WO2011024896A1 - ジクロロジケトピロロピロール顔料、これを含有する色材分散物およびその製造方法 - Google Patents
ジクロロジケトピロロピロール顔料、これを含有する色材分散物およびその製造方法 Download PDFInfo
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- WO2011024896A1 WO2011024896A1 PCT/JP2010/064484 JP2010064484W WO2011024896A1 WO 2011024896 A1 WO2011024896 A1 WO 2011024896A1 JP 2010064484 W JP2010064484 W JP 2010064484W WO 2011024896 A1 WO2011024896 A1 WO 2011024896A1
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- JNNHVXMCVRYTTN-UHFFFAOYSA-N O=C(C1=C(c(cc2)ccc2Cl)N2)NC(c(cc3)ccc3Cl)=C1C2=O Chemical compound O=C(C1=C(c(cc2)ccc2Cl)N2)NC(c(cc3)ccc3Cl)=C1C2=O JNNHVXMCVRYTTN-UHFFFAOYSA-N 0.000 description 1
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- 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
- C09B57/00—Other synthetic dyes of known constitution
- C09B57/004—Diketopyrrolopyrrole dyes
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- 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
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
- C09B67/0084—Dispersions of dyes
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- 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
- C09B57/00—Other synthetic dyes of known constitution
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- 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
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0001—Post-treatment of organic pigments or dyes
- C09B67/0002—Grinding; Milling with solid grinding or milling assistants
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- 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
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0001—Post-treatment of organic pigments or dyes
- C09B67/0022—Wet grinding of pigments
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- 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
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0025—Crystal modifications; Special X-ray patterns
- C09B67/003—Crystal modifications; Special X-ray patterns of diketopyrrolopyrrole
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- 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
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
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- 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
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
- C09B67/0034—Mixtures of two or more pigments or dyes of the same type
- C09B67/0039—Mixtures of diketopyrrolopyrroles
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- 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
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0097—Dye preparations of special physical nature; Tablets, films, extrusion, microcapsules, sheets, pads, bags with dyes
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
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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
Definitions
- the present invention relates to a dichlorodiketopyrrolopyrrole pigment, a dispersion containing the same, and a method for producing the same.
- Patent document 1 discloses that diketopyrrolopyrrole pigment obtained by the acid paste method is subjected to salt milling in an organic solvent in the presence of a dye derivative, thereby suppressing crystal growth and obtaining a small primary particle size.
- the acid paste method is not preferable for safety because concentrated sulfuric acid is used.
- salt milling requires the use of a specially finely processed inorganic salt, which is costly.
- Patent Document 2 a crude dichlorodiketopyrrole pigment in which ⁇ -type crystal modification and ⁇ -type crystal modification are mixed is once dried and then in the presence of a grinding agent (water-soluble inorganic salt such as sodium chloride) and a wetting agent. Discloses a method of wet pulverization. As a result, a fine and sized ⁇ -type crystal modified dichlorodiketopyrrole pigment is obtained, and it is stated that it is possible to transfer the crystal transformation to ⁇ -type in the process of further refinement or granulation. Yes.
- a grinding agent water-soluble inorganic salt such as sodium chloride
- a diketopyrrolopyrrole pigment obtained by direct synthesis without using the acid paste method can be used to obtain a fine and sized ⁇ -type crystal modified dichlorodiketopyrrole pigment.
- the crude dichlorodiketopyrrole pigment containing the ⁇ -type crystal modification and ⁇ -type crystal modification used in this method tends to have a larger particle size than that of the ⁇ -type crystal modification alone.
- the manufacturing procedure disclosed here has a production limitation that requires a wet pulverization step for miniaturization.
- the inorganic salt used as a milling agent in this wet pulverization step causes a cost increase. A method that is more efficient and advantageous in terms of cost is desired.
- Patent Document 3 by using an ⁇ -type diketopyrrolopyrrole pigment in which the ratio of the X-ray diffraction peak intensity between predetermined plane indices falls within a predetermined range as a color filter, the viewing angle dependency and contrast of a liquid crystal display or the like are increased. It is stated that the ratio improves.
- the diketopyrrolopyrrole pigment having the X-ray diffraction peak pattern as described above specifically, the diketo is reacted by reacting the raw material (substrate) at a high temperature (preferably 70 ° C. to 80 ° C.) in the presence of a strong base.
- An alkali metal salt of a pyrrolopyrrole pigment is formed and then slowly added to a stirred protonated medium so as to avoid a temperature rise to obtain a crude diketopyrrolopyrrole crystal, which is then crystallized.
- a method is mentioned. However, in this method, since the pigment solution is hot, the solubility of the pigment in the vicinity of the precipitated particles is increased and particle growth is likely to occur. In order to slowly add the pigment solution, the particles generated at the initial stage of the addition are aged and added later. There is a limit to the miniaturization of pigment particles for reasons such as easy growth due to lamination of pigment solutes.
- a particle growth inhibitor such as a pigment derivative coexists at the time of particle precipitation for the purpose of suppressing the growth of pigment particles, but there is a concern about decomposition or side reaction of the particle growth inhibitor under high temperature and strong base conditions during synthesis. Is not realistic. Further, since the pigment solution is slowly added, there is a problem that productivity is low.
- the pigment fine particles obtained here are assumed to be completely ⁇ -type transformed, that is, to have an ⁇ -type crystallinity of about 1, and diketopyrrolo in which ⁇ -type crystals and ⁇ -type crystals are mixed. No mention is made of performance improvements such as contrast ratio with pyrrole pigments.
- Patent Document 4 discloses a red pigment having a half-value width of an intensity peak in the range of 28 to 29 degrees of 2 ⁇ in an X-ray diffraction pattern of 0.600 degrees or more and 0.800 degrees or less, and a predetermined photosensitive resin component.
- a red color resist ink containing is disclosed. Thereby, when producing a color filter using ink, the heat-resistant crystal precipitation property at the time of high temperature exposure of a coating film is improved.
- Patent Document 5 discloses a color filter to which a p-dichlorodiketopyrrolopyrrole pigment showing at least one diffraction peak having a Bragg angle of 28 ⁇ 1 ° and a half width of 0.6 ° or more in an X-ray diffraction spectrum is applied.
- This color filter has a high contrast and a good hue, and has been shown to suppress the occurrence of display defects due to image sticking during image display.
- An object of the present invention is to provide a dispersion of colorant fine particles composed of a dichlorodiketopyrrolopyrrole pigment, which can achieve high contrast when used as a color filter and can keep the viscosity of a dispersion as a raw material low. To do.
- the present invention further provides a color material dispersion of dichroic diketopyrrolopyrrole pigments that can be suitably used for a color filter, efficiently and cost-effectively under mild conditions without requiring an extra step. It is an object of the present invention to provide a production method that can be prepared with reduced burden on the environment and that can be suitably adapted to mass production.
- the object of the present invention is to solve the problems of a specific pigment particularly suitable as a colorant for a color filter as described above, and to improve other characteristics. That is, the heat resistance of the p-dichlorodiketopyrrolopyrrole pigment is improved, the color filter using the p-dichlorodiketopyrrolopyrrole pigment is made high in contrast, has a bright red hue, and has a higher temporal stability (as a color filter).
- An object of the present invention is to provide a p-dichlorodiketopyrrolopyrrole pigment that achieves no deterioration such as discoloration or reduction in contrast even when used for a predetermined period.
- the colorant fine particles comprising a dichlorodiketopyrrolopyrrole pigment that can be suitably used for a color filter
- a method for producing a coloring material comprising a dichlorodiketopyrrole pigment having an ⁇ -type crystallinity and crystallite size within this specific range fine particles of a dichlorodiketopyrrolopyrrole pigment prepared by a reprecipitation method are grown. It has been found that it can be produced efficiently and with reduced cost burden by contacting the organic solvent in the presence of an inhibitor to convert the crystal transformation into ⁇ -form.
- the present invention has been made on the basis of the above findings, that is, the above problems have been solved by the following means.
- a color material dispersion containing a particle growth inhibitor and a color material fine particle comprising a dichlorodiketopyrrolopyrrole pigment, wherein the ⁇ -type crystallinity of the color material fine particle is 0.65 to 0.90 (-151)
- the crystallite size in the crystal plane direction is 6.0 to 13.0 nm, and the crystallite size in the (111) crystal plane direction is in the range of 5.0 to 23.0 nm.
- Material dispersion (2) The color material dispersion as described in (1), which is produced through the following steps [i] and [ii].
- a dichlorodiketopyrrolopyrrole pigment containing a dichlorodiketopyrrolopyrrole pigment dissolved in a good solvent is brought into contact with a poor solvent that is hardly soluble in the pigment and compatible with the good solvent.
- Fine particles of the dichlorodiketopyrrolopyrrole pigment obtained in the step [i] are brought into contact with a crystal-type-adjusting organic solvent in the presence of the particle growth inhibitor.
- (3) The color material dispersion according to (1) or (2), wherein the crystal growth inhibitor is represented by the following general formula (1).
- P represents an organic dye compound residue that may have a substituent.
- X represents a single bond or a divalent linking group.
- Y represents —NR 2 R 3 , a sulfo group, or a carboxyl group.
- R 2 and R 3 are each independently a hydrogen atom, an alkyl group, an alkenyl group, or a phenyl group which may have a substituent, or a complex formed by R 2 and R 3 together.
- R 3 and R 4 are each independently Represents a hydrogen atom or a substituted or unsubstituted alkyl group, provided that at least one of R 3 and R 4 is a substituted or unsubstituted alkyl group.
- Colorant fine particles comprising the dichlorodiketopyrrolopyrrole pigment according to any one of (1) to (5), which are produced through the following steps [i] and [ii] The manufacturing method of the coloring material dispersion containing this.
- a dichlorodiketopyrrolopyrrole pigment containing a dichlorodiketopyrrolopyrrole pigment dissolved in a good solvent is brought into contact with a poor solvent that is hardly soluble in the pigment and compatible with the good solvent.
- n an integer of 1 to 4.
- P is a quinacridone pigment compound residue or a diketopyrrolopyrrole pigment compound residue.
- a method for producing a dispersion (11) The method for producing a color material dispersion according to (10), wherein the particle growth inhibitor is represented by the following general formula (2). (Wherein, X 1 and X 2 each independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aromatic group.
- R 3 and R 4 are each independently Represents a hydrogen atom or a substituted or unsubstituted alkyl group, provided that at least one of R 1 and R 2 is a substituted or unsubstituted alkyl group.)
- the dichlorodiketopyrrole pigment fine particles produced in the step [i] are substantially in the ⁇ -type crystal transformation, (6) to (11), A method for producing a color material dispersion.
- Any one of (6) to (13), wherein the step [ii] is performed without drying the dichlorodiketopyrrolopyrrole pigment particles produced in the step [i].
- (18) Mixing the both liquids with the good solvent and / or the poor solvent containing the dispersant, or preparing a solution containing the dispersant in the good solvent separately from these and mixing with the two liquids
- a coloring composition comprising the dichlorodiketopyrrolopyrrole pigment according to any one of (15) to (18).
- the color material dispersion of the present invention is highly suitable for production as a color filter raw material, and has an excellent effect of realizing high contrast and good quality particularly when used as a color filter.
- the dichlorodiketopyrrolopyrrole pigment of the present invention is particularly suitable as a color material for a color filter, and has excellent heat resistance, high contrast, a bright red hue, and high temporal stability. Has an effect.
- the colorant dispersion of this embodiment has a particle growth inhibitor and an ⁇ -type crystallinity of 0.65 to 0.90, a crystallite size in the direction of ( ⁇ 151) crystal plane of 6.0 to 13.0 nm, ( 111) A fine particle of a dichlorodiketopyrrolopyrrole pigment having a crystallite size in the crystal plane direction in the range of 5.0 to 23.0 nm is included.
- the viscosity of the dispersion liquid can be maintained at a low viscosity by setting the crystallite diameter within a specific range, and this embodiment has been achieved.
- the ⁇ -type crystallinity exceeds the above range, for example, it is extremely high so that it cannot be realized if the ⁇ -type crystallinity exceeds, for example, the ⁇ -type crystallinity. Contrast can be achieved. The reason is not clear.
- the interaction between the pigment particles that increases the viscosity of the dispersion when the ⁇ -type crystallinity is suppressed is due to the presence of the particle growth inhibitor or the crystallite size being set within a specific range. It can be reduced and a low-viscosity dispersion can be obtained.
- the color material dispersion of the present embodiment is [i] a step of bringing a pigment solution containing a dichlorodiketopyrrolopyrrole pigment dissolved in a solvent into contact with a poor solvent to produce fine particles of a dichlorodiketopyrrolopyrrole pigment, [Ii] ⁇ -type crystallization of dichlorodiketopyrrolopyrrole pigment by contacting fine particles of dichlorodiketopyrrolopyrrole pigment obtained in [i] above with a crystal-type adjusting organic solvent in the presence of a particle growth inhibitor. It is preferable that it has passed through the process which raises a degree.
- the ⁇ -type crystallinity of the dichlorodiketopyrrolopyrrole pigment is not particularly limited as long as it is in the above range, but is preferably 0.68 to 0.80, more preferably 0.70 to 0.78.
- the ⁇ -type crystallinity not more than the above upper limit value, particle growth is suppressed and the color filter can be made high contrast.
- the viscosity of a dispersion liquid can be restrained low by setting it as the said lower limit or more.
- JP-A-58-210084 can be referred to for the ⁇ -type crystal modification
- JP-A-8-48908 for the ⁇ -type crystal modification.
- Crystal transformation in the fine particles of the obtained dichlorodiketopyrrolopyrrole pigment can be confirmed by powder X-ray diffraction measurement using CuK ⁇ rays.
- the ⁇ -type crystallinity and crystallite size are It is defined as the value determined by the following method.
- An operation is performed to draw a straight line and obtain a pattern obtained by removing the X-ray diffraction intensity value represented by the straight line from the X-ray diffraction intensity value obtained in (1).
- the pattern obtained by removing the diffraction intensity represented by the straight line L in contact with the point A and the point B is obtained from the X-ray diffraction intensity value of FIG.
- the removed X-ray diffraction pattern is used.
- An example of the X-ray diffraction pattern with the background removed is shown in FIG. (3) From the X-ray diffraction pattern obtained by removing the background determined in (2), the ⁇ -type crystallinity is calculated by the following formula.
- ⁇ -type crystallinity I ⁇ / (I ⁇ + I ⁇ )
- the lengths of the lines L1 and L2 correspond to I ⁇ and I ⁇ .
- Step [ii] Step of increasing ⁇ -type crystallinity
- fine particles of the dichlorodiketopyrrolopyrrole pigment obtained by the reprecipitation method of Step [i] as described below are used as a crystal-type adjusting organic solvent.
- the reprecipitation method will be described later.
- the fine particles of the dichlorodiketopyrrolopyrrole pigment obtained by the reprecipitation method consist of a mixed state of ⁇ -type crystal modification and ⁇ -type crystal modification or ⁇ -type crystal modification.
- the ⁇ -type crystallinity of the fine pigment particles obtained by the reprecipitation method varies depending on the reprecipitation conditions and coexisting materials described later, but is usually 0.15 to 0.55.
- the fine particles of the dichlorodiketopyrrolopyrrole pigment obtained by the reprecipitation method are preferably substantially in the ⁇ -type crystal modification, and the ⁇ -type crystallinity at this time is 0.15 to 0.40.
- the crystal-type adjusting organic solvent is not particularly limited, but ether solvents (eg, tetrahydrofuran, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, etc.), sulfoxide solvents (eg, dimethyl sulfoxide, hexamethylene sulfoxide, sulfolane, etc.) Ester solvents (eg, ethyl acetate, n-butyl acetate, ethyl lactate, etc.), amide solvents (eg, N, N-dimethylformamide, 1-methyl-2-pyrrolidone, etc.), aromatic hydrocarbon solvents (For example, toluene, xylene, etc.), aliphatic hydrocarbon solvents (for example, octane), nitrile solvents (for example, acetonitrile), halogen solvents (for example, carbon tetrachloride, dichloromethane, etc.), alcohol solvent
- an ether solvent, an ester solvent, an alcohol solvent, a ketone solvent, a mixture thereof, or a mixture of these with water is more preferable, and a propylene glycol monomethyl ether acetate as a main component is particularly preferable.
- the poor solvent used here is also used as a dispersion medium in the preparation of the dispersion in the next step, but propylene glycol monomethyl ether acetate is a general-purpose solvent for the final dispersion, which improves cost performance by using it in both steps. To do.
- the fine particles of the dichlorodiketopyrrolopyrrole pigment used in the crystal type adjusting step are preferably used without being dried after being precipitated by the reprecipitation method, these organic solvents are used as the solvent for the crystal type adjusting step.
- a part of the good and poor solvents at the time of precipitation water used for washing with water, or another solvent substituted for these may be mixed, and it is preferable that water is mixed.
- the good solvent used at the time of reprecipitation may cause excessive particle growth, it is desirable not to coexist in the crystal type adjustment step.
- the conditions for bringing the fine particles of the dichlorodiketopyrrolopyrrole pigment into contact with the crystal-type-adjusting organic solvent are not particularly limited, but both are maintained while maintaining the stirring state so that the ratio of the crystal-type-adjusting organic solvent and the pigment fine particles does not become uneven. It is preferable to make it contact. Moreover, there is no restriction
- the temperature in consideration of the type of organic solvent used and the time required to increase the ⁇ -type crystallinity. Specifically, ⁇ 10 ° C. to 100 ° C. is preferable, and 0 ° C. to 80 ° C. is more preferable. Further, the amount of the crystal-type adjusting organic solvent is not particularly limited, but if the amount of the organic solvent is too small, there is a concern about unevenness at the time of crystal-type adjustment or unintentional coalescence between pigment particles.
- a crystal-type adjusting organic solvent in an amount such that the pigment concentration at the time of mold adjustment ranges from 0.1% to 50%.
- materials other than the crystal-type adjusting organic solvent that coexists at the time of crystal-type adjustment but it is preferable that a particle growth inhibitor described later coexists, and other materials include acid, base, inorganic Salts, viscosity modifiers, surfactants, antifoaming agents, polymer dispersing agents and the like may be included.
- the base coexists, the rate of increase of the ⁇ -type crystallinity increases, but the particle growth is promoted. Therefore, it is desirable to adjust the crystal type adjustment time.
- the good solvent for the pigment used in step [i] of the present embodiment may cause excessive particle growth, and therefore it is preferable not to coexist in step [ii].
- the step of increasing the ⁇ -type crystallinity in step [ii] of the present embodiment is preferably performed in the presence of a particle growth inhibitor.
- a particle growth inhibitor By performing an operation to increase the ⁇ -type crystallinity in the presence of a particle growth inhibitor, excessive particle growth when increasing the ⁇ -type crystallinity can be suppressed, and the crystallite size of the dichlorodiketopyrrole pigment Can be limited to the preferred range of this embodiment.
- the particle growth inhibitor may be added at the same time as step [i] or at the same time as step [i] after completion of step [i], but preferably before step [i].
- adding the same or another raw material before the start of process [ii] can also be performed preferably.
- preferred type and amount of the particle growth inhibitor used in step [ii] of the present embodiment preferred materials and amounts used can be used when they are contained in step [i] described below.
- the dichlorodiketopyrrolopyrrole pigment obtained by obtaining step [ii] has a crystallite size in the ( ⁇ 151) crystal plane direction of 6 nm or more and 13 nm or less, and 6 nm or more and 11.0 or less. It is particularly preferable that the thickness is 6 nm or more and 9.0 nm or less.
- the crystallite size in the (111) crystal plane direction is 5.0 nm or more and 23 nm or less, preferably 5.0 nm or more and 20 nm or less, and particularly preferably 10 nm or more and 18 nm or less.
- the mechanism by which the viscosity of the dispersion can be reduced by limiting the range of the crystallite size is not clear, but it is as follows when including the estimation.
- the state in which (-151) crystal plane direction and (111) crystal plane direction both realize the above preferred range is that the main particle growth direction of dichlorodiketopyrrolopyrrole pigment is grown by the particle growth inhibitor. It is considered that the state of inhibition, that is, the state of interaction with the additional layer of pigment molecules on the crystal surface is limited. This is presumed that the interaction between particles in these directions is also kept low, and as a result, the viscosity of the dispersion is reduced.
- the present embodiment is characterized in that both the crystallite size in the ( ⁇ 151) crystal plane direction and the (111) crystal plane direction of the crystal grain are set in a specific range.
- the value of the half-value width calculated by fitting using the data analysis software Igor Pro manufactured by Wave Metrics as a Voig function is used.
- the crystallite size is calculated from the half-width of the diffraction peak calculated in (2) and the Scherrer equation below.
- D K ⁇ / (10 ⁇ B ⁇ cos A)
- B Bobs-b here, D: Crystallite size (nm)
- Bobs full width at half maximum (rad) calculated in (2)
- b X-ray diffractometer angular resolution correction coefficient, half-value width (rad) when measuring standard silicon crystal.
- Measurement conditions in the present embodiment are as follows.
- X-ray diffractometer RINT2500 manufactured by Rigaku Corporation Goniometer: RINT2000 vertical goniometer manufactured by Rigaku Corporation Sampling width: 0.01 ° Step time: 1 second diverging slit: 2 ° Scattering slit: 2 ° Receiving slit: 0.6mm Tube: Cu Tube voltage: 55KV Tube current: 280 mA
- the reaction in order to increase the time, (i) increase the temperature in the crystallization step, (ii) suppress the amount of the crystal growth inhibitor, (iii) delay the timing of addition, or (iv) the reaction
- One example is to increase the time.
- the type, addition amount, and addition of the crystal growth inhibitor in the crystallization step It is effective to properly select a crystal growth solvent and the like.
- it is effective to increase the ratio of the growth inhibitor having a high growth suppression effect in the (111) plane direction.
- the compounds represented are mentioned as specific examples of this.
- the crystallite size measurement conditions of the first embodiment can be referred to.
- the fine particles of the dichlorodiketopyrrolopyrrole pigment applied in the step [ii] are preferably used without being dried after being precipitated by the reprecipitation method, and the dispersed state in the dispersion medium is preferably used. It is preferable that it is maintained.
- drying means that the concentration of the pigment fine particles is increased to 60% or more.
- the step [ii] is preferably performed in the absence of a grinding agent.
- the grinding material include media such as zirconia beads, glass beads, and agate balls, and water-soluble inorganic salts such as sodium chloride, potassium chloride, calcium chloride, barium chloride, and sodium sulfate.
- washing treatment after increasing the ⁇ -type crystallinity of the fine particles of the dichlorodiketopyrrolopyrrole pigment in the above step [ii], washing treatment, addition of an adsorbing material, or cooling is performed so as to prevent this from excessively increasing. It is preferable to perform such treatment.
- the specific procedure of the water washing treatment is not particularly limited. For example, an excessive amount of water (ion-exchanged water or distilled water) having a mass of 100 to 10,000 times that of the target pigment fine particles is used, and the above-mentioned pigment coexisting with the pigment fine particles is used.
- the embodiment which pours a crystallization promotion organic solvent is mentioned.
- the temperature of the water used for this washing is preferably 0-30 ° C., and the ambient temperature during the washing is preferably 5-25 ° C.
- the below-mentioned particle growth inhibitor, a dispersing agent, etc. can be used as an adsorption material.
- the temperature when the cooling treatment is performed is preferably set to a temperature lower by 10 ° C. or more than the temperature of step [ii], and specifically, is preferably in the range of ⁇ 15 ° C. to 20 ° C.
- the pigment concentration after these treatments can be increased by an operation such as concentration or drying, if necessary.
- concentration or drying method there are no particular restrictions on the concentration or drying method, but when drying, in order to avoid excessive aggregation of pigment fine particles due to drying, freeze drying or after replacing the solvent with an organic solvent such as alcohol or acetone. It is preferable to perform drying, and it is also preferable to mix with a dispersant before drying.
- the concentration of the pigment fine particles in the dispersion when applied to the step [ii] is not particularly limited, but is preferably 0.1 to 50% by mass, and 1 to 25% by mass. It is more preferable.
- the average particle diameter refers to the number average diameter unless otherwise specified.
- the average particle size of the pigment fine particles is preferably 100 nm or less, more preferably 75 nm or less, and particularly preferably 50 nm or less. The lower limit is not particularly limited, but is practically 2 nm to 3 nm or more.
- the ratio (Mv / Mn) of the volume average particle diameter (Mv) and the number average particle diameter (Mn) is used as an index representing the uniformity (monodispersity) of the particles, unless otherwise specified.
- the monodispersity of pigment fine particles (primary particles) in the present invention, monodispersity means the degree of uniform particle size), that is, Mv / Mn is 1.0 to 2.0. Is more preferable, 1.0 to 1.8 is more preferable, and 1.0 to 1.5 is particularly preferable.
- Examples of the method for measuring the particle size of the organic particles include microscopy, mass method, light scattering method, light blocking method, electrical resistance method, acoustic method, and dynamic light scattering method. Particularly preferred.
- Examples of the microscope used for the microscopy include a scanning electron microscope and a transmission electron microscope.
- Examples of the particle measuring apparatus using the dynamic light scattering method include Nikkiso's Nanotrac UPA-EX150 and Otsuka Electronics' dynamic light scattering photometer DLS-7000 series (both are trade names).
- dichlorodiketopyrrolopyrrole pigment dissolved in a solvent is brought into contact with a poor solvent to produce dichlorodiketopyrrolopyrrole pigment fine particles.
- a dichlorodiketopyrrole pigment dissolved in a solvent means a dichlorodiketopyrrole pigment obtained by dissolving a previously synthesized dichlorodiketopyrrole pigment in a good solvent, and a dichlorodiketopyrrole pigment from a raw material in the synthesis solvent. It means both dichlorodiketopyrrole pigments that are dissolved in a synthesis solvent in the state of alkali metal salt or the like when synthesized and produced.
- the compatibility of the solvent (good solvent) for dissolving the dichlorodiketopyrrolopyrrole pigment and the poor solvent is preferably such that the amount of the good solvent dissolved in the poor solvent is 30% by mass or more, and 50% by mass or more. It is more preferable. There is no particular upper limit on the amount of good solvent dissolved in the poor solvent, but it is practical to mix them in an arbitrary ratio.
- the good solvent is not particularly limited, but an organic acid (eg, formic acid, dichloroacetic acid, methanesulfonic acid, etc.), an organic base (eg, diazabicycloundecene (DBU), tetrabutylammonium hydroxide, sodium methoxide, etc.) ), Aqueous solvents (eg, water, hydrochloric acid, aqueous sodium hydroxide), alcoholic solvents (eg, methanol, ethanol, n-propanol, etc.), ketone solvents (eg, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), Ether solvents (eg, tetrahydrofuran, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, etc.), sulfoxide solvents (eg, dimethyl sulfoxide, hexamethylene sulfoxide, s
- an organic acid, an organic base, an aqueous solvent, an alcohol solvent, a ketone solvent, an ether solvent, a sulfoxide solvent, an ester solvent, an amide solvent, or a mixture thereof is more preferable, and an organic acid, an organic base , Sulfoxide solvents, amide solvents, or mixtures thereof are particularly preferred.
- organic acids include, but are not limited to, sulfonic acid compounds, carboxylic acid compounds, acid anhydride compounds, and the like.
- sulfonic acid compound examples include alkyl sulfonic acid, halogenated alkyl sulfonic acid, and aromatic sulfonic acid, and the alkyl chain and aromatic ring may be unsubstituted or substituted.
- sulfonic acid compound used in the present embodiment include methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, heptafluoropropanesulfonic acid, Nonafluorobutanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, xylenesulfonic acid, dodecylbenzenesulfonic acid, naphthalenesulfonic acid, chlorobenzenesulfonic acid, aminobenzenesulfonic acid, 1,5-naphthalenedisulfonic acid tetrahydrate, etc. Can be mentioned.
- carboxylic acid compound examples include alkyl carboxylic acids, halogenated alkyl carboxylic acids, and aromatic carboxylic acids.
- the alkyl chain and the aromatic ring may be unsubstituted or substituted with the substituent T.
- Specific examples of carboxylic acid compounds include formic acid, acetic acid, propionic acid, butyric acid, trifluoroacetic acid, trichloroacetic acid, tribromoacetic acid, difluoroacetic acid, dichloroacetic acid, dibromoacetic acid, fluoroacetic acid, chloroacetic acid, bromoacetic acid, chlorodifluoroacetic acid , Cyanoacetic acid, phenoxyacetic acid, diphenylacetic acid, thioacetic acid, mercaptoacetic acid, mercaptopropionic acid, 2-chloropropionic acid, 2,2-dichloropropionic acid, 3-chloropropionic acid, 2-bromopropionic
- an acid anhydride in addition to carboxylic acid and sulfonic acid, an acid anhydride can be used as the acid, specifically, acetic anhydride, propionic acid anhydride, trifluoromethanesulfonic acid anhydride, And acid anhydrides such as trichloroacetic anhydride.
- organic acids other than these include isopropyl phosphate, methyl phosphate, phenylphosphonic acid, ethylenediaminetetraphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, and methylenediphosphonic acid.
- alkylsulfonic acid alkylsulfonic acid, alkylcarboxylic acid, halogenated alkylcarboxylic acid, and aromatic sulfonic acid are preferable, and methanesulfonic acid, trifluoromethanesulfonic acid, ethanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, chloroacetic acid.
- methanesulfonic acid, trifluoromethanesulfonic acid, ethanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, chloroacetic acid formic acid, toluenesulfonic acid, and dodecylbenzenesulfonic acid are more preferable.
- organic bases include primary amines, secondary amines, tertiary amines, quaternary amines, anilines, piperidines, piperazines, amidines, formamidines, pyridines, Examples include, but are not limited to, guanidines, morpholines, nitrogen-containing heterocycles, metal alkoxides and the like. Among these, tertiary amines, quaternary amines, morpholines, nitrogen-containing heterocycles, metal alkoxides and the like are preferable.
- sulfoxide solvent examples include dimethyl sulfoxide, diethyl sulfoxide, hexamethylene sulfoxide, sulfolane and the like.
- examples of the amide solvent include N, N-dimethylformamide, 1-methyl-2-pyrrolidone, 2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, 2-pyrrolidinone, ⁇ -Caprolactam, formamide, N-methylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropanamide, hexamethylphosphoric triamide and the like.
- the temperature at normal pressure is preferably ⁇ 10 to 150 ° C., more preferably ⁇ 5 to 130 ° C., and particularly preferably 0 to 100 ° C.
- the pigment When the pigment is uniformly dissolved in a good solvent, generally, in the case of a pigment having an alkaline dissociable group in the molecule, there is no alkali, but there is no alkaline dissociable group, and a nitrogen atom to which a proton is easily added is present. It is preferred that acidity be used when there are many in the molecule.
- quinacridone, diketopyrrolopyrrole, and disazo condensation compound pigments are alkaline
- phthalocyanine compound pigments are acidic.
- inorganic bases such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, and barium hydroxide can also be used as the base used when dissolving with alkali.
- the amount of the base to be used is not particularly limited, but in the case of an inorganic base, it is preferably 1.0 to 30 molar equivalents, more preferably 1.0 to 25 molar equivalents, and 1.0 Particularly preferred is ⁇ 20 molar equivalents.
- the amount is preferably 1.0 to 100 molar equivalents, more preferably 5.0 to 100 molar equivalents, and particularly preferably 20 to 100 molar equivalents with respect to the pigment.
- inorganic acids such as sulfuric acid, hydrochloric acid, and phosphoric acid can be used as the acid used when dissolving in an acidic state.
- the amount of the acid to be used is not particularly limited, but it is often used in excess compared to the base, and is preferably 3 to 500 molar equivalents, more preferably 10 to 500 molar equivalents, based on the pigment. Particularly preferred is 30 to 200 molar equivalents.
- the alkali or acid When mixing an inorganic base or an inorganic acid with an organic solvent and using it as a good solvent for a pigment, the alkali or acid is completely dissolved, so it has a high solubility in some water or lower alcohol or other alkali or acid.
- a solvent can be added to the organic solvent.
- the amount of water or lower alcohol is preferably 50% by mass or less, more preferably 30% by mass or less, based on the total amount of the pigment solution. Specifically, water, methanol, ethanol, n-propanol, isopropanol, butyl alcohol and the like can be used.
- the viscosity of the pigment solution is preferably 0.5 to 100.0 mPa ⁇ s, and more preferably 1.0 to 50.0 mPa ⁇ s.
- the pigment solution may contain the above pigment and other components as required in a good solvent.
- An acid an organic compound etc. which has an acidic group
- a base an organic compound which has basicity
- organic base organic compound having a basic group
- a pyridazine derivative, a pyrimidine derivative, a pyrazine derivative, a triazine derivative, etc. are mentioned,
- an alkylamine, an arylamine, and an imidazole derivative are mentioned.
- the carbon number of the organic compound having a basic group is preferably 6 or more, more preferably 8 or more, and further preferably 10 or more.
- examples of the alkylamine include butylamine, amylamine, hexylamine, heptylamine, octylamine, 2-hexylhexylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine.
- Tetradecylamine pentadecylamine, hexadecylamine, octadecylamine, isobutylamine, t-butylamine, 1-methylbutylamine, 1-ethylbutylamine, t-amylamine, 3-aminoheptane, t-octylamine, 1,4 -Diaminobutane, 1,6-hexadiamine, 1,8-diaminooctane, 1,10-diaminodecane, 1,12-diaminododecane, dibutylamine, dihexylamine, dioctylamine, bis (2- Tylhexyl) amine, didecylamine, N-methyloctadecylamine, triethylamine, tripropylamine, N, N-dimethylbutylamine, N-methyldibutylamine, tributylamine, tripent
- organic polymer compounds having a basic group such as polyallylamine and polyvinylamine.
- arylamine examples include N, N-dibutylaniline, 4-butylaniline, 4-pentylamine, 4-hexylamine, 4-heptylaniline, 4-octylaniline, 4-decylaniline, 4-dodecylaniline, 4 -Tetradecylaniline, 4-hexadecylaniline, 4-butoxyaniline, 4-pentyloxyaniline, 4-hexyloxyaniline, 4-hexyloxyaniline, etc., preferably 4-octylaniline, 4-decylaniline 4-dodecylaniline, 4-tetradecylaniline, 4-hexadecylaniline, 4-pentyloxyaniline, 4-hexyloxyaniline, 4-hexyloxyaniline, and the like, more preferably 4-decylaniline, 4 -Dodecyl aniline, - tetradecyl aniline, 4-hexadecy
- imidazole derivative examples include 1- (10-hydroxydecyl) imidazole, 1-butylimidazole, 2-undecylimidazole, 2-heptadecylimidazole and the like.
- organic compound which has the said basic group the organic compound comprised by a basic group and a heterocyclic group is also preferable.
- organic compounds include 2-aminopyridine, 3-aminopyridine, 1- (2-aminophenyl) pyrrole, 5-aminopyrazole, 3-amino-5-methylpyrazole, 5-amino-1- Ethylpyrazole, 3-aminotriazole, 2-aminothiazole, 5-aminoindole, 2-aminobenzthiazole, 5-aminobenzimidazole, N, N-dimethyl-5-aminobenzimidazole, phthalimide, 5-aminobenzimidazolone N, N-dimethyl-5-aminobenzimidazolone, 5-aminouracil, 6-aminouracil, uracil, thymine, adenine, guanine, melamine, aminopyrazine, 8-aminoquinoline, 3-aminoquino
- the organic compound having a basic group is preferably an organic compound composed of a basic group and a heterocyclic group.
- the organic compound having a basic group is preferably in the range of 0.01 to 30% by mass, more preferably in the range of 0.05 to 20% by mass, and more preferably 0.05 to 15% with respect to the pigment. It is particularly preferable to be in the range of mass%.
- pigment derivatives described in JP-A No. 2007-9096 and JP-A No. 7-331182 can be exemplified.
- the pigment derivative referred to here is derived from a pigment derivative compound derived from an organic pigment as a parent substance and manufactured by chemically modifying the parent structure, or by a pigmentation reaction of a chemically modified pigment precursor.
- a pigment derivative type compound examples include “EFKA 6745 (phthalocyanine derivative)” manufactured by EFKA, “Solsperse 5000 (phthalocyanine derivative)” manufactured by Lubrizol (all are trade names), and the like.
- the amount used is preferably in the range of 0.5 to 30% by weight, more preferably in the range of 3 to 20% by weight, and more preferably in the range of 5 to 15% by weight with respect to the pigment. It is especially preferable that it is in the range.
- the poor solvent is not particularly limited, but the solubility of the dichlorodiketopyrrolopyrrole pigment in the poor solvent is preferably 0.02% by mass or less, and more preferably 0.01% by mass or less. There is no particular lower limit to the solubility of the pigment in the poor solvent, but 0.0001% by mass or more is practical considering the commonly used one.
- the poor solvent is not particularly limited, but an aqueous solvent (for example, water, hydrochloric acid, sodium hydroxide aqueous solution), an alcohol solvent (for example, methanol, ethanol, n-propanol, etc.), a ketone solvent (for example, methyl ethyl ketone, Methyl isobutyl ketone, cyclohexanone, etc.), ether solvents (eg, tetrahydrofuran, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, etc.), sulfoxide solvents (eg, dimethyl sulfoxide, hexamethylene sulfoxide, sulfolane, etc.), ester solvents ( For example, ethyl acetate, n-butyl acetate, ethyl lactate, etc.), amide solvents (eg, N, N-dimethylformamide, 1-methyl-2-pyrrolidon
- an aqueous solvent, an alcohol solvent, a ketone solvent, a sulfoxide solvent, an ester solvent, an amide solvent, a nitrile solvent, or a mixture thereof is more preferable, and an aqueous medium, an alcohol solvent, or a mixture thereof. Is particularly preferred.
