WO2006043571A1 - カプセル化物及びその製造方法、並びにインク組成物 - Google Patents
カプセル化物及びその製造方法、並びにインク組成物 Download PDFInfo
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- WO2006043571A1 WO2006043571A1 PCT/JP2005/019148 JP2005019148W WO2006043571A1 WO 2006043571 A1 WO2006043571 A1 WO 2006043571A1 JP 2005019148 W JP2005019148 W JP 2005019148W WO 2006043571 A1 WO2006043571 A1 WO 2006043571A1
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- ionic
- group
- surfactant
- polymerizable
- capsule
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
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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
- 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
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
-
- 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
- C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
- Y10T428/2991—Coated
- Y10T428/2998—Coated including synthetic resin or polymer
Definitions
- the present invention relates to an encapsulated product, a method for producing the same, and an ink composition.
- capsules of various substances have been performed in many industrial and technical fields.
- many capsules such as pigments and pigments have been put into practical use.
- many drug capsules have been tried for the purpose of enhancing efficacy, reducing toxicity, imparting stability, delaying effects, and the like.
- a phase separation method coacervation method
- a submerged drying method interface precipitation method
- a spray drying method a pan coating method
- a submerged curing coating method an interfacial polymerization method
- interfacial inorganic method Reaction methods, in-situ polymerization methods, etc.
- the core material is limited, it is difficult to design the shell layer (core material coating layer) thickness! / ⁇ , it is difficult to encapsulate one core material It is difficult to freely design the functional group on the capsule surface, it is easy to produce particles with a uniform surface state, and it is difficult to encapsulate in the nano-order, to a relatively unstable compound It is difficult to apply, the solvent used at the time of manufacturing the drug is easily mixed into the product, or the properties of the obtained capsule are unsatisfactory. It was.
- the dispersant simply adsorbs on the surface of the pigment particles.
- the dispersant adsorbed on the pigment particle surface may be detached.
- the ejection stability characteristic that the ink is stably ejected in a certain direction
- pigment inks using pigments dispersed with dispersants tend to desorb these dispersants, making dispersion unstable even when stored for long periods of time. Cheap.
- Patent Document 1 Japanese Patent Publication No. 7-94634
- Patent Document 2 JP-A-8-59715
- Patent Document 3 Japanese Patent Laid-Open No. 2003-306661
- Patent Document 4 JP-A-5-339516 Patent Document 5: JP-A-8 302227 Patent Document 6: JP-A-8 302228 Patent Document 7: JP-A-8 81647 Patent Document 8: JP-A-5 320276 Patent Document 9: JP-A-8 218015 Patent Document 10 JP-A-8-295837 Patent Document 11 JP-A-9 3376 Patent Document 12 JP-A-8-183920 Patent Document 13 JP-A-10-46075 Patent Document 14 JP-A-10-292143 Patent Document 15 Japanese Patent Laid-Open No. 11--80633 Patent Document 16 Japanese Patent Laid-Open No. 11--349870 Patent Document 17 Japanese Patent Laid-Open No. 2000-7961 Patent Document 18 Japanese Patent Laid-Open No.
- Patent Document 19 Japanese Patent Laid-Open No. 9 217019 Patent Document 20 Japanese Patent Laid-Open No. 9 316353 Patent Document 21 Japanese Patent Laid-Open No. 9 104834 Patent Document 22 Japanese Patent Laid-Open No. 9 151342 Patent Document 23 Japanese Patent Laid-Open No. 10--140065 Patent Document 24 Japanese Patent Laid-Open No. 11-152424 Patent Document 25 JP-A-11-— 166145 JP Patent Document 26 JP-A-11-199783 Patent Document 27 Japanese Patent Laid-Open No. 11-209209 Patent Document 28 Japanese Patent Laid-Open No. 9 286939 Patent Document 29 Japanese Patent Laid-Open No. 2000-44852 Patent Document 30 Japanese Patent Laid-Open No. 2000-53897 Patent Document 31 Japanese Patent Laid-Open No. 2000-53898 Patent Document 32 Japanese Patent Laid-Open No. 2000-53899 Patent Document 33: Japanese Unexamined Patent Publication No. 2000-53900
- the present invention has been made in view of the above-mentioned problems, and the object of the present invention is to provide an encapsulated product capable of highly exhibiting various functions in various industrial and technical fields, and It is in providing the manufacturing method.
- the present invention provides (1) the core material is not limited, (2) the thickness of the shell layer (core material covering layer) can be freely designed, and (3) one core material. Capsule can be obtained, (4) Capability can be separated by core material and shell material, (5) Particles with uniform surface state can be produced, (6) Capsule in nano order (7) Can produce particles with uniform particle size, (8) Environmentally friendly, (9) Toxic or detoxified by capsules of certain core materials such as toxicity It is an object of the present invention to provide a capsule product satisfying all of the above (1) to (9).
- the present invention also provides:
- An object of the present invention is to provide a capsule product satisfying all of the above (i) to (V).
- the present invention provides a capsule product capable of highly exhibiting various other functions other than the force required to satisfy all of the above (1) to (9) and (i) to (v). It is an object of the present invention to provide a method for producing a capsule product.
- the polymer is a repeating structural unit derived from an ionic monomer having the same type of charge as that of the ionic polymerizable surfactant C, together with a repeating structural unit derived from the ionic polymerizable surfactant C.
- the encapsulated product according to (1) which has a structural unit.
- polymer further has a repeating structure derived from a nonionic polymerizable surfactant D having a nonionic group, a hydrophobic group, and a polymerizable group Capsule container according to.
- the nonionic surfactant e is an ionic polymerizable surfactant E further having a polymerizable group, and in some cases, the nonionic surfactant e is a repeating structural unit constituting the polymer.
- the “ionic group” of the ionic surfactant a and / or the ionic polymerizable surfactant A is the ionic surfactant b and / or the ionic polymerizable surfactant B.
- the ionic surfactant b and / or the ionic surfactant B and / or the hydrophobic group of the ionic polymerizable surfactant B is the ionic surfactant c and / or Toward the “hydrophobic group” of the ionic polymerizable surfactant, the ionic surfactant c and / or the “ionic group” of the ionic polymerizable surfactant are encapsulated.
- the capsule according to any one of (1) to (8), wherein the capsule is present in the outermost layer.
- Ionic surfactant having an ionic group and a hydrophobic group on the surface of the core substance a and Z or an ionic polymerizable interface having an ionic group, a hydrophobic group and a polymerizable group Step of adsorbing the active agent A, (mouth) the ionic surfactant a and Z or the ionic polymerizable surfactant B and / or the ionic monomer having an opposite charge to the surfactant A (2) A step of adding and mixing the ionic surfactants A and Z or the ionic polymerizable surfactant A having the same or opposite charge as the ionic surfactant A.
- Ionic surfactant having an ionic group and a hydrophobic group on the surface of the core substance a and Z or an ionic polymerizable interface having an ionic group, a hydrophobic group and a polymerizable group Step of adsorbing the active agent A, (mouth) the ionic surfactant a and Z or the ionic polymerizable surfactant B and / or the ionic monomer having an opposite charge to the surfactant A (2) A step of adding and mixing the ionic surfactants A and Z or the ionic polymerizable surfactant A having the same or opposite charge as the ionic surfactant A.
- C The method for producing an encapsulated product according to (13), comprising at least a step of adding and mixing a hydrophobic monomer, and (e) a step of adding a polymerization initiator thereto to perform polymerization.
- R and R each independently represents an alkyl group having 1 to 10 carbon atoms, m and n are
- the number of repeating units, m + n is 0-10 on average.
- the capsule capsule of the present invention can use either an inorganic substance or an organic substance as the core substance.
- inorganic particles, organic particles, polymer particles and the like can be used, and the core substance is not limited. It is also possible to reduce the toxicity or make it harmless by encapsulating a toxic core material.
- the thickness of the shell layer (core material coating (polymer) layer) can be freely designed, and the functions of the core material and the shell material can be separated. Even with a strong force, particles having a uniform surface state can be produced.
- the capsule product of the present invention can encapsulate one core substance, and can be easily encapsulated in nano order.
- the capsule product of the present invention can produce particles (powder) having a uniform particle size.
- the capsule product of the present invention can be produced by an aqueous reaction without using a solvent, it does not adversely affect the environment.
- the capsule product produced using the production method of the present invention when used as a coloring material for ink, an ink having excellent dispersion stability in an aqueous dispersion can be obtained. .
- This ink can provide a recorded matter having excellent fastness and abrasion resistance.
- the capsule product manufactured using the manufacturing method of the present invention is used as an ink for ink jet recording, a recorded product having excellent ejection stability from the recording head and excellent image quality can be obtained. .
- the polymer of the coating layer of the core material can be freely designed according to the intended function, and can be easily obtained by selecting the functional group of the outermost shell. Capsule with properties can be obtained.
- the capsule material according to the present invention is a capsule material in which at least a core material adsorbed with an ionic surfactant is coated with a coating layer containing a polymer as a main component, and the ionic surface active material adsorbed on the core material.
- a coating layer containing a polymer as a main component containing a polymer as a main component, and the ionic surface active material adsorbed on the core material.
- Such capsules are prepared in an aqueous dispersion of at least a core material on which an ionic surfactant is adsorbed, an ionic polymerizable surfactant having an opposite charge to these ionic surfactants, and Z Alternatively, after adding and mixing an ionic monomer, the ionic polymerizable surfactant having the same or opposite charge as that of the ionic surfactant adsorbed on the core material is mixed, emulsified, and then added with a polymerization initiator. By polymerizing in water, a polymer coating layer is formed and can be suitably produced.
- the inventor of the present invention provides an ionic surfactant having an ionic group and a hydrophobic group on the surface of a core substance.
- An ionic polymerizable surfactant C having the same or opposite charge as that of the activator a, and a step of adding and mixing a polymerization initiator and then polymerizing by adding a polymerization initiator to the ionic surfactant.
- the present inventor has a step of adsorbing an ionic surfactant a having an ionic group and a hydrophobic group on the surface of the core substance, and has an opposite charge to the ionic surfactant a.
- Polymerization surfactant C The manufacturing method including the process of adding and mixing, and the process of adding a polymerization initiator to this and polymerizing, or the ion which has an ionic group and a hydrophobic group on the surface of a core substance
- ionic surfactants B and Z or ionic monomers that are in contact with the core substance via the ionic surfactant a and have an opposite charge to the ionic surfactant a.
- the present inventor has a step of adsorbing an ionic surfactant a having an ionic group and a hydrophobic group on the surface of the core substance, and has an opposite charge to the ionic surfactant a.
- a production method including a step of adding a polymerization initiator to this and superposing a hydrophobic monomer, or an ionic surfactant having an ionic group and a hydrophobic group on the surface of the core substance a
- Adsorbing ionic surfactant b having an opposite charge to ionic surfactant a
- adsorbing ionic surfactant b having the same or opposite charge as ionic surfactant a Add surfactant c and mix The step of contacting the core substance via the i
- the ionic surfactant b having the opposite charge to the ionic surfactant a and the ionic surfactant c having the same or opposite charge as the ionic surfactant a The knowledge that the core material is coated with the polymer was obtained. Further, the present inventor has shown that the capsule discoloration material obtained by using coloring material particles such as pigment as the core substance exhibits excellent dispersion stability in an aqueous medium and excellent discharge stability from the recording head. In addition, the ink composition containing the capsule discoloration material is excellent in glossiness and image clarity on a recording medium such as plain paper or an inkjet-dedicated media, and excellent in abrasion resistance and fastness. It was found that an image can be formed. The present inventor has completed the present invention based on these findings.
- the ionic polymerizable surfactant having a charge opposite to the ionic group of the ionic surfactant adsorbed to the core substance and Z or the ionic monomer are ionically bonded, Of ionically-bonded ionic polymerizable surfactants and hydrophobic groups of Z or ionic monomers and ionic polymerizable surfactants having the same or opposite charge as ionic surfactants adsorbed on the core material A structure in which the hydrophobic groups face each other and the ionic groups of the ionic polymerizable surfactant are oriented toward the aqueous phase is formed, and the polymer layer is formed on the core material by the polymerization reaction in this formed state. Is formed.
- the arrangement form of the polymerizable polymerizable surfactant, the ionic monomer, etc. is extremely highly controlled, and the outer shell forms a state in which the ionic groups are oriented toward the aqueous phase. Then, by the polymerization reaction, the ionic polymerizable surfactant, the ionic monomer, and the like are transferred to the polymer in this highly controlled form, and a polymer layer is formed on the core substance. As a result, the structure of the capsule container of the present invention is controlled with extremely high accuracy.
- FIG. 1 is a diagram showing an outline of an encapsulated color material and a method for producing the same according to the present invention.
- Fig. 2 shows a ionic surfactant 2 '(ionic surfactant a) having a negatively charged ionic group 21 and a hydrophobic group 22 adsorbed on the surface of the core material 1.
- FIG. 3 is a view showing a state where a cation polymerizable surfactant 4 (ionic polymerizable surfactant C) and a hydrophobic monomer 5 coexist.
- the cationic polymerizable surfactant 3 is arranged so that its cationic group 31 is adsorbed to the core substance 1 and directed to the arionic group 21 of the ergonal surfactant 2 ′. Adsorbs with strong bonds. Then, the hydrophobic group 32 and the polymerizable group 33 of the cationic polymerizable surfactant 3 are polymerized with the hydrophobic group 42 of the cationic polymerizable surfactant 4 by hydrophobic interaction.
- the functional groups 43 are facing each other, and the cationic groups 41 of the cationic polymerizable surfactant 4 are present in the direction in which the aqueous solvent exists, that is, in the direction farthest from the core substance 1.
- Hydrophobic monomer 5 is formed by the hydrophobic group 32 and polymerizable group 33 of cationic polymerizable surfactant 3 and the hydrophobic group 42 and polymerizable group 43 of cation polymerizable surfactant 4 facing each other. Present in the hydrophobic phase.
- FIG. 3 shows the presence of negatively charged ionic group 21 adsorbed on the surface of core material 1 and hydrophobic group 22 ionic surfactant 2 '(ionic surfactant a) and positive charge.
- a cationic surfactant 3 ′ (ionic surfactant b) having a cationic group 31 and a hydrophobic group 32 having a negative charge, and a cationic group 3 having a negative charge and a hydrophobic group 42
- FIG. 4 is a diagram showing a state where 4 ′ (ionic surfactant c) and hydrophobic monomer 5 coexist.
- the cationic surfactant 3 ′ is arranged so that its cationic group 31 faces the ionic group 21 of the cationic surfactant 2 ′ adsorbed on the core substance 1, and has a strong ionic bond. Adsorb at. Then, the hydrophobic group 32 of the cationic surfactant 3 ′ is opposed to the hydrophobic group 42 of the cationic surfactant 4 ′ by the hydrophobic interaction, and the cationic surfactant 3 ′.
- the 4 ′ er-on group 41 is present in the direction in which the aqueous solvent exists, that is, in the direction farthest from the core substance 1.
- Hydrophobic monomer 5 exists in the hydrophobic phase formed by facing the hydrophobic group 32 of the cationic surfactant 3 and the hydrophobic group 42 of the cationic surfactant 4 '! / RU
- Fig. 4 shows a cation polymerizable surfactant 2 having a negatively charged ionic group 21, a hydrophobic group 22 and a polymerizable group 23 adsorbed on the surface of the core material 1 (ionic polymerizable interface).
- Activating agent A) cationic polymerizable surfactant (ionic polymerizable surfactant B) having cationic group 31 with positive charge, hydrophobic group 32 and polymerizable group 33 (not shown! ⁇ may be a cationic monomer having at least a positively charged cationic group and a polymerizable group in place of B.), a negatively charged ionic group 41 and a hydrophobic group.
- FIG. 1 shows a cation polymerizable surfactant 2 having a negatively charged ionic group 21, a hydrophobic group 22 and a polymerizable group 23 adsorbed on the surface of the core material 1 (ionic polymerizable interface).
- Activating agent A) cationic polymerizable surfact
- a cationic polymerizable surfactant 4 (ionic polymerizable surfactant C) having a hydrophobic group 42 and a polymerizable group 43 and a hydrophobic monomer 5 coexist.
- the cationic polymerizable surfactant 3 is arranged so that its cationic group 31 faces the cationic group 21 of the cationic polymerizable surfactant 2 adsorbed on the core substance 1, and is strongly ionic. Adsorb by binding. Then, with respect to the polymerizable group 33 of the thione polymerizable surfactant 3, the hydrophobic group 42 and the polymerizable group 43 of the ionic polymerizable surfactant 4 face each other by hydrophobic interaction.
- the ionic group 41 of the cationic polymerizable surfactant 4 is present in the direction in which the aqueous solvent exists, that is, in the direction farthest from the core substance 1! /.
- the hydrophobic monomer 5 is formed by the hydrophobic group 32 and the polymerizable group 33 of the cationic polymerizable surfactant 3 and the hydrophobic group 42 and the polymerizable group 43 of the cation polymerizable surfactant 4 facing each other. Present in the hydrophobic phase.
- FIG. 5 shows a ionic polymerizable surfactant 2 (an ionic polymerizable interface) having a negatively charged ionic group 21, a hydrophobic group 22, and a polymerizable group 23 adsorbed on the surface of the core material 1.
- Activator A a cathodic group having a positively charged cationic group 31, a hydrophobic group 32 and a polymerizable group 33.
- Polymerizable polymerizable surfactant 3 (ionic polymerizable surfactant B) (not shown!), But in place of B, a cationic monomer having at least a positively charged cationic group and a polymerizable group
- anionic polymerizable surfactant 4 (an ionic polymerizable surfactant C) having a negatively charged anionic group 41, a hydrophobic group 42, and a polymerizable group 43.
