WO2016052055A1 - ゲル粒子、感光性組成物、インク組成物、ゲル粒子の水分散物の製造方法、及び画像形成方法 - Google Patents
ゲル粒子、感光性組成物、インク組成物、ゲル粒子の水分散物の製造方法、及び画像形成方法 Download PDFInfo
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- WO2016052055A1 WO2016052055A1 PCT/JP2015/074796 JP2015074796W WO2016052055A1 WO 2016052055 A1 WO2016052055 A1 WO 2016052055A1 JP 2015074796 W JP2015074796 W JP 2015074796W WO 2016052055 A1 WO2016052055 A1 WO 2016052055A1
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- gel particles
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- active energy
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- 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
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- 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
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- C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
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- 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
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- 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
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- B41J2202/03—Specific materials used
Definitions
- the present disclosure relates to gel particles, a photosensitive composition, an ink composition, a method for producing an aqueous dispersion of gel particles, and an image forming method.
- Image forming methods for forming an image on a recording medium such as paper based on an image data signal include an electrophotographic method, a sublimation type thermal transfer method, a melt type thermal transfer method, and an ink jet method.
- the ink jet method can be implemented with an inexpensive apparatus, and ink is ejected only to a required image portion to form an image directly on a recording medium. Is cheap. Furthermore, there is little noise and it is excellent as an image forming method.
- Ink jet methods there is an image forming method using an ink for ink jet recording that can be cured by irradiation with active energy rays. According to this method, it is possible to improve the recording speed and form an image by irradiating the active energy ray immediately after ink ejection or after a certain time and curing the ink droplets.
- Inks curable by irradiation with active energy rays generally contain a polymerizable compound and a polymerization initiator.
- JP 2012-532238 A discloses a polymerization initiator in which one or more bisacylphosphine oxide moieties are bonded to an oligomer or polymer skeleton via a phosphorus atom.
- Japanese Patent Application Laid-Open No. 2006-28514 discloses a polymer initiator comprising a dendritic polymer central portion having at least one initiation functional group as a terminal.
- Japanese Patent Application Laid-Open No. 6-80625 discloses a polymer compound based on a triphenylsulfonium salt unit.
- low molecular weight components such as an unreacted polymerizable compound, a polymerization initiator, and a polymerization initiator residue in the cured film.
- Components having a molecular weight of 1000 or less may remain, and these low molecular weight components may contribute to various problems. For example, a phenomenon in which a low molecular weight component remaining in a cured film moves from the cured film to the outside, so-called migration may occur.
- the amount of migration of low molecular weight components from the cured film is large, the odor of the cured film becomes strong, especially when the ink is used for package printing for food packaging, etc. May occur.
- the low molecular weight component may remain in the cured film, and if the low molecular weight component remains in the film, the physical properties of the cured film may be adversely affected. Accordingly, there is a need for an ink composition that suppresses migration of low molecular weight components and does not impair film properties.
- One embodiment of the present invention has been made in view of the above circumstances, and the occurrence of migration in which a low molecular weight component moves from the cured film to the outside of the film is suppressed, and a film having excellent film strength (for example, It is an object of the present invention to provide gel particles, a photosensitive composition, an ink composition, a method for producing an aqueous dispersion of gel particles, and an image forming method.
- R each independently represents a monovalent group or * -L-, and at least one R in each formula is * -L-.
- L represents a divalent organic group, and * represents a bonding site with a three-dimensional crosslinked structure.
- ⁇ 3> The gel particle according to ⁇ 1> or ⁇ 2>, further having a hydrophilic group on the surface.
- ⁇ 4> The gel particle according to any one of ⁇ 1> to ⁇ 3>, which contains a polymerizable monomer.
- a photosensitive composition comprising the gel particles according to any one of ⁇ 1> to ⁇ 4> and water.
- An ink composition comprising the gel particles according to any one of ⁇ 1> to ⁇ 4>, water, and a colorant.
- Oil phase components including isocyanate compounds, polymerizable monomers, and organic solvents Gel particles having an oil phase component mixed with an aqueous phase component containing water and emulsifying the emulsion to obtain an emulsion, and a gelling step of heating and gelling the emulsion
- a method for producing an aqueous dispersion ⁇ 10> The method for producing an aqueous dispersion of gel particles according to ⁇ 9>, further comprising a mixing step of mixing the gel particles obtained in the gelation step, water, and a colorant.
- An image forming method comprising:
- gel particles and a photosensitive composition that can suppress the occurrence of migration in which a low molecular weight component moves from the inside of a cured film to the outside of the film and obtain a film (for example, an image) having excellent film strength.
- Product, ink composition, method for producing an aqueous dispersion of gel particles, and an image forming method are provided.
- (meth) acrylate means at least one of acrylate and methacrylate.
- light is a concept including active energy rays such as ⁇ rays, ⁇ rays, electron rays, ultraviolet rays, visible rays, and infrared rays.
- active energy rays such as ⁇ rays, ⁇ rays, electron rays, ultraviolet rays, visible rays, and infrared rays.
- ultraviolet rays may be referred to as “UV (Ultra Violet) light”.
- LED Light Emitting Diode
- the gel particles have a polymerizable group and a functional group that generates radicals upon irradiation with active energy rays, and have a three-dimensional crosslinked structure including at least one bond selected from a urethane bond and a urea bond.
- the use of the gel particles is not particularly limited, and the gel particles can be used for, for example, an ink composition, a coating agent, an adhesive, a paint, and the like.
- the details of the mechanism of action in one embodiment of the present invention are unknown, but are presumed as follows.
- the gel particles have a polymerizable group and a functional group that generates radicals upon irradiation with active energy rays, so that when the gel particles are irradiated with active energy rays, the functional groups that generate radicals upon irradiation with active energy rays are used. Radicals are generated. Thereby, between the gel particles adjacent to each other, the polymerizable group present in one gel particle and the polymerizable group present in the other gel particle easily react to form a crosslinked structure between the gel particles. Form.
- the gel particles can form a cured film without using a polymerization initiator, and low molecular weight components resulting from unreacted polymerization initiator residues and polymerization initiator residues may remain in the cured film. Few. That is, it is considered that the occurrence of migration of low molecular weight components in the cured film is suppressed and the physical properties of the formed film are not impaired. Moreover, it is thought that a gel particle can form the film
- the gel particles have a functional group that generates radicals upon irradiation with active energy rays
- the range of selection of functional groups that generate radicals upon irradiation with active energy rays that can be introduced is widened.
- the width of will also expand. Therefore, the curing sensitivity can be improved as compared with the conventional case.
- acylphosphine oxide compounds are photopolymerization initiators that are particularly excellent in curing sensitivity to irradiation with active energy rays.
- acylphosphine oxide compounds have low solubility in water, it has heretofore been difficult to contain them in aqueous compositions.
- Gel particles are a functional group that generates radicals upon irradiation of active energy rays in the three-dimensional structure of the gel particles. It is not necessary to use a photopolymerization initiator such as an acylphosphine oxide compound as an independent component.
- the functional group that generates radicals upon irradiation with active energy rays is a group having an acylphosphine oxide structure
- sensitivity to light particularly sensitivity to LED light
- the wavelength of the LED light is preferably 355 nm, 365 nm, 385 nm, 395 nm, or 405 nm.
- the gel particle has a polymerizable group means that the gel particle contains at least one of a polymerizable group contained in the three-dimensional crosslinked structure and a polymerizable group not contained in the three-dimensional crosslinked structure. It means having. That is, in the gel particles, the polymerizable group may exist as a part of the three-dimensional crosslinked structure or may exist as a part other than the three-dimensional crosslinked structure.
- the polymerizable group exists as a part other than the three-dimensional crosslinked structure” means that a monomer having a polymerizable group (hereinafter, also referred to as “polymerizable monomer”) is present in the gel particles, separately from the three-dimensional crosslinked structure. It is included. In any case, the polymerizable group is preferably present on the surface part of the gel particle (contact part with water). “The gel particles have a polymerizable group” can be confirmed by, for example, Fourier transform infrared spectroscopy (FT-IR) analysis. The details of the polymerizable group that the gel particles have and the monomer (polymerizable monomer) having the polymerizable group will be described later.
- FT-IR Fourier transform infrared spectroscopy
- the “three-dimensional crosslinked structure” refers to a three-dimensional network structure formed by crosslinking.
- Gel particles are formed by forming a three-dimensional cross-linked structure in the particles. That is, in the present specification, it is synonymous that the particles have a three-dimensional cross-linking structure and that the particles are gel particles.
- a gel particle having a three-dimensional crosslinked structure is contained in a composition such as an ink composition.
- the following operation is performed at a liquid temperature of 25 ° C.
- a sample is taken from the ink composition.
- 100 mass times tetrahydrofuran (THF) with respect to the total solid content in the sample is added and mixed to prepare a diluted solution.
- the obtained diluted solution is centrifuged at 80,000 rpm for 40 minutes. After centrifugation, visually check for residue.
- the residue is re-dispersed with water to prepare a re-dispersion, and the obtained re-dispersion is subjected to light scattering using a wet particle size distribution analyzer (LA-910, manufactured by Horiba, Ltd.).
- LA-910 manufactured by Horiba, Ltd.
- the particle size distribution is measured by the method.
- the particle size distribution can be confirmed by the above operation, it is determined that the ink composition contains gel particles having a three-dimensional crosslinked structure.
- the three-dimensional crosslinked structure can be formed by a reaction between a trifunctional or higher functional isocyanate compound or a bifunctional isocyanate compound and a compound having two or more active hydrogen groups.
- a raw material for producing gel particles since it contains at least one compound having three or more reactive groups (isocyanate group or active hydrogen group), the cross-linking reaction proceeds in three dimensions, resulting in a three-dimensional network structure.
- the three-dimensional crosslinked structure in the gel particles is preferably a product formed by a reaction between a trifunctional or higher functional isocyanate compound and water.
- the three-dimensional crosslinked structure in the gel particles is more preferably a product formed from a reaction between a trifunctional or higher functional isocyanate compound having a functional group that generates radicals upon irradiation with active energy rays and water.
- the trifunctional or higher functional isocyanate compound is a compound having three or more isocyanate groups in the molecule, and a compound synthesized by a method described later and a known compound can be used.
- Examples of the trifunctional or higher functional isocyanate compound include a trifunctional or higher functional aromatic isocyanate compound and a trifunctional or higher functional aliphatic isocyanate compound.
- Known compounds include, for example, compounds described in “Polyurethane Resin Handbook” (edited by Keiji Iwata, published by Nikkan Kogyo Shimbun (1987)).
- the trifunctional or higher functional isocyanate compound is preferably a compound having three or more isocyanate groups in the molecule represented by the following general formula 1.
- X represents an n-valent organic group.
- n is 3 or more.
- n is preferably from 3 to 10, more preferably from 3 to 8, and even more preferably from 3 to 6.
- the trifunctional or higher functional isocyanate compound is preferably a compound derived from a bifunctional isocyanate compound (a compound having two isocyanate groups in the molecule).
- the trifunctional or higher functional isocyanate compound is selected from isophorone diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, m-xylylene diisocyanate, and dicyclohexylmethane 4,4′-diisocyanate. More preferably, it is an isocyanate compound derived from at least one kind. “Induced” means that the above compound is used as a raw material and includes a structure derived from the raw material.
- trifunctional or higher functional isocyanate compound examples include bifunctional or higher functional isocyanate compounds (compounds having two or more isocyanate groups in the molecule) and trifunctional or higher functional polyols, polyamines, and polythiols.
- adduct adduct with a compound having two or more active hydrogen groups
- a trifunctional or higher functional isocyanate compound adduct type
- a trifunctional or higher functional isocyanate compound trimer biuret type or isocyanurate type
- a compound having three or more isocyanate groups in the molecule such as a formalin condensate of benzene isocyanate is also preferable.
- These trifunctional or higher functional isocyanate compounds may be a mixture containing a plurality of compounds, and the compound represented by the following general formula 2 or general formula 3 is preferably the main component of these mixtures, Other components may be included.
- the “active hydrogen group” means at least one group selected from a hydroxyl group, a primary amino group, a secondary amino group, and a mercapto group.
- the adduct type trifunctional or higher functional isocyanate compound is preferably a compound represented by the following general formula 2 or general formula 3.
- X represents an (l + m + n) -valent organic group
- l, m, and n are each 0 or more, and l + m + n is 3 or more.
- l + m + n is preferably 3 to 10, more preferably 3 to 8, and further preferably 3 to 6.
- Y 1 , Y 2 , Y 3 , Y 4 , and Y 5 each independently represent O, S, or NH, and O or S is preferable, and O is more preferable.
