuran (THF), place 12 hours.Then filter the THF solution of body to be measured, measure the molecular weight that is dissolved in the body to be measured in filtrate.In mensuration, use gel permeation chromatography (GPC) method, calculate molecular weight by the typical curve that uses polystyrene standard to make.Below record an example of condition determination.
GPC device: the HLC-8120GPC processed of Tosoh Co., Ltd.
Chromatographic column: three posts of the TSK Guardcolumn processed SuperH-HT/SK-GEL/SuperHM-M of Tosoh Co., Ltd.
Flow velocity: 1.0ml/min (THF)
As the resin with acidic group, preferably use Abietyl modified maleic acid resin.Abietyl modified maleic acid resin has and comprises sour polar group and nonpolar rosin skeleton.This comprises sour polar group is the carboxyl that obtained by unreacted colophonic acid and the carboxyl of maleic acid, reacts and compatible with the polar group of adhesive resin.On the other hand, the nonpolar portion of nonpolar rosin skeleton and adhesive resin is compatible.In addition, the amino that comprises sour polar group and basic-dyeable fibre (unreacted basic-dyeable fibre in salify product) of Abietyl modified maleic acid resin reacts.
There is the acid number of resin of acidic group preferably in 100 to 300mgKOH/g scope.If acid number is little, the compatibility of resin and salify product becomes insufficient sometimes.In addition, if acid number is large, when using this coloured composition as the painted resist use of alkali-developable described later, easily produce poor visualization.It should be noted that, the acid number here refers to the value that the method by specifying in JIS K-0070 is measured.
Salify product for example utilizes following method to carry out with the mixing of resin with acidic group.
(1) by the method that is dissolved in resin in solvent and salify product and mixes
(2) by melting resin and the salify product method of mixing
It should be noted that, salify product can also utilize other method to carry out with the mixing of resin with acidic group.
The concrete example of above-mentioned mixing method (1) and (2) is recorded as follows.Here illustrate that using rhodamine is the example of basic-dyeable fibre and Abietyl modified maleic acid resin.
(1) by the method that is dissolved in resin in solvent and salify product and mixes
(1-1)
Be that basic-dyeable fibre is dissolved in water by rhodamine, stir this solution on one side, add wherein organic sulfonic acid isoequilibrium compound on one side.Like this, rhodamine is the amino (NHC of basic-dyeable fibre 2h 5) be combined with the acidic group of equilibrium compound, obtain salify product.It should be noted that, thereby equilibrium compound also can make it be dissolved in the form (SO with for example sodium sulfonate in the alkaline solutions such as NaOH before salt-forming reaction 3na) use.
(1-2)
Then, in the aforementioned solution that contains salify product, add Abietyl modified maleic acid resin.Specifically, first in the above-mentioned solution that contains salify product, add the alkaline aqueous solutions such as sodium hydrate aqueous solution, this solution is adjusted to neutrality.Then, in this solution, add and be dissolved in the Abietyl modified maleic acid resin of alkaline aqueous solution, and stir.Then, in this solution, add the mineral acid such as hydrochloric acid and sulfuric acid, solution is adjusted to acidity.Make thus Abietyl modified maleic acid resin become insoluble.Then filter, wash and be dried, obtain coloured composition.It should be noted that, also can after this coloured composition be ground into if desired to desired granularity.
(2) by melting resin and the salify product method of mixing
By salify product, there is the resin of acidic group, be that Abietyl modified maleic acid resin is put in mixing rolls such as adding heat kneading machine, Banbury, triple-roller mill, two roller mills, vibromill, bowl mill, masher and extruder here, at the temperature more than the softening point of resin with acidic group, carry out melting mixing.Thus, in the resin with acidic group, salify product disperses equably.It should be noted that, the resin at the coloured composition of this gained in having acidic group is by the form of salify product coating.Then, this coloured composition carried out to coarse crushing and pulverize to be adjusted into desired granularity.
Salify product with the mass ratio (salify product: the resin with acidic group) of resin with acidic group preferably in the scope of 70: 30 to 95: 5.The shared ratio in coloured composition of the resin with acidic group is larger, and colour rendering more reduces.Specifically, be subject to the very large impact of the form and aspect of coloured composition from the color of resin with acidic group.In addition, the shared ratio in coloured composition of the resin with acidic group is less, improves the dispersed effect of salify product in adhesive resin and becomes less.Salify product with the mass ratio (salify product: the resin with acidic group) of resin with acidic group more preferably in the scope of 75: 25 to 90: 10.
[other colorant]
In order for example to make thermotolerance further improve, in this coloured composition, can also further contain pigment.
For red colored composition, for example, can use the red pigments such as C.I. paratonere 168,177,179,242 and 254.In addition, in red colored composition, can be used together C.I. pigment yellow 13,138,139,150, orange pigment or the orange salify products such as yellow uitramarine or weld salify product or C.I. pigment orange 38,43,71 and 73 such as 185 and 214.
For green coloring composition, for example, can use C.I. pigment Green 7, the viridine greens such as 36 and 58.In addition, in green coloring composition, can be used together above-mentioned yellow uitramarine or yellow salify product.
For blue colored composition, for example, can use the blue pigments such as C.I. pigment blue 15,15:1,15:2,15:3,15:4,15:6 and 80.In addition, in blue colored composition, can be used together violet pigment or the cudbear salify products such as C.I. pigment violet 19 and 23.
For yellow coloring composition, can use above-mentioned yellow uitramarine or yellow salify product.
For magenta coloured composition, for example, can use C.I. pigment red 122,144,146,169,192,202, the magenta pigment such as 207 and 209.In addition, in magenta coloured composition, can be used together above-mentioned yellow uitramarine or yellow salify product.
For cyan coloured composition, for example, can use C.I. pigment blue 15: 1,15:2,15:4,15:3,15:6 and the blue pigments such as 80.In addition, in cyan coloured composition, can be used together violet pigment or the cudbear salify products such as C.I. pigment violet 19 and 23.
With regard to guaranteeing sufficient brightness, with respect to above-mentioned salify product 100 mass parts, pigment composition is preferably below 500 mass parts.Now, even if colorant contains more pigment compared with above-mentioned salify product, also can realize high brightness.
(miniaturization of pigment)
Above-mentioned pigment for example can grind to process by salt and carry out miniaturization.The primary particle size of pigment is more than the finely disseminated aspect colorant carrier is preferably 20nm.In addition, this primary particle size is preferably below 100nm from the aspect that can form the filter section that contrast is higher than (contrast ratio).The particularly preferred scope of primary particle size is 25 to 85nm.
It should be noted that, the primary particle size of pigment is obtained by the electron micrograph that utilizes the TEM (transmission electron microscope) of pigment to obtain.Specifically, first from TEM image, select 1 pigment particles as primary particle that can see entirety.Then, by the line segment of selecting length maximum in the line segment of 2 on the profile of this pigment particles image of connection.Using this line segment as the 1st line segment.Then, by selecting the line segment intersecting vertically therebetween with the 1st line segment in the line segment of 2 on the profile of this pigment particles image of connection.Using this line segment as the 2nd line segment.Then, by the length L of the 1st line segment 1length L with the 2nd line segment 2mean value as average length L avobtain, then obtain length and average length L on one side avthe cubical volume V equating.100 above pigment particles are carried out to above mensuration and calculating, using the mean value of volume V as average external volume V avobtain.To there is this average external volume V avthe length on cubical one side as the average primary particle diameter of pigment particles.
Salt mill is processed and is referred to following processing: the mixing rolls such as kneader, two roller mills, triple-roller mill, bowl mill, masher and the sand mill for potpourri of pigment, water-soluble inorganic salt and water-miscible organic solvent are heated while mechanically mixing, then remove water-soluble inorganic salt and water-miscible organic solvent by washing.Water-soluble inorganic salt plays a role as grinding aid.When salt mill, utilize large young pathbreaker's pigment of the hardness of inorganic salts to pulverize.By carrying out optimization by pigment being carried out to the salt mill condition while processing, can obtain the pigment that primary particle size width very little and its distribution is narrow, have sharp-pointed size-grade distribution.
As water-soluble inorganic salt, for example, can use sodium chloride, barium chloride, potassium chloride or sodium sulphate.From the aspect of price, preferably use sodium chloride (salt).From two aspects for the treatment of effeciency and production efficiency, in the time that the gross mass of pigment is made as to 100 mass parts, water-soluble inorganic salt preferably uses, more preferably uses with the amount in the scope of 300 to 1000 mass parts with the amount in the scope of 50 to 2000 mass parts.
Water-miscible organic solvent performance makes pigment and the moistening effect of water-soluble inorganic salt, as long as dissolving (mixing) in water and the solvent that does not make inorganic salts used substantially dissolve, is not particularly limited.But in order to become temperature rise in the time that salt grinds, the evaporable state of solvent, from the aspect of security, preferably boiling point is 120 DEG C of above high boiling solvents.For example can use 2-methyl cellosolve, butoxy ethanol, 2-(isoamoxy) ethanol, 2-(own oxygen base) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, aqueous polyglycol, 1-methoxy-2-propanol, 1-ethoxy-2-propyl alcohol, dipropylene glycol, dipropylene glycol monomethyl ether, DPE or aqueous polypropylene glycol.In the time that the gross mass of pigment is made as to 100 mass parts, water-miscible organic solvent preferably uses, more preferably uses with the amount in the scope of 50 to 500 mass parts with the amount in the scope of 5 to 1000 mass parts.
When pigment is carried out to the processing of salt mill, can also add resin.Kind to this resin is not particularly limited, for example, can use natural resin, modified natural resin, synthetic resin or the synthetic resin through natural resin modification.This resin is at room temperature preferably solid and is water-insoluble, more preferably solvable to above-mentioned organic solvent part.In the time that the gross mass of pigment is made as to 100 mass parts, the use amount of resin is preferably in the scope of 5 to 200 mass parts.
When pigment is carried out to salt mill processing (miniaturization), also preferably meanwhile add above-mentioned salify product.Because such salify product is water insoluble and alcohol, therefore can obtain better colorant.
< transparent resin >
Transparent resin is used for making colorant, particularly salify product to disperse and/or dissolves.As transparent resin, for example, can enumerate thermoplastic resin and thermoset resin.It should be noted that, colorant is for example the potpourri of salify product or salify product and pigment here.
As transparent resin, preferably in visible region, spectral transmission is more than 80%, more preferably more than 95% in 400 to 700nm full wavelength coverage.When coloured composition is used with the form of the painted resist of alkali-developable, the alkali-soluble vinyl resin that preferably monomer copolymerization that contains acidic groups and ethylene linkage is formed.In addition, in order further to improve photo sensitivity, can also use the energy ray-curable resin with ethylene linkage.
As thermoplastic resin, for example can enumerate acryl resin, butyral resin, styrene-maleic acid copolymer, haloflex, chlorinated polypropylene, Polyvinylchloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate (PVA), polyurethane series resin, vibrin, vinyl resin, alkyd resin, polystyrene resin, polyamide, rubber series resin, thermoprene is resin, cellulose family, tygon (HDPE, LDPE), polybutadiene and polyimide resin.
As the alkali soluble resin that the monomer copolymerization that contains acidic groups and ethylene linkage is formed, for example, can enumerate the resin with the acidic groups such as carboxyl and sulfonic group.As concrete alkali soluble resin, for example, can enumerate acryl resin, alpha-olefin-maleic acid (acid anhydride) multipolymer, styrene-Styrene Sulfonic Acid Copolymer, ethene-(methyl) acrylic copolymer and isobutylene-maleic acid (acid anhydride) multipolymer with acidic groups.Wherein, due to thermotolerance and transparent high, therefore preferably use at least a kind of resin being selected from the styrene-Styrene Sulfonic Acid Copolymer that there is the acryl resin of acidic groups and there is acidic groups, the acryl resin particularly preferably with acidic groups.
As the energy ray-curable resin with ethylene linkage, for example, can use and there is isocyanate group, aldehyde radical and epoxy radicals isoreactivity substituent (methyl) thereby acyclic compound or cinnamic acid and there is hydroxyl, carboxyl and the substituent macromolecule of amino isoreactivity and react the photocrosslinking reaction groups such as (methyl) acryloyl group and styryl are incorporated into the resin in this macromolecule.(methyl) acyclic compound that in addition, can also use macromolecule that styrene-maleic anhydride copolymer and alpha-olefin-copolymer-maleic anhydride etc. are contained to acid anhydrides (methyl) acrylic acid hydroxyalkyl acrylate etc. to have hydroxyl carries out half esterification and the resin that obtains.
As the energy ray-curable resin with ethylene linkage, for example, can enumerate by following method (a) or (b) import the resin of ethylene linkage.
About method (a), for example, first by making to there is the monomer of epoxy radicals and ethylene linkage and more than other a kind monomer generation copolymerization, thereby obtain the multipolymer on side chain with epoxy radicals.Then, make the epoxy radicals generation addition reaction of unsaturated monacid carboxyl and the side chain with ethylene linkage and carboxyl, then the hydroxyl of acid anhydrides and generation is reacted.Like this, obtain the resin that has imported ethylene linkage and carboxyl.
As the monomer with epoxy radicals and ethylene linkage, for example can enumerate (methyl) glycidyl acrylate, (methyl) acrylic acid methyl ethylene oxidic ester, (methyl) acrylic acid 2-glycidoxy ethyl ester, (methyl) acrylic acid 3,4 epoxy radicals butyl esters and (methyl) acrylic acid 3,4 epoxy radicals cyclohexyls.They can use separately, and also two or more kinds may be used.From subsequent processing and unsaturated monacid reactive viewpoint, preferably (methyl) glycidyl acrylate.
As unsaturated monoacid, for example, can enumerate (methyl) acrylic acid, crotonic acid, o-, m-or p-vinyl benzoic acid and (methyl) acrylic acid α position hydrogen atom and be replaced the monocarboxylic acids such as the substituent forming by haloalkyl, alkoxy, halogen atom, nitro or cyano group.They can use separately, and also two or more kinds may be used.
As acid anhydrides, for example, can enumerate tetrabydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride and maleic anhydride etc.They can use separately, and also two or more kinds may be used.
As the substituting of sour acid anhydrides with 2 carboxyls, or except thering is the sour acid anhydrides of 2 carboxyls, can also use the tetracarboxylic dianhydride such as tricarboxylic acid anhydride or pyromellitic acid anhydride such as sour acid anhydrides, such as trimellitic anhydride with more than 3 carboxyl.Now, after hydroxyl and anhydride reaction, residual acid anhydride base can be hydrolyzed.
As acid anhydrides, can also use tetrabydrophthalic anhydride and maleic anhydride etc. to there is the acid anhydrides of ethylene linkage.Can further increase like this ethylene linkage.
It should be noted that as the similar approach of method (a), for example, have following method.First, make to have the monomer of carboxyl and ethylene linkage and more than other a kind monomer generation copolymerization, thereby obtain having the multipolymer of carboxyl on side chain.Then, make to have the part generation addition reaction of the monomer of ethylene linkage and epoxy radicals and the carboxyl of side chain.Like this, obtain the resin that has imported ethylene linkage and carboxyl.
About method (b), for example, first make to have the monomer and unsaturated monoacid or other monomer generation copolymerization with carboxyl and ethylene linkage of hydroxyl and ethylene linkage, thereby obtain the multipolymer on side chain with hydroxyl.Then, the isocyanate group of the monomer with isocyanate group and ethylene linkage and the hydroxyl of side chain are reacted.Like this, obtained importing the resin of ethylene linkage and carboxyl.
As the monomer with hydroxyl and ethylene linkage, for example, can enumerate (methyl) acrylic acid hydroxyalkyl acrylate classes such as (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-or 3-hydroxy propyl ester, (methyl) acrylic acid 2-, 3-or 4-hydroxyl butyl ester, (methyl) acrylic acid glyceride and cyclohexanedimethanol list (methyl) acrylate.They can use separately, and also two or more kinds may be used.In addition, can also use the compound that adds the oxides such as polyethylene oxide, epoxypropane and epoxy butane and form on (methyl) acrylic acid hydroxyalkyl acrylate, (gathering) ester list (methyl) acrylate that for example at least 1 in addition (gathering) gamma-valerolactone, (gathering) 6-caprolactone and (gathering) 12-hydroxy stearic acid forms on polyethers list (methyl) acrylate or (methyl) acrylic acid hydroxyalkyl acrylate.The viewpoint of sneaking into from the foreign matter suppressing film, preferably (methyl) acrylic acid 2-hydroxy methacrylate or (methyl) acrylic acid glyceride.
As the monomer with isocyanate group and ethylene linkage, for example, can enumerate isocyanic acid 2-(methyl) acryloxy ethyl ester and isocyanic acid 1, two [(methyl) acryloxy] ethyl esters of 1-.They can use separately, and also two or more kinds may be used.
It should be noted that, as thermoplastic resin, the resin simultaneously with alkali-soluble ability and energy line curing performance is also suitable for color composition for color filter.
As thermoset resin, for example, can enumerate epoxy resin, benzo guanamine resin, Abietyl modified maleic acid resin, Abietyl modified fumaric resin, melamine resin, Lauxite and phenolics.
From the viewpoint that colorant is dispersed or dissolved, the weight-average molecular weight of resin (Mw) preferably in 10,000 to 100,000 scope, more preferably in 10,000 to 80,000 scope.In addition, number-average molecular weight (Mn) is preferably in 5,000 to 50,000 scope.The weight-average molecular weight (Mw) of resin is preferably below 10 with the ratio Mw/Mn of number-average molecular weight (Mn).
From film forming and the good aspect of various tolerance, in the time that the gross mass of colorant is made as to 100 mass parts, transparent resin preferably uses with amounts more than 30 mass parts.In addition, high from colorant concentration, to show good color characteristics aspect, in the time that the gross mass of colorant is made as to 100 mass parts, transparent resin preferably uses with the amount below 500 mass parts.
< disperses >
This coloured composition can be manufactured by following method: by the colorant of the salify product that contains basic-dyeable fibre and equilibrium compound, transparent resin and the colorant carrier being formed by the solvent using as required, preferably together with the dispersing aiies such as pigment derivative in the processing of the various dispersion means such as triple-roller mill, two roller mills, sand mill, kneader and masher.In addition, this coloured composition can also by make multiple colorant be scattered in respectively colorant carrier in after they are mixed to manufacture.
(dispersing aid)
In colorant is scattered in to colorant carrier time, can suitably use the dispersing aiies such as pigment derivative, resin type spreading agent and surfactant.The ability excellence of the toner that is scattered here and there of dispersing aid, prevent that the effect of cohesion again of the colorant after disperseing is large.Therefore,, in the time that use utilizes dispersing aid to make coloured composition that colorant forms in being scattered in colorant carrier, can obtain the color filter that spectral transmission is high.
As pigment derivative, for example, can enumerate the compound that has imported alkali subtituent, acidic substituent and maybe can have substituent phthalimide methyl in the organic pigment such as organic pigment and organic dyestuff, anthraquinone, acridone or triazine.
Wherein preferred pigments derivant.Its structure is as shown in following formula (1).
P-Ln formula (1)
Wherein, P represents organic pigment residue, anthraquinone residue, acridone residue or three zin residues, and L represents that alkali subtituent, acidic substituent maybe can have substituent phthalimide methyl, and n is 1 to 4 integer.
As the organic pigment that forms organic pigment residue, for example, can enumerate diketopyrrolo-pyrrole series pigments; The azo pigments such as azo, bisdiazo and polyazo; The phthualocyanine pigments such as copper phthalocyanine, copper halide phthalocyanine and metal-free phthalocyanine; The anthraquione pigmentss such as amino anthraquinones, diamido DIANTHRAQUINONE, anthracene pyrimidine, flavanthrene, embedding dianthrone, indanthrene, pyrrole amerantrone and violanthrone; Quinacridone pigment; Dioxazine series pigments; Purple cyclic ketones series pigments; Perylene pigment; Thioindigo series pigments; Isoindoline series pigments; Isoindolinone pigment; Quinophthalone series pigments; Intellectual circle's series pigments; And metal complex series pigments.
As pigment derivative, for example, can use the material of recording in No. 5-9469, No. 63-305173, Japanese kokai publication sho, No. 57-15620, Japanese Patent Publication, No. 59-40172, Japanese Patent Publication, No. 63-17102, Japanese Patent Publication and Japanese Patent Publication.They can use separately or mix two or more use.
From improving dispersed viewpoint, the use level of pigment derivative with respect to colorant 100 mass parts be preferably 1 mass parts above, more preferably 3 mass parts above, most preferably be 5 mass parts more than.In addition, from thermotolerance and sunproof viewpoint, the use level of pigment derivative with respect to colorant 100 mass parts be preferably 50 mass parts following, more preferably 30 mass parts following, most preferably be below 25 mass parts.
Resin type spreading agent contains to have and is adsorbed in the colorant compatibility position of colorant character and has the position of compatibility with colorant carrier, and the effect of performance is be adsorbed in colorant and make the decentralized stabilization of colorant in colorant carrier.As concrete resin type spreading agent, for example can use polyurethane, the polycarboxylates such as polyacrylate, unsaturated polyester acid amides, poly carboxylic acid, poly carboxylic acid (part) amine salt, poly carboxylic acid ammonium salt, poly carboxylic acid alkylamine salt, polysiloxane, long-chain polyaminoamide phosphate, hydroxyl polycarboxylate, their modifier, by poly-(low-grade alkylidene imines) with there is the oiliness spreading agent such as acid amides or its salt of the reaction formation of the polyester of free carboxy, (methyl) acrylic acid-styrol copolymer, (methyl) acrylic acid-(methyl) acrylate copolymer, styrene-maleic acid copolymer, the water soluble resin such as polyvinyl alcohol (PVA) and polyvinyl pyrrolidone or water-soluble high-molecular compound, polyester is spreading agent, modified polyacrylate is spreading agent, ethylene oxide/propylene oxide additive compound, and phosphate is spreading agent.They can use separately or mix two or more use.Resin type spreading agent is not limited to these.
As surfactant, for example, can enumerate basic salt, odium stearate, sodium alkyl naphthalene sulfonate, alkyl diphenyl base ether sodium disulfonate, lauryl sulfate monoethanolamine, triethanolamine lauryl sulfate, Texapon Special, the stearic acid monoethanolamine of NaLS, polyoxyethylene alkyl ether sulfate salt, neopelex, styrene-propene acid copolymer, the anionic surfactant such as monoethanolamine and polyoxyethylene alkyl ether phosphate of styrene-propene acid copolymer; The nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylplenyl ether, polyoxyethylene alkyl ether phosphate, Tween-60 and polyethyleneglycol lauryl; The cationic surfactants such as alkyl quaternary ammonium salts or their ethylene oxide adduct; The amphoteric surfactantes such as alkyl betaine and alkyl imidazoline such as alkyl dimethyl aminoacetic acid betaine.They can use separately or mix two or more use.Surfactant is not limited to these.
< solvent >
Thereby be coated on the substrates such as glass substrate with shaping filter joint for ease of colorant being scattered in be fully easy in colorant carrier to reach for example mode of 0.2 to 5 μ m according to dry film thickness, in coloured composition, can contain solvent.
As solvent, for example, can enumerate 1,2,3-trichloropropane, 1,3-butanediol, 1,3-BDO, benzylalcohol, 1,3-BDO diacetate esters, Isosorbide-5-Nitrae-dioxs, 2-HEPTANONE, 2-methyl isophthalic acid, 3-propane diol, Isophorone, 3,3,5-trimethylcyclohexanone, 3-ethoxyl ethyl propionate, 3-methyl isophthalic acid, 3-butanediol, MMB, acetic acid 3-methoxyl-3-methyl butyl ester, 3-methoxybutanol, acetic acid 3-methoxyl butyl ester, 4-heptanone, m-xylene, between diethylbenzene, m-dichlorobenzene, DMA, DMF, normal-butyl alcohol, n-butylbenzene, n-propyl acetate, o-xylene, ortho-chlorotolu'ene, adjacent diethylbenzene, o-dichlorobenzene, parachlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butyl benzene, gamma-butyrolacton, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, butyl cellosolve, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, the tertiary butyl ether of ethylene glycol list, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol ether, ethylene glycol ether, glycol monoethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol list isopropyl ether, diethylene glycol monoethyl ether acetic acid esters, diethylene glycol monobutyl ether, butyl carbitol acetate, diethylene glycol monomethyl ether, cyclohexanol, adnoral acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetic acid esters, DPE, Dipropylene glycol mono-n-butyl Ether, dipropylene glycol list propyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, Tri(propylene glycol)butyl ether,mixture of isomers, Tripropylene glycol monomethyl Ether, propylene-glycol diacetate, propylene glycol phenyl ether, dihydroxypropane single-ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, propylene glycol monomethyl ether propionate, benzylalcohol, methyl isobutyl ketone, methyl cyclohexanol, n-Amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate and dibasic acid ester.
Wherein, from the dispersiveness of colorant and the aspect of favorable solubility, preferably use the aromatic series such as ketone or the benzylalcohol alcohols such as ethyl glycol acetate class, cyclohexanone such as propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate.
Solvent can use separately a kind or mix two or more use.In addition, form the aspect of the filter section of the homogeneous film thickness of target from coloured composition being adjusted to suitable viscosity, in the time that the gross mass of colorant is made as to 100 mass parts, solvent preferably uses with the amount of 800 to 4000 mass parts.
This coloured composition can further add optical polymerism composition and/or Photoepolymerizationinitiater initiater, thereby uses as photosensitive coloring composition for color filter (resist).
< optical polymerism composition >
As the monomer using in optical polymerism composition or oligomer, for example, can enumerate (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) cyclohexyl acrylate, (methyl) propenoic acid beta-carboxyl ethyl ester and (methyl) acrylic acid three and encircle the simple functions such as decyl ester (methyl) esters of acrylic acid; Polyglycol two (methyl) acrylate, 1, two senses (methyl) esters of acrylic acids such as 6-hexanediol two (methyl) acrylate, triethylene glycol two (methyl) acrylate and tripropylene glycol two (methyl) acrylate; Multifunctional (methyl) acrylate more than trifunctional such as trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol six (methyl) acrylate and dipentaerythritol five (methyl) acrylate; 1,6-hexanediol diglycidyl ether, bisphenol A diglycidyl ether, neopentylglycol diglycidyl ether and novolac resin etc. are as (methyl) acrylic acid epoxy ester of epoxy compound and (methyl) acrylic acid reactant; Polyester, polyurethane, isocyanuric acid ester and methylolation melamine etc. are through various (methyl) esters of acrylic acid of modification; And the monomer except (methyl) acrylate such as (methyl) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol bisthioglycolate vinyl ether, pentaerythrite trivinyl ether, (methyl) acrylamide, N-hydroxymethyl (methyl) acrylamide, N-vinyl formamide, vinyl cyanide.They can use separately or mix two or more use.Monomer or oligomer are not limited to these.
< Photoepolymerizationinitiater initiater >
In the time being saved by color composition for color filter shaping filter by the photoetching process of utilizing ultraviolet ray irradiation, can in this coloured composition, add Photoepolymerizationinitiater initiater etc.
