WO2024257877A1 - ブロックポリマー及びそれを用いた着色材料分散液並びにインク組成物 - Google Patents

ブロックポリマー及びそれを用いた着色材料分散液並びにインク組成物 Download PDF

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WO2024257877A1
WO2024257877A1 PCT/JP2024/021786 JP2024021786W WO2024257877A1 WO 2024257877 A1 WO2024257877 A1 WO 2024257877A1 JP 2024021786 W JP2024021786 W JP 2024021786W WO 2024257877 A1 WO2024257877 A1 WO 2024257877A1
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segment
mass
functional group
block polymer
monomer
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French (fr)
Japanese (ja)
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裕崇 川上
裕佳子 濱崎
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Mikuni Color Ltd
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Mikuni Color Ltd
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Priority to EP24823490.8A priority patent/EP4729553A1/en
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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
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/04—Physical treatment, e.g. grinding or treatment with ultrasonic vibrations
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/10—Treatment with macromolecular organic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/322—Pigment inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D17/00—Pigment pastes, e.g. for mixing in paints

Definitions

  • aqueous inks using pigments the pigments are not soluble in water, so when they are used in ink compositions, it is important to stably disperse the pigments in water as fine particles.
  • aqueous inks using pigments have a problem of alteration of the recording liquid due to aggregation and precipitation of the pigments, that is, so-called storage stability.
  • storage stability it is particularly required that the viscosity and particle size remain within a suitable range even when stored for a long time.
  • Other requirements include excellent color characteristics such as color development and gloss, the ink not clogging the nozzles, and quick recovery from nozzle clogging after a long period of inactivity; in other words, excellent ink ejection stability.
  • Patent Document 2 also proposes a method for improving storage stability, ejection stability, and redispersibility by using a block polymer and a pigment derivative. Specifically, as in Patent Document 1, a hydrophobic segment made of a monomer having one aromatic ring is used, but the use of a derivative is intended to improve storage stability, ejection stability, and redispersibility.
  • Patent Document 3 Besides using block polymers, for example, in Patent Document 3, a water-insoluble polymer dispersant is used to coat (encapsulate) a colorant, thereby dealing with the deterioration of storage stability. Furthermore, Patent Document 4 proposes a method for realizing excellent storage stability, redispersibility, and color properties by using a monomer containing a biphenyl group in the hydrophobic segment of a block polymer.
  • the present inventors have found that even when the block polymer described in Patent Document 1 is used, the redispersibility related to the ejection stability is insufficient. Furthermore, when a pigment derivative is used as described in Patent Document 2, it has been found that the problem of color deterioration occurs, and the problem of color characteristics cannot be solved. Furthermore, in the method using a water-insoluble polymer as in Patent Document 3, the highly hydrophobic nature of the dispersant causes a problem that re-dispersibility during head cleaning operation is poor. Furthermore, when the block polymer described in Patent Document 4 is used, the storage stability is improved, but the redispersibility is insufficient, and there is a risk of the ejection stability being reduced depending on the usage environment and the ink composition. In particular, the present inventors have found that sufficient redispersibility tends not to be obtained in ink compositions having a high ratio of solvent.
  • the above object can be solved by using as a dispersant a block polymer having segments containing structural units derived from specific monomers in a specific ratio.
  • the above object can be solved by using as a dispersant a block polymer having segments containing specific functional groups in a specific ratio.
  • the following block polymer and a coloring material dispersion using the block polymer are provided.
  • the present invention provides (1) A block polymer having at least one segment (A) satisfying the following (a1) and (a2) and at least one segment (B) satisfying the following (b1) and (b2), and having a peak top molecular weight of 3,000 or more and 16,000 or less.
  • Peak top molecular weight is 750 or more.
  • the proportion of the total mass of the constituent units derived from the monomer having a hydrophobic functional group and the total mass of the constituent units derived from the monomer having a hydrophilic functional group in the segment (A) is 10 mass% or more, and the proportion of the total mass of the constituent units derived from the monomer having a hydrophobic functional group and the total mass of the constituent units derived from the monomer having a hydrophilic functional group in the segment (B) is 10 mass% or more;
  • a method for producing a printing ink comprising mixing the coloring material dispersion liquid according to (10) above with an organic solvent, a resin and a preservative.
  • a printing ink containing at least the block polymer according to any one of (1) to (9) above, a coloring material, an organic solvent, a resin, and a preservative. is located.
  • the block polymer of the present invention By incorporating the block polymer of the present invention, it is possible to obtain a coloring material dispersion that has excellent storage stability and redispersibility, and can be used to prepare an ink composition that achieves color characteristics.
  • FIG. 1 is a photograph of the coating film obtained in Example 6.
  • FIG. 1 is a photograph of the coating film obtained in Example 7.
  • FIG. 1 is a photograph of the coating film obtained in Example 8.
  • the block polymer of the first invention of this application is characterized by having at least one segment (A) that satisfies the following (a1) and (a2) and at least one segment (B) that satisfies the following (b1) and (b2): (a1): Having a structural unit derived from a monomer having a hydrophobic functional group and a structural unit derived from a monomer having a hydrophilic functional group, the mass ratio between the two (total mass of structural units derived from monomers having hydrophobic functional groups/total mass of structural units derived from monomers having hydrophilic functional groups) is 2.3 or more and 19.0 or less.