- Z represents a divalent organic group.
- R 1 , R 2 , R 3 , R 4 , and R 5 each independently represent a divalent organic group.
- the organic groups represented by R 1 , R 2 , R 3 , R 4 , and R 5 are each independently an alkylene group optionally having a substituent having 1 to 20 carbon atoms, or 1 to 20 carbon atoms. It is preferably a cycloalkylene group which may have a substituent or an arylene group which may have a substituent having 1 to 20 carbon atoms.
- R 1 , R 2 , R 3 , R 4 , and R 5 are each independently the following (3-1) to (3-11), (4-1) to (4-2), and (5-1) It is more preferably a group selected from the groups represented by (5-7). * Indicates a binding site.
- R 1 , R 2 , R 3 , R 4 , and R 5 are each independently a group (5-3) derived from isophorone diisocyanate (IPDI), hexamethylene diisocyanate (Group derived from HDI) (5-7), group derived from trimethylhexamethylene diisocyanate (TMHDI) (5-5, 5-6), group derived from 1,3-bis (isocyanatomethyl) cyclohexane (5-4), a group (5-1) derived from m-xylylene diisocyanate (XDI), or a group (5-2) derived from dicyclohexylmethane 4,4′-diisocyanate Are more preferable (* indicates a binding site).
- IPDI isophorone diisocyanate
- TMHDI trimethylhexamethylene diisocyanate
- XDI m-xylylene diisocyanate
- 5-2 derived from dicyclohexylmethane 4,4
- the synthesis of an adduct-type trifunctional or higher functional isocyanate compound can be performed by reacting a compound having three or more active hydrogen groups in a molecule described later with a bifunctional or higher functional isocyanate compound described later.
- the active hydrogen group means a hydroxyl group, a primary amino group, a secondary amino group, and a mercapto group.
- the adduct-type trifunctional or higher functional isocyanate compound is, for example, a compound having three or more active hydrogen groups in the molecule and a bifunctional or higher functional isocyanate compound heated in an organic solvent with stirring (50 ° C. to 100 ° C. Or by stirring at a low temperature (0 ° C. to 70 ° C.) while adding a catalyst such as stannous octylate and an amine compound (synthetic scheme 1 below).
- a catalyst such as stannous octylate and an amine compound
- a bifunctional or higher functional isocyanate compound having a mole number (number of molecules) of 0.6 times or more is used with respect to the number of moles (equivalent number of active hydrogen groups).
- the number of moles of the bifunctional or higher isocyanate compound is preferably 0.6 to 5 times, more preferably 0.6 to 3 times, and more preferably 0.8 to 2 times the number of moles of the active hydrogen group. Further preferred.
- An adduct-type trifunctional or higher functional isocyanate compound is prepared by synthesizing an adduct (prepolymer) of a compound having two active hydrogen groups in the molecule and a bifunctional or higher functional isocyanate compound. It can also be obtained by reacting a compound having three or more active hydrogen groups (synthetic scheme 2 below).
- bifunctional or higher isocyanate compound examples include a bifunctional or higher aromatic isocyanate compound and a bifunctional or higher aliphatic isocyanate compound.
- bifunctional or higher isocyanate compound examples include isophorone diisocyanate (IPDI), m-phenylene diisocyanate, p-phenylene diisocyanate, 2,6-tolylene diisocyanate, 2,4-tolylene diisocyanate (TDI), naphthalene-1 , 4-diisocyanate, diphenylmethane-4,4′-diisocyanate (MDI), 3,3′-dimethoxy-biphenyl diisocyanate, 3,3′-dimethyldiphenylmethane-4,4′-diisocyanate, m-xylylene diisocyanate (XDI) P-xylylene diisocyanate, 4-chloroxylylene-1,3-diisocyanate, 2-methylxylylene-1,3-diisocyanate, 4,4′-diphenylpropane diisocyanate, 4,4′-dipheni Hexafluoride
- IPDI isophorone diisocyanate
- HDI hexamethylene diisocyanate
- TMHDI trimethylhexamethylene diisocyanate
- HXDI 1,3-bis (isocyanatomethyl) cyclohexane
- XDI m-xylylene diene Isocyanate
- dicyclohexylmethane-4,4′-diisocyanate are preferred.
- bifunctional or higher functional isocyanate compound a bifunctional isocyanate compound derived from the above compound can also be used.
- Duranate registered trademark
- D101, D201, A101 (manufactured by Asahi Kasei Corporation) and the like can be mentioned.
- the compound having three or more active hydrogen groups in the molecule is a compound having three or more groups in the molecule selected from hydroxyl group, primary amino group, secondary amino group, and mercapto group.
- Examples thereof include compounds having the structures represented by the following (9-1) to (9-13). In the structure below, n represents an integer selected from 1 to 100.
- adduct type trifunctional or higher functional isocyanate compound a compound obtained by reacting a compound having two or more active hydrogen groups in the molecule with a bifunctional or higher functional isocyanate compound in the combination shown in Table 1 below is preferably used.
- the adduct type trifunctional or higher functional isocyanate compound is preferably NCO102 to NCO105, NCO107, NCO108, NCO111, and NCO113, and more preferably NCO103 to NCO105, NCO109.
- adduct type trifunctional or higher functional isocyanate compound commercially available products may be used.
- D-110, D-120N, D-140N, and D-160N are more preferable.
- biuret type or isocyanurate type trifunctional or higher functional isocyanate compound is preferably a compound represented by the following formula 4 or 5.
- R 6 , R 7 , R 8 , R 9 , R 10 , and R 11 each independently represent a divalent organic group.
- the organic groups represented by R 6 , R 7 , R 8 , R 9 , R 10 , and R 11 are each independently an alkylene group having 1 to 20 carbon atoms which may have a substituent, or a substituent. It is preferably a cycloalkylene group having 1 to 20 carbon atoms which may have a cycloalkyl group or an arylene group having 1 to 20 carbon atoms which may have a substituent.
- R 6 , R 7 , R 8 , R 9 , R 10 , and R 11 are each independently (3-1) to (3-11), (4-1) to (4-2), and A group selected from the groups represented by (5-1) to (5-7) is preferred. * Indicates a binding site.
- R 6 , R 7 , R 8 , R 9 , R 10 , and R 11 are each independently a group (5-3) derived from isophorone diisocyanate (IPDI), hexa Groups derived from methylene diisocyanate (HDI) (5-7), groups derived from trimethylhexamethylene diisocyanate (TMHDI) (5-5), groups derived from 1,3-bis (isocyanatomethyl) cyclohexane ( 5-4), a group (5-1) derived from m-xylylene diisocyanate (XDI), and a group (5-2) derived from dicyclohexylmethane 4,4′-diisocyanate are more preferable ( * Indicates a binding site).
- IPDI isophorone diisocyanate
- HDI methylene diisocyanate
- TMHDI trimethylhexamethylene diisocyanate
- XDI m-xylylene diisocyanate
- biuret type trifunctional or higher functional isocyanate compound commercially available products may be used.
- D-165N, NP1100 manufactured by Mitsui Chemicals
- Desmodur registered trademark
- N3200 Sud Bayer
- Duranate registered trademark
- 24A-100 manufactured by Asahi Kasei Corporation
- isocyanurate type trifunctional or higher functional isocyanate compound commercially available products may be used.
- D-127, D-170N, D-170HN, D-172N, D-177N Mitsubishi Chemical Co., Ltd.
- Duranate registered trademark
- 24A-100 manufactured by Asahi Kasei Co., Ltd.
- D-127 manufactured by Mitsui Chemicals, Inc.
- TKA-100 manufactured by Asahi Kasei Corporation
- TSE -100 manufactured by Asahi Kasei Corporation
- the gel particles are preferably produced by reacting the above-described trifunctional or higher functional isocyanate compound with water or a compound having two or more active hydrogen groups.
- a compound to be reacted with a trifunctional or higher functional isocyanate compound water is generally used.
- By reacting the trifunctional or higher functional isocyanate compound with water a three-dimensional crosslinked structure having a urea bond is formed.
- compounds that react with trifunctional or higher functional isocyanate compounds include compounds having two or more active hydrogen groups. Examples of compounds having two or more active hydrogen groups include polyfunctional alcohols and polyfunctional phenols.
- a polyfunctional amine having a hydrogen atom on a nitrogen atom, or a polyfunctional thiol can also be used.
- polyfunctional alcohol examples include propylene glycol, glycerin, trimethylolpropane, 4,4 ′, 4 ′′ -trihydroxytriphenylmethane, and the like.
- polyfunctional amine examples include diethylenetriamine and tetraethylenepentamine.
- polyfunctional thiol examples include 1,3-propanedithiol and 1,2-ethanedithiol.
- polyfunctional phenol examples include bisphenol A. These compounds may be used individually by 1 type, and may use 2 or more types together.
- the compound having two or more active hydrogen groups includes compounds having three or more active hydrogen groups in the aforementioned molecule.
- the gel particles have a functional group that generates radicals upon irradiation with active energy rays.
- the functional group that generates radicals upon irradiation with active energy rays may be present on the surface of the gel particle, or may be present inside the gel particle.
- the functional group that generates radicals upon irradiation with active energy rays is preferably bonded to the three-dimensional crosslinked structure of the gel particles by a covalent bond.
- the functional group that generates radicals upon irradiation with active energy rays may be bonded to the three-dimensional crosslinked structure by one covalent bond, or may be bonded by two or more covalent bonds.
- the functional group that generates radicals upon irradiation with active energy rays is called a “main chain type” functional group in which all of the generated radical species are all covalently bonded to the gel particle.
- An embodiment in which a part of radical species is bonded to the gel particle by a covalent bond is referred to as a “side chain type” functional group.
- a functional group that generates radicals upon irradiation with active energy rays is present in the gel particles, so that radicals (starting species) are generated upon irradiation with active energy rays.
- this initiating species propagates to the polymerizable group, the polymerizable group can be bonded to the polymerizable group present in the adjacent gel particles to form a crosslinked structure.
- the presence of a functional group capable of generating radicals upon irradiation of active energy rays and a polymerizable group in the gel particle facilitates the propagation of the starting species, so that a film with high sensitivity and excellent film strength can be formed.
- Functional groups that generate radicals upon irradiation with active energy rays include acetophenone structure represented by the following general formula A, monoacylphosphine oxide structure represented by the following general formula B, and bisacyl represented by the following general formula C.
- a group having at least one structure selected from phosphine oxide structures is preferred.
- R each independently represents a monovalent group or * -L-, and at least one of R in each formula is * -L-. .
- L represents a divalent organic group, and * represents a bonding site with a three-dimensional crosslinked structure.
- a monovalent group represented by R is an aliphatic group, an organic group such as an aromatic group, -H, -OH, -SH, -NH , -NH 2, or the like -L-R 1 can be mentioned, It is preferably —H, —OH, —SH, —NH, —NH 2 or —LR 1 .
- R 1 represents a monovalent organic group, and is preferably —H, —OH, —SH, —NH, or —NH 2 .
- the divalent organic group represented by L includes a divalent aliphatic group, a divalent aromatic group, a divalent heterocyclic group, —O—, —S—, —NH—, —CO—, — It is preferably SO—, —SO 2 — or a combination thereof.
- Functional groups that generate radicals upon irradiation with active energy rays are represented by the ⁇ -aminoalkylphenone structure represented by the following general formula D, the ⁇ -hydroxyalkylphenone structure represented by the following general formula E, and the following general formula F: And a group having at least one structure selected from a monoacylphosphine oxide structure and a bisacylphosphine oxide structure represented by the following general formula G.
- each R independently represents a monovalent group or * -L-, and at least one of R in each formula is * -L. -.
- L represents a divalent organic group, and * represents a bonding site with a three-dimensional crosslinked structure.
- a preferred embodiment of R is the same as R in General Formula A, General Formula B, and General Formula C.
- Functional groups that generate radicals upon irradiation with active energy rays are represented by the ⁇ -aminoalkylphenone structure represented by the following general formula H, the ⁇ -hydroxyalkylphenone structure represented by the following general formula I, and the following general formula J. And a group having at least one structure selected from a monoacylphosphine oxide structure represented by the following general formula K, and a bisacylphosphine oxide structure represented by the following general formula L: Is more preferable.
- the functional group that generates radicals upon irradiation with active energy rays has a monoacylphosphine oxide structure represented by the following general formula J and a bisacylphosphine oxide structure represented by the following general formula K. And a group having at least one structure selected from bisacylphosphine oxide structures represented by the following general formula L.