As Photoepolymerizationinitiater initiater, for example, can enumerate 4-phenoxy group dichloroacetophenone, the 4-tert-butyl group-dichloroacetophenone, diethoxy acetophenone, 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl propane-1-ketone, 1-hydroxycyclohexylphenylketone, 2-methyl isophthalic acid-[4-(methyl sulfo-) phenyl]-2-morpholino propane-1-ketone, 2-(dimethylamino)-2-[(4-aminomethyl phenyl) methyl]-1-[4-(4-morpholinyl) phenyl]-1-butanone and 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-acetophenone based compounds such as butane-1-ketone, the benzoin based compounds such as benzoin, benzoin methyl ether, benzoin ethylether, benzoin isopropyl ether and benzyl dimethyl ketal, benzophenone, benzoyl benzoic acid, benzoyl methyl benzoate, 4-phenyl benzophenone, dihydroxy benaophenonel, propenyl benzophenone, 4-benzoyl-4 '-methyldiphenyl base sulfide and 3,3 ', the benzophenone based compounds such as 4,4 '-tetra-(t-butylperoxy carbonyl) benzophenone, thioxanthones, CTX, 2-methyl thioxanthones, isopropyl thioxanthone, 2, the thioxanthones based compounds such as 4-diisopropyl thioxanthones and 2,4-diethyl thioxanthone, 2, 4, the chloro-s-triazine of 6-tri-, 2-phenyl-4, two (the trichloromethyl)-s-triazines of 6-, 2-(p-methoxyphenyl)-4, two (the trichloromethyl)-s-triazines of 6-, 2-(p-methylphenyl)-4, two (the trichloromethyl)-s-triazines of 6-, 2-piperonyl-4, two (the trichloromethyl)-s-triazines of 6-, 2, two (the trichloromethyl)-6-styryl-s-triazines of 4-, 2-(naphthalene-1-yl)-4, two (the trichloromethyl)-s-triazines of 6-, 2-(4-methoxyl-naphthalene-1-yl)-4, two (the trichloromethyl)-s-triazines of 6-, 2, 4-trichloromethyl-(piperonyl)-6-triazine and 2, the triazine based compounds such as 4-trichloromethyl-(4 '-methoxyl-styrene)-6-triazine, 1,2-acetyl caproyl, 1-[4-(phenyl sulfo-)-, 2-(O-benzoyl oximes)] and the oxime ester based compound such as O-(acetyl group)-N-(1-phenyl-2-oxo-2-(4 '-methoxyl-naphthyl) ethylidene) hydramine, the phosphine based compounds such as two (2,4,6-trimethylbenzoyl) phenyl phosphine oxides and TMDPO, the quinone based compounds such as 9,10-phenanthrenequione, camphorquinone and EAQ, borate-based compound, carbazole based compound, imidazole compound, and two luxuriant titanium sub-group compound.
These Photoepolymerizationinitiater initiaters can use separately a kind or mix two or more use with ratio arbitrarily.These Photoepolymerizationinitiater initiaters, with respect to colorant 100 mass parts in color composition for color filter, preferably use with the amount of 5 to 200 mass parts, from the viewpoint of photo-curable and developability, more preferably use with the amount of 10 to 150 mass parts.
< sensitizer >
In blue coloring composition for color filter, also can contain sensitizer.
As sensitizer, for example, can enumerate the unsaturated ketone taking chalcone (chalcone) derivant and two benzylideneacetones etc. as representative, taking benzil and camphorquinone etc. as representative 1,2-derovatives, benzoin derivatives, fluorene derivative, naphthoquinone derivatives, anthraquinone derivative, xanthene derivant, thioxanthene derivative, xanthone derivant, thioxanthone derivates, coumarin derivative, coumarin ketone derivates, cyanine derivant, Merocyanine derivatives, the polymethine pigments such as oxonols derivant, acridine derivatives, azine derivatives, thiazine derivative, oxazine derivatives, indoline derivative thing, azulene derivatives, azulenes (azulenium) derivant, the sour cyanines derivant in side, derivatives of porphyrin, Tetraphenyl porphyrin derivative, triarylmethane derivatives, Tetrabenzoporphyrin derivant, four pyrazines porphyrazine (tetrapyrazino porphyrazine) derivant, phthalocyanine derivates, four azepine porphyrazine derivants, four quinoxalines porphyrazine derivant, naphthalene phthalocyanine (naphthalocyanine) derivant, sub-phthalocyanine derivates, pyran derivate, thiapyran (thiopyrylium) derivant, Tetraphylline derivant, wheel ene derivative, spiropyran derivatives, spiral shell uh oxazine derivatives, sulfo-spiropyran derivatives, metal arene complex compound, organic ruthenium complex compound, Michler's keton derivant, alpha-acyloxy ester, acylphosphine oxide, glyoxalic acid aminomethyl phenyl ester, benzil, 9,10-phenanthrenequione, camphorquinone, EAQ, 4, the different phthal.ophenone of 4 '-diethyl, 3,3 ', or 4,4 '-tetra-(t-butylperoxy carbonyl) benzophenone and 4,4 '-diethylamino benzophenone.
The sensitizer of recording in " special different Machine energy material " (, シ mono-エ system シ mono-in 1986) that " Machine can property pigment chemistry " (, the シ mono-エ system シ mono-in 1981) that more specifically can enumerate that the people such as " pigment Ha Application De Block Star Network " (, Talk Talk society in 1986), the former letter in great river that the people such as the former letter in great river write writes and the gloomy loyal three bright people of grade in pond write.Sensitizer is not limited to these.In addition, in coloured composition, also can contain the sensitizer that ultraviolet is shown to absorption to the light display of near infrared region.
Sensitizer can use two or more with ratio arbitrarily.In the time using sensitizer, in the time that Photoepolymerizationinitiater initiater contained in coloured composition is made as to 100 mass parts, its use level is preferably in the scope of 3 to 60 mass parts, from the viewpoint of photo-curable and developability, more preferably in the scope of 5 to 50 mass parts.Or sensitizer can for example use with the amount of 0.1 to 60 mass parts with respect to Photoepolymerizationinitiater initiater 100 mass parts in coloured composition.
< amine compound >
In color composition for color filter, can further contain the amine compound playing a part molten hydrogen reduction of depositing.
As this amine compound, for example can enumerate triethanolamine, methyldiethanolamine, triisopropanolamine, 4-dimethylaminobenzoic acid methyl esters, EDMAB, 4-dimethylaminobenzoic acid isopentyl ester, benzoic acid 2-dimethylamino ethyl ester, 4-dimethylaminobenzoic acid 2-Octyl Nitrite and N, N-dimethyl-p-toluidine.
< levelling agent >
In order to optimize the levelability of the composition on transparency carrier, in this coloured composition, preferably also add levelling agent.As levelling agent, preferably on main chain, there is the dimethyl siloxane of polyether structure or polyester construction.As the object lesson of dimethyl siloxane on main chain with polyether structure, for example, can enumerate the FZ-2122 processed of TORAYDOWCORNING company and the BYK-333 processed of BYK-Chemie company.As the object lesson of dimethyl siloxane on main chain with polyester construction, for example, can enumerate the BYK-310 processed of BYK-Chemie company and BYK-370.Also can and with thering is the dimethyl siloxane on the dimethyl siloxane of polyether structure and main chain with polyester construction on main chain.In the time that the gross mass of coloured composition is made as to 100 quality %, the content of levelling agent is conventionally preferably in the scope of 0.003 to 0.5 quality %.
As levelling agent, be the compound in molecule with hydrophobic group and hydrophilic group, be the one of so-called surfactant, useful especially be in thering is hydrophilic group the dissolubility to water little, in the time making an addition in coloured composition, show and reduce feature that its capillary ability is low and the levelling agent good to the wetting state of glass plate.Wherein, preferably use under the addition that there will not be the paint film defect causing owing to bubbling and can fully suppress electrostatic levelling agent.As the levelling agent with this preferred characteristics, for example, preferably use the dimethyl polysiloxane with polyoxyalkylene unit.As polyoxyalkylene unit, for example, there are polyethylene oxide unit and polypropyleneoxide unit.Dimethyl polysiloxane also can have polyethylene oxide unit and polypropyleneoxide unit the two.
Bonding mode polyoxyalkylene unit and dimethyl polysiloxane can be that polyoxyalkylene unit is bonded in any in the segmented copolymer type that terminal-modified type that the end bonding of the pendant type, polyoxyalkylene unit and the dimethyl polysiloxane that form in the repetitive of dimethyl polysiloxane forms and polyoxyalkylene unit and dimethyl polysiloxane alternately repeat the straight chain shape that bonding forms.As the dimethyl polysiloxane with polyoxyalkylene unit, for example, can enumerate FZ-2110, the FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203 and the FZ-2207 that are sold by TORAYDOWCORNING Co., Ltd..The dimethyl polysiloxane with polyoxyalkylene unit is not limited to these.
In levelling agent, also can auxiliarily add the surfactant of anionic property, cationic, nonionic or both sexes.Surfactant can use separately a kind, also can mix two or more use.
As the anionic surfactant who auxiliarily makes an addition in levelling agent, for example, can enumerate alkali salt, sodium alkyl naphthalene sulfonate, alkyl diphenyl base ether sodium disulfonate, lauryl sulfate monoethanolamine, triethanolamine lauryl sulfate, Texapon Special, stearic acid monoethanolamine, odium stearate, the NaLS of polyoxyethylene alkyl ether sulfate salt, neopelex, styrene-propene acid copolymer, monoethanolamine and the polyoxyethylene alkyl ether phosphate of styrene-propene acid copolymer.
As the cationic surfactant auxiliarily making an addition in levelling agent, for example, can enumerate alkyl quaternary ammonium salts or their ethylene oxide adduct.As the nonionic surfactant auxiliarily making an addition in levelling agent, for example, can enumerate the amphoteric surfactantes such as alkyl betaine, alkyl imidazoline such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylplenyl ether, polyoxyethylene alkyl ether phosphate, Tween-60, polyethylene glycol monolaurate, alkyl dimethyl aminoacetic acid betaine and fluorine system or silicone-based surfactant.
< hardening agent and curing accelerator >
For solidifying of auxiliary heat thermosetting resin, in this coloured composition, also can contain as required hardening agent and curing accelerator etc.
As hardening agent, for example phenolic aldehyde is that resin, amine compound, acid anhydrides, active ester, carboxylic acid based compound and sulfonic acid based compound are useful.Hardening agent is not particularly limited to these.As long as the hardening agent that can react with thermoset resin, can use any hardening agent.Wherein, the compound and the amine that preferably have more than 2 phenol hydroxyl in 1 molecule are hardening agent.
As curing accelerator, for example, can enumerate dicyandiamide, benzyl dimethyl amine, 4-(dimethylamino)-N, N-dimethyl benzyl amine, 4-methoxyl-N, N-dimethyl benzyl amine and 4-methyl-N, the amines such as N-dimethyl benzyl amine; The quarternary ammonium salt compounds such as triethyl benzyl ammonia chloride; The block isocyanate compound of dimethylamine etc.; Imidazoles, glyoxal ethyline, 2-ethyl imidazol(e), 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyano ethyl-2-phenylimidazole and 1-(2-the cyano ethyl)-imdazole derivatives such as 2-ethyl-4-methylimidazole two ring type amidine compound and salt thereof; The phosphorus compounds such as triphenylphosphine; The guanidine amines such as melamine, guanamines, acetylguanamine and benzoguanamine; And 2,4-diamido-6-methacryloxyethyl-S-triazine, 2-vinyl-2,4-diamido-S-triazine, 2-vinyl-4, the S-pyrrolotriazine derivatives such as 6-diamido-S-triazine isocyanuric acid addition product and 2,4-diamido-6-methacryloxyethyl-S-triazine isocyanuric acid addition product.Curing accelerator can be used alone a kind, also can and use two or more.The content of curing accelerator is taking thermoset resin total amount as benchmark is preferably in the scope of 0.01 to 15 quality %.
Other additive component > of <
For make composition through time viscosity stabilization, in this coloured composition, can contain storage stabilizing agent.In addition, in order to improve and the adaptation of transparency carrier, in this coloured composition, also can contain the closely sealed improving agents such as silane coupling agent.
As storage stabilizing agent, for example, can enumerate benzyl trimethyl chloride; The aliquats such as diethyl hydramine; The organic acid such as lactic acid, oxalic acid and methyl ether thereof; Tert-butyl pyrocatechol; The organic phosphines such as tetraethyl phosphine and tetraphenyl phosphine; And phosphite.Storage stabilizing agent with respect to colorant 100 mass parts in coloured composition, for example, can use with the amount of 0.1 to 10 mass parts.
As closely sealed improving agent, for example, can enumerate the vinyl silanes classes such as vinyl three ('beta '-methoxy ethoxy) silane, vinyl Ethoxysilane and vinyltrimethoxy silane; γ-methacryloxypropyl trimethoxy silane etc. (methyl) propenyl silanes; β-(3,4-epoxy radicals cyclohexyl) ethyl trimethoxy silane, β-(3,4-epoxy radicals cyclohexyl) methyltrimethoxy silane, β-(3,4-epoxy radicals cyclohexyl) the epoxy radicals silicone hydride class such as ethyl triethoxysilane, β-(3,4-epoxy radicals cyclohexyl) methyl triethoxysilane, γ-glycidoxypropyltrime,hoxysilane and γ-glycidoxy propyl-triethoxysilicane; The amino silane classes such as N-β (amino-ethyl) gamma-amino propyl trimethoxy silicane, N-β (amino-ethyl) γ aminopropyltriethoxy silane, N-β (amino-ethyl) gamma-amino propyl group methyldiethoxysilane, γ aminopropyltriethoxy silane, gamma-amino propyl trimethoxy silicane, N-phenyl-gamma-amino propyl trimethoxy silicane and N-phenyl-γ aminopropyltriethoxy silane; And the silane coupling agents such as Thiosilicane class such as γ mercaptopropyitrimethoxy silane and γ-sulfydryl propyl-triethoxysilicane.Closely sealed improving agent is with respect to colorant 100 mass parts in coloured composition, for example can be with the amount of 0.01 to 10 mass parts, preferably use with the amount of 0.05 to 5 mass parts.
< oversize grain remove >
Preferably utilize the means such as centrifuging, sintering filter and membrane filter from this coloured composition, to remove more than 5 μ m oversize grain, preferably oversize grain more than 1 μ m, more preferably oversize grain more than 0.5 μ m and the dust of sneaking into.Like this, preferably coloured composition is not in fact containing particle more than 0.5 μ m.In addition, more preferably coloured composition does not contain in fact particle more than 0.3 μ m.
" color filter "
Then, the color filter of the 2nd form of the present invention is described.
The color filter of the 2nd form contains absorption spectrum difference, regularly arranged multiple filter sections typically.The color filter of a form possesses at least 1 red filter joint, at least 1 green filter joint and at least 1 blue electric-wave filter joint.The color filter of another form possesses at least 1 magenta filter section, at least 1 cyan filter section and at least 1 yellow filter joint.In the color filter of the 2nd form, at least 1 of these filter sections is formed by above-mentioned color composition for color filter.
The manufacture method > of < color filter
This color filter for example can be manufactured by print process or photoetching process.
While utilizing print process, only, by using the printing of the coloured composition of modulating as printing-ink and dry repeating, can form the filter section of patterning.Therefore, print process is low cost, mass productivity excellence.And then, due to the development of printing technology, also can utilize printing to form the fine pattern with high dimensional accuracy and smoothness.
The ink using in printing preferably has on galley or blanket (blanket) and can not be dried and curing composition.In addition, in print process, the control of the mobility of the ink on printing machine is also important.The mobility of ink can be controlled by adjusting ink viscosity with spreading agent or extender pigment.
While utilizing photoetching process, compared with print process, can be with higher accurate manufacturing technique color filter.
Utilize photoetching process shaping filter when joint, the above-mentioned coloured composition of modulating as solvent develop type or the painted resist of alkali-developable is utilized to the coating processes such as spraying process, spin-coating method, slot coated method and rolling method so that the mode that dry film thickness reaches in the scope of for example 0.2 to 5 μ m is coated on transparency carrier.Dry coating as required, by contact with this film or the mask with predetermined pattern of contactless state setting, utilizes ultraviolet ray to expose to this film.Afterwards, film be impregnated in solvent or alkaline-based developer or by solvent or alkaline-based developer and is sprayed on film, remove uncured portion from film.Obtain thus the Thinfilm pattern corresponding to the filter section of certain look.Except using the filter section coloured composition of other colors, repeat operation same as described above, form the Thinfilm pattern corresponding to remaining filter section.Afterwards, by these Thinfilm patterns are burnt till, obtain color filter.It should be noted that, burn till also and can in the time of each formation Thinfilm pattern, carry out.
In the time developing, as alkaline-based developer, for example, use the aqueous solution of sodium carbonate and NaOH etc.Also can use the organic base such as dimethyl benzyl amine and triethanolamine.In addition, also can in developer solution, add defoamer or surfactant.
In addition, in order to improve ultraviolet exposure sensitivity, also can and be dried on the painted resist film forming at the above-mentioned painted resist of coating and be coated with water-soluble or alkali soluble resin, for example polyvinyl alcohol (PVA) or water soluble acrylic resin, this film is dried, carry out afterwards ultraviolet exposure.Prevent that by film water-soluble or that alkali soluble resin forms the polymerization of painted resist film from being hindered by oxygen.
Color filter also can utilize the method manufacture beyond print process and photoetching process.For example can manufacture color filter by electrodeposition process or transfer printing.Above-mentioned coloured composition all can use in either method.
In addition, utilizing electrodeposition process to manufacture color filter is to prepare to be provided with the substrate of nesa coating on an interarea, uses this nesa coating as electrode, makes colloidal particle to electrophoresis on nesa coating, thus shaping filter joint.In addition, utilizing transfer printing to manufacture color filter is to have shaping filter joint on the above-mentioned interarea of transfer printing substrate sheet of release property at an interarea in advance, then this filter section is transferred to substrate from transfer printing substrate sheet.
Can also on transparency carrier, before shaping filter joint, form the black matrix" as light-shielding pattern.As black matrix", for example, can use the mineral compound films such as the multilayer film such as metal film, chromium/chromium oxide film, titanium nitride film such as chromium film or light screening material is scattered in to the resin molding forming in resin.
Also can form on transparency carrier, form before color filter circuit, for example contain thin film transistor (TFT) (TFT) active matrix circuit.In addition, also can be on color filter further form as required lid and be coated with other the layer such as (over coat) film and nesa coating.
The substrate that forms color filter also can be opaque.For example color filter can also form on reflection substrate.
0 the 2nd form
Below, the 2nd form of the present invention is described.
Proposed the blue pixel at color filter in No. 11-223720, Japanese kokai publication hei in and with triphenyl methane based dye and xanthene based dye.At this, be that acid dyes and xanthene are that acid dyes mixes by triphenyl methane, and investigate use metal complex to improve tolerance.But present situation is, only depend on mixing acid dyes, colour rendering is also insufficient, cannot obtain high brightness.In addition, this technology must not expected the heavy metal complex using by the viewpoint from carrying capacity of environment, therefore also has room for improvement.
People of the present invention conduct in-depth research repeatedly, found that, the salify product being obtained by triarylmethane based dye and xanthene based dye by use is as the colorant of blue coloring composition for color filter, can realize high brightness and wide color reproduction region, can also realize excellent tolerance, complete the invention of this form based on this discovery.
Be that the 2nd form of the present invention is a kind of blue coloring composition for color filter, it contains transparent resin and colorant, and above-mentioned colorant contains the salify product being formed by triarylmethane based dye and xanthene based dye.
It should be noted that, xanthene is pigment as recorded in No. 2005-292305, TOHKEMY, for example, as the pigment of magenta and known.The range of choice of pigment that can be used for the filter section of magenta is extremely narrow, has excellent dichroism but xanthene is pigment.Specifically, xanthene is pigment compared with the quinacridone pigment of magenta, and the transmissivity of short wavelength side (400 to 500nm) is higher.Therefore, xanthene is that pigment is used in a lot of magenta filter sections.
The blue coloring composition for color filter of the 2nd form contains the salify product being formed by triarylmethane based dye and rhodamine based dye as colorant.Therefore,, by formed the filter section of color filter by this blue colored composition, except can realizing high brightness and wide color reproduction region, can also realize excellent tolerance.
In addition, existing combination has copper phthalocyanine blue pigment with in the Optical transmission spectrum of the blue coloring composition for color filter of dioxazine series pigments etc., peak position is positioned near 450nm, and the short wavelength side transmissivity below 450nm sharply reduces.
On the other hand, the blue coloring composition for color filter of this form use triarylmethane is that pigment and xanthene are that the salify product of pigment is as at least a portion of colorant.Therefore, while using the blue coloring composition for color filter of this form, compare with the situation of the combination of dioxazine series pigments with using copper phthalocyanine blue pigment, can realize high-transmission rate by the short wavelength side below 450nm.And it is long that a lot of luminescent spectrums backlight such as cold-cathode tube have spike in 425 to 440nm wavelength coverage or near it.Therefore the filter section, being obtained by the blue coloring composition for color filter of this form can be realized high brightness.
" color composition for color filter "
As mentioned above, the color composition for color filter of the 2nd form of the present invention is the blue coloring composition for color filter that contains transparent resin and colorant.The salify product that this colorant contains triarylmethane based dye and xanthene based dye.Xanthene based dye is for example basic-dyeable fibre, equilibrium compound or their potpourri in the 1st form.On the other hand, triarylmethane based dye is also for example basic-dyeable fibre, equilibrium compound or their potpourri in the 1st form.It should be noted that, in the 2nd form, equilibrium compound typically has the molecular weight in the above-mentioned scope of the equilibrium compound in the 1st form, but also can have this extraneous molecular weight.
< colorant >
The colorant using in the 2nd form contains the salify product being formed by triarylmethane based dye and xanthene based dye.
By the salify of triarylmethane based dye and xanthene based dye, as previously mentioned, in 425 to 440nm wavelength coverage or near it, can realize high-transmission rate.Therefore, there is copper phthalocyanine with the existing filter section of triazine dioxin pigment is compared with combination, can realize high brightness and wide colorrendering quality.In addition, can also realize high thermotolerance, photostability and solvent resistance.
[triarylmethane based dye]
First, triarylmethane based dye is described.
The triarylmethane based dye that can here preferably use presents blueness, purple or green, and has the form of acid dyes and/or the form of basic-dyeable fibre.
Present the dyestuff that blueness, purple or green dyestuff refer to the direct dyess such as the acid dyess such as basic-dyeable fibre, C.I. acid blue, C.I. acid violet and C.I. acid green such as for example belonging to C.I. alkali blue, C.I. alkalescence purple and C.I. Viride Nitens, the direct indigo plant of C.I., the direct purple of C.I. and C.I. direct green.Here, direct dyes is in structure, to have sulfonic dyestuff.In this form, regard direct dyes as acid dyes.
Triarylmethane is that basic-dyeable fibre passes through with respect to center carbon potential in the NH of contraposition 2or the oxidation of OH base and take quinone structure, develop the color thus.Triarylmethane based dye is mainly basic-dyeable fibre, but becomes acid dyes by importing sulfonic group.
Triarylmethane is that basic-dyeable fibre is according to NH 2and the number of OH base and be divided into following 3 types.Wherein, triamido triarylmethane based dye is preferred from the aspect that blueness is developed the color well.
A) diamido triarylmethane based dye
B) triamido triarylmethane based dye
C) there is the rosolic acid based dye of OH base
Triamido triarylmethane based dye is preferred from tone excellence, the aspect more excellent than the daylight fastness of other dyestuff.In addition, particularly preferably as the Bisphenylnaphthylmethane dyes of basic-dyeable fibre.
Triarylmethane based dye has the dichroism high in 400 to 430nm wavelength coverage internal transmission factor.But triarylmethane based dye is the same with common dyestuff, photostability and thermotolerance extremely lack.Be the color filter of triarylmethane based dye for the colour display device for requiring high reliability or color image pickup apparatus, characteristic is inadequate.Here, in order to improve this shortcoming, by triarylmethane based dye to use with the form of the salt of xanthene based dye.
Be basic-dyeable fibre as triarylmethane, for example, can enumerate C.I. alkali blue 1 (alkaline dark blue 6G), C.I. alkali blue 5 (alkaline dark blue BX), C.I. Blue 7 (Victoria's ethereal blue), C.I. alkali blue 26, C.I. alkaline purple 1 (methyl violet) and C.I. alkaline purple 3 (crystal violet).Wherein, from the aspect of excellent color reproducing performance, preferably use C.I. Blue 7.
Be acid dyes as triarylmethane, for example, preferably use C.I. Blue VRS (edible blue No. 101), C.I. acid blue 3 (acid ethereal blue), C.I. acid blue 5 (the blue I in color lake), C.I. Acid Blue 7 (the blue II in color lake), C.I. acid blue 9 (edible blue No. 1), C.I. acid blue 22, CC.I. acid blue 83, C.I. acid blue 90, C.I. acid blue 93, C.I. Blue VRS 00, C.I. Blue VRS 03, C.I. Blue VRS 04 or C.I. Blue VRS 09.
Wherein, particularly preferably use C.I. Blue VRS, C.I. acid blue 3 or C.I. acid blue 93.
[xanthene based dye]
Below, xanthene based dye is described.
The xanthene based dye that can preferably use in this form presents redness or purple, and has the form of acid dyes and/or the form of basic-dyeable fibre.
Presenting redness or purple refers to and for example belongs to the alkaline purple directly directly dyestuff of the direct dyes such as purple of red and C.I. of the acid dyess such as basic-dyeable fibre, C.I. acid red and C.I. acid violet or C.I. that waits of the red and C.I. of C.I. alkalescence.Here, direct dyes is in structure, to have sulfonic dyestuff.In this form, regard direct dyes as acid dyes.
Xanthene based dye has the dichroism high in 400 to 430nm wavelength coverage internal transmission factor.But xanthene based dye is the same with common dyestuff, photostability and thermotolerance extremely lack.Be the color filter of xanthene based dye for the colour display device for requiring high reliability or color image pickup apparatus, characteristic is inadequate.Here, in order to improve this shortcoming, by xanthene based dye to use with the form of the salt of triarylmethane based dye.
The optical transmission rate that the scope internal transmission factor that the optical transmission rate that the optical transmission rate that xanthene based dye is preferably 650nm to wavelength is is 600nm more than 90%, to wavelength is is 500 to 550nm more than 75%, at wavelength is is 400nm below 5%, to wavelength is more than 70%.More preferably the optical transmission rate that the scope internal transmission factor that the optical transmission rate that the optical transmission rate that is 650nm to wavelength is is 600nm more than 95%, to wavelength is is 500 to 550nm more than 80%, at wavelength is is 400nm below 10%, to wavelength is more than 75%.
Be acid dyes as xanthene, preferably use C.I. CI 45430 (erythrosine: edible red No. 3), C.I. acid red 52 (acid rhodamine), C.I. acid red 87 (eosin G: edible red No. 103), C.I. acid red 92 (the red PB of acid flame: edible red No. 104), rose red b (edible red No. 5), acid rhodamine G, acid red 289 or C.I. acid violet 9.
Wherein, particularly preferably use C.I. acid red 52, C.I. acid red 87 or C.I. acid red 289.
Be basic-dyeable fibre as xanthene, for example, can enumerate C.I. alkali red 1:1 (rhodamine 6G CP), C.I. red 8 (rhodamine Gs) of alkalescence and C.I. alkaline purple 10 (rhodamine B).
Wherein, preferably use C.I. alkali red 1:1 or C.I. alkaline purple 10.
In xanthene based dye, rhodamine based dye because colour rendering and tolerance are excellent preferably.