- the aqueous medium refers to water alone or water and water-soluble organic solvent or inorganic salt solution, for example, water, hydrochloric acid, sodium hydroxide aqueous solution, potassium hydroxide aqueous solution and the like.
- the alcohol solvent include methanol, ethanol, isopropyl alcohol, n-propyl alcohol, 1-methoxy-2-propanol and the like.
- the solubility in the good solvent is related to the pigment.
- the solubility should be sufficiently higher than the solubility in the poor solvent.
- the solubility difference is preferably 0.2% by mass or more, and more preferably 0.5% by mass or more. There is no particular upper limit on the difference in solubility between the good solvent and the poor solvent, but it is practical that the difference is 50% by mass or less in consideration of a commonly used pigment.
- the state of the poor solvent is not particularly limited, and a range from normal pressure to subcritical and supercritical conditions can be selected.
- the temperature at normal pressure is preferably ⁇ 30 to 100 ° C., more preferably ⁇ 10 to 60 ° C., and particularly preferably 0 to 30 ° C.
- the viscosity of the pigment solution is preferably 0.5 to 100.0 mPa ⁇ s, and more preferably 1.0 to 50.0 mPa ⁇ s.
- the stirring speed is preferably 100 to 10000 rpm, more preferably 150 to 8000 rpm, and particularly preferably 200 to 6000 rpm.
- a pump or the like may be used for the addition, or it may not be used.
- addition in a liquid or addition outside a liquid may be sufficient, addition in a liquid is more preferable.
- the inner diameter of the supply pipe is preferably 0.1 to 200 mm, more preferably 0.2 to 100 mm.
- the rate at which the liquid is supplied from the supply pipe is preferably 1 to 10,000 ml / min, more preferably 5 to 5000 ml / min.
- the Reynolds number is a dimensionless number representing the state of fluid flow and is represented by the following equation.
- Re represents the Reynolds number
- ⁇ represents the density of the pigment solution [kg / m 3 ]
- U represents the relative speed [m / s] when the pigment solution and the poor solvent meet
- L represents the equivalent diameter [m] of the flow path or supply port where the pigment solution and the poor solvent meet
- ⁇ represents the viscosity coefficient [Pa ⁇ s] of the pigment solution.
- the equivalent diameter L refers to the diameter of the equivalent circular pipe when assuming an opening diameter of a pipe having an arbitrary cross-sectional shape or a circular pipe equivalent to the flow path.
- the value of the equivalent diameter L is not specifically limited, For example, it is synonymous with the preferable internal diameter of the supply port mentioned above.
- the relative speed U when the pigment solution and the poor solvent meet is defined by the relative speed in the direction perpendicular to the surface of the portion where both meet. That is, for example, when the pigment solution is injected and mixed in a stationary poor solvent, the injection speed from the supply port becomes equal to the relative speed U.
- the value of the relative speed U is not particularly limited, but is preferably 0.5 to 100 m / s, and more preferably 1.0 to 50 m / s.
- the density ⁇ of the pigment solution is a value determined by the type of material selected, but is practically, for example, 0.8 to 2.0 kg / m 3 .
- the viscosity coefficient ⁇ of the pigment solution is also a value determined by the material used, the ambient temperature, and the like, but its preferred range is synonymous with the preferred viscosity of the pigment solution described above.
- it can be obtained by adjusting the Reynolds number to 60 or more to control the particle diameter of the pigment nanoparticles, preferably 100 or more, and more preferably 150 or more.
- favorable pigment nanoparticles can be obtained by controlling and controlling in the range of 100,000 or less, which is preferable. Or it is good also as conditions which raised Reynolds number so that the average particle diameter of the nanoparticle obtained may be 60 nm or less. At this time, within the above range, it is possible to control and obtain pigment nanoparticles having a smaller particle size by increasing the Reynolds number.
- the mixing ratio of the pigment solution and the poor solvent is preferably 1/50 to 2/3, more preferably 1/40 to 1/2, and particularly preferably 1/20 to 3/8.
- the particle concentration in the liquid when organic fine particles are precipitated is not particularly limited, but the organic particles are preferably in the range of 10 to 40,000 mg, more preferably in the range of 20 to 30000 mg, particularly with respect to 1000 ml of the solvent. The range is preferably 50 to 25000 mg.
- the preparation scale for generating fine particles is not particularly limited, but the preparation amount of the poor solvent is preferably 10 to 2000 L, more preferably 50 to 1000 L.
- a “particle growth inhibitor” may be contained in at least one of the pigment solution and the poor solvent, preferably in the pigment solution. Good. By using this particle growth inhibitor, it is preferable because the crystallite size is not increased carelessly and good performance can be further obtained as a color material for a color filter.
- a pigment derivative (also referred to as a dye derivative) in which a substituent is introduced into the pigment molecular skeleton, an organic compound composed of the aforementioned basic group and heterocyclic group, a polymer dispersant, and the like are preferably used. Of these, pigment derivatives are particularly preferred.
- the pigment derivative that is preferably used as the particle growth inhibitor in this embodiment can be represented by the following general formula (1).
- P- [X- (Y) k] n General formula (1)
- P represents an organic dye compound residue that may have a substituent (the organic dye residue includes an organic dye or a residue of a derivative thereof), and X is a single bond or a divalent group.
- X is preferably an organic linking group, and specific examples of X include a direct bond, —O—, —S. —, —CO—, —SO 2 —, —NR 1 —, —CONR 1 —, —SO 2 NR 1 —, —NR 1 CO—, —NR 1 SO 2 — (wherein R 1 is a hydrogen atom, An alkyl group or a hydroxyalkyl group), an alkyl having 18 or less carbon atoms which may have a substituent.
- K represents an integer of 1 or 2
- n represents an integer of 1 to 4.
- a “compound” or “agent” represented by a predetermined general formula represents the compound of the structural formula itself.
- the meaning includes the salt.
- a diketopyrrolopyrrole derivative, a quinacridone derivative, an anthraquinone derivative, a dianthraquinone derivative, a benzoindole derivative, and a thiazine indigo derivative are preferable, and among them, a diketopyrrolopyrrole derivative and a quinacridone derivative are preferable.
- diketopyrrolopyrrole derivatives are effective in suppressing crystal growth in the (111) crystal plane direction
- quinacridone derivatives are effective in suppressing crystal growth in the (-151) crystal plane direction.
- a diketopyrrolopyrrole derivative and a quinacridone derivative in combination in this embodiment.
- These derivatives include acidic derivatives having acidic substituents such as sulfonic acid groups and carboxyl groups, basic derivatives having basic substituents such as dialkylamino groups and pyrazolylmethyl groups, phthalimidomethyl groups and imidazolylmethyl groups. Any neutral derivative having a functional substituent can be preferably used.
- pigment derivatives that can be preferably used in the present embodiment include JP-A-56-118462, JP-A-63-264664, JP-A-1-217077, JP-A-3-9961, and JP-A-3- No.
- JP-A-3-153780 JP-A-3-45662, JP-A-4-285669, JP-A-6-145546, JP-A-6-212088, JP-A-6-240158 Any of those described in JP-A-10-30063, JP-A-10-195326 and the like can be preferably used.
- the growth inhibitor used in the present embodiment is preferably further represented by the following general formula (2).
- X 1 and X 2 each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aromatic group.
- a hydrogen atom, a chlorine atom, a methyl group, a t-butyl group, and a phenyl group is preferable, and any of a hydrogen atom and a chlorine atom is more preferable.
- R 3 and R 4 each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group. However, at least one of R 3 and R 4 represents a substituted or unsubstituted alkyl group.
- the alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, which may be linear, branched or cyclic.
- the group examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl period, an isopropyl group, and an isobutyl group, and a methyl group, an ethyl group, a propyl group, and a pentyl group.
- R 1 and R 2 are not both methyl groups.
- examples of the substituent include a halogen atom, aryl group, heterocyclic group, cyano group, carboxyl group, alkoxy group, aryloxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryl Oxycarbonyloxy, amino group (including anilino group), acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, alkylthio group, arylthio group , Heterocyclic thio group, sulfamoyl group, alkyl and arylsulfinyl group, alkyl and arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamo
- R 3 and R 4 are preferably substituents represented by any one of the following general formulas (R-1) to (R-4).
- Q 1 represents an alkyl group or an aromatic group.
- Q 2 represents a cyclic aliphatic group or an aromatic group.
- Q 3 represents an alkyl group or an aromatic group.
- Q 4 represents an aromatic group.
- P represents an integer.
- Q 1 is an alkyl group or an aromatic group (including an aryl group).
- Q2 is a cyclic aliphatic group or an aromatic group (including an aryl group).
- Q3 is an alkyl group or an aromatic group (including an aryl group).
- Q4 is an aromatic group (including an aryl group).
- Alkyl and aromatic are the same as those described above.
- p represents an integer and is preferably 1 to 3. Specific examples of R 3 and R 4 are given below.
- pigment derivative compounds suitably used as the crystal growth inhibitor are shown below, but the present invention is not limited thereto.
- the presence or absence of the crystal growth inhibitor can be determined by solid-state 13 C CP / MAS NMR measurement (AVANCE DSX-300 spectrometer manufactured by Bruker BioSpin Co., Ltd. and 4 mm ⁇ HFX CP / MAS probe). ).
- the solid 13 C CP / MAS NMR measurement can be performed as follows. The pigment fine particle dispersion is subjected to suction filtration using a membrane filter (MILLIPORE cut size: 0.05 ⁇ m) to prepare a concentrated paste.
- the concentrated paste was set on a solid 13 C CP / MAS NMR sample stage, and based on the Goldman-Shen pulse sequence, 1 H 90 ° pulse width 4.5 ⁇ s, waiting time 200 ⁇ s for initial solvent selection, CP contact time 1 ms Then, the measurement is performed by changing the spin diffusion time from 0.5 to 200 ms.
- the number of integration is 4096 times, and the repetition time is 3 to 10 seconds with 5 times the 1 H spin-lattice relaxation time of the sample as a guide.
- the rotation speed of magic angle spinning is 8000 to 10000 Hz depending on the sample.
- polymer compound examples include “Disperbyk-2000, 2001” manufactured by BYK Chemie, “EFKA 4330, 4340” manufactured by EFKA, and the like.
- graft polymer examples include “Solsperse 24000, 28000, 32000, 38500, 39000, 55000” manufactured by Lubrizol, “Disperbyk-161, 171, 174” manufactured by BYK Chemie, and the like.
- terminal-modified polymer include “Solsperse 3000, 17000, 27000” manufactured by Lubrizol (all are trade names).
- the molecular weight is preferably 500 to 200000, more preferably 1000 to 70000.
- the term “molecular weight” means a mass average molecular weight unless otherwise specified, and the molecular weight and the degree of dispersion are values measured by the following measuring methods.
- the molecular weight and degree of dispersion are measured using GPC (gel filtration chromatography) unless otherwise specified.
- the gel packed in the column used in the GPC method is preferably a gel having an aromatic compound as a repeating unit, and examples thereof include a gel made of a styrene-divinylbenzene copolymer. Two to six columns are preferably connected and used.
- the solvent used include ether solvents such as tetrahydrofuran and amide solvents such as N-methylpyrrolidinone, but ether solvents such as tetrahydrofuran are preferred.
- the measurement is preferably performed at a solvent flow rate in the range of 0.1 to 2 mL / min, and most preferably in the range of 0.5 to 1.5 mL / min. By performing the measurement within this range, the apparatus is not loaded and the measurement can be performed more efficiently.
- the measurement temperature is preferably 10 to 50 ° C, most preferably 20 to 40 ° C.
- the amount of the particle growth inhibitor used in the step [i] is preferably in the range of 1 to 60% by mass with respect to the pigment in order to further improve the intended effect on the fine particles of the dichlorodiketopyrrolopyrrole pigment.
- a more preferred range is 3 to 30% by mass, and a further more preferred range is 5 to 20% by mass.
- the particle size adjusting agents may be used alone or in combination.
- centrifuge any device may be used as the centrifuge as long as the fine pigment particles can be precipitated.
- a device having a skimming function a function of sucking a supernatant layer during rotation and discharging it out of the system
- a continuous centrifuge that continuously discharges solid matter, and the like can be given.
- Centrifugation conditions are preferably 50 to 10,000, more preferably 100 to 8000, and particularly preferably 150 to 6000 in terms of centrifugal force (a value representing how many times the gravity acceleration is applied).
- the temperature at the time of centrifugation depends on the solvent type of the dispersion, but is preferably ⁇ 10 to 80 ° C., more preferably ⁇ 5 to 70 ° C., and particularly preferably 0 to 60 ° C.
- a solvent removal step a method of concentrating the solvent by sublimation by vacuum freeze-drying, a method of drying and concentrating the solvent by heating or decompression, a method combining them, or the like can also be used.
- the extraction solvent is not particularly limited as long as it is a solvent capable of extracting the pigment from the mixed liquid after the pigment fine particles are precipitated, and any of them can be preferably used. It is.
- propylene glycol monomethyl acetate is particularly preferable in that it can also serve as a solvent for increasing the ⁇ -type crystallinity and a solvent for dispersion in step [ii] of the present embodiment.
- a washing solvent such as water or methanol after the above operation and repeat the above operation again.
- these unnecessary components can be removed preferably between step [i] and step [ii] of the present embodiment or after step [ii], but step [ii] includes step [i]. In order not to bring in the good solvent, it is preferable to carry out between step [i] and step [ii].
- the good solvent and the poor solvent can be removed using the third solvent.
- the kind of 3rd solvent is not specifically limited, It is preferable that it is an organic solvent, for example, an ester compound solvent, an alcohol compound solvent, an aromatic compound solvent, an aliphatic compound solvent is preferable, an ester compound solvent, an aromatic compound solvent or Aliphatic compound solvents are more preferred, and ester compound solvents are particularly preferred.
- the third solvent may be a pure solvent based on the above solvent or a mixed solvent composed of a plurality of solvents.
- third solvent not only the above-mentioned third solvent but also a fourth solvent to be described later is used as a medium for the dispersion composition, which is a generic term for solvents different from both the good solvent and the poor solvent. It is referred to as “third solvent”.
- ester compound solvent examples include 2- (1-methoxy) propyl acetate, ethyl acetate, and ethyl lactate.
- alcohol compound solvent examples include methanol, ethanol, n-butanol, isobutanol and the like.
- aromatic compound solvent examples include benzene, toluene, xylene and the like.
- aliphatic compound solvent examples include n-hexane and cyclohexane.
- ethyl lactate, ethyl acetate, ethanol, and 2- (1-methoxy) propyl acetate are preferable, and ethyl lactate and 2- (1-methoxy) propyl acetate are more preferable. These may be used alone or in combination of two or more.
- the third solvent is not the same as the good solvent or the poor solvent.
- the timing of the addition of the third solvent is not particularly limited as long as it is after the precipitation of the pigment fine particles.
- the third solvent may be added to the mixed liquid in which the fine particles are precipitated, or after removing a part of the solvent in the mixed liquid. It may be added, or all may be added after removal (concentration) in advance. That is, the third solvent can be used as a substitution solvent, and the solvent component consisting of the good solvent and the poor solvent in the dispersion liquid in which the fine particles are precipitated can be substituted with the third solvent.
- the third solvent can be added after the good solvent and the poor solvent are completely removed (concentrated) and taken out as pigment particle powder.
- the third solvent is added to replace the solvent, and the second solvent removal step (The solvent may be removed and powdered by the second removal). Thereafter, a pigment dispersant and / or a solvent can be added to obtain a desired pigment dispersion composition.
- the good solvent and the poor solvent are completely removed (concentrated) and taken out as pigment particle powder, and then the third solvent and / or the pigment dispersant can be added to obtain a desired pigment dispersion composition.
- the amount of the third solvent added is not particularly limited, but is preferably 100 to 300,000 parts by mass, more preferably 500 to 10,000 parts by mass with respect to 100 parts by mass of the water-insoluble colorant fine particles.
- the pigment fine particles can be used, for example, in a dispersed state in a vehicle.
- vehicle refers to a portion of a medium in which a pigment is dispersed when it is in a liquid state, a portion that is liquid and binds to the pigment to harden a coating film (binder). And a component (organic solvent) to be dissolved and diluted.
- the concentration of fine particles in the dispersion composition of fine particles after redispersion is appropriately determined according to the purpose, but preferably the fine particles are 2 to 30% by mass, and preferably 4 to 20% by mass with respect to the total amount of the dispersion composition. More preferred is 5 to 15% by mass.
- the amount of the binder and dissolved dilution component is appropriately determined depending on the type of pigment and the like, but the binder is preferably 1 to 30% by mass with respect to the total amount of the dispersion composition.
- the content is more preferably 3 to 20% by mass, and particularly preferably 5 to 15% by mass.
- the dissolved and diluted component is preferably 5 to 80% by mass, and more preferably 10 to 70% by mass.
- the aggregation state of the pigment fine particles is spontaneously solved in the third solvent without adding another dispersant or the like. It preferably has a property of dispersing in a medium, and this property is referred to as “self-dispersible” or “self-dispersible”.
- a pigment dispersant or the like may be added during redispersion of the fine particles.
- a pigment dispersant or the like may be added during redispersion of the fine particles. From this point of view, there is a case where distinction is made between aggregation that is difficult to redisperse and soft aggregation that can be redispersed.
- a dispersion method using ultrasonic waves or a method of applying physical energy can be used.
- the ultrasonic irradiation device used preferably has a function capable of applying an ultrasonic wave of 10 kHz or higher, and examples thereof include an ultrasonic homogenizer and an ultrasonic cleaner.
- the liquid temperature is preferably 1 to 100 ° C., more preferably 5 to 60 ° C.
- the temperature control method can be performed by controlling the dispersion temperature, controlling the temperature of the temperature adjusting layer that controls the temperature of the dispersion, and the like.
- disperser used when dispersing the pigment nanoparticles by applying physical energy, for example, dispersers such as kneaders, roll mills, atriders, super mills, dissolvers, homomixers, and sand mills. Can be mentioned. Further, a high-pressure dispersion method and a dispersion method using fine particle beads are also preferable.
- pigment dispersants include polymer dispersants (for example, linear polymers, block polymers, graft polymers, terminal-modified polymers, etc.), surfactants (polyoxyethylene alkyl phosphate ester, poly Oxyethylene alkylamine, alkanolamine, etc.), pigment derivatives and the like.
- the dispersant acts to adsorb on the surface of the pigment and prevent reaggregation.
- a block polymer, a graft polymer, and a terminal-modified polymer having an anchor site to the pigment surface can be cited as preferred structures.
- the pigment derivative has an effect of promoting the adsorption of the polymer dispersant by modifying the pigment surface.
- the polymer compound include “Disperbyk-2000, 2001” manufactured by BYK Chemie, “EFKA 4330, 4340” manufactured by EFKA, and the like.
- the graft polymer include “Solsperse 24000, 28000, 32000, 38500, 39000, 55000” manufactured by Lubrizol, “Disperbyk-161, 171, 174” manufactured by BYK Chemie, and the like.
- the terminal-modified polymer include “Solsperse 3000, 17000, 27000” manufactured by Lubrizol (all are trade names).
- the pigment derivative (hereinafter also referred to as “pigment derivative-type dispersant”) is derived from an organic pigment as a parent substance, and is produced by chemically modifying the parent structure, Alternatively, it is defined as a pigment derivative type dispersant obtained by a pigmentation reaction of a chemically modified pigment precursor. Generally, it is also called a synergist type dispersant.
- a functional group such as a pigment derivative having an acidic group, a pigment derivative having a basic group, or a phthalimidomethyl group described in JP-A-2007-9096, JP-A-7-331182, or the like.
- the introduced pigment derivative is preferably used.
- Examples of commercially available products include “EFKA 6745 (phthalocyanine derivative), 6750 (azo pigment derivative)” manufactured by EFKA, “Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative)” manufactured by Lubrizol (any) Also product name).
- Examples of the linear polymer include an alkali-soluble resin described later, and it is also preferable to use the linear polymer in combination with the pigment derivative. Only one pigment dispersant may be used, or two or more pigment dispersants may be used in combination.
- the photocurable composition includes a dispersion composition of fine particles of the pigment, a photopolymerizable compound, and a photopolymerization initiator (hereinafter sometimes referred to as a photopolymerization initiator system), preferably, Contains alkali-soluble resin.
- a photopolymerization initiator system preferably, Contains alkali-soluble resin.
- the pigment fine particles and the method for producing the dispersion composition have already been described in detail.
- the content of the fine particles in the photocurable composition is preferably 3 to 90% by mass with respect to the total solid content (in the present invention, the total solid content means the total composition excluding the organic solvent), and 20 More preferably, it is ⁇ 80% by mass, and further preferably 25 ⁇ 60% by mass. If this amount is too large, the viscosity of the dispersion increases, which may cause problems in production suitability. If the amount is too small, the coloring power is not sufficient. Moreover, you may use it in combination with a normal pigment for toning. As the pigment, those described above can be used.
- the photopolymerizable compound (hereinafter sometimes referred to as a polymerizable monomer or a polymerizable oligomer) has two or more ethylenically unsaturated double bonds and is polyfunctionalized by addition polymerization upon irradiation with light.
- a monomer is preferred.
- Examples of such a photopolymerizable compound include compounds having at least one addition-polymerizable ethylenically unsaturated group in the molecule and having a boiling point of 100 ° C. or higher at normal pressure.
- Examples include monofunctional acrylates and monofunctional methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) ) Acrylate, trimethylolethane triacrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane diacrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, di Pentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, hexane All di (meth) acrylate, trimethylolpropane tri (acryloyloxy
- urethane acrylates described in JP-B-48-41708, JP-B-50-6034 and JP-A-51-37193; JP-A-48-64183, JP-B-49-43191 And polyester acrylates described in Japanese Patent Publication No. 52-30490; polyfunctional acrylates such as epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid, and methacrylates.
- trimethylolpropane tri (meth) acrylate pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate are preferable.
- polymerizable compound B described in JP-A-11-133600 can also be mentioned as a preferable example.
- the photopolymerizable compound may be used alone or in combination of two or more.
- the content of the photocurable composition with respect to the total solid content is generally 5 to 50% by mass, and 10 to 40% by mass. Is preferred. If this amount is too large, it becomes difficult to control the developability, which causes a problem in production suitability. If the amount is too small, the curing power at the time of exposure is insufficient.
- a photopolymerization initiator system refers to a mixture that exhibits a photopolymerization initiation function by a combination of a plurality of compounds).
- the vicinal polyketaldonyl compound disclosed in US Pat. No. 2,367,660, the acyloin ether compound described in US Pat. No. 2,448,828, the ⁇ -hydrocarbon described in US Pat. No. 2,722,512 Substituted aromatic acyloin compounds, polynuclear quinone compounds described in US Pat. Nos. 3,046,127 and 2,951,758, triarylimidazole dimers described in US Pat.
- oxime-based compounds such as 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, O— Benzoyl-4 '-(benzmercapto) benzoyl-hexyl-ketoxime, 2,4,6-trimethylphenylcarbonyl-diphenylphosphonyl oxide, hexafluorophospho-trialkylphenylphosphonium salt, and the like may be mentioned as suitable ones. it can.
- the photopolymerization initiator or the photopolymerization initiator system may be used alone or in combination of two or more, but it is particularly preferable to use two or more. When at least two kinds of photopolymerization initiators are used, display characteristics, particularly display unevenness, can be reduced.
- the content of the photopolymerization initiator or photopolymerization initiator system with respect to the total solid content of the photocurable composition is generally 0.5 to 20% by mass, and preferably 1 to 15% by mass. If this amount is too large, the sensitivity becomes too high and control becomes difficult. If the amount is too small, the exposure sensitivity becomes too low.
- Alkali-soluble resin As an alkali-soluble resin, it can be added at the time of preparing a photocurable composition or an inkjet ink for a color filter. Is also preferable.
- the alkali-soluble resin can be added to both or one of the poor solvent for adding the pigment solution and the pigment solution to form pigment fine particles. Alternatively, it is also preferable to add an alkali-soluble resin solution at the time of forming pigment fine particles in a separate system.
- alkali-soluble resin a binder having an acidic group is preferable, and an alkali-soluble polymer having a polar group such as a carboxylic acid group or a carboxylic acid group in the side chain is preferable.
- alkali-soluble polymer having a polar group such as a carboxylic acid group or a carboxylic acid group in the side chain. Examples thereof include JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, JP-A-59-53836, and JP-A-57-36.
- Methacrylic acid copolymer acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer as described in JP-A-59-71048 Etc.
- the cellulose derivative which has a carboxylic acid group, carboxylate, etc. in a side chain can also be mentioned, In addition to this, what added the cyclic acid anhydride to the polymer which has a hydroxyl group can also be used preferably.
- copolymers of benzyl (meth) acrylate and (meth) acrylic acid described in US Pat. No. 4,139,391, benzyl (meth) acrylate and (meth) acrylic acid are used. And multi-component copolymers with other monomers.
- the alkali-soluble resin may be used alone or in the form of a composition used in combination with a normal film-forming polymer.
- the addition amount of pigment to 100 parts by mass of fine particles is 10 to 200 parts by mass. Generally, it is preferably 25 to 100 parts by mass.
- the side chain of the alkali-soluble resin may have a polymerizable group, and a UV curable resin or a thermosetting resin is also useful.
- a resin having a water-soluble atomic group in a part of the side chain can be used.
- O Photocurable resin In a photocurable composition, you may use the organic solvent (4th solvent) for photocurable composition preparation other than the said component further.
- the organic solvent (4th solvent) include, but are not limited to, alcohol solvents, ketone solvents, ether solvents, sulfoxide solvents, ester solvents, amide solvents, aromatic hydrocarbon solvents, aliphatic hydrocarbons.
- Preferable examples include a system solvent, a nitrile solvent, or a mixture thereof.
- the ether solvent include propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate.
- ester solvent examples include 1,3-butylene glycol diacetate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, butyl acetate, ethyl Examples thereof include carbitol acetate and butyl carbitol acetate.
- aromatic hydrocarbon solvent examples include toluene and xylene.
- aliphatic hydrocarbon solvent examples include cyclohexane and n-octane. These solvents may be used alone or in combination of two or more.
- a solvent having a boiling point of 180 ° C. to 250 ° C. can be used if necessary.
- the content of the organic solvent is preferably 10 to 95% by mass with respect to the total amount of the photocurable composition.
- an appropriate surfactant is contained in the photocurable composition.
- Suitable surfactants include those disclosed in JP-A Nos. 2003-337424 and 11-133600.
- content of surfactant 5 mass% or less is preferable with respect to photocurable composition whole quantity.
- the photocurable composition preferably contains a thermal polymerization inhibitor.
- the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl) -6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2-mercaptobenzimidazole, phenothiazine and the like.
- the content of the thermal polymerization inhibitor is preferably 1% by mass or less with respect to the total amount of the photocurable composition.
- a colorant in addition to the colorant (pigment), a colorant (dye or pigment) can be added to the photocurable composition as necessary.
- a pigment among the colorants it is desirable that the pigment is uniformly dispersed in the photocurable composition.
- Specific examples of the dyes or pigments include the coloring materials described in JP-A-2005-17716 [0038]-[0040] and JP-A-2005-361447 [0068]-[0072]. And the colorants described in JP-A-2005-17521 [0080] to [0088] can be suitably used.
- the auxiliary dye or pigment content is preferably 5% by mass or less based on the total amount of the photocurable composition.
- the photocurable composition can contain an ultraviolet absorber as necessary.
- the ultraviolet absorber include salicylate series, benzophenone series, benzotriazole series, cyanoacrylate series, nickel chelate series, hindered amine series and the like in addition to the compounds described in JP-A-5-72724.
- content of a ultraviolet absorber 5 mass% or less is preferable with respect to the photocurable composition whole quantity.
- the photocurable composition may contain “adhesion aid” described in JP-A No. 11-133600, other additives, and the like in addition to the above-described additives.
- the photocurable composition can be made into an inkjet ink by appropriately adjusting its composition.
- the inkjet ink may be a normal inkjet ink such as for printing, but among them, the inkjet ink for the color filter is preferable.
- the ink-jet ink is not particularly limited as long as it contains the pigment fine particles, and is preferably a medium containing a polymerizable monomer and / or a polymerizable oligomer containing the pigment fine particles.
- the polymerizable monomer and / or polymerizable oligomer those described above for the photocurable composition can be used.
- the viscosity at the time of injection is preferably 5 to 25 mPa ⁇ s, more preferably 8 to 22 mPa ⁇ s, and particularly preferably 10 to 20 mPa ⁇ s (in the present invention, unless otherwise specified) It is a value at 25 ° C.).
- the viscosity can be adjusted by adjusting the type and amount of components contained in the ink. The viscosity can be measured, for example, by a normal apparatus such as a conical plate type rotational viscometer or an E type viscometer.
- the surface tension of the ink upon ejection is preferably 15 to 40 mN / m from the viewpoint of improving the flatness of the pixel (in the present invention, the surface tension is a value at 23 ° C. unless otherwise specified). ). More preferably, it is 20 to 35 mN / m, and most preferably 25 to 30 mN / m.
- the surface tension can be adjusted by the addition of a surfactant and the type of solvent.
- the surface tension is obtained by using a measuring device such as a surface tension measuring device (CBVP-Z, manufactured by Kyowa Interface Science Co., Ltd.) or a fully automatic balanced electro surface tension meter ESB-V (manufactured by Kyowa Scientific Co., Ltd.). It can be measured by the plate method.
- Ink jet ink for color filters can be sprayed by continuously ejecting charged ink and controlled by an electric field, intermittently ejecting ink using piezoelectric elements, or intermittently using ink by heating and foaming.
- Various methods such as a method of spraying can be employed.
- a normal method such as a method of thermally curing ink, a method of photocuring, or a method of ejecting droplets after forming a transparent image receiving layer on a substrate in advance. Can be used.
- An ordinary ink jet head (hereinafter also simply referred to as a head) can be applied, and a continuous type or a dot on demand type can be used.
- the thermal head is preferably a type having an operation valve as described in JP-A-9-323420 for discharging.
- the piezo head for example, the heads described in European Patent A277,703, European Patent A278,590 and the like can be used.
- the head preferably has a temperature control function so that the temperature of the ink can be controlled.
- the drive frequency is preferably 1 to 500 kHz.
- a heating step of performing heat treatment can be provided. That is, a substrate having a layer photopolymerized by light irradiation is heated in an electric furnace, a dryer or the like, or an infrared lamp is irradiated.
- the heating temperature and time depend on the composition of the photosensitive dark color composition and the thickness of the formed layer, but generally from about 120 ° C. to obtain sufficient solvent resistance, alkali resistance, and ultraviolet absorbance. Heating at about 250 ° C. for about 10 minutes to about 120 minutes is preferred.
- the pattern shape of the color filter thus formed is not particularly limited, and may be a general black matrix stripe shape, a lattice shape, or a delta arrangement. May be.
- partition wall it is preferable to prepare a partition wall in advance before the pixel forming step using the color filter inkjet ink described above, and to apply ink to a portion surrounded by the partition wall.
- Any partition may be used, but in the case of manufacturing a color filter, it is preferably a light-blocking partition having a black matrix function (hereinafter also simply referred to as “partition”).
- the partition wall can be produced by the same material and method as those of a normal color filter black matrix. For example, paragraph numbers [0021] to [0074] of JP 2005-3861 A, black matrices described in paragraph numbers [0012] to [0021] of JP 2004-240039 A, and JP 2006-17980 A. And the inkjet black matrix described in paragraphs [0009] to [0044] of JP-A-2006-10875.
- the thickness of the coating film using the photocurable composition can be appropriately determined depending on the application, but is preferably 0.5 to 5.0 ⁇ m, and preferably 1.0 to 3.0 ⁇ m. Is more preferable.
- the above-mentioned monomer or oligomer is polymerized to form a polymerized film of the photocurable composition, and a color filter having the polymerized film can be produced (about production of a color filter) Will be described later.)
- Polymerization of the photopolymerizable compound can be carried out by allowing a photopolymerization initiator or a photopolymerization initiator system to act upon irradiation with light.
- the said coating film can be formed by apply
- Slit nozzles and slit coaters described in Japanese Patent Laid-Open No. 2001-310147 and the like are preferably used.
- spin coating is excellent in that a thin film having a thickness of 1 to 3 ⁇ m can be applied uniformly and with high accuracy, and can be widely used for producing color filters.
- slit coating suitable for coating a substrate that is wider and larger in area than spin coating has been used in order to increase manufacturing efficiency and manufacturing cost. It has come to be adopted in the production of. From the viewpoint of liquid-saving properties, slit coating is superior to spin coating, and a uniform coating film can be obtained with a smaller amount of coating liquid.
- a coating head having a slit (gap) with a width of several tens of microns at the tip and a length corresponding to the coating width of a rectangular substrate is maintained at a clearance (gap) of several tens to several hundreds of microns with the substrate.
- this is a coating method in which a coating liquid supplied from a slit is applied to a substrate with a predetermined discharge amount by giving a constant relative speed between the substrate and the coating head.
- This slit coating is (1) less liquid loss compared to spin coating, (2) cleaning process is reduced because there is no flying of the coating liquid, and (3) the scattered liquid components are applied to the coating film again.
- slit coating is suitable for producing a color filter for a large-screen liquid crystal display device, and is expected as an advantageous coating method for reducing the amount of coating liquid.
- coating in the said preparation method can be performed with a normal coating device etc.
- Preferred specific examples of the slit coater are the same as described above.
- the color filter is preferably excellent in contrast.
- contrast means a value measured by a measurement method employed in Examples described later unless otherwise specified.
- the high contrast of the color filter means that the bright and dark discrimination when combined with the liquid crystal can be increased, and this is a very important performance in order to replace the liquid crystal display with a CRT.
- the chromaticity of all the single colors of red (R), green (G), and blue (B) by the F10 light source are the values shown in the table below (hereinafter referred to as this
- the difference ( ⁇ E) from the “target chromaticity”) is preferably in the range of 5 or less, more preferably 3 or less, and particularly preferably 2 or less.
- the chromaticity is measured with a microspectrophotometer (manufactured by Olympus Optical Co., Ltd .; OSP100 or 200), calculated as a result of the F10 light source field of view of 2 degrees, and expressed as an xyY value in the xyz color system. Further, the difference from the target chromaticity is represented by a color difference of the La * b * color system.
- a liquid crystal display device provided with a color filter has high contrast, excellent descriptive power such as black spots, and the VA method is particularly preferable. It can also be suitably used as a large-screen liquid crystal display device such as a notebook personal computer display or a television monitor.
- the color filter can be used for a CCD device and exhibits excellent performance.
- the p-dichlorodiketopyrrolopyrrole pigment (see the following formula (I)) has a crystallite size of 9 nm or less in the direction perpendicular to the plane ( ⁇ 1, 5: 1) calculated from the X-ray diffraction pattern,
- the crystallite size is preferably 6 or more, and more preferably 7 to 8.5 nm.
- the method for obtaining the crystallite size in the (-1: 1) plane perpendicular direction of the p-dichlorodiketopyrrolopyrrole pigment from the X-ray diffraction pattern is the conditions shown in the following examples, unless otherwise specified. According to the procedure.
- the primary particle diameter becomes fine particles, and by dispersing this, a high contrast dispersion liquid can be prepared.
- the heat resistance at the time of setting it as a dispersion liquid and a color resist can be hold
- the ⁇ -type crystallinity of the p-dichlorodiketopyrrolopyrrole pigment is not particularly limited as long as it is 60% or more, but is preferably 65 to 82%, more preferably 70 to 80%.
- the ⁇ -type crystallinity is not more than the above upper limit value, crystal growth can be suppressed and the color filter can have high contrast.
- the above lower limit value or more the properties of the ⁇ -type crystal can be expressed, and a desired color can be obtained.
- the crystal modification of the p-dichlorodiketopyrrolopyrrole pigment reference can be made, for example, to JP-A-58-210084 for the ⁇ -type crystal modification.
- the p-dichlorodiketopyrrolopyrrole pigment of this embodiment is used as a color filter for the first time by defining the specific crystallite size and the specific ⁇ -type crystallinity in the fine particles obtained by the reprecipitation method.
- it has achieved “heat resistance” and “high contrast”, which are difficult to realize as being in conflict with each other, and also improved “red hue” and “stability over time”.
- the reason for this is not clear, but the fine particles obtained by the reprecipitation method have a sharp particle size distribution. Therefore, the progress of Ostwald ripening is small even when the ⁇ crystallization is advanced, and the ⁇ crystallization remains as monodispersed fine particles. I think it can be promoted.
- pigment fine particles obtained by the reprecipitation method to be described later are crystallized by wet grinding with a grinding material to obtain the desired ⁇ -type crystallinity.
- a grinding material to obtain the desired ⁇ -type crystallinity.
- materials used as the grinding material include water-soluble inorganic salts such as sodium chloride, potassium chloride, calcium chloride, barium chloride, and sodium sulfate, ceramic beads such as zirconia beads and titania beads, glass beads, and steel beads.
- the mass is more preferably 1 to 20 times.
- the wetting agent used in the present embodiment the same crystallization solvent as described later can be used. Among them, a high boiling point solvent is preferably used, and 1-butanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol monomethyl ether, ethyl lactate, and propylene glycol monomethyl ether acetate are more preferable.
- JP 2008-24873 A may be referred to.
- pigment fine particles obtained by a reprecipitation method to be described later are crystallized by contacting with an organic solvent, and the desired ⁇ -type crystallinity is obtained. And so on.
- a solution in which the good solvent and / or the poor solvent used in the reprecipitation method is mixed with the dispersant and the two solutions are mixed, or separately, a solution in which the good solvent contains the dispersant. It is preferable to use pigment fine particles in which at least 10% by mass of the dispersant contained in the solvent is embedded.