- each R independently represents a monovalent group
- L represents a divalent organic group
- * represents tertiary. It represents the binding site with the original cross-linked structure.
- Preferred embodiments of R and L are the same as R and L in General Formula A, General Formula B, and General Formula C.
- a compound having a functional group that generates radicals upon irradiation with active energy rays can be used.
- This compound should have at least a functional group capable of generating radicals upon irradiation with active energy rays.
- at least one active hydrogen group and at least one functional group capable of generating radicals upon irradiation with active energy rays are included.
- the compound which has is preferable.
- compounds having at least one active hydrogen group and functional groups that generate radicals upon irradiation with at least one active energy ray are shown.
- one embodiment of the present invention is not limited to this structure.
- an isocyanate group of a bifunctional or higher functional isocyanate compound, at least one active hydrogen group, and at least An isocyanate compound into which a functional group that generates radicals by irradiation of active energy rays is introduced is prepared by reacting active hydrogen atoms of a compound having a functional group that generates radicals by irradiation of one active energy ray.
- the reaction can be carried out by reacting an isocyanate compound into which a functional group that generates radicals upon irradiation with the activated energy ray is introduced and water or a compound having two or more active hydrogen groups described above.
- the radicals are irradiated by irradiation with at least one active hydrogen group and active energy rays in the combinations shown in Table 2 below. It is preferable to use a compound obtained by reacting a compound having at least one of the generated functional groups (initiator in Table 2) with a bifunctional or higher isocyanate compound (isocyanate compound in Table 2).
- These compounds having at least one active hydrogen group and at least one functional group capable of generating radicals upon irradiation with active energy rays may be one kind or a combination of two or more kinds. May be.
- An active hydrogen group of a compound (indicated as an initiator in Table 2) having at least one active hydrogen group and a functional group that generates radicals upon irradiation with at least one active energy ray, and a bifunctional or higher functional isocyanate compound (Table 2)
- the number of moles of active hydrogen groups in the compound having at least one active hydrogen group and a functional group that generates a radical upon irradiation with at least one active energy ray is 2 or more. It is preferable to carry out the reaction in an amount that is 0.01 to 0.6 times (1 mol% to 60 mol%) of the number of moles of isocyanate groups of the isocyanate compound, and 0.05 to 0.5 times (5 mol% to 50 mol). %), More preferably 0.1 times to 0.4 times (10 mol% to 40 mol%). It is further preferred that the reaction in an amount of.
- the gel particles have a polymerizable group.
- the gel particles may have a polymerizable group by introducing a polymerizable group into the three-dimensional crosslinked structure, and the polymerizable monomer is included in the interior of the gel particle (the void of the three-dimensional crosslinked structure). May have a polymerizable group. Moreover, both may coexist.
- the gel particles preferably have a polymerizable group on the surface of the gel particles from the viewpoints of sensitivity and crosslinkability.
- the gel particles have a polymerizable group, gel particles adjacent to each other can be bonded to form a crosslinked structure by irradiation with active energy rays, and a film having high crosslinkability and excellent film strength is formed. be able to.
- a method for introducing a polymerizable group into the gel particles for example, when forming a three-dimensional cross-linked structure having at least one kind selected from a urethane bond and a urea bond, , A method of reacting water or a compound having two or more active hydrogen groups as described above with a polymerizable compound as a polymerizable group-introducing monomer, and when producing a trifunctional or higher functional isocyanate compound as described above, A compound having two or more active hydrogen groups as described above by reacting the aforementioned bifunctional or higher isocyanate compound with a polymerizable compound as a polymerizable group-introducing monomer and introducing a polymerizable group in advance.
- a polymerizable compound as a polymerizable group-introducing monomer together with the components constituting the gel particle when producing the gel particle Dissolved in an oil phase component, the addition of water phase components in the oil phase component, mixing, and a method of emulsification.
- Examples of the polymerizable compound used for introducing the polymerizable group into the gel particle include a compound having at least one active hydrogen group and having at least one terminal ethylenically unsaturated bond.
- a compound having at least one active hydrogen group and at least one terminal having an ethylenically unsaturated bond can be represented by the following structural formula (a). L 1 Lc m Z n (a)
- L 1 represents an m + n-valent linking group
- m and n are each independently an integer selected from 1 to 100
- Lc represents a monovalent ethylenically unsaturated group.
- Z represents an active hydrogen group.
- L 1 represents a divalent or higher aliphatic group, a divalent or higher aromatic group, a divalent or higher heterocyclic group, —O—, —S—, —NH—, —N ⁇ , —CO—, —SO. It is preferably —, —SO 2 — or a combination thereof.
- m and n are each independently preferably 1 to 50, more preferably 2 to 20, still more preferably 3 to 10, and particularly preferably 3 to 5.
- Examples of the monovalent ethylenically unsaturated group represented by Lc include allyl group, vinyl group, acryloyl group, methacryloyl group, and acrylamide group.
- Z is preferably OH, SH, NH or NH 2 , more preferably OH or NH 2 , and even more preferably OH.
- n represents an integer selected from 1 to 90, for example.
- a commercially available product may be used.
- the introduction of the polymerizable group into the gel particle has an isocyanate group of a trifunctional or higher functional isocyanate compound and at least one active hydrogen group, and at least one terminal is ethylenic.
- An isocyanate compound having a polymerizable group introduced by reacting with an active hydrogen group of a compound having an unsaturated bond is prepared, and the prepared isocyanate compound having an introduced polymerizable group and two or more active hydrogens described above This can be carried out by reacting a group-containing compound.
- the gel particles preferably further have a hydrophilic group on the surface.
- the gel particles have a hydrophilic group on the surface thereof, whereby dispersibility in an aqueous medium is further improved. Therefore, when the gel particles are applied to the ink composition or the photosensitive composition, the dispersibility of the gel particles in the ink composition or the like can be further improved.
- the hydrophilic group may exist as a part of the three-dimensional crosslinked structure, or may exist as a part other than the three-dimensional crosslinked structure.
- the hydrophilic group exists as a part other than the three-dimensional crosslinked structure” means that the gel particle contains an organic compound having a hydrophilic group separately from the three-dimensional crosslinked structure.
- the hydrophilic groups present on the surface of the gel particles include carboxylic acid groups, carboxylic acid group salts, phosphonic acid groups, phosphonic acid group salts, phosphoric acid groups, phosphoric acid group salts, sulfonic acid groups, sulfonic acid Examples thereof include a salt of a group, a sulfate group, a salt of a sulfate group, a group having a polyether structure, and a group having a betaine structure.
- the “hydrophilic group” is distinguished from the above-described active hydrogen groups (hydroxy group, primary amino group, secondary amino group, and mercapto group).
- carboxylic acid group salt, sulfonic acid group salt, sulfuric acid group salt, phosphonic acid group salt, and phosphoric acid group salt are salts formed by neutralization during the production of gel particles. Also good.
- the gel particle When the gel particle has a hydrophilic group on its surface, the gel particle may have only one kind of hydrophilic group or two or more kinds.
- the hydrophilic group introduced to the surface of the gel particle is preferably at least one selected from a group having a polyether structure, a carboxylic acid group, and a salt of the carboxylic acid group.
- the introduction of the hydrophilic group to the surface of the gel particle is performed by reacting the above-described trifunctional or higher isocyanate compound and the above-described compound having two or more active hydrogen groups with the compound having a hydrophilic group. Can be done. Further, when the above-described trifunctional or higher functional isocyanate compound is produced, the bifunctional or higher functional isocyanate compound is reacted with a compound having a hydrophilic group to introduce a hydrophilic group in advance and the two previously described. It can also be performed by reacting the above compound having an active hydrogen group.
- Examples of the compound having a hydrophilic group used for introduction of the hydrophilic group onto the surface of the gel particle include the compounds having the above-described hydrophilic group.
- the compound having a hydrophilic group a compound having a group having a polyether structure, a compound having a carboxylic acid group, and a compound having a salt of a carboxylic acid group are preferable.
- Examples of the compound containing a group having a polyether structure include a compound having a polyoxyalkylene chain.
- Specific examples include polyethylene oxide, polypropylene oxide, polytetramethylene oxide, polystyrene oxide, polycyclohexylene oxide, polyethylene oxide-polypropylene oxide-block copolymer, polyethylene oxide-polypropylene oxide random copolymer, and the like.
- polyethylene oxide, polypropylene oxide, and polyethylene oxide-polypropylene oxide block copolymers are preferable, and polyethylene oxide is more preferable.
- Examples of the compound having a group having a polyether structure include polyethylene oxide monoethers (monoethers include, for example, monomethyl ether and monoethyl ether), and polyethylene oxide monoesters (as monoesters). Are preferably monoacetic acid ester, mono (meth) acrylic acid ester, etc.).
- the compound having a carboxylic acid group or other ionic hydrophilic group include the following.
- the compound having a carboxylic acid group or other ionic hydrophilic group may be partially neutralized using an inorganic salt machine such as sodium hydroxide and an organic base such as triethylamine.
- a compound having a hydrophilic group isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), trimethylhexamethylene
- IPDI isophorone diisocyanate
- HDI hexamethylene diisocyanate
- TMHDI 1,3-bis (isocyanatemethyl) cyclohexane
- XDI m-xylylene diisocyanate
- HMDI dicyclohexylmethane-4,4′-diisocyanate
- TMP trimethylolpropane
- XDI m-xylylene diisocyanate
- EO polyethylene glycol monomethyl ether
- a carboxylic acid group or a salt of a carboxylic acid group as a hydrophilic group onto the surface of the gel particle, 2,2-bis (hydroxymethyl) propionic acid (DMPA) or 2,2-bis (hydroxymethyl) propionic acid
- DMPA 2,2-bis (hydroxymethyl) propionic acid
- the salt of the carboxylic acid group is preferably a sodium salt, potassium salt, triethylamine salt or dimethylethanolamine salt, more preferably a sodium salt or triethylamine salt.
- the amount of the compound having a hydrophilic group used for introducing a hydrophilic group to the surface of the gel particle is preferably 0.1% by mass to 50% by mass, and preferably 0.1% by mass to 45% with respect to the mass of the gel particle. % By mass is more preferable, 0.1% by mass to 40% by mass is more preferable, 1% by mass to 35% by mass is further preferable, and 3% by mass to 30% by mass is further preferable.
- the gel particles preferably further contain a polymerizable monomer.
- the aspect in which the gel particles encapsulate the polymerizable monomer is advantageous from the viewpoint of improving the film curing sensitivity and the film hardness.
- the gel particles include a polymerizable monomer
- the polymerizable group of the polymerizable monomer functions as a polymerizable group that the gel particles have.
- the polymerizable monomer encapsulated in the gel particles (hereinafter also referred to as an encapsulated polymerizable monomer) can be selected from polymerizable monomers having radically polymerizable ethylenically unsaturated bonds.
- polymerizable monomer is encapsulated in gel particles means that the polymerizable monomer is contained in the gel particles.
- the “inside of the gel particle” here means a void having a three-dimensional crosslinked structure.
- the gel particles preferably have an encapsulation rate (% by mass) of the polymerizable monomer of 50% by mass or more, more preferably 70% by mass or more, and further preferably 80% by mass or more.
- the encapsulation rate of at least one type of polymerizable monomer is in the above range.
- the inclusion ratio (% by mass) of the polymerizable monomer is the ratio of the polymerizable monomer contained in the gel particle to the total amount of the polymerizable monomer in the aqueous dispersion when the aqueous dispersion of the gel particle is prepared. It means quantity and refers to the value obtained as follows. The method for producing an aqueous dispersion of gel particles will be described later.
- -Measurement method of the encapsulation rate (% by mass) of polymerizable monomers The following operation is performed under the condition of a liquid temperature of 25 ° C. The following operations are performed using the aqueous dispersion as it is when the aqueous dispersion does not contain a pigment. When the aqueous dispersion contains a pigment, the aqueous dispersion is first centrifuged by centrifugation. The pigment is removed from the aqueous dispersion, and the dispersion is removed from the aqueous dispersion.
- sample 1 an aqueous dispersion of gel particles to be measured for the encapsulation rate (% by mass) of the polymerizable monomer was prepared, and two samples of the same mass (hereinafter referred to as “Sample 1” and “Sample”) were prepared from the prepared aqueous dispersion.
- Sample 2 To sample 1, 100 mass times tetrahydrofuran (THF) is added to the total solid content of sample 1 and mixed to prepare a diluted solution. The obtained diluted solution is centrifuged at 80,000 rpm (round per minute; the same applies hereinafter) for 40 minutes. A supernatant liquid (hereinafter referred to as “supernatant liquid 1”) generated by centrifugation is collected.