[the salify product being formed by triarylmethane based dye and xanthene based dye]
The salify product being formed by triarylmethane based dye and xanthene based dye is preferably any of following 2 forms.
(A) be that basic-dyeable fibre and xanthene are the salify product that acid dyes forms by triarylmethane
(B) be that acid dyes and xanthene are the salify product that basic-dyeable fibre forms by triarylmethane
They can be obtained by the combination of aforesaid acid dyes and basic-dyeable fibre.
Form (A) in the situation that, specifically, the reaction stability of the combination of the combination of the combination of the combination of the combination of the combination of C.I. Blue 7 and C.I. acid red 289, C.I. Blue 7 and C.I. acid red 52, C.I. Blue 7 and C.I. acid red 87, C.I. Blue 7 and C.I. acid red 92, C.I. alkaline purple 3 and C.I. acid red 87 and C.I. alkaline purple 3 and C.I. acid red 52 and colour rendering are excellent especially.Can certainly use the salify product being obtained by other combination.
In form (B) situation, specifically, the reaction stability of the combination of the combination of the combination of the combination of C.I. alkali red 1:1 and C.I. Blue VRS, C.I. alkali red 1:1 and C.I. acid blue 93, C.I. alkaline purple 10 and C.I. Blue VRS and C.I. alkali red 1:1 and C.I. acid blue 3 and colour rendering are excellent especially.Certainly also for example can use other salify product being obtained by the combination of aforementioned dyestuff.
Wherein, be that acid dyes and rhodamine are the tolerance excellence of the salify product that forms of basic-dyeable fibre by triarylmethane, thereby particularly preferably.
The salify product of triarylmethane based dye and xanthene based dye can synthesize by known method in the past.
Be for example acid dyes and xanthene while being basic-dyeable fibre using triarylmethane, can be to make triarylmethane be that to add wherein xanthene after acid dyes is dissolved in water be basic-dyeable fibre or its aqueous solution and stir, thus there is salt-forming reaction.Obtaining thus triarylmethane is the sulfonic group (for example-SO of acid dyes 3h or-SO 3na) be the salify product that the amino of basic-dyeable fibre is combined into xanthene.
In addition, be acid dyes and triarylmethane while being basic-dyeable fibre using xanthene, can be to make xanthene be that to add wherein triarylmethane after acid dyes is dissolved in water be basic-dyeable fibre or its aqueous solution and stir, thus there is salt-forming reaction.Obtaining thus xanthene is the sulfonic group (for example-SO of acid dyes 3h or-SO 3na) be the salify product that the amino of basic-dyeable fibre is combined into triarylmethane.
[thering is the resin of acidic group]
Above-mentioned salify product with in the 1st form, illustrated the same, the resin by use with acidic group carries out modification, can make more stable look material.
Have the resin of acidic group, the resin for example with acidic groups such as carboxyls or rosin ester, Abietyl modified maleic acid resin or Abietyl modified fumaric resin if this salify product adds, the compatibility in adhesive resin, dispersiveness and the dispersiveness in solvent significantly improve.Consequently, can realize more excellent colour rendering, thermotolerance and photostability.Here, as acidic group, preferably carboxyl (COOH) or sulfonic group (for example-SO 3h or-SO 3na).
Wherein preferably use Abietyl modified maleic acid resin.Abietyl modified maleic acid resin comprises and has sour polar group and nonpolar rosin skeleton.This has sour polar group is from the carboxyl of unreacted colophonic acid and the carboxyl of maleic acid, and the part of the polar group of itself and adhesive resin reacts and be compatible.On the other hand, the nonpolar portion of nonpolar rosin skeleton and adhesive resin is compatible.In addition, the amino with sour polar group and basic-dyeable fibre (unreacted basic-dyeable fibre in salify product) of Abietyl modified maleic acid resin reacts.
In addition, have in the scope that the weight-average molecular weight of the resin of acidic group illustrated typically in the 1st form.But the weight-average molecular weight here, with the resin of acidic group can be also outside the scope illustrating in the 1st form.
Salify product for example utilizes following method to carry out with the mixing of resin with acidic group.Here as an example, the resin with acidic group is Abietyl modified maleic acid resin.
(1) Abietyl modified maleic acid resin is dissolved in and in solvent and in this solution, adds the method that salify product mixes
(2) use mixing roll etc. by melting Abietyl modified maleic acid resin and the salify product method of mixing
It should be noted that, salify product also can be undertaken by other method with the mixing of the resin with acidic group.
Salify product with have the resin of acidic group, for example with the mass ratio (salify product: the resin with acidic group) of Abietyl modified maleic acid resin preferably in the scope of 70: 30 to 95: 5.The shared ratio in coloured composition of the resin with acidic group is larger, and colour rendering more reduces.Specifically, the impact from the color of resin with acidic group, the form and aspect of coloured composition being brought is larger.In addition, the shared ratio in coloured composition of the resin with acidic group is less, improves the dispersed effect of salify product in adhesive resin and becomes less.Salify product with the mass ratio (salify product: the resin with acidic group) of resin with acidic group more preferably in the scope of 75: 25 to 90: 10.
There is for example rosin ester of resin of acidic group or the acid number of Abietyl modified maleic acid resin preferably in 20 to 200mgKOH/g scope.During using this coloured composition as the painted anticorrosive additive material use of alkali-developable, the effect of the alkali soluble groups when carboxyl of resin is brought into play as colorant adsorption group and develops, aliphatic group and aromatic group performance are as the effect of the affinity groups facing to toner carrier and solvent.Therefore, dispersiveness or dissolubility, developability and the permanance of the acid number of resin to pigment and salify product exerts an influence.Specifically, acid number hour, the compatibility of resin and salify product becomes insufficient sometimes.In addition, acid number hour, when using this coloured composition as the painted anticorrosive additive material use of for example alkali-developable, uncured coloured composition becomes insufficient sometimes to the dissolubility of developer solution.On the other hand, when acid number is large, when using this coloured composition as the painted anticorrosive additive material use of for example alkali-developable, exposure portion is also likely developed and removes.It should be noted that, the acid number here refers to the value that the method by specifying in JIS K-0070 is measured.
[other colorant]
In this coloured composition, can in the scope that is not an impediment to effect, further add other colorant.Wherein, if also with salify product and organic pigment, can realize more excellent tolerance.
As organic pigment, preferably use phthualocyanine pigment, dioxazine series pigments, anthraquione pigmentss, azo pigment or quinacridone pigment.
Wherein, particularly preferably use phthualocyanine pigment Huo dioxazine series pigments.
As phthalocyanine blue pigment, for example, can enumerate C.I. pigment blue 15, C.I. pigment blue 15: 1, C.I. pigment blue 15: 2, C.I. pigment blue 15: 3, C.I. pigment blue 15: 4 and C.I. pigment blue 15: 6.Wherein, preferably there is the copper phthalocyanine blue pigment of the structure of ε type, β type or α type.These preferred pigment are C.I. pigment blue 15 specifically: 6, C.I. pigment blue 15: 3 and C.I. pigment blue 15: 1.
In addition, as dioxazine series pigments, preferably use C.I. pigment Violet 23.
These pigment, in the time that the amount of above-mentioned salify product is made as to 100 mass parts, preferably use with the amount below 50 mass parts.
Particularly, by above-mentioned salify product and copper phthalocyanine series pigments and/or dioxazine series pigments used time, good weatherability can be obtained, and brightness higher when using pigment monomer can be obtained.
(miniaturization of pigment)
Above-mentioned pigment for example can grind to process by salt and carry out miniaturization.In the scope that the primary particle size of pigment preferably illustrated in the 1st form.Salt mill is processed can be by for example carrying out with the same method illustrating in the 1st form.In addition, salt mill for example can use and same water-soluble organic-inorganic salt, water-miscible organic solvent and the resin that in the 1st form, illustrated in processing.In the scope that the use amount of various materials preferably illustrated in the 1st form.
< transparent resin >
Transparent resin is used for making colorant, particularly salify product to disperse and/or dissolves.As transparent resin, for example, can use and the same transparent resin illustrating in the 1st form.In addition, in the scope that the use amount of transparent resin preferably illustrated in the 1st form.
< solvent >
Identical with the coloured composition of the 1st form, thereby be coated on the substrates such as glass substrate with shaping filter joint for ease of colorant being scattered in be fully easy in colorant carrier to reach for example mode of 0.2 to 5 μ m according to dry film thickness, in this coloured composition, can contain solvent.As solvent, for example, can use and the same solvent illustrating in the 1st form.In addition, in the scope that the use amount of solvent preferably illustrated in the 1st form.
< disperses >
This coloured composition can be by manufacturing with the same method illustrating in the 1st form.
(dispersing aid)
In colorant is scattered in to colorant carrier time, with the 1st homomorphosis, can use the dispersing aiies such as pigment derivative, resin type spreading agent and surfactant.
As pigment derivative, for example, can use and the same pigment derivative illustrating in the 1st form.The use level of pigment derivative is from improving dispersed aspect, with respect to colorant 100 mass parts be preferably 0.5 mass parts above, more preferably 1 mass parts above, most preferably be 3 mass parts more than.In addition, the use level of pigment derivative, from thermotolerance and sunproof viewpoint, is preferably below 40 mass parts, most preferably is below 35 mass parts with respect to colorant 100 mass parts.
As resin type spreading agent, for example, can use and the same resin type spreading agent illustrating in the 1st form.As commercially available resin type spreading agent, for example, can enumerate the Disperbyk-101 of BYK Chemie Japan company system, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150 and 2155, Anti-Terra-U, 203 and 204, BYK-P104, P104S, 220S and 6919, Lactimon, Lactimon-WS and Bykumen, the SOLSPERSE-3000 of Lubrizol company of Japan system, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000 and 76500, the EFKA-46 of Ciba Japan company system, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502 and 1503, the Ajisper PA111 of Ajinomoto Fine-Techno company system, PB711, PB821, PB822 and PB824.
As surfactant, for example, can use and the same surfactant illustrating in the 1st form.
While adding resin type spreading agent and/or surfactant, their total amount in the time that the total amount of colorant is made as to 100 mass parts preferably in the scope of 0.1 to 55 mass parts, more preferably in the scope of 0.1 to 45 mass parts.When the total use level of resin type spreading agent and surfactant is lacked, be difficult to obtain their additive effect.In addition, when this total use level is many, too much spreading agent can affect dispersion sometimes.
This coloured composition can further add optical polymerism composition and/or Photoepolymerizationinitiater initiater, thereby uses as photosensitive coloring composition for color filter (resist).
< optical polymerism composition >
As the monomer using in optical polymerism composition or oligomer, for example, can enumerate (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) cyclohexyl acrylate, (methyl) propenoic acid beta-carboxyl ethyl ester, polyglycol two (methyl) acrylate, 1,6-hexanediol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, tripropylene glycol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, 1,6-hexanediol diglycidyl ether two (methyl) acrylate, bisphenol A diglycidyl ether two (methyl) acrylate, neopentylglycol diglycidyl ether two (methyl) acrylate, dipentaerythritol six (methyl) acrylate, dipentaerythritol five (methyl) acrylate, (methyl) acrylic acid three encircles decyl ester, ester acrylate, (methyl) acrylate of methylolation melamine, (methyl) acrylic acid epoxy ester, acrylate and the methacrylates such as ammonia ester acrylate, (methyl) acrylic acid, styrene, vinyl acetate, the vinyl ether such as hydroxyethyl vinyl ether, ethylene glycol bisthioglycolate vinyl ether and pentaerythrite trivinyl ether, (methyl) acrylamide, N-hydroxymethyl (methyl) acrylamide, N-vinyl formamide, and vinyl cyanide.They can be used alone or mix two or more use.Monomer or oligomer must not be defined in these.
The total use level of these monomers and oligomer is in the time being made as 100 mass parts by the gross mass of colorant, preferably in the scope of 5 to 400 mass parts, from the viewpoint of photo-curable and developability, more preferably in the scope of 10 to 300 mass parts.
< Photoepolymerizationinitiater initiater >
In the time being saved by blue coloring composition for color filter shaping filter by the photoetching process of utilizing ultraviolet ray irradiation, in this coloured composition, add Photoepolymerizationinitiater initiater etc.As Photoepolymerizationinitiater initiater, for example, can use and the same Photoepolymerizationinitiater initiater illustrating in the 1st form.Use when Photoepolymerizationinitiater initiater, its use level preferably with in the 1st form, illustrated identical.
< sensitizer >
In blue coloring composition for color filter, can further contain sensitizer.
As sensitizer, for example, can use and the same sensitizer illustrating in the 1st form.Use when sensitizer, its use level preferably with in the 1st form, illustrated identical.
< amine compound >
In blue coloring composition for color filter, can further contain the amine compound playing a part molten hydrogen reduction of depositing.As amine compound, for example, can use and the same amine compound illustrating in the 1st form.
< levelling agent >
In order to optimize the levelability of the composition on transparency carrier, in this blue colored composition, preferably further add levelling agent.
As levelling agent, for example, can use and the same levelling agent illustrating in the 1st form.Use when levelling agent, its use level preferably with in the 1st form, illustrated identical.
In levelling agent, also can auxiliarily add the surfactant of anionic property, cationic, nonionic or both sexes.Surfactant can use separately a kind, also can mix two or more use.As these surfactants, for example, can use and the same surfactant illustrating in the 1st form.
< hardening agent and curing accelerator >
For solidifying of auxiliary heat thermosetting resin, in this blue colored composition, also can contain as required hardening agent and curing accelerator etc.As hardening agent and curing accelerator, for example, can use and the same hardening agent and the curing accelerator that in the 1st form, illustrated.Use when curing accelerator, its use level preferably with in the 1st form, illustrated identical.
Other additive component > of <
For make composition through time viscosity stabilization, in this blue colored composition, can contain storage stabilizing agent.In addition, in order to improve and the adaptation of transparency carrier, in this blue colored composition, also can contain the closely sealed improving agents such as silane coupling agent.
As storage stabilizer and closely sealed improving agent, for example, can use and the same storage stabilizer and the closely sealed improving agent that in the 1st form, illustrated.While using storage stabilizer and/or closely sealed improving agent, its use level preferably with in the 1st form, illustrated identical.
The method for making > of < coloured composition
This blue colored composition, for example can be by following method manufacture in the time that the form with solvent develop type or the painted anticorrosive additive material of alkali-developable is used.First, colorant is mixed with the colorant carrier that contains transparent resin and optional organic solvent.Then, utilize the dispersion means such as triple-roller mill, two roller mills, sand mill, kneader and masher to process them, colorant is dispersed in colorant carrier.Then, other resin, solvent, spreading agent and the adjuvant etc. of mixed light polymerizable monomer and/or oligomer, Photoepolymerizationinitiater initiater and use as required in the colorant dispersion so obtaining.As above operation can obtain blue colored composition.
< oversize grain remove >
With in the 1st form, illustrated the same, the dust of preferably removing oversize grain and sneaking into from this coloured composition.Preferably this coloured composition, in fact not containing particle more than 0.5 μ m, does not more preferably contain in fact particle more than 0.3 μ m.
" color filter "
Then, the color filter of the 2nd form of the present invention is described.
The color filter of the 2nd form contains absorption spectrum difference, regularly arranged multiple filter sections typically.The color filter of a form possesses at least 1 red filter joint, at least 1 green filter joint and at least 1 blue electric-wave filter joint.In the color filter of the 2nd form, at least 1 blue electric-wave filter joint is formed by above-mentioned blue coloring composition for color filter.
Red filter joint for example can form with the common red colored composition that contains red pigment and pigment carrier.As red pigment, for example can use C.I. paratonere 7,14,41,48:1,48:2,48:3,48:4,57:1,81,81:1,81:2,81:3,81:4,122,146,168,169,177,178,184,185,187,200,202,208,210,242,246,254,255,264,270,272,273,274,276,277,278,279,280,281,282,283,284,285,286 or 287.Substituting or except red pigment, can also use red salify product of presenting of basic-dyeable fibre and acid dyes as red pigment.For example can use the salify product illustrating in the 1st form.
In red colored composition, can be used together the orange pigments such as C.I. pigment orange 43,71 and 73, C.I. pigment yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, the yellow uitramarines such as 220 and 221, or their potpourri.In addition, can also use orange and/or yellow salify product of presenting of basic-dyeable fibre and acid dyes.For example can use the salify product illustrating in the 1st form.
Green filter joint for example can form with the common green coloring composition that contains viridine green and pigment carrier.As viridine green, for example, can use C.I. pigment Green 7,10,36,37 or 58.
In green coloring composition, can be used together yellow uitramarine.As can and the yellow uitramarine of use, for example can enumerate C.I. pigment yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220 and 221.Substituting or except yellow uitramarine, can also use yellow salify product of presenting of basic-dyeable fibre and acid dyes as yellow uitramarine.For example can use the salify product illustrating in the 1st form.
The manufacture method > of < color filter
This color filter for example can be by manufacturing with the identical method illustrating in the 1st form.
0 the 3rd form
Below, the 3rd form of the present invention is described.
People of the present invention conduct in-depth research repeatedly, found that, be that basic-dyeable fibre and xanthene are the colorant of the salify product that forms of acid dyes as color composition for color filter by using by xanthene, can realize high brightness and wide color reproduction region, can also realize excellent tolerance, complete the invention of this form based on this discovery.
Be that the 3rd form of the present invention is a kind of color composition for color filter, it contains transparent resin and colorant, and it is that basic-dyeable fibre and xanthene are the salify product that acid dyes forms that above-mentioned colorant contains by xanthene.
It is that basic-dyeable fibre and xanthene are that the salify product that forms of acid dyes is as colorant that the color composition for color filter of the 3rd form contains by xanthene.Therefore,, by formed at least one filter section of color filter by this coloured composition, except can realizing high brightness and wide color reproduction region, can also realize excellent tolerance.This color composition for color filter is particularly preferred for the filter section of blueness or magenta.
It should be noted that, in blue electric-wave filter joint in the past, use the combination of for example copper phthalocyanine blue pigment and dioxazine series pigments.Combination has copper phthalocyanine blue pigment with in the Optical transmission spectrum of the blue coloring composition for color filter of dioxazine series pigments etc., peak position is positioned near 450nm, and the short wavelength side transmissivity below 450nm sharply reduces.
On the other hand, it is that basic-dyeable fibre and xanthene are the salify product that forms of acid dyes at least a portion as colorant that the color composition for color filter of this form uses by xanthene, preferably uses together with phthualocyanine pigment., while using the color filter of this form to use composition, compare with the situation of the combination of dioxazine series pigments with using copper phthalocyanine blue pigment for this reason, can realize high-transmission rate by the short wavelength side below 450nm.And it is long that a lot of luminescent spectrums backlight such as cold-cathode tube have spike in 425 to 440nm wavelength coverage or near it.Therefore the filter section, being obtained by the color composition for color filter of this form can be realized high brightness.
In addition, present situation is that the range of choice of the complementary colors pigment that uses in the color filter of complementary colors is extremely narrow, is difficult to obtain the complementary colors pigment with excellent dichroism.This point is also to adopt in the imaging apparatus of complementary colors color filter to be difficult to one of reason obtaining excellent colorrendering quality.Particularly, for magenta filter section, be difficult to obtain sufficient dichroism.For example low in the transmissivity of short wavelength side (400 to 450nm) as the C.I. pigment red 122 of quinacridone magenta pigment, be therefore difficult to optimize the color balance of color filter.
Xanthene based dye is as for example showing the dyestuff of magenta and known.Xanthene based dye has excellent dichroism.Specifically, xanthene be pigment compared with quinacridone pigment, high in 400 to 450nm wavelength coverages or near the transmissivity it.Therefore, to be pigment be used in many magenta filter sections xanthene as recorded in No. 2005-292305, TOHKEMY.But as mentioned above, dyestuff tolerance compared with pigment is poor.
The coloured composition of this form is compared with quinacridone pigment, high in the transmissivity of short wavelength side (400 to 450nm).And, if use the coloured composition of this form, can obtain the filter section of tolerance excellence.Therefore,, if the coloured composition of this form is used for to the filter section of magenta, can obtain the complementary colors color filter of for example color balance and tolerance excellence.
" color composition for color filter "
As mentioned above, the color composition for color filter of the 3rd form of the present invention is the color composition for color filter that contains transparent resin and colorant.It is that basic-dyeable fibre and xanthene are the salify product that acid dyes forms that this colorant contains by xanthene.For example xanthene is that basic-dyeable fibre and xanthene are that acid dyes is respectively basic-dyeable fibre and the equilibrium compound of the 1st form.It should be noted that, in the 3rd form, equilibrium compound typically has the molecular weight in the above-mentioned scope of equilibrium compound in the 1st form, but also can have this extraneous molecular weight.
< colorant >
It is that acid dyes and xanthene are the salify product that basic-dyeable fibre forms that the colorant using in the 3rd form contains by three xanthenes.
This colorant for example with copper phthalocyanine used time, in 425 to 440nm wavelength coverage or its annex can realize high-transmission rate.Therefore, there is copper phthalocyanine with combination with the existing blue electric-wave filter joint of triazine dioxin pigment is compared, can realize high brightness and wide colorrendering quality.In addition, the transmissivity of the wavelength coverage due to 400 to 450nm is high, can obtain the complementary colors color filter of color balance excellence.
[xanthene is that acid dyes and xanthene are basic-dyeable fibre]
Below, be that acid dyes and xanthene are that basic-dyeable fibre describes to xanthene.
(xanthene based dye)
The xanthene based dye that can preferably use here presents redness or purple, and has the form of acid dyes and/or the form of basic-dyeable fibre.
Presenting redness or purple refers to and for example belongs to the alkaline purple directly directly dyestuff of the direct dyes such as purple of red and C.I. of the acid dyess such as basic-dyeable fibre, C.I. acid red and C.I. acid violet or C.I. that waits of the red and C.I. of C.I. alkalescence.Here, direct dyes is in structure, to have sulfonic group (SO 3h ,-SO 3na) dyestuff.In this form, regard direct dyes as acid dyes.In addition, in oil-soluble dyes, there is sulfonic group and have in fact and in this form, be also considered acid dyes as the dyestuff of the function as acid dyes.
Xanthene is that acid dyes and xanthene are that basic-dyeable fibre has the dichroism of holding high-transmission rate in 400 to 450nm wavelength coverage internal transmission factor.But xanthene is that acid dyes and xanthene are that basic-dyeable fibre is the same with common dyestuff, photostability and thermotolerance extremely lack.Be xanthene be acid dyes and xanthene be basic-dyeable fibre for the color filter for requiring high reliability, characteristic is inadequate.Here,, in order to improve this shortcoming, using xanthene is that acid dyes and xanthene are the salt of basic-dyeable fibre.Such salt is the salify product having between the dyestuff of fast eolor base, therefore excellent color reproducing performance.
Xanthene is that acid dyes and xanthene are that optical transmission rate that basic-dyeable fibre is preferably 650nm to wavelength is that the optical transmission rate that is 600nm more than 90%, to wavelength is that the scope internal transmission factor that is 500 to 550nm more than 75%, at wavelength is to be 400nm below 5%, to wavelength optical transmission rate is more than 70%.More preferably the optical transmission rate that the scope internal transmission factor that the optical transmission rate that the optical transmission rate that is 650nm to wavelength is is 600nm more than 95%, to wavelength is is 500 to 550nm more than 80%, at wavelength is is 400nm below 10%, to wavelength is more than 75%.
(xanthene is acid dyes)
Be acid dyes as xanthene, preferably use C.I. CI 45430 (erythrosine: edible red No. 3), C.I. acid red 52 (acid rhodamine), C.I. acid red 87 (eosin G: edible red No. 103), C.I. acid red 92 (the red PB of acid flame: edible red No. 104), C.I. acid red 289, C.I. acid red 388, rose red b (edible red No. 5), acid rhodamine G or C.I. acid violet 9.
Wherein, particularly preferably use C.I. acid red 52, C.I. acid red 87, C.I. acid red 92, C.I. acid red 289 or C.I. acid red 388.
(xanthene is basic-dyeable fibre)
Be basic-dyeable fibre as xanthene, for example, can enumerate C.I. alkali red 1:1 (rhodamine 6G CP), C.I. red 8 (rhodamine Gs) of alkalescence and C.I. alkaline purple 10 (rhodamine B).
Wherein, particularly preferably use C.I. alkali red 1:1 or C.I. alkaline purple 10.
Xanthene is in basic-dyeable fibre, rhodamine be basic-dyeable fibre due to colour rendering and tolerance excellent and particularly preferably.
[being that acid dyes and xanthene are the salify product that basic-dyeable fibre forms by xanthene]
Xanthene is that acid dyes and xanthene are that the salify product of basic-dyeable fibre has high thermotolerance, photostability and solvent resistance.This salify product is preferably at least a kind in following combination.
Specifically, C.I. the combination of alkali red 1:1 and C.I. acid red 52, C.I. the combination of alkali red 1:1 and C.I. acid red 87, C.I. the combination of alkali red 1:1 and C.I. acid red 92, C.I. the combination of alkali red 1:1 and C.I. acid red 289, C.I. the combination of alkali red 1:1 and C.I. acid red 388, C.I. the combination of alkaline purple 10 and C.I. acid red 52, C.I. the combination of alkaline purple 10 and C.I. acid red 87, C.I. the combination of alkaline purple 10 and C.I. acid red 92, C.I. the combination of alkaline purple 10 and C.I. acid red 289, C.I. the combination of alkaline purple 10 and C.I. acid red 388, C.I. alkaline red 8 and the combination of C.I. acid red 52, C.I. alkaline red 8 and the combination of C.I. acid red 87, C.I. alkaline red 8 and the combination of C.I. acid red 92, C.I. alkaline red 8 and the combination of C.I. acid red 289, and the reaction stability of the combination of C.I. alkalescence red 8 and C.I. acid red 388 and colour rendering excellence especially.Can certainly use the salify product being obtained by other combination.
Xanthene is that basic-dyeable fibre and xanthene are that the salify product of acid dyes can synthesize by known method in the past.
For example can be to make xanthene be that to add wherein xanthene after acid dyes is dissolved in water be basic-dyeable fibre or its aqueous solution and stir, thus salt-forming reaction be there is.Obtaining thus xanthene is the sulfonic group (for example-SO of acid dyes 3h or-SO 3na) be the salify product that the amino of basic-dyeable fibre is combined into xanthene.
[thering is the resin of acidic group]
The resin that above-mentioned salify product has acidic group by use carries out modification, can make more stable look material.About thering is the item of resin of acidic group, with in the 2nd form, illustrated identical.
[other colorant]
In this coloured composition, can in the scope that is not an impediment to effect, further add other colorant.Wherein, if also with salify product and organic pigment, can realize more excellent tolerance.
While forming blueness or cyan filter section by this coloured composition, as with the organic pigment of salify product use, for example can enumerate phthualocyanine pigment, dioxazine series pigments, anthraquione pigmentss, azo pigment and quinacridone pigment.Wherein, preferably use phthualocyanine pigment Huo dioxazine series pigments.
As phthualocyanine pigment, for example, can enumerate C.I. pigment blue 15, C.I. pigment blue 15: 1, C.I. pigment blue 15: 2, C.I. pigment blue 15: 3, C.I. pigment blue 15: 4 and C.I. pigment blue 15: 6.Wherein, preferably there is the copper phthalocyanine of the structure of ε type, β type or α type.These preferred pigment are C.I. pigment blue 15 specifically: 6, C.I. pigment blue 15: 3 and C.I. pigment blue 15: 1.