- a nonionic polymerizable surfactant 8 (nonionic polymerizable surfactant D) having a nonionic group 81, a hydrophobic group 82, and a polymerizable group 83, and a hydrophobic monomer 5 It is a figure showing the state where it coexists.
- the cationic polymerizable surfactant 3 is arranged so that its cationic group 31 is adsorbed to the core substance 1 and directed toward the er-on group 21 of the er-on-polymerizable surfactant 2. Adsorbs with strong binding.
- the hydrophobic group 32 and the polymerizable group 33 of the cationic polymerizable surfactant 3 are hydrophobically interacted with the hydrophobic group 42 and the polymerizable group of the cationic polymerizable surfactant 4 by hydrophobic interaction.
- the hydrophobic group 82 and the polymerizable group 83 of the group 43 and the nonionic polymerizable surfactant 8 face each other, and the ionic group 41 of the ionic polymerizable surfactant 4 and the nonionic group 41 are nonionic.
- the nonionic group 81 of the polymerizable surfactant 8 is present in the direction in which the aqueous solvent exists, that is, in the direction farthest from the core substance 1.
- Hydrophobic monomer 5 is composed of hydrophobic group 32 and polymerizable group 33 of cationic polymerizable surfactant 3, hydrophobic group 42 and polymerizable group 43 of nonionic polymerizable surfactant 4 and nonionic
- the hydrophobic group 82 of the polymerizable surfactant 8 and the polymerizable group 83 are present in the hydrophobic phase formed by facing each other.
- Fig. 6 shows the ionic surfactant 2 ′ (ionic surfactant a) having a negatively charged ionic group 21 and a hydrophobic group 22, and Z or a negatively charged ionic group.
- Anionic polymerizable surfactant 2 having an ionic group 21, a hydrophobic group 22 and a polymerizable group 23 (ionic polymerizable surfactant A), a nonionic group 91 and a non-ionic group having a hydrophobic group 92
- Ionic surfactant 9 '(nonionic polymerizable surfactant e) and nonionic polymerizable surfactant 9 having Z or nonionic group 91, hydrophobic group 92, and polymerizable group 9 3 is adsorbed (contacted) to the surface of the core material, and has a cationic group 31 having a positive charge, a hydrophobic group 32, and a polymerizable group 33.
- FIG. 4 is a diagram showing a state in which a cationic polymerizable surfactant 4 (ionic polymerizable surfactant C) having a hydrophobic group 42 and a polymerizable group 43 coexists with a hydrophobic monomer 5. .
- Cationic polymerizable surfactant 3 is a cationic surfactant 31 in which the cationic group 31 is adsorbed to the core substance 1 and the cationic group 2 and the Z- or cationic polymerization of the cationic group 2 '. It is arranged to face the ionic group 21 of the surfactant 2 and adsorbs with a strong ionic bond.
- the hydrophobic group 32 and the polymerizable group 33 of the cationic polymerizable surfactant 3 are hydrophobically interacted with the hydrophobic group 42 and the polymerizable group 34 of the cationic polymerizable surfactant 4 by hydrophobic interaction.
- Hydrophobic monomer 5 is a mixture of hydrophobic group 32 and polymerizable group 33 of cationic polymerizable surfactant 3 with hydrophobic group 42 and polymerizable group 43 of cation polymerizable surfactant 4 facing each other. It exists in the sparsely formed phase.
- a polymerization initiator is added to the mixed solution of FIG. 2, and the cationic polymerizable surfactant 3 (not shown, but has at least a positively charged cationic group and a polymerizable group).
- the core material 1 is coated with the polymer layer 60 by polymerizing the), the ionic polymerizable surfactant 4 and the hydrophobic monomer, and the encapsulated product 100 is produced.
- the capsule material 100 is very well dispersed in the aqueous solvent.
- FIG. 8 shows a case where a polymerization initiator is added to the mixed solution of FIG.
- FIG. 9 shows a case where a polymerization initiator is added to the mixed solution of FIG.
- FIG. 10 shows the case where the polymerization initiator is added to the mixed solution of FIG. 5 for polymerization
- FIG. 11 shows the case where the polymerization initiator is added to the mixed solution of FIG. 6 for polymerization.
- the aspect ratio (long / short) of the encapsulated product of the present invention is 1.0 to 1.3, and the Zingg index is 1.0 to 1.3 (more preferably 1.0 to 1.2). It is preferable.
- the method for setting the aspect ratio and the Zingg index within the above ranges is not particularly limited, but the capsule material in which the core material having an ionic group on the surface is coated with the polymer by the above-described manufacturing method can easily satisfy this condition. Can meet.
- the aspect ratio and the Zingg index are not easily within the above ranges in the capsulated product prepared by a method other than the emulsion polymerization method such as the acid precipitation method or the phase inversion emulsification method.
- the capsule pigment of the present invention in which the core material is a pigment has an aspect ratio and a Zingg index within the above ranges, and becomes a spherical shape. It will be excellent. Further, since it is a true sphere, the encapsulated pigment is arranged on the recording medium at a high density when landing on a recording medium such as paper, and the printing density and color development can be expressed with high efficiency. In addition, since it is spherical, it has excellent dispersibility and dispersion stability.
- the core material of the capsule product of the present invention is not particularly limited. Specifically, the color material, inorganic material, organic material, inorganic-organic composite particle, inorganic colloid, polymer particle, metal oxide (silica, titer, etc.) ).
- the capsule product of the present invention has an effect of improving the handling of such a dangerous chemical or the like.
- the properties of the molded product can be improved.
- the inorganic colloid can be used for a highly transparent hard coat layer.
- pigments such as inorganic pigments and organic pigments that can develop a desired color
- dyes that are insoluble or hardly soluble in water such as disperse dyes and oil-soluble dyes can be mentioned.
- a color material when encapsulated by the method of the present invention, it can be used as a colorant for paints, pigment inks, toners and the like.
- inorganic pigments include carbon blacks (C. 1. pigment black 7) such as furnace black, lamp black, acetylene black, and channel black, or iron oxide pigments.
- Organic pigments include azo pigments (including azo lakes, insoluble azo pigments, condensed azo pigments, and chelate azo pigments), polycyclic pigments (eg, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments).
- Quinacridone pigments dioxane pigments, thioindigo pigments, isoindolinone pigments, quinofuranone pigments, etc.
- dye chelates including basic dye-type chelates or acidic dye-type chelates
- nitro pigments nitroso Pigments, erlin black, and the like can be used.
- inorganic pigments used for black include the following carbon blacks, for example, No. 2300, No. 900, MCF88, No. 33, No. 40, No. 45, No. 52 manufactured by Mitsubishi Ryogaku. MA7, MA8, MA100, No2200B, etc. (above, trade names); Columbia Rav en5750, Raven5250, Raven5000, Raven3500, Ravenl255, Raven700, etc. (above, trade names); Cabot Regal 400R, Regal 330R, Regal 660R, Mogul L, Monarch 700, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, etc.
- Color Black FW1 from Degussa , Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW200, Color Black S150, Color Black S160, Color Black S170, Printex 35, Printex U, Printex V, Printex 140U, Special Black 6, Special Black 5, Special Black 4A, Special Black 4 etc. It can be used.
- a black organic pigment such as Erlin Black (C. 1. Pigment Black 1) can be used.
- Yellow organic pigments include C ⁇ Pigment Yellow 1, C ⁇ Pigment Yellow 2, CIPigme nt Yellow 3, ClPigment Yellow 4, ClPigment Yellow 5, ClPigment Yellow 6, CI Pigment Yellow 7, ClPigment Yellow 10, ClPigment Yellow 11, CI Pigment Yellow
- Magenta organic pigments include CI Pigment Red 1, C ⁇ Pigment Red 2, ClPigment Red 3, ClPigment Red 4, ClPigment Red 5, ClPigment Red 6, ClPigment Red 7, C ⁇ Pigment Red 8, Cl Pigment Red 9, ClPigment Red 10, C ⁇ Pigment Red 11, CI Pigment Red 12, ClPigment Red 14, ClPigment Red 15, ClPigment Red 16, CI Pigment Red 17, ClPigment Red 18, ClPigment Red 19, ClPigment Red 21, CI Pigment Red 22, ClPigment Red 23, ClPigment Red 30, ClPigment Red 31, CI Pigment Red 32, ClPigment Red 37, ClPigment Red 38, ClPigment Red 40, CI Pigment Red 41, ClPigment Red 42, ClPigment Red 48 (Ca), C ⁇ Pigment Red 48 (Mn), C ⁇ Pigment Red 57 (Ca), ClPigment Red 57: 1, ClP
- Cyan Pigment Blue 1 CIPigment Blue 2, CIPigment Blue 15, CIPigment Blue 15: 1, CIPigment Blue 15: 2, CIPigment Blue 15 : 3, CIPigment Blue 15:34, CIPigment Blue 15: 4, CIPigment Blue 16, C ⁇ Pigment Blue 18, CIPigment Blue 22, CIPigment Blue 25, CIPigment Blue 6 0, C ⁇ Pigment Blue 65, CIPigment Blue 66, CIVat Blue 4, CIVat Blue 60 isotropic S.
- organic pigments other than magenta, cyan, and yellow include, for example, I. Pigment Green 7, I. Pigment Green 10, I. Pigment Brawn ⁇ , I. Pigment Brawn 5, I. .Pigme nt Brawn 25, CIPigment Brawn 26, CIPigment Orange 1, CIPigment Orange 2, CIPigment Orange 5, CIPigment Orange 7, CIPigment Orange C 4, CIPigment Orange ⁇ 4, CIPigment Orange 15, CIPigment Orange lb, CIPigment Orange 24, CIPigment Orange 34, CIPigment Orange 36, CIPigment Orange 38, CIPigment Orange 40, CIPigment Orange 43, CIPigment Orange 63, and the like.
- dyes that are insoluble or hardly soluble in water such as disperse dyes and oil-soluble dyes, can also be suitably used.
- the ionic surfactant used in the present invention is not particularly limited as long as it has an ionic group and a hydrophobic group.
- the ionic group is appropriately selected according to the use of the encapsulated product, which may be either an anionic group or a cationic group.
- ionic surfactants those having a ionic group are referred to as cationic surfactants, and those having a cationic group are referred to as cationic surfactants.
- anionic group examples include a sulfonic acid group, a sulfinic acid group, a carboxyl group, a phosphoric acid group, a sulfonic acid ester group, a sulfinic acid ester group, a phosphoric acid ester group, and these Those selected from the group of salts can be preferably exemplified.
- the salt examples include Na salt, K salt, Ca salt, and organic amine salt.
- the cationic group is preferably a group of force selected from primary ammonium cation, secondary ammonium cation, tertiary ammonium cation, and quaternary ammonium cation.
- R is a hydrophobic group, and examples thereof include the following.
- the cationic groups of the above-mentioned cationic groups include Cl_, Br ", ⁇ , CH OSO-, C H OS
- an alkyl group having 8 to 16 carbon atoms and an aryl group force such as a phenyl group or a phenyl group, a group force that is selected from one or two or more selected alkyl groups in a molecule. And can have both aryl groups.
- anionic surfactant examples include fatty acid salts, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfonates, a-olefin sulfonates, dialkyl sulfosuccinates, ⁇ -sulfonated fatty acid salts, ⁇ — Methyl-oleyl taurine, alkyl sulfate, sulfated oil, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl phenyl ether sulfate, polyoxyethylene styrenated phenol ether sulfate, alkyl phosphate, polyoxy Examples thereof include ethylene alkyl ether phosphate, polyoxyethylene alkyl phenol ether phosphate, and naphthalene sulfonate formaldehyde condensate.
- cationic surfactants include primary fatty amine salts, secondary fatty amine salts, tertiary fatty amine salts, tetraalkyl ammonium salts, trialkylbenzil ammonium salts, alkyl pyridinium salts. , 2 -alkyl- 1-alkyl-1 -hydroxyethyl imidazoline salt, polyethylene polyamine fatty acid amide salt, polyethylene polyamine fatty acid amide urea condensate salt, polyethylene quaternary fatty acid amide urea condensate quaternary ammonia And salts. [0025] [Ionic polymerizable surfactant]
- the ionic polymerizable surfactant used in the present invention is an ionic surfactant having the ionic group, the hydrophobic group, and a polymerizable group.
- the polymerizable group an unsaturated hydrocarbon group capable of radical polymerization is preferable, and specifically, a vinyl group, a aryl group, an allyloyl group, a methacryloyl group, a propenyl group, a vinylidene group, and a vinyl group are preferable.
- -Len group power as the group power is preferably a selected group. Of these, an aryl group, a metathalyl group, and an attalyloyl group are particularly preferable.
- an alkyl group having 8 to 16 carbon atoms a group force such as a phenol group, a fullerene group such as a phenol group, or the like is selected. It can also have both an alkyl group and an aryl group.
- the ionic group is appropriately selected according to the use of the capsule product, which may be either a ionic group or a cationic group.
- the ionic polymerizable surfactant has a ionic group or a cationic group as the ionic group
- the ionic polymerizable surfactant and the cationic polymerizable surfactant respectively. It is called an agent.
- the ionic polymerizable surfactant used in the present invention is a ionic surfactant having a ionic group, a hydrophobic group, and a polymerizable group.
- a sulfonic acid group, a sulfinic acid group, a carboxyl group, a phosphoric acid group, a sulfonic acid ester group, a sulfinic acid ester group, a phosphoric acid ester group, and those selected from the group of these salts are suitable.
- the salt include Na salt, K salt, Ca salt, and organic amine salt.
- an alkyl group having 8 to 16 carbon atoms and an aryl group force such as a phenyl group or a phenyl group, a group force that is selected from one or two or more selected alkyl groups in a molecule. And can have both aryl groups.
- an unsaturated hydrocarbon group capable of radical polymerization is preferable.
- a vinyl group, a allyl group, an allyloyl group, a methacryloyl group, a propenyl group, a vinylidene group, and a vinyl group are preferable.
- Group force that also provides the Ren base force It is preferably a selected group. Among these Particularly preferred are an aryl group, a methacryloyl group, and an acryloyl group.
- anionic polymerizable surfactant examples include an anionic aryl as described in JP-B-49-46291, JP-B-1-24142, or JP-A-62-104802.
- anionic propenyl derivatives as described in JP-A-62-221431, as described in JP-A-62-34947 or JP-A-55-11525
- examples thereof include an anionic acrylic acid derivative and an anionic itaconic acid derivative described in JP-B-46-34898 or JP-A-51-30284.
- R 21 and R 31 are each independently a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms,
- Z 1 is a carbon-carbon single bond or a formula:
- M is an integer of 2 to 20
- X is a group represented by Formula 1 SO M 1 ,
- M 1 is an alkali metal, an ammonium salt, or an alkanolamine.
- R 22 and R 32 are each independently a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and D is a carbon-carbon single bond or a formula:
- N is an integer of 2 to 20
- Y is a group represented by the formula 1 SO M 2 ,
- M 2 is an alkali metal, ammonium salt, or aranolamine.
- the compound represented by is preferred.
- Examples of the anionic polymerizable surfactant represented by the formula (31) include compounds described in JP-A-5-320276 or JP-A-10-316909. . By appropriately adjusting the value of m in the formula (31), it is possible to adjust the hydrophilicity of the capsule colorant particle surface obtained by encapsulating the colorant particle.
- Preferable polymerizable surfactants represented by the formula (31) include compounds represented by the following formula (310), and more specifically, the following formulas (31a) to ( And compounds represented by 31d).
- Adeka Soap SE-10N manufactured by Asahi Denka Kogyo Co., Ltd. is a compound in which M 1 is NH 10 in the compound represented by the formula (310). Asahi Denka Kogyo Co., Ltd.
- the anionic polymerizable surfactant used in the present invention includes, for example, general
- p 9 or 11
- q is an integer of 2 to 20
- A is a group represented by 1 SO ⁇
- M 3 is an alkali metal, an ammonium salt or an alkanolamine].
- the compound represented by these is preferable.
- Examples of the preferred anionic polymerizable surfactant represented by the formula (33) include the following compounds.
- a commercial item can also be used as said anionic polymerizable surfactant.
- Examples of commercially available products include AQUALON KH series (AQUALON KH-5, AQUALON KH-10) (trade name) manufactured by Daiichi Kogyo Seiyaku Co., Ltd., and the like.
- Aqua opening KH-5 is a mixture of a compound represented by the above formula (33), wherein r is 9 and s is 5, and a compound where r is 11 and s is 5.
- Aqualon KH-10 is a compound represented by the above formula wherein r is 9 and s is 10, and r is 11 and s is 10.
- the anionic polymerizable surfactant used in the present invention is preferably a compound represented by the following formula (34).
- R is an alkyl group having 8 to 15 carbon atoms
- n is an integer of 2 to 20
- X is —SO
- a commercial item can also be used as said anionic polymerizable surfactant.
- Examples of commercially available products include Adeka Soap SR Series (Adeka Soap SR-10, SR-20, SR-1025) (trade name) manufactured by Asahi Denka Kogyo Co., Ltd., and the like.
- Adekaria soap SR series, in the above general formula (34), B is represented by NH
- anionic polymerizable surfactant used in the present invention a compound represented by the following formula (A) can also be used.
- R 4 represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, 1 represents a number of 2 to 20, M 4 represents an alkali metal, an ammonium salt, or an alkanolamine.
- a commercially available product can also be used as the anionic polymerizable surfactant. Examples of commercially available products include AQUALON HS series (AQUALON HS-10, HS-20, and HS-1025) (trade name) manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
- examples of the ru-on polymerizable surfactant used in the present invention include sodium alkylarylsulfosuccinate represented by the general formula (35).
- a commercial item can also be used as said anionic polymerizable surfactant.
- Replacement paper (Rule 26) [0042]
- Examples of the anionic polymerizable surfactant used in the present invention include methacryloyloxypolyoxyalkylene sulfate sodium salt represented by the general formula (36). In the following formula, n is 1-20.