- supernatant liquid 1 A supernatant liquid (hereinafter referred to as “supernatant liquid 1”) generated by centrifugation is collected.
- the sample 1 is extracted into the supernatant liquid 1.
- the mass of the polymerizable monomer contained in the collected supernatant liquid 1 is measured by liquid chromatography (for example, a liquid chromatography apparatus manufactured by Waters).
- the mass of the obtained polymerizable monomer is defined as “total amount of polymerizable monomer”.
- the sample 2 is subjected to centrifugal separation under the same conditions as the centrifugal separation performed on the diluent.
- a supernatant liquid hereinafter referred to as “supernatant liquid 2”) generated by centrifugation is collected.
- the polymerizable monomer that was not included in the gel particles (that is, free) was extracted into the supernatant liquid 2.
- the mass of the polymerizable monomer contained in the collected supernatant liquid 2 is measured by liquid chromatography (for example, a liquid chromatography apparatus manufactured by Waters Co., Ltd.).
- the mass of the obtained polymerizable monomer is defined as “free amount of polymerizable monomer”.
- Examples of the polymerizable monomer having an ethylenically unsaturated bond capable of radical polymerization used as an encapsulating polymerizable monomer include monomers having an ethylenically unsaturated group, acrylonitrile, styrene, various unsaturated polyesters, and unsaturated polyethers. And radical polymerizable monomers such as unsaturated polyamide and unsaturated urethane.
- the inclusion polymerizable monomer is preferably a monomer having an ethylenically unsaturated group.
- the inclusion polymerizable monomer may be used alone or in combination of two or more.
- the inclusion polymerizable monomer is preferably at least one of a (meth) acrylate monomer and a vinyl ether monomer, and more preferably a (meth) acrylate monomer.
- inclusion polymerizable monomer examples include 2-hydroxyethyl acrylate, butoxyethyl acrylate, carbitol acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, benzyl acrylate, tridecyl acrylate, 2-phenoxyethyl acrylate, bis (4-acrylic).
- Roxypolyethoxyphenyl) propane polyethylene glycol diacrylate, polypropylene glycol diacrylate, dipentaerythritol tetraacrylate, trimethylolpropane triacrylate (for example, A-TMPT manufactured by Shin-Nakamura Chemical Co., Ltd.), pentaerythritol triacrylate (for example, , Shin-Nakamura Chemical Co., Ltd.
- A-TMM-3L ditrimethylolpropane tetraacrelane
- AD-TMP manufactured by Shin-Nakamura Chemical Co., Ltd.
- dipentaerythritol pentaacrylate for example, SR-399E manufactured by Sartomer
- dipentaerythritol hexaacrylate for example, A-DPH manufactured by Shin-Nakamura Chemical Co., Ltd.
- Oligoester acrylate N-methylol acrylamide, diacetone acrylamide, epoxy acrylate, isobornyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, dicyclopentanyl acrylate, neopentyl glycol propylene oxide adduct diacrylate
- Acrylate monomers such as (NPPGODA) (for example, SR9003 manufactured by Sartomer); methyl methacrylate, n-butyl methacrylate, allyl me
- trimethylolpropane triacrylate pentaerythritol triacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate, cyclohexane dimethanol vinyl ether (, trimethylpropane trivinyl ether (TMPTVE), dipentaerythritol) Hexaacrylate or neopentyl glycol propylene oxide adduct diacrylate is preferred, and dipentaerythritol pentaacrylate, cyclohexanedimethanol vinyl ether, or trimethylpropane trivinyl ether is more preferred.
- TMPTVE trimethylpropane trivinyl ether
- the inclusion polymerizable monomer is preferably a polyfunctional polymerizable monomer, more preferably a trifunctional or higher functional polymerizable monomer, and further preferably a tetrafunctional or higher functional polymerizable monomer from the viewpoint of crosslinkability and film strength.
- Examples of the encapsulating polymerizable monomer include, for example, JP-A-7-159983, JP-B-7-31399, JP-A-8-224982, JP-A-10-863, and JP-A-9-134011.
- photocurable polymerizable monomers used in photopolymerizable compositions described in JP-A-2004-514014 and other publications are known, and these can also be applied to gel particles.
- encapsulating monomer such as AH-600, AT-600, UA-306H, UA-306T, UA-306I, UA-510H, UF-8001G, DAUA.
- polymerizable monomers include NPGPODA (neopentyl glycol propylene oxide adduct diacrylate, Sartomer), SR399E (dipentaerythritol pentaacrylate, Sartomer), ATMM-3L (pentaerythritol triacrylate, Shin-Nakamura Chemical Co., Ltd.) )), A-DHP (dipentaerythritol hexaacrylate, Shin-Nakamura Chemical Co., Ltd.) and the like can be suitably used.
- NPGPODA neopentyl glycol propylene oxide adduct diacrylate, Sartomer
- SR399E dipentaerythritol pentaacrylate, Sartomer
- ATMM-3L pentaerythritol triacrylate, Shin-Nakamura Chemical Co., Ltd.
- A-DHP dipentaerythritol hexaacrylate, Shin-Nakamura Chemical Co
- the encapsulated polymerizable monomer is obtained by dissolving the encapsulated polymerizable monomer as an oil phase component together with the components constituting the gel particle when the gel particles are produced, and adding, mixing and emulsifying the water phase component to the oil phase component. , And can be contained inside the gel particles.
- the molecular weight of the encapsulated polymerizable monomer is preferably from 100 to 100,000, more preferably from 100 to 30,000, even more preferably from 100 to 10,000, even more preferably from 100 to 1,000, as a weight average molecular weight. It is preferably 100 to 900, more preferably 100 to 800, and particularly preferably 150 to 750.
- the lower limit of the weight average molecular weight of the encapsulating polymerizable monomer may be 200 or 250.
- the weight average molecular weight can be measured by gel permeation chromatography (GPC). The measuring method is as described later.
- the content of the encapsulating polymerizable monomer in the gel particles is preferably 0.1% by mass to 75% by mass, more preferably 0.5% by mass to 60% by mass with respect to the total solid content of the gel particles. More preferably, it is 1% by mass to 50% by mass.
- the volume average particle diameter of the gel particles is preferably 0.01 ⁇ m to 10.0 ⁇ m, more preferably 0.01 ⁇ m to 5 ⁇ m, and further preferably 0.05 ⁇ m to 1 ⁇ m from the viewpoint of dispersibility. .
- the volume average particle diameter of the gel particles can be measured by a light scattering method.
- a value measured by a wet particle size distribution measuring device LA-910 (manufactured by Horiba, Ltd.) is used.
- Whether or not a component other than the polymerizable monomer is encapsulated in the gel particles can be confirmed by a method similar to the method for examining whether or not the polymerizable monomer is encapsulated. However, for compounds having a molecular weight of 1,000 or more, the masses of the compounds contained in the above supernatant liquid 1 and supernatant liquid 2 were measured by gel permeation chromatography (GPC). The amount of inclusion (mass%) of the compound is determined.
- HLC registered trademark
- TSKgel registered trademark
- Super Multipore HZ-H 4.6 mmID ⁇
- 15 cm, Tosoh Corp. can be used and THF (tetrahydrofuran) can be used as an eluent.
- Measurement conditions are as follows: the sample concentration is 0.45 mass%, the flow rate is 0.35 ml / min, the sample injection amount is 10 ⁇ l, the measurement temperature is 40 ° C., and a differential refractive index (RI) detector is used. be able to.
- the calibration curve is “Standard sample TSK standard, polystyrene” of Tosoh Corporation: “F-40”, “F-20”, “F-4”, “F-1”, “A-5000”, “A -2500 ",” A-1000 ", and” n-propylbenzene ".
- the ink composition has a polymerizable group and a functional group that generates radicals upon irradiation with active energy rays, and a gel particle having a three-dimensional crosslinked structure including at least one bond selected from a urethane bond and a urea bond. , Water and a colorant. Since the ink composition contains the gel particles of one embodiment of the present invention described above, the occurrence of migration of low molecular weight components is suppressed, and a film (for example, an image) excellent in film strength can be obtained.
- the ink composition can be suitably used for inkjet recording.
- the gel particles are preferably contained in an amount of 1% by mass to 50% by mass with respect to the total mass of the ink composition, and 3% by mass to 40% by mass. More preferably, it is contained in an amount of 5% by mass to 35% by mass.
- content of a gel particle is a value also including the mass of those compounds, when compounds, such as a polymerizable monomer, are included in the inside of a particle
- the total solid content of the gel particles is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, further preferably 80% by mass or more, based on the total solid content of the ink composition. 85 mass% or more is especially preferable.
- the upper limit of the total solid content of the gel particles may be 100% by mass with respect to the total solid content of the ink composition.
- the ink composition contains solid components other than the gel particles, 99% by mass or less is preferable, and 95% by mass. The following is more preferable.
- the ink composition contains water, but the amount of water is not particularly limited. Among them, the preferable content of water is 10% to 99% by mass, more preferably 20% to 95% by mass, and further preferably 30% to 90% by mass with respect to the total mass of the ink composition. More preferably, it is 50 mass% to 90 mass%.
- the ink composition contains at least one colorant.
- a coloring agent There is no restriction
- the pigment is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include known organic pigments and inorganic pigments. Resin particles dyed with dyes, commercially available pigment dispersions and surfaces Treated pigments (for example, pigments dispersed in water, liquid organic compounds or insoluble resins, and pigment surfaces treated with resins, pigment derivatives, etc.) are also included.
- organic pigments and inorganic pigments include yellow pigments, red pigments, magenta pigments, blue pigments, cyan pigments, green pigments, orange pigments, purple pigments, brown pigments, black pigments, and white pigments.
- yellow pigments include C.I. I.
- red pigments or magenta pigments examples include C.I. I. Pigment Red 193 and other monoazo lake pigments, 38 and other disazo pigments, 2, 5, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 22, 23, 31, 32, 112, 114, 146, 147, 150, 170, 184, 187, 188, 210, 213, 238, 245, 253, 256, 258, 266, 268, 269, etc.
- blue pigments or cyan pigments include C.I. I.
- Naphthol AS pigments such as CI Pigment Blue 25 and 26, phthalocyanine pigments such as 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17: 1, 75, and 79
- Dye lake pigments such as 1:56, 61, 62, anthraquinone pigments such as 60, indigo pigments such as 63, and dioxazine pigments such as 80 are preferable.
- green pigments include C.I. I. Dye lake pigments such as CI Pigment Green 1 and 4, phthalocyanine pigments such as 7 and 36, and azomethine metal complex pigments such as 8 are preferable.
- the orange pigment include C.I. I. Pigment Orange 1 monoazo pigment, 2, 3, 5 etc.
- Anthraquinone pigments such as 61, isoindolinone pigments such as 61, isoindoline pigments such as 66, azomethine metal complex pigments such as 68, and diketopyrrolopyrrole pigments such as 71, 73 and 81 are preferred.
- brown pigments examples include C.I. I. BONA lake pigments such as CI Pigment Brown 5, condensed azo pigments such as 23, 41 and 42, and benzimidazolone pigments such as 25 and 32 are preferred.
- purple pigments include C.I. I. Pigment violet 1, 2, 3, 27 etc. dyed lake pigments, 13, 17, 25, 50 etc. naphthol AS pigments, 5: 1 etc. anthraquinone lake pigments, 19 etc. quinacridone pigments, 23, 37 etc. dioxazine pigments
- a perylene pigment such as No. 29, benzimidazolone pigment such as No. 32, and a thioindigo pigment such as No. 38 are preferred.
- black pigments examples include C.I. I.
- Indazine pigments such as CI pigment black 1, carbon black as 7, graphite as 10, magnetite as 11, anthraquinone pigment as 20 and perylene pigment as 31 and 32 are preferable.
- white pigments include C.I. I. Pigment White 4 Zinc oxide, 6 Titanium oxide, 7 Zinc sulfide, 12 Zirconium oxide (zirconium white), 18 Calcium carbonate, 19 Aluminum oxide / silicon oxide (Kaolin clay), 21 Or the barium sulfate which is 22, the aluminum hydroxide (alumina white) which is 23, the silicon oxide which is 27, and the calcium silicate which is 28 are preferable.
- the inorganic particles used in the white pigment may be simple substances, or may be oxides such as silicon, aluminum, zirconium, and titanium, organometallic compounds, and composite particles with organic compounds.