  • the block polymer of the second invention of the present application is characterized in that it has at least one segment (A') that satisfies the following (a1') and (a2), and at least one segment (B') that satisfies the following (b1') and (b2).
  • the monomer having a hydrophobic functional group refers to a monomer having at least one of the above-mentioned hydrophobic functional groups. Any monomer having a hydrophobic functional group can be used without any particular limitation.
  • these monomers having hydrophobic functional groups those having a phenyl group or a biphenyl group are preferred, and those having one phenyl group and a molecular weight of 140 to 200 are more preferred, of which phenyl acrylate, phenyl methacrylate and phenoxyethyl acrylate are even more preferred, with phenoxyethyl acrylate being the most preferred.
  • Block polymers using these preferred monomers have a moderate level of hydrophobicity and are superior in redispersibility and storage stability.
  • these preferred monomers have aromatic rings, when the coloring material has an aromatic ring as described below, ⁇ - ⁇ interactions are expressed, which is thought to be further advantageous in terms of storage stability.
  • the monomers having hydrophobic functional groups those having a LogP of 2.0 or more and 5.0 or less are preferred. Within this range, the strength of hydrophobicity is adequate, and redispersibility and storage stability are superior. More preferably, the LogP of the monomer having a hydrophobic functional group is 2.0 or more and 3.0 or less.
  • the measurement of LogP is based on the method for measuring the partition coefficient described in "OECD GUIDELINE FOR TESTING OF CHEMICALS, "Partition Coefficient (n-octanol/water), High Performance Liquid Chromatography (HPLC) Method", Adopted by the Council on 30th March 1989." Alternatively, other methods capable of obtaining an equivalent value may be used.
  • the hydrophilic functional group means a functional group having hydrophilicity
  • the hydrophobic functional group in the block polymer of the present invention is not particularly limited, but is preferably one that ionizes to generate an anion by neutralizing with an alkali compound, and representative examples include a carboxy group, a phosphate group, and a sulfonic acid group. These are particularly excellent in wet friction resistance.
  • a carboxy group is particularly preferred, which has a good hydrophilicity and can realize a well-balanced combination of redispersibility and solubility in a solvent of a pigment dispersion using the obtained block polymer.
  • the monomer having a hydrophilic functional group means a monomer having at least one of the above-mentioned hydrophilic functional groups.
  • the monomer having a hydrophilic functional group used in the present invention is not particularly limited, but representative examples include acrylic acid, methacrylic acid, maleic acid, itaconic acid, vinylphosphonic acid, and vinylsulfonic acid.
  • monomers having hydrophilic functional groups those with a LogP of -2.0 or more and 1.0 or less are preferred. Within this range, the hydrophilicity is adequate and the storage stability is superior. It is more preferred that the LogP of monomers having hydrophilic functional groups is 0.0 or more and 1.0 or less.
  • the method for measuring LogP is as described above.
  • Block polymer of the first invention [Segment A]
  • the block polymer of the first invention of this application has one or more segments (A) described below.
  • segment (A) plays a role in adsorbing the block polymer to the coloring material mainly due to its hydrophobicity, thereby imparting dispersibility.
  • Segment (A) contains the above-described constituent units derived from monomers having a hydrophobic functional group and constituent units derived from monomers having a hydrophilic functional group, and the mass ratio between the two (total mass of constituent units derived from monomers having a hydrophobic functional group/total mass of constituent units derived from monomers having a hydrophilic functional group) is 2.3 or more and 19.0 or less.
  • the mass ratio of the structural unit derived from a monomer having a hydrophobic functional group and the structural unit derived from a monomer having a hydrophilic functional group within the above range, it is possible to exhibit excellent redispersibility and storage stability.
  • the segments (A) of different polymers repel each other slightly due to hydrophilic-hydrophobic interaction, and the adsorption, entanglement, and aggregation of the polymers are suppressed, and many polymers can efficiently adsorb to the coloring material and impart dispersibility.
  • the mass ratio between the two is more preferably from 4.0 to 19.0, and even more preferably from 5.0 to 12.0, in which case better redispersibility and storage stability can be achieved.
  • the monomer having a hydrophobic functional group and the monomer having a hydrophilic functional group may be polymerized in the above ratio during synthesis of the block polymer.
  • H-NMR, GPC, acid value titration, etc. may be used.
  • the peak top molecular weight of segment (A) is 750 or more. If the peak top molecular weight is less than 750, the adsorption force to the material may be insufficient, and redispersibility may be deteriorated.
  • the peak top molecular weight of segment (A) is preferably 1000 or more, more preferably 2000 or more.
  • the method for measuring the peak top molecular weight is as shown in the Examples, but is not limited to this method as long as similar results are obtained.
  • the mass ratio of segment (A) is preferably 25% by mass or more and 75% by mass or less. If the proportion of segment (A) is less than 25% by mass, the pigment adsorption performance is insufficient and redispersibility and storage stability tend to be low. On the other hand, if the proportion of segment (A) is more than 75% by mass, it may not dissolve in the solvent.
  • the proportion of segment (A) is more preferably 55% by mass or more and 75% by mass or less, and most preferably 55% by mass or more and 65% by mass or less.
  • the order of the constituent units derived from each monomer in segment (A) is not particularly limited, but random is preferable.