- anionic polymerizable surfactant used in the present invention for example, a compound represented by the general formula (37) can be used.
- anionic polymerizable surfactant Commercially available products can be used as the anionic polymerizable surfactant, and this is the case with Antox MS-60 from Enomoto Emulsifier Co., Ltd.
- anionic polymerizable surfactants exemplified above can be used alone or as a mixture of two or more.
- the cationic polymerizable surfactant used in the present invention comprises a cationic group, a hydrophobic group, and replacement paper (Rule 26). Furthermore, it is a cationic surfactant having a polymerizable group.
- the cationic group is preferably a group of force selected from primary ammonium cation, secondary ammonium cation, tertiary ammonium cation, and quaternary ammonium cation.
- R is a hydrophobic group, and examples thereof include the following.
- the hydrophobic group an alkyl group having 8 to 16 carbon atoms and an aryl group force such as a phenyl group or a phenyl group, a group force that is selected from one or two or more selected alkyl groups in a molecule. And can have both aryl groups.
- OSO— can be mentioned.
- an unsaturated hydrocarbon group capable of radical polymerization is preferable.
- a vinyl group, a allyl group, an allyloyl group, a methacryloyl group, a propenyl group, a vinylidene group, and a vinyl group are preferable.
- Group force that also provides the Ren base force It is preferably a selected group. Of these, an aryl group, a methacryloyl group, and an attalyloyl group are particularly preferable.
- cationic polymerizable surfactant examples include a general formula RR 1 R 2 R 3 N +
- R is a polymerizable group
- R 1 , R 2 , and R 3 are each an alkyl group and a phenyl group having 8 to 16 carbon atoms.
- Arylene groups such as a phenylene group, Xl3 ⁇ 4Cl_, Br ", ⁇ , CH OSO-, CH OSO-, 1, m
- n 1 or 0, respectively.
- examples of the polymerizable group include those described above.
- cationic polymerizable surfactant examples include dimethylaminoethyl octyl chloride methacrylate, dimethylaminoethyl cetyl chloride methacrylate, dimethylaminoethyl decyl methacrylate methacrylate, dimethylaminoethyl dodecyl methacrylate methacrylate. And salt, dimethylaminoethyl tetradecyl methacrylate tetralide silk salt, and the like.
- the cationic polymerizable surfactants exemplified above may be used alone or in combination of two or more. It can be used as a mixture.
- the nonionic polymerizable surfactant used in the present invention has a nonionic group, a hydrophobic group, and a polymerizable group.
- Nonionic groups include hydroxyl groups, polyoxyethylene groups, polyglycerin groups, and the like.
- an alkyl group having 8 to 16 carbon atoms and an aryl group force such as a phenyl group or a phenyl group, a group force that is selected from one or two or more selected alkyl groups in a molecule. And can have both aryl groups.
- an unsaturated hydrocarbon group capable of radical polymerization is preferable.
- a vinyl group, a allyl group, an allyloyl group, a methacryloyl group, a propenyl group, a vinylidene group, and a vinyl group are preferable.
- Group force that also provides the Ren base force It is preferably a selected group.
- an aryl group, a methacryloyl group, and an attalyloyl group are particularly preferable.
- Examples of the hydrophobic group and the polymerizable group include the same groups as described above.
- nonionic polymerizable surfactant used in the present invention a compound represented by the following formula (100) can be used.
- R & u represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and n represents a number of 5 to 50.
- nonionic polymerizable surfactant used in the present invention a compound represented by the following formula (103) can be used.
- 1 represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and n represents a number of 5 to 50.
- Nonionic polymerizable surfactant examples include the Neugen series (Neugen N-10, N-20, N-30, N-50) (trade names) manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
- the following formula (104) represents Neugen N-20.
- R is an alkyl group having 8 to 15 carbon atoms, and n is an integer of 5 to 50. ]
- Nonionic polymerizable surfactant examples include Adeka Soap ER series (Adeka Soap ER-10, ER-20, ER-30, ER-40) (above, trade names) manufactured by Asahi Denki Kogyo Co., Ltd. Can do.
- nonionic polymerizable surfactant used in the present invention a compound represented by the following formula (106) can be used.
- R 53 represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and n represents a number of 5 to 50.
- nonionic polymerizable surfactant used in the present invention examples include poly (ethylene glycol monopropylene glycol) monometatalylate (trade name: BLEMMER 50PEP-300 manufactured by Nippon Oil & Fats Co., Ltd.> Formula (108)), polyethylene glycol polypropylene Glycol monometatalylate (trade name Blemmer 70PEP-350B made by Nippon Oil & Fats Co., Ltd.> Formula (109)), Polyethylene glycol Polypropylene glycol monoatalylate (Product name Blemmer AEP series ⁇ made by Nippon Oil & Fats Co., Ltd.>) Glycol-Tetramethylene Glycol) Mono-Atalylate (trade name Blemmer AET series manufactured by Nippon Oil & Fats Corporation) , La Uroxy polyethylene glycol monometatalylate (Blenmer PLE—200 made by Nippon Oil & Fats Co., Ltd.> Formula (110)), Lauroxy polyethylene glycol monoacrylate
- the ionic monomer used in the present invention is a compound having an ionic group and a polymerizable group and is water-soluble.
- the ionic group is appropriately selected according to the use of the capsule product, which may be either a ionic group or a cationic group.
- the anionic group was selected from the group consisting of a sulfonic acid group, a sulfinic acid group, a carboxyl group, a phosphoric acid group, a sulfonic acid ester group, a sulfinic acid ester group, a phosphoric acid ester group, and salts thereof.
- the salt include Na salt, K salt, Ca salt, and organic amine salt.
- the cationic group is preferably a group of force selected from primary ammonium cation, secondary ammonium cation, tertiary ammonium cation, and quaternary ammonium cation.
- R is a hydrophobic group, and examples thereof include the following.
- the cationic groups of the above-mentioned cationic groups include Cl_, Br ", ⁇ , CH OSO-, CH OS
- ionic group has a ionic group or a cationic group
- they are referred to as an ionic water-soluble monomer and a cationic water-soluble monomer, respectively.
- Commercially available products can be used as the above cationic water-soluble monomers, such as Atariester DMC (Mitsubishi Rayon Co., Ltd.), Atariester DML60 (Mitsubishi Rayon Co., Ltd.), and C-1615 (Daiichi Kogyo). Pharmaceutical Co., Ltd.).
- the cationic water-soluble monomers exemplified above can be used alone or as a mixture of two or more.
- Preferred examples of the water-soluble water-soluble monomer that can be used in the present invention include specific examples of monomers having a carboxyl group such as acrylic acid, methacrylic acid, crotonic acid, propylacrylic acid, and isopropylacrylic acid.
- Acid 2-Ataryl oxyschetil succinic acid, 2-Atalyl oxyschetil phthalic acid, 2-methacryloyl oxyschetil succinic acid, 2-methacryloyl oxyschetil phthalic acid, itaconic acid, fumaric acid, And maleic acid.
- acrylic acid and methacrylic acid are preferable.
- Examples of the monomer having a sulfonic acid group include 4 styrene sulfonic acid and salts thereof, vinyl sulfonic acid and salts thereof, sulfoethyl acrylate and salts thereof, sulfoethyl methacrylate and salts thereof, and sulfoalkyl acrylate.
- sulfoalkyl metatalylate and its salt examples include sulfopropyl attalate and its salt, sulfopropyl metatalylate and its salt, sulfoaryl attalate and its salt, sulfoaryl metatalylate and its salt, butylacrylamide
- examples thereof include sulfonic acid and its salt, 2-acrylamido-2-methylpropane sulfonic acid and its salt.
- the monomer having a phosphone group examples include phosphoric acid group-containing (meth) acrylates such as phosphomethytalate. Examples above The key-on water-soluble monomers can be used alone or as a mixture of two or more.
- the ionic surfactant a used in the present invention is used for the purpose of adsorbing to the core substance, and the ionic group may be either ionic or cationic.
- the ionic surfactant a used in the present invention is the same as that described in the item of the ionic surfactant described above.
- the ionic polymerizable surfactant A used in the present invention is used for the purpose of adsorbing to the core substance, and the ionic group may be either ionic or cationic.
- the ionic polymerizable surfactant A used in the present invention is the one described in the above-mentioned item of the ionic polymerizable surfactant, the item of the anionic polymerizable surfactant, and the item of the cationic polymerizable surfactant. The same.
- the ionic polymerizable surfactant B used in the present invention has an opposite charge to the ionic groups of the ionic surfactant a and Z or the ionic polymerizable surfactant A.
- the ionic polymerizable surfactant and the cationic polymerizable surfactant used as the ionic polymerizable surfactant B used in the present invention are the above-mentioned items of the ionic polymerizable surfactant and the anionic polymerizable surfactant. The same as described in the section of surfactant and the section of cationic polymerizable surfactant.
- the ionic polymerizable surfactant C used in the present invention has the same kind or opposite charge with respect to the ionic groups of the ionic surfactant a and Z or the ionic polymerizable surfactant A.
- the ionic polymerizable surfactant and cationic polymerizable surfactant used as the ionic polymerizable surfactant C used in the present invention are the above-mentioned items of the ionic polymerizable surfactant and the anionic polymerizable surfactant.
- Surfactant items and cationic polymerizable interfaces The same as described in the item of the activator.
- the nonionic polymerizable surfactant D used in the present invention is the same as that described in the item of the nonionic polymerizable surfactant described above.
- the nonionic group of the nonionic polymerizable surfactant D is present in the outermost layer of the capsule product.
- a nonionic surfactant e when the ionic surfactants a and Z or the ionic polymerizable surfactant A are adsorbed on the surface of the core material, a nonionic surfactant e is used in combination, The surfactants a and Z or the ionic polymerizable surfactant A may be adsorbed on the surface of the core substance.
- This nonionic surfactant e has a nonionic group and a hydrophobic group, and examples of the nonionic group include a hydroxyl group, a polyoxyethylene group, and a polyglycerin group.
- an alkyl group having 8 to 16 carbon atoms, a fuller group force such as a fullerene group, a fullerene group, or the like is selected.
- the molecule may have both an alkyl group and an aryl group.
- nonionic surfactants e include polyethylene glycols such as polyethylene glycol lauryl ether, polyethylene glycol tridecyl ether, polyethylene glycol cetyl ether, polyethylene glycol stearyl ether, and polyethylene glycol oleyl ether.
- Alkyl ether polyethylene glycol nonyl phenyl ether, polyethylene glycol octyl phenyl ether, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol monoremonoleate, sorbitan monolaurate, sorbitan monomyristate, sonorebitan Monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trio , Polyethylene glycol sorbitan monolaurate, polyethylene glycol sorbitan monostearate, polyethylene glycol sorbitan monooleate, glycerin fatty acid monoester, glycerol monostearate, polyglycerol oleate ester, polyglycerol laurate ester, Polyglycerol stearic acid ester, lauric acid diethanolamide, oleic acid diethanolamide, hydroxyethyl laurylamine, polyethylene glycol laurylamine, polyethylene glyco
- a nonionic surfactant E when adsorbing the ionic surfactants a and Z or the ionic polymerizable surfactant A on the surface of the core material, a nonionic surfactant E is used in combination. It may be adsorbed on the surface of the core material together with the surfactants a and Z or the ionic polymerizable surfactant A.
- the nonionic polymerizable surfactant E used in the present invention is the same as that described in the above-mentioned item of the nonionic polymerizable surfactant.
- the hydrophobic monomer means a polymerizable monomer having at least a hydrophobic group and a polymerizable group in its structure, and the hydrophobic group is an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic group.
- Group power of the group hydrocarbon group can be exemplified.
- Examples of the aliphatic hydrocarbon group include a methyl group, an ethyl group, and a propyl group.
- Examples of the alicyclic hydrocarbon group include a cyclohexyl group, a dicyclopental group, a dicyclopental group, and an isobornyl group.
- Examples of the aromatic hydrocarbon group include a benzyl group, a fullyl group, and a naphthyl group.
- the same ones described in the item of the ionic polymerizable surfactant described above can be used.
- hydrophobic monomer examples include styrene derivatives such as styrene, methyl styrene, butyl toluene, dimethylol styrene, chloro styrene, dichloro styrene, t-butyl styrene, bromo styrene, p-chloromethyl styrene; methyl acrylate , Ethyl acrylate, isopropyl acrylate, n-butyl acrylate, butoxetyl acrylate, isobutyl acrylate, n-amyl acrylate, isoamyl acrylate, n-hexyl acrylate, octyl acrylate, decyl Atarylate, dodecyl acrylate, octadecyl acrylate, benzyl acrylate, acrylate acrylate,
- physical properties and chemical properties are the structure of hydrophobic monomers and hydrophobic properties. It is determined by the copolymer structure and the like. Therefore, it is possible to select a hydrophobic monomer according to the performance required for the encapsulated product. For example, it is obtained when the capsule material of the present invention using a color material as a core material is used as a recording material.
- the fixability and abrasion resistance of the recorded material can be controlled by controlling the glass transition point (Tg) of the copolymer (copolymer) coated / colored with the colorant particles.
- glass transition temperature a state where a very large force is required for a slight deformation (glass state), a state where a large deformation occurs with a small force
- glass transition temperature a state where a large deformation occurs with a small force
- glass transition temperature glass transition temperature
- the glass transition point of the homopolymer obtained by homopolymerization of the monomer used in synthesizing the copolymer and the homopolymer of the monomer can be calculated from the Fox equation.
- Tg is the glass transition temperature of the polymer obtained, and i is a different monomer.
- Tg is the glass transition temperature of the homopolymer of monomer i used for polymerization.
- X represents the weight fraction of monomer i with respect to the total weight of monomers to be polymerized.
- the polymer in the case where the temperature environment where the capsule of the present invention is placed is higher than the glass transition point of the copolymer coated with the core material of the capsule of the present invention, The polymer enters a state where large deformation occurs with a small force, and further melts when the melting point is reached. At this time, if another encapsulated product is present in the vicinity, the encapsulated products are fused to form a film. Even if the ambient temperature does not reach the melting point, the encapsulated products have strong power. If the conditions are such that the copolymer molecules covering the capsules can be entangled with each other, the copolymers (copolymers) may fuse together. .
- the capsule material of the present invention using a color material as a core substance is used as an ink jet ink
- a recording medium such as plain paper or a dedicated recording medium for ink jet recording
- the present invention Disappears from the vicinity of the capsule particles by penetrating water and Z or water-soluble organic solvent around the capsule particles into plain paper and recording media for ink jet recording.
- the capsule particles become close to each other.
- the glass transition point (Tg) of the copolymer covering the colorant particles, which are the core material of the capsule particles is below room temperature, the capillary pressure generated in the gaps between the encapsulated particles.
- the copolymer (copolymer) covering the colorant particles is fused to form a film in a state of enveloping (including) the colorant.
- the glass transition point of the copolymer covering the colorant particles of the encapsulated product of the present invention is preferably 30 ° C or lower, more preferably 15 ° C or lower, and further preferably 10 ° C or lower.
- the encapsulated material is more preferably formed at room temperature.
- the glass transition point of the copolymer (copolymer) coated with the color material particles of the encapsulated material is set. It is preferable to design so as to be 30 ° C or less, more preferably 15 ° C or less, and further preferably 10 ° C or less. However, if the glass transition point is lower than -20 ° C, the solvent resistance tends to decrease, so care must be taken.
- the hydrophobic monomer those satisfying the respective required characteristics described above are appropriately selected, and the addition amount thereof is arbitrarily determined.
- the glass transition of the copolymer covering the color material particles as the core material of the capsule material particles By setting the point (Tg) to be equal to or lower than the fixing temperature, the copolymer (copolymer) covering the colorant particles is fused and the colorant is enclosed (included) in the recording medium. Films can be formed on plain paper, and fixability and abrasion resistance of the colorant on the recording medium can be obtained. In this case, the glass transition of the copolymer coated with the colorant particles of the capsule product of the present invention.
- the point is preferably set to a temperature that does not affect the electrophotographic process other than the fixing process, particularly the development process and the transfer process.
- Hydrophobic monomers have the required properties such as film formability, coating film strength, electrical properties, chemical resistance, water resistance, light resistance, weather resistance, and optical properties, which are required as toner physical properties. What is satisfied is appropriately selected, and the amount added is arbitrarily determined.
- a monomer represented by the following general formula (2) is further added as long as the effects of the present invention are not impaired. Can be used.
- R 1 represents a hydrogen atom or a methyl group.
- R 2 represents a t-butyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, or a heterocyclic group.
- m represents an integer of 0 to 3
- n represents an integer of 0 or 1.
- examples of the alicyclic hydrocarbon group represented by R 2 include a cycloalkyl group, a cycloalkenyl group, an isobornyl group, a dicyclopentanyl group, a dicyclopentenyl group, and an adamantane group.
- examples of the heterocyclic group include a tetrahydrofuran group.
- the presence of the R 2 group, which is a “bulky” group, in the polymer that constitutes the cell wall material can suppress the penetration of the organic solvent in the ink composition into the interior of the polymer.
- the solvent resistance of the coloring material can be made excellent.
- the ink composition for ink-jet recording coexisting with a water-soluble organic solvent can be used to disperse the colorant particles, the storage stability of the ink composition, and the discharge of the ink composition from the ink-jet head. 'Gender can be improved.
- a polymer having a repeating structural unit derived from a monomer having a long-chain alkyl group has flexibility. Therefore, a repeating structural unit derived from a crosslinking monomer force described later and a repeating structural unit derived from a monomer having a long-chain alkyl group and a repeating structural unit derived from a monomer represented by Z or the general formula (2).
- a capsule wall material polymer having excellent mechanical strength and excellent solvent resistance can be synthesized together with preferable plasticity.