- alcohol compound solvents such as methanol and 1-butanol
- ester compound solvents such as ethyl acetate and ethyl lactate
- propylene glycol monomethyl ether acetate propylene glycol monomethyl ether acetate
- ketone compound solvents such as acetone and methyl ethyl ketone
- nitrile compound solvents ether compound solvents And organic base solvents
- these may be used alone or as a mixed solvent with water, and further as a mixed solvent thereof.
- alcohol compound solvents and ester compound solvents are preferable, and methanol, 2-butanol, diethylene glycol, and propylene glycol monomethyl ether acetate are more preferable.
- the colored composition of the present embodiment contains p-dichlorodiketopyrrolopyrrole pigment having the specific crystallite size and ⁇ -type crystallinity.
- the p-dichlorodiketopyrrolopyrrole pigment is preferably contained as nanometer-sized fine particles, and the concentration is not particularly limited, but is preferably 2 to 30% by mass, more preferably 8 to 16% by mass. preferable.
- embedding means a state in which part or all of the molecules of the dispersing agent are taken into the fine particles.
- the state in which all of the dispersing agent is taken in is a state in which the whole molecule of the added dispersing agent is encapsulated in the fine particles 10 (see the embedded embedding dispersant 2b), and part of the dispersing agent is taken in.
- a part or functional group of the added dispersant is encapsulated in the particles and the rest of the particles extend outside the particles (see the external embedding dispersant 2a).
- the fine particles of the present embodiment can be described as embedding a specific dispersant 2 as a disperse phase with the pigment 1 as shown in FIG. 5 as a continuous phase if schematically illustrated. You may have by taking in or adhering.
- the embedded dispersing agent 2 there are shown an embedded embedding dispersant 2b in which the whole molecule is encapsulated and an outer embedding dispersing agent 2a in which a part thereof extends outward.
- the outward extending portion 2o of the external embedding dispersant 2a is continuous with the internal portion 2i, and the outward extending portion 2o has a steric repulsive portion, while the internal portion 2i is insoluble in water. It is preferable to have a portion that exhibits an interaction that attracts the coloring material.
- the preferred molecular structure of the embedding dispersant and its design embodiment are as described above.
- the crystallized portion ( ⁇ -type crystallization portion). ) 1b and a non-crystallized portion (non- ⁇ -type crystallized portion) 1a are mixed.
- the ⁇ -type crystallized portion 1b may be partially present at a plurality of locations as illustrated, or may be present at a single location.
- the shape of the crystallized portion 1b is not particularly limited, and needless to say, it does not have to be circular in cross section as shown in the figure.
- the non- ⁇ -type crystallized portion is a portion that is not an ⁇ -type crystal transformation, and may be in an amorphous state or a ⁇ -type crystal transformation.
- a specific dispersant is allowed to coexist in at least one of a good solvent or a poor solvent, and the pigment is dissolved in the good solvent together with or separately from the good solvent.
- the dispersant is preferably a polymer dispersant having a mass average molecular weight of 1000 or more, and more preferably a polymer dispersant having a specific structural site as described later.
- the pigment fine particles of this embodiment are preferably produced in the coexistence of the dispersing agent.
- the good solvent side and / Or mixed by containing the dispersant on the poor solvent side, or (ii) prepared separately by mixing with both the solutions prepared by dissolving the dispersant in a good solvent It is preferably a build-up fine particle embedding a dispersant.
- the solubility of the embedding dispersant in the good solvent is preferably 4.0% by mass or more, and more preferably 10.0% by mass or more. Although there is no particular upper limit to the solubility, it is practical that the solubility is 70% by mass or less in consideration of a commonly used polymer compound.
- the solubility of the embedding dispersant in the poor solvent is preferably 0.02% by mass or less, and more preferably 0.01% by mass or less.
- the dispersing agent partially or wholly incorporated into the inside of the particle is not simply merely physically adsorbed on the particle surface as in the prior art, but is immobilized and irreversibly incorporated within the particle. For this reason, unless the fine particles are destroyed or dissolved, the dispersion medium and / or the composition solvent usually does not release or desorb. Therefore, the fine particles embedded with the dispersant have a high dispersion effect that the aggregation of the particles can be suppressed, and the dispersion stability is extremely high even if the amount of the dispersant used is small. The characteristics of the fine particles embedded with such a dispersing agent can be confirmed, for example, by measuring the amount that the dispersing agent does not desorb even after repeated washing with a solvent in which the dispersing agent dissolves.
- the method for efficiently embedding the dispersing agent in the particles is not particularly limited.
- a specific dispersing agent can be selected and used, or by adjusting process conditions such as a channel mixing method.
- process conditions such as a channel mixing method.
- grains is demonstrated in detail.
- the dispersant In order to embed the dispersant in the particles by the usual reprecipitation method, it is preferable to use a specific dispersant. At this time, if all the dispersant molecules are encapsulated in the particles and all the functional groups necessary for the dispersion are also encapsulated in the particles, it may not be possible to sufficiently fulfill the role of imparting the dispersibility of the dispersant. For this reason, it is preferable that all the functional groups necessary for the dispersion are not included in the particles. In order to appropriately encapsulate the dispersant in the fine particles and impart dispersion stability, it is preferable to use a dispersant that satisfies the following requirements.
- the medium in which the dispersant can be dissolved is compatible with the medium in which the pigment used in combination can be dissolved;
- the dispersant is a polymer dispersant having a mass average molecular weight of 1000 or more, (3) The dispersant is precipitated by mixing with a poor solvent, but the deposition rate is slower than the pigment precipitation, (4)
- the dispersant contains at least one functional group that interacts with the pigment; By satisfying the above requirement, it is preferable that the dispersing agent can be efficiently and appropriately included in the particles.
- the dispersant to be embedded used in the present embodiment is preferably used after being dissolved in a good solvent for dissolving the pigment, a good solvent prepared separately from this, or a poor solvent.
- the following method is mentioned as a preferable embodiment of dissolution and mixing of the dispersant.
- (1) A method in which a dispersant is co-dissolved in a good solvent together with a pigment, and is brought into contact with a poor solvent and precipitated.
- a pigment solution and a dispersant solution are separately prepared and brought into contact with a poor solvent.
- the fine particles of this embodiment may be prepared by any of these methods, but it is preferable that the dispersant-dissolved solution is compatible with the pigment-dissolved solution. If the dispersant solution and the pigment solution are not compatible, mixing with the poor solvent may prevent the dispersant from being sufficiently incorporated into the particles.
- the methods (1) and (2) are particularly preferably used.
- the dispersant in order to incorporate the dispersant into the particles, is preferably a polymer dispersant having a mass average molecular weight of 1000 or more, more preferably 3000 to 300,000, and particularly preferably It is 5000 or more and 100,000 or less. If the molecular weight of the dispersant is too low, the proportion of the dispersant incorporated into the particle may decrease, and if it is too large, aggregation of the dispersant may increase and redispersibility may deteriorate.
- the dispersion of the dispersant is preferably narrow, that is, monodisperse.
- the degree of dispersion of the dispersant is represented by a ratio of the number average molecular weight to the mass average molecular weight, and a dispersant having a dispersity in the range of 1.0 to 5.0 is preferable, and a range of 1.0 to 4.0 is particularly preferable. Is used.
- the dispersant for embedding in the fine particles used in the present embodiment (hereinafter, sometimes referred to as “embedding dispersant” to be distinguished from a simple dispersant) is dissolved in a good solvent in advance, and this is dissolved in a poor solvent. What precipitates by mixing with is preferable.
- the pigment is also preferably dissolved in a good solvent and has a property of being precipitated and brought into fine particles when brought into contact with a poor solvent. In the precipitation behavior of molecules in the formation of such fine particles, when the deposition rate of the dispersant is significantly higher (faster) than the deposition rate of the pigment, the dispersant is deposited before the dispersant is sufficiently incorporated into the particles. End up.
- the deposition rate of the dispersant is lower than the deposition rate of the pigment. And the state which takes in this dispersing agent in microparticles
- fine-particles can be controlled by adjusting the deposition rate of the embedding dispersing agent in this way as needed.
- the deposition rate of the embedding dispersant is preferably slower than that of the pigment, and the preferred rate is the type of pigment, the affinity between the pigment and the dispersant, Depending on the precipitation rate of the pigment, the structure of the dispersant, the solvent affinity between the good solvent and the poor solvent, and the like, it is preferable to determine the precipitation rate ratio between the pigment and the dispersant based on each particle forming condition.
- a preferable dispersing agent for incorporating the embedding dispersant into the particles and further preventing the embedded dispersing agent from being released in the dispersion medium or the composition medium will be described.
- the chemical structure of the embedding dispersant is changed so that the dispersing agent and the pigment are interacted with each other at the stage of precipitation through the mixing process. It is preferable to design. In this embodiment, it is preferable to mix the embedding dispersant and the pigment in a state dissolved in a solvent. However, if the interaction between the dispersant and the pigment is small at this time, the dispersant is taken into the particles.
- the rate may be too small, or the embedded dispersant may be easily released in the dispersion medium or the composition medium, or the dispersion stability may deteriorate. Therefore, it is preferable to use an embedding dispersant having a structural part that attracts and interacts strongly with the pigment, and it is preferable to firmly fix the dispersant to the particles by strengthening this interaction.
- the embedding dispersant introduced into the system when the fine particles are formed is embedded. That is, with respect to the mass (A) of the added embedding dispersant, the percentage of the mass (B) of the dispersant incorporated and embedded in the particles ((B) / (A) ⁇ 100) ( Hereinafter, this rate may be referred to as “dispersing agent uptake rate.”) Is preferably 10% by mass or more. If the dispersant uptake rate is too small, initial dispersibility and dispersion stability may not be sufficient. Further, the dispersant uptake rate ((B) / (A)) is more preferably 20% by mass or more, and particularly preferably 30% by mass or more. Although there is no particular upper limit on the dispersant uptake rate, the upper limit in calculation is 100% by mass, and it is practical that it is 98% or less.
- the amount of the embedding dispersant incorporated is the ratio of the fine particles to the mass of components other than the dispersant, that is, the fine particles are considered to be the continuous phase formed by the embedding dispersant forming the dispersed phase and the pigment, etc. % Of the ratio of the mass (X) of the embedding dispersant forming the above dispersed phase to the mass (Y) of the continuous phase of ((X) / (Y) ⁇ 100) (hereinafter, this ratio is referred to as “dispersant When it is referred to as “embedding rate”), it is 5 to 200% by mass, and more preferably 8 to 160% by mass.
- the interaction attracting with the embedding dispersant or a pigment preferable as a structural site thereof means an interaction between molecules or the adsorptive property or affinity between the structural sites, specifically, hydrogen bonding interaction, ⁇
- Other examples include hydrophobic interaction based on thermodynamic factors. Any of the above-described interactions may be used as the interaction between the dispersant or the structural portion thereof and the pigment, and any of the above-mentioned interactions may be used, but in particular, a hydrogen bond interaction, a ⁇ - ⁇ interaction, an ionic interaction. It is effective to be an action. Therefore, it is preferable to introduce a site exhibiting the above-mentioned interaction as a partial structure of the embedding / dispersing agent, whereby the dispersing agent is easily taken into the particles and easily embedded.
- the hydrogen bond interaction occurs in a molecule in which hydrogen is covalently bonded to an atom having high electronegativity such as fluorine, oxygen, or nitrogen, and in this case, a polar molecule is generated.
- the hydrogen atom is charged to a positive charge smaller than 1, and as a result, an interaction occurs when an attempt is made to adsorb a negatively charged atom such as oxygen contained in another nearby molecule.
- a dispersant having a functional group that easily causes the above-described interaction via a hydrogen bond with a pigment is used, the incorporation rate of the dispersant into the fine particles can be increased.
- ⁇ - ⁇ interaction is a dispersion force acting between aromatic rings of organic compound molecules, and is also called stacking interaction.
- aromatic compounds have a strong planar structure and abundant electrons delocalized by the ⁇ -electron system, so that the London dispersion force is particularly strong. Therefore, the force attracting each other increases as the number of ⁇ electrons increases.
- a dispersant having a functional group that easily interacts with the pigment by ⁇ - ⁇ can be used, the incorporation rate of the dispersant into the fine particles can be increased.
- the ion-ion interaction is an interaction that occurs between charged ions. For example, because different charges attract each other, if the molecular design is such that the dispersant has a charge different from that of the water-insoluble target substance in the dispersion medium, the interaction between the dispersant and the pigment becomes stronger, and the dispersion within the fine particles of the dispersant The uptake rate can be increased.
- the preferred molecular structure of the dispersant varies depending on the type of the target pigment.
- a polymer compound having a heterocyclic moiety is added to impart a hydrogen bonding interaction.
- a polymer compound having a nitrogen-containing heterocyclic moiety can be used preferably.
- a dispersant having an aromatic ring as a partial structure is preferable in order to impart ⁇ - ⁇ interaction or hydrophobic interaction.
- what has a heterocycle and an aromatic ring simultaneously in the same molecular skeleton is especially preferable.
- heterocyclic partial structure of the preferred dispersant used in the present embodiment include the following sites (I-1) to (I-29) and phthalocyanine-based, insoluble azo-based, azo lake-based, anthraquinone-based, quinacridone , Dioxazine, diketopyrrolopyrrole, anthrapyridine, ansanthrone, indanthrone, flavanthrone, perinone, perylene, thioindigo, and other organic dye structures.
- the unit having these sites is preferably 1.0 to 99.0 mol%, more preferably 3.0 to 95.0 mol% of the entire unit constituting the polymer compound. Particularly preferably, it is introduced in the range of 0 to 90.0 mol%.
- a dispersant having the following sites (II-1) to (II-4) can be used.
- the unit having these sites is preferably 1.0 to 99.0 mol%, more preferably 3.0 to 95.0 mol% of the entire unit constituting the polymer compound. Particularly preferably, it is introduced in the range of 0 to 90.0 mol%.
- the embedding / dispersing agent is preferably a polymer compound having the above-described interaction group in a partial structure, but further includes an organic solvent medium (for example, an alcohol solvent, a ketone solvent, an ether solvent, a sulfoxide solvent, an ester solvent).
- an organic solvent medium for example, an alcohol solvent, a ketone solvent, an ether solvent, a sulfoxide solvent, an ester solvent.
- Preferable examples include solvents, amide solvents, aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, nitrile solvents, and mixtures thereof.
- ketone solvents, ether solvents, ester solvents An aromatic hydrocarbon solvent, an aliphatic hydrocarbon solvent, or a mixture thereof is more preferable.
- Examples of the ketone solvent include methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone and the like.
- Examples of the ether solvent include propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate.
- Examples of the ester solvent include 1,3-butylene glycol diacetate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, butyl acetate, ethyl Examples thereof include carbitol acetate and butyl carbitol acetate.
- Examples of the aromatic hydrocarbon solvent include toluene and xylene.
- Examples of the aliphatic hydrocarbon solvent include cyclohexane and n-octane. These solvents may be used alone or in combination of two or more.
- a solvent having a boiling point of 180 ° C. to 250 ° C. can be used if necessary.
- the content of the organic solvent is preferably 10 to 95% by mass with respect to the total amount of the photocurable composition.
- reactive diluents eg 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, ethoxylated phenyl (meth) acrylate, isobornyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxytetraethylene glycol
- Polymeric compounds such as (meth) acrylate, N-vinyl-2-pyrrolidone, N-acryloylmorpholine) and the like preferably have a partial structure having high affinity. Since the steric repulsive part has an affinity for the dispersion medium, dispersibility can be imparted in the dispersion medium by the part (2o part in FIG. 1) of the embedding dispersant outside the particle.
- the affinity site for the dispersion medium is not particularly limited, and examples thereof include (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, and itaconic acid diesters.
- Preferred examples include (meth) acrylamides, styrenes, vinyl ethers, vinyl ketones, olefins, maleimides, (meth) acrylonitrile, and the like.
- Examples of (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate , Isobutyl (meth) acrylate, t-butyl (meth) acrylate, amyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate (meth) acrylate, phenyl (meth) acrylate , 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-methoxyethyl (meth) acrylate , 2- (Ethoxyethyl) (meth) acrylate,
- crotonates examples include butyl crotonate and hexyl crotonate.
- vinyl esters examples include vinyl acetate, vinyl chloroacetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, and vinyl benzoate.
- maleic acid diesters examples include dimethyl maleate, diethyl maleate, and dibutyl maleate.
- fumaric acid diesters examples include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.
- itaconic acid diesters examples include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.
- (Meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, Nn-butyl (Meth) acrylamide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N- Diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-nitrophenyl acrylamide, N-ethyl-N-phenyl acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone acrylamide, N-methylo Le acrylamide, N- hydroxyethyl
- styrenes examples include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethyl
- acidsic substance for example, t-Boc and the like
- vinyl ethers include methyl vinyl ether, ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, octyl vinyl ether, methoxyethyl vinyl ether, and phenyl vinyl ether.
- vinyl ketones examples include methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.
- olefins examples include ethylene, propylene, isobutylene, butadiene, and isoprene.
- maleimides examples include maleimide, butyl maleimide, cyclohexyl maleimide, and phenyl maleimide.
- the embedding dispersant used in the present embodiment is a polymer dispersion having a structural portion that exhibits an interaction attracting the pigment composed of an aromatic ring and a nitrogen-containing cyclic hydrocarbon group and / or a quaternary ammonium group. It is preferable that it is an agent.
- the aromatic ring and the nitrogen-containing cyclic hydrocarbon group and / or the quaternary ammonium group are preferably in the same structural site, and they may be linked to each other to form a ring.
- the dispersant used in the present embodiment can introduce various functional groups in addition to the interaction group attracting the above-described pigment.
- functional groups include a hydrophobic group, an acid group, a basic group, a cross-linking group, a photopolymerizable group, a heat-polymerizable group, etc., depending on the dispersion medium, the medium type of the composition, or the use of the composition.
- the unit having these functional groups is preferably 95 mol% or less, more preferably 90.0 mol% or less, and more preferably 85 mol% or less of the entire unit constituting the polymer compound. It is particularly preferable.
- the embedding dispersant is preferably a water-insoluble polymer compound. If the polymer compound is water-soluble, it may be difficult to incorporate the dispersant into the fine particles when it is brought into contact with a poor solvent containing water as a main component.
- Examples of the acidic group include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and acrylic acid dimer. Further, an addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, or cyclohexanedicarboxylic anhydride, (meth) acrylic acid ⁇ - Carboxy-polycaprolactone can also be used.
- a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate
- a cyclic anhydride such as maleic anhydride, phthalic anhydride, or cyclohexanedicarboxylic anhydride
- acrylic acid ⁇ - Carboxy-polycaprolactone can also be used.
- Examples of the carboxyl group precursor include anhydride-containing monomers such as maleic anhydride, itaconic anhydride, and citraconic anhydride.
- Examples of the vinyl monomer having a sulfonic acid group include 2-acrylamido-2-methylpropanesulfonic acid
- examples of the vinyl monomer having a phosphoric acid group include phosphoric acid mono (2-acryloyloxyethyl ester) and phosphoric acid mono (1-methyl-2-acryloyloxyethyl ester) and the like.
- Basic groups include N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, 1- (N, N-dimethylamino) -1, (meth) acrylic acid, 1-dimethylmethyl, N, N-dimethylaminohexyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-diisopropylaminoethyl (meth) acrylate, N (meth) acrylic acid, N-di-n-butylaminoethyl, N, N-di-i-butylaminoethyl (meth) acrylate, morpholinoethyl (meth) acrylate, piperidinoethyl (meth) acrylate, 1-pyrrole (meth) acrylate Dinoethyl, N, N-methyl-2-pyrrol
- a monomer having a urea group, a urethane group, a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, or a hydroxyl group It is also possible to use a monomer having a urea group, a urethane group, a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, or a hydroxyl group.
- n-butyl (meth) acrylate isobutyl (meth) acrylate, t-butyl (meth) acrylate, amyl (meth) acrylate, n-hexyl (meth) acrylate, (meth ) Cyclohexyl acrylate, t-butyl cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, t-octyl (meth) acrylate, isobornyl (meth) acrylate, (meth) Mention may be made of dodecyl acrylate, octadecyl (meth) acrylate, stearyl (meth) acrylate, oleyl (meth) acrylate, adamantyl (meth) acrylate, and monomers having the following structure.
- the other functional group is more preferably a vinyl monomer polymer or copolymer having a hydrocarbon group having 4 or more carbon atoms, and a hydrocarbon group having 6 to 24 carbon atoms. It is particularly preferable that the monomer has a polymer or copolymer.
- a monomer containing an ionic functional group can be used.
- ionic vinyl monomers anionic vinyl monomers, cationic vinyl monomers
- alkali metal salts of vinyl monomers having the acidic group organic amines (for example, triethylamine, dimethylaminoethanol, etc.) And the like.
- the nitrogen-containing vinyl monomer is an alkyl halide (alkyl group: C1-18, halogen atom: chlorine atom, bromine atom or iodine atom): Benzyl halides such as benzyl chloride and benzyl bromide; alkylsulfonic acid esters such as methanesulfonic acid (alkyl group: C1-18); arylsulfonic acid alkylesters such as benzenesulfonic acid and toluenesulfonic acid (alkyl group: C1— 18); dialky sulfate (Alkyl group: C1 ⁇ 4) that is quaternized with such, like dialkyl diallyl ammonium salts.
- alkyl halide alkyl group: C1-18, halogen atom: chlorine atom, bromine atom or iodine atom
- Benzyl halides such as benzyl chloride and benzyl bromide
- the fine particles of the present embodiment can also be used as a colorant for inkjet recording ink.
- the main component of the dispersion medium and / or the composition medium is an aqueous solvent (for example, water and a water / water-soluble organic solvent mixture.
- water-soluble organic solvents examples include glycerin, 1,2,6-hexanetriol, Trimethylolpropane, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, dipropylene glycol, 2-butene-1,4-diol, 2-ethyl-1,3-hexanediol, 2 Alkanediols such as methyl-2,4-pentanediol, 1,2-octanediol, 1,2-hexanediol, 1,2-pentanediol, 4-methyl-1,2-pentanediol (polyhydric alcohols) ); Glucose, Mannose, Fructose, Ribo Sugars such as xylose, arabinose, galactose, aldonic acid, glucitol, maltose, cellobiose, lactose, suc
- Polyhydric alcohols are useful for the purpose of drying inhibitors and wetting agents.
- glycerin ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-butanediol 2,3-butanediol, 1,4-butanediol, 3-methyl-1,3-butanediol, 1,5-pentanediol, tetraethylene glycol, 1,6-hexanediol, 2-methyl-2,
- Examples thereof include 4-pentanediol, polyethylene glycol, 1,2,4-butanetriol, 1,2,6-hexanetriol, and the like.
- the form of polymerization of the embedding dispersant having the interaction group, the steric repulsion dispersing group, and various functional groups is not particularly limited, but the unit having the interaction group, the unit having the steric repulsion dispersion group, various types Polymers or copolymers of vinyl monomers in units having functional groups (for example, alkyl methacrylate homopolymers, styrene homopolymers, alkyl methacrylate / styrene copolymers, polyvinyl butyral, etc.) , Ester polymers (eg, polycaprolactone), ether polymers (eg, polytetramethylene oxide), urethane polymers (eg, polyurethane made of tetramethylene glycol and hexamethylene diisocyanate), amide polymers (eg, Polyamide 6 and polyamide 66 ), Silicone polymer (e.g., polydimethylsiloxane, etc.), carbonate-based polymers
- the polymer compound is preferably a polymer or copolymer of each vinyl monomer, an ester polymer, an ether polymer, or a modified product or copolymer thereof. From the viewpoint of adjusting solubility in a solvent, cost, ease of synthesis, etc., the polymer compound is most preferably a polymer or copolymer of each vinyl monomer.
- a method by radical polymerization can be applied.
- Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing a vinyl monomer polymer or copolymer by radical polymerization can be easily set by those skilled in the art. The conditions can also be determined experimentally.
- the polymer dispersant used as the embedding dispersant can be used in any binding form. Specifically, any (co) polymers of random (co) polymers, block (co) polymers, and graft (co) polymers can be used. In particular, block (co) polymers, grafts (Co) polymers are preferred.
- the polymer compound is not particularly limited, but a vinyl monomer polymer or copolymer (for example, alkyl methacrylate homopolymer, styrene homopolymer, alkyl methacrylate / styrene copolymer, Polyvinyl butyral, etc.), ester polymers (eg, polycaprolactone), ether polymers (eg, polytetramethylene oxide), urethane polymers (eg, polyurethane made of tetramethylene glycol and hexamethylene diisocyanate), amides Polymer (for example, polyamide 6, polyamide 66, etc.), silicone-based polymer (for example, polydimethylsiloxane), carbonate-based polymer (for example, polycarbonate synthesized from bisphenol A and phosgene) And the like.
- a vinyl monomer polymer or copolymer for example, alkyl methacrylate homopolymer, styrene homopoly
- the polymer compound is preferably a polymer or copolymer of a vinyl monomer, an ester polymer, an ether polymer, or a modified product or copolymer thereof.
- the polymer compound is particularly preferably a vinyl monomer polymer or copolymer.
- (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, (meth) acrylamides Styrenes, vinyl ethers, vinyl ketones, olefins, maleimides, (meth) acrylonitrile and the like are preferable examples.
- Examples of (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate , Isobutyl (meth) acrylate, t-butyl (meth) acrylate, amyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, 2-Methylhexyl acrylate, t-octyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, (meth
- crotonates examples include butyl crotonate and hexyl crotonate.
- vinyl esters examples include vinyl acetate, vinyl chloroacetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, and vinyl benzoate.
- maleic acid diesters examples include dimethyl maleate, diethyl maleate, and dibutyl maleate.
- fumaric acid diesters examples include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.
- itaconic acid diesters examples include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.
- (Meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, Nn-butyl (Meth) acrylamide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N- Diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-nitrophenyl acrylamide, N-ethyl-N-phenyl acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone acrylamide, N-methylo Le acrylamide, N- hydroxyethyl
- styrenes examples include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethyl
- acidsic substance for example, t-Boc and the like
- vinyl ethers include methyl vinyl ether, ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, octyl vinyl ether, methoxyethyl vinyl ether, and phenyl vinyl ether.
- vinyl ketones examples include methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.
- olefins examples include ethylene, propylene, isobutylene, butadiene, and isoprene.
- maleimides examples include maleimide, butyl maleimide, cyclohexyl maleimide, and phenyl maleimide.
- the polymer compound is more preferably a polymer or copolymer of a vinyl monomer having a hydrocarbon group having 4 or more carbon atoms, and further having a hydrocarbon group having 6 to 24 carbon atoms.
- a monomer polymer or copolymer is particularly preferred.
- Examples include n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, amyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate T-butylcyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, t-octyl (meth) acrylate, isobornyl (meth) acrylate, dodecyl (meth) acrylate, Specific examples include octadecyl (meth) acrylate, stearyl (meth) acrylate, oleyl (meth) acrylate, and adamantyl (meth) acrylate.
- vinyl monomer examples include a vinyl monomer having an acidic group and a vinyl monomer having a basic group.
- vinyl monomer having an acidic group examples include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, and cinnamic acid. And acrylic acid dimer.
- an addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, or cyclohexanedicarboxylic anhydride, (meth) acrylic acid ⁇ - Carboxy-polycaprolactone can also be used.
- Examples of the carboxyl group precursor include anhydride-containing monomers such as maleic anhydride, itaconic anhydride, and citraconic anhydride.
- Examples of the vinyl monomer having a sulfonic acid group include 2-acrylamido-2-methylpropanesulfonic acid
- examples of the vinyl monomer having a phosphoric acid group include phosphoric acid mono (2-acryloyloxyethyl ester) and phosphoric acid mono (1-methyl-2-acryloyloxyethyl ester) and the like.
- (meth) acrylic acid esters include N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, and (meth) acrylic.
- Examples of (meth) acrylamides include N- (N ′, N′-dimethylaminoethyl) acrylamide, N- ( N ', N'-dimethylaminoethyl) methacrylamide, N- (N', N'-diethylaminoethyl) acrylamide, N- (N ', N'-diethylaminoethyl) methacrylamide, N- (N', N ' -Dimethylaminopropyl) acrylamide, N- (N ', N'-dimethylaminopropyl) methacrylamide, N- (N', N'-diethylaminopropyl) acrylamide, N- (N ', N'-diethylaminopropyl) methacryl Amide, 2- (N, N-dimethylamino) ethyl (meth) acrylamide, 2- (N N-diethylamino) ethyl
- a monomer having a urea group, a urethane group, a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, or a hydroxyl group include monomers having the following structure.
- a monomer containing an ionic functional group can be used.
- ionic vinyl monomers anionic vinyl monomers, cationic vinyl monomers
- alkali metal salts of vinyl monomers having the acidic group organic amines (for example, triethylamine, dimethylaminoethanol, etc.) And the like.
- the nitrogen-containing vinyl monomer is an alkyl halide (alkyl group: C1-18, halogen atom: chlorine atom, bromine atom or iodine atom): Benzyl halides such as benzyl chloride and benzyl bromide; alkylsulfonic acid esters such as methanesulfonic acid (alkyl group: C1-18); arylsulfonic acid alkylesters such as benzenesulfonic acid and toluenesulfonic acid (alkyl group: C1— 18); dialky sulfate (Alkyl group: C1 ⁇ 4) that is quaternized with such, like dialkyl diallyl ammonium salts.
- alkyl halide alkyl group: C1-18, halogen atom: chlorine atom, bromine atom or iodine atom
- Benzyl halides such as benzyl chloride and benzyl bromide
- the polymer compound is preferably a monomer having an organic dye structure or a heterocyclic structure.
- the monomer having an organic dye structure or a heterocyclic structure include, for example, phthalocyanine, insoluble azo, azo lake, anthraquinone, quinacridone, dioxazine, diketopyrrolopyrrole, anthrapyridine, anthanthrone Ron, flavanthrone, perinone, perylene, and thioindigo dye structures such as thiophene, furan, xanthene, pyrrole, pyrroline, pyrrolidine, dioxolane, pyrazole, pyrazoline, pyrazolidine, imidazole, oxazole, thiazole, oxadi Azole, triazole, thiadiazole, pyran, pyridine, piperidine, dioxane, morpholine, pyridazine, pyrimidine,
- the polymer compound is a monomer polymer or copolymer represented by the general formula (11) Is preferred.
- the terminal group may be any atom or any group, and may simply be a hydrogen atom, a polymerization terminator residue, or the like.
- R 1 represents a hydrogen atom or a methyl group
- J represents —CO—, —COO—, —CONR 6 —, —OCO—, a phenylene group, or —C 6 H 4 CO— group
- 6 represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group
- W 1 represents a single bond, a linear, branched, or cyclic alkylene group, or an aralkylene group
- P represents a heterocyclic group.
- J is preferably —CO—, a phenylene group or a benzoyl group.
- R 6 represents a hydrogen atom, an alkyl group (for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an n-hexyl group, an n-octyl group, a 2-hydroxyethyl group), an aryl Represents a group (for example, a phenyl group), preferably a hydrogen atom, a methyl group, or an ethyl group.
- the alkylene group represented by W 1 is preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 1 to 4 carbon atoms.
- a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, an octylene group, a decylene group, and the like can be given.
- a methylene group, an ethylene group, or a propylene group is preferable.
- the aralkylene group represented by W 1 is preferably an aralkylene group having 7 to 13 carbon atoms, and examples thereof include a benzylidene group and a cinnamylidene group.
- the arylene group represented by W 1 is preferably an arylene group having 6 to 12 carbon atoms, and examples thereof include a phenylene group, a cumenylene group, a mesitylene group, a tolylene group, and a xylylene group, and among them, a phenylene group is particularly preferable. .
- R 32 and R 33 each independently represent hydrogen or an alkyl group, and preferred examples include hydrogen, a methyl group, an ethyl group, and a propyl group.
- linking groups represented by W 1 a single bond or an alkylene group is preferable, and a methylene group, an ethylene group, or a 2-hydroxypropylene group is more preferable.
- P represents a heterocyclic group, and among them, a heterocyclic residue constituting an organic pigment is preferable, and phthalocyanine series, insoluble azo series, azo lake series, anthraquinone series, quinacridone series, dioxazine series, diketopyrrolo Examples thereof include heterocyclic residues that form pyrrole, anthrapyrimidine, ansanthrone, indanthrone, flavanthrone, perinone, perylene, thioindigo, and quinophthalone pigments.
- the heterocyclic residues include thiophene, furan, xanthene, pyrrole, pyrroline, pyrrolidine, dioxolane, pyrazole, pyrazoline, pyrazolidine, imidazole, oxazole, thiazole, oxadiazole, triazole, thiadiazole, pyran, pyridine, piperidine, dioxane, morpholine , Pyridazine, pyrimidine, piperazine, triazine, trithiane, isoindoline, isoindolinone, benzimidazolone, benzothiazole, succinimide, phthalimide, naphthalimide, hydantoin, indole, quinoline, barbitur, thiobarbitur, carbazole, acridine, acridone Quinacridone, anthraquinone, phthalimide, quinaldine, quino
- benzimidazolone indole, quinoline, barbitur Thiobarbitur, carbazole, acridine, acridone, anthraquinone, and phthalimide are particularly preferred.
- These heterocyclic residues can be appropriately selected in view of the structure or electronic properties of the pigment used.
- R 1 represents a hydrogen atom or a methyl group.
- Y represents —NH—, —O—, or —S—.
- W 2 represents a single bond or a divalent linking group, and is preferably a single bond, a linear, branched or cyclic alkylene group, or an aralkylene group.
- P represents a heterocyclic group.
- the preferred range of W 2 is the same as W 1 in the general formula (11).
- P in the above formula is the same as P in the general formula (1).
- P in the repeating unit represented by the general formulas (11), (12), and (13) is represented by the following general formula (4) or a tautomer structure thereof. Is also preferred.
- R 2 represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group.
- R 3 represents a hydrogen atom, an alkyl group, an aryl group, a halogen atom, or an azo group.
- tautomerism Tautomerism is reversible interconversion between isomers, and is a phenomenon in which hydrogen atoms are rearranged mainly by proton rearrangement.
- the tautomers are those that can reach an equilibrium state in which both isomers can coexist with each other, and the isomers that can convert each other have a high isomerization rate.
- it occurs by a rearrangement reaction of a hydrogen atom, that is, a proton accompanied by conversion of a single bond and a double bond.
- the rate of isomerization and the equilibrium ratio vary depending on the temperature, pH, liquid phase or solid phase, and in the case of a solution, the type of solvent. Even when equilibrium is reached for several hours to several days, it is often referred to as tautomerism.
- the chemical structure (part) exhibiting the above tautomerism in the polymer compound is referred to as a tautomer structure (part), and the tautomerization in the repeating unit represented by the general formula (4) is performed.
- the chemical structure (tautomer structure) obtained by the reaction is as shown in the following formulas (a) to (h).
- R 2 is preferably a hydrogen atom, a methyl group, an ethyl group, a 2-ethylhexyl group, or a phenyl group.
- R 3 preferably has an azo structure represented by the following general formula (7).
- R 23 represents a substituted or unsubstituted aromatic ring or a hetero atom-containing heterocycle (for example, an oxygen atom, a sulfur atom, a nitrogen atom, etc.).
- the structure of the aromatic ring and the heterocyclic ring is preferably a 5-membered to 6-membered monocyclic or bicondensed ring.
- a benzothiazole thiadiazole ring is preferred.
- the polymer compound is also preferably a graft copolymer containing a repeating unit obtained by copolymerizing a polymerizable oligomer having an ethylenically unsaturated double bond at the terminal.
- a polymerizable oligomer having an ethylenically unsaturated double bond at the terminal is also called a macromonomer because it is a compound having a predetermined molecular weight.
- This specific polymerizable oligomer is preferably composed of a polymer chain part and a part of a polymerizable functional group having an ethylenically unsaturated double bond at its terminal.
- a group having an ethylenically unsaturated double bond is present only at one end of the polymer chain.
- a (meth) acryloyl group and a vinyl group are preferable, and a (meth) acryloyl group is particularly preferable.
- the macromonomer preferably has a polystyrene-equivalent number average molecular weight (Mn) in the range of 1,000 to 20,000, and particularly preferably in the range of 2,000 to 10,000.
- the polymer chain part is a homopolymer or copolymer formed from at least one monomer selected from the group consisting of alkyl (meth) acrylate, styrene and derivatives thereof, acrylonitrile, vinyl acetate and butadiene, or polyethylene oxide. Polypropylene oxide and polycaprolactone are generally used.
- the polymerizable oligomer is preferably an oligomer represented by the following general formula (5).
- R 9 and R 11 each independently represent a hydrogen atom or a methyl group
- R 10 is an alkylene group having 1 to 12 carbon atoms (preferably an alkylene group having 2 to 4 carbon atoms, and a substituent ( For example, it may have a hydroxyl group) and may be further linked via an ester bond, an ether bond, an amide bond, etc.
- Z represents a phenyl group or an alkyl group having 1 to 4 carbon atoms.
- a phenyl group or —COOR 12 (wherein R 12 represents an alkyl group having 1 to 6 carbon atoms, a phenyl group or an arylalkyl group having 7 to 10 carbon atoms), and q is from 20 to 200 is there.
- Z is preferably a phenyl group or —COOR 12 (wherein R 12 is an alkyl group having 1 to 12 carbon atoms).
- Preferred examples of the polymerizable oligomer (macromonomer) include polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate and poly-i-butyl (meth) acrylate, and (meth) at one molecular end of polystyrene.
- a polymer having an acryloyl group bonded thereto can be exemplified.
- the polymerizable oligomer is preferably not only a polymerizable oligomer represented by the general formula (5) but also a polymerizable oligomer represented by the following general formula (6).