- the pigment, the dispersant, the medium, and the like so that the volume average particle diameter of the pigment particles is preferably 0.005 ⁇ m to 0.5 ⁇ m, more preferably 0.01 ⁇ m to 0.45 ⁇ m, still more preferably 0.015 ⁇ m to 0.4 ⁇ m. Selection, dispersion conditions, and filtration conditions are preferably set.
- the volume average particle size and particle size distribution of the pigment particles are determined by a dynamic light scattering method using a commercially available particle size measuring device such as a wet particle size distribution measuring device LA-910 (manufactured by Horiba, Ltd.). It is obtained by measuring the average particle diameter.
- water-soluble dyes examples include acid dyes and direct dyes. Acid dyes and direct dyes have a structure having an acid group as a solubilizing group. Examples of acidic groups include sulfonic acid groups and salts thereof, carboxylic acid groups and salts thereof, phosphoric acid groups and salts thereof. The number of acidic groups may be one, multiple, or a combination.
- the chemical structure of the chromophore contained in the water-soluble dye includes azo, phthalocyanine, triphenylmethane, xanthene, pyrazolone, nitro, stilbene, quinoline, methine, thiazole, quinoneimine, and indigoid. Type, rhodamine type, anthraquinone type, anthraquinone type and the like.
- the content of the colorant in the ink composition can be appropriately selected, but is preferably 0.1% by mass to 30% by mass, and preferably 0.5% by mass with respect to the total mass of the ink composition. More preferably, it is ⁇ 20% by mass.
- a pigment dispersant may be used as necessary when preparing the pigment particles.
- the pigment dispersant that can be used include higher fatty acid salts and alkyl sulfates. , Alkyl ester sulfate, alkyl sulfonate, sulfosuccinate, naphthalene sulfonate, alkyl phosphate, polyoxyalkylene alkyl ether phosphate, polyoxyalkylene alkyl phenyl ether, polyoxyethylene polyoxypropylene glycol, glycerin Activators such as esters, sorbitan esters, polyoxyethylene fatty acid amides, amine oxides, or styrene, styrene derivatives, vinyl naphthalene derivatives, acrylic acid, acrylic acid derivatives, maleic acid, maleic acid derivatives, itaconic acid, itaconic acid derivatives, fumar Acid, a
- various dispersing machines such as a ball mill, a sand mill, an attritor, a roll mill, an agitator, a Henschel mixer, a colloid mill, an ultrasonic homogenizer, a pearl mill, a wet jet mill, and a paint shaker can be used.
- a centrifugal separator or a filter for the purpose of removing coarse particles of the pigment dispersion.
- sensitizer It is preferable to add a sensitizer to the ink composition in order to promote the decomposition of the functional group that generates radicals by irradiation with active energy rays of the gel particles by irradiation with active energy rays.
- the sensitizer absorbs specific active energy rays and enters an electronically excited state.
- the sensitizer in an electronically excited state comes into contact with a functional group that generates radicals upon irradiation with active energy rays, and causes an action such as electron transfer, energy transfer, and heat generation. It promotes the chemical change of the functional group that generates oxygen, that is, decomposition and generation of radicals.
- sensitizers examples include benzophenone, thioxanthone, especially also isopropylthioxanthone, anthraquinone and 3-acylcoumarin derivatives, terphenyl, styryl ketone and 3- (aroylmethylene) thiazoline, camphorquinone, eosin, Examples include rhodamine and erythrosine.
- a compound represented by the general formula (i) described in JP2010-24276A and a compound represented by the general formula (I) described in JP-A-6-107718 can be suitably used. .
- the sensitizer is at least one selected from thioxanthone, isopropylthioxanthone, and benzophenone from the viewpoint of compatibility with LED light and reactivity with functional groups that generate radicals upon irradiation with active energy rays. At least one selected from thioxanthone and isopropylthioxanthone is more preferable, and isopropylthioxanthone is still more preferable.
- the sensitizer may be contained singly or in combination of two or more.
- the sensitizer When the ink composition contains a sensitizer, the sensitizer has the effect of one embodiment of the present invention from the viewpoint that the reactivity with a functional group that generates radicals upon irradiation with active energy rays is further improved. It may be included in the gel particles as long as it is not impaired.
- the content of the sensitizer is preferably 0.1% by mass to 25% by mass with respect to the total mass of the ink composition.
- a polymerization inhibitor may be added from the viewpoint of enhancing the storage stability.
- the polymerization inhibitor include p-methoxyphenol, quinones such as hydroquinone and methoxybenzoquinone, phenothiazine, catechol, alkylphenols, alkylbisphenols, zinc dimethyldithiocarbamate, copper dimethyldithiocarbamate, copper dibutyldithiocarbamate, and salicylic acid.
- Examples thereof include copper, thiodipropionic acid esters, mercaptobenzimidazole, phosphites, etc., and p-methoxyphenol, catechols, and quinones are preferable, and hydroquinone, benzoquinone, p-methoxyphenol, TEMPO, TEMPOL, and cupron Al, tris (N-nitroso-N-phenylhydroxylamine) aluminum salt, and the like are more preferable.
- UV absorber An ultraviolet absorber may be used in the ink composition from the viewpoint of improving the weather resistance of the resulting film and preventing discoloration.
- Examples of the ultraviolet absorber include known ultraviolet absorbers such as benzotriazole compounds, benzophenone compounds, triazine compounds, and benzoxazole compounds.
- Organic solvent In order to improve the adhesion to the recording medium, the following organic solvent may be added to the ink composition.
- Alcohols eg, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol, tertiary butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol, etc.
- Polyhydric alcohols for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol, 2- Methylpropanediol, etc.
- Polyhydric alcohol ethers for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl
- the content of the solvent is preferably 1% by mass to 30% by mass and more preferably 1% by mass to 20% by mass with respect to the total mass of the ink composition.
- a surfactant may be added to the ink composition.
- the surfactant used in the ink composition is distinguished from the surfactant used at the time of gel particle production.
- examples of the surfactant include those described in JP-A Nos. 62-173463 and 62-183457. Examples thereof include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, acetylene glycols, polyoxyethylene / polyoxypropylene block copolymers, and siloxanes.
- An organic fluoro compound may be used in place of the surfactant.
- the organic fluoro compound is preferably hydrophobic.
- organic fluoro compound examples include fluorine surfactants, oily fluorine compounds (eg, fluorine oil) and solid fluorine compound resins (eg, tetrafluoroethylene resin). Examples described in Japanese Patent Publications (columns 8 to 17) and JP-A No. 62-135826.
- the ink composition may contain a polymerizable compound, a water-soluble resin, a water-dispersible resin, and the like outside the gel particles as necessary from the viewpoints of film physical properties, adhesion, and ejection property control. Good.
- the ink composition contains a polymerizable compound outside the gel particles means that the ink composition contains a polymerizable compound that is not included in the gel particles. The same applies when a water-soluble resin, a water-dispersible resin, or the like is contained outside the gel particles.
- the ink composition preferably contains a polymerizable compound outside the gel particles.
- the crosslinking efficiency between the gel particles can be improved, and a film with higher film strength can be formed. Furthermore, crosslinking proceeds with high efficiency even for active energy rays (light) having a low exposure illuminance (for example, 40 mJ / cm 2 to 70 mJ / cm 2 ).
- the polymerizable compound examples include radically polymerizable compounds such as compounds having an ethylenically unsaturated group, acrylonitrile, styrene, unsaturated polyester, unsaturated polyether, unsaturated polyamide, and unsaturated urethane.
- radically polymerizable compounds such as compounds having an ethylenically unsaturated group, acrylonitrile, styrene, unsaturated polyester, unsaturated polyether, unsaturated polyamide, and unsaturated urethane.
- the polymerizable compound is preferably a water-soluble or water-dispersible polymerizable compound. “Water-soluble” means a property in which the amount dissolved in 100 g of distilled water at 25 ° C.
- Water dispersibility refers to the property of being insoluble in water and being dispersed in water.
- water-insoluble means a property in which the amount dissolved in 100 g of distilled water at 25 ° C. is 1 g or less when dried at 105 ° C. for 2 hours.
- the polymerizable compound includes a compound having at least one selected from the group consisting of an amide structure, a polyethylene glycol structure, a polypropylene glycol structure, a carboxyl group, and a salt of a carboxy group. preferable.
- examples of the polymerizable compound that can be contained outside the gel particles include (meth) acrylic acid, sodium (meth) acrylate, potassium (meth) acrylate, N, N. -Dimethylacrylamide, N, N-diethylacrylamide, morpholine acrylamide, N-2-hydroxyethyl (meth) acrylamide, N-vinylpyrrolidone, N-vinylcaprolactam, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meta ) Acrylate, 2-hydroxypropyl (meth) acrylate, glycerin monomethacrylate, N- [tris (3-acryloylaminopropyloxymethylene) methyl] acrylamide, diethylene glycol bis (3-acryloylaminoproyl) ether Polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, compounds represented by the following
- each of the plurality of R 1 independently represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group
- each of the plurality of R 2 independently represents a hydrogen atom or a methyl group
- L 1 each independently represents a single bond or a divalent linking group.
- each of the plurality of R 3 independently represents a hydrogen atom or a methyl group
- each of the plurality of L 2 independently represents an alkylene group having 1 to 8 carbon atoms
- a plurality of k and p Each independently represents 0 or 1
- a plurality of m each independently represents an integer of 0 to 8, provided that at least one of k and p is 1.
- a plurality of R 4 s each independently represent a hydrogen atom or a methyl group
- a plurality of n s each independently represents an integer of 1 to 8
- l represents an integer of 0 or 1.
- Z 1 represents a residue obtained by removing q hydrogen atoms from a hydroxyl group of a polyol
- q represents an integer of 3 to 6
- a plurality of R 5 s independently represent a hydrogen atom or a methyl group.
- a plurality of L 3 s each independently represents an alkylene group having 1 to 8 carbon atoms.
- Specific examples of the compounds represented by the general formula (a) to the general formula (d) include compounds represented by the following AM-1 to AM-4.
- the above AM-1 to AM-4 can be synthesized by the method described in Japanese Patent No. 05591858.
- Water-soluble resin or water-dispersible resin that can be contained outside the gel particles There is no restriction
- Examples of the structure of the water-soluble resin or water-dispersible resin include a chain structure, a branched (branched) structure, a star structure, a crosslinked structure, and a network structure.
- Water-soluble” in the water-soluble resin is synonymous with “water-soluble” in the above-mentioned “water-soluble polymerizable compound”, and “water-dispersible” in the water-dispersible resin is the same as “water-dispersible polymerization”. It is synonymous with “water dispersibility” in the “soluble compound”.
- water-soluble resin or water-dispersible resin examples include carboxy group, carboxy group salt, sulfo group, sulfo group salt, sulfuric acid group, sulfuric acid group salt, phosphonic acid group, phosphonic acid group salt, phosphoric acid group, phosphorous group
- a resin having a functional group selected from a salt of an acid group, an ammonium base, a hydroxyl group, a carboxylic acid amide group, and an alkyleneoxy group is preferable.
- an alkali metal cation such as sodium or potassium, an alkaline earth metal cation such as calcium or magnesium, an ammonium cation, or a phosphonium cation is preferable, and an alkali metal cation is particularly preferable.
- the alkyl group contained in the ammonium group of the ammonium base is preferably a methyl group or an ethyl group.
- the counter anion of the ammonium base is preferably a halogen anion such as chlorine or bromine, a sulfate anion, a nitrate anion, a phosphate anion, a sulfonate anion, a carboxylate anion, or a carbonate anion, and a halogen anion, a sulfonate anion, or Carboxylic acid anions are particularly preferred.
- a substituent on the nitrogen atom of the carboxylic acid amide group an alkyl group having 8 or less carbon atoms is preferable, and an alkyl group having 6 or less carbon atoms is particularly preferable.
- the resin having an alkyleneoxy group preferably has an alkyleneoxy chain composed of repeating alkyleneoxy groups. The number of alkyleneoxy groups contained in the alkyleneoxy chain is preferably 2 or more, and particularly preferably 4 or more.
- the ink composition has a viscosity of preferably 3 mPa ⁇ s to 15 mPa ⁇ s, more preferably 3 mPa ⁇ s to 13 mPa ⁇ s, when the ink composition is 25 ° C. to 50 ° C.
- the viscosity of the ink composition at 25 ° C. is preferably 50 mPa ⁇ s or less.
- the control range of the temperature of the ink composition is preferably set to ⁇ 5 ° C. of the set temperature, more preferably ⁇ 2 ° C. of the set temperature, and further preferably set to ⁇ 1 ° C.
- the viscosity of the ink composition is a viscometer: VISCOMETER TV-22 (manufactured by Toki Sangyo Co., Ltd.).