- the ink composition containing the capsule-colored material particles coated with such a polymer is excellent in dispersion stability and long-term storage even when it contains a water-soluble organic solvent. Excellent discharge stability. Furthermore, an image of a printed matter printed using the ink composition containing the force-pellder-colored material particles has a good fixability to a recording medium such as paper or a dedicated ink jet medium. Furthermore, this ink composition can obtain an image excellent in abrasion resistance, durability and solvent resistance.
- the capsule product of the present invention is obtained by coating a core substance with a material mainly composed of a polymer.
- a material mainly composed of a polymer In addition to the above-mentioned various surfactants, polymerizable surfactants and hydrophobic monomers, the capsule material of the present invention is used.
- Other polymerizable monomer components can be used as long as the effects of the above are not impaired.
- examples of other polymerizable monomers used in the present invention include a crosslinkable monomer.
- the swelling of the polymer by the organic solvent can suppress the penetration of the organic solvent into the polymer, and can improve the solvent resistance of the capsule wall material.
- an inkjet recording ink coexisting with a water-soluble organic solvent is used.
- the dispersibility of the color material particles, the storage stability of the ink composition, and the dischargeability of the ink composition from the ink jet head can be improved.
- crosslinkable monomer used in the present invention examples include one or more unsaturated hydrocarbon groups selected from a bur group, a allyl group, an talyloyl group, a methacryloyl group, a probe group, a vinylidene group, and a beylene group. And compounds having two or more compounds.
- crosslinkable monomer examples include, for example, ethylene glycol ditalylate, diethylene glycol ditalylate, triethylene glycol ditalylate, tetraethylene glycol ditalylate, polyethylene glycol ditalylate, aryl arylate, and bis ( Acryloxetyl) hydroxyethyl isocyanurate, bis (ataryloxynepentylglycol) adipate, 1,3 butylene glycol ditalylate, 1,6 hexanediol ditalylate, neopentylglycol ditalylate, propylene glycol diester Acrylate, Polypropylene glycol ditalylate, 2 Hydroxy 1,3 Diacryloxypropane, 2, 2 Bis [4- (Atyloxy) phenol] propane, 2, 2 Bis [4— (Aryloxy Toxyl) phenol] propane, 2,2 bis [4- (Atalyloxyethoxy'jetoxy
- the polymer having a repeating structural unit derived from the above crosslinkable monomer force or the polymer having a repeating structural unit derived from the monomer force represented by the general formula (2) has a glass transition temperature (Tg). It has the advantage of high mechanical strength, heat resistance and solvent resistance.
- capsule colorant particles coated with such a crosslinkable monomer and a polymer containing a large amount of Z or the monomer represented by the above general formula (2) as a copolymerization component were used in an ink composition for ink jet recording.
- a recording medium such as paper or an inkjet-dedicated medium.
- problems may arise when the fixing property of the encapsulated color material to the recording medium and the abrasion resistance of the obtained image are lowered. Therefore, it is preferable to appropriately adjust the amount of the crosslinkable monomer and the monomer represented by Z or the general formula (2).
- the polymer constituting the capsule wall material of the capsule product of the present invention is obtained by polymerizing an ionic polymerizable surfactant, an ionic monomer, and a hydrophobic monomer.
- This polymerization reaction can be performed using a known polymerization initiator, and it is particularly preferable to use a radical polymerization initiator. In the present invention, it is collected in the manufacture of capsules. It is preferable to use a polymerization initiator suitable for the polymerization method used. In the case of using the emulsion polymerization method and the emulsion polymerization method, a water-soluble polymerization initiator is preferred as the polymerization initiator.
- persulfates such as potassium persulfate, ammonium persulfate, and sodium persulfate.
- Hydrogen peroxide 2,2-azobis mono (2-methylpropionamidine) dihydrochloride, water-soluble azo compound compounds such as 4,4-azobis mono (4-cyananovalerate), etc.
- oxidants such as potassium persulfate, ammonium persulfate, sodium persulfate, hydrogen peroxide, etc. and reduction of sodium sulfite, sodium hyposulfite, ferrous sulfate, ferrous nitrate, thiourea, etc.
- a redox initiator combined with an agent can also be used.
- oil-soluble polymerization initiators such as peroxides such as butyl (peroxy-2-ethylhexanoate), 2,5 dimethyl 2,5 di (2 ethahexanolperoxy) hexane, etc. Better ,.
- the capsule product of the present invention is obtained by coating a core material with a material mainly composed of a polymer.
- the capsule material absorbs ultraviolet rays as long as the effects of the present invention are not impaired.
- Other components such as an agent, a light stabilizer, an antioxidant, a flame retardant, a plasticizer, and a wax can be contained in the polymer.
- Capsule wall material of capsules can be synthesized by a polymerization reaction.
- This polymerization reaction can be performed using a reaction vessel equipped with an ultrasonic generator, a stirrer, a reflux condenser, a dropping funnel, and a temperature controller. preferable.
- the capsule container according to the embodiment of the present invention is preferably manufactured by the following procedure.
- an ionic surfactant a having an ionic group and a hydrophobic group is adsorbed on the surface of the core substance.
- the core material is solid, the core material is put into ion-exchanged water in which the ionic surfactant a is dissolved, mixed, and then the mixed solution is mixed with a ball mill, roll mill, Eiger mill, or jet mill. It is preferable that the ionic surfactant a be sufficiently adsorbed on the core substance by carrying out a dispersion treatment in a general dispersing machine such as the above.
- the substance to be adsorbed on the core substance should have at least an ionic group, and an ionic polymerizable surfactant having a polymerizable group is used as an ionic surfactant. Also good.
- a nonionic surfactant may be used in combination, and this nonionic surfactant has a polymerizable group! / ⁇ May be.
- the ionic surfactant a that has not been adsorbed to the core substance by ultrafiltration or the like. If a large amount of unadsorbed ionic surfactant remains, the production amount of polymer particles as a by-product increases, resulting in insufficient core material encapsulation. However, since the dispersion of the core substance may become unstable if it is removed too much, it is preferable to appropriately determine the degree of ultrafiltration in consideration of the dispersion stability and the state of capsules. .
- ionic polymerizable surfactants B and Z having an opposite charge to the ionic surfactant a are added to the dispersion of the core material adsorbing the ionic surfactant a. Or, add ion monomer and mix. At this time, the mixture is irradiated with ultrasonic waves so that the ionic groups of the ionic polymerizable surfactants B and Z or the ionic monomer are easily ionically bonded to the ionic groups of the ionic surfactant a. It is preferable.
- ionic polymerizable surfactants B and Z having an opposite charge to ionic surfactant a or ionic monomer to the dispersion of the core material adsorbing ionic surfactant a
- the amount is 0.5 to 2 times mol of the total number of ionic groups of the ionic surfactant a (that is, the amount of ionic groups present on the surface of the core material lg used [molZg]).
- a range of 0.8 to 1.2 times mole is more preferable.
- the ionic polymerizable surfactants B and Z or ionic monomer having an opposite charge to these are set to 0.
- the ionic polymerizable surfactants B and Z or ionic monomer having an opposite charge to these are set to 0.
- a hydrophobic monomer is added.
- the timing of adding the hydrophobic monomer may be after (IV).
- the polymerizable monomer may be a cross-linkable monomer, a compound represented by the above general formula (2), and other known polymerizable monomer groups, as long as the effects of the invention are not impaired.
- the selected monomer can be used in combination.
- an ionic polymerizable surfactant C having the same or opposite charge as the ionic surfactant a is added and mixed.
- the addition amount of the ionic polymerizable surfactant C is the same as that of the ionic polymerizable surfactant B and Z or the ionic monomer.
- the addition amount is preferably in the range of 0.5 to 10 moles, more preferably in the range of 0.5 to 5 moles.
- the ionic polymerizable surfactant B and Z or ion having the opposite charge to the ionic surfactant a on the surface of the core material on which the ionic surfactant a is adsorbed An ion having electrostatic charge attached electrostatically, possibly having a hydrophobic monomer on the outside, and further having a charge of the same or opposite to that of the ionic group of the ionic surfactant a on the outside It is presumed that the polymerizable polymerizable surfactant C orients its ionic group toward the aqueous phase to form an admicell.
- nonionic polymerizable surfactant D can be used in combination with ionic polymerizable surfactant C.
- the addition amount of the nonionic polymerizable surfactant is the sum of the addition amount of the ionic polymerizable surfactant C and the ionic polymerizable surfactant B.
- / or the ionic monomer is adjusted so as to be in the range of 0.5 to 10 moles, more preferably in the range of 0.5 to 5 moles.
- the ratio of the nonionic polymerizable surfactant D and the ionic polymerizable surfactant C is appropriately determined depending on the properties required for the obtained capsule product.
- ultrasonic irradiation is not necessarily required when formation of admicelle can be obtained without performing ultrasonic irradiation in the above steps.
- a polymerization initiator is added to the mixed solution prepared as described above to conduct a polymerization reaction.
- the polymerization initiator may be added all at once or separately at a temperature at which the polymerization initiator is activated, or may be added continuously.
- the mixture may be heated to a temperature at which the polymerization initiator is activated! / ⁇ .
- an aqueous solution obtained by dissolving a water-soluble polymerization initiator in ion-exchanged water is dropped into an aqueous dispersion in a reaction vessel at a predetermined dropping rate. This can be carried out more preferably.
- an oil-soluble polymerization initiator in miniemulsion polymerization, it can be suitably carried out by dissolving it in a hydrophobic monomer and adding it as it is.
- the activity of the polymerization initiator can be suitably carried out by raising the temperature to a temperature at which the polymerization initiator is cleaved and initiator radicals are generated.
- the charged polymerization initiator is cleaved to generate initiator radicals, which attack the polymerizable group of the ionic polymerizable surfactant and the polymerizable group of the ionic monomer and hydrophobic monomer to cause the polymerization reaction. Occur.
- the polymerization temperature and the polymerization reaction time are suitably different depending on the type of polymerization initiator used and the type of the above-mentioned polymerizable compound, and it is easy to set the polymerization conditions.
- the polymerization temperature is preferably in the range of 40 ° C to 90 ° C, and the polymerization time is preferably 3 hours to 12 hours.
- the ionic surfactant a the ionic polymerizable surfactants B and C, and, if necessary, a hydrophobic monomer, a crosslinkable monomer, and the general formula
- the compound represented by (2) and other known polymerizable monomers are each 1 type or 2 More than seeds can be used.
- the emulsified state of the mixed solution is often good without using an emulsifier. Therefore, it is not always necessary to use an emulsifier, but it is possible to use at least one selected from the group forces of known ion-based, non-one and cationic emulsifiers as required.
- the pH of the obtained aqueous dispersion of the capsule product of the present invention is preferably ultrafiltration.
- the ionic surfactant a having an ionic group and a hydrophobic group is adsorbed on the surface of the core substance.
- ionic monomers having an opposite charge to ionic surfactant a and ionic polymerizable surfactants B and Z having an opposite charge to ionic surfactant a are adsorbed.
- polymerizable monomer containing a hydrophobic monomer is added.
- a polymerizable monomer containing a hydrophobic monomer is added after adding ionic polymerizable surfactant C.
- an ionic polymerizable surfactant C having the same or opposite charge as that of the ionic group of the ionic surfactant a is added and mixed.
- the arrangement form of the ionic polymerizable surfactant and polymerizable monomer molecules existing around the core substance is extremely highly controlled, and the ionic group (anionic group or cationic group) is water in the outermost layer. It is thought that an orientation state is formed toward the phase side.
- the capsule product of the present invention was obtained.
- the hydrophobic monomer is covered, the repeating structural unit derived from the ionic polymerizable surfactant B, the repeating structural unit derived from the ionic polymerizable surfactant C, and the hydrophobic monomer power A polymer having repeating structural units is formed around the core material.
- the polymerization method of the present invention suppresses the formation of water-soluble oligomers and polymers as by-products.
- the aqueous dispersion of capsules obtained using the polymerization method of the present invention has a low viscosity and excellent dispersibility and dispersion stability. As mentioned above, this is the outermost layer of the capsule This is probably because an ionic group (a-on group or cationic group) forms a highly oriented state toward the aqueous phase.
- an inkjet ink composition using a capsule material obtained by the polymerization method of the present invention using colorant particles as a core substance is excellent in dispersion stability, excellent in ejection stability from a recording head, and is usually It is possible to obtain printed images with high color density and high density that resist bleeding.
- the capsule product obtained by using the polymerization method of the present invention can introduce functional groups such as ionic groups and nonionic groups in the outermost layer in a highly oriented state, these functional groups It is also possible to easily introduce a functional group having a more specific function by using. As a result, composite functional fine particles having several unique functions can be obtained.
- the encapsulated product of the present invention is produced using ionic surfactant b and ionic surfactant c instead of ionic polymerizable surfactant B and ionic polymerizable surfactant C described above. It is also possible. In that case, it is essential to add a hydrophobic monomer.
- a wall material mainly composed of a polymer is formed on the core material via the ionic surfactant a.
- the appropriate addition amount is the same as the appropriate addition amount of ionic polymerizable surfactant B and ionic polymerizable surfactant C. It is the same.
- the capsule product of the present invention obtained as described above has high dispersion stability with respect to an aqueous solvent. This is because the core material is completely covered with the polymer layer (the coated material is This is probably because the hydrophilic group of the polymer layer of the capsule wall material is regularly oriented toward the aqueous solvent.
- a pigment is put into ion-exchanged water in which a ionic polymerizable surfactant is dissolved, and after mixing, this mixed solution is put into a general dispersing machine such as a ball mill, a roll mill, an Eiger mill, or a jet mill. Then, dispersion treatment is performed to adsorb the cationic polymerizable surfactant on the pigment particle surface. After this, by ultrafiltration, the non-adsorbed key properties on the pigment particles Remove the polymerizable surfactant. At this time, since the dispersion of the core substance may become unstable if it is removed too much, the degree of ultrafiltration or the like is appropriately determined by considering the dispersion stability and the state of capsules.
- a cationic polymerizable surfactant and Z or a cationic water-soluble monomer are added to and mixed with the dispersion having a pigment strength that has adsorbed the ionic polymerizable surfactant.
- the cationic polymerizable surfactant and the cationic group of Z or the cationic water-soluble monomer are more easily ionically bonded to the cationic group of the cationic polymerizable surfactant. It is preferable to irradiate the mixture with ultrasound.
- the addition amount of the cationic polymerizable surfactant and Z or the cationic water-soluble monomer to the pigment dispersion is the total moles of ionic groups of the ionic polymerizable surfactant adsorbed on the pigment. It is preferably in the range of 0.5 to 2 times mol with respect to the number (that is, the amount of ionic groups [molZg] present on the pigment surface of the pigment particle lg) 0.8 to 1.2 times mol. More preferred to be in the range.
- Cationic polymerizable surfactant and Z or cationic water-soluble monomer 0.5 times the total molar amount of ionic group of ionic polymerizable surfactant adsorbed on the pigment particle surface
- a capsule soot pigment having good dispersibility can be obtained by the subsequent polymerization reaction.
- the addition amount of the cationic polymerizable surfactant and Z or the cationic water-soluble monomer to 2 times mole or less, the generation of polymer particles (particles that can only be a polymer) can be suppressed.
- a hydrophobic monomer is added and mixed.
- the polymerizable monomer in addition to the hydrophobic monomer, a group consisting of a crosslinkable monomer, a compound represented by the above general formula (2), and other known polymerizable monomers as long as the effects of the invention are not impaired.
- Monomers selected from these can be used in combination.
- the timing of adding these hydrophobic monomers may be after the addition of the anionic polymerizable surfactant described later.
- an anionic polymerizable surfactant is added and mixed.
- the addition amount of the anionic polymerizable surfactant is in the range of 0.5 to 10 times mol with respect to the cationic polymerizable surfactant and Z or cationic water-soluble monomer. Is more preferably in the range of 0.5 mole to 5 moles.
- the addition amount is 0.5 times mol or less.
- the polymerization initiator may be added to the above mixed solution heated to a temperature at which the polymerization initiator is activated, or the polymerization initiator may be added all at once or dividedly or continuously. In addition, after adding the polymerization initiator, the mixed solution may be heated to a temperature at which the polymerization initiator is activated.
- a water-soluble polymerization initiator or an oil-soluble polymerization initiator can be used as the polymerization initiator. However, when using a water-soluble polymerization initiator, it is dissolved in pure water and added dropwise to the mixed solution in the reaction vessel. Is preferred.
- an oil-soluble polymerization initiator when using an oil-soluble polymerization initiator, it can be suitably carried out by dissolving it in a hydrophobic monomer and adding it as it is.
- the polymerization temperature and polymerization reaction time vary depending on the type of polymerization initiator used and the type of polymerizable monomer, but those skilled in the art can easily set preferable polymerization conditions as appropriate.
- the polymerization temperature is preferably in the range of 40 ° C to 90 ° C.
- the polymerization time is preferably 3 hours to 12 hours.
- the ionic polymerizable surfactant and the polymerizable monomer molecules are arranged in a highly advanced manner around the pigment particles, and the outermost layer is anionic.
- the group is in a state of being densely oriented by force toward the aqueous phase.
- a capsule pigment pigment coated with a polymer in a highly controlled form around the pigment particles is obtained.
- the production of water-soluble oligomers and polymers as by-products is suppressed.
- a low-viscosity encapsulated pigment dispersion can be obtained, and a purification process such as ultrafiltration can be facilitated.
- the encapsulated pigment obtained in the present invention has a form in which pigment particles are coated with a polymer which is a capsule wall material. If desired, an anti-oxidation agent is added to the mixture before or during the polymerization reaction. These additives can be contained in the polymer by adding a plasticizer or the like. A known material can be used as such an acid-proofing agent or plasticizer.