In addition, as dioxazine series pigments, preferably use C.I. pigment Violet 23.
These pigment, from the viewpoint of dichroism, in the time that the amount of above-mentioned salify product is made as to 100 mass parts, preferably use with the amount in the scope of 2 to 100 mass parts.
Particularly using above-mentioned coloured composition as blueness or cyan coloured composition use time, by by above-mentioned salify product and copper phthalocyanine series pigments and/or dioxazine series pigments use, can realize good weatherability, and can realize higher brightness.
In the time forming magenta filter section by above-mentioned coloured composition, the object of adjusting for color, can and use above-mentioned salify product and other redness or magenta pigment.As can and other pigment of use, for example can enumerate C.I. pigment red 122, C.I. paratonere 192, C.I. paratonere 202, C.I. Pigment Red 207 and C.I. paratonere 209.Wherein, from the aspect of thermotolerance, photostability and solvent resistance excellence, preferably use quinacridone pigment.
These pigment from widening chroma areas, obtain the viewpoint of excellent dichroism, in the time that the quality of above-mentioned salify product is made as to 100 mass parts, preferably use with the amount below 40 mass parts.
(miniaturization of pigment)
Above-mentioned pigment for example can grind to process by salt and carry out miniaturization.In the scope that the primary particle size of pigment preferably illustrated in the 1st form.Salt mill processing example is as can be by carrying out with the same method illustrating in the 1st form.In addition, salt mill for example can use and same water-soluble organic-inorganic salt, water-miscible organic solvent and the resin that in the 1st form, illustrated in processing.In the scope that the use amount of various materials preferably illustrated in the 1st form.
< transparent resin >
Transparent resin is used for making colorant, particularly salify product to disperse and/or dissolves.As transparent resin, for example, can use and the same transparent resin illustrating in the 1st form.In addition, use amount of transparent resin etc. for example also can with in the 1st form, illustrated identical.
< disperses >
This coloured composition can be by manufacturing with the same method illustrating in the 1st form.
(dispersing aid)
In colorant is scattered in to colorant carrier time, with the 1st homomorphosis, can use the dispersing aiies such as pigment derivative, resin type spreading agent and surfactant.
As pigment derivative, for example, can use and the same pigment derivative illustrating in the 1st form.The use level of pigment derivative is from improving dispersed aspect, preferably with in the 2nd form, illustrated identical.
As resin type spreading agent, for example, can use and the same resin type spreading agent illustrating in the 1st form.As commercially available resin type spreading agent, for example, can use the resin type spreading agent of example in the 2nd form.
As surfactant, for example, can use and the same surfactant illustrating in the 1st form.
While adding resin type spreading agent and/or surfactant, in the scope that their total amount preferably illustrated in the 2nd form.
This coloured composition can further add optical polymerism composition and/or Photoepolymerizationinitiater initiater, thereby uses as photosensitive coloring composition for color filter (resist).
< optical polymerism composition >
For optical polymerism composition, for example, can use monomer or the oligomer of example in the 2nd form.In the scope that total use level of these monomers and oligomer preferably illustrated in the 2nd form.
< Photoepolymerizationinitiater initiater >
In the time being saved by color composition for color filter shaping filter by the photoetching process of utilizing ultraviolet ray irradiation, in this coloured composition, for example add Photoepolymerizationinitiater initiater etc.As Photoepolymerizationinitiater initiater, for example, can use and the same Photoepolymerizationinitiater initiater illustrating in the 1st form.Use when Photoepolymerizationinitiater initiater, its use level preferably with in the 1st form, illustrated identical.
< sensitizer >
In color composition for color filter, can further contain sensitizer.
As sensitizer, for example, can use and the same sensitizer illustrating in the 1st form.Use when sensitizer, its use level preferably with in the 1st form, illustrated identical.
< amine compound >
In color composition for color filter, can further contain the amine compound playing a part molten hydrogen reduction of depositing.As amine compound, for example, can use and the same amine compound illustrating in the 1st form.
< levelling agent >
In order to optimize the levelability of the composition on transparency carrier, in this coloured composition, preferably further add levelling agent.
As levelling agent, for example, can use and the same levelling agent illustrating in the 1st form.Use when levelling agent, its use level preferably with in the 1st form, illustrated identical.
In levelling agent, also can auxiliarily add the surfactant of anionic property, cationic, nonionic or both sexes.Surfactant can use separately a kind, also can mix two or more use.As these surfactants, for example, can use and the same surfactant illustrating in the 1st form.
< hardening agent and curing accelerator >
For solidifying of auxiliary heat thermosetting resin, in this coloured composition, also can contain as required hardening agent and curing accelerator etc.As hardening agent and curing accelerator, for example, can use and the same hardening agent and the curing accelerator that in the 1st form, illustrated.Use when curing accelerator, its use level preferably with in the 1st form, illustrated identical.
Other additive component > of <
For make composition through time viscosity stabilization, in this coloured composition, can contain storage stabilizing agent.In addition, in order to improve and the adaptation of transparency carrier, in this coloured composition, also can contain the closely sealed improving agents such as silane coupling agent.
As storage stabilizer and closely sealed improving agent, for example, can use and the same storage stabilizer and the closely sealed improving agent that in the 1st form, illustrated.While using storage stabilizer or closely sealed improving agent, its use level preferably with in the 1st form, illustrated identical.
< oversize grain remove >
With in the 1st form, illustrated identical, the dust of preferably removing oversize grain and sneaking into from this coloured composition.Preferably this coloured composition, in fact not containing particle more than 0.5 μ m, does not more preferably contain in fact particle more than 0.3 μ m.
" color filter "
Then, the color filter of the 3rd state of the present invention is described.
The color filter of the 2nd form contains absorption spectrum difference, regularly arranged multiple filter sections typically.The color filter of a form possesses at least 1 red filter joint, at least 1 green filter joint and at least 1 blue electric-wave filter joint.The color filter of another form possesses at least 1 magenta filter section, at least 1 cyan filter section and at least 1 yellow filter joint.In the color filter of the 1st form, at least 1 of these filter sections is formed by above-mentioned color composition for color filter.
Red filter joint for example can be formed by the red colored composition that contains red pigment and pigment carrier.In red colored composition, for example can use C.I. paratonere 7, C.I. paratonere 14, C.I. pigment red 41, C.I. pigment red 4 8:1, C.I. pigment red 4 8:2, C.I. pigment red 4 8:3, C.I. pigment red 4 8:4, C.I. paratonere 57:1, C.I. pigment red 81, C.I. pigment red 81: 1, C.I. pigment red 81: 2, C.I. pigment red 81: 3, C.I. pigment red 81: 4, C.I. pigment red 122, C.I. pigment red 146, C.I. paratonere 168, C.I. paratonere 169, C.I. paratonere 177, C.I. paratonere 178, C.I. paratonere 184, C.I. paratonere 185, C.I. paratonere 187, C.I. paratonere 200, C.I. paratonere 202, C.I. paratonere 208, C.I. pigment red 21 0, C.I. paratonere 242, C.I. paratonere 246, C.I. paratonere 254, C.I. paratonere 255, C.I. paratonere 264, C.I. paratonere 270, C.I. paratonere 272, C.I. paratonere 273, C.I. paratonere 274, C.I. paratonere 276, C.I. paratonere 277, C.I. paratonere 278, C.I. paratonere 279, C.I. paratonere 280, C.I. paratonere 281, C.I. paratonere 282, C.I. paratonere 283, C.I. paratonere 284, C.I. paratonere 285, C.I. paratonere 286, and the red pigment such as C.I. paratonere 287.In addition, for example can also use the salify product that presents respectively red basic-dyeable fibre and acid dyes.
Red colored composition can also further contain C.I. pigment orange 43, 71 and the orange pigment such as C.I. pigment orange 73, C.I. pigment yellow 1, C.I. pigment yellow 2, C.I. pigment yellow 3, C.I. pigment yellow 4, C.I. pigment yellow 5, C.I. pigment yellow 6, C.I. pigment yellow 10, C.I. pigment Yellow 12, C.I. pigment yellow 13, C.I. pigment Yellow 14, C.I. pigment yellow 15, C.I. pigment yellow 16, C.I. pigment yellow 17, C.I. pigment yellow 18, C.I. pigment yellow 24, C.I. pigment yellow 31, C.I. pigment yellow 32, C.I. pigment yellow 34, C.I. pigment yellow 35, C.I. pigment yellow 35:1, C.I. pigment yellow 36, C.I. pigment yellow 36:1, C.I. pigment yellow 37, C.I. pigment yellow 37:1, C.I. pigment yellow 40, C.I. pigment yellow 42, C.I. pigment yellow 43, C.I. pigment yellow 53, C.I. pigment yellow 55, C.I. pigment yellow 60, C.I. pigment yellow 61, C.I. pigment yellow 62, C.I. pigment yellow 63, C.I. pigment yellow 65, C.I. pigment yellow 73, C.I. pigment yellow 74, C.I. pigment yellow 77, C.I. pigment yellow 81, C.I. pigment yellow 83, C.I. pigment yellow 93, C.I. pigment yellow 94, C.I. pigment yellow 95, C.I. pigment yellow 97, C.I. pigment yellow 98, C.I. pigment yellow 100, C.I. pigment yellow 101, C.I. pigment yellow 104, C.I. pigment yellow 106, C.I. pigment yellow 108, C.I. pigment yellow 109, C.I. pigment yellow 110, C.I. pigment yellow 113, C.I. pigment yellow 114, C.I. pigment yellow 115, C.I. pigment yellow 116, C.I. pigment yellow 117, C.I. pigment yellow 118, C.I. pigment yellow 119, C.I. pigment Yellow 12 0, C.I. pigment Yellow 12 3, C.I. pigment Yellow 12 6, C.I. pigment Yellow 12 7, C.I. pigment Yellow 12 8, C.I. pigment Yellow 12 9, C.I. pigment yellow 13 8, C.I. pigment yellow 13 9, C.I. pigment yellow 147, C.I. pigment yellow 150, C.I. pigment yellow 151, C.I. pigment yellow 152, C.I. pigment yellow 153, C.I. pigment yellow 154, C.I. pigment yellow 155, C.I. pigment yellow 156, C.I. pigment yellow 161, C.I. pigment yellow 162, C.I. pigment yellow 164, C.I. pigment yellow 166, C.I. pigment yellow 167, C.I. pigment yellow 168, C.I. pigment yellow 169, C.I. pigment yellow 17 0, C.I. pigment yellow 17 1, C.I. pigment yellow 17 2, C.I. pigment yellow 17 3, C.I. pigment yellow 17 4, C.I. pigment yellow 17 5, C.I. pigment yellow 17 6, C.I. pigment yellow 17 7, C.I. pigment yellow 17 9, C.I. pigment yellow 180, C.I. pigment yellow 181, C.I. pigment yellow 182, C.I. pigment yellow 185, C.I. pigment yellow 187, C.I. pigment yellow 188, C.I. pigment yellow 193, C.I. pigment yellow 194, C.I. pigment yellow 198, C.I. pigment yellow 199, C.I. pigment yellow 213, C.I. pigment yellow 214, C.I. pigment yellow 218, C.I. pigment yellow 219, C.I. pigment yellow 220, and the yellow uitramarine such as C.I. pigment yellow 221, or 2 above combinations in them.In addition, can also use the salify product that presents respectively orange and/or yellow basic-dyeable fibre and acid dyes.
Green filter joint for example can be formed by the green coloring composition that contains viridine green and pigment carrier.As viridine green, for example, can use C.I. pigment Green 7, C.I. naphthol green 10, C.I. pigment green 36, C.I. naphthol green 37 or C.I. naphthol green 58.
Green coloring composition can further contain yellow uitramarine.As can and the yellow uitramarine of use, for example can enumerate C.I. pigment yellow 1, C.I. pigment yellow 2, C.I. pigment yellow 3, C.I. pigment yellow 4, C.I. pigment yellow 5, C.I. pigment yellow 6, C.I. pigment yellow 10, C.I. pigment Yellow 12, C.I. pigment yellow 13, C.I. pigment Yellow 14, C.I. pigment yellow 15, C.I. pigment yellow 16, C.I. pigment yellow 17, C.I. pigment yellow 18, C.I. pigment yellow 24, C.I. pigment yellow 31, C.I. pigment yellow 32, C.I. pigment yellow 34, C.I. pigment yellow 35, C.I. pigment yellow 35:1, C.I. pigment yellow 36, C.I. pigment yellow 36:1, C.I. pigment yellow 37, C.I. pigment yellow 37:1, C.I. pigment yellow 40, C.I. pigment yellow 42, C.I. pigment yellow 43, C.I. pigment yellow 53, C.I. pigment yellow 55, C.I. pigment yellow 60, C.I. pigment yellow 61, C.I. pigment yellow 62, C.I. pigment yellow 63, C.I. pigment yellow 65, C.I. pigment yellow 73, C.I. pigment yellow 74, C.I. pigment yellow 77, C.I. pigment yellow 81, C.I. pigment yellow 83, C.I. pigment yellow 93, C.I. pigment yellow 94, C.I. pigment yellow 95, C.I. pigment yellow 97, C.I. pigment yellow 98, C.I. pigment yellow 100, C.I. pigment yellow 101, C.I. pigment yellow 104, C.I. pigment yellow 106, C.I. pigment yellow 108, C.I. pigment yellow 109, C.I. pigment yellow 110, C.I. pigment yellow 113, C.I. pigment yellow 114, C.I. pigment yellow 115, C.I. pigment yellow 116, C.I. pigment yellow 117, C.I. pigment yellow 118, C.I. pigment yellow 119, C.I. pigment Yellow 12 0, C.I. pigment Yellow 12 3, C.I. pigment Yellow 12 6, C.I. pigment Yellow 12 7, C.I. pigment Yellow 12 8, C.I. pigment Yellow 12 9, C.I. pigment yellow 13 8, C.I. pigment yellow 13 9, C.I. pigment yellow 147, C.I. pigment yellow 150, C.I. pigment yellow 151, C.I. pigment yellow 152, C.I. pigment yellow 153, C.I. pigment yellow 154, C.I. pigment yellow 155, C.I. pigment yellow 156, C.I. pigment yellow 161, C.I. pigment yellow 162, C.I. pigment yellow 164, C.I. pigment yellow 166, C.I. pigment yellow 167, C.I. pigment yellow 168, C.I. pigment yellow 169, C.I. pigment yellow 17 0, C.I. pigment yellow 17 1, C.I. pigment yellow 17 2, C.I. pigment yellow 17 3, C.I. pigment yellow 17 4, C.I. pigment yellow 17 5, C.I. pigment yellow 17 6, C.I. pigment yellow 17 7, C.I. pigment yellow 17 9, C.I. pigment yellow 180, C.I. pigment yellow 181, C.I. pigment yellow 182, C.I. pigment yellow 185, C.I. pigment yellow 187, C.I. pigment yellow 188, C.I. pigment yellow 193, C.I. pigment yellow 194, C.I. pigment yellow 198, C.I. pigment yellow 199, C.I. pigment yellow 213, C.I. pigment yellow 214, C.I. pigment yellow 218, C.I. pigment yellow 219, C.I. pigment yellow 220, and C.I. pigment yellow 221.In addition, can also and use the salify product that presents respectively yellow basic-dyeable fibre and acid dyes.
Cyan filter section for example can be formed by the cyan coloured composition that contains blue pigment or green pigment and pigment carrier.As blue pigment, for example, can use C.I. pigment blue 15, C.I. pigment blue 15: 1, C.I. pigment blue 15: 2, C.I. pigment blue 15: 3, C.I. pigment blue 15: 4, C.I. pigment blue 15: 6, C.I. pigment blue 16, C.I. alizarol saphirol 22, C.I. pigment blue 60 or C.I. alizarol saphirol 64.Wherein, preferably as C.I. pigment blue 15, the C.I. pigment blue 15 of copper phthalocyanine series pigments: 1, C.I. pigment blue 15: 2, C.I. pigment blue 15: 3, C.I. pigment blue 15: 4 and C.I. pigment blue 15: 6.In addition, can also use the salify product that presents respectively blue basic-dyeable fibre and acid dyes.
Yellow filter joint for example can be formed by the yellow coloring composition that contains yellow uitramarine and pigment carrier.As yellow uitramarine, for example can be used as can with the exemplified pigment of the yellow uitramarine of viridine green use.In addition, can also use the salify product that presents respectively yellow basic-dyeable fibre and acid dyes.
The manufacture method > of < color filter
This color filter for example can be by manufacturing with the identical method illustrating in the 1st form.
Notebook inventive embodiment below, but the present invention is not subject to the restriction of these embodiment.It should be noted that, if not otherwise specified, " part " refers to " mass parts ".
First, the various assay methods that carry out in embodiment and comparative example etc. are described.
The weight-average molecular weight (Mw) of acryl resin is the weight-average molecular weight (Mw) of polystyrene conversion.This weight-average molecular weight (Mw) is used TSKgeL chromatographic column (Tosoh company system), utilization are equipped with the GPC (Tosoh company system, HLC-8120GPC) of RI detecting device and use THF to record as developing solvent.
Mean grain size after the pulverizing of salify product and rhodamine based compound is the use Multisizer 3 processed of Beckmancoulter company, is the volume average particle size obtaining under the condition of 100 μ m in aperture.
In addition, the miniaturization degree of pigment is evaluated by the specific surface area of pigment particles.The mensuration of specific surface area is to use automatic steam adsorbance determinator (Japanese Bel company's system " BELSORP18 "), utilization to use BET (Brunauer-Emmett-Teller) method of nitrogen to carry out.
Below, the miniaturization method of the manufacture method to the acrylic resin soln using in embodiment and comparative example, salify product and rhodamine based compound and pigment describes.
" test 1 "
Test 1 relates to the 1st form.In test 1, will be designated as " embodiment " corresponding to the example of the 1st form, other examples are designated as to " comparative example ".
The manufacture method > of < acrylic resin soln
(preparation of acrylic resin soln 1)
On 4 mouthfuls of flasks of detachable, thermometer, cooling tube, nitrogen ingress pipe and stirring apparatus are installed, in this reaction vessel, are packed into 70.0 parts of cyclohexanone.Be warming up to 80 DEG C, in by reaction vessel, carry out after nitrogen displacement, with the times of 2 hours by dropper drip 13.3 parts of n-BMAs, 4.6 parts of 2-hydroxyethyl methacrylates, 4.3 parts of methacrylic acids, to 7.4 parts of cumenyl phenol ring oxidative ethane modification acrylates (Toagosei Co., Ltd's system " ARONIX M110 ") and 2, the potpourri that 2 '-azobis isobutyronitrile is 0.4 part.After dropping finishes, reaction is proceeded to 3 hours again, obtain weight-average molecular weight and be the solution of 26000 acryl resin.Be cooled to after room temperature the about 2g of sample tree lipoprotein solution.Within 20 minutes, make it dry by it is heated at 180 DEG C, measure nonvolatile component.According to the nonvolatile component content so obtaining, the mode that reaches 20 quality % according to nonvolatile component in previously synthetic resin solution is added propylene glycol methyl ether acetate (PGMAC), thereby has prepared acrylic resin soln 1.
The manufacture method > of < salify product
(rhodamine is tied to form the generation of salt product 1,1-1,1-2 and 1-3)
By 2,8-diaminostilbene-naphthols-5,7-disulfonic acid (molecular weight is 334) adds in the sodium hydroxide solution of 7 to 15 % by mole, fully stirs this solution, thereby obtains its sodium salt.By this 2,8-diaminostilbene-naphthols-5,7-sodium disulfonate brine solution is heated to after 70 to 90 DEG C, little by little drips wherein rhodamine 6G CP dyestuff (C.I. alkali red 1:1).Rhodamine 6G CP dyestuff also can use with the form of aqueous solution.After the dropping of rhodamine 6G CP dyestuff finishes, for it is fully reacted, this solution is stirred 40 to 60 minutes at 70 to 90 DEG C.The terminal of reaction is dropwise reaction liquid and ooze out moment of disappearance on filter paper.Ooze out judgement while disappearance and obtained salify product.Stirring while letting cool to room temperature, carrying out suction filtration, then wash.After washing, use dryer in residual salify product, to remove moisture from filter paper, obtain as rhodamine 6G CP dyestuff and 2,8-diaminostilbene-naphthols-5, the rhodamine of the salify product of 7-disulfonic acid is tied to form salt product 1.
Then, be tied to form and in salt product 1, add Abietyl modified maleic acid resin (acid number is 130, weight-average molecular weight is 1000, the MALKYD No.32 processed of Huang Chuan chemical company) 20 mass parts at the rhodamine of 100 mass parts, mix with pressurization kneader.This mixing is material temperature to be set in to 120 DEG C carry out 30 minutes.After cooling, use mechanical crusher (the KRYPTRON KTM1 processed of Earthtechnica company type) to carry out Crushing of Ultrafine, the mean grain size that acquisition is tied to form salt product 1-1 as rhodamine is the particle of 10 μ m.
In addition, be tied to form and in salt product 1, add Abietyl modified maleic acid resin (acid number is 35, weight-average molecular weight is 3500, the MALKYD No.8 processed of Huang Chuan chemical company) 20 mass parts at the rhodamine of 100 mass parts, mix with pressurization kneader.This mixing is material temperature to be set in to 120 DEG C carry out 30 minutes.After cooling, use mechanical crusher (the KRYPTRON KTM1 processed of Earthtechnica company type) to carry out Crushing of Ultrafine, the mean grain size that acquisition is tied to form salt product 1-2 as rhodamine is the particle of 10 μ m.
In addition, be tied to form and in salt product 1, add thermoplastic polyester 20 mass parts at the rhodamine of 100 mass parts, mix with pressurization kneader.As thermoplastic polyester, use the vibrin (acid number is that 10mgKOH/g, OH value are that 43mgKOH/g, weight-average molecular weight are 3500) being formed by terephthalic acid (TPA), m-phthalic acid, trimellitic acid, epoxypropane addition bisphenol-A and ethylene glycol.It should be noted that, this molecular weight is to try to achieve under the condition identical with Abietyl modified maleic acid resin.In addition, this mixing is material temperature to be set in to 120 DEG C carry out 30 minutes.After cooling, use mechanical crusher (the KRYPTRON KTM1 processed of Earthtechnica company type) to carry out Crushing of Ultrafine, the mean grain size that acquisition is tied to form salt product 1-3 as rhodamine is the particle of 10 μ m.
(rhodamine is tied to form the generation of salt product 2 and 2-1)
By naphthalidine-3,6,8-trisulfonic acid (Koch's acid) (molecular weight is 383) adds in the sodium hydroxide solution of 7 to 15 % by mole, and this solution is fully stirred, and obtains thus its sodium salt.By these naphthalidine-3,6,8-trisulfonic acid (Koch's acid) sodium-salt aqueous solution is heated to after 70 to 90 DEG C, little by little drips wherein rhodamine 6G CP dyestuff (C.I. alkali red 1:1).Rhodamine 6G CP dyestuff also can use with the form of aqueous solution.After the dropping of rhodamine 6G CP dyestuff finishes, for it is reacted fully, this solution is stirred 40 to 60 minutes at 70 to 90 DEG C.The terminal of reaction is dropwise reaction liquid and ooze out moment of disappearance on filter paper.Ooze out judgement while disappearance and obtained salify product.Stirring while letting cool to room temperature, carrying out suction filtration, then wash.After washing, use dryer in residual salify product, to remove moisture from filter paper, obtained as rhodamine 6G CP dyestuff and naphthalidine-3, the rhodamine of the salify product of 6,8-trisulfonic acid (Koch's acid) is tied to form salt product 2.
Then, be tied to form and in salt product 2, add Abietyl modified maleic acid resin (acid number is 100, weight-average molecular weight is 1600, the MALKYD No.3002 processed of Huang Chuan chemical company) 20 mass parts at the rhodamine of 100 mass parts, mix with pressurization kneader.This mixing is material temperature to be set in to 120 DEG C carry out 30 minutes.After cooling, use mechanical crusher (the KRYPTRON KTM1 processed of Earthtechnica company type) to carry out Crushing of Ultrafine, the mean grain size that acquisition is tied to form salt product 2-1 as rhodamine is the particle of 10 μ m.
(rhodamine is tied to form the generation of salt product 3 and 3-1)
Rylnthracene sulfonin (molecular weight is 258) is added in the sodium hydroxide solution of 7 to 15 % by mole, this solution is stirred fully, obtained thus its sodium salt.This rylnthracene sulfonin sodium-salt aqueous solution is heated to after 70 to 90 DEG C, little by little drips wherein rhodamine B dyestuff (C.I. alkaline purple 1 0).Rhodamine B dyestuff also can use with the form of aqueous solution.After the dropping of rhodamine B dyestuff finishes, for it is reacted fully, this solution is stirred 40 to 60 minutes at 70 to 90 DEG C.The terminal of reaction is dropwise reaction liquid and ooze out moment of disappearance on filter paper.Ooze out judgement while disappearance and obtained salify product.Stirring while letting cool to room temperature, carrying out suction filtration, then wash.After washing, use dryer in residual salify product, to remove moisture from filter paper, obtained being tied to form salt product 3 as the rhodamine of the salify product of rhodamine B dyestuff and rylnthracene sulfonin.
Then, be tied to form and in salt product 3, add Abietyl modified maleic acid resin (acid number is 100, weight-average molecular weight is 1600, the MALKYD No.3002 processed of Huang Chuan chemical company) 20 mass parts at the rhodamine of 100 mass parts, mix with pressurization kneader.This mixing is material temperature to be set in to 120 DEG C carry out 30 minutes.After cooling, use mechanical crusher (the KRYPTRON KTM1 processed of Earthtechnica company type) to carry out Crushing of Ultrafine, the mean grain size that acquisition is tied to form salt product 3-1 as rhodamine is the particle of 10 μ m.
(rhodamine is tied to form the generation of salt product 4 and 4-1)
Phosphotungstic acid (molecular weight is 2880) is added in the sodium hydroxide solution of 7 to 15 % by mole, this solution is stirred fully, obtained thus its sodium salt.This sodium phosphotungstate brine solution is heated to after 70 to 90 DEG C, little by little drips rhodamine 6G CP dyestuff (C.I. alkali red 1:1).Rhodamine 6G CP dyestuff also can use with the form of aqueous solution.After the dropping of rhodamine 6G CP dyestuff finishes, for it is reacted fully, this solution is stirred 40 to 60 minutes at 70 to 90 DEG C.The terminal of reaction is dropwise reaction liquid and ooze out moment of disappearance on filter paper.Ooze out judgement while disappearance and obtained salify product.Stirring while letting cool to room temperature, carrying out suction filtration, then wash.After washing, use dryer in residual salify product, to remove moisture from filter paper, obtained being tied to form salt product 4 as the rhodamine of the salify product of rhodamine 6G CP dyestuff and phosphotungstic acid.
Then, be tied to form and in salt product 4, add Abietyl modified maleic acid resin (acid number is 100, weight-average molecular weight is 1600, the MALKYD No.3002 processed of Huang Chuan chemical company) 20 mass parts at the rhodamine of 100 mass parts, mix with pressurization kneader.This mixing is material temperature to be set in to 120 DEG C carry out 30 minutes.After cooling, use mechanical crusher (the KRYPTRON KTM1 processed of Earthtechnica company type) to carry out Crushing of Ultrafine, the mean grain size that acquisition is tied to form salt product 4-1 as rhodamine is the particle of 10 μ m.