- the photosensitive composition has a three-dimensional cross-linked structure having a polymerizable group and a functional group that generates radicals upon irradiation with active energy rays, and having at least one bond selected from a urethane bond and a urea bond. And water.
- the gel particles and water used in the photosensitive composition can be the same as those used in the ink composition described above. Since the photosensitive composition contains the gel particles of one embodiment of the present invention described above, the occurrence of migration of low molecular weight components is suppressed, and a film having excellent film strength can be obtained.
- the photosensitive composition preferably further contains a polymerizable compound outside the gel particles from the viewpoint of film strength.
- the photosensitive composition which is formed by irradiation with active energy rays, is excellent in film strength. Therefore, it is suitable for various uses such as coating agents, adhesives, paints, etc. Can be used.
- the method for producing an aqueous dispersion of gel particles is not particularly limited as long as an aqueous dispersion of gel particles including the gel particles having the above-described configuration and water can be produced.
- the method for producing an aqueous dispersion of gel particles of the present embodiment described below is preferable from the viewpoint of easily obtaining an aqueous dispersion of gel particles.
- the method for producing an aqueous dispersion of gel particles of the present embodiment is a trifunctional or higher functional isocyanate compound having a functional group that generates radicals upon irradiation with active energy rays.
- An oil phase component containing a polymerizable monomer and an organic solvent hereinafter also referred to as “oil phase component A”
- oil phase component A a trifunctional or higher functional isocyanate compound having a functional group that generates radicals upon irradiation with active energy rays
- a polymerizable property is a trifunctional or higher functional isocyanate compound having a functional group that generates radicals upon irradiation with active energy rays.
- oil phase component B An oil phase component (hereinafter also referred to as “oil phase component B”) containing a trifunctional or higher functional isocyanate compound having a group and an organic solvent, a polymerizable group and a functional group that generates radicals upon irradiation with active energy rays.
- oil phase component C An oil phase component (hereinafter, also referred to as “oil phase component C”) containing a trifunctional or higher functional isocyanate compound, a polymerizable monomer, and an organic solvent, and an active energy Any one selected from trifunctional or higher functional isocyanate compounds having a functional group that generates radicals upon irradiation with radiation, trifunctional or higher functional isocyanate compounds having a polymerizable group, a polymerizable monomer, and an oil phase component containing an organic solvent Any oil phase component selected from oil phase components (hereinafter also referred to as “oil phase component D”) and an aqueous phase component containing water are mixed and emulsified to obtain an emulsion; And a gelation step of gelling by heating the emulsion.
- the oil phase component A, the oil phase component B, and the oil phase component D are preferable from the viewpoint that an aqueous dispersion of gel particles can be more easily produced.
- the manufacturing method of this embodiment may have another process as needed. According to the manufacturing method of the present embodiment, the above-described aqueous dispersion of gel particles can be easily manufactured.
- the emulsification step mixes and emulsifies any oil phase component selected from oil phase component A, oil phase component B, oil phase component C, and oil phase component D and an aqueous phase component containing water. This is a step of obtaining an emulsion.
- a trifunctional or higher functional isocyanate compound having a radical generating functional group, a trifunctional or higher functional isocyanate compound having a polymerizable group, an oil phase component B containing an organic solvent, and a radical generated by irradiation of the polymerizable group and active energy rays A trifunctional or higher functional isocyanate compound having a radical generating functional group, a trifunctional or higher functional isocyanate compound having a polymerizable group, an oil phase component B containing an organic solvent, and a radical generated by irradiation of the polymerizable group and active energy rays.
- Gel particles having a functional group to be generated can be obtained.
- Polymerizable monomer contained in oil phase component A, oil phase component C, and oil phase component D, and trifunctional or higher functional isocyanate compound having a polymerizable group contained in oil phase component B, oil phase component C, and oil phase component D Is considered to be a polymerizable group present on the surface of the gel particle, or on the surface and in the vicinity of the surface.
- Examples of the organic solvent contained in the oil phase component include ethyl acetate and methyl ethyl ketone.
- the oil phase component may contain other components as necessary in addition to the above components.
- the other components include compounds having the above-described hydrophilic group.
- gel particles having a hydrophilic group on the surface can be obtained.
- the trifunctional or higher functional isocyanate compound is as described in the above-mentioned gel particle section.
- the trifunctional or higher functional isocyanate compound is selected from isophorone diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, 1,3-bis (isocyanatemethyl) cyclohexane, m-xylylene diisocyanate, and dicyclohexylmethane 4,4'-diisocyanate.
- Isocyanate compounds derived from at least one of the above are preferred.
- the water phase component may contain other components as needed in addition to water.
- an aqueous phase component May contain a neutralizing agent.
- the hydrophilic group such as a carboxy group is neutralized by mixing the oil phase component and the water phase component, A salt such as a carboxy group is formed. This formed salt also functions as a hydrophilic group of the gel particles.
- the neutralizing agent include sodium hydroxide.
- a raw material for forming gel particles having a three-dimensional crosslinked structure containing at least one bond selected from a urethane bond and a urea bond by reaction with an isocyanate group in addition to water, as described above
- a polyfunctional alcohol, a polyfunctional phenol, a polyfunctional amine having a hydrogen atom on a nitrogen atom, a polyfunctional thiol, or the like may be used.
- polyfunctional alcohols for example, propylene glycol, glycerin, trimethylolpropane, etc.
- polyfunctional amines for example, bis (hexamethylene) triamine, ethylenediamine, diethylenetriamine, etc.
- polyfunctional thiols for example, pentaerythritol tetra
- 3-mercaptopropionate and the like
- polyfunctional alcohols are particularly preferred.
- These compounds may be used alone or in combination of two or more. These compounds are added to the oil phase component and / or the aqueous phase component depending on the solubility and the like.
- surfactant in addition to the above-described raw materials.
- the above-mentioned surfactant is mentioned, for example.
- surfactants used for emulsification dispersion are considered to be excellent surfactants having a relatively long-chain hydrophobic group.
- surfactants surfactants described in “Surfactant Handbook” (Nishiichiro et al., Published by Sangyo Tosho (1980)), specifically alkyl sulfates, alkyl sulfonic acids, alkyl benzene sulfonic acids, etc. Alkali metal salts are preferred, and alkyl sulfate salts are more preferred.
- the alkyl chain length of the alkyl sulfate ester salt is preferably 12 or more, and more preferably 16 or more.
- Surfactants include sodium salts and polycarboxylates of aromatic sulfonic acid formalin condensates such as polymer type surfactant sodium naphthalene sulfonate formalin condensate, and polyoxyethylene as reactive surfactant. Also included are 1- (allyloxymethyl) alkyl ether sulfates and polyoxyethylene nonylpropenyl phenyl ether sulfates. High molecular surfactants and reactive surfactants can be particularly preferably used from the viewpoint of suppressing migration.
- the surfactant may be added to either the oil phase component or the aqueous phase component, but is usually added to the aqueous phase component because of its low solubility in organic solvents.
- the amount of the surfactant is preferably 0.1% by mass to 5% by mass and more preferably 0.5% by mass to 3% by mass with respect to the total solid content of the oil phase component.
- total solid content corresponds to the total solid content of the gel particles to be produced.
- the amount of the trifunctional or higher functional isocyanate compound having a functional group that generates radicals upon irradiation with active energy rays in the oil phase component is not particularly limited. % Is preferred.
- the amount of the trifunctional or higher functional isocyanate compound having a polymerizable group in the oil phase component is not particularly limited, and is preferably 10% by mass to 70% by mass with respect to the total solid content, for example.
- the amount of the trifunctional or higher functional isocyanate compound having a polymerizable group in the oil phase component and a functional group that generates radicals upon irradiation with active energy rays is not particularly limited.
- the mass is preferably 25% by mass.
- the amount of the polymerizable monomer in the oil phase component is not particularly limited, and is preferably 0.1% by mass to 75% by mass with respect to the total solid content, for example.
- the amount of the organic solvent is not particularly limited, and is appropriately selected depending on the type and amount of components contained in the oil phase component.
- the amount of water is not particularly limited, and is appropriately selected depending on the type and amount of components contained in the oil phase component.
- the amount of the compound having a hydrophilic group in the oil phase component is not particularly limited, and is, for example, 0.1% by mass to 40% with respect to the total solid content. It is preferable that it is mass%.
- Each component contained in the oil phase component may be simply mixed, all the components may be mixed at once, or each component may be divided into several parts and mixed.
- the method for mixing the oil phase component and the aqueous phase component is not particularly limited, and examples thereof include mixing by stirring.
- the method for emulsifying the mixture obtained by mixing is not particularly limited, and examples thereof include emulsification using an emulsifying device (for example, a disperser) such as a homogenizer.
- the number of rotations of the disperser in the emulsification is, for example, 5000 rpm to 20000 rpm, and preferably 10,000 rpm to 15000 rpm.
- the rotation time in emulsification is, for example, 1 minute to 120 minutes, preferably 3 minutes to 60 minutes, more preferably 3 minutes to 30 minutes, and further preferably 5 minutes to 15 minutes.
- the gelling step is a step of heating the above-mentioned emulsion to cause gelation.
- a three-dimensional cross-linked structure containing at least one selected from a urethane bond and a urea bond is obtained by the reaction of the trifunctional or higher isocyanate compound with water by crosslinking of the isocyanate groups by heating the emulsion.
- the heating temperature (reaction temperature) of the emulsion in the gelation step is preferably 35 ° C to 70 ° C, more preferably 40 ° C to 60 ° C.
- the heating time (reaction time) in the gelation step is preferably 6 hours to 50 hours, more preferably 12 hours to 40 hours, and even more preferably 15 hours to 35 hours.
- the gelling step preferably includes a step of distilling off the organic solvent from the emulsion.
- the mixing step may include a step of mixing the gel particles, water, and colorant obtained in the gelation step.
- the method for mixing the gel particles, water, and the colorant is not particularly limited. Moreover, you may use a gel particle in the state of a dispersion liquid.
- the colorant is as described as the colorant contained in the aqueous dispersion of gel particles described above.
- the manufacturing method of this embodiment may have other processes other than an emulsification process, a gelatinization process, and a mixing process as needed. Examples of other steps include a step of adding other components.
- the other components to be added are as already described as other components that can be contained in the aqueous dispersion of gel particles.
- the aqueous dispersion of gel particles produced by the method for producing an aqueous dispersion of gel particles can be suitably used for an ink composition, a coating agent, an adhesive, a paint, and the like.
- the image forming method includes an ink application step of applying the above-described ink composition onto a recording medium, and an irradiation step of irradiating the ink composition applied onto the recording medium with active energy rays. By performing these steps, a film (for example, an image) made of the ink composition fixed on the recording medium is formed.
- ink application process Ink application process
- the ink application process is not limited as long as the ink composition is applied to the recording medium.
- an aspect in which the ink composition by the ink jet method is applied on the recording medium is particularly preferable.
- an ink jet recording apparatus used when the ink applying process ink jet method is applied is not particularly limited, and a known ink jet recording apparatus capable of achieving a target resolution is arbitrarily selected and used. be able to. That is, any known inkjet recording apparatus including a commercially available product can discharge the ink composition onto the recording medium in the image forming method.
- Examples of the ink jet recording apparatus include an apparatus including an ink supply system, a temperature sensor, and a heating unit.
- the ink supply system includes, for example, an original tank containing an ink composition, a supply pipe, an ink supply tank immediately before the inkjet head, a filter, and a piezo-type inkjet head.
- the piezo-type inkjet head preferably has a multi-size dot of 1 pl to 100 pl, more preferably 8 pl to 30 pl, preferably 320 dpi ⁇ 320 dpi to 4000 dpi ⁇ 4000 dpi (dot per inch), more preferably 400 dpi ⁇ 400 dpi to 1600 dpi ⁇ 1600 dpi. More preferably, it can be driven so that ejection can be performed at a resolution of 720 dpi ⁇ 720 dpi.
- dpi represents the number of dots per 2.54 cm (1 inch).
- the ink jet recording apparatus preferably includes a means for stabilizing the ink composition temperature.
- the parts to be kept at a constant temperature are all the piping systems and members from the ink tank (intermediate tank if there is an intermediate tank) to the nozzle ejection surface. That is, heat insulation and heating can be performed from the ink supply tank to the inkjet head portion.
- the temperature control method is not particularly limited, but for example, it is preferable to provide a plurality of temperature sensors in each piping portion and perform heating control according to the flow rate of the ink composition and the environmental temperature.
- the temperature sensor can be provided near the ink supply tank and the nozzle of the inkjet head.