  • various forms such as random copolymers, block copolymers, and alternating copolymers can be used as the form of segment (A), but among them, random copolymers are particularly preferable.
  • Segment (A) may contain any other constituent units in addition to the constituent units derived from monomers having hydrophobic functional groups and the constituent units derived from monomers having hydrophilic functional groups.
  • segment (A) is taken as 100% by mass
  • the total mass of the constituent units derived from monomers having hydrophobic functional groups and the constituent units derived from monomers having hydrophilic functional groups in segment (A) is preferably 10% by mass or more, more preferably 25% by mass or more, and even more preferably 50% by mass or more, and it is most preferable that 100% by mass, i.e., segment (A) is composed only of constituent units derived from monomers having hydrophobic functional groups and constituent units derived from monomers having hydrophilic functional groups.
  • segment (B) The block polymer of the first invention of this application has one or more segments (B) described below. In dispersing coloring materials, etc., it is believed that the segment (B) plays a role in dissolving the block polymer in an aqueous solvent mainly due to its hydrophilicity.
  • Segment (B) contains a constituent unit derived from the monomer having a hydrophobic functional group and a constituent unit derived from the monomer having a hydrophilic functional group, and the mass ratio between the two (mass of the constituent unit derived from the monomer having a hydrophobic functional group/mass of the constituent unit derived from the monomer having a hydrophilic functional group) is 0.43 or more and less than 2.30.
  • the mass ratio of the structural unit derived from the monomer having a hydrophobic functional group and the structural unit derived from the monomer having a hydrophilic functional group within the above range, the redispersibility can be improved and the viscosity of the coloring material dispersion or ink can be reduced to a suitable range.
  • the reason why the redispersibility is improved is believed to be that by including the structural unit derived from the monomer having a hydrophilic functional group within the above ratio, the polymer can be uniformly dissolved in the aqueous solvent, and many polymers can be efficiently adsorbed to the coloring material.
  • the reason why the viscosity can be reduced is believed to be that by including the structural unit derived from the hydrophilic functional group within the above ratio, the polymer can be sufficiently dissolved in the solvent, and by including the structural unit derived from the hydrophobic functional group within the above ratio, the segments (B) of different polymers are slightly repelled by hydrophilic-hydrophobic interactions, so that adsorption, aggregation, and entanglement are unlikely to occur, and the polymer is easily loosened.
  • the mass ratio between the two is more preferably from 0.50 to 1.50, and even more preferably from 0.67 to 1.00. By keeping it within this range, the viscosity reduction and redispersibility are excellent when used in a dispersion or ink.
  • the monomers may be polymerized in the above ratio during synthesis of the block polymer.
  • H-NMR, GPC, acid value titration, etc. may be used.
  • the mass ratio of segment (B) is preferably 25% by mass or more and 75% by mass or less. If the mass ratio of segment (B) is less than 25% by mass, it may not dissolve in a solvent. On the other hand, if the mass ratio of segment (B) is more than 75% by mass, the pigment adsorption performance is insufficient and redispersibility and storage stability tend to be low.
  • the mass ratio of segment (B) is more preferably 25% by mass or more and 45% by mass or less, and most preferably 35% by mass or more and 45% by mass or less.
  • the order of the constituent units composed of each monomer in segment (B) is not particularly limited, but is preferably random.
  • various forms such as random copolymers, block copolymers, and alternating copolymers can be used as the form of segment (B), with random copolymers being particularly preferred.
  • Segment (B) may contain any constitutional unit other than the constitutional unit derived from a monomer having a hydrophobic functional group and the constitutional unit derived from a monomer having a hydrophilic functional group.
  • the total ratio of the structural units derived from monomers having hydrophobic functional groups and the structural units derived from monomers having hydrophilic functional groups in the segment (B) is preferably 10% by mass or more, more preferably 25% by mass or more, and even more preferably 50% by mass or more, and it is most preferable that 100% by mass, that is, the segment (B) is composed only of structural units derived from monomers having hydrophobic functional groups and structural units derived from monomers having hydrophilic functional groups.
  • the block polymer of the first invention of this application may have two or more of the above-described segment (A) and segment (B) in each block polymer. In order to more effectively exert the effects of the present invention, however, it is preferable that each block polymer contains one of each of them.
  • the block polymer of the first invention of this application may contain portions other than the segment (A) and the segment (B) as long as the effects of the invention are not impaired.
  • the total mass of the segment (A) and the segment (B) is preferably 50% by mass or more. More preferably, it is 90% by mass or more, and most preferably, it is 100% by mass, that is, the block polymer is composed only of the segment (A) and the segment (B). Within the above range, the effects of the present invention can be more effectively exhibited.
  • the ratio of segment (A) to segment (B) is preferably 25:75 to 75:25, more preferably 55:45 to 75:25, and particularly preferably 55:45 to 65:35. By keeping it within these preferred ranges, the storage stability is more excellent.
  • the ratio of the segment (A) and the segment (B) can be adjusted during synthesis of the block polymer.
  • the block polymer of the present invention can be synthesized, for example, by polymerizing the segment (A) and then adding the segment (B), and the amount of the monomer added at this time may be adjusted so that the segments are polymerized and synthesized in the above-mentioned ratio.
  • H-NMR, GPC, acid value titration, etc. can be used.