(rhodamine is tied to form the generation of salt product 5 and 5-1)
Tartrazines (edible yellow No. 4: C.I. acid yellow 23) (molecular weight is 534) is added in the sodium hydroxide solution of 7 to 15 % by mole, this solution is stirred fully, obtained thus its sodium salt.This tartrazines sodium-salt aqueous solution is heated to after 70 to 90 DEG C, little by little drips wherein rhodamine 6G CP dyestuff (C.I. alkali red 1:1).Rhodamine 6G CP dyestuff also can use with the form of aqueous solution.After the dropping of rhodamine 6G CP dyestuff finishes, for it is reacted fully, this solution is stirred 40 to 60 minutes at 70 to 90 DEG C.The terminal of reaction is dropwise reaction liquid and ooze out moment of disappearance on filter paper.Ooze out judgement while disappearance and obtained salify product.Stirring while letting cool to room temperature, carrying out suction filtration, then wash.After washing, use dryer in residual salify product, to remove moisture from filter paper, obtained being tied to form salt product 5 as the rhodamine of the salify product of rhodamine 6G CP dyestuff and tartrazines.
Then, be tied to form and in salt product 5, add Abietyl modified maleic acid resin (acid number is 100, weight-average molecular weight is 1600, the MALKYD No.3002 processed of Huang Chuan chemical company) 20 mass parts at the rhodamine of 100 mass parts, mix with pressurization kneader.This mixing is material temperature to be set in to 120 DEG C carry out 30 minutes.After cooling, use mechanical crusher (the KRYPTRON KTM1 processed of Earthtechnica company type) to carry out Crushing of Ultrafine, the mean grain size that acquisition is tied to form salt product 5-1 as rhodamine is the particle of 10 μ m.
(rhodamine is tied to form the generation of salt product 10 and 10-1)
2-amino-1-naphthalene sulfonic aicd (tobias acid) (molecular weight is 223) is added in the sodium hydroxide solution of 9 % by mole, this solution is stirred fully, obtained thus its sodium salt.This 2-amino-1-naphthalene sulfonic aicd (tobias acid) sodium-salt aqueous solution is heated to after 85 DEG C, little by little drips rhodamine 6G CP dyestuff (C.I. alkali red 1:1).Rhodamine 6G CP dyestuff also can use with the form of aqueous solution.After the dropping of rhodamine 6G CP dyestuff finishes, for it is reacted fully, at 85 DEG C, stir 55 minutes.The terminal of reaction is dropwise reaction liquid and ooze out moment of disappearance on filter paper.Ooze out judgement while disappearance and obtained salify product.Stirring while letting cool to room temperature, carrying out suction filtration, then wash.After washing, use dryer in residual salify product, to remove moisture from filter paper, obtained being tied to form salt product 10 as the rhodamine of the salify product of rhodamine 6G CP dyestuff and 2-amino-1-naphthalene sulfonic aicd (tobias acid).
Then, be tied to form and in salt product 10, add Abietyl modified maleic acid resin (acid number is 100, weight-average molecular weight is 1600, the MALKYDNo.3002 processed of Huang Chuan chemical company) 20 mass parts at the rhodamine of 100 mass parts, mix with pressurization kneader.This mixing is material temperature to be set in to 120 DEG C carry out 30 minutes.After cooling, use mechanical crusher (the KRYPTRON KTM1 processed of Earthtechnica company type) to carry out Crushing of Ultrafine, the mean grain size that acquisition is tied to form salt product 10-1 as rhodamine is the particle of 10 μ m.
(triarylmethane is tied to form the generation of salt product 1 and 1-1)
By 2,8-diaminostilbene-naphthols-5,7-disulfonic acid (molecular weight is 334) adds in the sodium hydroxide solution of 7 to 15 % by mole, and this solution is stirred fully, has obtained thus its sodium salt.By this 2,8-diaminostilbene-naphthols-5,7-sodium disulfonate brine solution is heated to after 70 to 90 DEG C, little by little drips wherein Victoria's ethereal blue dyestuff (C.I. Blue 7).Victoria's ethereal blue dyestuff also can use with the form of aqueous solution.After the dropping of Victoria's ethereal blue dyestuff finishes, for it is reacted fully, this solution is stirred 40 to 60 minutes at 70 to 90 DEG C.The terminal of reaction is dropwise reaction liquid and ooze out moment of disappearance on filter paper.Ooze out judgement while disappearance and obtained salify product.Stirring while letting cool to room temperature, carrying out suction filtration, then wash.After washing, use dryer in residual salify product, to remove moisture from filter paper, obtained as Victoria's ethereal blue dyestuff and 2,8-diaminostilbene-naphthols-5, the triarylmethane of the salify product of 7-disulfonic acid is tied to form salt product 1.
Then, be tied to form and in salt product 1, add Abietyl modified maleic acid resin (acid number is 130, weight-average molecular weight is 1000, the MALKYD No.32 processed of Huang Chuan chemical company) 20 mass parts at the triarylmethane of 100 mass parts, mix with pressurization kneader.This mixing is material temperature to be set in to 120 DEG C carry out 30 minutes.After cooling, use mechanical crusher (the KRYPTRON KTM1 processed of Earthtechnica company type) to carry out Crushing of Ultrafine, the mean grain size that acquisition is tied to form salt product 1-1 as triarylmethane is the particle of 10 μ m.
(triarylmethane is tied to form the generation of salt product 2 and 2-1)
By naphthalidine-3,6,8-trisulfonic acid (Koch's acid) (molecular weight is 383) adds in the sodium hydroxide solution of 7 to 15 % by mole, and this solution is stirred fully, has obtained thus its sodium salt.By these naphthalidine-3,6,8-trisulfonic acid (Koch's acid) sodium-salt aqueous solution is heated to after 70 to 90 DEG C, little by little drips peacock green dyestuff (C.I. Viride Nitens 4).Peacock green dyestuff also can use with the form of aqueous solution.After the dropping of peacock green dyestuff finishes, for it is reacted fully, this solution is stirred 40 to 60 minutes at 70 to 90 DEG C.The terminal of reaction is dropwise reaction liquid and ooze out moment of disappearance on filter paper.Ooze out judgement while disappearance and obtained salify product.Stirring while letting cool to room temperature, carrying out suction filtration, then wash.After washing, use dryer in residual salify product, to remove moisture from filter paper, obtained as peacock green dyestuff and naphthalidine-3, the triarylmethane of the salify product of 6,8-trisulfonic acid (Koch's acid) is tied to form salt product 2.
Then, be tied to form and in salt product 2, add Abietyl modified maleic acid resin (acid number is 200, weight-average molecular weight is 750, the MALKYD No.31 processed of Huang Chuan chemical company) 20 mass parts at the triarylmethane of 100 mass parts, mix with pressurization kneader.This mixing is material temperature to be set in to 120 DEG C carry out 30 minutes.After cooling, use mechanical crusher (the KRYPTRON KTM1 processed of Earthtechnica company type) to carry out Crushing of Ultrafine, the mean grain size that acquisition is tied to form salt product 2-1 as triarylmethane is the particle of 10 μ m.
(triarylmethane is tied to form the generation of salt product 10 and 10-1)
2-amino-1-naphthalene sulfonic aicd (tobias acid) (molecular weight is 223) is added in the sodium hydroxide solution of 9 % by mole, this solution is stirred fully, obtained thus its sodium salt.This 2-amino-1-naphthalene sulfonic aicd (tobias acid) (molecular weight is 223) sodium-salt aqueous solution is heated to after 85 DEG C, little by little drips Victoria's ethereal blue dyestuff (C.I. Blue 7).Victoria's ethereal blue dyestuff also can use with the form of aqueous solution.After the dropping of Victoria's ethereal blue dyestuff finishes, for it is reacted fully, at 85 DEG C, stir 55 minutes.The terminal of reaction is dropwise reaction liquid and ooze out moment of disappearance on filter paper.Ooze out judgement while disappearance and obtained salify product.Stirring while letting cool to room temperature, carrying out suction filtration, then wash.After washing, use dryer in residual salify product, to remove moisture from filter paper, obtained being tied to form salt product 10 as the triarylmethane of the salify product of Victoria's ethereal blue dyestuff and 2-amino-1-naphthalene sulfonic aicd (tobias acid).
Then, be tied to form and in salt product 10, add Abietyl modified maleic acid resin (acid number is 200, weight-average molecular weight is 750, the MALKYD No.31 processed of Huang Chuan chemical company) 20 mass parts at the triarylmethane of 100 mass parts, mix with pressurization kneader.This mixing is material temperature to be set in to 120 DEG C carry out 30 minutes.After cooling, use mechanical crusher (the KRYPTRON KTM1 processed of Earthtechnica company type) to carry out Crushing of Ultrafine, the mean grain size that acquisition is tied to form salt product 10-1 as triarylmethane is the particle of 10 μ m.
(triarylmethane is tied to form the generation of salt product 11 and 11-1)
1-amino-5-naphthalene sulfonic acids (Laurent's acid) (molecular weight is 223) is added in the sodium hydroxide solution of 9 % by mole, this solution is stirred fully, obtained thus its sodium salt.This 1-amino-5-naphthalene sulfonic acids (Laurent's acid) (molecular weight is 223) sodium-salt aqueous solution is heated to after 85 DEG C, little by little drips Victoria's ethereal blue dyestuff (C.I. Blue 7).Victoria's ethereal blue dyestuff also can use with the form of aqueous solution.After the dropping of Victoria's ethereal blue dyestuff finishes, for it is reacted fully, at 85 DEG C, stir 55 minutes.The terminal of reaction is dropwise reaction liquid and ooze out moment of disappearance on filter paper.Ooze out judgement while disappearance and obtained salify product.Stirring while letting cool to room temperature, carrying out suction filtration, then wash.After washing, use dryer in residual salify product, to remove moisture from filter paper, obtained being tied to form salt product 11 as the triarylmethane of the salify product of Victoria's ethereal blue dyestuff and 1-amino-5-naphthalene sulfonic acids (Laurent's acid).
Then, be tied to form and in salt product 11, add Abietyl modified maleic acid resin (acid number is 200, weight-average molecular weight is 750, the MALKYD No.31 processed of Huang Chuan chemical company) 20 mass parts at the triarylmethane of 100 mass parts, mix with pressurization kneader.This mixing is material temperature to be set in to 120 DEG C carry out 30 minutes.After cooling, use mechanical crusher (the KRYPTRON KTM1 processed of Earthtechnica company type) to carry out Crushing of Ultrafine, the mean grain size that acquisition is tied to form salt product 11-1 as triarylmethane is the particle of 10 μ m.
(triarylmethane is tied to form the generation of salt product 12 and 12-1)
1-hydroxyl-4-naphthalene sulfonic acids (NW acid) (molecular weight is 224) is added in the sodium hydroxide solution of 9 % by mole, this solution is stirred fully, obtained thus its sodium salt.This 1-hydroxyl-4-naphthalene sulfonic acids (NW acid) (molecular weight is 224) sodium-salt aqueous solution is heated to after 85 DEG C, little by little drips Victoria's ethereal blue dyestuff (C.I. Blue 7).Victoria's ethereal blue dyestuff also can use with the form of aqueous solution.After the dropping of Victoria's ethereal blue dyestuff finishes, for it is reacted fully, at 85 DEG C, stir 55 minutes.The terminal of reaction is dropwise reaction liquid and ooze out moment of disappearance on filter paper.Ooze out judgement while disappearance and obtained salify product.Stirring while letting cool to room temperature, carrying out suction filtration, then wash.After washing, use dryer in residual salify product, to remove moisture from filter paper, obtained being tied to form salt product 12 as the triarylmethane of the salify product of Victoria's ethereal blue dyestuff and 1-hydroxyl-4-naphthalene sulfonic acids (NW acid).
Then, be tied to form and in salt product 12, add Abietyl modified maleic acid resin (acid number is 200, weight-average molecular weight is 750, the MALKYD No.31 processed of Huang Chuan chemical company) 20 mass parts at the triarylmethane of 100 mass parts, mix with pressurization kneader.This mixing is material temperature to be set in to 120 DEG C carry out 30 minutes.After cooling, use mechanical crusher (the KRYPTRON KTM1 processed of Earthtechnica company type) to carry out Crushing of Ultrafine, the mean grain size that acquisition is tied to form salt product 12-1 as triarylmethane is the particle of 10 μ m.
(flavine is tied to form the generation of salt product 1 and 1-1)
Rylnthracene sulfonin (molecular weight is 258) is added in the sodium hydroxide solution of 7 to 15 % by mole, this solution is stirred fully, obtained thus its sodium salt.This rylnthracene sulfonin sodium-salt aqueous solution is heated to after 70 to 90 DEG C, little by little drips flavine dyestuff (C.I. basic yellow 1).Flavine dyestuff also can use with the form of aqueous solution.After the dropping of flavine dyestuff finishes, for it is reacted fully, this solution is stirred 40 to 60 minutes at 70 to 90 DEG C.The terminal of reaction is dropwise reaction liquid and ooze out moment of disappearance on filter paper.Ooze out judgement while disappearance and obtained salify product.Stirring while letting cool to room temperature, carrying out suction filtration, then wash.After washing, use dryer in residual salify product, to remove moisture from filter paper, obtained being tied to form salt product 1 as the flavine of the salify product of flavine dyestuff and rylnthracene sulfonin.
Then, be tied to form and in salt product 1, add Abietyl modified maleic acid resin (acid number is 300, weight-average molecular weight is 450, the MALKYD No.33 processed of Huang Chuan chemical company) 20 mass parts at the flavine of 100 mass parts, mix with pressurization kneader.This mixing is material temperature to be set in to 120 DEG C carry out 30 minutes.After cooling, use mechanical crusher (the KRYPTRON KTM1 processed of Earthtechnica company type) to carry out Crushing of Ultrafine, the mean grain size that acquisition is tied to form salt product 1-1 as flavine is the particle of 10 μ m.
(methylene blue is tied to form the generation of salt product 1 and 1-1)
By 2,8-diaminostilbene-naphthols-5,7-disulfonic acid (molecular weight is 334) adds in the sodium hydroxide solution of 7 to 15 % by mole, and this solution is stirred fully, has obtained thus its sodium salt.By this 2,8-diaminostilbene-naphthols-5,7-sodium disulfonate brine solution is heated to after 70 to 90 DEG C, little by little drips methylene blue FZ dyestuff (C.I. alkali blue 9).Methylene blue FZ dyestuff also can use with the form of aqueous solution.After the dropping of methylene blue FZ dyestuff finishes, for it is reacted fully, this solution is stirred 40 to 60 minutes at 70 to 90 DEG C.The terminal of reaction is dropwise reaction liquid and ooze out moment of disappearance on filter paper.Ooze out judgement while disappearance and obtained salify product.Stirring while letting cool to room temperature, carrying out suction filtration, then wash.After washing, use dryer in residual salify product, to remove moisture from filter paper, obtained as methylene blue FZ dyestuff and 2,8-diaminostilbene-naphthols-5, the methylene blue of the salify product of 7-disulfonic acid is tied to form salt product 1.
Be tied to form and in salt product 1, add Abietyl modified maleic acid resin (acid number is 130, weight-average molecular weight is 1000, the MALKYD No.32 processed of Huang Chuan chemical company) 20 mass parts at the methylene blue of 100 mass parts, mix with pressurization kneader.This mixing is material temperature to be set in to 120 DEG C carry out 30 minutes.After cooling, use mechanical crusher (the KRYPTRON KTM1 processed of Earthtechnica company type) to carry out Crushing of Ultrafine, the mean grain size that acquisition is tied to form salt product 1-1 as methylene blue is the particle of 10 μ m.
(rhodamine is tied to form the generation of salt product 6 and 6-1)
3-hydroxy-2-naphthoic acid (molecular weight is 188) is added in the sodium hydroxide solution of 7 to 15 % by mole, this solution is stirred fully, obtained thus its sodium salt.This 3-hydroxy-2-naphthoic acid sodium-salt aqueous solution is heated to after 70 to 90 DEG C, little by little drips rhodamine 6G CP dyestuff (C.I. alkali red 1:1).Rhodamine 6G CP dyestuff also can use with the form of aqueous solution.After the dropping of rhodamine 6G CP dyestuff finishes, for it is reacted fully, this solution is stirred 40 to 60 minutes at 70 to 90 DEG C.The terminal of reaction is dropwise reaction liquid and ooze out moment of disappearance on filter paper.Ooze out judgement while disappearance and obtained salify product.Stirring while letting cool to room temperature, carrying out suction filtration, then wash.After washing, use dryer in residual salify product, to remove moisture from filter paper, obtained being tied to form salt product 6 as the rhodamine of the salify product of rhodamine 6G CP dyestuff and 3-hydroxy-2-naphthoic acid.
Then, be tied to form and in salt product 6, add Abietyl modified maleic acid resin (acid number is 130, weight-average molecular weight is 1000, the MALKYD No.32 processed of Huang Chuan chemical company) 20 mass parts at the rhodamine of 100 mass parts, mix with pressurization kneader.This mixing is material temperature to be set in to 120 DEG C carry out 30 minutes.After cooling, use mechanical crusher (the KRYPTRON KTM1 processed of Earthtechnica company type) to carry out Crushing of Ultrafine, the mean grain size that acquisition is tied to form salt product 6-1 as rhodamine is the particle of 10 μ m.
The manufacture method > of < rhodamine based compound
(generation of rhodamine based compound 1-1)
In rhodamine 6G CP dyestuff (C.I. alkali red 1:1) 100 mass parts, add Abietyl modified maleic acid resin (acid number is 35, weight-average molecular weight is 3600, the MALKYD No.8 processed of Huang Chuan chemical company) 50 mass parts, mix with pressurization kneader.This mixing is material temperature to be set in to 120 DEG C carry out 45 minutes.After cooling, use mechanical crusher (the KRYPTRON KTM1 processed of Earthtechnica company type) to carry out Crushing of Ultrafine, having obtained as the mean grain size of rhodamine based compound 1-1 is the particle of 10 μ m.
The manufacture method > of < miniaturization pigment
(generation of red micro pigment 1)
Using the C.I. paratonere 254 that as diketopyrrolo-pyrrole is red pigment, (Ciba Japan company system " IRGAZIN RED 2030 ", specific surface area are 65m 2360 parts of/g) 200 parts, 1400 parts, sodium chloride and diethylene glycols pack in 1 gallon of kneader of stainless steel (aboveground making is made), at 80 DEG C mixing 6 hours.Then, this mixing thing is put in the warm water of 8 liters, be heated to 80 DEG C while stir 2 hours and make pulp-like.Repeatedly filter and wash to remove after sodium chloride and diethylene glycol, at 85 DEG C, dry diel, obtains the red micro pigment 1 of 190 parts.The specific surface area of red micro pigment 1 is 80m 2/ g.
(generation of green micro pigment 1)
Using the C.I. pigment green 36 that as phthalocyanine is viridine green, (Toyo Ink Manufacturing Co., Ltd.'s system " LIONOL GREEN 6YK ", specific surface area are 60m 2360 parts of/g) 200 parts, 1400 parts, sodium chloride and diethylene glycols are encased in 1 gallon of kneader of stainless steel (aboveground making is made), at 80 DEG C mixing 6 hours.Then, this mixing thing is dropped in the warm water of 8 liters, be heated to 80 DEG C while stir 2 hours and make pulp-like.Repeatedly filter and wash to remove after sodium chloride and diethylene glycol, at 85 DEG C, dry diel, obtains the green micro pigment 1 of 190 parts.The specific surface area of green micro pigment 1 is 75m 2/ g.
(generation of yellow micro pigment 1)
Using the C.I. pigment yellow 150 that as nickel complex is yellow uitramarine, (Lanxess company system " E-4GN ", specific surface area are 100m 2360 parts of/g) 200 parts, 1400 parts, sodium chloride and diethylene glycols are encased in 1 gallon of kneader of stainless steel (aboveground making is made), at 80 DEG C mixing 6 hours.Then, this mixing thing is dropped in the warm water of 8 liters, be heated to 80 DEG C while stir 2 hours and make pulp-like.Repeatedly filter and wash to remove after sodium chloride and diethylene glycol, at 85 DEG C, dry diel, obtains the yellow micro pigment 1 of 190 parts.The specific surface area of yellow micro pigment 1 is 130m 2/ g.
(generation of blue micro pigment 1)
C.I. pigment blue 15 using as phthalocyanine being blue pigment: 6 (Toyo Ink Manufacturing Co., Ltd.'s system " LIONOL BLUE ES ", specific surface area are 60m 2360 parts of/g) 200 parts, 1400 parts, sodium chloride and diethylene glycols are encased in 1 gallon of kneader of stainless steel (aboveground making is made), at 80 DEG C mixing 6 hours.Then, this mixing thing is dropped in the warm water of 8 liters, be heated to 80 DEG C while stir 2 hours and make pulp-like.Repeatedly filter and wash to remove after sodium chloride and diethylene glycol, at 85 DEG C, dry diel, obtains the blue micro pigment 1 of 190 parts.The specific surface area of blue micro pigment 1 is 80m 2/ g.
(generation of purple micro pigment 1)
Using the C.I. pigment Violet 23 that as dioxazine is violet pigment, (Toyo Ink Manufacturing Co., Ltd.'s system " LIONOGEN VIOLET RL ", specific surface area are 75m 2360 parts of/g) 200 parts, 1400 parts, sodium chloride and diethylene glycols are encased in 1 gallon of kneader of stainless steel (aboveground making is made), at 80 DEG C mixing 6 hours.Then, this mixing thing is dropped in the warm water of 8 liters, be heated to 80 DEG C while stir 2 hours and make pulp-like.Repeatedly filter and wash to remove after sodium chloride and diethylene glycol, at 85 DEG C, dry diel, obtains the purple micro pigment 1 of 190 parts.The specific surface area of purple micro pigment 1 is 95m 2/ g.
[embodiment 1 to 16 and comparative example 1 to 7]
(embodiment 1: color composition for color filter (D-1))
By after following potpourri uniform stirring, use the zirconia bead that diameter is 0.5mm, utilize Eiger grinding machine (Eiger Japan company system " Mini Model M-250MKII ") to carry out 5 hours dispersion treatment.Then, dispersion liquid is filtered with the filter of 5.0 μ m, obtain color composition for color filter (D-1).
Rhodamine is tied to form salt product 1:11.0 part
Acrylic resin soln 1:40.0 part
Propylene glycol methyl ether acetate (PGMAC): 48.0 parts
Resin type spreading agent (EFKA4300): 1.0 parts
(embodiment 2 to 16 and comparative example 1 to 7: color composition for color filter (D-2) is to (D-23))
Replace with the colorant shown in table 1 except rhodamine being tied to form to salt product 1, similarly operate with the coloured composition (D-1) of embodiment 1, prepared color composition for color filter (D-2) to (D-23).
Table 1
Coloured composition Colorant
Embodiment 1 D-1 Rhodamine is tied to form salt product 1
Embodiment 2 D-2 Rhodamine is tied to form salt product 1-1
Embodiment 3 D-3 Rhodamine is tied to form salt product 1-2
Embodiment 4 D-4 Rhodamine is tied to form salt product 1-3
Embodiment 5 D-5 Rhodamine is tied to form salt product 2-1
Embodiment 6 D-6 Rhodamine is tied to form salt product 3-1
Embodiment 7 D-7 Rhodamine is tied to form salt product 4-1
Embodiment 8 D-8 Rhodamine is tied to form salt product 5-1
Embodiment 9 D-9 Triarylmethane is tied to form salt product 1-1
Embodiment 10 D-10 Triarylmethane is tied to form salt product 2-1
Embodiment 11 D-11 Flavine is tied to form salt product 1-1
Embodiment 12 D-12 Methylene blue is tied to form salt product 1-1
Comparative example 1 D-13 Rhodamine is tied to form salt product 6-1
Comparative example 2 D-14 Rhodamine based compound 1-1
Comparative example 3 D-15 Red micro pigment 1
Comparative example 4 D-16 Green micro pigment 1
Comparative example 5 D-17 Yellow micro pigment 1
Comparative example 6 D-18 Blue micro pigment 1
Comparative example 7 D-19 Purple micro pigment 1
Embodiment 13 D-20 Rhodamine is tied to form salt product 10-1
Embodiment 14 D-21 Triarylmethane is tied to form salt product 10-1
Embodiment 15 D-22 Triarylmethane is tied to form salt product 11-1
Embodiment 16 D-23 Triarylmethane is tied to form salt product 12-1
[evaluation of coloured composition]
Carry out as follows evaluation and the heat-resistance test of coloured composition (D-1) to the color characteristics of (D-23).
(color characteristics and stable on heating evaluation method)
On glass substrate, be coated with each coloured composition (D-1) to (D-23) so that present the form and aspect shown in table 2 under illuminant-C, substrate is heated 20 minutes at 230 DEG C.Then, use microspectrophotometer (Olympus Optical Co., Ltd. system " OSP-SP200 ") to measure to the brightness Y of the substrate that is so formed with dyed layer.
Table 2
In addition, use microspectrophotometer (Olympus Optical Co., Ltd. system " OSP-SP200 ") to measure the aberration 1 (L* (1) under illuminant-C to being formed with the aforesaid substrate of dyed layer, a* (1), b* (1)).Then, the aforesaid substrate that is formed with dyed layer, for the heat resistant test that heats 1 hour in baking oven at 250 DEG C, is then measured to the aberration 2 (L* (2), a* (2), b* (2)) under illuminant-C.
Use these values of chromatism, calculate chromatic aberration rate Δ Eab* by following calculating formula.Then, press the thermotolerance of following 4 grade evaluation films according to this chromatic aberration rate Δ Eab*.
&Delta;Eab * = [ L * ( 2 ) - L * ( 1 ) ] 2 + [ a * ( 2 ) - a * ( 1 ) ] 2 + [ b * ( 2 ) - b * ( 1 ) ] 2
◎: Δ Eab* is lower than 1.5
Zero: Δ Eab* is more than 1.5 but lower than 3.0
△: Δ Eab* is more than 3.0 but lower than 5.0
×: Δ Eab* is more than 5.0
Color characteristics and stable on heating evaluation result are shown in table 3.
Table 3
(color characteristics and stable on heating evaluation result)
The coloured composition (D-1) to (D-12) that contains salify product in use and (D-20) to (D-23) during as colorant, with use the coloured composition (D-15) to (D-19) that only contains pigment as compared with the situation of colorant, can obtain higher brightness Y.In the coloured composition (D-14) of comparative example 2 owing to having used not and the colorant of equilibrium compound (anion component) salify, therefore colour developing weak, there is no a colouring power, therefore result is that brightness is low.
In addition, be also the coloured composition (D-1) to (D-12) that contains salify product in use for thermotolerance and obtained good result during (D-20) to (D-23).While containing with use the coloured composition (D-1) to (D-4) that rhodamine is tied to form salt product 1 compared with the result of gained, using molecular weight in 400 to 12000 scope, when the Abietyl modified maleic acid resin of acid number in 100 to 300mgKOH/mg scope, realize the brightness substantially equal with other situation, and realized more excellent thermotolerance.
From the above results, the coloured composition that contains specific salify product is all being brought into play excellent performance aspect color characteristics and thermotolerance two.
[embodiment 17 to 46 and comparative example 8 to 12]
(embodiment 13: anticorrosive additive material (R-1))
By after following potpourri uniform stirring, with the filter filtration of 1.0 μ m, obtain alkali-developable anticorrosive additive material (R-1).