- R 13 represents a hydrogen atom or a methyl group
- R 14 represents an alkylene group having 1 to 8 carbon atoms.
- Q represents —OR 15 or —OCOR 16 .
- R 15 and R 16 represent a hydrogen atom, an alkyl group, or an aryl group.
- n represents 2 to 200.
- R 13 represents a hydrogen atom or a methyl group.
- R 14 represents an alkylene group having 1 to 8 carbon atoms. Among them, an alkylene group having 1 to 6 carbon atoms is preferable, and an alkylene group having 2 to 3 carbon atoms is more preferable.
- Q represents —OR 15 or —OCOR 16 .
- R 15 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a phenyl group, or a phenyl group substituted with an alkyl group having 1 to 18 carbon atoms.
- R 16 represents an alkyl group having 1 to 18 carbon atoms.
- N represents 2 to 200, preferably 5 to 100, and particularly preferably 10 to 100.
- Examples of the polymerizable oligomer represented by the general formula (6) include polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polyethylene glycol polypropylene glycol mono (meth) acrylate, and polytetramethylene glycol monomethacrylate. These may be commercially available products or may be appropriately synthesized. As described above, the polymerizable monomer represented by the general formula (6) is also available as a commercial product.
- Examples of the commercial product include methoxypolyethylene glycol methacrylate (trade names: NK ester M-40G, M-90G, M -230G (above, manufactured by Shin-Nakamura Chemical Co., Ltd.); Trade name: Blemmer PME-100, PME-200, PME-400, PME-1000, PME-2000, PME-4000 (above, NOF Corporation) Polyethylene glycol monomethacrylate (trade names: Blemmer PE-90, PE-200, PE-350, manufactured by NOF Corporation), polypropylene glycol monomethacrylate (trade names: Blemmer PP-500, PP-800, PP-1000 (manufactured by NOF Corporation), polyethylene glycol polypropylene glycol mono Tacrylate (trade name: Blemmer 70PEP-350B, manufactured by NOF Corporation), polyethylene glycol polytetramethylene glycol monomethacrylate (trade name: BREMMER 55PET-800, manufactured by NOF Corporation), polypropylene glyco
- polycaprolactone monomers are also preferable, and commercially available products include polycaprolactone monomethacrylate (trade name: Plaxel FM2D, FM3, FM5, FA1DDM, FA2D, Daicel Chemical). Kogyo Co., Ltd.).
- a radical polymerization method For the production of a vinyl monomer polymer or copolymer, for example, a radical polymerization method can be applied.
- Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing a vinyl monomer polymer or copolymer by radical polymerization can be easily set by those skilled in the art. The conditions can also be determined experimentally.
- the polymer or copolymer of the vinyl monomer may be a polymer compound having a functional group at the terminal.
- the functional group is preferably a functional group excellent in adsorbability to the deposited pigment.
- the polymer compound having a functional group at the terminal can be polymerized using, for example, a method of performing radical polymerization using a chain transfer agent containing a functional group, or a polymerization initiator containing a functional group (eg, radical polymerization, cationic polymerization). , Anionic polymerization, etc.).
- a method of performing radical polymerization using a chain transfer agent containing a functional group or a polymerization initiator containing a functional group (eg, radical polymerization, cationic polymerization). , Anionic polymerization, etc.).
- Examples of the chain transfer agent capable of introducing a functional group at the terminal of the polymer compound include, for example, mercapto compounds (for example, thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N- (2-mercaptopropionyl) glycine, 2-mercaptonicotinic acid, 3- [N- (2-mercaptoethyl) carbamoyl] propionic acid, 3- [N- (2-mercaptoethyl) amino] propionic acid, N- (3-mercaptopropionyl) alanine, 2-mercaptoethanesulfonic acid, 3-mecaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto- 2-propanol, 3-mercapto-2 Butan
- Examples of the polymerization initiator capable of introducing a functional group at the terminal of the polymer compound include 2,2′-azobis (2-cyanopropanol), 2,2′-azobis (2-cyanopentanol), 4, 4′-azobis (4-cyanovaleric acid), 4,4′-azobis (4-cyanovaleric acid chloride), 2,2′-azobis [2- (5-methyl-2-imidazolin-2-yl) propane ], 2,2′-azobis [2- (2-imidazolin-2-yl) propane], 2,2′-azobis [2- (3,4,5,6-tetrahydropyrimidin-2-yl) propane] 2,2′-azobis ⁇ 2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane ⁇ , 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) -Propionamide] etc.
- the derivatives thereof include 2,2′-azobis (2-cyanopropanol), 2,2′-azobis
- a polymer compound represented by the following general formula (21) may be used as a dispersant.
- [Chemical formula 1] Formula (21) (HOOC-) m —R 1 — (— COO — [— R 3 —COO—] n —R 2 ) t (Wherein R 1 is a tetravalent tetracarboxylic acid compound residue, R 2 is a monoalcohol residue, R 3 is a lactone residue, m is 2 or 3, n is an integer of 1 to 50, and t is (4 -M).)
- the polymer compound of the general formula (21) may have a repeating unit represented by the following general formula (22).
- [Chemical 2] General formula (22) —CH 2 —C (R 14 ) (YR 15 —Z) —
- R 14 represents a hydrogen atom or a substituted or unsubstituted alkyl group.
- R 15 represents a single bond or a divalent linking group.
- Z represents a group having a nitrogen-containing heterocyclic structure.
- the amount of the embedding dispersant used is not particularly limited, but when the pigment fine particles are precipitated, the amount added to the system is preferably in the range of 10 to 300 parts by mass with respect to 100 parts by mass of the pigment. A range of 10 to 120 parts by mass is more preferable, and a range of 20 to 100 parts by mass is particularly preferable. As described above, it is preferable that 10% by mass or more of the embedding dispersant to be added to the reprecipitation method is embedded in the fine particles of the present embodiment.
- the embedding dispersant may be used alone or in combination of two or more.
- the content of the embedding dispersant is not particularly limited, but the upper limit is an amount added in the system, and the lower limit is practically an amount embedded in fine particles. Specifically, it is preferably 1 to 294% by mass, more preferably 2 to 99% by mass.
- Examples of commercially available block polymers include “Disperbyk-2000, 2001” manufactured by BYK Chemie, “EFKA 4330, 4340” manufactured by EFKA, and the like.
- Examples of commercially available graft type polymers include “Solsperse 24000, 28000, 32000, 38500, 39000, 55000” manufactured by Lubrizol, “Disperbyk-161, 171, 174” manufactured by BYK Chemie, and the like.
- Examples of commercially available terminally modified polymers include “Solsperse 3000, 17000, 27000” manufactured by Lubrizol (all commercially available polymers are trade names).
- the embedding dispersant is preferably used in the range of 0.1 to 0.4 parts by mass, more preferably in the range of 0.1 to 0.2 parts by mass with respect to 1 part by mass of the pigment. preferable.
- crystal growth inhibitor For this embodiment, it is preferable that a crystal growth inhibitor coexists when forming pigment fine particles by a reprecipitation method, and an organic compound composed of a basic group and a heterocyclic group is added. Is also preferable. In addition to what has been described in the first embodiment, the following may be mentioned as preferable in this embodiment. Such an organic compound is not particularly specified.
- the addition amount of the organic compound composed of the basic group and the heterocyclic group is preferably in the range of 0.01 to 40% by mass, and in the range of 0.05 to 30% by mass with respect to the pigment. More preferably, it is particularly preferably in the range of 0.05 to 25% by mass.
- the pigment derivative referred to here is derived from a pigment derivative compound derived from an organic pigment as a parent substance and manufactured by chemically modifying the parent structure, or by a pigmentation reaction of a chemically modified pigment precursor.
- a pigment derivative type compound examples include “EFKA 6745 (phthalocyanine derivative)” manufactured by EFKA and “Solsperse 5000 (phthalocyanine derivative)” manufactured by Lubrizol (all are trade names).
- the amount used is preferably in the range of 0.5 to 40% by mass, more preferably in the range of 3 to 30% by mass, and more preferably in the range of 5 to 25% by mass with respect to the pigment. It is especially preferable that it is in the range.
- the above crystal growth inhibitor is preferably embedded in the pigment fine particles.
- the confirmation of the embedding or the measurement of the amount can be confirmed, for example, in the same manner as the embedding dispersant, the uptake rate is preferably 0.5 to 40% by mass, and the embedding rate is The content is preferably 1 to 30% by mass.
- Specific examples of the pigment derivative include compounds SS-1 and SS-2 shown in Examples.
- the fine particles of the pigment of the present embodiment are preferably those in which the embedding dispersant having the above specific structure portion is mainly used and embedded in the fine particles, but a non-embedded dispersant may be used in combination.
- Dispersants used in combination are, for example, viscosity adjustment of the dispersion, imparting reactivity with the embedding dispersant, imparting interaction with the embedding dispersant, imparting affinity with the dispersion medium, and precipitation with a poor solvent. It can be used for the purpose of deaggregating particles, the purpose of adjusting the size of fine particles, the purpose of adjusting the affinity between a good solvent and a poor solvent, and the purpose of imparting affinity to a dispersion medium.
- Ordinary dispersants such as surfactants, low molecular dispersants and polymer dispersants can be used in combination.
- the ratio of the dispersant used in combination is not particularly limited, but it is preferably used in the range of 0.01 to 1 part by mass with respect to 1 part by mass of the embedding dispersant, and 0.05 to 0.5 It is more preferable to use in the range of parts by mass.
- a polymer compound can be used as the dispersant used in combination. Specifically, styrene, a styrene derivative, vinyl naphthalene, a vinyl naphthalene derivative, an aliphatic alcohol ester of an ⁇ , ⁇ -ethylenically unsaturated carboxylic acid, an acrylic, etc.
- Acid acrylic acid derivative, methacrylic acid, methacrylic acid derivative, maleic acid, maleic acid derivative, alkenyl sulfonic acid, vinylamine, allylamine, itaconic acid, itaconic acid derivative, fumaric acid, fumaric acid derivative, vinyl acetate, vinylphosphonic acid, vinyl At least two or more monomers selected from pyrrolidone, acrylamide, N-vinylacetamide, N-vinylformamide and derivatives thereof (of which at least one is a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a hydroxyl group, Any of alkylene oxide A block copolymer composed of a monomer having a functional group), a random copolymer, a graft copolymer, a modified product thereof, a salt thereof, and the like. Alternatively, natural polymer compounds such as albumin, gelatin, rosin, shellac, starch, gum arabic and sodium alginate, and modified
- Example I-1 and Comparative Example I-1 Pigment C.I. to 220 ml of dimethyl sulfoxide at room temperature.
- I. Pigment Red 254 (trade name: Irgazine Red 2030, manufactured by Ciba Specialty Chemicals Co., Ltd.), and 1.1 g of the pigment derivative compounds S-1 and S-2 as particle growth inhibitors, 21.5 ml of a tetramethylammonium hydroxide 25% aqueous solution was added and stirred.
- an organic pigment solution in which the pigment was dissolved in a good solvent was obtained.
- 2000 ml of water containing 70 ml of 1 mol / l hydrochloric acid was prepared as a poor solvent.
- the temperature of the organic pigment solution was controlled at 5 ° C.
- the organic pigment solution was NP-KX-500 in the poor solvent stirred at 500 rpm with a GK-0222-10 type Lamond Stirrer (trade name, manufactured by Fujisawa Pharmaceutical Co., Ltd.).
- An organic pigment solution and a poor solvent were brought into contact with each other by injecting using a large-capacity non-pulsating flow pump (trade name, manufactured by Nippon Seimitsu Chemical Co., Ltd.) to precipitate organic pigment fine particles.
- the pigment dispersion prepared by the above procedure is subjected to vacuum filtration with an aspirator using Nutsche and filter paper (Advantech Co., Ltd., No. 2 (trade name)) with a diameter of 9 cm, thereby containing a fine pigment material. Got.
- Nutsche and filter paper Advanced Chemical Co., Ltd., No. 2 (trade name)
- the paste was washed with water to remove the good solvent and water-soluble ions.
- the washing of the paste with water was repeated until the conductivity when the paste was dispersed to a pigment concentration of 5% was 1 ms / m or less.
- a water paste having a solid content concentration of 30% containing the pigment and the particle growth inhibitor was prepared as water paste 1-1W.
- the X-ray diffraction of the pigment powder obtained by separately drying a part of 1-1W was measured to calculate the crystal transformation ratio of the pigment in 1-1W.
- Sample 1-1P which is a red powder color material (hereinafter sometimes referred to as “pigment” or “pigment substance”) containing a dichlorodiketopyrrole pigment and a particle growth inhibitor, was obtained.
- 1-1P is a characteristic Bragg angle (2 ⁇ ) of the dichlorodiketopyrrolopyrrole pigment of ⁇ -type crystal modification.
- a pigment dispersion 1-1D of the present invention was prepared by bead mill dispersion of a pigment substance, a dispersant and a solvent mixture having the following composition. Dispersion was performed with a sand grinder mill BSG-01 (manufactured by AIMEX) using zirconia beads having a diameter of 0.5 mm for 1 hour at 1500 rpm and then using zirconia beads having a diameter of 0.05 mm for 4 hours at 2500 rpm.
- Pigment derivative 1-1P 12.0 parts by mass Pigment derivative 1 0.75 parts by mass Pigment derivative 2 0.75 parts by mass Dispersant resin 1 8.1 parts by mass Propylene glycol monomethyl ether acetate 78.4 parts by mass ⁇
- the structures of pigment derivatives 1 and 2 are shown below.
- Dispersing resin 1 “Ajisper PB821” (trade name) manufactured by Ajinomoto Fine Techno Co., Ltd. Amine value: 10 mgKOH / g Acid value: 17 mg KOH / g
- the obtained pigment dispersion 1-1D was confirmed to contain fine pigment particles having a volume weighted average diameter of 20.0 nm (converted to the same volume sphere) and a coefficient of variation of 15%.
- pigment fine particles were prepared in the same manner except that the conditions of the pigment fine particles were changed as shown in Table 1 below, and evaluated in the same manner.
- Viscosity characteristics evaluation The viscosity characteristics of the obtained pigment dispersion were measured with a rotational viscometer (RE-85L viscometer [trade name] manufactured by Toki Sangyo Co., Ltd.) at 25 ° C. The following ranking was performed. 6: Viscosity value is less than 8 mPa ⁇ s. The best level. 5: Viscosity value of 8 mPa ⁇ s or more and less than 10 mPa ⁇ s. Very good level. 4: Viscosity value of 10 mPa ⁇ s or more and less than 15 mPa ⁇ s. Good level.
- Dye Dispersion 1-1D For the method of preparing Dye Dispersion 1-1D, only the type of particle growth inhibitor, amount added, addition timing, and crystal conversion conditions were changed as shown in Table 1, and the bead mill dispersion time was only optimized. Dispersions were prepared by different methods to obtain dye dispersions 1-2D to 1-25D. These dye dispersions were evaluated in the same manner as the dye dispersion 1-1D. The particle growth inhibitors used here are shown in Tables 1-1 and 1-2 below. Similarly, with respect to the method of preparing the pigment dispersion 1-3D, the type, addition amount, addition timing, and crystal conversion conditions of the particle growth inhibitor were changed as shown in Table 1-1, and the bead mill dispersion time was further changed. Dispersions were prepared by a method different only in the adjustment of dyes to obtain dye dispersions 1-26D to 1-41D. The particle growth inhibitors used here are shown in Table 1-3 below.
- the ⁇ -type crystallinity, the ( ⁇ 151) plane crystallite size, and the (111) plane crystallite size are within the preferred range of the present invention, that is, the equivalent ⁇ crystallinity, the ( ⁇ 151) plane crystallite size and
- FIG. 4 shows the relationship (excerpt) between the pregelatinization rate and the crystallite size in the examples and comparative examples.
- the same plot symbol indicates a sample with the same type and amount of crystal growth inhibitor during crystal conversion. If there are multiple plots with the same symbol (plot shape), crystal growth It means that the type and amount of the inhibitor used are the same and the ⁇ -type crystallinity is changed by changing the temperature and / or time of crystal conversion.
- the crystallite size tends to increase as the ⁇ -type crystallinity increases. That is, the upward trend in the plot of FIG.
- the pigment dispersion prepared by the above procedure was filtered off using Nutsche and filter paper, and then washed with 300 g of methanol cooled to 10 ° C. and 1000 ml of water.
- the obtained red paste was dispersed again in a mixture of 400 g of methanol and 400 g of water, and again filtered by using a Nutsche to obtain an aqueous paste of diketopyrrolopyrrole pigment, which was dried at 80 ° C. for 24 hours, By further pulverizing, a coarse crystal powder composed of a mixed crystal of ⁇ type and ⁇ type was obtained.
- the obtained crude crystal powder was subjected to crystal conversion by adding 1500 g of isobutyl alcohol and 5.6 g of 25% aqueous sodium hydroxide solution to a solution cooled to 10 ° C. and stirring for 6 hours, and then adjusted the pH to 7 or less with acetic acid. Thereafter, Nutsche filtration was performed again, and this was washed by sequentially sprinkling 1000 g of methanol cooled to 10 ° C. and 1000 g of water, and dried to prepare coloring matter 3-1P. Also, with respect to the method for preparing the dye dispersion 1-1D of Example I-1, a dispersion was prepared by replacing the dye substance with 3-1P and further optimizing the dispersion time to obtain a dispersion 3-1D. It was.
- the pigment dispersion prepared in the above procedure was filtered using Nutsche and filter paper, and then washed with 3000 g of methanol cooled to 0 ° C and 1000 ml of water cooled to 5 ° C. Methanol was added to the obtained red paste to make a suspension with a methanol concentration of about 90%, and crystal conversion was performed by stirring at 5 ° C. for 3 hours.
- This was filtered using a Nutsche, further washed with 1000 ml of water at 5 ° C., filtered, dried at 80 ° C. for 24 hours, and further pulverized to prepare a pigment substance 3-2P.
- a dispersion was prepared by replacing the dye substance with 3-2P and further optimizing the dispersion time to obtain a dispersion 3-2D. It was.
- the pigment substances 3-1P and 3-2P have crystallite sizes that are out of the scope of the present invention and their dispersion properties are not good.
- Example I-2 Comparative Example I-2
- a dye dispersion was prepared by the method described below.
- Preparation of pigment dispersion 2-1D Before the crystal conversion step, the water paste 1-1W was dried and pulverized. To 9 parts by mass of the obtained powder, 189 parts by mass of propylene glycol monomethyl ether acetate and 21 parts by mass of water were added, and the temperature was 40 ° C.
- a dye dispersion was prepared in the same manner as the dye dispersion 1-1D of Example I-1, except that the crystal was converted by stirring for 12 hours to obtain a dye dispersion 2-1D. At this time, after finishing the crystal change treatment, the sample was immediately washed with water so as to prevent excessive crystallization.
- a dye dispersion was prepared by the same method as that for the dye dispersion 2-1D to obtain a dye dispersion 2-2D.
- a sand grinder mill BSG-01 [trade name] manufactured by AIMEX
- the crystal conversion was carried out by using 40 parts by mass (bulk weight ratio of about 50%) and stirring at 1500 rpm for 16 hours while controlling at 40 ° C. At this time, after finishing the crystal change treatment, the sample was immediately washed with water so as to prevent excessive crystallization.
- Example 2-1D Drying before crystal conversion (Sample 2-1D) and further using an attrition agent (Sample 2-2D) prolongs the conversion process time for obtaining the same degree of ⁇ crystallinity, and further improves the contrast characteristics. There was a tendency to decrease. At this time, increases in the ( ⁇ 151) plane crystallite size and the crystal plane (111) plane crystallite size were observed, and the decrease in contrast characteristics was considered to correlate with the decrease in crystallite size.
- Drying prior to the crystal conversion step can lead to agglomeration of the pigment particles, resulting in non-uniform crystal conversion, resulting in the formation of excessively grown particles by increasing the ⁇ crystallinity, leading to a decrease in contrast characteristics. It was estimated that there was sex. Moreover, it was estimated that the use of the milling agent resulted in a decrease in the efficiency of ⁇ crystallization due to the suppression of ⁇ crystallization or ⁇ crystallization due to destruction of ⁇ crystals.
- a pigment dispersion was prepared by the same method as that of the pigment dispersion 1-1D to obtain a pigment dispersion 2-3D. However, immediately after crystal conversion, it is rapidly cooled to 5 ° C., and when concentrated by Nutsche filtration, propylene glycol monomethyl ether acetate is added in place of ion-exchanged water and filtration is repeated twice to change the solvent to propylene glycol monomethyl ether acetate. After the replacement, a dye dispersion was immediately prepared without drying.
- the amount of propylene glycol monomethyl ether acetate added in the dye dispersion preparation step was adjusted so that the dye substance concentration in the finished dye dispersion was equal to the dye dispersion 1-1D.
- the obtained dye dispersion was evaluated in the same manner as in Example I-1. Here, the ⁇ crystallinity and crystallite size were measured by adding water to a part of the dye dispersion after replacing the solvent with propylene glycol monomethyl ether acetate to completely stop crystal conversion and then drying. This was performed on the obtained pigment powder. The results are shown in Table 2.
- Dye dispersion 2-3D showed improved contrast and viscosity characteristics over dye dispersion 1-1D, indicating that it is effective not to dry before preparing the dispersion. Further, it was confirmed that even if water washing was not performed after crystal conversion, the dispersion after the conversion was cooled and immediately dispersed, so that no adverse effects due to excessive crystallization were observed.
- a dye dispersion was prepared by a method different from that for preparing the dye dispersion 2D except that 2000 ml of methanol containing 70 ml of 1 mol / l hydrochloric acid was used as a poor solvent to obtain a dye dispersion 2-5D.
- the obtained dye dispersion was evaluated in the same manner as in Example I-1. The results are shown in Table 2.
- the crystal form before the crystal conversion operation was in a mixed state of ⁇ type and ⁇ type, and the contrast characteristics were lowered as compared with the dye dispersion liquid 2-1D.
- the dye dispersion was prepared by a solvent extraction (so-called flushing method) instead of Nutsche filtration before the crystal conversion, and only by changing the crystal conversion time. It was prepared as a pigment dispersion 2-6D.
- the procedure of washing with solvent extraction was as follows. After obtaining a dispersion 1-1S in which organic pigment fine particles were dispersed in a solvent, 40% by weight of propylene glycol monomethyl ether acetate was added to 1-1S and stirred for 5 minutes.
- the solvent composition mainly consists of propylene glycol monomethyl ether acetate
- the upper layer containing the pigment and the solvent composition mainly consists of water and DMSO.
- the solvent composition mainly consists of water and DMSO.
- pigment dispersion 2-6W having been desalted was obtained.
- 2-6W was a pigment dispersion comprising about 85% propylene glycol monomethyl ether acetate and about 15% water as a solvent composition.
- the obtained 2-6W was aged at 40 ° C. for 1 hour for crystal conversion, then immediately cooled to 5 ° C., and the solvent was replaced with propylene glycol monomethyl ether acetate by Nutsche filtration in the same manner as in the dispersion 2-3D. As a result, dispersion 2-6D was obtained.
- the obtained dye dispersion was evaluated in the same manner as in Example I-1.
- the ⁇ crystallinity and crystallite size were measured by adding water to a part of the dye dispersion after replacing the solvent with propylene glycol monomethyl ether acetate to completely stop crystal conversion and then drying. This was performed on the obtained pigment powder.
- the results are shown in Table 2. It was confirmed that the present invention is also effective when desalting and pigment extraction are performed by the flushing method.
- a pigment dispersion was prepared by the same method as that of the pigment dispersion 1-1D to obtain a pigment dispersion 2-7D. However, when the water paste 1-1CW that had undergone the crystal conversion was dried, it was dried by freeze-drying instead of drying at 100 ° C. for 2 hours using an oven. Table 2 shows the results of evaluation similar to Example I-1 for the obtained dye dispersion. Dye dispersion 2-7D showed improved contrast and viscosity characteristics over dye dispersion 1-1D, indicating that it was effective to perform drying by freeze-drying. Similarly, dye dispersions were prepared for the samples 1-26D to 1-41D, and good production suitability and product performance were confirmed for the samples of the present invention.
- Example I-3 Comparative Example I-3 ⁇ Create color filter> A color filter was prepared by the following procedure using the dye dispersion 2-3D obtained in Example I-2. As a result, good contrast was obtained as a color filter, and the dye dispersion of the present invention was suitable for a color filter. It was confirmed that it can be used for.
- K pigment dispersion 1 and propylene glycol monomethyl ether acetate are weighed, mixed at a temperature of 24 ° C. ( ⁇ 2 ° C.), stirred at 150 rpm for 10 minutes, and then methyl ethyl ketone, binder 2 , Hydroquinone monomethyl ether, DPHA solution, polymerization initiator A (2,4-bis (trichloromethyl) -6- [4 '-(N, N-bisethoxycarbonylmethyl) amino-3'-bromophenyl] -s- Triazine) and surfactant 1 were weighed out, added in this order at a temperature of 25 ° C. ( ⁇ 2 ° C.), and stirred at 150 rpm for 30 minutes at a temperature of 40 ° C. ( ⁇ 2 ° C.).
- ⁇ Binder 2> -Polymer (benzyl methacrylate / methacrylic acid 78/22 molar ratio random copolymer, molecular weight 38,000) 27 parts by mass / propylene glycol monomethyl ether acetate 73 parts by mass ⁇ Surfactant 1> ⁇ Megafuck F-780-F (Product name: Dainippon Ink & Chemicals, Inc.) : The composition is the following C 6 F 13 CH 2 CH 2 OCOCH ⁇ CH 2 40 parts by mass and H (OCH (CH 3 ) CH 2 ) 7 OCOCH ⁇ CH 2 Copolymer (molecular weight 30,000) of 55 parts by mass and 5 (parts) H (OCH 2 CH 2 ) 7 OCOCH ⁇ CH 2 30 parts by mass, 70 parts by mass of methyl ethyl ketone
- a heat-treated pixel R was formed in the same process as the formation of the black (K) image using the colored photosensitive resin composition R1 having the composition shown in Table 4 below on the substrate on which the image K was formed.
- the film thickness of the photosensitive resin layer R1 and the coating amount of the pigment are shown below.
- the preparation procedure of the colored photosensitive resin composition was the same as that of the colored photosensitive resin composition K1.
- Photosensitive resin film thickness ( ⁇ m) 1.60 Pigment coating amount (g / m 2 ) 1.00 C. I. P. R. 254 coating amount (g / m 2 ) 0.80 C. I. P. R. 177 coating amount (g / m 2 ) 0.20
- R pigment dispersion 2-1D 40 parts by mass R pigment dispersion 2 (CIPR177) 4.5 parts by mass Propylene glycol monomethyl ether acetate 7.6 parts by mass Methyl ethyl ketone 37 parts by mass Binder 1 0.7 parts by mass DPHA liquid 3.8 parts by mass 2-Trichloromethyl- (p-styrylstyryl) 1,3,4-oxadiazole 0.12 parts by weight Polymerization initiator A 0.05 parts by weight Phenothiazine 0.01 parts by weight Surfactant 1 0.06 parts by weight ⁇ ⁇
- GT-2 (trade name: manufactured by FUJIFILM Electronics Materials)
- CF yellow-EX3393 (trade name: manufactured by Mikuni Color Co., Ltd.)
- ⁇ B pigment dispersion 1> CF Bull-EX3357 (trade name: manufactured by Mikuni Color Co., Ltd.) ⁇ B pigment dispersion 2> CF Bull-EX3383 (trade name: manufactured by Mikuni Color Co., Ltd.) ⁇ Binder 3> ⁇ Polymer (benzyl methacrylate / methacrylic acid / methyl methacrylate random copolymer of 36/22/42 molar ratio, molecular weight 38,000) 27 parts by mass / propylene glycol monomethyl ether acetate 73 parts by mass
- ITO electrodes The glass substrate on which each pixel is formed is put into a sputtering apparatus, and 1300 mm thick ITO (indium tin oxide) is vacuum-deposited on the entire surface at 100 ° C., and then annealed at 240 ° C. for 90 minutes to crystallize the ITO. A transparent electrode was formed to complete the color filter A1.
- Example II-1 Preparation of organic pigment nanoparticle dispersion> Dimethyl sulfoxide (Wako Pure Chemical Industries, Ltd.) is used as a good solvent, and pigment C.I. I. 50 parts of Pigment Red 254 (Irgaphor Red BT-CF, trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.) is dispersed, and 52.3 parts of a 25% methanol solution of tetramethylammonium hydroxide is added dropwise to the pigment solution. 1 was prepared. The viscosity of this pigment solution was measured using Viscomate VM-10A-L (trade name, manufactured by CBC Materials).
- Organic pigment particles are formed by injecting 100 parts at a flow rate of 400 ml / min from a liquid feed pipe having a flow path diameter of 1.1 mm using a large-capacity non-pulsating flow pump (trade name, manufactured by Nippon Seimitsu Chemical Co., Ltd.).
- a pigment nanoparticle dispersion liquid 1 was prepared.
- the organic pigment nanoparticle dispersion 1 prepared by the above procedure was concentrated at 5000 rpm for 90 minutes using a H-112 type centrifugal filter manufactured by Kokusan Co., Ltd. and a P89C type filter cloth manufactured by Shikishima Canvas Co., Ltd. 1100 parts of ion-exchanged water was added and mixed, followed by centrifugal filtration.
- organic pigment nanoparticle concentrated paste 1 was recovered.
- the organic pigment nanoparticle concentrated paste 1 was dried in an oven at 100 ° C. for 2 hours to obtain an organic pigment powder 1a.
- the organic pigment powder 1a having the above composition and 110 parts of propylene glycol monomethyl ether acetate are mixed and wet-ground with a sand grinder mill BSG-01 (manufactured by AIMEX) using zirconia beads having a diameter of 0.5 mm at 1500 rpm for 1 hour.
- An organic pigment nanoparticle dispersion liquid 1a was prepared.
- Example II-2 (Synthesis of polymer P-1) The following monomer solution was introduced into a nitrogen-substituted three-necked flask, stirred with a stirrer (Shinto Kagaku Co., Ltd .: Three-One Motor), heated while flowing nitrogen into the flask, heated to 78 ° C., and stirred for 30 minutes. To do. Then, the following initiator solution is added to said liquid, and it heat-stirs at 78 degreeC for 2 hours. The following initiator solution is further added after heating and stirring, and the operation of heating and stirring at 78 ° C. for 2 hours is repeated twice in total. After the last 2 hours of stirring, the mixture is subsequently heated and stirred at 90 degrees for 2 hours. The obtained reaction solution was poured into 1500 parts of isopropanol while stirring, and the resulting precipitate was collected by filtration and dried by heating to obtain a graft polymer P-1 (mass average molecular weight 10,000).
- a stirrer Shinto Kagaku
- MAA methacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.) NMP; 1-methyl-2-pyrrolidone (manufactured by Wako Pure Chemical Industries, Ltd.)
- first solvent 1,000 parts of N-methylpyrrolidone was mixed with 70.5 parts of a 25% aqueous solution of tetramethylammonium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.), and this was heated to 80 ° C. .
- I. Pigment Red 254 (Irgaphor Red BT-CF, trade name, manufactured by Ciba Specialty Chemicals) 50 parts and 10.0 parts of graft copolymer P-1 were added to prepare Pigment Solution 2.
- the viscosity of this pigment solution 2 was measured using Viscomate VM-10A-L (manufactured by CBC Materials). As a result, the viscosity when the liquid temperature of the pigment solution 2 was 25 ° C.
- the pigment solution 2 feed pipe has a flow path diameter and a supply port diameter of 2.2 mm.
- the supply port is placed in a poor solvent, and 100 parts are injected at a flow rate of 200 ml / min to form organic pigment particles.
- Liquid 2 was prepared.
- the organic pigment nanoparticle dispersion 2 prepared by the above procedure was concentrated at 5000 rpm for 90 minutes using a H-112 type centrifugal filter manufactured by Kokusan Co., Ltd. and a P89C type filter cloth manufactured by Shikishima Canvas Co., Ltd. 1100 parts of ion-exchanged water was added and mixed, followed by centrifugal filtration. Again, 1100 parts of ion-exchanged water was added and mixed, followed by centrifugal filtration.
- the obtained organic pigment nanoparticle concentrated paste 2 was recovered.
- To this organic pigment nanoparticle concentrated paste 2 150 parts of propylene glycol monomethyl ether was added and stirred at 20 ° C. for 8 hours. Then, an H-112 type centrifugal filter manufactured by Kokusan Co., Ltd. and a P89C type filter cloth manufactured by Shikishima Canvas Co., Ltd. were used. The mixture was concentrated at 5000 rpm for 90 minutes, and then 1100 parts of ion exchange water was added and mixed, followed by centrifugal filtration. Again, 1100 parts of ion-exchanged water was added and mixed, followed by centrifugal filtration. The obtained organic pigment nanoparticle concentrated paste 2a was recovered. The organic pigment nanoparticle concentrated paste 2a was dried in an oven at 100 ° C. for 2 hours to obtain an organic pigment powder 2.
- Example II-3 Dimethyl sulfoxide (Wako Pure Chemical Industries, Ltd.) is used as a good solvent, and pigment C.I. I. 50 parts of Pigment Red 254 (Irgaphor Red BT-CF, trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.) is dispersed, and 52.3 parts of a 25% methanol solution of tetramethylammonium hydroxide is added dropwise to the pigment solution. 3 was prepared. The viscosity of this pigment solution was measured using Viscomate VM-10A-L (trade name, manufactured by CBC Materials). As a result, when the liquid temperature of the pigment solution was 24.5 ° C., the viscosity was 14.3 mPa ⁇ s.
- Viscomate VM-10A-L trade name, manufactured by CBC Materials
- the pigment dispersion Liquid 3 was prepared.
- the temperature of the organic pigment nanoparticle dispersion liquid 3 was controlled at 50 ° C. and stirred for 2 hours to prepare an organic pigment nanoparticle dispersion liquid 3a.
- the organic pigment nanoparticle dispersion liquid 3a prepared by the above procedure was concentrated for 90 minutes at 5000 rpm using an H-112 type centrifugal filter manufactured by Kokusan Co., Ltd. and a P89C type filter cloth manufactured by Shikishima Canvas Co., Ltd.
- Example II-4 Dimethyl sulfoxide (Wako Pure Chemical Industries, Ltd.) is used as a good solvent, and pigment C.I. I. 50 parts of Pigment Red 254 (Irgaphor Red BT-CF, trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.) and 10 parts of Compound SS-1 were dispersed therein, and a tetramethylammonium hydroxide 25% methanol solution 61.1 was dispersed therein. A pigment solution 4 was prepared by dropping a portion. The viscosity of this pigment solution was measured using Viscomate VM-10A-L (trade name, manufactured by CBC Materials).
- the temperature of the solution was controlled at 5 ° C.
- the pigment solution 4 was added to a large amount of NP-KX-500 in a poor solvent stirred at 700 rpm with a GK-0222-10 type Lamond Stirrer (trade name, manufactured by Fujisawa Pharmaceutical Co., Ltd.). It inject
- the pigment solution 4 feed pipe has a flow path diameter and a supply port diameter of 2.2 mm. The supply port is placed in a poor solvent, and 100 parts are injected at a flow rate of 200 ml / min to form organic pigment particles. Liquid 4 was prepared.
- the organic pigment nanoparticle dispersion liquid 4 prepared by the above procedure was concentrated at 5000 rpm for 90 minutes using an H-112 type centrifugal filter manufactured by Kokusan Co., Ltd. and a P89C type filter cloth manufactured by Shikishima Canvas Co., Ltd. 1100 parts of ion-exchanged water was added and mixed, followed by centrifugal filtration. Again, 1100 parts of ion-exchanged water was added and mixed, followed by centrifugal filtration. The obtained organic pigment nanoparticle concentrated paste 4 was recovered. To this organic pigment nanoparticle concentrated paste 4, 150 parts of propylene glycol monomethyl ether was added and stirred at 20 ° C.
- Example II-5 Dimethyl sulfoxide (Wako Pure Chemical Industries, Ltd.) is used as a good solvent, and pigment C.I. I. 50 parts of Pigment Red 254 (Irgazine Red 2030, trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.), 10 parts of Compound SS-1 and 15 parts of Compound SS-2 are dispersed therein, and tetramethylammonium hydroxide 25 is dispersed therein.
- a pigment solution 5 was prepared by dropping 64.1 parts of a% methanol solution. The viscosity of this pigment solution was measured using Viscomate VM-10A-L (trade name, manufactured by CBC Materials).
- the temperature of the solution was controlled at 5 ° C.
- the pigment solution 5 was added to a large NP-KX-500 type in a poor solvent stirred at 400 rpm with a GK-0222-10 type Lamond Stirrer (trade name, manufactured by Fujisawa Pharmaceutical Co., Ltd.). It inject
- the flow path diameter and the supply port diameter of the feeding pipe of the pigment solution 5 was 2.2 mm, putting the supply port into a poor solvent, and injecting 100 parts at a flow rate of 200 ml / min, organic pigment particles are formed, and the pigment dispersion Liquid 5 was prepared.
- the organic pigment nanoparticle dispersion 5 prepared by the above procedure was concentrated for 80 minutes at 6000 rpm using an H-112 type centrifugal filter manufactured by Kokusan Co., Ltd. and a P89C type filter cloth manufactured by Shikishima Canvas Co., Ltd. 1100 parts of ion-exchanged water was added and mixed, followed by centrifugal filtration. Again, 1100 parts of ion-exchanged water was added and mixed, followed by centrifugal filtration. The obtained organic pigment nanoparticle concentrated paste 5 was recovered. To this organic pigment nanoparticle concentrated paste 5, 180 parts of propylene glycol monomethyl ether was added and stirred at 20 ° C. for 14 hours.