- the head unit to be heated is thermally shielded or insulated so that the apparatus main body is not affected by the temperature from the outside air.
- the recording medium is not particularly limited, and a known recording medium can be used as a support or a recording material.
- the recording medium include paper, paper laminated with plastic (eg, polyethylene, polypropylene, polystyrene, etc.), metal plate (eg, aluminum, zinc, copper, etc.), plastic film (eg, polyvinyl chloride resin, two Cellulose acetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc.), paper or plastic laminated or vapor-deposited with the above metals A film etc.
- plastic eg, polyethylene, polypropylene, polystyrene, etc.
- metal plate eg, aluminum, zinc, copper, etc.
- plastic film eg, polyvinyl chloride resin, two Cellulose acetate,
- the ink composition is excellent in adhesion, it can be suitably used as a recording medium for a non-absorbing recording medium, and a plastic substrate such as polyvinyl chloride, polyethylene terephthalate, polyethylene is preferable, and polyvinyl chloride.
- a resin base material is more preferable, and a polyvinyl chloride resin sheet or film is more preferable.
- An irradiation process will not be limited if it is a process of irradiating an active energy ray to the ink composition provided on the recording medium.
- the crosslinking reaction of the gel particles in the ink composition proceeds to fix the image and improve the film strength of the image.
- UV light ultraviolet rays
- visible rays visible rays
- electron beams electron beams
- UV light ultraviolet rays
- the peak wavelength of the active energy ray (light) depends on the absorption characteristics of the sensitizer used as necessary, but is preferably, for example, 200 nm to 405 nm, more preferably 220 nm to 390 nm, and 220 nm. More preferably, it is ⁇ 385 nm. In the case where a sensitizer is not used in combination, for example, it is preferably 200 nm to 310 nm, more preferably 200 nm to 280 nm.
- Exposure surface illuminance when the active energy ray (light) is irradiated for example, 10mW / cm 2 ⁇ 2000mW / cm 2, preferably, it is appropriate to be irradiated with 20mW / cm 2 ⁇ 1000mW / cm 2 .
- LED Light Emitting Diode
- LD Laser Diode
- a metal halide lamp an ultra high pressure mercury lamp, a high pressure mercury lamp, a medium pressure mercury lamp, a low pressure mercury lamp, an LED, or a blue-violet laser is preferable.
- an ultrahigh pressure mercury lamp capable of irradiating light with a wavelength of 365 nm, 405 nm, or 436 nm an ultrahigh pressure mercury lamp capable of irradiating light with a wavelength of 365 nm, 405 nm, or 436 nm
- a high pressure mercury lamp capable of irradiating with a wavelength of 365 nm, 405 nm, or 436 nm
- An LED capable of light irradiation with a wavelength of 355 nm, 365 nm, 385 nm, 395 nm, or 405 nm is more preferable, and an LED capable of light irradiation with a wavelength of 355 nm, 365 nm, 385 nm, 395
- the gel particles have a functional group that generates radicals upon irradiation with active energy rays
- a photopolymerization initiator that cannot be conventionally used in water-based inks, for example, light
- a structure similar to that of a photopolymerization initiator such as an acylphosphine oxide compound having excellent sensitivity to water but low solubility in water can be selected.
- a monoacylphosphine oxide structure represented by the general formula J a bisacylphosphine oxide structure represented by the general formula K, and a bisacylphosphine oxide structure represented by the general formula L having an absorption wavelength of 350 nm to 450 nm
- a gel particle having a group containing at least one structure selected from the above and a sensitizer such as a thioxanthone compound are used in combination, an LED is particularly preferable as the light source.
- an active energy ray (light) having a peak wavelength at 380 nm to 450 nm, which is longer than ultraviolet rays can be preferably used.
- a group comprising at least one structure selected from a monoacylphosphine oxide structure represented by general formula J, a bisacylphosphine oxide structure represented by general formula K, and a bisacylphosphine oxide structure represented by general formula L
- a metal halide lamp, an intermediate pressure mercury lamp, or a low pressure mercury lamp is preferable.
- the ink composition applied on the recording medium may be irradiated with such UV light, for example, for 0.01 seconds to 120 seconds, preferably 0.1 seconds to 90 seconds. Is appropriate.
- the irradiation conditions and the basic irradiation method the irradiation conditions and the irradiation method disclosed in JP-A-60-132767 can be similarly applied to one embodiment of the present invention.
- a light source is provided on both sides of the head unit including the ink ejection device, and the head unit and the light source are scanned by a so-called shuttle method, or another light source that is not driven and driven is used. Is preferred.
- the irradiation with the active energy ray is performed after a certain period of time (for example, 0.01 seconds to 120 seconds, preferably 0.01 seconds to 60 seconds) after ink landing and heat drying.
- the image forming method may further include a heat drying step after the ink application step and before the irradiation step, if necessary.
- a heat drying step it is preferable that the ink composition discharged onto the recording medium is fixed with an image by evaporating water and a water-soluble organic solvent used in combination as necessary.
- the heating means is not limited as long as it can dry water and a water-soluble organic solvent used in combination as required, but a heat drum, hot air, an infrared lamp, a heat oven, a heat plate heating or the like is used. Can do.
- the heating temperature is preferably 40 ° C. or higher, more preferably about 40 ° C. to 150 ° C., and further preferably about 40 ° C. to 80 ° C.
- the drying / heating time can be appropriately set in consideration of the composition of the ink composition to be used and the printing speed.
- the ink composition fixed by heating is irradiated with active energy rays in an irradiation step as necessary, and is further photofixed.
- fixing with UV light is preferable.
- TMP Trimethylolpropane
- HDI hexamethylene diisocyanate
- AcOEt ethyl acetate
- TMP Trimethylolpropane
- IPDI isophorone diisocyanate
- AcOEt ethyl acetate
- TMP Trimethylolpropane
- XDI m-xylylene diisocyanate
- AcOEt ethyl acetate
- NCO104, NCO105, NCO112, and INT-NCO1 to INT-NCO27 shown in Tables 3 and 4 below were prepared in the same manner as NCO103, NCO109, and INT-NCO1, INT-NCO9, and INT-NCO11.
- the indication of “initiator” in Table 4 represents an exemplary compound of a compound having at least one active hydrogen group and a functional group that generates radicals by at least one active energy ray as described above, and “isocyanate compound” "Represents a bifunctional or higher isocyanate compound.
- ⁇ Gelification process> The obtained emulsion was added to 25 g of distilled water, stirred at room temperature for 30 minutes, and then stirred at 50 ° C. for 3 hours to distill off ethyl acetate. Thereafter, the mixture is further stirred at 50 ° C. for 24 hours, diluted with distilled water so that the solid content concentration of the obtained dispersion of gel particles is 20% by mass, and the dispersion of gel particles 1 (water of gel particles) Dispersion) was obtained.
- the volume average particle diameter of the gel particles measured by the light scattering method was 0.15 ⁇ m.
- a wet particle size distribution measuring device LA-910 manufactured by Horiba, Ltd.
- the ink composition prepared above was manufactured using RK PRINT COAT INSTRUMENTS K Hand Coater No. It was applied to a substrate (vinyl chloride (PVC) sheet (Avery 400 GLOSS WHITE PERMANENT)) with a thickness of 12 ⁇ m using 2 bars. After coating, the coating film was dried at 60 ° C. for 3 minutes to remove moisture and obtain a sample for ink composition evaluation. The following evaluation was performed about the obtained sample. The evaluation results are shown in Table 6 below.
- Evaluation criteria 0 The cut edge is smooth and all the lattices are not peeled off.
- 3 Partial or full peeling is observed along the edge of the cut portion of the coating film, or partial or full peeling is observed in various parts of the lattice. The location where peeling is observed exceeds 15% of the total number of lattices and is 35% or less.
- Partial or full peeling is observed along the edge of the cut part of the coating film, or partial or full peeling is observed in various parts of the lattice. The location where peeling is observed exceeds 35% of the total number of lattices and is 65% or less. 5: The place where peeling was observed exceeds 65% of the total number of lattices. In the above evaluation, 0 to 1 was evaluated as a practically acceptable level.
- the ink composition evaluation sample obtained above was exposed with a Deep UV lamp (SP-7, manufactured by USHIO INC.) Under the condition of 8000 mJ / cm 2 energy.
- SP-7 Deep UV lamp
- the surface of the printed material exposed under an energy condition of 8000 mJ / cm 2 was rubbed with a cotton swab impregnated with water, and visually evaluated according to the following criteria.
- the ink composition was manufactured using RK PRINT COAT INSTRUMENTS K Hand Coater No. Using 2 bars, it was applied to an aluminum plate with a thickness of 12 ⁇ m. After coating, the coating film was dried at 60 ° C. for 3 minutes to remove moisture. The surface of this coating was rubbed with a sponge impregnated with water. For each of the coating film before rubbing with a sponge and the coating film after rubbing, Fourier transform infrared spectroscopic measurement (FT-IR) was performed. From the obtained results, the residual ratio of gel particles was calculated based on the following formula. Calculated.
- FT-IR Fourier transform infrared spectroscopic measurement
- Residual ratio of gel particles (Intensity of peak derived from gel particle in coating film after rubbing with sponge / Intensity of peak derived from gel particle in coating film before rubbing with sponge) ⁇ 100
- the peak derived from the gel particles is a peak at 1700 cm ⁇ 1 .
- the redispersibility of the ink composition was evaluated according to the following evaluation criteria.
- Evaluation criteria A The occurrence of dot omission was not observed, and an image with good image quality was obtained.
- B Occurrence of dot omission was slightly observed, but it was practically satisfactory for image quality.
- C Occurrence of dot missing occurs, which impedes the image quality practically.
- D Unable to discharge.
- a solid image (0.01 m 2 or more) was formed on a recording medium (Avery 400 GLOSS WHITE PERMANENT, manufactured by Avery Dennison Co., Ltd.) using an inkjet printer (Roland DG, SP-300V).
- the recording medium after dropping was placed in a glass sealed container so that the water-ethanol mixed solution would not volatilize, and left at 40 ° C. for 10 days.
- the total elution amount (overall migration amount: OML) of the elution component eluted from the solid image contained in the water-ethanol mixed solution was measured and evaluated according to the following evaluation criteria.
- the total volume was measured by allowing the water-ethanol mixture to volatilize after standing for 10 days and measuring the mass of the remaining components.
- Evaluation criteria 0 The cut edge is smooth and all the lattices are not peeled off.
- 3 Partial or full peeling is observed along the edge of the cut portion of the coating film, or partial or full peeling is observed in various parts of the lattice. The location where peeling is observed exceeds 15% of the total number of lattices and is 35% or less.
- Partial or full peeling is observed along the edge of the cut part of the coating film, or partial or full peeling is observed in various parts of the lattice. The location where peeling is observed exceeds 35% of the total number of lattices and is 65% or less. 5: The place where peeling was observed exceeds 65% of the total number of lattices. In the above evaluation, 0 to 1 was evaluated as a practically acceptable level.
- -Pencil hardness- An ink cured film produced in the same manner as that used in the adhesion evaluation was subjected to a pencil hardness test based on JIS K5600-5-4 (1999).
- the allowable range of hardness is HB or more, and preferably H or more.
- Printed materials with an evaluation result of B or less are not preferred because scratches may occur when the printed materials are handled. Note that UNI (registered trademark) manufactured by Mitsubishi Pencil Co., Ltd. was used as the pencil.
- Examples 2 to 33 are shown below.
- gel particles were prepared by the method shown below, and an ink composition and a photosensitive composition were prepared using the prepared dispersion of gel particles in the same manner as in Example 1.
- Various evaluations were made. The evaluation results are shown in Table 6 below.
- Example 2 to Example 16 The trifunctional or higher functional isocyanate compound (INT-NCO1) used in Example 1 is a trifunctional or higher functional isocyanate compound (INT-NCO) into which a functional group that generates radicals by active energy rays is introduced as shown in Table 5 below.
- a dispersion of gel particles 2 to 16 was prepared in the same manner as in Example 1 except that the above was changed.
- ⁇ Gelification process> The obtained emulsion was added to 25 g of distilled water, stirred at room temperature for 30 minutes, and then stirred at 50 ° C. for 3 hours to distill off ethyl acetate. Thereafter, the mixture was further stirred at 50 ° C. for 24 hours, and diluted with distilled water so that the solid content concentration of the obtained dispersion of gel particles was 20% by mass, whereby a dispersion of gel particles 17 was obtained.
- the volume average particle diameter of the gel particles measured by the light scattering method was 0.15 ⁇ m.