  • Block polymer of the second invention [Segment (A')]
  • the block polymer of the second invention of this application has one or more segments (A') described below.
  • the segment (A') is adsorbed to the coloring material mainly due to its hydrophobicity, and plays a role in imparting dispersibility.
  • Segment (A') contains the hydrophobic functional groups and hydrophilic functional groups described above, and the molar ratio of the two (total amount of hydrophobic functional groups in the segment/total amount of hydrophilic functional groups in the segment) is 0.85 or more and 8.50 or less.
  • the molar ratio between the two is more preferably from 1.50 to 8.50, and even more preferably from 1.50 to 5.00, in which case better redispersibility and storage stability can be exhibited.
  • the above-mentioned monomer having a hydrophobic functional group and the monomer having a hydrophilic functional group may be polymerized so that the amounts of the functional groups are in the above ratio when synthesizing the block polymer.
  • H-NMR, GPC, acid value titration, etc. may be used.
  • the peak top molecular weight of segment (A') is 750 or more. If the peak top molecular weight is less than 750, the adsorption force to the material may be insufficient, and redispersibility may be deteriorated.
  • the peak top molecular weight of segment (A') is preferably 1000 or more, more preferably 2000 or more.
  • the method for measuring the peak top molecular weight is as shown in the Examples, but is not limited to this method as long as similar results are obtained.
  • the mass ratio of segment (A') is preferably 25% by mass or more and 75% by mass or less. If the proportion of segment (A') is less than 25% by mass, the pigment adsorption performance is insufficient and redispersibility and storage stability tend to be low. On the other hand, if the proportion of segment (A') is more than 75% by mass, it may not dissolve in the solvent.
  • the proportion of segment (A') is more preferably 55% by mass or more and 75% by mass or less, and most preferably 55% by mass or more and 65% by mass or less.
  • the segment (A') typically has a constituent unit derived from a monomer having a hydrophobic functional group and a constituent unit derived from a monomer having a hydrophilic functional group, but is not limited thereto. Segment (A') may contain any other structural unit besides the structural unit derived from a monomer having a hydrophobic functional group and the structural unit derived from a monomer having a hydrophilic functional group.
  • segment (A') When segment (A') is 100% by mass, the total mass of the structural unit derived from a monomer having a hydrophobic functional group and the structural unit derived from a monomer having a hydrophilic functional group in segment (A') is preferably 10% by mass or more, more preferably 25% by mass or more, and even more preferably 50% by mass or more, and most preferably 100% by mass, i.e., composed only of structural units derived from a monomer having a hydrophobic functional group and structural units derived from a monomer having a hydrophilic functional group. By setting it within the above preferred range, the effect of the present invention can be more effectively exhibited.
  • the order of the constituent units derived from each monomer in the segment (A') is not particularly limited, but is preferably random. That is, in the present invention, the segment (A') may be in the form of a random copolymer, a block copolymer, an alternating copolymer, or the like, and among these, a random
  • segment (A') When segment (A') is taken as 100% by mass, the ratio of the total mass of the hydrophobic functional groups and the hydrophilic functional groups in segment (A') is preferably 5% by mass or more, more preferably 20% by mass or more, and most preferably 35% by mass or more. By keeping it within the above preferred range, the effects of the present invention can be more effectively exhibited.
  • the block polymer of the second invention of this application has one or more segments (B') described below.
  • the segment (B') plays a role of dissolving the block polymer in a solvent mainly due to its hydrophilicity.
  • Segment (B') contains the hydrophobic functional group described above and the hydrophilic functional group described above, and the molar ratio of the two (total amount of hydrophobic functional groups in the segment/total amount of hydrophilic functional groups in the segment) is 0.16 or more and less than 0.85.
  • the redispersibility can be improved and the viscosity of the coloring material dispersion or ink can be reduced to a suitable range.
  • the reason why the redispersibility is improved is believed to be that the inclusion of the hydrophilic functional group within the above ratio allows the polymer to be uniformly dissolved in the aqueous solvent, and many polymers can be efficiently adsorbed to the coloring material.
  • the reason why the viscosity can be reduced is believed to be that the inclusion of the hydrophilic functional group within the above ratio allows the polymer to be sufficiently dissolved in the solvent, and the inclusion of the hydrophobic functional group within the above ratio causes the segments (B) of different polymers to slightly repel each other due to hydrophilic-hydrophobic interactions, making it difficult for adsorption, aggregation, and entanglement to occur, and the polymer becomes easily loosened.
  • the molar ratio between the two is more preferably from 0.25 to 0.60, and even more preferably from 0.25 to 0.45, in which case better redispersibility and storage stability can be achieved.
  • the above-mentioned monomer having a hydrophobic functional group and the monomer having a hydrophilic functional group may be polymerized so that the functional groups are in the above ratio when synthesizing the block polymer.
  • H-NMR, GPC, acid value titration, etc. may be used.
  • the peak top molecular weight of segment (B') is 750 or more. If the peak top molecular weight is less than 750, the solubility is insufficient, the viscosity increases, and redispersibility may deteriorate.
  • the peak top molecular weight of segment (B') is preferably 1000 or more, more preferably 2000 or more.
  • the method for measuring the peak top molecular weight is as shown in the Examples, but is not limited to this method as long as similar results are obtained.