Coloured composition (D-8): 50.0 parts
Coloured composition (D-11): 10.0 parts
Acrylic resin soln 1:11.0 part
Trimethylolpropane triacrylate: 4.2 parts
(chemical company of Xin Zhong village system " NK ESTER ATMPT ")
Photoepolymerizationinitiater initiater (Ciba Japan company system " IRGACURE 907 "): 1.2 parts
Sensitizer (soil conservation ケ paddy chemical company system " EAB-F "): 0.4 part
Propylene glycol methyl ether acetate (PGMAC): 23.2 parts
(embodiment 17 to 46 and comparative example 8 to 12: anticorrosive additive material (R-2) is to (R-35))
Coloured composition is replaced to the coloured composition shown in table 4 and change as shown in table 4 its use level, similarly operate with anticorrosive additive material (R-1) in addition, obtain alkali-developable anticorrosive additive material (R-2) to (R-35).It should be noted that, when also with multiple coloured composition, when the entirety of anticorrosive additive material is made as to 100 parts, the total amount of coloured composition is 60 parts.
Table 4
[evaluation of anticorrosive additive material]
Carry out as follows evaluation and tolerance (thermotolerance, photostability and the solvent resistance) test of anticorrosive additive material (R-1) to the color characteristics of (R-35).
(evaluation of color characteristics)
Painting erosion resistant agent material on glass substrate.Specifically, the thickness that by red anticorrosive additive material (R-1) to (R-12), (R-27) to (R-29) and (R-32) reaches x=0.640, y=0.330 with the colourity under illuminant-C is coated with.The thickness that by green anticorrosive additive material (R-13 to 18) and (R-30) reaches x=0.300, y=0.600 with the colourity under illuminant-C is coated with.The thickness that by blue anticorrosive additive material (R-19) to (R-26), (R-31) and (R-33) reaches x=0.150, y=0.060 to (R-35) with the colourity under illuminant-C is coated with.Then, substrate is heated 20 minutes at 230 DEG C, on substrate, form thus dyed layer.Then, use microspectrophotometer (Olympus Optical Co., Ltd. system " OSP-SP200 ") to measure to the brightness Y of the substrate that is formed with dyed layer.Evaluation result is shown in table 5.
Table 5
To red anticorrosive additive material (R-1) to (R-12), (R-27) to (R-29) and (R-32) carry out in the steps below the test of tolerance (thermotolerance, photostability and solvent resistance).
(method of heat-resistance of film test)
Painting erosion resistant agent material on transparency carrier is so that dry coating reaches approximately 2.5 μ m, and across the mask with predetermined pattern, to this film, ultraviolet ray exposes.By this film spraying alkaline-based developer is removed to uncured portion, thereby form desirable pattern.Then, it is heated 1 hour in baking oven at 230 DEG C.After letting cool, use microspectrophotometer (Olympus Optical Co., Ltd. system " OSP-SP200 ") to measure the aberration 1 (L* (1), a* (1), b* (1)) of gained film under illuminant-C.Then,, for the heat resistant test that heats 1 hour in baking oven at 250 DEG C, be then determined at the aberration 2 (L* (2), a* (2), b* (2)) under illuminant-C.
Use these values of chromatism, calculate chromatic aberration rate Δ Eab* by following calculating formula.Then, press the thermotolerance of following 4 grade evaluation films according to chromatic aberration rate Δ Eab*.
&Delta;Eab * = [ L * ( 2 ) - L * ( 1 ) ] 2 + [ a * ( 2 ) - a * ( 1 ) ] 2 + [ b * ( 2 ) - b * ( 1 ) ] 2
◎: Δ Eab* is lower than 1.5
Zero: Δ Eab* is more than 1.5 but lower than 3.0
△: Δ Eab* is more than 3.0 but lower than 5.0
×: Δ Eab* is more than 5.0
(method of film light fastness test)
Make test substrate according to testing identical step with heat-resistance of film, use microspectrophotometer (Olympus Optical Co., Ltd. system " OSP-SP200 ") to measure the aberration 1 (L* (1) under illuminant-C, a* (1), b* (1)).Then substrate is put into light fastness test machine (TOYOSEIKI company system " SUNTEST CPS+ "), placed 500 hours.Take out after substrate, measure the aberration 2 (L* (2), a* (2), b* (2)) under illuminant-C.Use these values of chromatism, similarly calculate chromatic aberration rate Δ Eab* with heat-resistance of film test, evaluate the photostability of film according to the benchmark same with thermotolerance with 4 grades.
(method of film solvent resistance test)
Make test substrate according to the step identical with heat-resistance test, use microspectrophotometer (Olympus Optical Co., Ltd. system " OSP-SP200 ") to measure the aberration 1 (L* (1) under illuminant-C, a* (1), b* (1)).Then, substrate is immersed in 1-METHYLPYRROLIDONE to 30 minutes.Take out after substrate, measure the aberration 2 (L* (2), a* (2), b* (2)) under illuminant-C.Use these values of chromatism, similarly calculate chromatic aberration rate Δ Eab* with heat-resistance of film test, evaluate the solvent resistance of film according to the benchmark same with thermotolerance with 4 grades.
What tolerance (thermotolerance, photostability, solvent resistance) was tested the results are shown in table 6.
Table 6
(evaluation result of color characteristics and tolerance)
By red anticorrosive additive material (R-1) to (R-12), (R-27) to (R-29) and (R-32) result of gained compare, using anticorrosive additive material (R-1) to (R-12), (R-27) and (R-32) time, be only compared with the situation of anticorrosive additive material (R-29) of pigment with using colorant, brightness Y is higher value.For green anticorrosive additive material (R-13) to (R-18) and (R-18) also same, in the time of the anticorrosive additive material that uses colorant only to be formed by pigment, compared with the situation of the anticorrosive additive material that contains salify product with use colorant, brightness is lower.Similarly, for blue resist (R-19) to (R-26), (R-31) and (R-33) also same to (R-35), in the time of the anticorrosive additive material that uses colorant only to be formed by pigment, compared with the situation of the anticorrosive additive material that contains salify product with use colorant, brightness is lower.In addition, using anticorrosive additive material when (R-28), owing to having used not and the colorant of equilibrium compound (anion component) salify, therefore colour developing weak, there is no colouring power, thereby result is that brightness is low.
In addition, using anticorrosive additive material (R-1) to (R-12), (R-27) to (R-29) and (R-32) time, thermotolerance also obtained to good result.The result of anticorrosive additive material (R-3) to (R-6) gained is compared, use to comprise and contain molecular weight in 400 to 12000 scope, when the anticorrosive additive material (R-4) of the coloured composition (D-2) of the Abietyl modified maleic acid resin of acid number in 100 to 300mgKOH/mg scope, compared with using anticorrosive additive material (R-3), (R-5) and situation (R-6), more excellent brightness and thermotolerance are realized.Using anticorrosive additive material when (R-27), although realized good color characteristics, because the molecular weight of equilibrium compound used in salify is lower than 250, therefore tolerance is poor.In the time using anticorrosive additive material (R-28), although realized tolerance more excellent when ratio uses anticorrosive additive material (R-27), as previously mentioned, brightness is low value.In addition, while using anticorrosive additive material (R-29), although realized good tolerance, brightness is low, color characteristics is poor.
(making of color filter)
On glass substrate, form the black matrix" as light-shielding pattern, then utilize spin coater to be coated with red anticorrosive additive material (anticorrosive additive material (R-1)).The thickness that red anticorrosive additive material reaches x=0.640, y=0.330 with the colourity under illuminant-C is coated with.To this film across ultra high pressure mercury light irradiation 300mJ/cm for photomask 2ultraviolet ray.Then, the spray development by this film for the alkaline-based developer in being made up of the aqueous sodium carbonate of 0.2 quality %, removes unexposed portion, and washs with ion exchange water.Then, this substrate is heated 20 minutes at 230 DEG C, form red filter joint.
Then,, on this substrate, utilize method same as described above to be coated with green anticorrosive additive material (anticorrosive additive material (R-13)).The thickness that green anticorrosive additive material reaches x=0.300, y=0.600 with the colourity under illuminant-C is coated with.This film, for saving above-mentioned identical exposure, development, wash and burn till with red filter, is formed to green filter joint.Then,, on this substrate, utilize method same as described above to be coated with blue anticorrosive additive material (anticorrosive additive material (R-19)).The thickness that blue anticorrosive additive material reaches x=0.150, y=0.06 with the colourity under illuminant-C is coated with.This film, for saving above-mentioned identical exposure, development, wash and burn till with red filter, is formed to blue electric-wave filter joint.As above operation, has obtained color filter.
As mentioned above, the salify product specifying by use, can obtain all color filters of excellence of color characteristics and thermotolerance, photostability and solvent resistance.
" test 2 "
Test 2 relates to the 2nd form.In test 2, will be designated as " embodiment " corresponding to the example of the 2nd form, other examples are designated as to " comparative example ".
The manufacture method > of < acrylic resin soln
(preparation of acrylic resin soln 1A)
On 4 mouthfuls of flasks of detachable, thermometer, cooling tube, nitrogen ingress pipe and stirring apparatus are installed, in this reaction vessel, are packed into 70.0 parts of cyclohexanone.Be warming up to 80 DEG C, in by reaction vessel, carry out after nitrogen displacement, with the times of 2 hours by dropper drip 13.3 parts of n-BMAs, 4.6 parts of 2-hydroxyethyl methacrylates, 4.3 parts of methacrylic acids, to 7.4 parts of cumenyl phenol ring oxidative ethane modification acrylates (Toagosei Co., Ltd's system " ARONIX M110 ") and 2, the potpourri that 2 '-azobis isobutyronitrile is 0.4 part.After dropping finishes, reaction is proceeded to 3 hours again, the solution of the acryl resin that to have obtained weight-average molecular weight be 26000.Be cooled to after room temperature the about 2g of sample tree lipoprotein solution.Within 20 minutes, make it dry by it is heated at 180 DEG C, measure nonvolatile component.According to the nonvolatile component content so obtaining, in previously synthetic resin solution, add propylene glycol methyl ether acetate (PGMAC) so that nonvolatile component reaches 20 quality %, thereby prepared acrylic resin soln 1A.
The manufacture method > of < salify product
(salify product 1A)
Having synthesized by Victoria's ethereal blue dyestuff (C.I. Blue 7) and xanthene according to following step is the salify product 1A that acid dyes (C.I. acid red 289) forms.
Be that acid dyes (C.I. acid red 289) adds in the sodium hydroxide solution of 7 to 15 % by mole by xanthene, this solution is stirred fully, obtained thus its sodium salt.Be that acid dyes sodium-salt aqueous solution is heated to after 70 to 90 DEG C by this xanthene, little by little drip wherein Victoria's ethereal blue dyestuff (C.I. Blue 7).Victoria's ethereal blue dyestuff also can use with the form of aqueous solution.After the dropping of Victoria's ethereal blue finishes, for it is reacted fully, at 70 to 90 DEG C, stir 40 to 60 minutes.The terminal of reaction is dropwise reaction liquid and ooze out moment of disappearance on filter paper.Ooze out judgement while disappearance and obtained salify product.Stirring while letting cool to room temperature, carrying out suction filtration, then wash.After washing, use dryer in residual salify product, to remove moisture from filter paper, having obtained as Victoria's ethereal blue dyestuff (C.I. Blue 7) and xanthene is the salify product 1A of the salify product of acid dyes (C.I. acid red 289).
(salify product 2A)
Having synthesized by Victoria's ethereal blue dyestuff (C.I. Blue 7) and rhodamine according to following step is the salify product 2A that acid dyes (C.I. acid red 52: acid rhodamine B) forms.
Be that acid dyes (C.I. acid red 52) adds in the sodium hydroxide solution of 7 to 15 % by mole by rhodamine, this solution is stirred fully, obtained thus its sodium salt.Be that acid dyes sodium-salt aqueous solution is heated to after 70 to 90 DEG C by this rhodamine, little by little drip Victoria's ethereal blue dyestuff (C.I. Blue 7).Victoria's ethereal blue dyestuff also can use with the form of aqueous solution.After the dropping of Victoria's ethereal blue finishes, for it is reacted fully, at 70 to 90 DEG C, stir 40 to 60 minutes.The terminal of reaction is dropwise reaction liquid and ooze out moment of disappearance on filter paper.Ooze out judgement while disappearance and obtained salify product.Stirring while letting cool to room temperature, carrying out suction filtration, then wash.After washing, use dryer in residual salify product, to remove moisture from filter paper, having obtained as Victoria's ethereal blue dyestuff (C.I. Blue 7) and rhodamine is the salify product 2A of the salify product of acid dyes (C.I. acid red 52).
(salify product 3A)
Having synthesized by Victoria's ethereal blue dyestuff (C.I. Blue 7) and xanthene according to following step is the salify product 3A that acid dyes (C.I. acid red 87: eosin) forms.
Be that acid dyes (C.I. acid red 87) adds in the sodium hydroxide solution of 7 to 15 % by mole by xanthene, this solution is stirred fully, obtained thus its sodium salt.Be that acid dyes sodium-salt aqueous solution is heated to after 70 to 90 DEG C by this xanthene, little by little drip Victoria's ethereal blue dyestuff (C.I. Blue 7).Victoria's ethereal blue dyestuff also can use with the form of aqueous solution.After the dropping of Victoria's ethereal blue finishes, for it is reacted fully, at 70 to 90 DEG C, stir 40 to 60 minutes.The terminal of reaction is dropwise reaction liquid and ooze out moment of disappearance on filter paper.Ooze out judgement while disappearance and obtained salify product.Stirring while letting cool to room temperature, carrying out suction filtration, then wash.After washing, use dryer in residual salify product, to remove moisture from filter paper, having obtained as Victoria's ethereal blue dyestuff (C.I. Blue 7) and xanthene is the salify product 3A of the salify product of acid dyes (C.I. acid red 87).
(salify product 4A)
Having synthesized by Victoria's ethereal blue dyestuff (C.I. Blue 7) and xanthene according to following step is the salify product 4A that acid dyes (C.I. acid red 92: the red B of flame) forms.
Be that acid dyes (C.I. acid red 92) adds in the sodium hydroxide solution of 7 to 15 % by mole by xanthene, this solution is stirred fully, obtained thus its sodium salt.Be that acid dyes sodium-salt aqueous solution is heated to after 70 to 90 DEG C by this xanthene, little by little drip Victoria's ethereal blue dyestuff (C.I. Blue 7).Victoria's ethereal blue dyestuff also can use with the form of aqueous solution.After the dropping of Victoria's ethereal blue finishes, for it is reacted fully, at 70 to 90 DEG C, stir 40 to 60 minutes.The terminal of reaction is dropwise reaction liquid and ooze out moment of disappearance on filter paper.Ooze out judgement while disappearance and obtained salify product.Stirring while letting cool to room temperature, carrying out suction filtration, then wash.After washing, use dryer in residual salify product, to remove moisture from filter paper, having obtained as Victoria's ethereal blue dyestuff (C.I. Blue 7) and xanthene is the salify product 4A of the salify product of acid dyes (C.I. acid red 92).
(salify product 5A)
Having synthesized by rhodamine 6G dyestuff (C.I. alkali red 1:1) and triphenyl methane according to following step is the salify product 5A that acid dyes (C.I. Blue VRS) forms.
Be that acid dyes (C.I. Blue VRS) adds in the sodium hydroxide solution of 7 to 15 % by mole by triphenyl methane, this solution is stirred fully, obtained thus its sodium salt.Be that acid dyes sodium-salt aqueous solution is heated to after 70 to 90 DEG C by this triphenyl methane, little by little drip rhodamine 6G dyestuff (C.I. alkali red 1:1).Rhodamine 6G dyestuff also can use with the form of aqueous solution.After the dropping of rhodamine 6G finishes, for it is reacted fully, at 70 to 90 DEG C, stir 40 to 60 minutes.The terminal of reaction is dropwise reaction liquid and ooze out moment of disappearance on filter paper.Ooze out judgement while disappearance and obtained salify product.Stirring while letting cool to room temperature, carrying out suction filtration, then wash.After washing, use dryer in residual salify product, to remove moisture from filter paper, having obtained as rhodamine 6G dyestuff (C.I. alkali red 1:1) and triphenyl methane is the salify product 5A of the salify product of acid dyes (C.I. Blue VRS).
(salify product 6A)
Having synthesized by rhodamine 6G dyestuff (C.I. alkali red 1:1) and triphenyl methane according to following step is the salify product 6A that acid dyes (C.I. acid blue 9 3) forms.
Be that acid dyes (C.I. acid blue 9 3) adds in the sodium hydroxide solution of 7 to 15 % by mole by triphenyl methane, this solution is stirred fully, obtained thus its sodium salt.Be that acid dyes sodium-salt aqueous solution is heated to after 70 to 90 DEG C by this triphenyl methane, little by little drip rhodamine 6G dyestuff (C.I. alkali red 1:1).Rhodamine 6G dyestuff also can use with the form of aqueous solution.After the dropping of rhodamine 6G finishes, for it is reacted fully, at 70 to 90 DEG C, stir 40 to 60 minutes.The terminal of reaction is dropwise reaction liquid and ooze out moment of disappearance on filter paper.Ooze out judgement while disappearance and obtained salify product.Stirring while letting cool to room temperature, carrying out suction filtration, then wash.After washing, use dryer in residual salify product, to remove moisture from filter paper, having obtained as rhodamine 6G dyestuff (C.I. alkali red 1:1) and triphenyl methane is the salify product 6A of the salify product of acid dyes (C.I. acid blue 9 3).
(salify product 7A)
Having synthesized by rhodamine B dyestuff (C.I. alkaline purple 1 0) and triphenyl methane according to following step is the salify product 7A that acid dyes (C.I. Blue VRS) forms.
Be that acid dyes (C.I. Blue VRS) adds in the sodium hydroxide solution of 7 to 15 % by mole by triphenyl methane, this solution is stirred fully, obtained thus its sodium salt.Be that acid dyes sodium-salt aqueous solution is heated to after 70 to 90 DEG C by this triphenyl methane, little by little drip rhodamine B dyestuff (C.I. alkaline purple 1 0).Rhodamine B dyestuff also can use with the form of aqueous solution.After the dropping of rhodamine B finishes, for it is reacted fully, at 70 to 90 DEG C, stir 40 to 60 minutes.The terminal of reaction is dropwise reaction liquid and ooze out moment of disappearance on filter paper.Ooze out judgement while disappearance and obtained salify product.Stirring while letting cool to room temperature, carrying out suction filtration, then wash.After washing, use dryer in residual salify product, to remove moisture from filter paper, having obtained as rhodamine 6G dyestuff (C.I. alkali red 1:1) and triphenyl methane is the salify product 7A of the salify product of acid dyes (C.I. Blue VRS).
(salify product 8A and 9A)
Having synthesized by rhodamine 6G dyestuff (C.I. alkali red 1:1) and triphenyl methane according to following step is the salify product 8A that acid dyes (C.I. acid blue 3) forms.
Be that acid dyes (C.I. acid blue 3) adds in the sodium hydroxide solution of 7 to 15 % by mole by triphenyl methane, this solution is stirred fully, obtained thus its sodium salt.Be that acid dyes sodium-salt aqueous solution is heated to after 70 to 90 DEG C by this triphenyl methane, little by little drip rhodamine 6G dyestuff (C.I. alkali red 1:1).Rhodamine 6G dyestuff also can use with the form of aqueous solution.After the dropping of rhodamine 6G finishes, for it is reacted fully, at 70 to 90 DEG C, stir 40 to 60 minutes.The terminal of reaction is dropwise reaction liquid and ooze out moment of disappearance on filter paper.Ooze out judgement while disappearance and obtained salify product.Stirring while letting cool to room temperature, carrying out suction filtration, then wash.After washing, use dryer in residual salify product, to remove moisture from filter paper, having obtained as rhodamine 6G dyestuff (C.I. alkali red 1:1) and triphenyl methane is the salify product 8A of the salify product of acid dyes (C.I. acid blue 3).
Then, in the salify product 8A of 100 mass parts, add Abietyl modified maleic acid resin (acid number be 130, the MALKYD No.32 processed of Huang Chuan chemical company) 30 mass parts, mix with pressurization kneader.This mixing is material temperature to be set in to 120 DEG C carry out 30 minutes.After cooling, carry out Crushing of Ultrafine with jet-stream wind formula comminutor (Japanese Pneumatic industrial group IDS-2 type processed), obtaining is the particle of 10 μ m as the mean grain size of salify product 9A.
(salify product 10A)
Synthesized the salify product 10A being formed by Victoria's ethereal blue dyestuff (C.I. Blue 7) and 1-naphthalene sulfonic aicd according to following step.
1-naphthalene sulfonic aicd is added in the sodium hydroxide solution of 7 to 15 % by mole, this solution is stirred fully, obtained thus its sodium salt.This 1-naphthalene sulfonic aicd sodium-salt aqueous solution is heated to after 70 to 90 DEG C, little by little drips Victoria's ethereal blue dyestuff (C.I. Blue 7).Victoria's ethereal blue dyestuff also can use with the form of aqueous solution.After the dropping of Victoria's ethereal blue dyestuff finishes, for it is reacted fully, at 70 to 90 DEG C, stir 40 to 60 minutes.The terminal of reaction is dropwise reaction liquid and ooze out moment of disappearance on filter paper.Ooze out judgement while disappearance and obtained salify product.Stirring while letting cool to room temperature, carrying out suction filtration, then wash.After washing, use dryer in residual salify product, to remove moisture from filter paper, obtained the salify product 10A as the salify product of Victoria's ethereal blue dyestuff and 1-naphthalene sulfonic aicd.
(salify product 11A)
Synthesized the salify product 11A being formed by rhodamine 6G dyestuff (C.I. alkali red 1:1) and 1-naphthalene sulfonic aicd according to following step.
1-naphthalene sulfonic aicd is added in the sodium hydroxide solution of 7 to 15 % by mole, this solution is stirred fully, obtained thus its sodium salt.This 1-naphthalene sulfonic aicd sodium-salt aqueous solution is heated to after 70 to 90 DEG C, little by little drips rhodamine 6G dyestuff (C.I. alkali red 1:1).Rhodamine 6G dyestuff also can use with the form of aqueous solution.After the dropping of rhodamine 6G dyestuff finishes, for it is reacted fully, at 70 to 90 DEG C, stir 40 to 60 minutes.The terminal of reaction is dropwise reaction liquid and ooze out moment of disappearance on filter paper.Ooze out judgement while disappearance and obtained salify product.Stirring while letting cool to room temperature, carrying out suction filtration, then wash.After washing, use dryer in residual salify product, to remove moisture from filter paper, obtained the salify product 11A as the salify product of rhodamine 6G dyestuff and 1-naphthalene sulfonic aicd.
The manufacture method > of < miniaturization pigment
(generation of blue micro pigment 1A)
C.I. pigment blue 15 using as phthalocyanine being blue pigment: 6 (Toyo Ink Manufacturing Co., Ltd.'s system " LIONOL BLUE ES ", specific surface area are 60m 2360 parts of/g) 200 parts, 1400 parts, sodium chloride and diethylene glycols are encased in 1 gallon of kneader of stainless steel (aboveground making is made), at 80 DEG C mixing 6 hours.Then, this mixing thing is dropped in the warm water of 8 liters, be heated to 80 DEG C while stir 2 hours and make pulp-like.Repeatedly filter and wash to remove after sodium chloride and diethylene glycol, at 85 DEG C, dry diel, obtains the blue micro pigment 1A of 190 parts.The specific surface area of blue micro pigment 1A is 80m 2/ g.
(generation of purple micro pigment 1A)
Using the C.I. pigment Violet 23 that as dioxazine is violet pigment, (Toyo Ink Manufacturing Co., Ltd.'s system " LIONOGEN VIOLET RL ", specific surface area are 75m 2360 parts of/g) 200 parts, 1400 parts, sodium chloride and diethylene glycols are encased in 1 gallon of kneader of stainless steel (aboveground making is made), at 80 DEG C mixing 6 hours.Then, this mixing thing is dropped in the warm water of 8 liters, be heated to 80 DEG C while stir 2 hours and make pulp-like.Repeatedly filter and wash to remove after sodium chloride and diethylene glycol, at 85 DEG C, dry diel, obtains the purple micro pigment 1A of 190 parts.The specific surface area of purple micro pigment 1A is 95m 2/ g.
(generation of red micro pigment 1A)
To be that 360 parts of 200 parts of the C.I. paratoneres 254 (Ciba Japan company system " IRGAZIN RED 2030 "), 1400 parts, sodium chloride of red pigment and diethylene glycols are encased in 1 gallon of kneader of stainless steel (aboveground making is made) as diketopyrrolo-pyrrole, at 80 DEG C mixing 6 hours.Then, this mixing thing is dropped in the warm water of 8 liters, be heated to 80 DEG C while stir 2 hours and make pulp-like.Repeatedly filter and wash to remove after sodium chloride and diethylene glycol, at 85 DEG C, dry diel, obtains the red micro pigment 1A of 190 parts.
(generation of green micro pigment 1A)
To be that 360 parts of 200 parts of the C.I. pigment green 36s (Toyo Ink Manufacturing Co., Ltd.'s system " LIONOL GREEN 6YK "), 1400 parts, sodium chloride of viridine green and diethylene glycols are encased in 1 gallon of kneader of stainless steel (aboveground making is made) as phthalocyanine, at 80 DEG C mixing 6 hours.Then, this mixing thing is dropped in the warm water of 8 liters, be heated to 80 DEG C while stir 2 hours and make pulp-like.Repeatedly filter and wash to remove after sodium chloride and diethylene glycol, at 85 DEG C, dry diel, obtains the green micro pigment 1A of 190 parts.
(generation of yellow micro pigment 1A)
Using being that 250 parts of 500 parts of the C.I. pigment yellow 13s 9 (Ciba Japan company system " IRGAPHOR YELLOW 2R-CF "), 500 parts, sodium chloride of yellow uitramarine and diethylene glycols are encased in 1 gallon of kneader of stainless steel (aboveground making is made) as isoindoline, mixing 8 hours at 120 DEG C.Then, this mixing thing is put in the warm water of 5 liters, be heated to 70 DEG C while stir 1 hour and make pulp-like.Repeatedly filter and wash to remove after sodium chloride and diethylene glycol, at 80 DEG C, dry diel, obtains the yellow micro pigment 1A of 490 parts.
(generation of yellow micro pigment 2A)
To be that 360 parts of 200 parts of the C.I. pigment yellows 150 (Lanxess company system " E-4GN "), 1400 parts, sodium chloride of yellow uitramarine and diethylene glycols are encased in 1 gallon of kneader of stainless steel (aboveground making is made) as nickel complex, at 80 DEG C mixing 6 hours.Then, this mixing thing is dropped in the warm water of 8 liters, be heated to 80 DEG C while stir 2 hours and make pulp-like.Repeatedly filter and wash to remove after sodium chloride and diethylene glycol, at 85 DEG C, dry diel, obtains the yellow micro pigment 2A of 190 parts.
The manufacture method > of < pigment dispersion
(preparation of pigment dispersion (P-1A))
By after following potpourri uniform stirring, use the zirconia bead that diameter is 0.5mm, utilize Eiger grinding machine (Eiger Japan company system " Mini Model M-250MKII ") to carry out 5 hours dispersion treatment.Then, dispersion liquid is filtered with the filter of 5.0 μ m, obtain pigment dispersion (P-1A).