- an unreacted substance contained in the encapsulated pigment dispersion obtained by the production method of the present invention. It is preferable to remove and purify a polymerizable compound using an activator or a hydrophobic monomer in advance.
- the amount of the unreacted material contained in the encapsulated pigment dispersion is preferably 50, OOOOppm or less, more preferably 10,000ppm or less.
- a centrifugal separation method, an ultrafiltration method, or the like can be used as a method for removing unreacted substances.
- the amount of the unreacted material can be easily measured using gas chromatography or liquid chromatography.
- the concentration of unreacted monomer in the encapsulated pigment dispersion By reducing the concentration of unreacted monomer in the encapsulated pigment dispersion, the image printed on plain paper will have better saturation and high print density (print density), and image bleeding The effect that generation
- images printed on dedicated media for ink-jet recording, in particular glossy media for ink-jet recording have a better gloss.
- the particle size of the encapsulated pigment is preferably 400 nm or less, more preferably 300 nm or less. Particularly preferred is 20 to 200 nm.
- the particle size of the encapsulated pigment can be measured using a commercially available dynamic light scattering particle size distribution analyzer, laser Doppler particle size distribution meter, etc.
- the glass transition temperature (Tg) of the polymer that is the main component of the capsule wall material of the capsule pigment of the present invention is further reduced.
- Tg glass transition temperature
- the glass transition temperature of the polymer which is the main component of the psel wall material
- the glass transition temperature of the polymer which is the main component of the psel wall material
- the Tg of the polymer which is the main component of the capsule wall material
- the capsule discoloration material is easily bonded on the recording medium, so that the image is further improved in abrasion resistance and recording. Since the adhesion to the medium is also improved, the temperature is more preferably 10 ° C. or less.
- the ink composition using the capsule pigment obtained by the above production method has a low viscosity and excellent dispersibility and dispersion stability, and particularly when used as an ink composition for ink jet recording. In addition to being excellent in the ejection stability from the paper, it is possible to obtain a printed image with high color and density on plain paper and a printed image having high gloss and image quality on a dedicated medium for inkjet recording.
- the capsule color material obtained when a color material is used as the core substance can be used in the ink composition, and is particularly preferable as the color material used in the ink for inkjet recording.
- the case where the color material particles are pigments is preferable.
- an ink composition for ink jet recording using a capsule pigment using a pigment as colorant particles in the capsule pigment color material obtained according to the present invention will be described.
- the ink composition for ink jet recording of the present invention is an aqueous ink composition, and the capsule capsule pigment is dispersed and contained in an aqueous medium.
- the content of the capsule cocoon pigment in the ink composition is preferably 1% to 20% by weight, more preferably 3% to 15% by weight, based on the total weight of the ink composition. preferable.
- the content is preferably 5% by weight to 15% by weight.
- the solvent used in the ink composition of the invention includes water and a water-soluble organic solvent. It may be preferred to further contain other ingredients if desired.
- a wetting agent having a high boiling water-soluble organic solvent power it is preferable to add to the ink composition of the present invention.
- a water-soluble organic solvent having a boiling point of 180 ° C. or higher is preferable.
- water-soluble organic solvent having a boiling point of 180 ° C or higher examples include ethylene glycol, propylene glycol, diethylene glycol, pentamethylene glycol, trimethylene glycol, 2-butene 1, 4-diol, 2-ethyl-1,3-hexanediol, 2-methyl-2,4-pentanediol, tripropylene glycol, polyethylene glycol with a molecular weight of 2,000 or less, 1,3 propylene glycol, isopropylene glycol, isobutylendalicol, glycerin, meso Mention may be made of erythritol and bentaerythritol.
- the high-boiling water-soluble organic solvent used in the present invention more preferably has a boiling point of 200 ° C or higher.
- One or more of these can be used in the ink composition of the present invention.
- a high-boiling water-soluble organic solvent By adding a high-boiling water-soluble organic solvent to the ink composition, the fluidity and redispersibility can be maintained for a long time even if it is left open (the ink composition is exposed to air at room temperature). An ink for inkjet recording that can be maintained can be obtained. Further, such an ink composition has high ejection stability from the ink jet nozzle because clogging of the ink jet nozzle is less likely to occur during printing using the ink jet printer or at the restart after the interruption of printing. An ink composition is obtained.
- the total content of water-soluble organic solvents including these high-boiling water-soluble organic solvents is preferably about 10 to 50% by weight, and more preferably 10 to 50% by weight with respect to the total weight of the ink composition. 30% by weight.
- the ink composition of the present invention further includes 2 pyrrolidone, N-methylpyrrolidone, ⁇ -force prolatatum, dimethyl sulfoxide, sulfolane, morpholine, ethyl morpholine, and 1,3 dimethyl-2-imidazolidinone.
- One or more polar solvents can be added that are selected to have equal forces. By adding a polar solvent, the effect of improving the dispersibility of the capsule-like pigment particles in the ink composition can be obtained, and the ink ejection stability can be improved.
- the content of these polar solvents is preferably 0.1% by weight to 20% by weight and more preferably 1% by weight to 10% by weight with respect to the total weight of the ink composition.
- the ink composition of the present invention preferably further contains a penetrant for the purpose of promoting the penetration of the aqueous solvent into the recording medium.
- a penetrant for the purpose of promoting the penetration of the aqueous solvent into the recording medium.
- alkyl ethers of polyhydric alcohols also called glycol ethers
- 1,2-alkyldiols are preferably used.
- alkyl ether of the polyhydric alcohol include ethylene glycol monomethyl ether, ethylene glycol monoethylenoate, ethylene glycol monobutenoate ethere, ethylene glycol monomethylate etherate, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether.
- 1,2-alkyldiol examples include 1,2-pentanediol and 1,2 monohexanediol.
- linear hydrocarbons such as 1,3 propanediol, 1,4 butanediol, 1,5 pentanediol, 1,6 hexanediol, 1,7 heptanediol, and 1,8 octanediol Diols can be enumerated, and these forces can be appropriately selected and used in the ink yarn composition of the present invention.
- propylene glycol monobutyl ether, dipropylene glycol monomono butylene ether, diethylene glycol monomono butyl ether, triethylene glycol monobutyl ether, 1,2-pentanediol, and 1,2-Hexanediol power It is preferable to use at least one selected as a penetrant.
- the content of these penetrants is preferably 1 to 20% by weight, more preferably 1 to LO weight%, based on the total weight of the ink composition. By making the penetrant content 1% by weight or more, an effect of improving the penetrability of the ink composition into the recording medium can be obtained.
- Bleeding can be prevented from occurring in an image printed using the object, and the viscosity of the ink composition can be prevented from becoming too high.
- a 1,2-alkyldiol such as 1,2-pentanediol or 1,2-hexanediol
- the drying property of the ink composition after printing becomes good, and , Image bleeding can be reduced.
- the ink composition of the present invention by including glycerin in the ink composition of the present invention, clogging of the ink jet nozzle is less likely to occur when the ink composition is used for ink jet recording, and the storage stability of the ink composition itself is further improved. It can also improve sex.
- acetylene glycol surfactant described later together with the glycol ether.
- the ink composition of the present invention preferably contains a surfactant, particularly a ionic surfactant and Z or a nonionic surfactant! /.
- a surfactant particularly a ionic surfactant and Z or a nonionic surfactant! /.
- an ionic surfactant include alkane sulfonate, a-olefin sulfonate, alkyl benzene sulfonate, alkyl naphthalene sulfonate, acyl acyl taurate, dialkyl sulfonate, Alkyl sulfate ester salts, sulfated oils, sulfates, polyoxyethylene alkyl ether sulfate ester salts, fatty acid salts, alkyl sarcosine salts, alkyl phosphate ester salts, polyoxyethylene alkyl ether phosphate ester salts, monoglycerite Examples thereof include phosphat
- non-ionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl ester, polyoxyethylene alkyl.
- examples thereof include amides, glycerin alkyl esters, sorbitan alkynole esters, sugar alkyl esters, polyhydric alcohol alkyl ethers, and alkanolamine fatty acid amides.
- anionic surfactants include sodium dodecinolebenzenesulfonate, sodium laurate, and ammonium salts of polyoxyethylene alkyl ether sulfate.
- the agent include polyoxyethylene noel phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl / refinenole ether, polyoxyethylene alkyl ether, polyoxyethylene oleyl ether, Ether compounds such as polyoxyethylene lauryl ether, polyoxyethylene alkyl ether, and polyoxyalkylene alkyl ether, and polyoxyethylene oleic acid, polyoxyethylene oleic acid ester, polyoxyethylene Examples include ester compounds such as tylene distearate, sorbitan laurate, sonolebitan monostearate, sorbitan monooleate, sorbitan sesquilate, polyoxyethylene monooleate, and polyoxyethylene stearate.
- the ink for inkjet recording according to the embodiment of the present invention desirably contains an acetylene glycol surfactant and Z or acetylene alcohol surfactant as the surfactant.
- an acetylene glycol surfactant and Z or acetylene alcohol surfactant as the surfactant.
- acetylene glycol surfactant used in the present invention include compounds represented by the following formula (6).
- m and n are numbers satisfying 0 ⁇ 111 + 11 ⁇ 50, respectively. Also
- R ⁇ RR 3 and R 4 are each independently an alkyl group (preferably an alkyl group having 6 or less carbon atoms).
- Particularly preferable compounds represented by the above formula (6) include 2, 4, 7, 9-tetramethyl-5-decyne-1,4,7-diol, 3,6-dimethyl-4-octyne-1,3,6-diol, and And 3,5-dimethyl-1, 1-hexyne, 3-ol, and the like.
- a compound represented by the above formula (6) it is commercially available as an acetylene glycol surfactant! It is also possible to use commercially available products, such as Surfynol 104, 82, 465, 485, 104PG50 and TG (trade names are also available from Air Products and Chemicals.
- Orphine STG and Orphin E1010 (trade names, manufactured by Nissin Chemical Co., Ltd.).
- An example of the acetylenanol-based surfactant is Surfynol 61 (trade name, available from Air Products and Chemicals. Inc.).
- acetylene glycol surfactants and / or acetylene alcohol surfactants are preferably in the range of 0.01 to 10% by weight, more preferably, based on the total weight of the ink composition. 0. It is preferable to use it in the range of 1 to 5% by weight.
- a polymer having a crosslinked structure in which pigment particles are derived from a crosslinkable monomer or a polymer having a repeating unit derived from a monomer force represented by the general formula (2) Alternatively, when the material is coated with a capsule wall material mainly composed of a polymer having both in its structure, the polymer has insufficient mechanical plasticity, although it has high mechanical strength, heat resistance, and solvent resistance. Thus, the fixing property of the color material to the recording medium tends to decrease the abrasion resistance. However, when used in combination with fine polymer particles having the above properties, fixing properties and abrasion resistance can be supplemented.
- the polymer fine particles used in the ink composition of the present invention include:
- the ionic group of the same kind as that of the capsule capsule pigment surface of the present invention is present on the surface, the glass transition temperature is 30 ° C. or less, and the volume average particle diameter is 10 to: LOOnm.
- the fine particles have film-forming properties, and when the ink composition of the present invention containing the polymer fine particles is printed on a recording medium such as plain paper or a dedicated ink jet recording medium, the solvent component in the ink composition ( Water is contained in the recording medium, the polymer particles and the capsule pigment particles are close to each other, and the polymer particles encapsulate the capsule pigment particles to form a polymer film.
- the force Pselui pigment in the ink can be more firmly fixed to the surface of the recording medium, so that an image having very excellent abrasion resistance and water resistance can be formed.
- the glass transition temperature of the polymer is preferably 30 ° C or less, as described above, and more preferably 15 ° C or less. It is particularly preferably 10 ° C or less.
- the glass transition temperature of the polymer can be adjusted by appropriately selecting the type and composition ratio of the monomer used.
- the glass transition temperature of the polymer the glass transition temperature obtained by temperature rise measurement using a thermal scanning calorimeter (DSC) was used.
- the polymer fine particles can be stably dispersed without being aggregated even if they coexist in the capsule pigment pigment particles of the invention and the ink composition.
- the particle diameter of the polymer fine particles is 10 to LOOnm in terms of volume average particle diameter. If so, the glossiness and image clarity of the image are improved.
- the specific polymer fine particle is preferably composed of a polymer containing at least 1 to 10% by weight of a repeating unit derived from an unsaturated vinyl monomer having an ionic group. Furthermore, it has a structure crosslinked by a crosslinkable monomer containing 1 to 10% by weight of a repeating unit derived from an unsaturated vinyl monomer having an ionic group and having two or more polymerizable double bonds. It is more preferable that it has a polymer strength containing 0.2 to 4% by weight of a structure derived from this crosslinkable monomer.
- crosslinkable monomers having two or more polymerizable double bonds are copolymerized with other polymerizable monomers to crosslink the polymer chain, and such crosslinking is performed.
- the ink composition makes the nozzle plate surface of the ink jet recording device more difficult to get wet, so it is possible to prevent the ink droplets from flying and improve the ejection stability. be able to.
- the polymer fine particles used in the present invention can be produced by a known emulsion polymerization method.
- polymer fine particles can be obtained by emulsion polymerization of an unsaturated vinyl monomer (unsaturated vinyl monomer) in water containing a polymerization initiator and an emulsifier.
- the unsaturated vinyl monomer can be the same as the above-mentioned hydrophobic monomer.
- the unsaturated vinyl monomer having an ionic group the same ionic monomer as described above can be used.
- a polymerization initiator, an emulsifier, a surfactant, a molecular weight adjusting agent, a neutralizing agent, and the like used in producing the polymer fine particles are used according to a known method.
- the anionic polymerizable surfactant described above is used as an emulsifier, the amount of the emulsifier in the liquid becomes very small because the anionic polymerizable surfactant is copolymerized with the monomer, and the foaming of the liquid is accompanied accordingly.
- the ejection stability of the ink composition is further enhanced.
- the same anionic polymerizable surfactant used for the encapsulated pigment of the present invention is used, the dispersion stability and the storage stability are particularly excellent.
- the polymer fine particles can be used as fine particle powder, but preferably in the form of a polymer emulsion in which the polymer fine particles are dispersed in an aqueous medium. Mix with other ingredients contained in the ink composition It is preferable.
- the amount of polymer fine particles contained in the ink composition is preferably about 0.01 to 10% by weight, more preferably about 0.01 to 5% by weight, based on the total weight of the ink composition.
- the ink composition of the present invention can contain a pH adjuster.
- a pH adjuster When the pigment particle or polymer particle surface has a ionic group, it is preferable to adjust the pH of the ink composition to 7 to 11, more preferably 8 to 9. It is preferable to use a composite.
- the pigment particle or polymer particle surface has a cationic group it is preferable to adjust the pH of the ink composition to 5 to 7, more preferably 6 to 7. It is preferable to use a compound.
- pH adjusters include sodium hydroxide, lithium hydroxide, lithium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, lithium carbonate, sodium phosphate, phosphorus Potassium phosphate, lithium phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, sodium oxalate, potassium oxalate, lithium oxalate, sodium borate, sodium tetraborate, potassium hydrogen phthalate, and hydrogen tartrate Al-metal salts such as potassium; ammonia; and methylamine, ethylamine, jetylamine, trimethylamine, triethylamine, tris (hydroxymethyl) aminomethane hydrochloride, triethanolamine, diethanolamine, jetylethanolamine, triethylamine Isopropenolamine And amines such as butyldiethanolamine, morpholine, and propanolamine.
- the addition of a hydroxyl-alkali compound or an amine alcohol to the ink composition can improve the dispersion stability of pigment particles having a ionic group in the ink.
- At least one selected from group forces such as urea, thiourea, and ethylene urea can be added to the ink composition of the present invention.
- one or more compounds (penetrating agent) selected from the group consisting of diethylene glycol monobutyl ether, triethylene glycol monomono butino ether, and 1,2-alkyldiol having 4 to 10 carbon atoms,
- one or more compounds (penetrating agent) selected from the group consisting of diethylene glycol monobutyl ether, triethylene glycol monomono butino ether, and 1,2-alkyldiol having 4 to 10 carbon atoms,
- the addition amount when the diethylene glycol monobutyl ether and Z or triethylene glycol monobutyl ether of (2) above are used as the penetrant is based on the total weight of the ink composition. 10% by weight or less is more preferable, 0.5 to 5% by weight is more preferable! / ,.
- diethylene glycol monobutyl ether and / or triethylene glycol monobutyl ether to the ink composition, the penetrability of the ink composition into the recording medium can be improved, and the print quality can be improved.
- Diethylene glycol monobutyl ether and Z or triethylene glycol monobutyl ether also have the effect of improving the solubility of acetylene glycol surfactants.
- the amount of additive when the above-mentioned (2) 1,2-alkyldiol having 4 to 10 carbon atoms is used as the penetrant is 15% of the total weight of the ink composition. It is preferable that it is below wt%.
- a 1,2 alkyl diol having 3 or less carbon atoms is used, sufficient penetration of the ink composition into the recording medium cannot be obtained, and 1,2-alkyl diols having more than 15 carbon atoms are difficult to dissolve in water. This is not preferable. If the amount of 1,2 alkyl diol in the ink composition exceeds 15% by weight, the viscosity of the ink composition tends to increase, such being undesirable.
- 1,2-alkyldiol specifically, it is preferable to use 1,2-pentanediol or 1,2-hexanediol. Either one can be used alone, or both can be used in combination. .
- 1,2-Pentanediol is preferably added in the range of 3 to 15% by weight based on the total weight of the ink composition. By adding 3% by weight or more of 1,2 pentanediol to the ink composition, an ink composition having good permeability can be obtained.
- 1,2-Hexanediol is preferably added in the range of 0.5 to 10% by weight with respect to the total weight of the ink composition, and an ink composition having good permeability can be obtained in the above range. .