  • Segment (B') typically has a constituent unit derived from a monomer having a hydrophobic functional group and a constituent unit derived from a monomer having a hydrophilic functional group, but is not limited thereto. Segment (B') may contain any other structural unit besides the structural unit derived from a monomer having a hydrophobic functional group and the structural unit derived from a monomer having a hydrophilic functional group.
  • segment (B') When segment (B') is 100% by mass, the total mass of the structural unit derived from a monomer having a hydrophobic functional group and the structural unit derived from a monomer having a hydrophilic functional group in segment (B') is preferably 10% by mass or more, more preferably 25% by mass or more, and even more preferably 50% by mass or more, and it is most preferable that 100% by mass, that is, segment (B') is composed only of structural units derived from a monomer having a hydrophobic functional group and structural units derived from a monomer having a hydrophilic functional group. By setting it within the above preferred range, the effect of the present invention can be more effectively exhibited.
  • each monomer in segment (B') is not particularly limited, but is preferably random. That is, in the present invention, various forms such as random copolymers, block copolymers, and alternating copolymers can be used as the form of segment (B'), and among them, random copolymers are particularly preferred.
  • segment (B') When segment (B') is taken as 100% by mass, the ratio of the total mass of the hydrophobic functional groups and the hydrophilic functional groups in segment (B') is preferably 5% by mass or more, more preferably 20% by mass or more, and most preferably 40% by mass or more. By keeping it within the above preferred range, the effects of the present invention can be more effectively exhibited.
  • the block polymer of the second invention of the present application may have two or more of the above-described segment (A') and segment (B') in each block polymer. In order to more effectively exert the effects of the present invention, however, it is preferable that the block polymer contains one of each.
  • the block polymer of the second invention of the present application may contain portions other than the segment (A') and the segment (B') as long as the effects of the present invention are not impaired.
  • the total mass of the segment (A') and the segment (B') is preferably 50% by mass or more. More preferably, it is 90% by mass or more, and most preferably, it is 100% by mass, that is, the block polymer is composed only of the segment (A') and the segment (B'). Within the above range, the effects of the present invention can be more effectively exhibited.
  • the ratio of segment (A') to segment (B') is preferably 25:75 to 75:25, more preferably 55:45 to 75:25, and particularly preferably 55:45 to 65:35. By keeping it within these preferred ranges, the storage stability is particularly excellent.
  • the ratio of segment (A') to segment (B') can be adjusted by the ratio of monomers used in the synthesis of the block polymer. In addition, when analyzing and confirming the obtained block polymer, H-NMR, GPC, acid value titration, etc. can be used.
  • the block structures of the block polymer of the first invention and the block polymer of the second invention are not particularly limited.
  • selectable block structures include AB block polymers, ABC triblock polymers, ABA triblock polymers, and triblock structures to which other polymer units are bonded.
  • AB block polymers and ABA triblock polymers are preferred, with AB block polymers being particularly preferred.
  • the acid value of the block polymer of the present invention is preferably 120 mgKOH/g or more and 190 mgKOH/g or less. If it exceeds 190 mgKOH/g, the affinity to the aqueous medium becomes too high, which may reduce the adsorption performance to the pigment and make dispersion difficult. Conversely, if the acid value is reduced to less than 120 mgKOH/g, the water solubility decreases, which may result in poor redispersibility.
  • the acid value is the amount of KOH (mg) required to neutralize 1 g of resin. Specifically, it can be measured by titrating a solution of resin dissolved in methoxypropanol with 1N NaOH solution.
  • the aqueous ink or coloring material dispersion using the block polymer of the present invention exhibits extremely excellent dispersibility and storage stability.
  • the inventors have found that existing block polymers used for pigment dispersion are not easily disintegrated because the hydrophobic parts and the hydrophilic parts aggregate in a solvent to form micelles, and many polymers remain in a micellar state without adsorbing to the pigment, and dispersion performance may not be fully exhibited.
  • the block polymer of the present invention described above has excellent storage stability and redispersibility, if it is used as a dispersant, there is no need to use a separate pigment derivative, and therefore the coloring material dispersion and ink using the block polymer of the present invention also have excellent color properties.
  • the block polymer of the first invention of the present application can be produced by polymerizing the above-mentioned monomer having a hydrophilic functional group and monomer having a hydrophobic functional group in the above-mentioned ratio.
  • the block polymer of the second invention of the present application can be produced by polymerizing the above-mentioned monomer having a hydrophilic functional group and monomer having a hydrophobic functional group in the above-mentioned ratio of the hydrophilic functional group and the hydrophobic functional group.
  • the method for producing (synthesizing) the block polymer is not particularly limited, and examples of the methods generally known for producing block polymers include atom transfer radical polymerization using a metal complex such as copper or ruthenium as a catalyst and an organic halide as an initiator, which is carried out by oxidation-reduction, the nitroxide method in which the -N-O radical of nitroxide is transferred, reversible addition-fragmentation chain transfer polymerization using a dithiocarboxylate ester, and iodine transfer polymerization.
  • a metal complex such as copper or ruthenium as a catalyst and an organic halide as an initiator
  • the block polymer of the present invention can be produced by first forming segment (A) and then adding a monomer to add segment (B); however, the production method is not limited to these methods as long as similar results can be obtained.