Blue micro pigment 1A:11.0 part
(C.I. pigment blue 15: 6)
Acrylic resin soln 1A:40.0 part
Propylene glycol methyl ether acetate (PGMAC): 48.0 parts
Resin type spreading agent: 1.0 parts
(Ciba Japan company system " EFKA4300 ")
(preparation of pigment dispersion (P-2A) to (P-6A))
Except blue micro pigment 1A is become the pigment shown in table 7, similarly operate with above-mentioned pigment dispersion (P-1A), prepare pigment dispersion (P-2A) to (P-6A).
Table 7
The manufacture method > of < redness and green anticorrosive additive material
(preparation of red anticorrosive additive material)
By after following potpourri uniform stirring, with the filter filtration of 1.0 μ m, obtain red anticorrosive additive material.
Pigment dispersion (P-3A): 50.0 parts
Pigment dispersion (P-4A): 10.0 parts
Acrylic resin soln 1A:11.0 part
Trimethylolpropane triacrylate: 4.2 parts
(chemical company of Xin Zhong village system " NK ESTER ATMPT ")
Photoepolymerizationinitiater initiater (Ciba Japan company system " IRGACURE 907 "): 1.2 parts
Sensitizer (soil conservation ケ paddy chemical company system " EAB-F "): 0.4 part
Ethylene glycol monomethyl ether acetate: 23.2 parts
(preparation of green anticorrosive additive material)
By after following potpourri uniform stirring, with the filter filtration of 1.0 μ m, obtain green anticorrosive additive material.
Pigment dispersion (P-5A): 45.0 parts
Pigment dispersion (P-6A): 15.0 parts
Acrylic resin soln 1A:11.0 part
Trimethylolpropane triacrylate: 4.2 parts
(chemical company of Xin Zhong village system " NK ESTER ATMPT ")
Photoepolymerizationinitiater initiater (Ciba Japan company system " IRGACURE 907 "): 1.2 parts
Sensitizer (soil conservation ケ paddy chemical company system " EAB-F "): 0.4 part
Ethylene glycol monomethyl ether acetate: 23.2 parts
[embodiment 47 to 55 and comparative example 13 to 16]
(embodiment 47: blue coloring composition for color filter (D-1A))
After following potpourri uniform stirring is mixed, use the zirconia bead that diameter is 0.5mm, utilize Eiger grinding machine (Eiger Japan company system " Mini Model M-250MKII ") to carry out 5 hours dispersion treatment.Then,, with the filter filtration of 5.0 μ m, obtain blue coloring composition for color filter (D-1A).
Salify product 1A:11.0 part
Acrylic resin soln 1A:40.0 part
Propylene glycol methyl ether acetate (PGMAC): 48.0 parts
Resin type spreading agent: 1.0 parts
(Ciba Japan company system " EFKA4300 ")
(embodiment 48 to 55 and comparative example 13 to 16: blue coloring composition for color filter (D-2A) is to (D-13A))
Except salify product 1A is become the colorant shown in table 8, similarly operate with blue coloring composition for color filter (D-1A), prepare blue coloring composition for color filter (D-2A) to (D-13A).
Table 8
Coloured composition Colorant
Embodiment 47 D-1A Salify product 1A
Embodiment 48 D-2A Salify product 2A
Embodiment 49 D-3A Salify product 3A
Embodiment 50 D-4A Salify product 4A
Embodiment 51 D-5A Salify product 5A
Embodiment 52 D-6A Salify product 6A
Embodiment 53 D-7A Salify product 7A
Embodiment 54 D-8A Salify product 8A
Embodiment 55 D-9A Salify product 9A
Comparative example 13 D-10A Salify product 10A
Comparative example 14 D-11A Salify product 11A
Comparative example 15 D-12A C.I. Blue VRS
Comparative example 16 D-13A C.I. acid red 289
[evaluation of blue coloring composition for color filter]
Carry out as follows the heat-resistance test of blue coloring composition for color filter (D-1A) to (D-13A).
(method of heat-resistance test)
The mode that reaches 2.0 μ m with thickness on glass substrate is coated with each coloured composition (D-1A) to (D-13A), and substrate is heated 20 minutes at 230 DEG C.To being formed with the aforesaid substrate of dyed layer, use microspectrophotometer (Olympus Optical Co., Ltd. system " OSP-SP200 ") to measure the aberration 1 (L* (1) under illuminant-C, a* (1), b* (1)).Then, the aforesaid substrate that is formed with dyed layer, for the heat resistant test that heats 1 hour in baking oven at 250 DEG C, is then determined to the aberration 2 (L* (2), a* (2), b* (2)) under illuminant-C.
Use these values of chromatism, calculate chromatic aberration rate Δ Eab* by following calculating formula, then, press the thermotolerance of following 4 grade evaluation films according to this chromatic aberration rate Δ Eab*.
&Delta;Eab * = [ L * ( 2 ) - L * ( 1 ) ] 2 + [ a * ( 2 ) - a * ( 1 ) ] 2 + [ b * ( 2 ) - b * ( 1 ) ] 2
◎: Δ Eab* is lower than 1.5
Zero: Δ Eab* is more than 1.5 but lower than 3.0
△: Δ Eab* is more than 3.0 but lower than 5.0
×: Δ Eab* is more than 5.0
Color characteristics and stable on heating evaluation result are shown in table 9.
Table 9
Coloured composition Thermotolerance
Embodiment 47 D-1A ○
Embodiment 48 D-2A ◎
Embodiment 49 D-3A ○
Embodiment 50 D-4A ○
Embodiment 51 D-5A ◎
Embodiment 52 D-6A ◎
Embodiment 53 D-7A ◎
Embodiment 54 D-8A ◎
Embodiment 55 D-9A ◎
Comparative example 13 D-10A ×
Comparative example 14 D-11A ×
Comparative example 15 D-12A ×
Comparative example 16 D-13A ×
(stable on heating evaluation result)
In the time that use contains specific salify product as the coloured composition (D-1A) to (D-9A) of colorant, obtain good result for thermotolerance.And, in the time using the salify product being obtained by rhodamine based dye, obtain good especially result.On the other hand, the salify product that contains dyestuff and colourless equilibrium composition in use or dyestuff are during as the coloured composition (D-10A) to (D-13A) of colorant, and chromatic aberration exceedes 5, and thermotolerance is relatively low.
From the above results, the coloured composition that contains specific salify product can be realized excellent performance aspect thermotolerance.
[embodiment 56 to 67 and comparative example 17 to 21]
(embodiment 56: anticorrosive additive material (R-1A))
By after following potpourri uniform stirring, with the filter filtration of 1.0 μ m, obtain anticorrosive additive material (R-1A).
Coloured composition (D-1A): 60.0 parts
Acrylic resin soln 1A:11.0 part
Trimethylolpropane triacrylate: 4.2 parts
(chemical company of Xin Zhong village system " NK ESTER ATMPT ")
Photoepolymerizationinitiater initiater (Ciba Japan company system " IRGACURE 907 "): 1.2 parts
Sensitizer (soil conservation ケ paddy chemical company system " EAB-F "): 0.4 part
Ethylene glycol monomethyl ether acetate: 23.2 parts
(embodiment 57 to 67 and comparative example 17 to 21: anticorrosive additive material (R-2A) is to (R-17A))
Change coloured composition into the coloured composition shown in table 10 or pigment dispersion, and change as shown in table 10 its use level, similarly operate with anticorrosive additive material (R-1A) in addition, obtained alkali-developable anticorrosive additive material (R-2A) to (R-17A).It should be noted that, in the anticorrosive additive material of a part, use pigment as colorant, in the time that the entirety of anticorrosive additive material is made as to 100 parts, the total amount of coloured composition and/or pigment dispersion is 60 parts.
Table 10
[evaluation of anticorrosive additive material]
Utilize following method to carry out evaluation and tolerance (thermotolerance, photostability and the solvent resistance) test of the color characteristics (brightness) of anticorrosive additive material (R-1A) to (R-17A).
(evaluation of color characteristics)
Painting erosion resistant agent material on glass substrate.Specifically, anticorrosive additive material (R-1A) to the thickness that (R-17A) reaches x=0.150, y=0.060 with the colourity under illuminant-C is coated with.These substrates are heated 20 minutes at 230 DEG C, on substrate, form thus dyed layer.Then, use microspectrophotometer (Olympus Optical Co., Ltd. system " OSP-SP200 ") to measure to the brightness Y of the substrate that is formed with dyed layer.
(method of heat-resistance of film test)
Painting erosion resistant agent material on transparency carrier is so that dry coating reaches approximately 2.5 μ m, and across the mask with predetermined pattern, to this film, ultraviolet ray exposes.By this film spraying alkaline-based developer is removed to uncured portion, form thus desirable pattern.Then, it is heated 1 hour in baking oven at 230 DEG C.After letting cool, use microspectrophotometer (Olympus Optical Co., Ltd. system " OSP-SP200 ") to measure the aberration 1 (L* (1), a* (1), b* (1)) of gained film under illuminant-C.Then,, for the heat resistant test that heats 1 hour in baking oven at 250 DEG C, be then determined at the aberration 2 (L* (2), a* (2), b* (2)) under illuminant-C.
Use these values of chromatism, calculate chromatic aberration rate Δ Eab* by following calculating formula.Then, press the thermotolerance of following 4 grade evaluation films according to chromatic aberration rate Δ Eab*.
&Delta;Eab * = [ L * ( 2 ) - L * ( 1 ) ] 2 + [ a * ( 2 ) - a * ( 1 ) ] 2 + [ b * ( 2 ) - b * ( 1 ) ] 2
◎: Δ Eab* is lower than 1.5
Zero: Δ Eab* is more than 1.5 but lower than 3.0
△: Δ Eab* is more than 3.0 but lower than 5.0
×: Δ Eab* is more than 5.0
(method of film light fastness test)
Make test substrate according to testing identical step with heat-resistance of film, use microspectrophotometer (Olympus Optical Co., Ltd. system " OSP-SP200 ") to measure the aberration 1 (L* (1) under illuminant-C, a* (1), b* (1)).Then, substrate is put into light fastness test machine (TOYOSEIKI company system " SUNTEST CPS+ "), place 500 hours.Take out after substrate, measure the aberration 2 (L* (2), a* (2), b* (2)) under illuminant-C.Use these values of chromatism, similarly calculate chromatic aberration rate Δ Eab* with heat-resistance of film test, evaluate the photostability of film according to the benchmark same with thermotolerance with 4 grades.
(method of film solvent resistance test)
Make test substrate according to the step identical with heat-resistance test, use microspectrophotometer (Olympus Optical Co., Ltd. system " OSP-SP200 ") to measure the aberration 1 (L* (1) under illuminant-C, a* (1), b* (1)).Then, substrate is immersed in 1-METHYLPYRROLIDONE to 30 minutes.Take out after substrate, measure the aberration 2 (L* (2), a* (2), b* (2)) under illuminant-C.Use these values of chromatism, similarly calculate chromatic aberration rate Δ Eab* with heat-resistance of film test, evaluate the solvent resistance of film according to the benchmark same with thermotolerance with 4 grades.
What tolerance (thermotolerance, photostability, solvent resistance) was tested the results are shown in table 11.
Table 11
(evaluation result of color characteristics and tolerance)
Contain salify product and dyestuff in use anticorrosive additive material (R-1A) to (R-15A) time, compared with using the situation of the anticorrosive additive material (R-17A) that is only made up of pigment of colorant, brightness Y becomes higher value.And in the time using anticorrosive additive material (R-9A), brightness is high especially.This can infer it is the surface process plastic resin treatment due to colorant, and the dispersiveness of colorant and dissolubility improve, thereby have obtained high brightness.
In addition, in the time using anticorrosive additive material (R-1A) to (R-12A), thermotolerance has also been obtained to good result.And, in the time that use utilizes the salify product that rhodamine based dye obtains, thermotolerance has been obtained to good especially result.
It should be noted that, even in the time of the anticorrosive additive material (R-17) that uses colorant only to be formed by pigment, thermotolerance has also been obtained to good result.On the other hand, the salify product that contains dyestuff and colourless equilibrium composition in use or dyestuff be during as the anticorrosive additive material (R-13A) to (R-16A) of colorant, and the variation of aberration exceedes 5, thermotolerance is relatively low.
From the above results, the anticorrosive additive material that contains specific salify product is all being brought into play excellent performance aspect color characteristics (brightness) and weatherability two.
[embodiment 68 to 79 and comparative example 22 to 26]
Make color filter by following method.
(embodiment 68: color filter (CF-1A))
On glass substrate, form the black matrix" as light-shielding pattern, then utilize spin coater to be coated with red anticorrosive additive material.The thickness that red anticorrosive additive material reaches x=0.640, y=0.330 with the colourity under illuminant-C is coated with.To this film across ultra high pressure mercury light irradiation 300mJ/cm for photomask 2ultraviolet ray.Then, the spray development by this film for the alkaline-based developer in being made up of the aqueous sodium carbonate of 0.2 quality %, removes unexposed portion, and washs with ion exchange water.Then, this substrate is heated 20 minutes at 230 DEG C, form red filter joint.
Then,, on this substrate, utilize method same as described above to be coated with green anticorrosive additive material.The thickness that green anticorrosive additive material reaches x=0.300, y=0.600 with the colourity under illuminant-C is coated with.This film, for saving above-mentioned identical exposure, development, wash and burn till with red filter, is formed to green filter joint.Then,, on this substrate, utilize method same as described above to be coated with blue anticorrosive additive material.The thickness that blue anticorrosive additive material reaches x=0.150, y=0.06 with the colourity under illuminant-C is coated with.This film, for saving above-mentioned identical exposure, development, wash and burn till with red filter, is formed to blue electric-wave filter joint.As above operation, has obtained color filter (CF-1A).
(making of liquid crystal indicator)
At the upper electrode being formed by indium tin oxide (ITO) that forms of color filter (CF-1A), form the oriented layer being formed by polyimide thereon.In addition, on a face of the glass substrate of preparing in addition, form tft array and pixel electrode, form the oriented layer being formed by polyimide thereon.
Then,, on the face that is provided with electrode of a glass substrate, use sealant to form the pattern of the frame shape with the path that the inner side of frame and outside are linked up.Then, these substrates are fit together in mode toward each other of electrode, the bead of sandwich next door in the situation that.
Then, in the inner space of the unit so obtaining by previous path injection liquid crystal composite.After seal path, on the two sides of unit, paste polaroid, thereby obtained display panels.
Then, combination of liquid crystals display panel and back light unit etc., thus complete liquid crystal indicator.
(embodiment 69 to 79 and comparative example 22 to 26: color filter (CF-2A) is to (CF-17A))
Except anticorrosive additive material being become the anticorrosive additive material shown in table 6, similarly operate with color filter (CF-1A) and above-mentioned liquid crystal indicator, made respectively color filter (CF-2A) to (CF-17A) and liquid crystal indicator.It should be noted that, the luminescent spectrum backlight using is shown in Fig. 1.
[evaluation of color filter (CF-1A) to (CF-17A)]
Make above-mentioned liquid crystal indicator color display, use microspectrophotometer (Olympus Optical Co., Ltd. system " OSP-SP200 ") to measure the brightness corresponding to the region of redness, green and blue electric-wave filter joint.Then obtained the brightness of white displays by these brightness.The results are shown in table 12.
Table 12
For the blue electric-wave filter joint of color filter (CF-17A), in such filter section, use the copper phthalocyanine all the time preferably using with the combination of dioxazine series pigments.On the other hand, for the blue electric-wave filter joint of color filter (CF-1A) to (CF-12A), use specific salify product.Color filter (CF-1A) to (CF-12A) and color filter (CF-17A) are compared, color filter (CF-1A) is in (CF-12A), blue and white for each, has obtained than the higher brightness of color filter (CF-17A).
In addition, for the blue electric-wave filter joint of color filter (CF-13A) to (CF-16A), use be the salify product of dyestuff and colourless equilibrium composition and the combination of dyestuff.Therefore,, although brightness is high, tolerance is relatively low.
Salify product as implied above, to specify by use, can obtain all blue electric-wave filter joints of excellence of color characteristics (brightness) and thermotolerance, photostability and solvent resistance.
" test 3 "
Test 3 relates to the 3rd form.In test 3, will be designated as " embodiment " corresponding to the example of the 3rd form, other examples are designated as to " comparative example ".
The manufacture method > of < acrylic resin soln
(preparation of acrylic resin soln 1B)
On 4 mouthfuls of flasks of detachable, thermometer, cooling tube, nitrogen ingress pipe and stirring apparatus are installed, in this reaction vessel, are packed into 70.0 parts of cyclohexanone.Be warming up to 80 DEG C, in by reaction vessel, carry out after nitrogen displacement, with the times of 2 hours by dropper drip 13.3 parts of n-BMAs, 4.6 parts of 2-hydroxyethyl methacrylates, 4.3 parts of methacrylic acids, to 7.4 parts of cumenyl phenol ring oxidative ethane modification acrylates (Toagosei Co., Ltd's system " ARONIX M110 ") and 2, the potpourri that 2 '-azobis isobutyronitrile is 0.4 part.After dropping finishes, reaction is proceeded to 3 hours again, obtain the solution of the acryl resin that weight-average molecular weight (Mw) is 26000.Be cooled to after room temperature the about 2g of sample tree lipoprotein solution.Within 20 minutes, make it dry by it is heated at 180 DEG C, measure nonvolatile component.According to the nonvolatile component content so obtaining, the mode that reaches 20 % by weight according to nonvolatile component in previously synthetic resin solution is added cyclohexanone, thereby has prepared acrylic resin soln 1B.
(preparation of acrylic resin soln 2B)
In 4 mouthfuls of flasks of detachable that thermometer, cooling tube, nitrogen ingress pipe, dropping pipe and stirring apparatus are installed, pack 207 parts of cyclohexanone into.Be warming up to 80 DEG C, in by reaction vessel, carry out after nitrogen displacement, drip 20 parts of methacrylic acids, potpourri to 1.33 parts of 20 parts of cumenyl phenol ring oxidative ethane modification acrylates (the ARONIX M110 processed of East Asia Synesis Company), 45 parts of methacrylic acid methyl, 8.5 parts of 2-hydroxyethyl methacrylates and 2,2 '-azobis isobutyronitriles by dropper with the times of 2 hours.After dropping finishes, reaction is proceeded to 3 hours again, obtained copolymer solution.
Then, stop the supply of nitrogen, with respect to this copolymer solution total amount, stir while inject dry air 1 hour.Then, be cooled to room temperature, at 70 DEG C, drip the potpourri of 26 parts of 6.5 parts of isocyanic acid 2-methacryloxy ethyl esters (the clear and Karenz MOI processed of electrician company), 0.08 part of dibutyl tin laurate and cyclohexanone with time of 3 hours.
Sample the about 2g of this resin solution, within 20 minutes, make it dry by heating at 180 DEG C, measure nonvolatile component.According to the nonvolatile component content so obtaining, in previously synthetic resin solution, add cyclohexanone so that nonvolatile component reaches 20 % by weight, thereby prepared acrylic resin soln 2B.It should be noted that, the weight-average molecular weight (Mw) of the contained acryl resin of this resin solution 2B is 18000.
(preparation of acrylic resin soln 3B)
In 4 mouthfuls of flasks of detachable that thermometer, cooling tube, nitrogen ingress pipe, dropping pipe and stirring apparatus are installed, pack 207 parts of cyclohexanone into.Be warming up to 80 DEG C, in by reaction vessel, carry out after nitrogen displacement, drip 20 parts of methacrylic acids, potpourri to 1.33 parts of 20 parts of cumenyl phenol ring oxidative ethane modification acrylates (the ARONIX M110 processed of East Asia Synesis Company), 45 parts of methacrylic acid methyl, 8.5 parts of glycerin monomethyl acrylic esters and 2,2 '-azobis isobutyronitriles by dropper with the times of 2 hours.After dropping finishes, reaction is proceeded to 3 hours again, obtained copolymer resin lipoprotein solution.
Then, stop nitrogen, with respect to this copolymer solution total amount, stir while inject dry air 1 hour.Then, be cooled to room temperature, at 70 DEG C, drip the potpourri of 26 parts of 6.5 parts of isocyanic acid 2-methacryloxy ethyl esters, 0.08 part of dibutyl tin laurate and cyclohexanone with time of 3 hours.
Sample the about 2g of this resin solution, within 20 minutes, make it dry by heating at 180 DEG C, measure nonvolatile component.According to the nonvolatile component content of acquisition like this, in previously synthetic resin solution, add cyclohexanone so that nonvolatile component reaches 20 % by weight, thereby prepared acrylic resin soln 3B.It should be noted that, the weight-average molecular weight (Mw) of the contained acryl resin of this resin solution 3B is 19000.
(preparation of acrylic resin soln 4B)
In 4 mouthfuls of flasks of detachable that thermometer, cooling tube, nitrogen ingress pipe, dropping pipe and stirring apparatus are installed, pack 370 parts of cyclohexanone into.Be warming up to 80 DEG C, in by reaction vessel, carry out after nitrogen displacement, drip the potpourri to 2.0 parts of 18 parts of cumenyl phenol ring oxidative ethane modification acrylates (the ARONIX M110 processed of East Asia Synesis Company), 10 parts of methacrylic acid benzyl esters, 18.2 parts of glycidyl methacrylate, 25 parts of methyl methacrylates and 2,2 '-azobis isobutyronitriles by dropper with the times of 2 hours.After dropping finishes, at 100 DEG C, react again 3 hours.Then, in this solution, add and make 1.0 parts of azobis isobutyronitriles be dissolved in 50 parts of solution that form of cyclohexanone, at 100 DEG C, react again 1 hour.Then, will be in reaction vessel by air displacement, in this container, drop into 0.5 part of 9.3 parts, acrylic acid (glycidyl 100%) and three (dimethylamino) phenol and 0.1 part of quinhydrones.At 120 DEG C, continue reaction 6 hours, reach at 0.5 o'clock at the acid number of solid constituent and finish reaction.Then, in the solution so obtaining, add 0.5 part of 19.5 parts of tetrabydrophthalic anhydrides (hydroxyl of generation 100%) and triethylamine, at 120 DEG C, react 3.5 hours, obtained the solution of acryl resin.
Be cooled to after room temperature, sample the about 2g of this solution, within 20 minutes, make it dry by heating at 180 DEG C, measure nonvolatile component.According to the nonvolatile component content of acquisition like this, in previously synthetic resin solution, add cyclohexanone so that nonvolatile component reaches 20 % by weight, thereby prepared acrylic resin soln 4B.It should be noted that, the weight-average molecular weight (Mw) of the contained acryl resin of this resin solution 4B is 19000.
The manufacture method > of < salify product
(salify product 1B)
Having synthesized by rhodamine 6G CP dyestuff (C.I. alkali red 1:1) and xanthene according to following step is the salify product 1B that acid dyes (C.I. acid red 289) forms.
Be that acid dyes (C.I. acid red 289) adds in the sodium hydroxide solution of 7 to 15 % by mole by xanthene, this solution is fully stirred.Then, this solution is heated to 70 to 90 DEG C, little by little drips wherein rhodamine 6G CP dyestuff (C.I. alkali red 1:1).Rhodamine 6G CP dyestuff also can use with the form of aqueous solution.After the dropping of rhodamine 6G CP dyestuff finishes, for it is reacted fully, at 70 to 90 DEG C, stir 40 to 60 minutes.The terminal of reaction is dropwise reaction liquid and ooze out moment of disappearance on filter paper.Ooze out judgement while disappearance and obtained salify product.Stirring while letting cool to room temperature, carrying out suction filtration, then wash.After washing, use dryer in residual salify product, to remove moisture from filter paper, having obtained as rhodamine 6G CP dyestuff (C.I. alkali red 1:1) and xanthene is the salify product 1B of the salify product of acid dyes (C.I. acid red 289).
(salify product 2B)
Synthesized the salify product 2B being formed by rhodamine 6G CP dyestuff (C.I. alkali red 1:1) and acid rhodamine (C.I. acid red 52) according to following step.
Acid rhodamine (C.I. acid red 52) is added in the sodium hydroxide solution of 7 to 15 % by mole, this solution is fully stirred.Then, this solution is heated to 70 to 90 DEG C, little by little drips wherein rhodamine 6G CP dyestuff (C.I. alkali red 1:1).Rhodamine 6G CP dyestuff also can use with the form of aqueous solution.After the dropping of rhodamine 6G CP dyestuff finishes, for it is reacted fully, at 70 to 90 DEG C, stir 40 to 60 minutes.The terminal of reaction is dropwise reaction liquid and ooze out moment of disappearance on filter paper.Ooze out judgement while disappearance and obtained salify product.Stirring while letting cool to room temperature, carrying out suction filtration, then wash.After washing, use dryer in residual salify product, to remove moisture from filter paper, obtained the salify product 2B as the salify product of rhodamine 6G CP dyestuff (C.I. alkali red 1:1) and acid rhodamine (C.I. acid red 52).
(salify product 3B)
Synthesized the salify product 3B being formed by rhodamine 6G CP dyestuff (C.I. alkali red 1:1) and eosin G (C.I. acid red 87) according to following step.
Eosin G (C.I. acid red 87) is added in the sodium hydroxide solution of 7 to 15 % by mole, this solution is fully stirred.Then, this solution is heated to 70 to 90 DEG C, little by little drips rhodamine 6G CP dyestuff (C.I. alkali red 1:1).Rhodamine 6G CP dyestuff also can use with the form of aqueous solution.After the dropping of rhodamine 6G CP dyestuff finishes, for it is reacted fully, at 70 to 90 DEG C, stir 40 to 60 minutes.The terminal of reaction is dropwise reaction liquid and ooze out moment of disappearance on filter paper.Ooze out judgement while disappearance and obtained salify product.Stirring while letting cool to room temperature, carrying out suction filtration, then wash.After washing, use dryer in residual salify product, to remove moisture from filter paper, obtained the salify product 3B as the salify product of rhodamine 6G CP dyestuff (C.I. alkali red 1:1) and eosin G (C.I. acid red 87).
(salify product 4B)
Synthesized the salify product 4B being formed by rhodamine 6G CP dyestuff (C.I. alkali red 1:1) and C.I. acid red 388 according to following step.
C.I. acid red 388 is added in the sodium hydroxide solution of 7 to 15 % by mole, this solution is fully stirred.Then, this solution is heated to 70 to 90 DEG C, little by little drips wherein rhodamine 6G CP dyestuff (C.I. alkali red 1:1).Rhodamine 6G CP dyestuff also can use with the form of aqueous solution.After the dropping of rhodamine 6G CP dyestuff finishes, for it is reacted fully, at 70 to 90 DEG C, stir 40 to 60 minutes.The terminal of reaction is dropwise reaction liquid and ooze out moment of disappearance on filter paper.Ooze out judgement while disappearance and obtained salify product.Stirring while letting cool to room temperature, carrying out suction filtration, then wash.After washing, use dryer in residual salify product, to remove moisture from filter paper, obtained the salify product 4B as the salify product of rhodamine 6G CP dyestuff (C.I. alkali red 1:1) and C.I. acid red 388.
(salify product 5B)
Having synthesized by rhodamine B dyestuff (C.I. alkaline purple 1 0) and xanthene according to following step is the salify product 5B that acid dyes (C.I. acid red 289) forms.