- Organic pigment powder 1a was prepared in the same manner as in Example II-1, and this was designated as organic pigment powder C2.
- the obtained organic pigment powders 1 to 5 (Examples) and C1 to C3 (Comparative Examples) were subjected to X-ray diffraction measurement by the following method to obtain ⁇ -type crystallinity and ( ⁇ 1, 5 1) plane crystallites. The size and average particle size were calculated. Table 1 shows the calculation results.
- ⁇ -type crystallinity I ⁇ / (I ⁇ + I ⁇ )
- the lengths of the lines L1 and L2 correspond to I ⁇ and I ⁇ .
- the ⁇ -type crystallinity of the dichlorodiketopyrrole pigment is low, there is a case where a clear peak does not appear in the vicinity of 28.1 ° which is a characteristic of the ⁇ -type crystal.
- the value of I ⁇ is zero.
- the ⁇ -type crystallinity value is never 1. This is because even if the diffraction peak derived from the ⁇ -type crystal does not exist at 27 °, the spread of the diffraction peak derived from the ⁇ -type crystal present on both sides of the diffraction peak takes 27 °. This is because it becomes a finite value.
- Crystallite size evaluation (1) Similarly to the method for determining the ⁇ -type crystallinity, powder X-ray diffraction measurement using CuK ⁇ rays was performed on the dichlorodiketopyrrole pigment in the range of Bragg angle (2 ⁇ ) from 23 ° to 30 °. Further, the X-ray diffraction pattern with the background removed was calculated in the same manner as the method for determining the ⁇ -type crystallinity.
- the half-value width value calculated by fitting the peak shape as a Voigt function using the data analysis software Igor Pro manufactured by Wave Metrics is used.
- the crystallite size is calculated from the half-width of the diffraction peak calculated in (2) and the Scherrer equation below.
- D K ⁇ / (10 ⁇ B ⁇ cosA)
- B Bobs-b here
- D Crystallite size (nm)
- Bobs full width at half maximum (rad) calculated in (2)
- b X-ray diffractometer angular resolution correction coefficient, half-value width (rad) when measuring standard silicon crystal.
- X-ray diffractometer RINT2500 manufactured by Rigaku Corporation Goniometer: RINT2000 vertical goniometer manufactured by Rigaku Corporation Sampling width: 0.01 ° Step time: 1 second diverging slit: 2 ° Scattering slit: 2 ° Receiving slit: 0.6mm Tube: Cu Tube voltage: 55KV Tube current: 280 mA
- Example II-6 Using the organic pigment powder 1 obtained in Example II-1, an organic pigment dispersion composition 1 having the following composition was prepared.
- Organic pigment powder A2 10.0 parts Dispersion resin 1 7.88 parts Pigment derivative 1 0.98 parts SS-1 0.97 parts Propylene glycol monomethyl ether acetate 79.75 parts
- pigment derivative 1 The structure of pigment derivative 1 is shown below.
- Main chain Mn 600, graft amount 9.3 mol% (vs. total amine), Acid value 10mgKOH / g, Mw: 10000 Ra: —CO—nC 7 H 15 or hydrogen atom v: 40, w: 5, x: 10, y + z: 45
- the organic pigment dispersion composition having the above composition was motor mill M-50 (manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm for 1 hour at 2000 rpm, and then using zirconia beads having a diameter of 0.05 mm and 2000 rpm. Was dispersed for 4 hours to obtain an organic pigment dispersion composition 11.
- the obtained organic pigment dispersion composition was subjected to contrast measurement, time-dependent contrast measurement, and heat resistance test by the following methods.
- Table 2 shows the calculation results. As is clear from Table 2, it was confirmed that the organic pigment powder prepared in the example can be prepared with a suitable organic pigment dispersion composition, unlike the organic pigment powder prepared in the comparative example.
- a color luminance meter (BM-5 manufactured by Topcon Corporation) was used for the measurement of chromaticity. Two polarizing plates, a sample, and a color luminance meter are installed at a position 13 mm from the backlight, a polarizing plate is placed at a position 40 mm to 60 mm, a cylinder 11 mm in diameter and 20 mm in length, and the light transmitted through this. was measured on a color luminance meter installed at a position of 400 mm through a polarizing plate installed at a position of 100 mm. The measurement angle of the color luminance meter was set to 2 °. The light quantity of the backlight was set so that the luminance when the two polarizing plates were installed in parallel Nicol was 1280 cd / m ⁇ 2> without the sample being installed.
- Organic pigment dispersion composition Contrast Aging contrast Heat resistance ⁇ 11 31 864 30256 3 12 28532 25432 2 13 26744 26002 3 14 27019 27120 3 15 29231 28866 3 C11 9214 9196 3 C12 32011 19326 1 C13 13548 13617 3 ⁇
- the p-dichlorodiketopyrrolopyrrole pigment (Example) of the present invention achieves a very high contrast in the color filter as compared with the comparative example, and the high contrast is maintained for a long time. It can be seen that it exhibits high heat resistance.
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Abstract
Description
特許文献1は、アシッドペースト法により得たジケトピロロピロール顔料を色素誘導体共存下、有機溶剤中でソルトミリングすることにより、結晶成長を抑制し、一次粒径の小さいものを得ることを開示する。しかしながらアシッドペースト法は濃硫酸を用いるため安全上好ましくない。またソルトミリングは特別に微細加工された無機塩を用いる必要があり、コスト上の制約がある。
しかしながら、この方法で用いられるα型結晶変態およびβ型結晶変態が混在している粗製ジクロロジケトピロール顔料は、β型結晶変態のみのものよりも粒径が大きくなりがちである。また、そもそも、ここで開示されている製造手順は微細化のための湿式粉砕の工程を必要とするという生産上の制約がある。さらにこの湿式粉砕の工程で摩砕剤として用いられる無機塩がコスト増の要因になる。より効率的でありコスト的にも有利になる方法が望まれる。
しかしながらこの方法では、顔料溶液が高温なために析出した粒子近傍の顔料溶解度が上がり粒子成長を生じやすい、顔料溶液をゆっくり添加するために、添加初期に生成した粒子が熟成や後から添加される顔料溶質の積層により成長しやすい等の理由により、顔料粒子の微細化に限界がある。顔料粒子の成長を抑制する目的で顔料誘導体等の粒子成長抑制剤を粒子析出時に共存させることが考えられるが、合成時の高温、強塩基条件下では粒子成長抑制剤の分解や副反応の懸念があり、現実的ではない。さらに顔料溶液の添加をゆっくり行うために、生産性が低いという問題がある。また、ここで得られる顔料の微粒子は完全にα型変態となったもの、つまりα型結晶化度をほぼ1としたものを前提としており、α型結晶とβ型結晶の混在したジケトピロロピロール顔料によるコントラスト比等の性能向上については何ら述べられていない。
本発明は、カラーフィルタとしたときに高いコントラストを実現し、その原料となる分散液の粘度を低く抑えることができる、ジクロロジケトピロロピロール顔料からなる色材微粒子の分散物の提供を目的とする。本発明はさらには、カラーフィルタに好適に使用可能なジクロロジケトピロロピロール顔料からなる色材微粒子の色材分散物を、余計な工程を必要とせずに温和な条件下で、効率良くかつコスト的な負担も抑えて調製することができ、大量生産にも好適に対応しうる製造方法の提供を目的とする。
また、確かに、上記特許文献に開示された技術を適用して結晶性の考慮されたp-ジクロロジケトピロロピロール顔料を用いることにより、カラーフィルタの製造や使用における「耐熱結晶析出性」や「焼き付きの防止性」といった熱的な影響に対して一定の効果がありうる。しかし、本発明者らの確認したところによれば、上記性能の良化を目的に例えば単に結晶性を高め結晶子サイズを大きくしたのでは、コントラストが低下してしまう。つまり、結晶子サイズの調節では耐熱性と高コントラスト化とは相反する特性となり、両者を高いレベルで満足することは困難であった。
上記の課題に鑑み、本発明者らは鋭意研究を行ったところ、ジクロロジケトピロール顔料の結晶変態を完全にα型結晶変態としてしまうのではなく、特定のα型結晶化度の範囲にとどめ、さらにX線回折測定によって決定されるジクロロジケトピロール顔料の結晶子サイズを特定の範囲に設定することによって、カラーフィルタに好適に用いることが可能なジクロロジケトピロロピロール顔料からなる色材微粒子が得られることを見出した。さらにこの特定の範囲のα型結晶化度および結晶子サイズのジクロロジケトピロール顔料からなる色材を製造する方法として、再沈法により調製されたジクロロジケトピロロピロール顔料の微粒子を、粒子成長抑制剤の存在下で有機溶媒に接触させて結晶変態をα型に変換することによって、効率的にかつコスト的な負担も抑えて製造できることを見出した。本発明は上記の知見に基づきなされたものであり、すなわち上記の課題は以下の手段により解決された。
(2)下記[i]及び[ii]の工程を経て製造されたことを特徴とする(1)に記載の色材分散物。
[[i]良溶媒に溶解させたジクロロジケトピロロピロール顔料を含む顔料溶液を前記顔料に対して難溶であり前記良溶媒に相溶する貧溶媒と接触させて、ジクロロジケトピロロピロール顔料の微粒子を生成させる工程。]
[[ii]前記[i]の工程で得られたジクロロジケトピロロピロール顔料の微粒子を、前記粒子成長抑制剤の存在下に結晶型調整有機溶媒と接触させて、ジクロロジケトピロロピロール顔料のα型結晶化度を高める工程。]
(3)前記結晶成長抑制剤が下記一般式(1)で表されることを特徴とする(1)又は(2)に記載の色材分散物。
P-[X-(Y)k]n・・・一般式(1)
(式中、Pは置換基を有してもよい有機色素化合物残基を表す。Xは単結合あるいは2価の連結基を表す。Yは-NR2R3、スルホ基、又はカルボキシル基を表す。R2とR3とは各々独立に水素原子、又は置換基を有してもよいアルキル基、アルケニル基、もしくはフェニル基、あるいはR2とR3とで一体となって形成される複素環を表す。kは1または2の整数を表す。nは1~4の整数を表す。)
(4)前記一般式(1)においてPがジケトピロロピロール顔料化合物残基又はキナクリドン顔料化合物残基である(1)~(3)のいずれか1項に記載の色材分散物。
(5)前記成長抑制剤が、さらに下記一般式(2)で表されることを特徴とする(4)に記載の色材分散物。
(6)下記[i]及び[ii]の工程を経て製造されることを特徴とする、(1)~(5)のいずれか1項に記載のジクロロジケトピロロピロール顔料からなる色材微粒子を含有する色材分散物の製造方法。
[[i]良溶媒に溶解させたジクロロジケトピロロピロール顔料を含む顔料溶液を前記顔料に対して難溶であり前記良溶媒に相溶する貧溶媒と接触させて、ジクロロジケトピロロピロール顔料の微粒子を生成させる工程。]
[[ii]前記[i]の工程で得られたジクロロジケトピロロピロール顔料の微粒子を、前記粒子成長抑制剤の存在下に結晶型調整有機溶媒と接触させて、ジクロロジケトピロロピロール顔料のα型結晶化度を高める工程。]
(7)前記ジクロロジケトピロロピロール顔料を含む顔料溶液が、ジクロロジケトピロロピロール顔料を塩基存在下で有機溶媒に溶解して得られたものであることを特徴とする(6)に記載の色材分散物の製造方法。
(8)前記[i]の工程を前記粒子成長抑制剤の存在下で行うことを特徴とする(6)又は(7)に記載の色材分散物の製造方法。
(9)前記結晶成長抑制剤が下記一般式(1)で表されることを特徴とする(6)~(8)のいずれか1項に記載の色材分散物の製造方法。
P-[X-(Y)k]n・・・一般式(1)
(式中、Pは置換基を有してもよい有機色素化合物残基を表す。Xは単結合あるいは2価の連結基を表す。Yは-NR2R3、スルホ基、又はカルボキシル基
を表す。R2とR3とは各々独立に水素原子、又は置換基を有してもよいアルキル基、アルケニル基、もしくはフェニル基、あるいはR2とR3とで一体となって形成される複素環を表す。kは1または2の整数を表す。nは1~4の整数を表す。)
(10)前記一般式(1)で表される粒子成長抑制剤において、Pがキナクリドン顔料化合物残基またはジケトピロロピロール顔料化合物残基であることを特徴とする(9)に記載の色材分散物の製造方法。
(11)前記粒子成長抑制剤が下記一般式(2)で表されることを特徴とする(10)に記載の色材分散物の製造方法。
(式中、X1及びX2は、各々独立に、水素原子、ハロゲン原子、置換もしくは無置換のアルキル基、または置換もしくは無置換の芳香族基を表す。R3及びR4は、各々独立に、水素原子、または置換もしくは無置換のアルキル基を表す。ただし、R1及びR2の少なくとも一方は置換もしくは無置換のアルキル基である。)
(12)前記[i]の工程で生成させたジクロロジケトピロール顔料の微粒子が、実質的にβ型結晶変態であることを特徴とする(6)~(11)のいずれか1項に記載の色材分散物の製造方法。
(13)前記[ii]の工程を摩砕剤の非存在下で行うことを特徴とする(6)~(12)のいずれか1項に記載の色材分散物の製造方法。
(14)前記[ii]の工程を、前記[i]の工程で生成したジクロロジケトピロロピロール顔料粒子を乾燥することなく行うことを特徴とする(6)~(13)のいずれか1項に記載の色材分散物の製造方法。
上記の課題に鑑み、本発明者らは鋭意研究を行ったところ、p-ジクロロジケトピロロピロール顔料を実質的にα型結晶変態とし、一方で結晶性については高めすぎず所定の結晶面方向における結晶子サイズを特定の値以下にすることで、かえってカラーフィルタとしたときに求められる上記特性のすべてを高いレベルでバランス良く満足することを見出した。本発明は上記の知見に基づきなされたものであり、すなわち上記の課題は以下の手段により解決された。
(16)ナノメートルサイズの微粒子であって、該微粒子に分散剤と顔料誘導体との少なくともどちらか一方を埋包させた構造を有する(15)に記載のジクロロジケトピロロピロール顔料。
(17)ジクロロジケトピロロピロール顔料を良溶媒に溶解した溶液と、前記良溶媒と相溶する前記顔料の貧溶媒とを混合し、この混合液中で生成させた微粒子であることを特徴とする(15)又は(16)に記載のジクロロジケトピロロピロール顔料。
(18)前記良溶媒及び/又は貧溶媒に分散剤を含有させて前記両液を混合して、又はこれらとは別に良溶媒に分散剤を含有させた溶液を準備し前記両液とともに混合して生成させた、前記分散剤を埋包する微粒子であって、前記溶媒中に含有させた分散剤の少なくとも10質量%が微粒子に埋包されている(17)に記載のジクロロジケトピロロピロール顔料。
(19)(15)~(18)のいずれか1項に記載のジクロロジケトピロロピロール顔料を含有することを特徴とする着色組成物。
(20)(19)に記載の着色組成物を用いて作成したことを特徴とするカラーフィルタ。
(21)少なくとも下記工程を含むことにより顔料の結晶子サイズおよび結晶化度を調整することを特徴とする、顔料微粒子の製造方法。
<1>顔料を良溶媒に溶解した溶液と、前記良溶媒と相溶し前記顔料の貧溶媒とを混合し、分散剤または顔料誘導体の少なくともどちらか一方の存在下、分散剤または顔料誘導体の少なくともどちらか一方を埋包させた構造を有する顔料微粒子を生成する
<2>前記生成した顔料微粒子を湿式粉砕する
(22)前記顔料微粒子に有機溶剤と接触させることにより結晶化度を調整することを特徴とする(21)記載の顔料微粒子の製造方法。
(23)顔料がジクロロジケトピロロピロール顔料であることを特徴とする(22)記載の顔料微粒子の製造方法。
本発明の色材分散物を用いることにより、カラーフィルタとしたときに高いコントラストを実現し、またその原料となる分散液の粘度を低く抑えることができる。
本発明の製造方法を用いることにより、余計な工程を必要とせずに、また強酸や高温加熱を必要としない温和な条件下で、目的のα型結晶化度および結晶子サイズとしたジクロロジケトピロロピロール顔料の分散物を効率良くかつ低コストで調製することができ、その大量生産にも好適に対応しうるという優れた作用効果を奏する。
また、本発明の色材分散物は、カラーフィルタの原料としての製造適性が高く、特にカラーフィルタとしたときに高いコントラストと良好な品質を実現するという優れた作用効果を奏する。
本発明の上記及び他の特徴及び利点は、下記の記載及び添付の図面からより明らかになるであろう。
本発明のジクロロジケトピロロピロール顔料は、カラーフィルタの色材として特に適し、高い耐熱性とともに、高コントラストを実現し、しかも鮮やかな赤の色相を呈し、高い経時安定性を実現するという優れた作用効果を奏する。
[第1実施形態]
本実施形態の色材分散物は、粒子成長抑制剤およびα型結晶化度を0.65~0.90、(-151)結晶面方向の結晶子サイズを6.0~13.0nm、(111)結晶面方向の結晶子サイズを5.0~23.0nmの範囲としたジクロロジケトピロロピロール顔料の微粒子を含むことを特徴とする。
従来α型結晶変態のジクロロジケトピロロピロール顔料をカラーフィルタに用いることは提案されていた(特許文献3参照)。これに対し、本実施形態のようにα型結晶化度を抑えた場合、カラーフィルタを高コントラストのものとする一方で、その原料分散液の粘度が高まり分散液の安定性が損なわれることが懸念された。本発明者らはα型結晶化度を抑えた場合においても、ジクロロジケトピロール顔料の結晶子サイズを特定の範囲に設定し、さらに好ましくは粒子成長抑制剤を共存させることによって所定面方向の結晶子径を特定の範囲とすることで、分散液の粘度が低粘度に維持可能なことを見出し、本実施形態を成すにいたった。また、α型結晶化度を上記の範囲にすることによりカラーフィルタとしたときに、α型結晶化度を上記範囲を超えて例えば完全にα型変態のものとしたのでは実現できないほど極めて高いコントラストを実現することができる。その理由は定かではない。推定を含めていえば、α型結晶化度を抑制した場合に分散液の粘度上昇をもたらす顔料粒子間の相互作用が、粒子成長抑制剤の存在ないし結晶子サイズを特定の範囲に設定したことによって軽減でき、低粘度の分散液がえられるものと考えられる。
(1) ジクロロジケトピロール顔料につき、CuKα線を用いた粉末X線回折測定を行う。測定は、日本工業規格JIS K03131(X線回折分析通則)に準じ、ブラッグ角(2θ)が、23°から30°の範囲で行う。図1にX線回折パターンを例示する。
(2) (1)で得られたX線回折パターンから、バックグラウンドを除去した回折パターンを求める。ここでバックグラウンドの除去方法は、上記測定パターンの低角側のブラッグ角(2θ)=23.3°付近のすそと高角側のブラッグ角(2θ)=29.7°付近のすそとに接する直線を引き、この直線で表されるX線回折強度の値を(1)で得られたX線回折強度の値から除去したパターンを求める操作を行う。図で例示(典型例)して説明すると、図1のX線回折強度の値から、A点およびB点に接する直線Lで表される回折強度を除去したパターンを求め、これをバックグラウンドを除去したX線回折パターンとする。バックグラウンドを除去したX線回折パターンの例を図2に示す。
(3) (2)で求められたバックグラウンドを除去したX線回折パターンから、下記式によりα型結晶化度を算出する。
α型結晶化度=Iα/(Iα+Iβ)
ここで、Iαはα型結晶変態の特徴的な回折ピークであるブラッグ角(2θ)=28.1±0.3°の回折ピークのバックグラウンド除去後の回折強度値、Iβはβ型結晶変態の特徴的な回折ピークであるブラッグ角(2θ)=27.0±0.3°付近の回折ピークのバックグラウンド除去後の回折強度値と定義する。図2の例では、線L1と線L2の長さがIβおよびIαに相当する。
これら定義において、ジクロロジケトピロール顔料のα型結晶化度が高くβ型結晶の特徴的なブラッグ角(2θ)=27°近傍に明確なピークが見られない場合でも、Iβの値はゼロとなることはなく、したがってα型結晶化度の値は1となることは無いことに注意が必要である。何故ならば、β型結晶由来の回折ピークが27°に存在しなくても、その両側に存在するα型結晶由来の回折ピークのすその広がりが27°にかかるため、27°の回折ピークは有限な値となるためである。また、同様にジクロロジケトピロール顔料のβ型結晶化度が高くα型結晶の特徴的なブラッグ角(2θ)=28.1°近傍に明確なピークが見られない場合でも、Iαの値はゼロとなることはなく、したがってα型結晶化度の値はゼロとなることは無い。何故ならば、ブラッグ角(2θ)=27°近傍に存在するβ型結晶由来の回折ピークの高角側のすその広がりが28.1°近傍までかかるため、28.1°の回折ピークは有限な値となるためである。
ジクロロジケトピロール顔料が実質的にβ型結晶変態状態である場合の、上記定義に基づくα型結晶化度は、β型結晶変態由来のブラッグ角(2θ)=27°近傍の回折ピーク強度およびそのすその広がりで与えられるブラッグ角(2θ)=28.1°の回折ピーク強度が再沈条件で変化するために一義的に決まらないが、通常0.15~0.40の範囲である。
なお、下記第2実施形態についても上記第1実施形態に適用される結晶化度の測定方法や条件を参考にすることができる。
本実施形態においては、後述のように工程[i]の再沈法で得られたジクロロジケトピロロピロール顔料の微粒子を、結晶型調整有機溶媒と接触させてα型結晶化度を高めることができる。再沈法についてはさらに後述するが、通常再沈法で得られたジクロロジケトピロロピロール顔料の微粒子はα型結晶変態とβ形結晶変態の混在状態またはβ型結晶変態からなる。再沈法で得られる顔料微粒子のα型結晶化度は後述する再沈条件や共存素材により変化するが、通常0.15~0.55である。本実施形態においては、再沈法で得るジクロロジケトピロロピロール顔料の微粒子は実質的にβ型結晶変態のものが好ましく、このときのα型結晶化度は0.15~0.40であるのものを工程[ii]の原料微粒子として用いることが好ましい。この観点から、工程[ii]における処理の前後において、α型結晶化度の差を0.23~0.65とすることが好ましい。
これらの中でも、エーテル系溶媒、エステル系溶媒、アルコール系溶媒、ケトン系溶媒、これらの混合物、またはこれらと水との混合物がより好ましく、プロピレングリコールモノメチルエーテルアセテートが主成分であるものが特に好ましい。ここで用いる貧溶媒は、次工程の分散液の調製における分散媒にも用いるが、プロピレングリコールモノメチルエーテルアセテートは最終分散液の汎用溶媒であり、両工程でこれを使用することでコストパフォーマンスが向上する。
また、結晶型調整工程で用いるジクロロジケトピロロピロール顔料の微粒子は、再沈法により析出させてから乾燥されずに用いることが好ましいことから、結晶型調整工程の溶媒としてはこれら有機溶剤に再沈時の良溶媒および貧溶媒の一部、水洗に用いた水、あるいはこれらを置換した別の溶媒が混在しても良く、中でも水が混在していることが好ましい。ただし、再沈時に用いた良溶媒は過度の粒子成長を招く恐れがあるため、結晶型調整工程には共存させないことが望ましい。
本実施形態の工程[ii]で用いる粒子成長抑制剤の好ましい種類および使用量は、後述する工程[i]に含有させる際に好ましい素材および使用量を用いることができる。
本実施形態においてはさらに、工程[ii]を得て得られるジクロロジケトピロロピロール顔料の(-151)結晶面方向の結晶子サイズが6nm以上13nm以下であり、6nm以上11.0以下であることが好ましく、6nm以上9.0nm以下であることが特に好ましい。また、(111)結晶面方向の結晶子サイズが5.0nm以上23nm以下であり、5.0nm以上20nm以下であることが好ましく、10nm以上18nm以下であることが特に好ましい。このような範囲にジクロロジケトピロロピロール顔料の所定の結晶面方向の結晶子サイズを調節することにより、α型結晶化度を制限した場合の分散液の粘度を低く抑えることができる。
(1) α型結晶化度の決定方法同様、ジクロロジケトピロール顔料につき、CuKα線を用いた粉末X線回折測定を、ブラッグ角(2θ)が、23°から30°の範囲で行う。さらにα型結晶化度の決定方法同様、バックグラウンドを除去したX線回折パターンを算出する。
(2) (1)で得たバックグラウンドを除去したX線回折パターンから、α型結晶変態由来のブラッグ角(2θ)=24.6±0.3°近傍の回折ピークおよび28.1±0.3°近傍の回折ピークそれぞれに対し、半値幅および回折ピークのブラッグ角(2θ)を求める。半値幅の算出は、上記測定範囲に存在する4つの回折ピーク(α型結晶変態由来のブラッグ角24.6°、25.6°、28.1°各近傍の3つのピークおよびβ型結晶変態由来のブラッグ角27°近傍のピーク)それぞれを市販のデータ解析ソフトを用いてピーク分離を行うことにより算出可能となる。本実施形態においては、Wave Metorics社製データ解析ソフト Igor Proを用い、ピーク形状をVoigt関数としてフィッティングを行い算出される半値幅の値を用いることとする。
(3) (2)で算出した回折ピーク半値幅および下記シェラーの式により結晶子サイズを算出する。
D=Kλ/(10×B×cosA)
B=Bobs-b
ここで、
D:結晶子サイズ(nm)
Bobs:(2)で算出した半値幅(rad)
b:X線回折装置角度分解能補正係数であり、標準シリコン結晶測定時の半値幅(rad)。本実施形態では下記装置構成および測定条件で標準シリコン結晶を測定し、b=0.2とした。
A:回折ピークブラッグ角2θ(rad)
K:シェラー定数(本実施形態ではK=0.94と定義する)
λ:X線波長(Å)(本実施形態ではCuKα線であるため、λ=1.54)
X線回折装置:(株)リガク社製RINT2500
ゴニオメーター:(株)リガク社製RINT2000縦型ゴニオメーター
サンプリング幅:0.01°
ステップ時間:1秒
発散スリット:2°
散乱スリット:2°
受光スリット:0.6mm
管球:Cu
管電圧:55KV
管電流:280mA
なお、後記第2実施形態についても上記第1実施形態の結晶子サイズの測定条件等を参考にすることができる。
本実施形態において工程[ii]に適用されるジクロロジケトピロロピロール顔料の微粒子は、再沈法により析出させてから乾燥されずに用いることがこのましく、分散媒体中に分散された状態が維持されたものであることが好ましい。ここで乾燥とは、顔料微粒子の濃度が60%以上に高まることをいう。
これら処理を経た顔料は必要に応じて濃縮や乾燥等の操作により、顔料濃度を高めることができる。濃縮または乾燥方法に特に制限はないが、乾燥を行う際には乾燥による顔料微粒子の過度な凝集を避けるために、凍結乾燥を行うか、あるいは溶剤をアルコールやアセトン等の有機溶媒に置換した後乾燥を行うことが好ましく、また乾燥前に分散剤と混合することも好ましい。
微粒子の粒径に関しては、計測法により数値化して集団の平均の大きさを表現する方法があるが、よく使用されるものとして、分布の最大値を示すモード径、積分分布曲線の中央値に相当するメジアン径、各種の平均径(数平均、長さ平均、面積平均、質量平均、体積平均等)などがある。本発明においては、特に断りのない限り、平均粒径とは数平均径をいう。本発明において顔料微粒子(一次粒子)の平均粒径は100nm以下が好ましく、75nm以下がより好ましく、50nm以下であることが特に好ましい。下限は特に限定されないが、2nmないし3nm以上であることが実際的である。
本実施形態においては、溶媒に溶解状態にあるジクロロジケトピロロピロール顔料を貧溶媒と接触させて、ジクロロジケトピロロピロール顔料の微粒子を生成させる。溶媒に溶解状態にあるジクロロジケトピロール顔料とは、あらかじめ合成済みのジクロロジケトピロール顔料を良溶媒に溶解した場合のジクロロジケトピロール顔料、およびジクロロジケトピロール顔料を原料から合成溶媒中で合成して生成させた際に、アルカリ金属塩などの状態で合成溶媒に溶解している状態のジクロロジケトピロール顔料の両者を意味する。このときジクロロジケトピロロピロール顔料を溶解させる溶媒(良溶媒)と貧溶媒との相溶性は、良溶媒の貧溶媒に対する溶解量が30質量%以上であることが好ましく、50質量%以上であることがより好ましい。良溶媒の貧溶媒に対する溶解量に特に上限はないが、任意の割合で混じり合うことが実際的である。
媒、またはこれらの混合物などが好適に挙げられる。
他の成分としては、特に限定されないが、酸(酸性基を有する有機化合物など)、塩基(塩基性を有する有機化合物など)が好適に挙げられる。なかでも本実施形態においては、塩基の存在化でジクロロジケトピロロピロール顔料を溶解することが好ましく、該塩基が有機塩基であることがより好ましい。
このような有機化合物としては、例えば、2-アミノピリジン、3-アミノピリジン、1-(2-アミノフェニル)ピロール、5-アミノピラゾール、3-アミノ-5-メチルピラゾール、5-アミノ-1-エチルピラゾール、3-アミノトリアゾール、2-アミノチアゾール、5-アミノインドール、2-アミノベンズチアゾール、5-アミノベンズイミダゾール、N,N-ジメチル-5-アミノベンズイミダゾール、フタルイミド、5-アミノベンズイミダゾロン、N,N-ジメチル-5-アミノベンズイミダゾロン、5-アミノウラシル、6-アミノウラシル、ウラシル、チミン、アデニン、グアニン、メラミン、アミノピラジン、8-アミノキノリン、3-アミノキノリン、9-アミノアクリジン、ASTRAブルー6GLL(塩基性フタロシアニン誘導体)、2-アミノアントラキノン、3-アミノアントラキノン、アクリドン、N-アクリドン、キナクリドン、NILEレッド、メチレンバイオレットナフタルイミドなどが挙げられる。好ましくは、2-アミノベンズチアゾール、5-アミノベンズイミダゾール、N,N-ジメチル-5-アミノベンズイミダゾール、5-アミノベンズイミダゾロン、N,N-ジメチル-5-アミノベンズイミダゾロン、5-アミノウラシル、6-アミノウラシル、ウラシル、チミン、アデニン、グアニン、メラミン、8-アミノキノリン、3-アミノキノリン、9-アミノアクリジン、ASTRAブルー6GLL(塩基性フタロシアニン誘導体)、2-アミノアントラキノン、3-アミノアントラキノン、アクリドン、N-アクリドン、キナクリドン、NILEレッド、メチレンバイオレットナフタルイミドが挙げられ、より好ましくは、9-アミノアクリジン、ASTRAブルー6GLL(塩基性フタロシアニン誘導体)、2-アミノアントラキノン、3-アミノアントラキノン、アクリドン、N-アクリドン、5-アミノベンズイミダゾール、N,N-ジメチル-5-アミノベンズイミダゾール、5-アミノベンズイミダゾロン、N,N-ジメチル-5-アミノベンズイミダゾロン、5-アミノウラシル、6-アミノウラシル、NILEレッド、メチレンバイオレットナフタルイミドが挙げられる。
-メチルイミダゾリウムテトラフルオロボレート等)、二硫化炭素溶媒、またはこれらの混合物などが好適に挙げられる。
これらの中でも、水系溶媒、アルコール系溶媒、ケトン系溶媒、スルホキシド系溶媒、エステル系溶媒、アミド系溶媒、ニトリル系溶媒、またはこれらの混合物がより好ましく、水性媒体、アルコール系溶媒、またはこれらの混合物が特に好ましい。
アルコール系溶媒としては、例えば、メタノール、エタノール、イソプロピルアルコール、n-プロピルアルコール、1-メトキシ-2-プロパノールなどが挙げられる。
Re=ρUL/μ ・・・ 数式(1)
数式(1)中、Reはレイノルズ数を表し、ρは顔料溶液の密度[kg/m3]を表し、Uは顔料溶液と貧溶媒とが出会う時の相対速度[m/s]を表し、Lは顔料溶液と貧溶媒とが出会う部分の流路もしくは供給口の等価直径[m]を表し、μは顔料溶液の粘性係数[Pa・s]を表す。
L=4A/p ・・・ 数式(2)
配管を通じて顔料溶液を貧溶媒に注入して粒子を形成することが好ましく、配管に円管を用いた場合には等価直径は円管の直径と一致する。例えば、液体供給口の開口径を変化させて等価直径を調節することができる。等価直径Lの値は特に限定されないが、例えば、上述した供給口の好ましい内径と同義である。
粒子成長抑制剤としては、顔料分子骨格に置換基を導入した顔料誘導体(色素誘導体とも呼ぶ)、前述の塩基性基と複素環基とで構成される有機化合物、高分子分散剤等を好ましく用いることができ、中でも顔料誘導体が特に好ましい。
P-[X-(Y)k]n・・・一般式(1)
(式中、Pは置換基を有してもよい有機色素化合物残基を表し(有機色素残基とは有機色素ないしその誘導体の残基を含む。)、Xは、単結合あるいは2価の連結基を表す。連結基としては、1~100個の炭素原子、0~10個の窒素原子、0~50個の酸素原子、1~200個の水素原子、および0~20個の硫黄原子から成り立つ基が含まれ、無置換でも置換基を更に有していてもよい。Xは、有機連結基であることが好ましく、Xの具体的な例として、直接結合、-O-、-S-、-CO-、-SO2-、-NR1-、-CONR1-、-SO2NR1-、-NR1CO-、-NR1SO2-(ここでR1は、水素原子、アルキル基、又はヒドロキシアルキル基を表す)、置換基を有してもよい炭素数18以下のアルキレン基およびアルキル基、置換基を有してもよいフェニル基、又はトリアジン残基、あるいはこれらの組み合わせを挙げることができる。Yは-NR2R3、スルホ基、又はカルボキシル基を表し、R2とR3とは各々独立に水素原子、又は置換基を有してもよいアルキル基、アルケニル基、もしくはフェニル基、またはR2とR3とで一体となって形成される複素環を表す。kは1または2の整数を表し、nは1~4の整数を表す。なお本発明において所定の一般式で表される「化合物」もしくは「剤」というとき、その構造式の化合物そのもののほか、当該化合物が塩を形成するものである場合、その塩を含む意味である。
本実施形態において好ましく使用できる顔料誘導体としては、特開昭56-118462号公報、特開昭63-264674号公報、特開平1-217077号公報、特開平3-9961号公報、特開平3-26767号公報、特開平3-153780号公報、特開平3-45662号公報、特開平4-285669号公報、特開平6-145546号公報、特開平6-212088号公報、特開平6-240158号公報、特開平10-30063号公報、特開平10-195326号公報等に記載のものをいずれも好ましく用いることが出来る。
R3及びR4において、アルキル基は、炭素原子数が好ましくは1~10、さらに好ましくは1~5のアルキル基であり、直鎖状、分岐状、環状のいずれでもよい。具体的な基としては、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル期、イソプロピレル基ン、イソブチル基が挙げられ、メチル基、エチル基、プロピル基、ペンチル基が好ましい。R1及びR2は両者がメチル基ではないことが好ましい。
以下に、R3,R4の具体例を挙げる。