  • initiator As the initiator (initiator compound) used in the production of the block polymer of the present invention, general azo initiators such as azobis(isobutyronitrile) (AIBN), azobis(2,4-dimethylvaleronitrile) (V65), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) (V70), and oxide initiators such as benzoyl peroxide, dicumyl peroxide, t-butyl peroxybenzoate (BPB), di(4-tert-butylcyclohexyl) peroxydicarbonate (PERKADOX16), potassium peroxydisulfate, etc. can be used without limitation.
  • AIBN is preferred.
  • the block polymer of the present invention When the block polymer of the present invention is used as a dispersant, it can be neutralized with an alkaline compound.
  • alkaline compounds that can be used as a neutralizing agent include KOH, NaOH, triethylamine, triethanolamine, ammonia, etc., and particularly preferred are tertiary amines with a boiling point of 100°C or less. By using a tertiary amine with a boiling point of 100°C or less, water resistance and wet friction resistance are further improved.
  • the colorant dispersion containing the block polymer of the present invention and the ink using the same have excellent water resistance and wet friction resistance. This is thought to be because, after printing with the ink, the amine compounds volatilize, causing the polymer that was solubilized by neutralization to become insoluble in water, improving the wet friction resistance of the printed matter.
  • the amount of alkaline compound to be added should be an amount that can neutralize 20% to 200% of the resin's acid value. It is preferably 40 to 180%, and more preferably 50 to 120%. If the neutralization rate is lower than that, the resin will precipitate over time, and if it is higher, the pH will rise, which may damage the printer head components. In addition, water resistance and wet friction resistance may deteriorate.
  • a water-insoluble coloring material is used.
  • the coloring material is a pigment or a water-insoluble dye.
  • water-insoluble includes so-called poorly water-soluble coloring materials that are difficult to completely dissolve in water.
  • pigments for yellow ink include C.I. Pigment Yellow 1, 2, 3, 12, 14, 16, 17, 73, 74, 75, 83, 93, 95, 97, 98, 109, 110, 114, 128, 129, 138, 139, 147, 150, 151, 154, 155, 180, and 185, and one or more of these can be used.
  • pigments for magenta ink examples include C.I. Pigment Red 5, 7, 12, 48 (Ca), 48 (Mn), 57 (Ca), 57:1, 112, 122, 123, 150, 168, 184, 202, 209; C.I. Pigment Violet 19, and the like, and one or more of these can be used.
  • pigments for cyan ink examples include C.I. Pigment Blue 1, 2, 3, 15:3, 15:4, 16, 22, and 60; C.I. Bat Blue 4 and 60; and any combination of these may be used alone or in combination.
  • pigments for black ink examples include carbon blacks (C.I. Pigment Black 7) such as furnace black, lamp black, acetylene black, and channel black, and organic pigments such as aniline black (C.I. Pigment Black 1).
  • Inorganic pigments such as titanium oxide and iron oxide can also be used.
  • the above various pigments may be pigments that have been mixed with a dispersant.
  • the dispersion of the present invention may also contain a disperse dye as a water-insoluble coloring material.
  • a disperse dye is a compound that is poorly soluble or insoluble in water. Specific examples of disperse dyes include the following: The yellow disperse dye is not particularly limited, but examples thereof include C.I.
  • orange disperse dyes include, but are not limited to, C.I. Disperse Orange 1, 3, 5, 7, 11, 13, 17, 20, 21, 25, 29, 30, 31, 32, 33, 37, 38, 42, 43, 44, 45, 46, 47, 48, 49, 50, 53, 54, 55, 56, 57, 58, 59, 61, 66, 71, 73, 76, 78, 80, 89, 90, 91, 93, 96, 97, 119, 127, 130, 139, and 142.
  • the red disperse dye is not particularly limited, but examples thereof include C.I.
  • Violet disperse dyes are not particularly limited, but examples thereof include C.I. Disperse Violet 1, 4, 8, 23, 26, 27, 28, 31, 33, 35, 36, 38, 40, 43, 46, 48, 50, 51, 52, 56, 57, 59, 61, 63, 69, and 77.
  • the green disperse dye is not particularly limited, but for example, C.I. Disperse Green 9 can be mentioned.
  • the blue disperse dye is not particularly limited, but examples thereof include C.I.
  • the aqueous medium used in the coloring material dispersion of the present invention is usually water, but a water-soluble organic solvent may be used if necessary.
  • the water-soluble organic solvent include 1,2-hexanediol, 1,6-hexanediol, 1,5-pentanediol, 2-pyrrolidone, N-methylpyrrolidone, triethylene glycol monobutyl ether, ethylene glycol, propylene glycol, triethylene glycol, and glycerin.
  • 1,2-hexanediol, 2-pyrrolidone, and triethylene glycol monobutyl ether are particularly preferred.
  • acetylene glycol-based and silicone-based may be added.
  • Commercially available products can be used, for example, acetylene glycol-based products such as Olfine Y, Surfynol 82, 440, 465, STG, and E1010, and polysiloxane-based compounds such as BYK302 and BYK348 (manufactured by BYK Japan) can be used.
  • Composition of colorant dispersion In the coloring material dispersion of the present invention, the blending ratio of each of the above components can be appropriately selected depending on the application. In addition to the above components, the coloring material dispersion of the present invention may contain other components depending on the application.