- the ink composition of each of the above embodiments is used in an ink jet recording method
- a solid wetting agent is used in the ink so that the ink jet nozzle is not easily clogged (improved clogging reliability).
- the content is preferably 3 to 20% by weight based on the total weight of the composition.
- the additive of the solid humectant is not limited to the above embodiments, and can be added to the ink composition using the capsule facet of the present invention.
- the solid wetting agent refers to a water-soluble substance that is solid at room temperature (25 ° C) and has a water retention function.
- Preferred solid wetting agents are sugars, sugar alcohols, hyaluronate, trimethylol propane, and 1,2,6 hexanetriol.
- sugars include monosaccharides, disaccharides, oligosaccharides (including trisaccharides and tetrasaccharides) and polysaccharides, preferably dalcoose, mannose, fructose, ribose, xylose, arabinose, galactose, aldone. Acid, Glucitol, Sorbit, Maltose, Cellobiose, Ratatoose, Sucrose, Tre Nose, loin, maltotriose and the like.
- saccharide means saccharide in a broad sense, and is used to include substances widely present in nature such as alginic acid, a-cyclodextrin, and cellulose.
- Acid sucrose eg, aldonic acid, uronic acid, etc.
- amino acid thiosaccharide, etc.
- sugar alcohols include maltitol, sorbitol, and xylitol.
- hyaluronate a commercially available sodium hyaluronate 1% aqueous solution (molecular weight 350,000) can be used.
- solid wetting agents are trimethylolpropane, 1,2,6-hexatriol, sugars, and sugar alcohols.
- One or more solid wetting agents can be added to the ink composition of the present invention.
- the ink composition By using a solid wetting agent in the ink composition, it is possible to suppress water evaporation of the ink by its water retention function, so that the viscosity of the ink composition increases around the ink jet nozzle of the ink jet printer. In addition, the formation of a film due to moisture evaporation of the ink composition also occurs, so that nozzle clogging is less likely to occur. In addition, since the solid wetting agent is chemically stable, the quality of the ink composition can be maintained over a long period of time without being decomposed in the ink composition.
- the ink composition can be stably ejected from the ink jet nozzle where the ink composition does not wet the nozzle plate.
- the above-mentioned effect is particularly excellent when a compound selected from trimethylolpropane, 1,2,6-hexanetriol, saccharides, and sugar alcohols is used as the solid moisturizing agent.
- the amount of the solid wetting agent added to the ink composition of the present invention is preferably 3 to 20% by weight based on the total weight of the total ink composition. I prefer to be%.
- the combination is preferably one or more selected from sugars, sugar alcohols, and hyaluronate salts, trimethylolpropane, and 1, 2, 6— Hexanetriol power A combination with one or more selected.
- a solid wetting agent is added to the ink composition in this combination, an increase in the viscosity of the ink composition can be suppressed.
- Solid moisture contained in the ink composition By making the amount of the lubricant 3% by weight or more, an effect of preventing clogging of the inkjet nozzle is obtained, and by making the amount of the solid wetting agent contained in the ink composition 20% by weight or less, the ink composition Since the ink jet nozzle force can be stably ejected, an ink composition having a sufficiently low viscosity can be obtained.
- the acetylene glycol surfactant (3) and Z or acetylene alcohol surfactant (3) are added to the ink composition.
- the strength is preferably 0.01 to LO weight% based on the total weight of the ink composition S, and particularly preferably 0.1 to 5 weight%.
- the ink compositions shown in the above embodiment examples are particularly excellent in the dispersion stability of the pigment and the ejection stability of the nozzle force of the ink jet head when used in the ink jet recording method. Stable printing with no clogging is possible.
- this ink composition has good dryability of the ink after printing when printed on a recording medium such as plain paper, recycled paper, and coated paper, and using this ink composition causes bleeding. A high-quality image having a high printing density and excellent color developability can be obtained.
- a dispersant such as a surfactant or a polymer dispersant, the acetylene glycol surfactant and the Z or acetylene alcohol surfactant, diethylene glycol monobutyl ether, etc.
- Ink compositions that use penetrants can easily dissipate the pigment from the surface of the pigment due to the strong shearing force generated when ejected through thin inkjet nozzles, resulting in deterioration of dispersibility. There is a tendency to become unstable.
- the ink composition obtained according to the present invention does not show such a phenomenon at all, and can discharge the ink composition stably for a long period of time through an inkjet nozzle.
- the encapsulated pigment particles obtained by the present invention have good solvent resistance, the above-mentioned penetrant may cause the pigment particle surface force, the polymer of the capsule wall material to be detached, or the polymer to swell.
- the pigment particles can be stably dispersed in the ink composition over a long period of time, and can be maintained in the same state.
- the ink composition using the capsule pigment obtained by the present invention has the advantages that it can be easily reduced in viscosity and can contain more pigment particles, and can use plain paper or recycled paper as a printing medium. Even in such a case, a sufficiently high printing density can be obtained.
- the encapsulated pigment obtained by the present invention has a true spherical shape, the fluidity of the ink composition using this pigment tends to be -ut-an. This is thought to be because the ionic groups on the surface of the capsule cocoon pigment are regularly and densely oriented toward the aqueous solvent side, and an effective electrostatic repulsive force is generated between the capsule ⁇ ⁇ pigments. it is conceivable that. Therefore, the ink composition using the force pseudo pigment obtained by the present invention in comparison with the conventional capsule pigment can improve the ejection stability of the ink composition from the ink jet head by the ink jet recording method. Excellent.
- the dispersibility and dispersion stability of the pigment are excellent (high dispersibility), so that the concentration of the colorant is increased for ink jet recording.
- An ink composition can be produced, and an image having a high printing density can be obtained by using the ink thread and composition.
- the ink composition obtained by the present invention is particularly preferred as an ink composition for use in an ink jet recording method, but its application is not limited! /.
- the ink composition prepared using the microcapsule pigment of the present invention preferably further comprises a compound represented by the following formula (1). [0175] [Chemical 36]
- R and R each independently represents an alkyl group having 1 to 10 carbon atoms, m and n are
- the number of repeating units, m + n is 0-10 on average.
- R and R each independently have 1 carbon atom.
- m and n are each the number of repeating units, and m + n is 0 to 10 on average 1S Less blurring and high color development on plain paper, on special paper
- R The carbon number of + R is preferably 5 or more and 15 or less, and m + n is preferably 0-7.
- the content of the compound in the ink composition comprising the compound of the above formula (1) is more preferably 0.1 to 20% by weight with respect to the total weight of the ink composition. Is 0.3 to LO weight percent. In order to obtain particularly good gloss and image clarity, 0.5 to LO weight% is preferred.
- ionic polymerizable surfactant Aqualon KH-10 (Daiichi Kogyo Seiyaku) used in this example has the following formula:
- a cationic polymerizable surfactant Aqualon KH-10 (Daiichi Kogyo Seiyaku) was dissolved in 850 g of ion-exchanged water, and 100 g of isoindolinone pigment (C.I. Pigment Red 122) was added thereto and mixed.
- This mixed solution was subjected to a dispersion treatment for 5 hours under the conditions of a bead filling rate of 70% and a rotation speed of 5,000 rpm using a disperser Eiger Motor Mill M250 (trade name, manufactured by Eiger Japan).
- This mixed solution was put into a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a temperature controller, a nitrogen introduction tube, and an ultrasonic generator, and irradiated with ultrasonic waves for 30 minutes.
- a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a temperature controller, a nitrogen introduction tube, and an ultrasonic generator, and irradiated with ultrasonic waves for 30 minutes.
- an aqueous solution prepared by dissolving 1.5 g of potassium persulfate, which is a polymerization initiator, in 100 g of ion-exchanged water was added dropwise, and while introducing nitrogen into the reaction vessel, 80 °
- the polymerization reaction was carried out at C for 6 hours.
- PH was adjusted to 8 with an aqueous solution of ImolZl potassium hydroxide and filtered through a membrane filter having a pore size of Lm to remove coarse particles.
- ultrafiltration by the crossflow method is performed using an ultrafiltration device, and the mixture is concentrated and solidified.
- a capsule dispersion pigment dispersion of the present invention was obtained with a concentration of 15% by weight.
- the volume average particle size of the capsule capsule pigment in the dispersion was measured with a laser Doppler type particle size distribution analyzer Microtrac UPA150 (trade name) manufactured by Leeds & North Kopp Co. As a result, it was 120 nm.
- the obtained dispersion was dried at room temperature to obtain a solid, which was subjected to thermal analysis using a thermal scanning calorimeter (Differential Scanning Calorimeter: DSC) DSC200 (trade name, manufactured by Seiko Electronics Co., Ltd.). As a result, the glass transition temperature of the coating polymer of capsule pigment particles was determined.
- DSC Thermal Scanning Calorimeter
- a cationic polymerizable surfactant 50 g of dimethylaminoethyloctyl chloride methacrylate was dissolved in 850 g of ion-exchanged water, and isoindolinone pigment (C.I. Pigment Red 122) lOOg was added thereto and mixed.
- This mixed solution was subjected to a dispersion treatment for 5 hours under the conditions of a bead filling rate of 70% and a rotational speed of 5,000 rpm using a disperser Eiger Motor Mill Model M250 (trade name, manufactured by Eiger Japan).
- the mixture was put into a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a temperature controller, a nitrogen inlet tube, and an ultrasonic generator.
- a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a temperature controller, a nitrogen inlet tube, and an ultrasonic generator.
- an aqueous solution prepared by dissolving 4.6 g of potassium persulfate as a polymerization initiator in 200 g of ion-exchanged water was added dropwise, and while introducing nitrogen into the reaction vessel, The polymerization reaction was carried out at C for 6 hours.
- PH was adjusted to 8 with an aqueous solution of ImolZl potassium hydroxide and filtered through a membrane filter having a pore size of Lm to remove coarse particles.
- dimethylaminoethyl methyl methacrylate salt as a cationic water-soluble monomer was added and mixed, followed by irradiation with ultrasonic waves for 30 minutes.
- 12.0 g of styrene and 18.0 g of n-butylmetatalylate were added to and mixed with the resulting mixture, and then 10.0 g of the cationic polymerizable surfactant methacrylic acid.
- Dimethylaminoethyloctyl chloride salt was added and mixed, and again irradiated with ultrasonic waves for 30 minutes.
- the mixture was put into a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a temperature controller, a nitrogen inlet tube, and an ultrasonic generator. After the reactor internal temperature was raised to 80 ° C, an aqueous solution prepared by dissolving 1.5 g of potassium persulfate, which is a polymerization initiator, in 100 g of ion-exchanged water was added dropwise, and while introducing nitrogen into the reaction vessel, 80 ° The polymerization reaction was carried out at C for 6 hours.
- PH was adjusted to 8 with an aqueous solution of ImolZl potassium hydroxide and filtered through a membrane filter having a pore size of Lm to remove coarse particles.
- ultrafiltration by the crossflow method is performed using an ultrafiltration device, and the mixture is concentrated and solidified.
- a capsule dispersion pigment dispersion of the present invention was obtained with a concentration of 15% by weight.
- the volume average particle size of the capsule capsule pigment in the dispersion was measured with a laser Doppler type particle size distribution meter Microtrac UPA150 (trade name) manufactured by Leeds & North Kopp Co. As a result, it was 180 nm.
- the obtained dispersion is dried at room temperature to obtain a solid, and this solid is heated using a thermal scanning calorimeter (Differential Scanning Calorimeter: DSC) DSC200 (trade name, manufactured by Seiko Electronics Co., Ltd.).
- DSC Thermal Scanning Calorimeter
- the glass transition temperature of the coating polymer of capsule pigment particles was determined to be 46 ° C.
- a cationic polymerizable surfactant 50 g of dimethylaminoethyloctyl chloride methacrylate was dissolved in 850 g of ion-exchanged water, and lOOg of C. LPigment Yellow 73 was added thereto and mixed. This mixed solution was subjected to dispersion treatment for 5 hours under the conditions of a bead filling rate of 70% and a rotation speed of 5,000 rpm using a disperser Eiger Motor Mill Model M250 (trade name, manufactured by Eiger Japan).
- the mixture was put into a reaction vessel equipped with a stirrer, reflux condenser, dropping funnel, temperature controller, nitrogen inlet tube, and ultrasonic generator, and the reaction volume was applied while irradiating ultrasonic waves for 30 minutes.
- aqueous solution prepared by dissolving 3.6 g of potassium persulfate as a polymerization initiator in 200 g of ion-exchanged water was dropped, and while introducing nitrogen into the reaction vessel, 80 °
- the polymerization reaction was carried out at C for 6 hours.
- PH was adjusted to 8 with an aqueous solution of ImolZl potassium hydroxide and filtered through a membrane filter having a pore size of Lm to remove coarse particles.
- ultrafiltration by the crossflow method is performed using an ultrafiltration device, and the mixture is concentrated and solidified.
- a capsule dispersion pigment dispersion of the present invention was obtained with a concentration of 15% by weight.
- the volume average particle diameter of the capsule capsule pigment in the dispersion was measured with a laser Doppler type particle size distribution analyzer Microtrac UPA150 (trade name) manufactured by Leeds & North Kopp Co. As a result, it was 120 nm.
- the obtained dispersion is dried at room temperature to obtain a solid, and this solid is subjected to thermal analysis using a thermal scanning calorimeter (differential scanning calorimeter: DSC) DSC200 (trade name, manufactured by Seiko Electronics Co., Ltd.).
- DSC differential scanning calorimeter
- DSC200 trade name, manufactured by Seiko Electronics Co., Ltd.
- a cationic polymerizable surfactant Aqualon KH-10 (Daiichi Kogyo Seiyaku) was dissolved in 850 g of ion-exchanged water, and 100 g of isoindolinone pigment (C.I. Pigment Red 122) was added thereto and mixed.
- This mixed solution was subjected to a dispersion treatment for 5 hours using a disperser Eiger Motor Mill Model M250 (trade name, manufactured by Eiger Japan Co., Ltd.) under the conditions of a bead filling rate of 70% and a rotation speed of 5, OOOOrpm.
- This mixed solution was put into a reaction vessel equipped with a stirrer, reflux condenser, dropping funnel, temperature controller, nitrogen inlet tube, and ultrasonic generator, and the reaction volume was irradiated while irradiating ultrasonic waves for 30 minutes.
- an aqueous solution prepared by dissolving 1.5 g of potassium persulfate, which is a polymerization initiator, in 100 g of ion-exchanged water was added dropwise, and while introducing nitrogen into the reaction vessel, 80 ° The polymerization reaction was carried out at C for 6 hours.
- PH was adjusted to 8 with an aqueous solution of ImolZl potassium hydroxide and filtered through a membrane filter having a pore size of Lm to remove coarse particles.
- ultrafiltration by the crossflow method is performed using an ultrafiltration device, and the mixture is concentrated and solidified.
- a capsule dispersion pigment dispersion of the present invention was obtained with a concentration of 15% by weight.
- the volume average particle diameter of the capsule capsule pigment in the dispersion was measured with a laser Doppler type particle size distribution analyzer Microtrac UPA150 (trade name) manufactured by Leeds & North Kopp Co. As a result, it was 120 nm.
- the obtained dispersion is dried at room temperature to obtain a solid, and this solid is subjected to thermal analysis using a thermal scanning calorimeter (differential scanning calorimeter: DSC) DSC200 (trade name, manufactured by Seiko Electronics Co., Ltd.).
- DSC differential scanning calorimeter
- DSC200 trade name, manufactured by Seiko Electronics Co., Ltd.
- a cationic polymerizable surfactant 50 g of dimethylaminoethyl dodecyl chloride methacrylate salt was dissolved in 850 g of ion-exchanged water, and lOOg of C. LPigment Yellow 73 was added thereto and mixed. This mixed solution was subjected to dispersion treatment for 5 hours under the conditions of a bead filling rate of 70% and a rotation speed of 5,000 rpm using a disperser Eiger Motor Mill Model M250 (trade name, manufactured by Eiger Japan).
- This mixed solution was put into a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a temperature controller, a nitrogen introduction tube, and an ultrasonic generator, and the reaction vessel was irradiated with ultrasonic waves for 30 minutes.
- aqueous solution prepared by dissolving 3.6 g of potassium persulfate as a polymerization initiator in 200 g of ion-exchanged water was dropped, and while introducing nitrogen into the reaction vessel, 80 °
- the polymerization reaction was carried out at C for 6 hours.
- PH was adjusted to 8 with an aqueous solution of ImolZl potassium hydroxide and filtered through a membrane filter having a pore size of Lm to remove coarse particles.
- ultrafiltration by the crossflow method is performed using an ultrafiltration device, and the mixture is concentrated and solidified.
- a capsule dispersion pigment dispersion of the present invention was obtained with a concentration of 15% by weight.
- the volume average particle diameter of the capsule capsule pigment in the dispersion was measured with a laser Doppler type particle size distribution analyzer Microtrac UPA150 (trade name) manufactured by Leeds & North Kopp Co. As a result, it was 120 nm.
- the obtained dispersion is dried at room temperature to obtain a solid, and this solid is subjected to thermal analysis using a thermal scanning calorimeter (differential scanning calorimeter: DSC) DSC200 (trade name, manufactured by Seiko Electronics Co., Ltd.).
- DSC differential scanning calorimeter
- DSC200 trade name, manufactured by Seiko Electronics Co., Ltd.
- Aon polymerizable surfactant Aqualon KH-10 (Daiichi Kogyo Seiyaku Co., Ltd.) 50 g was dissolved in ion-exchanged water 850 g, and isoindolinone pigment (CI pigment red 12 2) 100 g was added thereto. And mixed. This mixed solution was subjected to a dispersion treatment for 5 hours under the conditions of a bead filling rate of 70% and a rotation speed of 5,000 rpm using a disperser Eiger Motor Mill M250 (trade name, manufactured by Eiger Japan). After the dispersion treatment, ultrafiltration was performed using an ultrafiltration device until the AQUALON KH-10Z pigment was 25Z100 (this value was also obtained for solid concentration and pigment concentration power). The solid content was adjusted to 15% by weight.