Be that acid dyes (C.I. acid red 289) adds in the sodium hydroxide solution of 7 to 15 % by mole by xanthene, this solution is fully stirred.Then, this solution is heated to 70 to 90 DEG C, little by little drips wherein rhodamine B dyestuff (C.I. alkaline purple 1 0).Rhodamine B dyestuff also can use with the form of aqueous solution.After the dropping of rhodamine B dyestuff finishes, for it is reacted fully, at 70 to 90 DEG C, stir 40 to 60 minutes.The terminal of reaction is dropwise reaction liquid and ooze out moment of disappearance on filter paper.Ooze out judgement while disappearance and obtained salify product.Stirring while letting cool to room temperature, carrying out suction filtration, then wash.After washing, use dryer in residual salify product, to remove moisture from filter paper, having obtained as rhodamine B dyestuff (C.I. alkaline purple 1 0) and xanthene is the salify product 5B of the salify product of acid dyes (C.I. acid red 289).
(salify product 6B)
Having synthesized by rhodamine B dyestuff (C.I. alkaline purple 1 0) and xanthene according to following step is the salify product 6B that acid dyes (the red PB:C.I. acid red 92 of acid flame) forms.
Red acid flame PB dyestuff (C.I. acid red 92) is added in the sodium hydroxide solution of 7 to 15 % by mole, this solution is fully stirred.Then, this solution is heated to 70 to 90 DEG C, little by little drips wherein rhodamine B dyestuff (C.I. alkaline purple 1 0).Rhodamine B dyestuff also can use with the form of aqueous solution.After the dropping of rhodamine B dyestuff finishes, for it is reacted fully, at 70 to 90 DEG C, stir 40 to 60 minutes.The terminal of reaction is dropwise reaction liquid and ooze out moment of disappearance on filter paper.Ooze out judgement while disappearance and obtained salify product.Stirring while letting cool to room temperature, carrying out suction filtration, then wash.After washing, use dryer in residual salify product, to remove moisture from filter paper, obtained the salify product 6B as the salify product of rhodamine B dyestuff (C.I. alkaline purple 1 0) and the red PB dyestuff of acid flame (C.I. acid red 92).
(salify product 7B)
Having synthesized by rhodamine G dyestuff (C.I. alkalescence red 8) and xanthene according to following step is the salify product 7B that acid dyes (C.I. acid red 289) forms.
Be that acid dyes (C.I. acid red 289) adds in the sodium hydroxide solution of 7 to 15 % by mole by xanthene, this solution is fully stirred.Then, this solution is heated to 70 to 90 DEG C, little by little drips wherein rhodamine G dyestuff (C.I. alkalescence red 8).Rhodamine G dyestuff also can use with the form of aqueous solution.After the dropping of rhodamine G dyestuff finishes, for it is reacted fully, at 70 to 90 DEG C, stir 40 to 60 minutes.The terminal of reaction is dropwise reaction liquid and ooze out moment of disappearance on filter paper.Ooze out judgement while disappearance and obtained salify product.Stirring while letting cool to room temperature, carrying out suction filtration, then wash.After washing, use dryer in residual salify product, to remove moisture from filter paper, having obtained as rhodamine G dyestuff (C.I. alkalescence red 8) and xanthene is the salify product 7B of the salify product of acid dyes (C.I. acid red 289).
(salify product 8B)
In the salify product 1B of 100 mass parts, add Abietyl modified maleic acid resin (acid number is the MALKYD No.32 processed of 130mgKOH/g, Huang Chuan chemical company) 30 weight portions, mix with pressurization kneader.This mixing is material temperature to be set in to 120 DEG C carry out 30 minutes.After cooling, use jet-stream wind formula comminutor (Japanese Pneumatic industrial group IDS-2 type processed) to carry out Crushing of Ultrafine, having obtained as the mean grain size of salify product 8B is the particle of 8 μ m.
The manufacture method > of < miniaturization pigment
(generation of red micro pigment 1B)
To be that 360 parts of 200 parts of the C.I. paratoneres 254 (Ciba Japan company system " IRGAZIN RED 2030 "), 1400 parts, sodium chloride of red pigment and diethylene glycols are encased in 1 gallon of kneader of stainless steel (aboveground making is made) as diketopyrrolo-pyrrole, at 80 DEG C mixing 6 hours.Then, this mixing thing is dropped in the warm water of 8 liters, be heated to 80 DEG C while stir 2 hours and make pulp-like.Repeatedly filter and wash to remove after sodium chloride and diethylene glycol, at 85 DEG C, dry diel, has obtained the red micro pigment of 190 parts.The specific surface area of red micro pigment is 65m 2/ g.
(generation of magenta micro pigment 1B)
To be encased in 1 gallon of kneader of stainless steel (aboveground making is made) as 360 parts of 200 parts of the C.I. pigment red 122s (Clariant company system " HOSTAPERM PINK E ") of quinacridone magenta pigment, 1400 parts, sodium chloride and diethylene glycols at 80 DEG C mixing 6 hours.Then, this mixing thing is dropped in the warm water of 8 liters, be heated to 80 DEG C while stir 2 hours and make pulp-like.Repeatedly filter and wash to remove after sodium chloride and diethylene glycol, at 85 DEG C, dry diel, has obtained the magenta micro pigment 1B of 190 parts.The specific surface area of magenta micro pigment 1B is 90m 2/ g.
(generation of green micro pigment 1B)
To be that 360 parts of 200 parts of the C.I. pigment green 36s (Toyo Ink Manufacturing Co., Ltd.'s system " LIONOL GREEN 6YK "), 1400 parts, sodium chloride of viridine green and diethylene glycols are encased in 1 gallon of kneader of stainless steel (aboveground making is made) as phthalocyanine, at 80 DEG C mixing 6 hours.Then, this mixing thing is dropped in the warm water of 8 liters, be heated to 80 DEG C while stir 2 hours and make pulp-like.Repeatedly filter and wash to remove after sodium chloride and diethylene glycol, at 85 DEG C, dry diel, has obtained the green micro pigment 1B of 190 parts.The specific surface area of green micro pigment 1B is 75m 2/ g.
(generation of blue micro pigment 1B)
C.I. pigment blue 15 using as phthalocyanine being blue pigment: 360 parts of 6 (Toyo Ink Manufacturing Co., Ltd.'s system " LIONOL BLUE ES ") 200 parts, 1400 parts, sodium chloride and diethylene glycols are encased in 1 gallon of kneader of stainless steel (aboveground making is made), at 80 DEG C mixing 6 hours.Then, this mixing thing is dropped in the warm water of 8 liters, be heated to 80 DEG C while stir 2 hours and make pulp-like.Repeatedly filter and wash to remove after sodium chloride and diethylene glycol, at 85 DEG C, dry diel, has obtained the blue micro pigment 1B of 190 parts.The specific surface area of blue micro pigment 1B is 80m 2/ g.
(generation of cyan micro pigment 1B)
C.I. pigment blue 15 using as phthalocyanine being green pigment: 360 parts of 3 (Toyo Ink Manufacturing Co., Ltd.'s system " LIONOL BLUE FG-7351 ") 200 parts, 1400 parts, sodium chloride and diethylene glycols are encased in 1 gallon of kneader of stainless steel (aboveground making is made), at 80 DEG C mixing 6 hours.Then, this mixing thing is dropped in the warm water of 8 liters, be heated to 80 DEG C while stir 2 hours and make pulp-like.Repeatedly filter and wash to remove after sodium chloride and diethylene glycol, at 85 DEG C, dry diel, has obtained the cyan micro pigment 1B of 190 parts.The specific surface area of cyan micro pigment 1B is 85m 2/ g.
(generation of yellow micro pigment 1B)
To be that 250 parts of 500 parts of the C.I. pigment yellow 13s 9 (Ciba Japan company system " IRGAPHOR YELLOW 2R-CF "), 500 parts, sodium chloride of yellow uitramarine and diethylene glycols are encased in 1 gallon of kneader of stainless steel (aboveground making is made) as isoindoline, at 120 DEG C mixing 8 hours.Then, this mixing thing is put in the warm water of 5 liters, be heated to 70 DEG C while stir 1 hour and make pulp-like.Repeatedly filter and wash to remove after sodium chloride and diethylene glycol, at 80 DEG C, dry diel, has obtained the yellow micro pigment 1B of 490 parts.The specific surface area of yellow micro pigment 1B is 80m 2/ g.
(generation of yellow micro pigment 2B)
To be that 360 parts of 200 parts of the C.I. pigment yellows 150 (Lanxess company system " E-4GN "), 1400 parts, sodium chloride of yellow uitramarine and diethylene glycols are encased in 1 gallon of kneader of stainless steel (aboveground making is made) as nickel complex, at 80 DEG C mixing 6 hours.Then, this mixing thing is dropped in the warm water of 8 liters, be heated to 80 DEG C while stir 2 hours and make pulp-like.Repeatedly filter and wash to remove after sodium chloride and diethylene glycol, at 85 DEG C, dry diel, has obtained the yellow micro pigment 2B of 190 parts.The specific surface area of yellow micro pigment 2B is 70m 2/ g.
(generation of purple micro pigment 1B)
To be that 360 parts of 200 parts of the C.I. pigment Violet 23s (Toyo Ink Manufacturing Co., Ltd.'s system " LIONOGEN VIOLET RL "), 1400 parts, sodium chloride of violet pigment and diethylene glycols are encased in 1 gallon of kneader of stainless steel (aboveground making is made) as dioxazine, at 80 DEG C mixing 6 hours.Then, this mixing thing is dropped in the warm water of 8 liters, be heated to 80 DEG C while stir 2 hours and make pulp-like.Repeatedly filter and wash to remove after sodium chloride and diethylene glycol, at 85 DEG C, dry diel, has obtained the purple micro pigment 1B of 190 parts.The specific surface area of purple micro pigment 1B is 95m 2/ g.
The manufacture method > of < pigment dispersion
(preparation of pigment dispersion (P-1B))
By after following potpourri uniform stirring, use the zirconia bead that diameter is 0.5mm, the dispersion treatment of utilizing Eiger grinding machine (Eiger Japan company system " Mini Model M-250MKII ") to carry out 5 hours.Then, dispersion liquid is filtered with the filter of 5.0 μ m, made pigment dispersion (P-1B).
Red micro pigment 1B:11.0 part
(C.I. paratonere 254)
Acrylic resin soln 1B:40.0 part
Propylene glycol methyl ether acetate (PGMAC): 48.0 parts
Resin type spreading agent: 1.0 parts
(Ciba Japan company system " EFKA4300 ")
(preparation of pigment dispersion (P-2B) to (P-8B))
Except red micro pigment 1B is changed to the pigment shown in table 13, similarly operate with above-mentioned pigment dispersion (P-1B), prepare pigment dispersion (P-2B) to (P-8B).
Table 13
The manufacture method > of < anticorrosive additive material
(preparation of red anticorrosive additive material)
By after following potpourri uniform stirring, with the filter filtration of 1.0 μ m, obtain red anticorrosive additive material.
Pigment dispersion (P-1B): 50.0 parts
Pigment dispersion (P-6B): 10.0 parts
Acrylic resin soln 1B:11.0 part
Trimethylolpropane triacrylate: 4.2 parts
(chemical company of Xin Zhong village system " NK ESTER ATMPT ")
Photoepolymerizationinitiater initiater (Ciba Japan company system " IRGACURE 907 "): 1.2 parts
Sensitizer (soil conservation ケ paddy chemical company system " EAB-F "): 0.4 part
Ethylene glycol monomethyl ether acetate: 23.2 parts
(preparation of green anticorrosive additive material)
By after following potpourri uniform stirring, with the filter filtration of 1.0 μ m, obtain green anticorrosive additive material.
Pigment dispersion (P-3B): 45.0 parts
Pigment dispersion (P-7B): 15.0 parts
Acrylic resin soln 1B:11.0 part
Trimethylolpropane triacrylate: 4.2 parts
(chemical company of Xin Zhong village system " NK ESTER ATMPT ")
Photoepolymerizationinitiater initiater (Ciba Japan company system " IRGACURE 907 "): 1.2 parts
Sensitizer (soil conservation ケ paddy chemical company system " EAB-F "): 0.4 part
Ethylene glycol monomethyl ether acetate: 23.2 parts
(preparation of cyan anticorrosive additive material)
By after following potpourri uniform stirring, with the filter filtration of 1.0 μ m, obtain cyan anticorrosive additive material.
Pigment dispersion (P-5B): 60.0 parts
Acrylic resin soln 1B:11.0 part
Trimethylolpropane triacrylate: 4.2 parts
(chemical company of Xin Zhong village system " NK ESTER ATMPT ")
Photoepolymerizationinitiater initiater (Ciba Japan company system " IRGACURE 907 "): 1.2 parts
Sensitizer (soil conservation ケ paddy chemical company system " EAB-F "): 0.4 part
Ethylene glycol monomethyl ether acetate: 23.2 parts
(preparation of yellow anticorrosive additive material)
By after following potpourri uniform stirring, with the filter filtration of 1.0 μ m, obtain yellow anticorrosive additive material.
Pigment dispersion (P-6B): 45.0 parts
Pigment dispersion (P-7B): 15.0 parts
Acrylic resin soln 1B:11.0 part
Trimethylolpropane triacrylate: 4.2 parts
(chemical company of Xin Zhong village system " NK ESTER ATMPT ")
Photoepolymerizationinitiater initiater (Ciba Japan company system " IRGACURE 907 "): 1.2 parts
Sensitizer (soil conservation ケ paddy chemical company system " EAB-F "): 0.4 part
Ethylene glycol monomethyl ether acetate: 23.2 parts
[embodiment 80 to 87 and comparative example 27 and 28]
(embodiment 80: color composition for color filter (D-1B))
By after following potpourri uniform stirring, use the zirconia bead that diameter is 0.5mm, the dispersion treatment of utilizing Eiger grinding machine (Eiger Japan company system " Mini Model M-250MKII ") to carry out 5 hours.Then, dispersion liquid is filtered with the filter of 5.0 μ m, obtained color composition for color filter (D-1B).
Salify product 1B:11.0 part
Acrylic resin soln 1B:40.0 part
Cyclohexanone: 48.0 parts
Resin type spreading agent: 1.0 parts
(Ciba Japan company system " EFKA4300 ")
(embodiment 81 to 87 and comparative example 27 and 28: color composition for color filter (D-2B) is to (D-10B))
Except salify product 1B is changed to the colorant shown in table 14, similarly operate with blue coloring composition for color filter (D-1B), prepare color composition for color filter (D-2B) to (D-10B).
Table 14
Coloured composition Colorant
Embodiment 80 D-1B Salify product 1B
Embodiment 81 D-2B Salify product 2B
Embodiment 82 D-3B Salify product 3B
Embodiment 83 D-4B Salify product 4B
Embodiment 84 D-5B Salify product 5B
Embodiment 85 D-6B Salify product 6B
Embodiment 86 D-7B Salify product 7B
Embodiment 87 D-8B Salify product 8B
Comparative example 27 D-9B C.I. Blue VRS
Comparative example 28 D-10B C.I. acid red 289
[evaluation of color composition for color filter]
Carry out the heat-resistance test of color composition for color filter (D-1B) to (D-10B) by the method same with test 2.Heat-resistance test the results are shown in table 15.
Table 15
Coloured composition Thermotolerance
Embodiment 80 D-1B ○
Embodiment 81 D-2B ○
Embodiment 82 D-3B ○
Embodiment 83 D-4B ○
Embodiment 84 D-5B ○
Embodiment 85 D-6B ○
Embodiment 86 D-7B ○
Embodiment 87 D-8B ◎
Comparative example 27 D-9B ×
Comparative example 28 D-10B ×
Contain specific salify product in use coloured composition (D-1B) to (D-8B) time, realized excellent thermotolerance.And, in the time that use has been carried out the coloured composition (D-8B) of the colorant of processing containing useful Abietyl modified maleic acid resin, realize excellent especially performance.On the other hand, in the time that use contains dyestuff as the coloured composition (D-9B) to (D-10B) of colorant, colourity change exceed 5, thermotolerance is low.
From the above results, the coloured composition that contains specific salify product can be realized excellent performance aspect thermotolerance.
[embodiment 88 to 108 and comparative example 29 to 32]
(embodiment 88: anticorrosive additive material (R-1B))
By after following potpourri uniform stirring, with the filter filtration of 1.0 μ m, obtain anticorrosive additive material (R-1B).
Coloured composition (D-1B): 10.0 parts
Pigment dispersion (P-4B): 50.0 parts
Acrylic resin soln 1B:11.0 part
Trimethylolpropane triacrylate: 4.2 parts
(chemical company of Xin Zhong village system " NK ESTER ATMPT ")
Photoepolymerizationinitiater initiater (Ciba Japan company system " IRGACURE 907 "): 1.2 parts
Sensitizer (soil conservation ケ paddy chemical company system " EAB-F "): 0.4 part
Ethylene glycol monomethyl ether acetate: 23.2 parts
(embodiment 89 to 108 and comparative example 29 to 32: anticorrosive additive material (R-2B) is to (R-25B))
Coloured composition (D-1B) and pigment dispersion (P-4B) are replaced to the coloured composition shown in table 16 or pigment dispersion, and change shown in table 16 its use level, similarly operate with anticorrosive additive material (R-1B) in addition, obtained alkali-developable anticorrosive additive material (R-2B) to (R-12B), (R-24B) to (R-26B) and (R-23B) to (R-25B).It should be noted that, in the anticorrosive additive material of a part, also with coloured composition and pigment dispersion, in the time that the entirety of anticorrosive additive material is made as to 100 parts, the total amount of coloured composition and/or pigment dispersion is 60 parts.
In addition, except acrylic resin soln 1B is replaced with acrylic resin soln 2B to 4B, similarly operate with anticorrosive additive material (R-1B), obtained respectively alkali-developable anticorrosive additive material (R-13B) to (R-15B).In addition, except acrylic resin soln 1B is replaced with acrylic resin soln 2B to 4B, similarly operate with anticorrosive additive material (R-16B), obtained respectively alkali-developable anticorrosive additive material (R-19B) to (R-21B).
Table 16
[evaluation of anticorrosive additive material (R-1B) to (R-25B)]
Carry out evaluation and tolerance (thermotolerance, photostability and the solvent resistance) test of the color characteristics (brightness) of anticorrosive additive material (R-1B) to (R-25B) by following method.
(evaluation of color characteristics)
Painting erosion resistant agent material on glass substrate.Specifically, the thickness that blue anticorrosive additive material reaches y=0.06 with the colourity under illuminant-C is coated with.The thickness that magenta anticorrosive additive material reaches x=0.348 with the colourity under illuminant-C is coated with.By these substrates are heated 20 minutes at 230 DEG C, on substrate, form dyed layer.Then, use microspectrophotometer (Olympus Optical Co., Ltd. system " OSP-SP200 ") to measure to the brightness Y of the substrate that has formed dyed layer.
(tolerance test)
Carry out and identical heat-resistance of film test, film light fastness test and the test of film solvent resistance in test 2, implemented.
(evaluation result of anticorrosive additive material)
Anticorrosive additive material (R-1B) to the evaluation result of (R-25B) is shown in table 17.
Table 17
The anticorrosive additive material (R-1B) to (R-22B) that contains salify product and dyestuff in use and (R-24B) time, only contain pigment as compared with the anticorrosive additive material (R-23B) and situation (R-25B) of colorant with using, realized higher brightness Y.And, in the time using anticorrosive additive material (R-8B), realize extra high brightness.This can infer it is the surface process plastic resin treatment due to colorant, and the dispersiveness of colorant and dissolubility improve, thereby have obtained high brightness.
In addition, when the anticorrosive additive material (R-1B) to (R-21B) that contains specific salify product in use, in tolerance test, also obtained good result.And, when the anticorrosive additive material that contains salify product and pigment in use, obtain good especially result.It should be noted that the anticorrosive additive material (R-12B) that contains salify product and dyestuff in use and (R-18B) time, although the result of tolerance test is slightly poor, belongs to practical no problem level.
In addition, only contain pigment as the anticorrosive additive material (R-23B) of colorant and (R-25B) time, although the result of tolerance test is good, brightness Y is low using.On the other hand, only contain dyestuff as the anticorrosive additive material (R-22B) of colorant and (R-24B) time using, the variation of aberration exceedes 5, tolerance is low.
In addition, during at use anticorrosive additive material (R-13B) to (R-15B) and (R-19B) to (R-21B), the result of tolerance test is also good.This can think that the curability of film is improved due to the active energy line curing resin by use with ethylene linkage.
From the above results, the anticorrosive additive material that contains specific salify product is all being brought into play excellent performance aspect color characteristics (brightness) and tolerance two.
[embodiment 109 to 129 and comparative example 36 to 39]
Made the color filter of former colour system and complementary colour system by the method for following record.
(embodiment 109: former colour system color filter (CF-1B))
On glass substrate, form the black matrix" as light-shielding pattern, then, use spin coater to be coated with red anticorrosive additive material.The thickness that red anticorrosive additive material reaches x=0.640 with the colourity under illuminant-C is coated with.To this film across ultra high pressure mercury light irradiation 300mJ/cm for photomask 2ultraviolet ray.Then, the spray development by this film for the alkaline-based developer in being made up of the aqueous sodium carbonate of 0.2 quality %, removes unexposed portion, and washs with ion exchange water.Then, this substrate is heated 20 minutes at 230 DEG C, form red filter joint.
Then,, on this substrate, utilize method same as described above to be coated with green anticorrosive additive material.The thickness that green anticorrosive additive material reaches y=0.600 with the colourity under illuminant-C is coated with.This film, for saving above-mentioned identical exposure, development, wash and burn till with red filter, is formed to green filter joint.Then,, on this substrate, utilize method same as described above to be coated with blue anticorrosive additive material (R-1B).The thickness that blue anticorrosive additive material reaches y=0.06 with the colourity under illuminant-C is coated with.This film, for saving above-mentioned identical exposure, development, wash and burn till with red filter, is formed to blue electric-wave filter joint.As above operation, has obtained color filter (CF-1B).
(making of liquid crystal indicator)
Except using color filter (CF-1B) to replace color filter (CF-1A), by having made liquid crystal indicator with the same method illustrating in embodiment 68.
(embodiment 110 to 123 and comparative example 36 and 37: former colour system color filter (CF-2B) is to (CF-17B))
Except anticorrosive additive material being changed to the anticorrosive additive material shown in table 18, similarly operate with color filter (CF-1B) and above-mentioned liquid crystal indicator, made respectively former colour system color filter (CF-2B) to (CF-17B) and liquid crystal indicator.
(embodiment 124: complementary colour system color filter (CF-18B))
On glass substrate, form the black matrix" as light-shielding pattern, then, use the red anticorrosive additive material of spin coater coated articles (R-16B).The thickness that magenta anticorrosive additive material (R-16B) reaches x=0.348 with the colourity under illuminant-C is coated with.To this film across ultra high pressure mercury light irradiation 300mJ/cm for photomask 2ultraviolet ray.Then, the spray development by this film for the alkaline-based developer in being made up of the aqueous sodium carbonate of 0.2 quality %, removes unexposed portion, and washs with ion exchange water.Then, this substrate is heated 20 minutes at 230 DEG C, form magenta filter section.
Then,, on this substrate, utilize method same as described above to be coated with yellow anticorrosive additive material.The thickness that yellow anticorrosive additive material reaches x=0.440 with the colourity under illuminant-C is coated with.By this film for the above-mentioned identical exposure of magenta filter section, development, wash and burn till, form yellow filter joint.Then,, on this substrate, utilize method coating cyan anticorrosive additive material same as described above.The thickness that cyan anticorrosive additive material reaches y=0.06 with the colourity under illuminant-C is coated with.By this film for the above-mentioned identical exposure of magenta filter section, development, wash and burn till, form cyan filter section.As above operation, has obtained color filter (CF-18B).
(making of liquid crystal indicator)
Except using color filter (CF-18B) to replace color filter (CF-1A), by having made liquid crystal indicator with the same method illustrating in embodiment 68.
(embodiment 125 to 129 and comparative example 38 and 39: complementary colour system color filter (CF-19B) is to (CF-25B))
Except magenta anticorrosive additive material is changed to the anticorrosive additive material shown in table 19, similarly operate with color filter (CF-18B) and above-mentioned liquid crystal indicator, made respectively complementary colour system color filter (CF-19B) to (CF-25B) and liquid crystal indicator.
[evaluation of color filter (CF-1B) to (CF-25B)]
Make above-mentioned liquid crystal indicator color display.Then,, to containing the liquid crystal display of former colour system color filter, use microspectrophotometer (Olympus Optical Co., Ltd. system " OSP-SP200 ") to measure the brightness that saves corresponding region with redness, green and blue electric-wave filter.In addition, to containing the liquid crystal display of complementary colour system color filter, use microspectrophotometer (Olympus Optical Co., Ltd. system " OSP-SP200 ") mensuration and cyan, magenta and yellow filter to save the brightness in corresponding region.Then obtained the brightness of white displays by these brightness.
To the table 18 that the results are shown in of the liquid crystal indicator acquisition that contains former colour system color filter.In addition, the table 19 that the results are shown in to the liquid crystal indicator acquisition that contains complementary colour system color filter.
Table 18
Table 19
In the blue electric-wave filter joint of former colour system color filter (CF-17B), use the preferably copper phthalocyanine of use and the combination of dioxazine series pigments all the time in blue electric-wave filter joint.On the other hand, color filter (CF-1B) to (CF-15B) uses specific salify product in blue electric-wave filter joint.Color filter (CF-1B) to (CF-15B) and color filter (CF-17B) are compared, and in color filter (CF-1B) to (CF-15B), blueness and white have obtained than the higher brightness of color filter (CF-17B).
In addition, in the blue electric-wave filter of color filter (CF-16B) joint, use dyestuff as colorant.Therefore, although the high tolerance of brightness is relatively low.
The same result that the magenta filter section of complementary colour system color filter had illustrated in also having obtained and having saved with the blue electric-wave filter of former colour system color filter.
By the above, the salify product specifying by use, can obtain all filter sections of excellence of color characteristics (brightness) and thermotolerance, photostability and solvent resistance.

Claims (9)

1. a color composition for color filter, it contains transparent resin and colorant, described colorant contains the salify product forming by basic-dyeable fibre with as the equilibrium compound of anion component, described equilibrium compound is at least a kind that is selected from heteropoly acid, organic sulfonic acid and organic carboxyl acid, the molecular weight of described heteropoly acid is 2202 to 3421, the molecular weight of described organic sulfonic acid is 223 to 400, and the molecular weight of described organic carboxyl acid is 257 to 400.
2. color composition for color filter according to claim 1, wherein, described equilibrium compound contains described organic sulfonic acid, and described organic sulfonic acid is naphthylamine sulfonic acid.
3. color composition for color filter according to claim 1, wherein, described colorant further contains the resin with acidic group.
4. color composition for color filter according to claim 3, wherein, described in there is acidic group the weight-average molecular weight of resin in 400 to 12000 scope.
5. color composition for color filter according to claim 3, wherein, described in there is acidic group resin be Abietyl modified maleic acid resin.
6. color composition for color filter according to claim 3, wherein, described in there is acidic group the acid number of resin in 100 to 300mgKOH/g scope.
7. color composition for color filter according to claim 1, wherein, described basic-dyeable fibre is at least a kind that is selected from triarylmethane based dye, rhodamine based dye, methylene blue based dye and flavine based dye.
8. color composition for color filter according to claim 1, wherein, further contains at least one of optical polymerism composition and Photoepolymerizationinitiater initiater.
9. a color filter, it possesses the filter section being formed by the color composition for color filter described in claim 1 to 8 any one.
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