  • the above-mentioned components may be dispersed by a known method.
  • the coloring material dispersion may be prepared by dispersing the above-mentioned components in a bead mill or other wet dispersing machine.
  • the dispersion of the present invention may be subjected to an appropriate crosslinking treatment after dispersion.
  • the crosslinking agent an epoxy resin having a glycidyl ether skeleton, a resin having an oxazoline group, or the like can be used.
  • the amount of crosslinking agent is preferably in the range of 0.5% to 60% of the resin. If it is less than this, the stabilizing effect of crosslinking cannot be exerted, and if it is more, redispersibility may deteriorate.
  • the crosslinking method is to add the crosslinking agent to the coloring material dispersion liquid that has been through the above dispersion process, and heat it to around 80°C to perform crosslinking.
  • the coloring material dispersion of the present invention can be subjected to an impurity removal process by ion exchange treatment or ultrafiltration treatment.
  • Ionic substances such as cations and anions (divalent metal ions, etc.) can be removed by ion exchange treatment, and dissolved impurities (residual substances from pigment synthesis, excess components in the dispersion composition, resins not adsorbed to organic pigments, contaminants, etc.) can be removed by ultrafiltration treatment.
  • the coloring material dispersion of the present invention can have a particle size distribution D50 of 135 nm or less, which is a preferred range.
  • the particle size distribution D50 of the coloring material dispersion is particularly preferably 110 nm or less, and most preferably 100 nm or less.
  • the time and intensity of dispersion may be appropriately adjusted when preparing the coloring material dispersion liquid, or coarse particles may be removed using a filter or the like.
  • the block polymer of the present invention has excellent storage stability and can maintain the above-mentioned preferred particle size for one week or more.
  • the method for measuring the particle size distribution D50 is as described in the Examples, but is not limited to this as long as similar results are obtained.
  • the block polymer of the present invention is less likely to cause aggregation or entanglement between polymers, and therefore an increase in viscosity is suppressed, so that the coloring material dispersion of the present invention can have a viscosity in the preferred range of 25 mPas or less.
  • the viscosity is particularly preferably 10 mPas or less, and most preferably 5 mPas or less.
  • the neutralization rate of the block polymer may be appropriately adjusted in accordance with the solvent when the coloring material dispersion liquid is prepared. Furthermore, the block polymer of the present invention has excellent storage stability and can maintain the above-mentioned preferred viscosity for one week or more. The method for measuring viscosity is as described in the Examples, but is not limited to this method as long as similar results are obtained.
  • the term "dispersion” means that a water-insoluble coloring material is dispersed in an aqueous medium, and includes so-called “ink” as well as a state in which a coloring material is dispersed in an aqueous medium in advance when producing the ink.
  • the coloring material dispersion of the present invention is used as an ink, it is preferable to prepare a dispersion in advance in which each of the components described above is dispersed, and then add other components according to the intended use.
  • the coloring material dispersion of the present invention is used to prepare an inkjet ink
  • other components such as an organic solvent, a resin, and a preservative may be added.
  • the organic solvent is not particularly limited, and examples thereof include polyhydric alcohols and pyrrolidones.
  • polyhydric alcohols include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, trimethylolpropane, and glycerin.
  • Polyhydric alcohols have the effect of increasing the wettability of the ink to paper and preventing drying inside the head nozzles, thereby increasing the moisture retention.
  • the content of the polyhydric alcohols can be 2% by mass or more and 30% by mass or less with respect to the total mass of the ink.
  • Resins have the function of increasing fixation, and examples of such resins include acrylic resins, fluorene resins, urethane resins, olefin resins, rosin-modified resins, terpene resins, ester resins, amide resins, epoxy resins, vinyl chloride resins, vinyl chloride-vinyl acetate copolymers, and ethylene vinyl acetate resins. These resins can be used alone or in combination of two or more. The resins used may be of the emulsion type or solution type. When resins are contained, their content can be 0.1% by mass or more and 6% by mass or less.
  • preservatives and antifungal agents examples include sodium benzoate, sodium pentachlorophenol, sodium 2-pyridinethiol-1-oxide, sodium sorbate, sodium dehydroacetate, 1,2-dibenzisothiazolin-3-one (Zeneca's Proxel CRL, Proxel BDN, Proxel GXL, Proxel XL.2, Proxel TN, Proxel LV), and 4-chloro-3-methylphenol (Bayer's Preventol CMK, etc.).
  • the neutralization rate of the block polymer may be appropriately adjusted in accordance with the solvent when preparing the coloring material dispersion.
  • the block polymer of the present invention has excellent storage stability and can maintain the above-mentioned preferred viscosity for one week or more.
  • the method for measuring the ink viscosity is as described in the Examples, but is not limited to this as long as similar results are obtained.
  • the application of the ink is not particularly limited, and examples thereof include printing inks that can be used in inkjet printing and inks for writing instruments, but the inks are particularly suitable for use as inkjet printing inks.
  • the pressure in the reaction vessel was reduced, and the solvent was distilled off to obtain block polymer 1.
  • the molecular weight was 6220 and the molecular weight distribution (Mw / Mn) was 1.21.
  • the acid value was 182 mg KOH / g.
  • Block polymers 2 to 12 were obtained by changing the monomer ratio as shown in Table 1 using the same procedure as for block polymer 1.