- dimethylaminoethyl methyl methacrylate salt as a cationic water-soluble monomer was added and mixed, followed by irradiation with ultrasonic waves for 30 minutes.
- 30 g of benzyl metatalylate, 10 g of isobutyl metatalylate, and 10 g of lauryl metatalylate were added to and mixed with the resulting mixture, and then dissolved in 100 g of ion-exchanged water.
- 25 g of the ionic polymerizable surfactant Aqualon KH-10 was added and mixed, and again irradiated with ultrasonic waves for 30 minutes.
- This mixed solution was put into a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a temperature controller, a nitrogen introduction tube, and an ultrasonic generator, and irradiated with ultrasonic waves for 30 minutes.
- a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a temperature controller, a nitrogen introduction tube, and an ultrasonic generator, and irradiated with ultrasonic waves for 30 minutes.
- an aqueous solution prepared by dissolving 2 g of potassium persulfate as a polymerization initiator in 100 g of ion-exchanged water was dropped, and nitrogen was introduced into the reaction vessel at 80 ° C.
- the polymerization reaction was performed for 6 hours.
- PH was adjusted to 8 with an aqueous solution of ImolZl potassium hydroxide and filtered through a membrane filter having a pore size of L m to remove coarse particles. Then limit Using an external filtration device, ultrafiltration by the cross flow method was performed and concentrated to obtain a dispersion of capsule capsule pigment of the present invention with a solid content concentration of 15% by weight.
- the volume average particle size of the capsule capsule pigment in the dispersion was measured with a laser Doppler particle size distribution analyzer Microtrac UPA150 (trade name) manufactured by Leeds & Northrop Co., Ltd., and found to be 200 nm.
- the obtained dispersion is dried at room temperature to obtain a solid, and this solid is subjected to thermal analysis using a thermal scanning calorimeter (differential scanning calorimeter: DSC) DSC200 (trade name, manufactured by Seiko Electronics Co., Ltd.).
- DSC differential scanning calorimeter
- the glass transition temperature of the coating polymer of the capsule pigment particles was determined and found to be 33 ° C.
- Adekaria Soap SR-10 (Asahi Denka Kogyo Co., Ltd.) 50g is dissolved in 850g of ion-exchanged water, and isoindolinone pigment (CI pigment red 122) lOOg is added to this. Mixed. This mixed solution was subjected to dispersion treatment for 5 hours under the conditions of a bead filling rate of 70% and a rotation speed of 5,000 rpm using a disperser Eiger Motor Mill Model M250 (trade name, manufactured by Eiger Japan). After the dispersion treatment, ultrafiltration was performed using an ultrafiltration device until the Adekari Soap SR-10Z pigment was 25Z100 (this value was also obtained for solid concentration and pigment concentration power). The solid content concentration was adjusted to 15% by weight.
- PH was adjusted to 8 with ImolZl aqueous potassium hydroxide solution
- coarse particles were removed by filtration through a membrane filter having a pore size of L m.
- ultrafiltration by a cross flow method was performed using an ultrafiltration apparatus, and the mixture was concentrated to obtain a dispersion of capsule capsule pigment of the present invention with a solid content concentration of 15% by weight.
- the volume average particle size of the capsule capsule pigment in the dispersion was measured with a laser Doppler type particle size distribution analyzer Microtrac UPA150 (trade name) manufactured by Leeds & North Kopp Co. As a result, it was 160 nm.
- the obtained dispersion is dried at room temperature to obtain a solid, and this solid is subjected to thermal analysis using a thermal scanning calorimeter (differential scanning calorimeter: DSC) DSC200 (trade name, manufactured by Seiko Electronics Co., Ltd.).
- DSC differential scanning calorimeter
- DSC200 trade name, manufactured by Seiko Electronics Co., Ltd.
- AEONINOL JS—2 manufactured by Sanyo Kasei Kogyo Co., Ltd. 50 g of an ion-polymerizable surfactant is dissolved in 850 g of ion-exchanged water, and isoindolinone pigment (CI pigment red 12 2) lOOg is added thereto. Mixed. This mixed solution was subjected to a dispersion treatment for 5 hours under the conditions of a bead filling rate of 70% and a rotation speed of 5,000 rpm using a disperser Eiger Motor Mill M250 (trade name, manufactured by Eiger Japan). After the dispersion treatment, ultrafiltration was performed using an ultrafiltration apparatus by crossflow method, and Eleminol JS-2 / Pigment was 25/100 (this value was also obtained for solid content concentration and pigment concentration power). The solid content concentration was adjusted to 15% by weight.
- the mixture was put into a reaction vessel equipped with a stirrer, reflux condenser, dropping funnel, temperature controller, nitrogen inlet tube, and ultrasonic generator, and the reaction volume was irradiated while irradiating ultrasonic waves for 30 minutes.
- aqueous solution prepared by dissolving 1.8 g of potassium persulfate, a polymerization initiator, in 100 g of ion-exchanged water was added dropwise, and nitrogen was introduced into the reaction vessel.
- the polymerization reaction was performed for 6 hours.
- PH was adjusted to 8 with an aqueous solution of ImolZl potassium hydroxide and filtered through a membrane filter having a pore size of Lm to remove coarse particles.
- ultrafiltration by a cross flow method was performed using an ultrafiltration apparatus, and the mixture was concentrated to obtain a dispersion of capsule capsule pigment of the present invention with a solid content concentration of 15% by weight.
- the volume average particle size of the capsule capsule pigment in the dispersion was measured with a laser Doppler type particle size distribution analyzer Microtrac UPA150 (trade name) manufactured by Leeds & North Kopp Co. As a result, it was 160 nm.
- the obtained dispersion is dried at room temperature to obtain a solid, and this solid is subjected to thermal analysis using a thermal scanning calorimeter (differential scanning calorimeter: DSC) DSC200 (trade name, manufactured by Seiko Electronics Co., Ltd.).
- DSC differential scanning calorimeter
- DSC200 trade name, manufactured by Seiko Electronics Co., Ltd.
- Adekaria Soap SE—ION manufactured by Asahi Denka Kogyo Co., Ltd. 50 g was dissolved in 850 g of ion-exchanged water, and isoindolinone pigment (CI pigment red 122) lOOg was added to this solution. Mixed. This mixed solution was subjected to dispersion treatment for 5 hours under the conditions of a bead filling rate of 70% and a rotation speed of 5, OOOrpm, using a disperser Eiger Motor Mill M250 type (trade name, manufactured by Eiger Japan). Cross-flow ultrafiltration is performed using an ultrafiltration device, and the ADEKA rear soap SE-10NZ pigment is processed to 25Z100 (this value is also obtained for solid concentration and pigment concentration power). The partial concentration was adjusted to 15% by weight.
- the mixed solution was put into a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a temperature controller, a nitrogen introduction tube, and an ultrasonic generator, and irradiated with ultrasonic waves for 30 minutes. After raising the internal temperature of the vessel to 80 ° C, ionize the polymerization initiator potassium persulfate 1.Og. An aqueous solution dissolved in 10 g of water to be exchanged was dropped, and a polymerization reaction was carried out at 80 ° C. for 6 hours while introducing nitrogen into the reaction vessel.
- PH was adjusted to 8 with an aqueous solution of ImolZl potassium hydroxide and filtered through a membrane filter having a pore size of Lm to remove coarse particles.
- ultrafiltration by a cross flow method was performed using an ultrafiltration apparatus, and the mixture was concentrated to obtain a dispersion of capsule capsule pigment of the present invention with a solid content concentration of 15% by weight.
- the volume average particle size of the capsule capsule pigment in the dispersion was measured with a laser Doppler type particle size distribution analyzer Microtrac UPA150 (trade name) manufactured by Leeds & North Kopp Co. As a result, it was 160 nm.
- the obtained dispersion is dried at room temperature to obtain a solid, and this solid is subjected to thermal analysis using a thermal scanning calorimeter (differential scanning calorimeter: DSC) DSC200 (trade name, manufactured by Seiko Electronics Co., Ltd.).
- DSC differential scanning calorimeter
- DSC200 trade name, manufactured by Seiko Electronics Co., Ltd.
- AEONINOL RS-30 manufactured by Sanyo Kasei Kogyo Co., Ltd. 50 g of the ion-on polymerizable surfactant was dissolved in 850 g of ion-exchanged water, and then lOOg of isoindolinone pigment (CI pigment red 122) was added and mixed. .
- This mixed solution was subjected to dispersion treatment for 5 hours under the conditions of a bead filling rate of 70% and a rotation speed of 5,000 rpm using a disperser Eiger Motor Mill Model M250 (trade name, manufactured by Eiger Japan). After the dispersion treatment, ultrafiltration was carried out using an ultrafiltration device, and processing was carried out until Eleminol RS-30Z pigment was 25Z100 (this value was also obtained for solid concentration and pigment concentration power). The solid content concentration was adjusted to 15% by weight.
- This mixture was put into a reaction vessel equipped with a stirrer, reflux condenser, dropping funnel, temperature controller, nitrogen inlet tube, and ultrasonic generator, and the reaction volume was applied while irradiating with ultrasonic waves for 30 minutes.
- aqueous solution prepared by dissolving 1.5 g of potassium persulfate, which is a polymerization initiator, in lOOg of ion-exchanged water was dropped, and while introducing nitrogen into the reaction vessel, 80 ° C
- the polymerization reaction was carried out at C for 6 hours.
- PH was adjusted to 8 with an aqueous solution of ImolZl potassium hydroxide and filtered through a membrane filter having a pore size of Lm to remove coarse particles.
- ultrafiltration by a cross flow method was performed using an ultrafiltration apparatus, and the mixture was concentrated to obtain a dispersion of capsule capsule pigment of the present invention with a solid content concentration of 15% by weight.
- the volume average particle size of the capsule capsule pigment in the dispersion was measured with a laser Doppler type particle size distribution analyzer Microtrac UPA150 (trade name) manufactured by Leeds & North Kopp Co. As a result, it was 160 nm.
- the obtained dispersion is dried at room temperature to obtain a solid, and this solid is subjected to thermal analysis using a thermal scanning calorimeter (differential scanning calorimeter: DSC) DSC200 (trade name, manufactured by Seiko Electronics Co., Ltd.).
- DSC differential scanning calorimeter
- DSC200 trade name, manufactured by Seiko Electronics Co., Ltd.
- Anon polymerizable surfactant Antox MS-60 (Nippon Emulsifier Co., Ltd.) 50 g was dissolved in 850 g of ion-exchanged water, and lOOg of C ⁇ Pigment Blue 15: 4 was added and mixed. This mixture was subjected to a dispersion treatment for 5 hours using a disperser Eiger Motor Mill Model M250 (trade name, manufactured by Eiger Japan) under conditions of a bead filling rate of 70% and a rotation speed of 5,000 rpm. After the dispersion treatment, ultrafiltration was carried out using an ultrafiltration device, and processing was performed until the Antox MS-60Z pigment was 25Z100 (this value was obtained from the solid concentration and the pigment concentration). The solid content concentration was adjusted to 15% by weight.
- This mixed solution was put into a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a temperature controller, a nitrogen introduction tube, and an ultrasonic generator. Raise the internal temperature of the vessel to 80 ° C, then ionize 1.5 g of potassium persulfate as the polymerization initiator. An aqueous solution dissolved in 10 g of water to be exchanged was dropped, and a polymerization reaction was carried out at 80 ° C. for 6 hours while introducing nitrogen into the reaction vessel. After the polymerization, PH was adjusted to 8 with an aqueous solution of ImolZl potassium hydroxide and filtered through a membrane filter having a pore size of Lm to remove coarse particles.
- This mixed solution was adjusted to pH 9.0 with lmol ⁇ potassium hydroxide aqueous solution.
- the mixture was put into a reaction vessel equipped with a stirrer, reflux condenser, dropping funnel, temperature controller, and nitrogen introduction tube, and the internal temperature of the reaction vessel was raised to 80 ° C, followed by polymerization.
- An aqueous solution prepared by dissolving 0.75 g of potassium persulfate as an agent in lOOg of ion-exchanged water was dropped, and a polymerization reaction was carried out at 80 ° C. for 5 hours while introducing nitrogen into the reaction vessel.
- the pH was adjusted to 8 with an aqueous solution of ImolZl sodium hydroxide and then filtered through a membrane filter having a pore size of 1 ⁇ m to remove coarse particles.
- ultrafiltration was performed by a crossflow method using an ultrafiltration apparatus, and the resultant was concentrated to obtain a dispersion of capsule-type pigment MCP 17 "of the present invention with a solid content concentration of 15% by weight.
- the volume average particle diameter of the obtained dispersion was measured with a laser Doppler particle size distribution analyzer Microtrac UPA150 (trade name) manufactured by Leeds & Northrop Co., Ltd., and found to be 145 nm.
- the glass transition temperature was found to be 18 ° C. when the types of monomer components constituting the polymer and their ratio force were also determined by the Fox equation.
- This mixture was put into a reaction vessel equipped with a stirrer, reflux condenser, dropping funnel, temperature controller, and nitrogen introduction tube, and the internal temperature of the reaction vessel was raised to 80 ° C, followed by polymerization.
- An aqueous solution obtained by dissolving 0.23 g of potassium persulfate as an agent in lOOg of ion-exchanged water was dropped, and a polymerization reaction was carried out at 80 ° C. for 5 hours while introducing nitrogen into the reaction vessel.
- the pH was adjusted to 8 with an aqueous solution of ImolZl sodium hydroxide and then filtered through a membrane filter having a pore size of 1 ⁇ m to remove coarse particles.
- This mixture was put into a reaction vessel equipped with a stirrer, reflux condenser, dropping funnel, temperature controller, and nitrogen inlet tube, and the internal temperature of the reaction vessel was raised to 80 ° C, and then polymerization was started.
- An aqueous solution obtained by dissolving 0.23 g of potassium persulfate as an agent in lOOg of ion-exchanged water was dropped, and a polymerization reaction was carried out at 80 ° C. for 5 hours while introducing nitrogen into the reaction vessel.
- the pH was adjusted to 8 with an aqueous solution of ImolZl sodium hydroxide and then filtered through a membrane filter having a pore size of 1 ⁇ m to remove coarse particles.
- ionic surfactant sodium dodecylbenzenesulfonate 50 g was dissolved in 850 g of ion-exchanged water, and 100 g of C ⁇ Pigment Blue 15: 4 having a volume average particle diameter of 60 nm was mixed and mixed therewith.
- This mixture was dispersed for 5 hours using a disperser Eiger Motor Mill Model M250 (manufactured by Eiger Japan) under conditions of a bead filling rate of 70% and a rotation speed of 5,000 rpm.
- ultrafiltration was performed using an ultrafiltration apparatus by a cross flow method, and the mixture was processed until foaming of the permeate disappeared, and the solid content concentration was adjusted to 10% by weight.
- the obtained pigment dispersion was subjected to thermogravimetry, and the weight loss value was determined.
- the adsorption amount of the surfactant sodium dodecylbenzenesulfonate was determined.
- the sodium dodecylbenzenesulfonate Z pigment was 25Z100. .
- This mixture was put into a reaction vessel equipped with a stirrer, reflux condenser, dropping funnel, temperature controller, and nitrogen introduction tube, and the internal temperature of the reaction vessel was raised to 80 ° C, followed by polymerization.
- An aqueous solution obtained by dissolving 0.23 g of potassium persulfate as an agent in lOOg of ion-exchanged water was dropped, and a polymerization reaction was carried out at 80 ° C. for 5 hours while introducing nitrogen into the reaction vessel.
- the pH was adjusted to 8 with an aqueous solution of ImolZl sodium hydroxide and then filtered through a membrane filter having a pore size of 1 ⁇ m to remove coarse particles.
- the dispersion treatment After the dispersion treatment, ultrafiltration was performed using an ultrafiltration apparatus by a cross flow method, and the mixture was treated until the permeated liquid disappeared to adjust the solid content concentration to 10% by weight.
- the obtained pigment dispersion was subjected to a flask combustion method to determine the sulfur content, and the adsorbed amount of the value-on surfactant sodium dodecylbenzenesulfonate was determined. As a result, the sodium dodecylbenzenesulfonate Z pigment was obtained. 13Z 100.
- This mixture was put into a reaction vessel equipped with a stirrer, reflux condenser, dropping funnel, temperature controller, and nitrogen introduction tube, and the internal temperature of the reaction vessel was raised to 80 ° C, and then polymerization was started.
- An aqueous solution prepared by dissolving 0.23 g of potassium persulfate as an agent in 100 g of ion-exchanged water was dropped, and a polymerization reaction was performed at 80 ° C. for 5 hours while introducing nitrogen into the reaction vessel.
- the pH was adjusted to 8 with an aqueous solution of ImolZl sodium hydroxide and then filtered through a membrane filter having a pore size of 1 ⁇ m to remove coarse particles.
- ultrafiltration was carried out by an ultrafiltration apparatus using a cross-flow method, followed by concentration to obtain a dispersion of capsule-type pigment MCP21 "of the present invention with a solid content concentration of 15% by weight.
- the volume average particle size of the obtained dispersion was measured with a laser Doppler particle size distribution analyzer Microtrac UPA150 (trade name) manufactured by Leeds & Northrop Co., Ltd., and the volume average particle size was 80 nm.
- the transition temperature was found to be 18 ° C. when the types of monomer components constituting the polymer and the ratio force were also determined by the Fox equation.