顔料微粒子分散体を、それぞれメンブレンフィルター(MILLIPORE製 カットサイズ:0.05μm)を用いて吸引ろ過し、濃縮ペーストを作製する。前記濃縮ペーストを固体13C CP/MAS NMRの試料台にセットし、Goldman-shenパルス系列に基づき、1H90°パルス幅4.5μs、初期の溶媒選択のための待ち時間200μs、CPコンタクトタイム1msとし、スピン拡散時間を0.5~200msまで変化させて測定を行う。積算回数は4096回、繰り返し時間は試料の1Hスピン-格子緩和時間の5倍を目安に3~10秒とする。マジックアングルスピニングの回転数は、試料により8000~10000Hzとする。
各々のスピン拡散時間におけるスペクトルをピーク分離によって顔料及び分散剤のピーク面積を算出し、一次元拡散モデルを仮定した拡散距離Lは、スピン拡散時間tmに対して、 L=1.1(tm)1/2 の関係にあることを用いて、溶媒分子からの距離に対するピーク面積のプロットから粒子構造を判断する。
高分子化合物としては、BYK Chemie社製「Disperbyk-2000、2001」、EFKA社製「EFKA4330、4340」等を挙げることができる。グラフト型高分子の例としては、ルーブリゾール社製「ソルスパース24000、28000、32000、38500、39000、55000」、BYK Chemie社製「Disperbyk-161、171、174」等が挙げられる。末端変性型高分子の例としては、ルーブリゾール社製「ソルスパース3000、17000、27000」、等を挙げることができる(いずれも商品名)。
分子量及び分散度は特に断らない限りGPC(ゲルろ過クロマトグラフィー)法を用いて測定する。GPC法に用いるカラムに充填されているゲルは芳香族化合物を繰り返し単位に持つゲルが好ましく、例えばスチレン-ジビニルベンゼン共重合体からなるゲルが挙げられる。カラムは2~6本連結させて用いることが好ましい。用いる溶媒は、テトラヒドロフラン等のエーテル系溶媒、N-メチルピロリジノン等のアミド系溶媒が挙げられるが、テトラヒドロフラン等のエーテル系溶媒が好ましい。測定は、溶媒の流速が0.1~2mL/minの範囲で行うことが好ましく、0.5~1.5mL/minの範囲で行うことが最も好ましい。この範囲内で測定を行うことで、装置に負荷がかからず、さらに効率的に測定ができる。測定温度は10~50℃で行うことが好ましく、20~40℃で行うことが最も好ましい。
装置:HLC-8220GPC(東ソー(株)製)
検出器:示差屈折計(RI検出器)
プレカラム:TSKGUARDCOLUMN MP(XL)
6mm×40mm(東ソー(株)製)
サンプル側カラム:以下の2本を直結(全て東ソー(株)製)
・TSK-GEL Multipore-HXL-M 7.8mm×300mm
リファレンス側カラム:サンプル側カラムに同じ
恒温槽温度:40℃
移動層:テトラヒドロフラン
サンプル側移動層流量:1.0mL/分
リファレンス側移動層流量:0.3mL/分
試料濃度:0.1重量%
試料注入量:100μL
データ採取時間:試料注入後16分~46分
サンプリングピッチ:300msec
本実施形態において、最終製品に不要な溶媒、塩基、塩類その他不要成分を除去するために、工程[i]によって得られた顔料微粒子析出後の混合液から、これらを除去することが望ましい。これら不要成分の除去工程としては、特に限定されないが、例えば、フィルタなどによりろ過する方法、遠心分離によって顔料微粒子を沈降させて濃縮する方法、抽出溶媒を加え顔料を抽出し不要分を含む相と相分離する方法(いわゆるフラッシング法)などが挙げられる。
フィルタろ過の装置は、例えば、減圧あるいは加圧ろ過のような装置を用いることができる。好ましいフィルタとしては、ろ紙、ナノフィルタ、ウルトラフィルタなどを挙げることができる。
遠心分離機は顔料微粒子を沈降させることができればどのような装置を用いてもよい。例えば、汎用の装置の他にもスキミング機能(回転中に上澄み層を吸引し、系外に排出する機能)付きのものや、連続的に固形物を排出する連続遠心分離機などが挙げられる。遠心分離条件は、遠心力(重力加速度の何倍の遠心加速度がかかるかを表す値)で50~10000が好ましく、100~8000がより好ましく、150~6000が特に好ましい。遠心分離時の温度は、分散液の溶剤種によるが、-10~80℃が好ましく、-5~70℃がより好ましく、0~60℃が特に好ましい。
また、溶媒分の除去工程として、真空凍結乾燥により溶媒を昇華させて濃縮する方法、加熱ないし減圧による溶媒を乾燥させて濃縮する方法、それらを組合せた方法などを用いることもできる。
顔料を抽出し不要分を含む相と相分離する方法においては、抽出溶媒としては顔料微粒子析出後の混合液から顔料を抽出可能な溶媒であれば特に制限はなく、いずれも好ましく用いることが可能である。抽出溶媒として、プロピレングリコールモノメチルアセテートは、本実施形態の工程[ii]におけるα型結晶化度を高めるための溶媒および分散用溶媒と兼ねることが可能である点で、特に好ましい。
顔料析出後の混合溶液からこれら不要成分を除去するために、上記の操作を行った後にたとえば水やメタノールなどの洗浄溶媒を加え、再度上記の操作を繰り返すことが好ましい。また、これら不要成分の除去操作は、本実施形態の工程[i]と工程[ii]の間もしくは工程[ii]の後いずれも好ましく行うことができるが、工程[ii]に工程[i]の良溶媒を持ち込まないために、工程[i]と工程[ii]の間に行うことが好ましい。
○ 溶媒
良溶媒、貧溶媒が含まれた状態で結晶化処理を行った場合、第3溶媒を用いて良溶媒・貧溶媒を除去することができる。第3溶媒の種類は特に限定されないが、有機溶媒であることが好ましく、例えば、エステル化合物溶媒、アルコール化合物溶媒、芳香族化合物溶媒、脂肪族化合物溶媒が好ましく、エステル化合物溶媒、芳香族化合物溶媒または脂肪族化合物溶媒がより好ましく、エステル化合物溶媒が特に好ましい。また、該第3溶媒は上記溶媒による純溶媒であっても、複数の溶媒による混合溶媒であってもよい。
なお、本実施形態においては、上記の第3溶媒に限らず後述する第4溶媒を含め、分散組成物の媒体とされる、前記良溶媒及び前記貧溶媒のいずれとも異なる溶媒を総称して「第3の溶媒」という。
すなわち、第3溶媒を置換用溶媒として用い、微粒子を析出させた分散液中の良溶媒及び貧溶媒からなる溶媒分を第3溶媒で置換することができる。
あるいは、良溶媒および貧溶媒を完全に除去(濃縮)し、顔料粒子粉末として取り出してから、第3溶媒を加えることもできる。
あるいは良溶媒および貧溶媒を完全に除去(濃縮)し、顔料粒子粉末として取り出してから、第3溶媒及び/又は顔料分散剤を添加して、所望の顔料分散組成物とすることができる。
第3溶媒の添加量は特に限定されないが、水不溶性色材の微粒子100質量部に対して、100~300000質量部であることが好ましく、500~10000質量部であることがより好ましい。
本実施形態において顔料の微粒子を第3の溶媒に再分散させるとき、別の分散剤等を添加しなくても、第3の溶媒中で顔料微粒子の凝集状態が自発的に解かれ媒体中に分散する性質を有することが好ましく、この性質があることを「自己分散しうる」ないし「自己分散性を有する」という。ただし、本実施形態において再分散性を一層向上させるために、微粒子の再分散時に顔料分散剤等を添加してもよい。ただし、本実施形態において再分散性を一層向上させるために、微粒子の再分散時に顔料分散剤等を添加してもよい。かかる観点から再分散困難な凝集(aggregate)と再分散可能な軟凝集(agglomerate)を区別していうことがある。
物理的なエネルギーを加えて顔料ナノ粒子を分散させる際に使用する分散機としては、特に制限はなく、例えば、ニーダー、ロールミル、アトライダー、スーパーミル、ディゾルバ、ホモミキサー、サンドミル等の分散機が挙げられる。また、高圧分散法や、微小粒子ビーズの使用による分散方法も好適なものとして挙げられる。
顔料分散剤としては、高分子分散剤(例えば、直鎖状高分子、ブロック型高分子、グラフト型高分子、末端変性型高分子等)、界面活性剤(ポリオキシエチレンアルキルリン酸エステル、ポリオキシエチレンアルキルアミン、アルカノールアミン等)、顔料誘導体等を挙げることができる。分散剤は、顔料の表面に吸着し、再凝集を防止する様に作用する。そのため、顔料表面へのアンカー部位を有するブロック型高分子、グラフト型高分子、末端変性型高分子が好ましい構造として挙げることができる。一方で、顔料誘導体は顔料表面を改質することで、高分子分散剤の吸着を促進させる効果を有する。
高分子化合物の例として、ブロック型高分子としては、BYK Chemie社製「Disperbyk-2000、2001」、EFKA社製「EFKA4330、4340」等を挙げることができる。グラフト型高分子の例としては、ルーブリゾール社製「ソルスパース24000、28000、32000、38500、39000、55000」、BYK Chemie社製「Disperbyk-161、171、174」等が挙げられる。末端変性型高分子の例としては、ルーブリゾール社製「ソルスパース3000、17000、27000」等を挙げることができる(いずれも商品名)。
線状高分子としては、後述するアルカリ可溶性樹脂を挙げることができ、上記顔料誘導体と併用することも好ましい。
顔料分散剤は、一種のみを用いてもよく、二種以上を併用して使用してもよい。
光重合性化合物(以下、重合性モノマーあるいは重合性オリゴマーと称する場合がある)としては、エチレン性不飽和二重結合を2個以上有し、光の照射によって付加重合する多官能モノマーであることが好ましい。そのような光重合性化合物としては、分子中に少なくとも1個の付加重合可能なエチレン性不飽和基を有し、沸点が常圧で100℃以上の化合物を挙げることができる。その例としては、ポリエチレングリコールモノ(メタ)アクリレート、ポリプロピレングリコールモノ(メタ)アクリレート及びフェノキシエチル(メタ)アクリレートなどの単官能アクリレートや単官能メタクリレート;ポリエチレングリコールジ(メタ)アクリレート、ポリプロピレングリコールジ(メタ)アクリレート、トリメチロールエタントリアクリレート、トリメチロールプロパントリ(メタ)アクリレート、トリメチロールプロパンジアクリレート、ネオペンチルグリコールジ(メタ)アクリレート、ペンタエリスリトールテトラ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート、ジペンタエリスリトールペンタ(メタ)アクリレート、ヘキサンジオールジ(メタ)アクリレート、トリメチロールプロパントリ(アクリロイルオキシプロピル)エーテル、トリ(アクリロイルオキシエチル)イソシアヌレート、トリ(アクリロイルオキシエチル)シアヌレート、グリセリントリ(メタ)アクリレート;トリメチロールプロパンやグリセリン等の多官能アルコールにエチレンオキシド又はプロピレンオキシドを付加した後(メタ)アクリレート化したもの等の多官能アクリレートや多官能メタクリレートを挙げることができる。また、特開平10-62986号公報に一般式(1)および(2)に記載のように、多官能アルコールにエチレンオキサイドやプロピレンオキサイドを付加させた後(メタ)アクリレート化した化合物も好適なものとして挙げられる。
これらの中で、トリメチロールプロパントリ(メタ)アクリレート、ペンタエリスリトールテトラ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート、ジペンタエリスリトールペンタ(メタ)アクリレートが好ましい。
また、この他、特開平11-133600号公報に記載の「重合性化合物B」も好適なものとして挙げることができる。
光重合開始剤又は光重合開始剤系(本発明において、光重合開始剤系とは複数の化合物の組み合わせで光重合開始の機能を発現する混合物をいう。)としては、米国特許第2367660号明細書に開示されているビシナルポリケタルドニル化合物、米国特許第2448828号明細書に記載されているアシロインエーテル化合物、米国特許第2722512号明細書に記載のα-炭化水素で置換された芳香族アシロイン化合物、米国特許第3046127号明細書及び同第2951758号明細書に記載の多核キノン化合物、米国特許第3549367号明細書に記載のトリアリールイミダゾール二量体とp-アミノケトンの組み合わせ、特公昭51-48516号公報に記載のベンゾチアゾール化合物とトリハロメチル-s-トリアジン化合物、米国特許第4239850号明細書に記載されているトリハロメチル-トリアジン化合物、米国特許第4212976号明細書に記載されているトリハロメチルオキサジアゾール化合物等を挙げることができる。特に、トリハロメチル-s-トリアジン、トリハロメチルオキサジアゾール及びトリアリールイミダゾール二量体が好ましい。
アルカリ可溶性樹脂としては、光硬化性組成物ないし、カラーフィルタ用インクジェットインクの調製時に添加することもできるが、前記微粒子の分散組成物を製造する際、または微粒子形成時に添加することも好ましい。顔料の溶液および顔料の溶液を添加して顔料の微粒子を生成させるための貧溶媒の両方もしくは一方にアルカリ可溶性樹脂を添加することもできる。またはアルカリ可溶性樹脂溶液を別系統で顔料の微粒子形成時に添加することも好ましい。
光硬化性組成物においては、上記成分の他に、更に光硬化性組成物調製用の有機溶媒(第4溶媒)を用いてもよい。第4溶媒の例としては、特に限定されないが、例えば、アルコール系溶媒、ケトン系溶媒、エーテル系溶媒、スルホキシド系溶媒、エステル系溶媒、アミド系溶媒、芳香族炭化水素系溶媒、脂肪族炭化水素系溶媒、ニトリル系溶媒、またはこれらの混合物などが好適に挙げられるが、なかでも、ケトン系溶媒、エーテル系溶媒、エステル系溶媒、芳香族炭化水素系溶媒、脂肪族炭化水素系溶媒、またはこれらの混合物などがより好ましい。
ケトン系溶媒としては、例えば、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン、2-ヘプタノン等が挙げられる。エーテル系溶媒としては、例えば、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート等が挙げられる。エステル系溶媒としては、例えば、1,3-ブチレングリコールジアセテート、3-メトキシプロピオン酸メチル、3-エトキシプロピオン酸メチル、3-エトキシプロピオン酸エチル、エチルセルソルブアセテート、乳酸エチル、酢酸ブチル、エチルカルビトールアセテート、ブチルカルビトールアセテート等が挙げられる。芳香族炭化水素系溶媒としては、例えば、トルエン、キシレン等が挙げられる。脂肪族炭化水素系溶媒としては、例えば、シクロヘキサン、n-オクタン等が挙げられる。
これらの溶媒は、単独で用いてもあるいは2種以上組み合わせて用いてもよい。また沸点が180℃~250℃である溶剤を必要によって使用することができる。有機溶媒の含有量は、光硬化性組成物全量に対して10~95質量%が好ましい。
光硬化性組成物はその組成を適宜に調節して、インクジェットインクとすることができる。インクジェットインクとしてはカラーフィルタ用以外にも、印字用等、通常のインクジェットインクとしてもよいが、なかでもカラーフィルタ用インクジェットインクとすることが好ましい。
インクジェットインクは前記の顔料微粒子を含むものであればよく、重合性モノマーおよび/または重合性オリゴマーを含む媒体に、前記の顔料微粒子を含有させたものであることが好ましい。ここで重合性モノマーおよび/または重合性オリゴマーとしては、先に光硬化性組成物において説明したものを用いることができる。
このとき、粘度の変動幅が±5%以内になるようインク温度を制御することが好ましい。射出時の粘度は5~25mPa・sであることが好ましく、8~22mPa・sであることがより好ましく、10~20mPa・sであることが特に好ましい(本発明において粘度は、特に断らない限り25℃のときの値である。)。前記射出温度の設定以外に、インクに含有させる成分の種類と添加量を調節することで、粘度の調整をすることができる。前記粘度は、例えば、円錐平板型回転粘度計やE型粘度計などの通常の装置により測定することができる。
また、射出時のインクの表面張力は15~40mN/mであることが、画素の平坦性向上の観点から好ましい(本発明において表面張力は、特に断らない限り23℃のときの値である。)。より好ましくは、20~35mN/m、最も好ましくは、25~30mN/mである。表面張力は、界面活性剤の添加や、溶剤の種類により調整することができる。前記表面張力は、例えば、表面張力測定装置(協和界面科学株式会社製、CBVP-Z)や、全自動平衡式エレクトロ表面張力計ESB-V(協和科学社製)などの測定器を用いて白金プレート方法により測定することができる。
また、各画素形成のために用いるインクジェット法に関しては、インクを熱硬化させる方法、光硬化させる方法、あらかじめ基板上に透明な受像層を形成しておいてから打滴する方法など、通常の方法を用いることができる。
このようにして形成されたカラーフィルタのパターン形状は特に限定されるものではなく、一般的なブラックマトリックス形状であるストライプ状であっても、格子状であっても、さらにはデルタ配列状であってもよい。
光硬化性組成物を用いた塗布膜における含有成分については、既に記載したものと同様である。また、光硬化性組成物を用いた塗布膜の厚さは、その用途により適宜定めることができるが、0.5~5.0μmであることが好ましく、1.0~3.0μmであることがより好ましい。この光硬化性組成物を用いた塗布膜においては、前述のモノマーもしくはオリゴマーを重合させて光硬化性組成物の重合膜とし、それを有するカラーフィルタを作製することができる(カラーフィルタの作製については後述する。)。光重合性化合物の重合は、光照射により光重合開始剤又は光重合開始剤系を作用させて行うことができる。
カラーフィルタは、コントラストに優れることが好ましい。本発明においてコントラストとは、特に断らない限り、後述する実施例において採用された測定方法により測定された値をいう。カラーフィルタのコントラストが高いということは液晶と組み合わせたときの明暗のディスクリミネーションが大きくできるということを意味しており、液晶ディスプレイがCRTに置き換わるためには非常に重要な性能である。
------------------------
R 0.656 0.336 21.4
G 0.293 0.634 52.1
B 0.146 0.088 6.90
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以下に、本発明の別の好ましい実施態様(第2実施形態)について説明するが、本発明はこれに限定して解釈されるものではない。なお、以下の説明においては第1実施形態と共通する点については省略するが、一部重複して説明するところ含む。
(a)ビーズミルによる湿式粉砕
本実施形態の一実施態様においては、後述する再沈法により得た顔料微粒子を磨砕材により湿式粉砕することにより結晶化し、目的のα型結晶化度とすることが好ましい。具体的には、例えば水溶性無機塩類と湿潤剤、例えば有機溶剤と共に液状組成物として粉砕する工程である。本実施形態において磨砕材として用いられる材料としては、塩化ナトリウム、塩化カリウム、塩化カルシウム、塩化バリウム、硫酸ナトリウム等の水溶性無機塩類やジルコニアビーズ、チタニアビーズ等のセラミックビーズ、ガラスビーズ、スチールビーズ等が挙げられる。これら磨砕剤の使用量は、多い方が顔料の磨砕効果は高いが、通常は、粗製ジクロロジケトピロロピロール顔料に対して0.5~50倍質量であることが好ましく、生産性、経済性の点から1~20倍質量であることがより好ましい。
本実施形態で用いる湿潤剤としては、後述する結晶化溶媒と同様のものを用いることができる。中でも高沸点溶媒を用いることが好ましく、1-ブタノール、エチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコールモノメチルエーテル、乳酸エチル、プロピレングリコールモノメチルエーテルアセテートがより好ましい。
上述したような磨砕材による湿式粉砕については、例えば特開2008-24873号公報などを参考にしてもよい。
本実施形態の別の実施態様として、後述する再沈法により得た顔料微粒子を、有機溶剤と接触させることにより結晶化し、目的のα型結晶化度とすることが挙げられる。このとき、後述するように再沈法に用いる前記良溶媒及び/又は貧溶媒に分散剤を含有させて前記両液を混合して、又はこれらとは別に良溶媒に分散剤を含有させた溶液を準備し前記両液とともに混合して、前記溶媒中に含有させた分散剤の少なくとも10質量%を埋包させた顔料微粒子を用いることが好ましい。
微粒子の粒径に関する定義や平均粒径及び単分散性の好ましい範囲については前記第1実施形態と同じである。
本実施形態において再沈法の手順及び条件等は第1実施形態と同じである。このとき上述した結晶成長抑制剤を用いてもよい。
本実施形態のp-ジクロロジケトピロロピロール顔料が微粒子であるとき、そこに分散剤を埋包することが好ましい。ここで埋包とは、分散剤の分子の一部もしくは全部が微粒子内に取り込まれた状態をいう。例えば図1に基づいていうと、分散剤の全部が取り込まれた状態とは添加した分散剤の分子全体が微粒子10内に内包された状態であり(内在埋包分散剤2b参照)、一部取り込まれた状態とは添加した分散剤の一部分または官能基が粒子内に内包されその残部粒子外方に延在する状態であり(外在埋包分散剤2a参照)、埋包というときにはこの両者を含む。
(1)分散剤を溶解しうる媒体が、組み合わせて用いられる顔料が溶解しうる媒体と相溶性がある関係にあること、
(2)分散剤が、質量平均分子量が1000以上の高分子分散剤であること、
(3)分散剤が、貧溶媒との混合により析出するが、その析出速度は顔料の析出より遅いものであること、
(4)分散剤が、顔料と相互作用性を有する官能基を少なくとも1つ含有すること、
の要件を達成することにより、上記分散剤を粒子に効率的かつ適度に内包させることができ好ましい。
(1)分散剤を顔料とともに良溶媒に共溶解させて、貧溶媒と接触させ、析出させる方法
(2)顔料溶解液と分散剤溶解液とを別々に作成しておき、貧溶媒と接触させ、析出させる方法
(3)顔料溶解液と貧溶媒とにそれぞれ分散剤を溶解した液どうしを接触させ、析出させる方法、などが挙げられる。
本実施形態の微粒子は、これらのいずれの方法で作製してもよいが、分散剤溶解溶液が顔料の溶解溶液と相溶性があることが好ましい。分散剤溶解液と顔料の溶解液が相溶しないと、貧溶媒との混合により、十分に分散剤が粒子内に取り込ませることができないことがある。上記の方法の中では、上記(1)(2)の方法が特に好ましく用いられる。
埋包分散剤を粒子に適度に埋包させるためには、該分散剤と顔料とが混合工程を経て析出される段階で、両者が引き合う相互作用を示すように埋包分散剤の化学構造を設計することが好ましい。本実施形態では、溶媒に溶解した状態で埋包分散剤と顔料とを混合させることが好ましいが、このとき該分散剤と顔料との上記相互作用が小さいと、分散剤の粒子内への取り込み率が小さくなりすぎたり、埋包された分散剤が、分散媒体や組成物媒体中で遊離しやすくなったり、分散安定性が悪化したりすることがある。そのため、顔料と強く引き合い相互作用する構造部位を有する埋包分散剤を用いることが好ましく、この相互作用を強くして分散剤を粒子にしっかりと固定化することが好ましい。
ケトン系溶媒としては、例えば、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン、2-ヘプタノン等が挙げられる。エーテル系溶媒としては、例えば、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート等が挙げられる。エステル系溶媒としては、例えば、1,3-ブチレングリコールジアセテート、3-メトキシプロピオン酸メチル、3-エトキシプロピオン酸メチル、3-エトキシプロピオン酸エチル、エチルセルソルブアセテート、乳酸エチル、酢酸ブチル、エチルカルビトールアセテート、ブチルカルビトールアセテート等が挙げられる。芳香族炭化水素系溶媒としては、例えば、トルエン、キシレン等が挙げられる。脂肪族炭化水素系溶媒としては、例えば、シクロヘキサン、n-オクタン等が挙げられる。
これらの溶媒は、単独で用いてもあるいは2種以上組み合わせて用いてもよい。また沸点が180℃~250℃である溶剤を必要によって使用することができる。有機溶媒の含有量は、光硬化性組成物全量に対して10~95質量%が好ましい。)、もしくは反応性希釈剤(例えば、2-ヒドロキシエチル(メタ)アクリレート、ベンジル(メタ)アクリレート、エトキシ化フェニル(メタ)アクリレート、イソボルニル(メタ)アクリレート、フェノキシエチル(メタ)アクリレート、フェノキシテトラエチレングリコール(メタ)アクリレート、N-ビニル-2-ピロリドン、N-アクリロイルモルフォリン等の重合性化合物。)などの分散媒体に親和性が高い部分構造も有してことが好ましい。立体反発性の部位が分散媒体に親和性があることにより、埋包分散剤の粒子外に出ている部分(図1中 2o部位)によって、分散媒体中で分散性を付与するとができる。
前記高分子化合物としては、特に限定されないが、ビニルモノマーの重合体もしくは共重合体(例えば、メタクリル酸アルキルの単独重合体、スチレン類の単独重合体、メタクリル酸アルキル/スチレン類の共重合体、ポリビニルブチラールなど)、エステル系ポリマー(例えば、ポリカプロラクトンなど)、エーテル系ポリマー(例えば、ポリテトラメチレンオキシドなど)、ウレタン系ポリマー(例えば、テトラメチレングリコールとヘキサメチレンジイソシアネートからなるポリウレタンなど)、アミド系ポリマー(例えば、ポリアミド6、ポリアミド66など)、シリコーン系ポリマー(例えば、ポリジメチルシロキサンなど)、カーボネート系ポリマー(例えば、ビスフェノールAとホスゲンから合成されるポリカーボネートなど)などが挙げられる。
R3で表される置換基は中でも、下記一般式(7)で表されるアゾ構造を有することが好ましい。
上記ポリマー鎖の部分は、アルキル(メタ)アクリレート、スチレンおよびその誘導体、アクリロニトリル、酢酸ビニル及びブタジエン、からなる群より選ばれる少なくとも一種のモノマーから形成される単独重合体あるいは共重合体、あるいはポリエチレンオキシド、ポリプロピレンオキシド、ポリカプロラクトンであることが一般的である。
上記重合性オリゴマーは、下記一般式(5)で表されるオリゴマーであることが好ましい。
上記重合性オリゴマー(マクロモノマー)の好ましい例としては、ポリメチル(メタ)アクリレート、ポリ-n-ブチル(メタ)アクリレート及びポリ-i-ブチル(メタ)アクリレート、ポリスチレンの分子末端の一個に(メタ)アクリロイル基が結合したポリマーを挙げることができる。市場で入手できるこのような重合性オリゴマーとしては、片末端メタクリロイル化ポリスチレンオリゴマー(Mn=6000、商品名:AS-6、東亜合成化学工業(株)製)、片末端メタクリロイル化ポリメチルメタクリレートオリゴマー(Mn=6000、商品名:AA-6、東亜合成化学工業(株)製)及び片末端メタクリロイル化ポリ-n-ブチルメタクリレートオリゴマー(Mn=6000、商品名:AB-6、東亜合成化学工業(株)製)を挙げることができる。
前記一般式(6)において、R13は、水素原子又はメチル基を表す。R14は、炭素数1~8のアルキレン基を表し、中でも、炭素数1~6のアルキレン基が好ましく、炭素数2~3のアルキレン基がより好ましい。Qは、-OR15又は-OCOR16を表す。ここで、R15は、水素原子、炭素数1~18のアルキル基、フェニル基、又は炭素数1~18のアルキル基で置換されたフェニル基を表す。R16は、炭素数1~18のアルキル基を表す。また、nは、2~200を表し、5~100が好ましく、10~100が特に好ましい。
一般式(6)で表される重合性モノマーは前記したように市販品としても入手可能であり、市販品としては、メトキシポリエチレングリコールメタクリレート(商品名:NKエステルM-40G,M-90G,M-230G(以上、新中村化学工業(株)製);商品名:ブレンマーPME-100,PME-200,PME-400,PME-1000,PME-2000、PME-4000(以上、日油(株)製))、ポリエチレングリコールモノメタクリレート(商品名:ブレンマーPE-90、PE-200、PE-350,日油(株)製)、ポリプロピレングリコールモノメタクリレート(商品名:ブレンマーPP-500、PP-800、PP-1000,日油(株)製)、ポリエチレングリコールポリプロピレングリコールモノメタクリレート(商品名:ブレンマー70PEP-350B,日油(株)製)、ポリエチレングリコールポリテトラメチレングリコールモノメタクリレート(商品名:ブレンマー55PET-800,日油(株)製)、ポリプロピレングリコールポリテトラメチレングリコールモノメタクリレート(商品名:ブレンマーNHK-5050,日油(株)製)、などが挙げられる。
また上記一般式(5)(6)の重合性オリゴマー以外にも、ポリカプロラクトンモノマーも好ましく、市販品としては、ポリカプロラクトンモノメタクリレート(商品名:プラクセル FM2D、FM3、FM5、FA1DDM、FA2D、ダイセル化学工業(株)製)などが挙げられる。
〔化1〕
一般式(21)
(HOOC-)m-R1-(-COO-[-R3-COO-]n-R2)t
(式中、R1は4価のテトラカルボン酸化合物残基、R2はモノアルコール残基、R3はラクトン残基、mは2または3、nは1~50の整数、tは(4-m)を表す。)
〔化2〕
一般式(22)
-CH2-C(R14)(Y-R15-Z)-
(式中、R14は水素原子、又は置換若しくは無置換のアルキル基を表す。R15は単結合、又は2価の連結基を表す。Yは-CO-、-C(=O)O-、-CONH-、-OC(=O)-、又はフェニレン基を表す。Zは含窒素複素環構造を有する基を表す。)
(1)ポリメタクリル酸メチル
(2)ポリプロピレングリコール
(3)ポリεカプロラクトン
(4)メタクリル酸メチル/スチレン共重合体
(5)メタクリル酸ベンジル/アクリル酸共重合体
(6)メタクリル酸メチル/ジメチルアミノプロピルアクリルアミド共重合体
(7)メタクリル酸メチル/上記構成成分Q-17を与えるモノマー共重合体
(8)メタクリル酸メチル/上記構成成分Q-17を与えるモノマー/末端メタクリロイル化ポリメチルメタクリレート共重合体
(9)上記構成成分M-1を与えるモノマー/スチレン/メタクリル酸共重合体
(10)上記構成成分M-1を与えるモノマー/末端メタクリロイル化ポリメチルメタクリレート/メタクリル酸共重合体
(11)上記構成成分M-1を与えるモノマー/末端メタクリロイル化ポリメチルメタクリレート/ジメチルアミノプロピルアクリルアミド共重合体
(12)上記構成成分Q-22を与えるモノマー/末端メタクリロイル化ポリスチレン/メタクリル酸共重合体
(13)上記構成成分Q-10を与えるモノマー/末端メタクリロイル化ポリブチルメタクリレート/メタクリル酸共重合体
(14)上記構成成分M-1を与えるモノマー/末端(メタ)アクリロイル化ポリエチレングリコールポリプロピレングリコール/メタクリル酸共重合体
(15)上記構成成分Q-4を与えるモノマー/末端(メタ)アクリロイル化ポリエチレングリコール/メタクリル酸共重合体
(16)上記構成成分Q-1を与えるモノマー/末端(メタ)アクリロイル化ポリプロピレングリコール/メタクリル酸共重合体
(17)上記構成成分M-1を与えるモノマー/末端メタクリロイル化ポリカプロラクトン/メタクリル酸共重合体
(18)上記構成成分Q-21を与えるモノマー/末端メタクリロイル化ポリスチレン/メタクリル酸/ジメチルアミノプロピルアクリルアミド共重合体
(19)上記構成成分M-1を与えるモノマー/末端メタクリロイル化ポリメチルメタクリレート共重合体
(20)上記構成成分Q-22を与えるモノマー/スチレン/ジメチルアミノプロピルアクリルアミド共重合体
(21)上記構成成分M-1を与えるモノマー/N,N-ジメチル-4-ビニルベンズアミド/メタクリル酸共重合体
(22)上記構成成分Q-23を与えるモノマー/4-tブチルスチレン/メタクリル酸共重合体
(23)上記構成成分M-3を与えるモノマー/メタクリル酸/末端メタクリロイル化ポリメチルメタクリレート共重合体
(24)上記構成成分Q-24を与えるモノマー/メタクリル酸/末端メタクリロイル化ポリカプロラクトン共重合体
(25)上記構成成分M-2を与えるモノマー/末端メタクリロイル化ポリメチルメタクリレート/末端(メタ)アクリロイル化ポリエチレングリコールポリプロピレングリコール共重合体
(26)上記構成成分M-7を与えるモノマー/メタクリル酸/末端メタクリロイル化ポリメチルメタクリレート/ポリエチレングリコールモノ(メタ)アクリレート共重合体
(27)上記構成成分Q-9を与えるモノマー/4-ビニルピリジン/末端メタクリロイル化ポリメチルメタクリレート共重合体
(28)上記構成成分M-10を与えるモノマー/末端メタクリロイル化ポリブチルメタクリレート/N-ビニルイミダゾール共重合体
(29)上記構成成分M-1を与えるモノマー/メタクリル酸/末端メタクリロイル化ポリn-ブチルメタクリレート/末端メタクリロイル化ポリメチルメタクリレート共重合体
(30)上記構成成分Q-4を与えるモノマー/アクリル酸/末端メタクリロイル化ポリメチルメタクリレート共重合体
(31)上記構成成分M-13を与えるモノマー/スチレン/メタクリル酸共重合体
(32)上記例示化合物M-1を与えるモノマー/メタクリル酸/末端メタクリロイル化ポリメチルメタクリレート/メタクリル酸ドデシル共重合体
(33)上記構成成分Q-1を与えるモノマー/メタクリル酸/末端メタクリロイル化ポリスチレン/メタクリル酸ステアリル共重合体
(34)メタクリル酸/末端メタクリロイル化ポリメチルメタクリレート/メタクリル酸イソボルニル共重合体
(35)メタクリル酸シクロヘキシル/4-ビニルピリジン共重合体
(36)上記構成成分Q-1を与えるモノマー/メタクリル酸ブチル共重合体
(37)上記構成成分M-1を与えるモノマー/スチレン/メタクリル酸/メタクリル酸メチル共重合体
(38)上記構成成分M-2を与えるモノマー/スチレン/メタクリル酸ブチルエステル共重合体
(39)上記構成成分Q-21を与えるモノマー/メタクリル酸tブチルエステル/メタクリル酸共重合体
(40)上記構成成分Q-10を与えるモノマー/スチレン/ブチルアクリルアミド共重合体
(41)メタクリル酸メチル/メタクリル酸共重合体
また、前記化合物に加えて市販の高分子化合物を使用してもよい。市販のブロック型高分子としては、BYK Chemie社製「Disperbyk-2000、2001」、EFKA社製「EFKA4330、4340」等を挙げることができる。市販のグラフト型高分子としては、ルーブリゾール社製「ソルスパース24000、28000、32000、38500、39000、55000」、BYK Chemie社製「Disperbyk-161、171、174」等が挙げられる。市販の末端変性型高分子としては、ルーブリゾール社製「ソルスパース3000、17000、27000」等を挙げることができる(市販ポリマーはいずれも商品名)。
本実施形態については、再沈法により顔料微粒子を形成する際に結晶成長抑制剤を共存させたものであることが好ましく、塩基性基と複素環基とで構成される有機化合物を添加することも好ましい。第1実施形態で述べたもののほか、本実施形態において好ましいものとして下記のものが挙げられる。
このような有機化合物としては、特に指定はないが、例えば2-アミノピリジン、3-アミノピリジン、1-(2-アミノフェニル)ピロール、5-アミノピラゾール、3-アミノ-5-メチルピラゾール、5-アミノ-1-エチルピラゾール、3-アミノトリアゾール、2-アミノチアゾール、5-アミノインドール、2-アミノベンズチアゾール、5-アミノベンズイミダゾール、N,N-ジメチル-5-アミノベンズイミダゾール、フタルイミド、5-アミノベンズイミダゾロン、N,N-ジメチル-5-アミノベンズイミダゾロン、5-アミノウラシル、6-アミノウラシル、ウラシル、チミン、アデニン、グアニン、メラミン、アミノピラジン、8-アミノキノリン、3-アミノキノリン、9-アミノアクリジン、ASTRAブルー6GLL(塩基性フタロシアニン誘導体)、2-アミノアントラキノン、3-アミノアントラキノン、アクリドン、N-アクリドン、キナクリドン、NILEレッド、メチレンバイオレットナフタルイミドなどが挙げられる。好ましくは、2-アミノベンズチアゾール、5-アミノベンズイミダゾール、N,N-ジメチル-5-アミノベンズイミダゾール、5-アミノベンズイミダゾロン、N,N-ジメチル-5-アミノベンズイミダゾロン、5-アミノウラシル、6-アミノウラシル、ウラシル、チミン、アデニン、グアニン、メラミン、8-アミノキノリン、3-アミノキノリン、9-アミノアクリジン、ASTRAブルー6GLL(塩基性フタロシアニン誘導体)、2-アミノアントラキノン、3-アミノアントラキノン、アクリドン、N-アクリドン、キナクリドン、NILEレッド、メチレンバイオレットナフタルイミドが挙げられ、より好ましくは、9-アミノアクリジン、ASTRAブルー6GLL(塩基性フタロシアニン誘導体)、2-アミノアントラキノン、3-アミノアントラキノン、アクリドン、N-アクリドン、5-アミノベンズイミダゾール、N,N-ジメチル-5-アミノベンズイミダゾール、5-アミノベンズイミダゾロン、N,N-ジメチル-5-アミノベンズイミダゾロン、5-アミノウラシル、6-アミノウラシル、NILEレッド、メチレンバイオレットナフタルイミドが挙げられる。
本実施形態の顔料の微粒子は、上記特定の構造部位を有する埋包分散剤を主として用い、微粒子に埋包させたものであることが好ましいが、埋包されない分散剤を併用してもよい。併用する分散剤は、例えば、分散物の粘度調製、上記埋包分散剤との反応性付与、上記埋包分散剤との相互作用性付与、分散媒体との親和性付与、貧溶媒で析出した粒子の解凝集をおこなう目的、微粒子のサイズを調製する目的、良溶媒と貧溶媒の親和性を調整する目的、分散媒体との親和性付与の目的で用いることができる。界面活性剤、低分子分散剤、高分子分散剤など、通常の分散剤を併用して用いることができる。併用する分散剤の使用割合は特に限定されるものではないが、上記埋包分散剤1質量部に対して0.01~1質量部の範囲で用いるのが好ましく、0.05~0.5質量部の範囲で用いるのがより好ましい。
第2実施形態における本項の好ましい材料、製造手順、条件等は、第1実施形態の[濃縮・溶媒除去工程]及び[カラーフィルタ用組成物の調製及びカラーフィルタの作製]の項で述べたものと同じである。
(実施例I-1・比較例I-1)
ジメチルスルホキシド220mlに、室温で、顔料C.I.ピグメントレッド254(商品名イルガジンレッド 2030、チバ・スペシャルティケミカルズ(株)社製)11g、および粒子成長抑制剤として前記の顔料誘導体化合物S-1およびS-2を各々1.1g含有させ、ここに、テトラメチルアンモニウムヒドロキシド25%水溶液21.5mlを添加し、攪拌した。このようにして、良溶媒に顔料が溶解した有機顔料溶液を得た。
これとは別に貧溶媒として、1mol/l塩酸70mlを含有した水2000mlを用意した。
上記の水ペースト1-1Wの30質量部に対し、プロピレングリコールモノメチルエーテルアセテート189質量部を加え、40℃の温度にてGK-0222-10型ラモンドスターラー(商品名、藤沢薬品工業社製)を用いて3時間攪拌することにより、結晶変換を行った。次いで、ヌッチェろ過により濃縮し、さらにイオン交換水を加え水洗し、再度ろ過を行うことを2回繰り返して溶媒を水に置換することにより結晶変換の過度な進行を停止した後、再度ヌッチェろ過により濃縮することにより、結晶変換を経たジクロロジケトピロロピロール顔料を含む固形分濃度30%の水ペーストを得、これを水ペースト1-1CWとした。得られた水ペースト1-1CWをオーブンを用いて100℃にて2時間かけて乾燥し、次いで乳鉢で180μm以下に粉砕して粉末状とした。このようにして、ジクロロジケトピロール顔料および粒子成長抑制剤を含む赤色の粉末状の色材(以下、「色素」ないし「色素物質」ということがある。)である試料1-1Pを得た。前述の方法により1-1PのX線回折を測定した結果、1-1Pはα型結晶変態のジクロロジケトピロロピロール顔料の特徴的なブラッグ角(2θ)である28.1±0.3°に回折ピークが観察され、上記操作により結晶変換が進行していることが確認された。また得られたX線回折結果から前述の方法によりα型結晶化度、(-151)面結晶子サイズ、(111)面結晶子サイズを算出した。算出結果を表1に示す。
下記組成からなる色素物質、分散剤および溶媒混合物をビーズミル分散することにより、本発明の色素分散液1-1Dを調製した。分散は、サンドグラインダーミルBSG-01(AIMEX社製)で、直径0.5mmのジルコニアビーズを用い、1500rpmで1時間、次いで直径0.05mmのジルコニアビーズを用い、2500rpmで4時間行った。
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前記色素物質1-1P 12.0 質量部
顔料誘導体1 0.75 質量部
顔料誘導体2 0.75 質量部
分散剤樹脂1 8.1 質量部
プロピレングリコールモノメチルエーテルアセテート 78.4 質量部
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顔料誘導体1、2の構造を以下に示す。
アミン価 :10mgKOH/g
酸 価 :17mgKOH/g