  • the physical properties (acid value, peak top molecular weight, Mw/Mn) of these block polymers 2 to 12 are shown in Table 1.
  • the resulting block polymers 2 to 12 were used to obtain resin solutions in the same manner as in the resin solution 1. Only 50% neutralized products were prepared for block polymers 2 to 5, 11, and 12, and only 120% neutralized products were prepared for block polymers 6, 9, and 10.
  • the system was heated to 70°C in an oil bath with nitrogen bubbling and stirring, and reacted for 6 hours after the temperature increase was completed, synthesizing polymer A'.
  • 119 parts of ALEN10 as a monomer having a hydrophobic functional group, 87.5 parts of methacrylic acid and 73.5 parts of acrylic acid as a monomer having a hydrophilic functional group, and 420 parts of methoxypropanol as a reaction solvent were added to the flask, and the mixture was reacted at 70°C for 8 hours while continuing to bubbling with nitrogen and stirring.
  • the GPC measurement was carried out under the following conditions.
  • Equipment HLC-8220GPC (Tosoh Corporation)
  • Detector RI (differential thermal refractive index detector)
  • Solvent degassed THF
  • Column Gelpack GL-R400M, GL-R440, GL-R450, guard column connected
  • Measurement concentration 10mg/ml
  • Flow rate 2.0ml/min.
  • Injection volume 150 ⁇ L/min
  • Column temperature 40°C
  • Example 1 40g of resin solution 1, 15g of P.R150, 5g of 1,2-hexanediol, and 40g of water were mixed and dispersed using 0.5mm zirconia beads and a paint shaker for 5 hours, and then further dispersed using 0.1mm zirconia beads for 20 hours.
  • the dispersion liquid recovered by separating the zirconia beads was centrifuged at 16,300 rpm for 10 minutes to remove coarse particles, thereby obtaining a pigment dispersion liquid.
  • the obtained pigment dispersion liquid, ion-exchanged water, and the clear ink mixed and prepared according to the composition shown in Table 3 were mixed according to the following composition to obtain an ink for evaluation.
  • Examples 2 to 5 Comparative Examples 1 to 6
  • Pigment dispersions and inks for evaluation were prepared in the same manner as in Example 1, except that the block polymer was changed as shown in Table 4, and then the following evaluations were carried out. The results are shown in Table 4.
  • a cone rotor type rotational viscometer (“TV25 Model” manufactured by Toki Sangyo Co., Ltd.) was used as the viscosity measuring device, and "Nanotrac wave II EX-150" (manufactured by Nikkiso Co., Ltd.) was used as the particle size distribution D50 measuring device.
  • Viatrac wave II EX-150 manufactured by Nikkiso Co., Ltd.
  • the particle size distribution D50 of the pigment dispersion 110 nm or less was rated as ⁇ , 135 nm or less was rated as ⁇ , and larger than 135 nm was rated as x.
  • the viscosity of the pigment dispersion was evaluated as follows: 10 mPas or less: ⁇ , 25 mPas or less: ⁇ , and higher than 25 mPas: ⁇ .
  • the ink viscosity was rated as ⁇ for 6 mPas or less, ⁇ for 7 mPas or less, and ⁇ for more than 7 mPas.
  • Examples 1 to 5 which use the block polymer of the present invention, in which both segment (A) (or segment (A')) and segment (B) (or segment (B')) contain a structural unit composed of a monomer having a hydrophobic functional group and a structural unit composed of a monomer having a hydrophilic functional group in a ratio within a specified range, have high redispersibility.
  • the viscosity and particle size distribution D50 remain within a suitable range for inkjet inks, demonstrating high storage stability.
  • Example 6 48 g of resin solution 2(1), 18 g of PB-15:3, 5 g of 1,2-hexanediol, and 29 g of water were mixed and dispersed using 0.5 mm zirconia beads and a paint shaker for 5 hours, and then further dispersed using 0.1 mm zirconia beads for 8 hours.
  • the dispersion liquid recovered by separating the zirconia beads was centrifuged at a rotation speed of 16,300 rpm for 10 minutes to remove coarse particles, thereby obtaining a pigment dispersion liquid.
  • Pigment dispersions were obtained in the same manner, except that Resin Dissolved Material 2(2) and Resin Dissolved Material 2(3) were used instead of Resin Dissolved Material 2(1).
  • the pigment dispersions obtained in Examples 6 to 8 were mixed in the following proportions to obtain inks for evaluation.
  • the surface conditioner used was "BYK-302" (product name, polyether-modified polydimethylsiloxane manufactured by Byk Chemie).
  • the D50 and viscosity of the pigment dispersion and the viscosity of the evaluation ink were measured by the methods described above. The results are shown in Table 5.
  • 1-a, 2-a, and 3-a show the state of the film coating after the wet friction test
  • 1-b, 2-b, and 3-b show the state of the white cotton cloth used in the wet friction test after the test.
  • the present invention makes it possible to obtain a block polymer that exhibits extremely excellent performance as a dispersant, a coloring material dispersion that uses said block polymer and has excellent performance, and an inkjet ink that uses them and has excellent performance.

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JP2011225834A (ja) 2010-04-01 2011-11-10 Dainichiseika Color & Chem Mfg Co Ltd インクジェット用水性顔料分散液及びインクジェット用水性顔料インク
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