- Ion-exchangeable surfactant AQUALON KH-10 (Daiichi Kogyo Seiyaku Co., Ltd.) 25g and nonionic polymerizable surfactant ADEKA rear soap ER-10 (Asahi Denka Kogyo) 25g ion-exchanged water 850g 100 g of C Pigment Blue 15: 4 having a volume average particle size of 60 nm was added and mixed.
- This mixed solution was subjected to a dispersion treatment for 5 hours under the conditions of a bead filling rate of 70% and a rotational speed of 5,000 rpm using a disperser Eiger Motor Mill M250 (manufactured by Aiga Ichi Japan).
- the dispersion treatment After the dispersion treatment, ultrafiltration was performed using an ultrafiltration apparatus by a cross flow method until the permeate was freed from foaming, and the solid content concentration was adjusted to 10% by weight.
- the obtained pigment dispersion was subjected to a flask combustion method to determine the sulfur content, and the value of the pigment dispersion was also determined to determine the adsorption amount of the aon polymerizable surfactant Aqualon KH-10
- the KH-IOZ pigment was 13Z100.
- This mixture was put into a reaction vessel equipped with a stirrer, reflux condenser, dropping funnel, temperature controller, and nitrogen inlet tube, and the internal temperature of the reaction vessel was raised to 80 ° C, followed by initiation of polymerization.
- An aqueous solution prepared by dissolving 0.23 g of potassium persulfate as an agent in 100 g of ion-exchanged water was dropped, and a polymerization reaction was performed at 80 ° C. for 5 hours while introducing nitrogen into the reaction vessel.
- the pH was adjusted to 8 with an aqueous solution of ImolZl sodium hydroxide and then filtered through a membrane filter having a pore size of 1 ⁇ m to remove coarse particles.
- a flask is charged with 250 g of methylethylketone, heated to 75 ° C with stirring under a nitrogen seal, and 170 g of n-butyl metatalylate, 58 g of n-butyl attalate, 2-hydroxyxetyl metathalyl.
- a mixture of 35 g of rate, 35 g of acrylic acid and 20 g of polymerization initiator perbutyl O was added dropwise over 2 hours, and the mixture was further reacted for 15 hours to obtain a vinyl polymer solution.
- 15 g of the above polymer solution is placed in a stainless steel beaker and dimethylethanolamine 0.8 g and magenta pigment (CI Pigment Red 122) together with 15g, then add ion-exchanged water to a total amount of 75g, and add 250g of zirconia beads with an average particle size of 0.5nm, and use a sand mill. And kneading for 4 hours. After completion of the kneading, the zirconium beads were separated by filtration to obtain a dispersion of a polymer having a carboxyl group neutralized with a base and a pigment dispersed in water. While stirring at room temperature, 1N hydrochloric acid was added until the resin was insoluble and fixed to the pigment.
- dimethylethanolamine 0.8 g and magenta pigment CI Pigment Red 122
- the pH at this time was 3-5.
- the aqueous medium containing the polymer-fixed pigment was filtered by suction and washed with water to obtain a water-containing cake. While stirring this water-containing cake with a disperser, 10% NaO H aqueous solution was added until the pH of the dispersion became 8.5 to 9.5, and after stirring for 1 hour, ion-exchanged water was added, The CI pigment red 122 encapsulated pigment MCP13 was obtained by adjusting the solid content concentration to 20%.
- a cationic polymerizable surfactant Aqualon KH-10 (Daiichi Kogyo Seiyaku) was dissolved in 850 g of ion-exchanged water, and 100 g of isoindolinone pigment (C.I. Pigment Red 122) was mixed and mixed. This mixed solution was subjected to a dispersion treatment for 5 hours under the conditions of a bead filling rate of 70% and a rotation speed of 5, OOrpm using an Eiger motor mill type M250 (trade name, manufactured by Eiger Japan).
- the unadsorbed AQUALON KH-10 was processed by ultrafiltration using the cross-flow method until the AQUALON KH-10Z pigment was 25Z100 (this value was also obtained for solid concentration and pigment concentration power).
- the solid content concentration was adjusted to 15% by weight.
- Aon polymerizable surfactant AQUALON KH-10 (Daiichi Kogyo Seiyaku) 50g Dissolved in 850 g of exchange water, 100 g of isoindolinone pigment (CI Pigment Red 122) was added to this and mixed.
- This mixed solution was subjected to a dispersion treatment for 5 hours under the conditions of a bead filling rate of 70% and a rotation speed of 5, OOrpm using an Eiger motor mill type M250 (trade name, manufactured by Eiger Japan).
- the unadsorbed AQUALON KH-10 was processed by ultrafiltration using the cross-flow method until the AQUALON KH-10Z pigment was 25Z100 (this value was also obtained for solid concentration and pigment concentration power).
- the solid content concentration was adjusted to 15% by weight.
- This mixed solution was put into a reaction vessel equipped with a stirrer, reflux condenser, dropping funnel, temperature controller, and nitrogen introduction tube, and the internal temperature of the reaction vessel was adjusted to 80 ° C while irradiating ultrasonic waves for 30 minutes. After the temperature was raised to C, an aqueous solution of 1.5 g of potassium persulfate, which is the polymerization initiator, dissolved in lOOg of ion-exchanged water was dropped, and the polymerization reaction was carried out at 80 ° C for 6 hours while introducing nitrogen into the reaction vessel. I went.
- Methyl ethyl ketone was distilled off using a rotary evaporator, and a 10% NaOH aqueous solution was added until the pH reached 8.5 to 9.5, followed by stirring for 1 hour. To this, ion-exchanged water was added to adjust the solid content concentration to 20%, and CI pigment red 122 encapsulated pigment MCP 16 was obtained.
- Polymer emulsion A was obtained by adjusting the concentration of polymer particles of the obtained polymer emulsion to 32% by weight.
- the obtained polymer emulsion A was applied on a flat plate so as to form a liquid film having a uniform thickness, and further air-dried at 30 ° C. to obtain a transparent resin film.
- This transparent film was subjected to thermal analysis using a thermal scanning refractive index (differential scanning calorimeter: DSC) DSC200 (trade name, manufactured by Seiko Electronics Co., Ltd.). As a result, the polymer particles in polymer emulsion A were analyzed.
- the glass transition temperature was 0 ° C.
- the volume average particle size of polymer particles contained in Polymer Emulsion A measured using a dynamic light scattering particle size distribution analyzer Microtrac UPA150 (trade name) manufactured by Leeds & Northrop is 40 nm. there were.
- (Ink 1) 15 g of glycerin, 5 g of triethylene glycol monobutyl ether, 2 g of 1,2-hexanediol, 5 g of trimethylolpropane, 2 g of 2-pyrrolidone, 1 g of orphin E1010, 0.05 g of proxel XL-2, and ion-exchanged water 36 65 g was mixed, and further 10 g% by weight of potassium hydroxide lg was added and mixed to obtain a liquid mixture. The liquid mixture was added to 33.3 g of the MCP1 dispersion, and the pigment was dispersed using a stirrer to obtain the target ink 1.
- inks 2 to 12 were prepared according to the method of preparing the ink 1 described above.
- encapsulated pigments, polymer fine particles and pigments are values indicated by solid content concentration.
- Ink 1-12, Ink 29-34, and Comparative Ink 1-2 are evaluated for color development, gloss, image clarity, abrasion resistance, water resistance, ejection stability, and print density (OD value on plain paper) as follows: The evaluation method was used.
- Ink cartridges 1 to 12, ink 29 to 34, and comparative inks 1 to 2 prepared as described above were filled into ink cartridges, and then loaded into an ink jet printer PX-600C (trade name, manufactured by Seiko Epson Corporation). Then, solid printing was performed on photographic paper gloss (trade name, manufactured by Seiko Epson Corporation) and Xerm P paper (trade name, manufactured by Xerox Co., Ltd.), and the C * value of the solid printed portion was measured. C * value is measured with a spectrophotometer (Daretag Macbeth, G replacement paper (Rule 26) RETAG SPM-50) was used. The color developability of each ink composition was evaluated using the following evaluation criteria A to D.
- A: C * is 80 or more
- C is 50 or more and less than 70
- ink cartridges 1 to 12, ink 29 to 34, and comparative inks 1 to 2 prepared as described above into ink cartridges, and load them into an ink jet printer EM-930C (trade name / manufactured by Seiko Epson Corporation).
- a solid image (100% duty) was printed at 1440 X 720dpi on photographic paper with high gloss> (trade name, manufactured by Z Seiko Epson Corporation).
- An automatic goniophotometer GP-200 (Murakami Color Research Laboratory) was used as the measuring device, and the measurement conditions were 12V, 50W, incident beam aperture diameter lmm, reflected light aperture diameter 1.5mm, N
- the specular gloss of the recording surface at an incident angle of 45 degrees was measured. The results were evaluated according to the following criteria.
- the printed matter (solid image) obtained in Evaluation 2 was measured with the touch panel image clarity measuring device ICM-1T (manufactured by Suga Test Instruments) to measure the image clarity of the printed surface (solid image) at an incident angle of 45 degrees. The results were evaluated according to the following criteria. [0249] [Evaluation criteria]
- Ink cartridges 1 to 12, ink 29 to 34, and comparative inks 1 to 2 prepared as described above were filled in ink cartridges, and loaded into an ink jet printer PX-600C (product name, manufactured by Seiko Epson Corporation). Then, solid printing was performed at 100% duty on the lOmmX 10mm area on the Superfine glossy film (trade name, manufactured by Seiko Epson Corporation), and left for 1 hour at a temperature of 25 ° C. Then, using the yellow water-based fluorescent pen ZEBRA PEN2 (trade name) (trade name, manufactured by Zebra Corporation), a load of 500 g is applied to the pen tip and the above print area is rubbed at a speed of lOmmZ seconds. Observed whether or not. The obtained results were evaluated using the following evaluation criteria.
- A There is no change over the entire paper including the printed part.
- B The force with which the coloring material is flowing slightly is also recognized.
- Ink 1-12, Ink 29-34, and Comparative Ink 1-2 prepared as described above were filled in an ink cartridge, and loaded into an ink jet printer PX-600C (Seiko Epson Corporation). An lmm crease was printed on the super fine paper manufactured by Epson Corporation, and the printing conditions such as missing dots and ink landing position deviation were visually observed and evaluated using the following evaluation criteria.
- A Even if the number of printed sheets is 10,000 or more, there is no missing dot or ink landing position deviation.
- B When the number of printed sheets is 1000 or more and less than 10000, dot missing or ink landing deviation occurs.
- C When the number of printed sheets is 100 or more and less than 1000, dot missing or ink landing deviation occurs. D: When the number of printed sheets is less than 100, missing dots or ink landing deviation occurs.
- Ink 1-12, Ink 29-34 and Comparative Ink 1-2 prepared as described above are filled in an ink cartridge, and this is loaded into an inkjet printer PX-600C (Seiko Epson Corporation).
- Solid Xerox P paper manufactured by Xerox Co., Ltd.
- AA OD value is 1.15 or more.
- the OD value is 1.15 or more.
- OD value is 1.10 or more and less than 1.15.
- Tables 5-1 to 5-3 show the evaluation results of the inks 1 to 12, inks 29 to 34, and comparative inks 1 and 2 for the above evaluation items.
- Table 5 shows the results when the capsules (capsule pigments) of the present invention were used for ink jet recording inks.
- Ink compositions related to inks 2, 29, 30, 31, and 34 have excellent ejection stability, and images printed on ink jet media have high gloss and image clarity, and are resistant to rubbing. It turns out that it is excellent also in the property and water resistance. It can also be seen that the image printed on plain paper has a high print density.
- the ink compositions according to inks 1, 3, 7, 8, 9, 10, 11, 4, 12, 32, and 33 gave better results than the ink compositions according to comparative examples 1 and 2.
- the ink composition according to inks 5 and 6 contains a polymer emulsion, it has high image clarity, excellent abrasion resistance, and an image printed on plain paper. It can be seen that it has a high print density. In particular, it is characterized by excellent abrasion resistance. “Preparation of ink composition (inks 17 to 26, comparative inks 3 to 8)”
- inks 17 to 26 and comparative inks 3 to 8 were prepared according to the methods of preparing the inks 1 to 12, inks 29 to 34, and comparative inks 1 to 2.
- the encapsulated pigment and the pigment are the values indicated by the solid content concentration.
- DMH-20 in Tables 6 to 8 above is a compound of the formula (1) having the following structure manufactured by Nippon Emulsifier Co., Ltd.
- butylethylpropanediol in Tables 6 to 8 above is also a compound of the formula (1) and has the following structure manufactured by Kyowa Hakko Chemical Co., Ltd.
- Table 9 shows the evaluation results. ⁇ Table 9: Evaluation results
- FIG. 1 is a diagram showing an outline of a capsule discoloration material and a method for producing the same according to the present invention.
- FIG. 2 Anionic surfactant with negative charge adsorbed on the surface of the core material and cationic polymerizable surfactant with positive charge (not shown is a substitute for the above cationic polymerizable surfactant) And a cationic monomer having at least a positively charged cationic group and a polymerizable group), a negatively charged cationic surfactant and a hydrophobic monomer may coexist. It is a schematic diagram showing the state.
- FIG. 3 Negatively charged anionic surfactant adsorbed on the surface of the core material, positively charged cationic surfactant, negatively charged cationic surfactant and hydrophobic monomer
- Anionic polymerizable surfactant having negative charge adsorbed on the surface of the core material and a cationic polymerizable surfactant having a positive charge May be a cationic monomer having at least a positively charged cationic group and a polymerizable group.), A negatively charged cationic surfactant and a hydrophobic monomer. It is a schematic diagram which shows the state which coexists.
- FIG. 5 Negatively charged anionic polymerizable surfactant adsorbed on the surface of the core material and a positively charged cationic polymerizable surfactant (not shown! Instead of the agent, a cationic monomer having at least a positively charged cationic group and a polymerizable group may be used.), A negatively charged cation polymerizable surfactant and a nonionic FIG. 3 is a schematic diagram showing a state where a polymerizable surfactant and a hydrophobic monomer coexist /!
- Negatively charged ionic surfactant and Z or ionic polymerizable surfactant, and nonionic surfactant and Z or nonionic polymerizable surfactant as core materials Cationic polymerizable surfactant with a positive charge adsorbed on the surface (not shown!
- a cationic monomer having at least a positively charged cationic group and a polymerizable group may be used.
- a negatively charged ion-polymerizable surfactant and a hydrophobic monomer co-exist with each other.
- FIG. 7 is a schematic diagram showing a state where the state shown in FIG. 2 is encapsulated.
- FIG. 8 is a schematic diagram showing a state where the state shown in FIG. 3 is encapsulated.
- FIG. 9 is a schematic diagram showing a state where the state shown in FIG. 4 is encapsulated.
- FIG. 10 is a schematic diagram showing a state where the state shown in FIG. 5 is encapsulated.
- FIG. 11 is a schematic diagram showing a state where the state shown in FIG. 6 is encapsulated.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Manufacturing Of Micro-Capsules (AREA)
- Ink Jet (AREA)
- Ink Jet Recording Methods And Recording Media Thereof (AREA)
Abstract
Description
Claims
Priority Applications (3)
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US11/665,777 US8524803B2 (en) | 2004-10-18 | 2005-10-18 | Encapsulation product, process for producing the same, and ink composition |
EP20050795833 EP1808225B1 (en) | 2004-10-18 | 2005-10-18 | Encapsulation product, process for producing the same, and ink composition |
JP2006543020A JP5245252B2 (ja) | 2004-10-18 | 2005-10-18 | カプセル化物及びその製造方法、並びにインク組成物 |
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JP2004-303093 | 2004-10-18 | ||
JP2004303093 | 2004-10-18 | ||
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JP2004-313163 | 2004-10-27 | ||
JP2005068168 | 2005-03-10 | ||
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US (1) | US8524803B2 (ja) |
EP (1) | EP1808225B1 (ja) |
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CN101208395B (zh) * | 2005-06-20 | 2011-05-25 | 精工爱普生株式会社 | 微囊化物、微囊化色材、其制造方法、墨液组合物、喷墨记录方法以及记录物 |
JP2010510357A (ja) * | 2006-11-20 | 2010-04-02 | ヒューレット−パッカード デベロップメント カンパニー エル.ピー. | 急速乾燥性の水性インクジェットインク |
US8460450B2 (en) | 2006-11-20 | 2013-06-11 | Hewlett-Packard Development Company, L.P. | Rapid drying, water-based ink-jet ink |
JP2009138162A (ja) * | 2007-12-10 | 2009-06-25 | Seiko Epson Corp | 導体パターン形成用インク、導体パターンおよび配線基板 |
JP2010090266A (ja) * | 2008-10-08 | 2010-04-22 | Seiko Epson Corp | インクジェット記録方式の印刷方法 |
CN101451037B (zh) * | 2008-12-30 | 2011-07-20 | 上海乐美文具有限公司 | 一种可擦中性墨水及其制造方法 |
US9025237B2 (en) | 2012-04-05 | 2015-05-05 | Seiko Epson Corporation | Electrophoresis particle, method of manufacturing electrophoresis particle, electrophoresis dispersion liquid, electrophoresis sheet, electrophoresis device and electronic apparatus |
EP4112698A4 (en) * | 2020-02-28 | 2024-01-24 | Matsumoto Yushi Seiyaku Kk | THERMO-EXPANDABLE MICROSPHERES, THEIR PRODUCTION METHOD AND THEIR USE |
Also Published As
Publication number | Publication date |
---|---|
EP1808225A1 (en) | 2007-07-18 |
EP1808225B1 (en) | 2014-04-16 |
US8524803B2 (en) | 2013-09-03 |
EP1808225A4 (en) | 2011-11-30 |
JPWO2006043571A1 (ja) | 2008-05-22 |
JP5245252B2 (ja) | 2013-07-24 |
US20090062462A1 (en) | 2009-03-05 |
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