1L三口フラスコに、PR254 20g、ジメチルスルホキシド400mL、tert-ブトキシカリウム18.48gを投入し、60度で攪拌溶解した。この液に、ヨウ化カリウム 1.3gおよびクロロアセトアニリド 14.25gを投入し、60℃にて、3時間攪拌した。反応液を塩酸20質量部を含む氷水1000質量部に放出し、固体を析出させた。析出物を2000質量部の水で洗浄し、続いてメタノール600質量部で洗浄することで化合物N-1を得た。化合物N-1であることは、H-NMR、MSにより確認した。H-NMRより、PR254:化合物N-1(1):化合物N-1(2)=37:62:2であることを確認した。
分散液1-1Dに関して以下の評価を行った。
(1)コントラスト評価
得られた色素分散液1-1Dをガラス基板上に厚みが2μmになるように塗布し、サンプルを作製した。バックライトユニットとして3波長冷陰極管光源(東芝ライテック(株)社製 商品名:FWL18EX-N)に拡散板を設置したものを用い、2枚の偏光板((株)サンリツ社製の偏光板 商品名:HLC2-2518)の間にこのサンプルを置き、偏光軸が平行のときと、垂直のときとの透過光量を測定し、その比によりコントラストを求めた(「1990年第7回色彩光学コンファレンス、512色表示10.4”サイズTFT-LCD用カラーフィルタ、植木、小関、福永、山中」等参照。)。2枚の偏光板、サンプル、色彩輝度計の設置位置は、バックライトから13mmの位置に偏光板を、40mm~60mmの位置に直径11mm長さ20mmの円筒を設置し、この中を透過した光を、65mmの位置に設置した測定サンプルに照射し、透過した光を、100mmの位置に設置した偏光板を通して、400mmの位置に設置した色彩輝度計で測定した。色彩輝度計の測定角は2°に設定した。バックライトの光量は、サンプルを設置しない状態で、2枚の偏光板をパラレルニコルに設置したときの輝度が1280cd/m2になるように設定した。
8:コントラスト比 10倍以上
7:コントラスト比 9倍以上10倍未満
6:コントラスト比 8倍以上9倍未満
5:コントラスト比 7倍以上8倍未満
4:コントラスト比 6倍以上7倍未満
3:コントラスト比 4倍以上6倍未満
2:コントラスト比 2倍以上4倍未満
1:コントラスト比 2倍未満
得られた色素分散液の粘度特性を、25℃の条件にて回転粘度計(東機産業(株)製RE-85L型粘度計[商品名])にて測定し、下記のランク付けを行った。
6:粘度値 8mPa・s未満。最も良好なレベル。
5:粘度値 8mPa・s以上10mPa・s未満。極めて良好なレベル。
4:粘度値10mPa・s以上15mPa・s未満。良好なレベル。
3:粘度値15mPa・s以上20mPa・s未満。許容レベル。
2:粘度値20mPa・s以上100mPa・s未満。問題なレベル。
1:粘度値100mPa・s以上。極めて問題なレベル。
また、同様に色素分散液1-3Dの作成方法に対して、粒子成長抑制剤の種類、添加量、および添加時期、結晶変換条件を表1-1記載のように変更し、さらにビーズミル分散時間を調節したことのみ異なる方法によって分散液を作成し、色素分散液1-26D~1-41Dを得た。ここで用いた粒子成長抑制剤を下表1-3に示す。
また、α型結晶化度、(-151)面結晶子サイズ、および(111)面結晶子サイズを本発明の好ましい範囲、すなわち同等のα結晶化度においては(-151)面結晶子サイズおよび(111)面結晶子サイズがより小さい値となるように設定するために、粒子成長抑制剤を顔料溶解時に添加し、結晶変換工程を粒子成長抑制剤の存在下で行うことが有効なことがわかる(分散液試料1-1Dと、試料1-11Dとを対比参照)。
特に、ジケトピロロピロール骨格およびキナクリドン骨格の色素誘導体を併用することにより、(-151)面結晶子サイズ、および(111)面結晶子サイズの両者に対し、有効に微細化することが可能なことがわかる(分散液試料1-1Dと試料1-15D又は1-16Dとを対比参照)。
さらに以下のようにして従来技術に基づき色素分散液を調整したが、本願発明の範囲となるものは得られないことを確認した。
ジクロロジケトピロロピロール顔料のアルカリ金属塩溶液を得る工程を、特許第4144655号公報の実施例と同様に行うことを試みたが顔料の析出が生じてしまいアルカリ金属塩溶液が得られなかった。この結果を受け、後述の方法によりジクロロジケトピロロピロール顔料のアルカリ金属塩溶液を作成した。
下記に示すように、貧溶媒組成、粒子形成条件および結晶変換条件を特許第4144655号公報の実施例I-1及びI-2に近いものに設定し、結晶変換溶媒としてイソブチルアルコールおよび苛性ソーダを用いることにより色素物質3-1Pおよび分散液3-1D、色素物質3-2Pおよび分散液3-2D、をそれぞれ作成した。
ジメチルスルホキシド308mlに、室温で、顔料C.I.ピグメントレッド254(商品名イルガジンレッド 2030、チバ・スペシャルティケミカルズ(株)社製)15.4gを含有させ、ここに、ナトリウムメトキシド(28%)メタノール溶液8.32gを添加し、攪拌した。このようにして、良溶媒に顔料が溶解したジクロロジケトピロロピロール顔料のアルカリ金属塩溶液を得、これを90℃に加熱した。
これとは別に貧溶媒として、メタノ-ル600g、水600g、酢酸2.6gを加え-10℃に冷却した溶液を準備した。この中に、先に得られた90℃のジケトピロロピロール顔料のアルカリ金属塩溶液を、調製液の温度が常に0℃以下になるように冷却しながらおよそ60分間にわたって少量ずつ添加した。このようにして、有機顔料微粒子を溶媒に分散させた分散液を得た。
得られた粗結晶粉末を、イソブチルアルコール1500g、25%苛性ソーダ水溶液5.6gを加え10℃に冷却した溶液に加え6時間攪拌することによって結晶変換を行い、次いで酢酸によってpHを7以下に調整した後、再度ヌッチェ濾過を行い、これを10℃に冷却したメタノール1000g、および水1000gを順次振りかけて洗浄し、乾燥することによって色素物質3-1Pを作成した。また実施例I-1の色素分散液1-1Dの調製方法に対し、色素物質を3-1Pに代え、さらに分散時間を最適化することによって分散液を作成し、分散液3-1Dを得た。
ジメチルスルホキシド308mlに、室温で、顔料C.I.ピグメントレッド254(商品名イルガジンレッド 2030、チバ・スペシャルティケミカルズ(株)社製)15.4gを含有させ、ここに、ナトリウムメトキシド(28%)メタノール溶液8.32gを添加し、攪拌した。このようにして、良溶媒に顔料が溶解したジクロロジケトピロロピロール顔料のアルカリ金属塩溶液を得、これを90℃に加熱した後、75℃に冷却した。
これとは別に貧溶媒として、メタノ-ル600g、水600g、酢酸6.76gを加え-10℃に冷却した溶液を準備した。この中に、先に得られた75℃のジケトピロロピロール顔料のアルカリ金属塩溶液を、調製液の温度が常に5℃以下になるように冷却しながらおよそ120分間にわたって少量ずつ添加した。このようにして、有機顔料微粒子を溶媒に分散させた分散液を得た。
以下に示す方法によって色素分散液を作成した。
(色素分散液2-1Dの作成)
結晶変換工程の前に水ペースト1-1Wを乾燥した後粉砕し、得られた粉末9質量部に対し、プロピレングリコールモノメチルエーテルアセテート189質量部および水21質量部を加え、40℃の温度にて用いて12時間攪拌することにより結晶変換を行ったこと以外は実施例I-1の色素分散液1-1Dと同様の方法によって色素分散液を作成し、色素分散液2-1Dを得た。このとき結晶変化処理を終了した後、過度の結晶化を防ぐようすみやかに試料を水洗した。
色素分散液2-1Dと同様の方法によって色素分散液を作成し、色素分散液2-2Dを得た。但し、結晶変換工程の際、ラモンドスターラーの代わりにサンドグラインダーミルBSG-01[商品名](AIMEX社製)を使用し、直径0.5mmのジルコニアビーズを摩砕剤として変換液10質量部に対し40質量部用い(嵩重点率約50%)、40℃に制御しながら1500rpmで16時間攪拌することにより結晶変換を行った。このとき結晶変化処理を終了した後、過度の結晶化を防ぐようすみやかに試料を水洗した。
これら結果と色素分散液1-1Dの結果の比較より、結晶変換工程の前に乾燥工程を行わず、さらに摩砕剤を用いないことが好ましく、それによりβ型結晶出発のジクロロジケトピロール顔料を色素誘導体共存下においてもα型へと効率良く結晶変換することが可能なことが示された。
色素分散液1-1Dと同様の方法によって色素分散液を作成し、色素分散液2-3Dを得た。但し、結晶変換後直ちに5℃に急冷し、ヌッチェろ過による濃縮の際、イオン交換水の代わりにプロピレングリコールモノメチルエーテルアセテートを加え再度ろ過を行うことを2回繰り返して溶媒をプロピレングリコールモノメチルエーテルアセテートに置換した後、乾燥を行うことなく直ちに色素分散液の調製を行った。この際、完成色素分散液中の色素物質濃度が色素分散液1-1Dと等しくなるよう、色素分散液調製工程で加えるプロピレングリコールモノメチルエーテルアセテートの量を調整した。得られた色素分散液に対し実施例I-1と同様の評価を行った。ここでα結晶化度および結晶子サイズの測定は、溶媒をプロピレングリコールモノメチルエーテルアセテートに置換した後の色素分散液の一部に水を加えて結晶変換を完全に停止した後、乾燥して得られた色素粉末に対して行った。結果を表2に示す。色素分散液2-3Dは色素分散液1-1Dに対しコントラストおよび粘度特性の改良が見られ、分散液調製前に乾燥を経ないことが有効なことが示された。また、結晶変換後に水洗を行わなくても、変換後の分散液を冷却し、直ちに分散を行うことにより、過度の結晶化による弊害は見られないことが確認された。
色素分散液2-1Dの作成方法に対し、有機顔料溶液を貧溶媒に添加し有機顔料微粒子を析出させる際の、有機顔料溶液の供給速度を流速3.3ml/minに変更し、約60分間かけて有機顔料微粒子を析出させることのみ異なる方法によって色素分散液を作成し、色素分散液2-4Dとした。
色素分散液2-4Dの作成方法に対し、貧溶媒として1mol/l塩酸70mlを含有したメタノール2000mlを用いたことのみ異なる方法によって色素分散液を作成し、色素分散液2-5Dとした。
得られた色素分散液に対し実施例I-1と同様の評価を行った。結果を表2に示す。色素分散液2-4Dおよび2-5Dは、結晶変換操作の前の結晶態様がα型とβ型の混在状態であり、色素分散液2-1Dに対しコントラスト特性の低下が見られた。このとき、(-151)面結晶子サイズおよび結晶面(111)面結晶子サイズの増加が見られ、コントラスト特性の低下はこれら結晶子サイズの増加に相関していると考えられた。顔料析出後に既にα型結晶態様のジクロロジケトピロール顔料が一部生成できるような、析出速度の低下や貧溶媒への溶剤の利用等の操作は顔料析出時の粒子サイズの増大を招き、このため結晶変換後の結晶子サイズも増加し、コントラスト特性の低下を引き起こしたものと推定される。これら結果より、顔料粒子析出の際のジクロロジケトピロール顔料の結晶態様としてはβ型がより好ましいことが示された。
色素分散液2-3Dの作成方法に対し、結晶変換前の水洗をヌッチェろ過で行う代わりに溶剤抽出(いわゆるフラッッシング法)で行い、さらに結晶変換時間を変更したことのみ異なる方法によって色素分散液を作成し、色素分散液2-6Dとした。溶剤抽出による水洗の手順は以下のように行った。有機顔料微粒子を溶媒に分散させた分散液1-1Sを得た後、1-1Sに対して40重量%のプロピレングリコールモノメチルエーテルアセテートを加え5分間攪拌した。得られた分散液を分液ロート内で静置することにより、溶媒組成として主にプロピレングリコールモノメチルエーテルアセテートからなり、顔料を含む上層と、溶媒組成として主に水およびDMSOからなり、顔料を殆ど含まない下層に分離させた。下層を廃棄することにより、分散液1-1S中に含まれる不要な塩類およびDMSOを廃棄した。次いで、残った上層に対して160重量%のイオン交換水を加えた後5分間攪拌した後、再度分液ロート内で静置することにより、溶媒組成として主にプロピレングリコールモノメチルエーテルアセテートからなり、顔料を含む上層と、溶媒組成として主に水からなり、顔料を殆ど含まない下層に分離させ、下層を廃棄することにより不要な塩類を廃棄した。
このようにして脱塩の完了した顔料分散液2-6Wを得た。2-6Wは溶媒組成としてプロピレングリコールモノメチルエーテルアセテート約85%、水約15%からなる色素分散液であった。得られた2-6Wを結晶変換のために40℃1時間熟成した後、直ちに5℃に急冷し、分散液2-3D同様ヌッチェろ過によって溶媒をプロピレングリコールモノメチルエーテルアセテートに置換した後直ちに分散を行うことにより、分散液2-6Dを得た。得られた色素分散液に対し実施例I-1と同様の評価を行った。ここでα結晶化度および結晶子サイズの測定は、溶媒をプロピレングリコールモノメチルエーテルアセテートに置換した後の色素分散液の一部に水を加えて結晶変換を完全に停止した後、乾燥して得られた色素粉末に対して行った。結果を表2に示す。本発明は、フラッシング法によって脱塩および顔料抽出を行った際にも有効であることが確認された。
色素分散液1-1Dと同様の方法によって色素分散液を作成し、色素分散液2-7Dを得た。但し、結晶変換を経た水ペースト1-1CWを乾燥させる際、オーブンを用いて100℃にて2時間かけて乾燥させる代わりに、凍結乾燥によって乾燥を行った。得られた色素分散液に対し実施例I-1と同様の評価を行った結果を表2に示す。色素分散液2-7Dは色素分散液1-1Dに対しコントラストおよび粘度特性の改良が見られ、乾燥を凍結乾燥で行うことが有効なことが示された。同様に、1-26D~1-41Dの試料についても色素分散液を調製し、本発明のものにおいては良好な製造適性及び製品性能を確認した。
<カラーフィルタの作成>
上記実施例I-2で得られた色素分散液2-3Dを用いて下記手順によりカラーフィルタを作成した結果、カラーフィルタとして良好なコントラストが得られ、本発明の色素分散液はカラーフィルタに好適に用いることが出来ることを確認した。
無アルカリガラス基板を、UV洗浄装置で洗浄後、洗浄剤を用いてブラシ洗浄し、更に超純水で超音波洗浄した。該基板を120℃3分熱処理して表面状態を安定化させた。
該基板を冷却し23℃に温調後、スリット状ノズルを有すガラス基板用コーター(エフ・エー・エス・アジア社製、商品名:MH-1600)にて、下記表3に記載の組成よりなる着色感光性樹脂組成物K1を塗布した。引き続きVCD(真空乾燥装置;東京応化工業(株)社製)で30秒間、溶媒の一部を乾燥して塗布層の流動性を無くした後、120℃で3分間プリベークして膜厚2.4μmの感光性樹脂層K1を得た。
―――――――――――――――――――――――――
K顔料分散物1(カーボンブラック) 25質量部
プロピレングリコールモノメチルエーテルアセテート
8.0質量部
メチルエチルケトン 53質量部
バインダー2 9.1質量部
ハイドロキノンモノメチルエーテル 0.002質量部
DPHA液 4.2質量部
重合開始剤A 0.16質量部
界面活性剤1 0.044質量部
―――――――――――――――――――――――――
次に、純水をシャワーノズルにて噴霧して、該感光性樹脂層K1の表面を均一に湿らせた後、KOH系現像液(KOH、ノニオン界面活性剤含有、商品名:CDK-1、富士フイルムエレクトロニクスマテリアルズ社製を100倍希釈した液)にて23℃で80秒、フラットノズル圧力0.04MPaでシャワー現像しパターニング画像を得た。引き続き、超純水を、超高圧洗浄ノズルにて9.8MPaの圧力で噴射して残渣除去を行い、ブラック(K)の画像Kを得た。引き続き、220℃で30分間熱処理した。
・カーボンブラック
(商品名:Nipex 35、デグサ ジャパン(株)社製)
13.1 質量部
・分散剤(下記化合物J1) 0.65 質量部
・ポリマー(ベンジルメタクリレート/メタクリル酸
=72/28モル比のランダム共重合物、分子量3.7万)
6.72 質量部
・プロピレングリコールモノメチルエーテルアセテート
79.53 質量部
・ポリマー
(ベンジルメタクリレート/メタクリル酸
=78/22モル比のランダム共重合物、分子量3.8万)
27 質量部
・プロピレングリコールモノメチルエーテルアセテート
73 質量部
<界面活性剤1>
・メガファックF-780-F
(商品名:大日本インキ化学工業(株)社製)
:組成は下記
C6F13CH2CH2OCOCH=CH2 40質量部と
H(OCH(CH3)CH2)7OCOCH=CH2
55質量部と
H(OCH2CH2)7OCOCH=CH2 5質量部と
の共重合体(分子量3万)
30質量部
・メチルエチルケトン 70質量部
前記画像Kを形成した基板に、下記表4に記載の組成よりなる着色感光性樹脂組成物R1を用い、前記ブラック(K)画像の形成と同様の工程で、熱処理済み画素Rを形成した。該感光性樹脂層R1の膜厚及び顔料の塗布量を以下に示す。なお、着色感光性樹脂組成物の調製手順は、上記着色感光性樹脂組成物K1と同様にした。
感光性樹脂膜厚(μm) 1.60
顔料塗布量(g/m2) 1.00
C.I.P.R.254塗布量(g/m2) 0.80
C.I.P.R.177塗布量(g/m2) 0.20
――――――――――――――――――――――――――――――――――
R色素分散液2-1D 40質量部
R顔料分散物2(CIPR177) 4.5質量部
プロピレングリコールモノメチルエーテルアセテート 7.6質量部
メチルエチルケトン 37質量部
バインダー1 0.7質量部
DPHA液 3.8質量部
2-トリクロロメチル-(p-スチリルスチリル)
1,3,4-オキサジアゾール 0.12質量部
重合開始剤A 0.05質量部
フェノチアジン 0.01質量部
界面活性剤1 0.06質量部
―――――――――――――――――――――――――――――――――――
―――――――――――――――――――――――――――――――――――
・C.I.P.R.177(商品名:Cromophtal Red A2B、
チバ・スペシャルティ・ケミカルズ(株)社製) 18質量部
・ポリマー(ベンジルメタクリレート/メタクリル酸=72/28モル比
のランダム共重合物、分子量3万) 12質量部
・プロピレングリコールモノメチルエーテルアセテート 70質量部
<バインダー1>
・ポリマー(ベンジルメタクリレート/メタクリル酸=78/22モル比
のランダム共重合物、分子量4万) 27質量部
・プロピレングリコールモノメチルエーテルアセテート 73質量部
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前記画像Kと画素Rを形成した基板に、下記表5に記載の組成よりなる着色感光性樹脂組成物G1を用い、前記ブラック(K)画像の形成と同様の工程で、熱処理済み画素Gを形成した。該感光性樹脂層G1の膜厚及び顔料の塗布量を以下に示す。なお、着色感光性樹脂組成物の調製手順は、上記着色感光性樹脂組成物K1と同様にした。
感光性樹脂膜厚(μm) 1.60
顔料塗布量(g/m2) 1.92
C.I.P.G.36塗布量(g/m2) 1.34
C.I.P.Y.150塗布量(g/m2) 0.58
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G顔料分散物1(CIPG36) 28質量部
Y顔料分散物1(CIPY150) 15質量部
プロピレングリコールモノメチルエーテルアセテート 29質量部
メチルエチルケトン 26質量部
シクロヘキサノン 1.3質量部
バインダー2 2.5質量部
DPHA液 3.5質量部
2-トリクロロメチル-(p-スチリルスチリル)
1,3,4-オキサジアゾール 0.12質量部
重合開始剤A 0.05質量部
フェノチアジン 0.01質量部
界面活性剤1 0.07質量部
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GT-2(商品名:富士フイルムエレクトロニクスマテリアルズ社製)
<Y顔料分散物1>
CFイエロ-EX3393(商品名:御国色素社製)
前記画像K、画素R及び画素Gを形成した基板に、下記表6に記載の組成よりなる着色感光性樹脂組成物B1を用い、前記ブラック(K)画像の形成と同様の工程で、熱処理済み画素Bを形成した。該感光性樹脂層B1の膜厚及び顔料の塗布量を以下に示す。なお、着色感光性樹脂組成物の調製手順は、上記着色感光性樹脂組成物K1と同様にした。
感光性樹脂膜厚(μm) 1.60
顔料塗布量(g/m2) 0.75
C.I.P.B.15:6塗布量(g/m2) 0.705
C.I.P.V.23塗布量(g/m2) 0.045
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B顔料分散物1(CIPB15:6) 8.6質量部
V顔料分散物2(CIPB15:6+CIPV23) 15質量部
プロピレングリコールモノメチルエーテルアセテート 28質量部
メチルエチルケトン 26質量部
バインダー3 17質量部
DPHA液 4.0質量部
2-トリクロロメチル-(p-スチリルスチリル)
1,3,4-オキサジアゾール 0.17質量部
フェノチアジン 0.02質量部
界面活性剤 0.06質量部
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CFブル-EX3357(商品名:御国色素社製)
<B顔料分散物2>
CFブル-EX3383(商品名:御国色素社製)
<バインダー3>
・ポリマー(ベンジルメタクリレート/メタクリル酸/メチルメタクリレート
=36/22/42モル比のランダム共重合物、分子量3.8万)
27質量部
・プロピレングリコールモノメチルエーテルアセテート 73質量部
各画素が形成されたガラス基板をスパッタ装置に入れて、100℃で1300Å厚さのITO(インヂウム錫酸化物)を全面真空蒸着した後、240℃で90分間アニールしてITOを結晶化し、ITO透明電極を形成しカラーフィルタA1として完成させた。
(実施例II-1)
<有機顔料ナノ粒子分散液の調整>
ジメチルスルホキシド(和光純薬社製)を良溶媒とし、良溶媒1000部に顔料C.I.ピグメントレッド254(Irgaphor Red BT-CF、商品名、チバ・スペシャルティ・ケミカルズ(株)製)50部を分散させ、ここにテトラメチルアンモニウムヒドロキシド25%メタノール溶液52.3部を滴下して顔料溶液1を調製した。この顔料溶液を、ビスコメイトVM-10A-L(商品名、CBCマテリアルズ社製)を用いて粘度を測定した結果、顔料溶液の液温が24.5℃の時の粘度が14.3mPa・sであった。これとは別に貧溶媒として、1mol/l塩酸水溶液(和光純薬社製)19部を含有したイオン交換水1000部を用意した。
ここで、10℃に温度コントロールし、GK-0222-10型ラモンドスターラー(商品名、藤沢薬品工業社製)により500rpmで攪拌した貧溶媒1000部に、顔料溶液1をNP-KX-500型大容量無脈流ポンプ(商品名、日本精密化学社製)を用いて、流路径1.1mmの送液配管から流速400ml/minで100部注入することにより、有機顔料粒子を形成し、有機顔料ナノ粒子分散液1を調製した。
上記の手順で調製した有機顔料ナノ粒子分散液1を(株)コクサン社製H-112型遠心濾過機および敷島カンバス(株)社製P89C型濾布を用いて5000rpmで90分濃縮し、次いでイオン交換水を1100部加え混合し、遠心濾過した。再度、イオン交換水を1100部加え混合し遠心濾過した。得られた有機顔料ナノ粒子濃縮ペースト1を回収した。
前記有機顔料ナノ粒子濃縮ペースト1をオーブンにより100℃で2時間乾燥することにより有機顔料粉末1aを得た。
上記組成の有機顔料粉末1aと、プロピレングリコールモノメチルエーテルアセテート110部を混合し、サンドグラインダーミルBSG-01(AIMEX社製)で、直径0.5mmのジルコニアビーズを用い、1500rpmで1時間湿式粉砕し、有機顔料ナノ粒子分散液1aを調製した。
これを(株)コクサン社製H-112型遠心濾過機および敷島カンバス(株)社製P89C型濾布を用いて5000rpmで90分濃縮し、次いでイオン交換水を1100部加え混合し、同様に遠心濾過した。再度、イオン交換水を1100部加え混合し遠心濾過した。得られた有機顔料ナノ粒子濃縮ペースト1aを回収した。
前記有機顔料ナノ粒子濃縮ペースト1aをオーブンにより100℃で2時間乾燥することにより有機顔料粉末1を得た。
(重合体P-1の合成)
下記のモノマー溶液を窒素置換した三口フラスコに導入し、攪拌機(新東科学(株):スリーワンモータ)にて攪拌し、窒素をフラスコ内に流しながら加熱して78℃まで昇温し30分攪拌する。続いて、下記の開始剤溶液を上記の液に添加し、2時間78℃で加熱攪拌する。加熱攪拌後、さらに下記開始剤溶液を添加し、78℃にて2時間加熱攪拌する操作を計2度繰り返す。最後の2時間攪拌後、引き続いて90度で2時間加熱攪拌する。得られた反応液をイソプロパノール1500部に攪拌しながら注ぎ、生じた沈殿を濾取して、加熱乾燥させることでグラフト重合体P-1(質量平均分子量10000)を得た。
・モノマーM-1 5.0部
・スチレン 14.0部
・メタクリル酸 2.0部
・1-メチル-2-ピロリドン 46.67部
・2.2’-アゾビス(イソ酪酸)ジメチル(和光純薬(株)製V-601)
1.2部
・1-メチル-2-ピロリドン 2部
NMP;1-メチル-2-ピロリドン(和光純薬社製)
ここで、15℃に温度コントロールし、GK-0222-10型ラモンドスターラー(商品名、藤沢薬品工業社製)により500rpmで攪拌した貧溶媒中に、顔料溶液2をNP-KX-500型大容量無脈流ポンプ(商品名、日本精密化学社製)を用いて注入した。顔料溶液2の送液配管の流路径及び供給口径を2.2mmとし、その供給口を貧溶媒中に入れ、流速200ml/minで100部注入することにより、有機顔料粒子を形成し、顔料分散液2を調製した。
上記の手順で調製した有機顔料ナノ粒子分散液2を(株)コクサン社製H-112型遠心濾過機および敷島カンバス(株)社製P89C型濾布を用いて5000rpmで90分濃縮し、次いでイオン交換水を1100部加え混合し、遠心濾過した。再度、イオン交換水を1100部加え混合し遠心濾過した。得られた有機顔料ナノ粒子濃縮ペースト2を回収した。
この有機顔料ナノ粒子濃縮ペースト2にプロピレングリコールモノメチルエーテル150部を加え、20℃で8時間攪拌後、コクサン社製H-112型遠心濾過機および敷島カンバス(株)社製P89C型濾布を用いて5000rpmで90分濃縮し、次いでイオン交換水を1100部加え混合し、遠心濾過した。再度、イオン交換水を1100部加え混合し遠心濾過した。得られた有機顔料ナノ粒子濃縮ペースト2aを回収した。前記有機顔料ナノ粒子濃縮ペースト2aをオーブンにより100℃で2時間乾燥することにより有機顔料粉末2を得た。
ジメチルスルホキシド(和光純薬社製)を良溶媒とし、良溶媒1000部に顔料C.I.ピグメントレッド254(Irgaphor Red BT-CF、商品名、チバ・スペシャルティ・ケミカルズ(株)製)50部を分散させ、ここにテトラメチルアンモニウムヒドロキシド25%メタノール溶液52.3部を滴下して顔料溶液3を調製した。この顔料溶液を、ビスコメイトVM-10A-L(商品名、CBCマテリアルズ社製)を用いて粘度を測定した結果、顔料溶液の液温が24.5℃の時の粘度が14.3mPa・sであった。これとは別に貧溶媒として、1mol/l塩酸水溶液(和光純薬社製)19部を含有したメタノール1000部を用意した。
ここで、5℃に温度コントロールし、GK-0222-10型ラモンドスターラー(商品名、藤沢薬品工業社製)により500rpmで攪拌した貧溶媒中に、顔料溶液3をNP-KX-500型大容量無脈流ポンプ(商品名、日本精密化学社製)を用いて注入した。顔料溶液3の送液配管の流路径及び供給口径を2.2mmとし、その供給口を貧溶媒中に入れ、流速200ml/minで100部注入することにより、有機顔料粒子を形成し、顔料分散液3を調製した。
前記有機顔料ナノ粒子分散液3を50℃に温度コントロールし、2時間攪拌し有機顔料ナノ粒子分散液3aを調製した。
上記の手順で調製した有機顔料ナノ粒子分散液3aを(株)コクサン社製H-112型遠心濾過機および敷島カンバス(株)社製P89C型濾布を用いて5000rpmで90分濃縮し、次いでイオン交換水を1100部加え混合し、遠心濾過した。再度、イオン交換水を1100部加え混合し遠心濾過した。得られた有機顔料ナノ粒子濃縮ペースト3を回収した。
前記有機顔料ナノ粒子濃縮ペースト3をオーブンにより100℃で2時間乾燥することにより有機顔料粉末3を得た。
ジメチルスルホキシド(和光純薬社製)を良溶媒とし、良溶媒1000部に顔料C.I.ピグメントレッド254(Irgaphor Red BT-CF、商品名、チバ・スペシャルティ・ケミカルズ(株)製)50部、化合物SS-1 10部を分散させ、ここにテトラメチルアンモニウムヒドロキシド25%メタノール溶液61.1部を滴下して顔料溶液4を調製した。この顔料溶液を、ビスコメイトVM-10A-L(商品名、CBCマテリアルズ社製)を用いて粘度を測定した結果、顔料溶液の液温が24.5℃の時の粘度が12.8mPa・sであった。これとは別に貧溶媒として、1mol/l塩酸水溶液(和光純薬社製)21部を含有したイオン交換水1000部を用意した。
上記の手順で調製した有機顔料ナノ粒子分散液4を(株)コクサン社製H-112型遠心濾過機および敷島カンバス(株)社製P89C型濾布を用いて5000rpmで90分濃縮し、次いでイオン交換水を1100部加え混合し、遠心濾過した。再度、イオン交換水を1100部加え混合し遠心濾過した。得られた有機顔料ナノ粒子濃縮ペースト4を回収した。
この有機顔料ナノ粒子濃縮ペースト4にプロピレングリコールモノメチルエーテル150部を加え、20℃で4時間攪拌後、コクサン社製H-112型遠心濾過機および敷島カンバス(株)社製P89C型濾布を用いて5000rpmで90分濃縮し、次いでイオン交換水を1100部加え混合し、遠心濾過した。再度、イオン交換水を1100部加え混合し遠心濾過した。得られた有機顔料ナノ粒子濃縮ペースト4aを回収した。前記有機顔料ナノ粒子濃縮ペースト4aをオーブンにより100℃で2時間乾燥することにより有機顔料粉末4を得た。
ジメチルスルホキシド(和光純薬社製)を良溶媒とし、良溶媒1000部に顔料C.I.ピグメントレッド254(イルガジンレッド2030、商品名、チバ・スペシャルティ・ケミカルズ(株)製)50部、化合物SS-1 10部、化合物SS-2 15部を分散させ、ここにテトラメチルアンモニウムヒドロキシド25%メタノール溶液64.1部を滴下して顔料溶液5を調製した。この顔料溶液を、ビスコメイトVM-10A-L(商品名、CBCマテリアルズ社製)を用いて粘度を測定した結果、顔料溶液の液温が24.5℃の時の粘度が10.8mPa・sであった。これとは別に貧溶媒として、1mol/l塩酸水溶液(和光純薬社製)23部を含有したイオン交換水1000部を用意した。
上記の手順で調製した有機顔料ナノ粒子分散液5を(株)コクサン社製H-112型遠心濾過機および敷島カンバス(株)社製P89C型濾布を用いて6000rpmで80分濃縮し、次いでイオン交換水を1100部加え混合し、遠心濾過した。再度、イオン交換水を1100部加え混合し遠心濾過した。得られた有機顔料ナノ粒子濃縮ペースト5を回収した。
この有機顔料ナノ粒子濃縮ペースト5にプロピレングリコールモノメチルエーテル180部を加え、20℃で14時間攪拌後、コクサン社製H-112型遠心濾過機および敷島カンバス(株)社製P89C型濾布を用いて6000rpmで80分濃縮し、次いでイオン交換水を1100部加え混合し、遠心濾過した。再度、イオン交換水を1100部加え混合し遠心濾過した。得られた有機顔料ナノ粒子濃縮ペースト5aを回収した。前記有機顔料ナノ粒子濃縮ペースト5aをオーブンにより100℃で2時間乾燥することにより有機顔料粉末5を得た。
C.I.ピグメントレッド254(Irgaphor Red BT-CF、商品名、チバ・スペシャルティ・ケミカルズ(株)製)そのものを有機顔料粉末C1とした。
実施例II-1と同様に有機顔料粉末1aを調製し、これを有機顔料粉末C2とした。
C.I.ピグメントレッド254(Irgaphor Red BT-CF、商品名、チバ・スペシャルティ・ケミカルズ(株)製):250部、塩化ナトリウム:2500部およびジエチレングリコール200部をステンレス1ガロンニーダーに仕込み、3時間混練した。つぎにこの混合物を2.5リットルの温水に投入し、約80℃まで加熱、攪拌した。約1時間撹拌してスラリー状とした後、濾過、水洗を5回くりかえして塩化ナトリウムおよび溶剤を除き、水ウエットケーキ顔料を得た。これを乾燥機にて90°C、18時間乾燥させて水分を蒸発し、有機顔料粉末C3を得た。
(1) ジクロロジケトピロール顔料に関して、CuKα線を用いた粉末X線回折測定を行った。測定は、日本工業規格JIS K03131(X線回折分析通則)に準じ、ブラッグ角(2θ)が、23°から30°の範囲で行った。図1にX線回折パターンを例示する。
(2) (1)で得られたX線回折パターンから、バックグラウンドを除去した回折パターンを求めた。ここでバックグラウンドの除去方法は、上記測定パターンの低角側のブラッグ角(2θ)=23.3°付近のすそと高角側のブラッグ角(2θ)=29.7°付近のすそとに接する直線を引き、この直線で表されるX線回折強度の値を(1)で得られたX線回折強度の値から除去したパターンを求める操作を行った。顔料粉末1の測定結果を示す図で例示して説明すると、図1のX線回折強度の値から、A点およびB点に接する直線Lで表される回折強度を除去したパターンを求め、これをバックグラウンドを除去したX線回折パターンとする。バックグラウンドを除去したX線回折パターンの例を図6に示す。
(3) (2)で求められたバックグラウンドを除去したX線回折パターンから、下記式によりα型結晶化度を算出する。
α型結晶化度=Iα/(Iα+Iβ)
ここで、Iαはα型結晶変態の特徴的な回折ピークであるブラッグ角(2θ)=28.1±0.3°の回折ピークのバックグラウンド除去後の回折強度値、Iβはβ型結晶変体の特徴的な回折ピークであるブラッグ角(2θ)=27.0±0.3°付近の回折ピークのバックグラウンド除去後の回折強度値と定義する。図6の例では、線L1と線L2の長さがIβおよびIαに相当する。
上記の定義において、ジクロロジケトピロール顔料のα型結晶化度が高い場合、β型結晶の特徴であるブラッグ角(2θ)=27±0.3°の位置に明確な回折ピークが見られないケースがあるが、この場合、Iβはバックグラウンド除去後のブラッグ角(2θ)=27.0°の回折強度値と定義する。また、ジクロロジケトピロール顔料のα型結晶化度が低い場合、α型結晶の特徴である28.1°付近に明確なピークを示さないケースがあるが、この場合、Iαはバックグラウンド除去後のブラッグ角(2θ)=28.1°の回折強度値と定義する。
これら定義において、ジクロロジケトピロール顔料のα型結晶化度が高くβ型結晶の特徴的なブラッグ角(2θ)=27°近傍に明確なピークが見られない場合でも、Iβの値はゼロとなることはなく、したがってα型結晶化度の値は1となることは無いことに注意が必要である。何故ならば、β型結晶由来の回折ピークが27°に存在しなくても、その両側に存在するα型結晶由来の回折ピークのすその広がりが27°にかかるため、27°の回折ピークは有限な値となるためである。また、同様にジクロロジケトピロール顔料のβ型結晶化度が高くα型結晶の特徴的なブラッグ角(2θ)=28.1°近傍に明確なピークが見られない場合でも、Iαの値はゼロとなることはなく、したがってα型結晶化度の値はゼロとなることは無い。何故ならば、ブラッグ角(2θ)=27°近傍に存在するβ型結晶由来の回折ピークの高角側のすその広がりが28.1°近傍までかかるため、28.1°の回折ピークは有限な値となるためである。
(1) α型結晶化度の決定方法同様、ジクロロジケトピロール顔料につき、CuKα線を用いた粉末X線回折測定を、ブラッグ角(2θ)が、23°から30°の範囲で行った。さらにα型結晶化度の決定方法同様、バックグラウンドを除去したX線回折パターンを算出した。
(2) (1)で得たバックグラウンドを除去したX線回折パターンから、α型結晶変態由来のブラッグ角(2θ)=24.6±0.3°近傍の回折ピークおよび28.1±0.3°近傍の回折ピークそれぞれに対し、半値幅および回折ピークのブラッグ角(2θ)を求める。半値幅の算出は、上記測定範囲に存在する4つの回折ピーク(α型結晶変態由来のブラッグ角24.6°、25.6°、28.1°各近傍の3つのピークおよびβ型結晶変態由来のブラッグ角27°近傍のピーク)それぞれを市販のデータ解析ソフトを用いてピーク分離を行うことにより算出可能となる。実施例においては、Wave Metorics社製データ解析ソフト Igor Proを用い、ピーク形状をVoigt関数としてフィッティングを行い算出される半値幅の値を用いることとする。
(3) (2)で算出した回折ピーク半値幅および下記シェラーの式により結晶子サイズを算出する。
D=Kλ/(10×B×cosA)
B=Bobs-b
ここで、
D:結晶子サイズ(nm)
Bobs:(2)で算出した半値幅(rad)
b:X線回折装置角度分解能補正係数であり、標準シリコン結晶測定時の半値幅(rad)。本発明では下記装置構成および測定条件で標準シリコン結晶を測定し、b=0.2とした。
A:回折ピークブラッグ角2θ(rad)
K:シェラー定数(K=0.94と定義する)
λ:X線波長(Å)(CuKα線であるため、λ=1.54)
X線回折装置:(株)リガク社製RINT2500
ゴニオメーター:(株)リガク社製RINT2000縦型ゴニオメーター
サンプリング幅:0.01°
ステップ時間:1秒
発散スリット:2°
散乱スリット:2°
受光スリット:0.6mm
管球:Cu
管電圧:55KV
管電流:280mA
得られた顔料粉末にポリビニルピロリドン(和光純薬(株)製)を混合し、乳酸エチル(和光純薬(株)製)で希釈した後、超音波ホモジナイザー(製品名:Model450 ブランソン製)で分散した。これを試料台に薄くスピンコートして撮影飼料とし、走査型電子顕微鏡にて粒子像を観察した。観察画像から、一次粒子が明瞭に識別できるもの400個に対して粒径測定を行い、数平均径を算出した。
――――――――――――――――――――――――――――――――
α化率 (-1 5 1) 平均粒径
結晶子サイズ (nm)
――――――――――――――――――――――――――――――――
実施例II-1 69% 8.0nm 15.2nm
実施例II-2 66% 8.2nm 18.1nm
実施例II-3 73% 8.6nm 16.6nm
実施例II-4 81% 9.0nm 17.8nm
実施例II-5 77% 8.9nm 18.2nm
比較例II-1 86% 14.2nm 32.4nm
比較例II-2 33% 計算不能 測定不能
比較例II-3 77% 11.2nm 24.2nm
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実施例II-1で得られた有機顔料粉末1を用い、下記組成の有機顔料分散組成物1を調製した。
有機顔料粉末A2 10.0部
分散樹脂1 7.88部
顔料誘導体1 0.98部
SS-1 0.97部
プロピレングリコールモノメチルエーテルアセテート
79.75部
得られた有機顔料分散組成物試料を、それぞれガラス基板上に厚みが2μmになるように塗布し、サンプルを作製した。バックライトユニットとして3波長冷陰極管光源(東芝ライテック(株)社製FWL18EX-N)に拡散板を設置したものを用い、2枚の偏光板((株)サンリツ社製の偏光板HLC2-2518)の間にこのサンプルを置き、偏光軸が平行のときと、垂直のときとの透過光量を測定し、その比をコントラストとした(「1990年第7回色彩光学コンファレンス、512色表示10.4”サイズTFT-LCD用カラーフィルタ、植木、小関、福永、山中」等参照。)。色度の測定には色彩輝度計((株)トプコン社製BM-5)を用いた。2枚の偏光板、サンプル、色彩輝度計の設置位置は、バックライトから13mmの位置に偏光板を、40mm~60mmの位置に直径11mm長さ20mmの円筒を設置し、この中を透過した光を、65mmの位置に設置した測定サンプルに照射し、透過した光を、100mmの位置に設置した偏光板を通して、400mmの位置に設置した色彩輝度計で測定した。色彩輝度計の測定角は2°に設定した。バックライトの光量は、サンプルを設置しない状態で、2枚の偏光板をパラレルニコルに設置したときの輝度が1280cd/m2になるように設定した。
さらに上記顔料分散組成物を分散30日後に再度上記と同様の方法で塗布し、上記と同様の方法でコントラストを測定し、経時コントラストとした。
得られた結果を下表に示した。
得られた有機顔料分散組成物試料を、それぞれガラス基板上に厚みが2μmになるように塗布し、サンプルを作製した。このサンプルを230℃、90分間ポストベークした。このようにして作成した塗布膜サンプルを前述の方法に従ってコントラスト評価を行った。
上記により得られたコントラスト値をポストベーク前の値に対する比として求め、下記のランク付けを行った。
3:コントラスト比 0.8倍以上1倍以下
2:コントラスト比 0.6倍以上0.8倍未満
1:コントラスト比 0.6倍未満
[表2]
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有機顔料分散組成物 コントラスト 経時コントラスト 耐熱性
――――――――――――――――――――――――――――――――
11 31864 30256 3
12 28532 25432 2
13 26744 26002 3
14 27019 27120 3
15 29231 28866 3
C11 9214 9196 3
C12 32011 19326 1
C13 13548 13617 3
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Claims (23)
- 粒子成長抑制剤とジクロロジケトピロロピロール顔料からなる色材微粒子とを含有する色材分散物であって、前記色材微粒子のα型結晶化度を0.65~0.90とし、(-151)結晶面方向の結晶子サイズを6.0~13.0nmとし、(111)結晶面方向の結晶子サイズを5.0~23.0nmの範囲としたことを特徴とする色材分散物。
- 下記[i]及び[ii]の工程を経て製造されたことを特徴とする請求項1に記載の色材分散物。
[[i]良溶媒に溶解させたジクロロジケトピロロピロール顔料を含む顔料溶液を前記顔料に対して難溶であり前記良溶媒に相溶する貧溶媒と接触させて、ジクロロジケトピロロピロール顔料の微粒子を生成させる工程。]
[[ii]前記[i]の工程で得られたジクロロジケトピロロピロール顔料の微粒子を、前記粒子成長抑制剤の存在下に結晶型調整有機溶媒と接触させて、ジクロロジケトピロロピロール顔料のα型結晶化度を高める工程。] - 前記結晶成長抑制剤が下記一般式(1)で表されることを特徴とする請求項1又は2に記載の色材分散物。
P-[X-(Y)k]n・・・一般式(1)
(式中、Pは置換基を有してもよい有機色素化合物残基を表す。Xは単結合あるいは2価の連結基を表す。Yは-NR2R3、スルホ基、又はカルボキシル基を表す。R2とR3とは各々独立に水素原子、又は置換基を有してもよいアルキル基、アルケニル基、もしくはフェニル基、あるいはR2とR3とで一体となって形成される複素環を表す。kは1または2の整数を表す。nは1~4の整数を表す。) - 前記一般式(1)においてPがジケトピロロピロール顔料化合物残基又はキナクリドン顔料化合物残基である請求項1~3のいずれか1項に記載の色材分散物。
- 下記[i]及び[ii]の工程を経て製造されることを特徴とする、請求項1~5のいずれか1項に記載のジクロロジケトピロロピロール顔料からなる色材微粒子を含有する色材分散物の製造方法。
[[i]良溶媒に溶解させたジクロロジケトピロロピロール顔料を含む顔料溶液を前記顔料に対して難溶であり前記良溶媒に相溶する貧溶媒と接触させて、ジクロロジケトピロロピロール顔料の微粒子を生成させる工程。]
[[ii]前記[i]の工程で得られたジクロロジケトピロロピロール顔料の微粒子を、前記粒子成長抑制剤の存在下に結晶型調整有機溶媒と接触させて、ジクロロジケトピロロピロール顔料のα型結晶化度を高める工程。] - 前記ジクロロジケトピロロピロール顔料を含む顔料溶液が、ジクロロジケトピロロピロール顔料を塩基存在下で有機溶媒に溶解して得られたものであることを特徴とする請求項6に記載の色材分散物の製造方法。
- 前記[i]の工程を前記粒子成長抑制剤の存在下で行うことを特徴とする請求項6又は7に記載の色材分散物の製造方法。
- 前記一般式(1)で表される粒子成長抑制剤において、Pがキナクリドン顔料化合物残基またはジケトピロロピロール顔料化合物残基であることを特徴とする請求項9に記載の色材分散物の製造方法。
- 前記[i]の工程で生成させたジクロロジケトピロール顔料の微粒子が、実質的にβ型結晶変態であることを特徴とする請求項6~11のいずれか1項に記載の色材分散物の製造方法。
- 前記[ii]の工程を摩砕剤の非存在下で行うことを特徴とする請求項6~12のいずれか1項に記載の色材分散物の製造方法。
- 前記[ii]の工程を、前記[i]の工程で生成したジクロロジケトピロロピロール顔料粒子を乾燥することなく行うことを特徴とする請求項6~13のいずれか1項に記載の色材分散物の製造方法。
- ジクロロジケトピロロピロール顔料におけるX線回折パターンより算出される(-1 5 1)面垂直方向の結晶子サイズが9nm以下であり、かつ該顔料のα型結晶化度が60%以上であるジクロロジケトピロロピロール顔料。
- ナノメートルサイズの微粒子であって、該微粒子に分散剤と顔料誘導体との少なくともどちらか一方を埋包させた構造を有する請求項15に記載のジクロロジケトピロロピロール顔料。
- p-ジクロロジケトピロロピロール顔料を良溶媒に溶解した溶液と、前記良溶媒と相溶する前記顔料の貧溶媒とを混合し、この混合液中で生成させた微粒子であることを特徴とする請求項15又は16に記載のジクロロジケトピロロピロール顔料。
- 前記良溶媒及び/又は貧溶媒に分散剤を含有させて前記両液を混合して、又はこれらとは別に良溶媒に分散剤を含有させた溶液を準備し前記両液とともに混合して生成させた、前記分散剤を埋包する微粒子であって、前記溶媒中に含有させた分散剤の少なくとも10質量%が微粒子に埋包されている請求項17に記載のジクロロジケトピロロピロール顔料。
- 請求項15~18のいずれか1項に記載のジクロロジケトピロロピロール顔料を含有することを特徴とする着色組成物。
- 請求項19に記載の着色組成物を用いて作成したことを特徴とするカラーフィルタ。
- 少なくとも下記工程を含むことにより顔料の結晶子サイズおよび結晶化度を調整することを特徴とする、顔料微粒子の製造方法。
(1)顔料を良溶媒に溶解した溶液と、前記良溶媒と相溶し前記顔料の貧溶媒とを混合し、分散剤または顔料誘導体の少なくともどちらか一方の存在下、分散剤または顔料誘導体の少なくともどちらか一方を埋包させた構造を有する顔料微粒子を生成する
(2)前記生成した顔料微粒子を湿式粉砕する - 前記顔料微粒子に有機溶剤と接触させることにより結晶化度を調整することを特徴とする請求項21記載の顔料微粒子の製造方法。
- 顔料がジクロロジケトピロロピロール顔料であることを特徴とする請求項22記載の顔料微粒子の製造方法。
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CN110568722B (zh) * | 2018-02-05 | 2021-06-25 | Tcl华星光电技术有限公司 | 蓝光截止膜及蓝光显示装置 |
Citations (67)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2367660A (en) | 1941-12-31 | 1945-01-23 | Du Pont | Process of photopolymerization |
US2448828A (en) | 1946-09-04 | 1948-09-07 | Du Pont | Photopolymerization |
US2722512A (en) | 1952-10-23 | 1955-11-01 | Du Pont | Photopolymerization process |
US2951758A (en) | 1957-05-17 | 1960-09-06 | Du Pont | Photopolymerizable compositions and elements |
US3046127A (en) | 1957-10-07 | 1962-07-24 | Du Pont | Photopolymerizable compositions, elements and processes |
US3549367A (en) | 1968-05-24 | 1970-12-22 | Du Pont | Photopolymerizable compositions containing triarylimidazolyl dimers and p-aminophenyl ketones |
JPS4864183A (ja) | 1971-12-09 | 1973-09-05 | ||
JPS4841708B1 (ja) | 1970-01-13 | 1973-12-07 | ||
JPS4943191B1 (ja) | 1969-07-11 | 1974-11-19 | ||
JPS506034B1 (ja) | 1970-08-11 | 1975-03-10 | ||
JPS5137193A (ja) | 1974-09-25 | 1976-03-29 | Toyo Boseki | |
JPS5148516B2 (ja) | 1973-02-07 | 1976-12-21 | ||
JPS5230490B2 (ja) | 1972-03-21 | 1977-08-09 | ||
US4139391A (en) | 1976-02-16 | 1979-02-13 | Fuji Photo Film Co., Ltd. | Light-sensitive resin composition and metal image-forming material using the same |
JPS5425957B2 (ja) | 1974-10-04 | 1979-08-31 | ||
JPS5434327B1 (ja) | 1970-12-28 | 1979-10-26 | ||
US4212976A (en) | 1973-06-15 | 1980-07-15 | Merck & Co., Inc. | 3,4α-Di-O-derivatives of mercaptomethylpyridine and pyridylmethyldisulfide |
US4239850A (en) | 1977-11-29 | 1980-12-16 | Fuji Photo Film Co., Ltd. | Photopolymerizable composition |
JPS56118462A (en) | 1980-02-25 | 1981-09-17 | Toyo Ink Mfg Co Ltd | Pigment composition |
JPS5812577B2 (ja) | 1973-12-21 | 1983-03-09 | ヘキスト アクチエンゲゼルシヤフト | 光重合可能な複写材料 |
JPS58210084A (ja) | 1982-05-17 | 1983-12-07 | チバ−ガイギ−・アクチエンゲゼルシヤフト | ピロロ〔3,4−c〕ピロ−ルの製法 |
JPS5944615A (ja) | 1982-09-07 | 1984-03-13 | Furuno Electric Co Ltd | ジヤイロ装置 |
JPS5953836A (ja) | 1982-09-21 | 1984-03-28 | Fuji Photo Film Co Ltd | 感光性平版印刷版 |
JPS5971048A (ja) | 1982-10-18 | 1984-04-21 | Mitsubishi Chem Ind Ltd | 光重合系感光性組成物 |
EP0277703A1 (en) | 1987-01-10 | 1988-08-10 | Xaar Limited | Droplet deposition apparatus |
JPS63264674A (ja) | 1987-04-22 | 1988-11-01 | Toyo Ink Mfg Co Ltd | 顔料組成物 |
JPH01195326A (ja) | 1988-01-29 | 1989-08-07 | Hitachi Ltd | 熱線式空気流量計 |
JPH01217077A (ja) | 1988-02-25 | 1989-08-30 | Toyo Ink Mfg Co Ltd | 顔料組成物,分散方法および塗料 |
JPH039961A (ja) | 1989-06-07 | 1991-01-17 | Toyo Ink Mfg Co Ltd | 顔料組成物および顔料の分散方法 |
JPH0326767A (ja) | 1989-06-23 | 1991-02-05 | Toyo Ink Mfg Co Ltd | 顔料分散剤および顔料組成物 |
JPH0345662A (ja) | 1989-07-13 | 1991-02-27 | Toyo Ink Mfg Co Ltd | 顔料分散剤,顔料組成物,塗料および印刷インキ |
JPH03153780A (ja) | 1989-11-10 | 1991-07-01 | Toyo Ink Mfg Co Ltd | カラーフィルター用着色組成物 |
JPH04285669A (ja) | 1990-11-08 | 1992-10-09 | Ciba Geigy Ag | ピラゾール含有顔料誘導体 |
JPH0572724A (ja) | 1991-01-29 | 1993-03-26 | Fuji Photo Film Co Ltd | 感光性転写材料及び画像形成方法 |
JPH06145546A (ja) | 1992-11-06 | 1994-05-24 | Dainichiseika Color & Chem Mfg Co Ltd | 顔料組成物及び顔料分散体 |
JPH06212088A (ja) | 1993-01-20 | 1994-08-02 | Dainippon Ink & Chem Inc | 顔料組成物及び塗料 |
JPH06240158A (ja) | 1992-12-25 | 1994-08-30 | Sumitomo Chem Co Ltd | 顔料誘導体およびその応用 |
JPH07331182A (ja) | 1994-04-15 | 1995-12-19 | Toyo Ink Mfg Co Ltd | 塗料組成物 |
JPH0848908A (ja) | 1994-06-29 | 1996-02-20 | Ciba Geigy Ag | ジケトピロロピロール顔料の新しい結晶変態 |
JPH09323420A (ja) | 1996-06-07 | 1997-12-16 | Canon Inc | 液体吐出ヘッド、液体吐出装置および液体吐出記録方法 |
JPH1030063A (ja) | 1996-02-13 | 1998-02-03 | Ciba Specialty Chem Holding Inc | 顔料組成物 |
JPH1062986A (ja) | 1996-08-21 | 1998-03-06 | Fuji Photo Film Co Ltd | 感放射線性着色組成物 |
JPH10195326A (ja) | 1996-12-31 | 1998-07-28 | Bayer Corp | 有機顔料組成物 |
JPH11133600A (ja) | 1997-10-30 | 1999-05-21 | Jsr Corp | 表示パネルスペーサー用感放射線性樹脂組成物 |
JP2001264528A (ja) | 2000-03-21 | 2001-09-26 | Toyo Ink Mfg Co Ltd | カラーフィルタ用顔料、それを用いたカラーフィルタ用着色組成物およびカラーフィルタ |
JP2001310147A (ja) | 2000-05-02 | 2001-11-06 | Tokyo Ohka Kogyo Co Ltd | スリットコータの予備吐出装置および予備吐出方法 |
JP2002079163A (ja) | 2000-09-05 | 2002-03-19 | Toppan Printing Co Ltd | スリットコータ |
JP2002265840A (ja) | 2001-03-12 | 2002-09-18 | Nippon Steel Chem Co Ltd | 赤色カラーレジストインキ及びカラーフィルター |
JP2003010767A (ja) | 2001-07-03 | 2003-01-14 | Toppan Printing Co Ltd | スリットノズルの洗浄方法及び洗浄機構 |
JP2003164787A (ja) | 2001-11-29 | 2003-06-10 | Canon Inc | 液体の吐出口 |
JP2003170098A (ja) | 2001-12-06 | 2003-06-17 | Shimadzu Corp | スリットコータ |
JP2003337424A (ja) | 2002-05-20 | 2003-11-28 | Fuji Photo Film Co Ltd | 画像形成材料 |
JP2004017043A (ja) | 2002-06-14 | 2004-01-22 | Samsung Electronics Co Ltd | 感光物質コーティング方法及び装置 |
JP2004089851A (ja) | 2002-08-30 | 2004-03-25 | Shimadzu Corp | スリットコータ |
JP2005003861A (ja) | 2003-06-11 | 2005-01-06 | Fuji Photo Film Co Ltd | カラーフィルターの製造方法 |
JP2005017521A (ja) | 2003-06-24 | 2005-01-20 | Fuji Photo Film Co Ltd | 感光性転写材料及び像形成方法 |
JP2005017716A (ja) | 2003-06-26 | 2005-01-20 | Fujifilm Arch Co Ltd | カラーフィルター用着色樹脂被膜、カラーフィルター用着色樹脂被膜の評価方法、並びに、カラーフィルター |
JP2005061447A (ja) | 2003-08-18 | 2005-03-10 | Hino Motors Ltd | 板金カラー |
JP2006010875A (ja) | 2004-06-23 | 2006-01-12 | Dainippon Printing Co Ltd | カラーフィルタおよびその製造方法 |
JP2006017980A (ja) | 2004-07-01 | 2006-01-19 | Toppan Printing Co Ltd | カラーフィルタの製造方法 |
JP2007009096A (ja) | 2005-07-01 | 2007-01-18 | Toyo Ink Mfg Co Ltd | 顔料組成物およびそれを用いた顔料分散体 |
WO2007013599A1 (ja) * | 2005-07-29 | 2007-02-01 | Fujifilm Corporation | 有機粒子の製造方法、有機粒子分散組成物の製造方法、およびそれにより得られる有機粒子分散組成物を含有するインクジェット記録用インク |
JP2007314681A (ja) * | 2006-05-26 | 2007-12-06 | Toyo Ink Mfg Co Ltd | 顔料組成物の製造方法 |
JP2008024873A (ja) | 2006-07-24 | 2008-02-07 | Toyo Ink Mfg Co Ltd | α型結晶変態ジクロロジケトピロロピロール顔料の製造方法、該方法で製造されたα型結晶変態ジクロロジケトピロロピロール顔料、およびそれを用いた着色組成物 |
WO2008044519A1 (fr) * | 2006-10-06 | 2008-04-17 | Toyo Ink Mfg. Co., Ltd. | PIGMENT DE α-DICÉTOPYRROLOPYRROLE, COMPOSITION COLORANTE CONTENANT CELUI-CI, ET FILM ROUGE |
JP2008139865A (ja) | 2006-11-08 | 2008-06-19 | Fujifilm Corp | カラーフィルタ及びそれを用いた液晶表示装置 |
WO2009054514A1 (ja) * | 2007-10-25 | 2009-04-30 | Fujifilm Corporation | 有機顔料微粒子およびその製造方法、それを含有する顔料分散組成物、光硬化性組成物、インクジェットインク、並びにそれらを用いたカラーフィルタ及びその製造方法 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH04144655A (ja) | 1990-10-08 | 1992-05-19 | Idemitsu Petrochem Co Ltd | 米穀の改質方法 |
US6057449A (en) * | 1998-06-02 | 2000-05-02 | Ciba Specialty Chemicals Corporation | Direct preparation of pyrrolo[3,4-c]pyrroles |
KR101396904B1 (ko) * | 2006-05-26 | 2014-05-19 | 토요잉크Sc홀딩스주식회사 | 안료 조성물의 제조 방법 |
TWI531623B (zh) * | 2007-12-26 | 2016-05-01 | 東洋油墨Sc控股股份有限公司 | 紅色彩色濾光片用顏料組成物、其製造方法、及使用它之著色組成物、及彩色濾光片 |
JP5438942B2 (ja) * | 2008-09-19 | 2014-03-12 | 富士フイルム株式会社 | 水不溶性化合物の微粒子およびその分散物、その微粒子及び分散物の製造方法、それらを用いたカラーフィルタ |
-
2010
- 2010-08-26 WO PCT/JP2010/064484 patent/WO2011024896A1/ja active Application Filing
- 2010-08-26 CN CN201080048744.0A patent/CN102597126B/zh not_active Expired - Fee Related
- 2010-08-26 EP EP10811945.4A patent/EP2471876B1/en not_active Not-in-force
- 2010-08-26 KR KR1020127007629A patent/KR101639701B1/ko active IP Right Grant
- 2010-08-27 TW TW099128820A patent/TWI495691B/zh not_active IP Right Cessation
Patent Citations (69)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2367660A (en) | 1941-12-31 | 1945-01-23 | Du Pont | Process of photopolymerization |
US2448828A (en) | 1946-09-04 | 1948-09-07 | Du Pont | Photopolymerization |
US2722512A (en) | 1952-10-23 | 1955-11-01 | Du Pont | Photopolymerization process |
US2951758A (en) | 1957-05-17 | 1960-09-06 | Du Pont | Photopolymerizable compositions and elements |
US3046127A (en) | 1957-10-07 | 1962-07-24 | Du Pont | Photopolymerizable compositions, elements and processes |
US3549367A (en) | 1968-05-24 | 1970-12-22 | Du Pont | Photopolymerizable compositions containing triarylimidazolyl dimers and p-aminophenyl ketones |
JPS4943191B1 (ja) | 1969-07-11 | 1974-11-19 | ||
JPS4841708B1 (ja) | 1970-01-13 | 1973-12-07 | ||
JPS506034B1 (ja) | 1970-08-11 | 1975-03-10 | ||
JPS5434327B1 (ja) | 1970-12-28 | 1979-10-26 | ||
JPS4864183A (ja) | 1971-12-09 | 1973-09-05 | ||
JPS5230490B2 (ja) | 1972-03-21 | 1977-08-09 | ||
JPS5148516B2 (ja) | 1973-02-07 | 1976-12-21 | ||
US4212976A (en) | 1973-06-15 | 1980-07-15 | Merck & Co., Inc. | 3,4α-Di-O-derivatives of mercaptomethylpyridine and pyridylmethyldisulfide |
JPS5812577B2 (ja) | 1973-12-21 | 1983-03-09 | ヘキスト アクチエンゲゼルシヤフト | 光重合可能な複写材料 |
JPS5137193A (ja) | 1974-09-25 | 1976-03-29 | Toyo Boseki | |
JPS5425957B2 (ja) | 1974-10-04 | 1979-08-31 | ||
US4139391A (en) | 1976-02-16 | 1979-02-13 | Fuji Photo Film Co., Ltd. | Light-sensitive resin composition and metal image-forming material using the same |
US4239850A (en) | 1977-11-29 | 1980-12-16 | Fuji Photo Film Co., Ltd. | Photopolymerizable composition |
JPS56118462A (en) | 1980-02-25 | 1981-09-17 | Toyo Ink Mfg Co Ltd | Pigment composition |
JPS58210084A (ja) | 1982-05-17 | 1983-12-07 | チバ−ガイギ−・アクチエンゲゼルシヤフト | ピロロ〔3,4−c〕ピロ−ルの製法 |
JPS5944615A (ja) | 1982-09-07 | 1984-03-13 | Furuno Electric Co Ltd | ジヤイロ装置 |
JPS5953836A (ja) | 1982-09-21 | 1984-03-28 | Fuji Photo Film Co Ltd | 感光性平版印刷版 |
JPS5971048A (ja) | 1982-10-18 | 1984-04-21 | Mitsubishi Chem Ind Ltd | 光重合系感光性組成物 |
EP0277703A1 (en) | 1987-01-10 | 1988-08-10 | Xaar Limited | Droplet deposition apparatus |
EP0278590A1 (en) | 1987-01-10 | 1988-08-17 | Xaar Limited | Droplet deposition apparatus |
JPS63264674A (ja) | 1987-04-22 | 1988-11-01 | Toyo Ink Mfg Co Ltd | 顔料組成物 |
JPH01195326A (ja) | 1988-01-29 | 1989-08-07 | Hitachi Ltd | 熱線式空気流量計 |
JPH01217077A (ja) | 1988-02-25 | 1989-08-30 | Toyo Ink Mfg Co Ltd | 顔料組成物,分散方法および塗料 |
JPH039961A (ja) | 1989-06-07 | 1991-01-17 | Toyo Ink Mfg Co Ltd | 顔料組成物および顔料の分散方法 |
JPH0326767A (ja) | 1989-06-23 | 1991-02-05 | Toyo Ink Mfg Co Ltd | 顔料分散剤および顔料組成物 |
JPH0345662A (ja) | 1989-07-13 | 1991-02-27 | Toyo Ink Mfg Co Ltd | 顔料分散剤,顔料組成物,塗料および印刷インキ |
JPH03153780A (ja) | 1989-11-10 | 1991-07-01 | Toyo Ink Mfg Co Ltd | カラーフィルター用着色組成物 |
JPH04285669A (ja) | 1990-11-08 | 1992-10-09 | Ciba Geigy Ag | ピラゾール含有顔料誘導体 |
JPH0572724A (ja) | 1991-01-29 | 1993-03-26 | Fuji Photo Film Co Ltd | 感光性転写材料及び画像形成方法 |
JPH06145546A (ja) | 1992-11-06 | 1994-05-24 | Dainichiseika Color & Chem Mfg Co Ltd | 顔料組成物及び顔料分散体 |
JPH06240158A (ja) | 1992-12-25 | 1994-08-30 | Sumitomo Chem Co Ltd | 顔料誘導体およびその応用 |
JPH06212088A (ja) | 1993-01-20 | 1994-08-02 | Dainippon Ink & Chem Inc | 顔料組成物及び塗料 |
JPH07331182A (ja) | 1994-04-15 | 1995-12-19 | Toyo Ink Mfg Co Ltd | 塗料組成物 |
JPH0848908A (ja) | 1994-06-29 | 1996-02-20 | Ciba Geigy Ag | ジケトピロロピロール顔料の新しい結晶変態 |
JPH1030063A (ja) | 1996-02-13 | 1998-02-03 | Ciba Specialty Chem Holding Inc | 顔料組成物 |
JPH09323420A (ja) | 1996-06-07 | 1997-12-16 | Canon Inc | 液体吐出ヘッド、液体吐出装置および液体吐出記録方法 |
JPH1062986A (ja) | 1996-08-21 | 1998-03-06 | Fuji Photo Film Co Ltd | 感放射線性着色組成物 |
JPH10195326A (ja) | 1996-12-31 | 1998-07-28 | Bayer Corp | 有機顔料組成物 |
JPH11133600A (ja) | 1997-10-30 | 1999-05-21 | Jsr Corp | 表示パネルスペーサー用感放射線性樹脂組成物 |
JP2001264528A (ja) | 2000-03-21 | 2001-09-26 | Toyo Ink Mfg Co Ltd | カラーフィルタ用顔料、それを用いたカラーフィルタ用着色組成物およびカラーフィルタ |
JP2001310147A (ja) | 2000-05-02 | 2001-11-06 | Tokyo Ohka Kogyo Co Ltd | スリットコータの予備吐出装置および予備吐出方法 |
JP2002079163A (ja) | 2000-09-05 | 2002-03-19 | Toppan Printing Co Ltd | スリットコータ |
JP2002265840A (ja) | 2001-03-12 | 2002-09-18 | Nippon Steel Chem Co Ltd | 赤色カラーレジストインキ及びカラーフィルター |
JP2003010767A (ja) | 2001-07-03 | 2003-01-14 | Toppan Printing Co Ltd | スリットノズルの洗浄方法及び洗浄機構 |
JP2003164787A (ja) | 2001-11-29 | 2003-06-10 | Canon Inc | 液体の吐出口 |
JP2003170098A (ja) | 2001-12-06 | 2003-06-17 | Shimadzu Corp | スリットコータ |
JP2003337424A (ja) | 2002-05-20 | 2003-11-28 | Fuji Photo Film Co Ltd | 画像形成材料 |
JP2004017043A (ja) | 2002-06-14 | 2004-01-22 | Samsung Electronics Co Ltd | 感光物質コーティング方法及び装置 |
JP2004089851A (ja) | 2002-08-30 | 2004-03-25 | Shimadzu Corp | スリットコータ |
JP2005003861A (ja) | 2003-06-11 | 2005-01-06 | Fuji Photo Film Co Ltd | カラーフィルターの製造方法 |
JP2005017521A (ja) | 2003-06-24 | 2005-01-20 | Fuji Photo Film Co Ltd | 感光性転写材料及び像形成方法 |
JP2005017716A (ja) | 2003-06-26 | 2005-01-20 | Fujifilm Arch Co Ltd | カラーフィルター用着色樹脂被膜、カラーフィルター用着色樹脂被膜の評価方法、並びに、カラーフィルター |
JP2005061447A (ja) | 2003-08-18 | 2005-03-10 | Hino Motors Ltd | 板金カラー |
JP2006010875A (ja) | 2004-06-23 | 2006-01-12 | Dainippon Printing Co Ltd | カラーフィルタおよびその製造方法 |
JP2006017980A (ja) | 2004-07-01 | 2006-01-19 | Toppan Printing Co Ltd | カラーフィルタの製造方法 |
JP2007009096A (ja) | 2005-07-01 | 2007-01-18 | Toyo Ink Mfg Co Ltd | 顔料組成物およびそれを用いた顔料分散体 |
WO2007013599A1 (ja) * | 2005-07-29 | 2007-02-01 | Fujifilm Corporation | 有機粒子の製造方法、有機粒子分散組成物の製造方法、およびそれにより得られる有機粒子分散組成物を含有するインクジェット記録用インク |
JP2007314681A (ja) * | 2006-05-26 | 2007-12-06 | Toyo Ink Mfg Co Ltd | 顔料組成物の製造方法 |
JP2008024873A (ja) | 2006-07-24 | 2008-02-07 | Toyo Ink Mfg Co Ltd | α型結晶変態ジクロロジケトピロロピロール顔料の製造方法、該方法で製造されたα型結晶変態ジクロロジケトピロロピロール顔料、およびそれを用いた着色組成物 |
WO2008044519A1 (fr) * | 2006-10-06 | 2008-04-17 | Toyo Ink Mfg. Co., Ltd. | PIGMENT DE α-DICÉTOPYRROLOPYRROLE, COMPOSITION COLORANTE CONTENANT CELUI-CI, ET FILM ROUGE |
JP4144655B2 (ja) | 2006-10-06 | 2008-09-03 | 東洋インキ製造株式会社 | α型ジケトピロロピロール顔料、それを用いた着色組成物、および赤色着色膜 |
JP2008139865A (ja) | 2006-11-08 | 2008-06-19 | Fujifilm Corp | カラーフィルタ及びそれを用いた液晶表示装置 |
WO2009054514A1 (ja) * | 2007-10-25 | 2009-04-30 | Fujifilm Corporation | 有機顔料微粒子およびその製造方法、それを含有する顔料分散組成物、光硬化性組成物、インクジェットインク、並びにそれらを用いたカラーフィルタ及びその製造方法 |
Non-Patent Citations (1)
Title |
---|
See also references of EP2471876A4 * |
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WO2016136921A1 (ja) * | 2015-02-27 | 2016-09-01 | エム・テクニック株式会社 | 顔料微粒子、顔料分散体、感光性着色組成物及びカラーフィルター |
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WO2018003595A1 (ja) * | 2016-06-29 | 2018-01-04 | Dic株式会社 | 樹脂着色用キナクリドン顔料 |
JP2021177243A (ja) * | 2017-03-07 | 2021-11-11 | 富士フイルム株式会社 | 積層体、光学フィルタ、固体撮像素子、画像表示装置、赤外線センサおよびキット |
WO2018163702A1 (ja) * | 2017-03-07 | 2018-09-13 | 富士フイルム株式会社 | 積層体、光学フィルタ、固体撮像素子、画像表示装置、赤外線センサおよびキット |
US20190361158A1 (en) * | 2017-03-07 | 2019-11-28 | Fujifilm Corporation | Laminate, optical filter, solid image pickup element, image display device, infrared sensor, and kit |
JPWO2018163702A1 (ja) * | 2017-03-07 | 2019-12-26 | 富士フイルム株式会社 | 積層体、光学フィルタ、固体撮像素子、画像表示装置、赤外線センサおよびキット |
US12078828B2 (en) * | 2017-03-07 | 2024-09-03 | Fujifilm Corporation | Laminate, optical filter, solid image pickup element, image display device, infrared sensor, and kit |
JP7233477B2 (ja) | 2017-03-07 | 2023-03-06 | 富士フイルム株式会社 | 積層体、光学フィルタ、固体撮像素子、画像表示装置、赤外線センサおよびキット |
WO2019054281A1 (ja) | 2017-09-15 | 2019-03-21 | 富士フイルム株式会社 | 組成物、膜、積層体、赤外線透過フィルタ、固体撮像素子および赤外線センサ |
WO2020059509A1 (ja) | 2018-09-20 | 2020-03-26 | 富士フイルム株式会社 | 硬化性組成物、硬化膜、赤外線透過フィルタ、積層体、固体撮像素子、センサ、及び、パターン形成方法 |
WO2021039205A1 (ja) | 2019-08-29 | 2021-03-04 | 富士フイルム株式会社 | 組成物、膜、近赤外線カットフィルタ、パターン形成方法、積層体、固体撮像素子、赤外線センサ、画像表示装置、カメラモジュール、及び、化合物 |
WO2022131191A1 (ja) | 2020-12-16 | 2022-06-23 | 富士フイルム株式会社 | 組成物、膜、光学フィルタ、固体撮像素子、画像表示装置および赤外線センサ |
WO2022130773A1 (ja) | 2020-12-17 | 2022-06-23 | 富士フイルム株式会社 | 組成物、膜、光学フィルタ、固体撮像素子、画像表示装置および赤外線センサ |
WO2023204062A1 (ja) * | 2022-04-21 | 2023-10-26 | 富士フイルム株式会社 | 樹脂組成物、樹脂組成物の製造方法、顔料誘導体、膜、光学フィルタ、固体撮像素子および画像表示装置 |
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KR101639701B1 (ko) | 2016-07-14 |
TWI495691B (zh) | 2015-08-11 |
KR20120066642A (ko) | 2012-06-22 |
CN102597126B (zh) | 2014-12-24 |
EP2471876A4 (en) | 2014-05-14 |
EP2471876B1 (en) | 2014-12-10 |
EP2471876A1 (en) | 2012-07-04 |
CN102597126A (zh) | 2012-07-18 |
TW201127909A (en) | 2011-08-16 |
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