- Example 18 ⁇ Emulsification process> -Preparation of oil phase components- Isocyanate compound INT-NCO9 (solid content 35% by mass) 22.34 g (a trifunctional or higher functional isocyanate compound into which a radical that generates radicals by active energy was introduced), 2.28 g of an isocyanate compound 2 into which a hydrophilic group was introduced, 7 g of dipentaerythritol pentaacrylate (manufactured by Sartomer, SR-399E) (encapsulated monomer) was dissolved in 12 g of ethyl acetate to obtain an oil phase component.
- Isocyanate compound INT-NCO9 solid content 35% by mass 22.34 g (a trifunctional or higher functional isocyanate compound into which a radical that generates radicals by active energy was introduced), 2.28 g of an isocyanate compound 2 into which a hydrophilic group was introduced, 7 g of dipentaerythritol pentaacryl
- ⁇ Gelification process> The obtained emulsion was added to 25 g of distilled water, stirred at room temperature for 30 minutes, and then stirred at 50 ° C. for 3 hours to distill off ethyl acetate. Thereafter, the mixture was further stirred at 50 ° C. for 24 hours, and diluted with distilled water so that the solid content concentration of the obtained dispersion of gel particles was 20% by mass, whereby a dispersion of gel particles 18 was obtained.
- the volume average particle diameter of the gel particles measured by the light scattering method was 0.15 ⁇ m.
- Example 19 to Example 21 The trifunctional or higher functional isocyanate compound (INT-NCO9) used in Example 18 was converted into a trifunctional or higher functional isocyanate compound (INT-NCO) into which a functional group capable of generating radicals was introduced as shown in Table 5 below.
- a dispersion of gel particles 19 to 21 was prepared in the same manner as in Example 18 except for the change.
- Example 22 ⁇ Emulsification process> -Preparation of oil phase components- Isocyanate compound INT-NCO9 (solid content 35% by mass) 17.3 g (trifunctional or higher functional isocyanate compound into which radicals that generate radicals by active energy rays are introduced), isocyanate compound 1 having a hydrophilic group introduced (solid content 50) (Mass%) 3.5 g, 2.28 g of isocyanate compound 2 having a hydrophilic group introduced, 7 g of dipentaerythritol pentaacrylate (manufactured by Sartomer, SR-399E) (encapsulated monomer) were dissolved in 12 g of ethyl acetate, An oil phase component was obtained.
- ⁇ Gelification process> The obtained emulsion was added to 25 g of distilled water, stirred at room temperature for 30 minutes, and then stirred at 50 ° C. for 3 hours to distill off ethyl acetate. Thereafter, the mixture was further stirred at 50 ° C. for 24 hours, and diluted with distilled water so that the solid content concentration of the obtained dispersion of gel particles was 20% by mass, whereby a dispersion of gel particles 22 was obtained.
- the volume average particle diameter of the gel particles measured by the light scattering method was 0.15 ⁇ m.
- Example 23 to Example 25 The trifunctional or higher functional isocyanate compound (INT-NCO9) used in Example 22 was converted into a trifunctional or higher functional isocyanate compound (INT-NCO) into which a functional group capable of generating radicals was introduced as shown in Table 5 below.
- a dispersion of gel particles 23 to 25 was prepared in the same manner as in Example 22 except for the change.
- ⁇ Gelification process> The obtained emulsion was added to 25 g of distilled water, stirred at room temperature for 30 minutes, and then stirred at 50 ° C. for 3 hours to distill off ethyl acetate. Thereafter, the mixture was further stirred at 50 ° C. for 24 hours, and diluted with distilled water so that the solid content concentration of the obtained dispersion of gel particles was 20% by mass, whereby a dispersion of gel particles 26 was obtained.
- the volume average particle diameter of the gel particles measured by the light scattering method was 0.15 ⁇ m.
- Example 27 to 30 A dispersion of gel particles 27 to 30 was prepared in the same manner as in Example 26 except that the encapsulating monomer (NPPGODA) used in Example 26 was changed to the encapsulating monomer shown in Table 5 below. did.
- Example 31 ⁇ Emulsification process> -Preparation of oil phase components- Isocyanate compound INT-NCO1 (solid content 35% by mass) 20 g (a trifunctional or higher functional isocyanate compound into which radicals are generated by active energy), isocyanate compound 1 having a hydrophilic group introduced (solid content 50% by mass) 3.2 g, INT-NCO28 (solid content 35% by mass) 20 g (a trifunctional or higher functional isocyanate compound into which a polymerizable group and a functional group capable of generating radicals by active energy were introduced) were dissolved in 2 g of ethyl acetate. An oil phase component was obtained.
- ⁇ Gelification process> The obtained emulsion was added to 25 g of distilled water, stirred at room temperature for 30 minutes, and then stirred at 50 ° C. for 3 hours to distill off ethyl acetate. Thereafter, the mixture was further stirred at 50 ° C. for 24 hours, and diluted with distilled water so that the solid content concentration of the obtained dispersion of gel particles was 20% by mass, whereby a dispersion of gel particles 31 was obtained.
- the volume average particle diameter of the gel particles measured by the light scattering method was 0.15 ⁇ m.
- ⁇ Gelification process> The obtained emulsion was added to 25 g of distilled water, stirred at room temperature for 30 minutes, and then stirred at 50 ° C. for 3 hours to distill off ethyl acetate. Thereafter, the mixture was further stirred at 50 ° C. for 24 hours, and diluted with distilled water so that the solid content concentration of the obtained dispersion of gel particles was 20% by mass, whereby a dispersion of gel particles 32 was obtained.
- the volume average particle diameter of the gel particles measured by the light scattering method was 0.15 ⁇ m.
- ⁇ Gelification process> The obtained emulsion was added to 25 g of distilled water, stirred at room temperature for 30 minutes, and then stirred at 50 ° C. for 3 hours to distill off ethyl acetate. Thereafter, the mixture was further stirred at 50 ° C. for 24 hours, and diluted with distilled water so that the solid content concentration of the obtained dispersion of gel particles was 20% by mass, whereby a dispersion of gel particles 33 was obtained.
- the volume average particle diameter of the gel particles measured by the light scattering method was 0.15 ⁇ m.
- sample 1A 100 mass times tetrahydrofuran (THF) with respect to the total solid content in sample 1A was added and mixed to prepare a diluted solution.
- the obtained diluted solution was centrifuged at 80,000 rpm for 40 minutes.
- the supernatant liquid produced by centrifugation (hereinafter referred to as “supernatant liquid 1A”) was collected.
- the mass of the polymerizable monomer contained in the collected supernatant liquid 1A was measured by a water chromatography device “Waters 2695” manufactured by Waters.
- the mass of the obtained polymerizable monomer was defined as “total amount of polymerizable monomer”.
- the sample 2A was subjected to centrifugation under the same conditions as the centrifugation performed for the diluent.
- the supernatant liquid generated by centrifugation (hereinafter referred to as “supernatant liquid 2A”) was collected.
- the mass of the polymerizable monomer contained in the collected supernatant 2A was measured by the liquid chromatography apparatus.
- the mass of the obtained polymerizable monomer was defined as “free amount of polymerizable monomer”. Based on the “total amount of polymerizable monomer” and the “free amount of polymerizable monomer”, the encapsulation rate (% by mass) of the polymerizable monomer was determined according to the following formula.
- Polymerization monomer encapsulation rate (mass%) ((total amount of polymerizable monomer ⁇ free amount of polymerizable monomer) / total amount of polymerizable monomer) ⁇ 100
- the encapsulating rate was 99% or more and the polymerizable monomer was encapsulated in all the gel particles of the gel particle dispersion using the polymerizable monomer for production.
- NCO103 solid content 35% by mass 20 g (trifunctional or higher isocyanate compound), an adduct of trimethylolpropane, xylene diisocyanate and polyethylene glycol monomethyl ether (Mitsui Chemicals, Takenate (registered trademark) D) -116N ethyl acetate 50 mass% solution, isocyanate compound 3) having a hydrophilic group introduced 3.2), dipentaerythritol pentaacrylate (manufactured by Sartomer, SR-399E) 7g (encapsulated monomer), Irgacure (registered trademark) 819 1 g (product of BASF) (encapsulated photopolymerization initiator) was dissolved in 12 g of ethyl acetate.
- aqueous phase component 0.32 g of Labelin FP (Daiichi Kogyo Seiyaku Co., Ltd.) was dissolved in 50 g of distilled water.
- the aqueous phase component was added to the oil phase component, mixed, and emulsified at 12000 rpm for 10 minutes using a homogenizer.
- the obtained emulsion was added to 25 g of distilled water, stirred at room temperature for 30 minutes, and then stirred at 50 ° C. for 3 hours to distill off ethyl acetate. Thereafter, the mixture was further stirred at 50 ° C.
- the dispersion of the comparative particles 1 was obtained.
- the volume average particle diameter of the particles measured by the light scattering method was 0.15 ⁇ m.
- a wet particle size distribution measuring device LA-910 manufactured by Horiba, Ltd. was used.
- the comparative particle 1 does not have a functional group that generates a radical when irradiated with active energy rays.
- Comparative Example 2 to Comparative Example 5 Comparative Particles 2 to Comparative Example 1 were the same as Comparative Example 1 except that the internal photopolymerization initiator (Irgacure (registered trademark) 819) used in Comparative Example 1 was changed to the internal photopolymerization initiator shown in Table 5 below.
- a dispersion of particles 5 was prepared. In the dispersion of comparative particles 2 to 5, none of the comparative particles 2 to 5 has a functional group that generates radicals when irradiated with active energy rays.
- Photopolymerization initiator 1 and photopolymerization initiator 2 in Table 5 are compounds having the structures shown below.
- Photopolymerization initiator 1 and photopolymerization initiator 2 are compounds described in paragraph numbers [0305] to [0308] of JP-T-2012-532238.
- A-TMPT is trimethylolpropane triacrylate
- ATMM-3L is pentaerythritol triacrylate
- AD-TMP ditrimethylolpropane tetraacrylate
- AD-DPH dipentaerythritol hexaacrylate (both manufactured by Shin-Nakamura Chemical Co., Ltd.) ).
- the ink compositions of the examples are excellent in adhesion, water resistance, solvent resistance, fixability, output, redispersibility, storage stability, and migration. Moreover, in the photosensitive composition of an Example, it turns out that it is excellent in adhesiveness and pencil hardness. From these facts, it can be seen that the example suppresses the occurrence of migration and provides a film having excellent film strength.
- Example 34 to Example 35 [Evaluation of ink composition using LED]
- the ink compositions of Examples 11 and 17 were evaluated using LEDs. Specifically, in the above-mentioned adhesion evaluation A, adhesion evaluation B, and pencil hardness evaluation, the exposure light source (ozone-less metal halide lamp MAN250L) was changed to an experimental 385 nm UV-LED irradiator (manufactured by CCS). The same operation was performed except that the exposure energy was changed to 300 mJ / cm 2 . The results are shown in Table 7.
- Example 36 [Preparation of ink composition] Using the dispersion of gel particles of Example 4, the cyan ink composition was prepared by mixing the components so that the cyan ink composition shown below was obtained.
- Example 37 to Example 40 The cyan ink composition of each example was prepared in the same manner as in Example 36, except that SR9035 (polymerizable compound) used in the cyan ink composition of Example 36 was changed to the polymerizable compound shown in Table 8 below. did.
- Example 41 to 45 The cyan ink composition of each example was prepared in the same manner as in Example 36 to Example 40 except that the gel particle 4 used in the cyan ink composition of Example 36 to Example 40 was changed to the gel particle 23. did.
- Evaluation criteria A The occurrence of dot omission was not observed, and an image with good image quality was obtained.
- B Occurrence of dot omission was slightly observed, but it was practically satisfactory for image quality.
- C Occurrence of dot missing occurs, which impedes the image quality practically.
- D Unable to discharge.
- SR9035 is ethoxylated trimethylolpropane triacrylate (manufactured by Sartomer), and AM-1 to AM-4 are compounds having the structures shown below.
- the ink compositions of Examples 36 to 45 are all excellent in adhesion, water resistance, solvent resistance, fixability, dischargeability, redispersibility, and storage stability. . From these results, it can be seen that the examples are excellent in dispersibility and redispersibility, are cured with high sensitivity, and an image excellent in film strength can be obtained.
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- Paints Or Removers (AREA)
Abstract
Description
活性エネルギー線の照射により硬化可能なインクは、一般的に、重合性化合物及び重合開始剤を含有している。
例えば、特開2012-532238号公報には、1つ以上のビスアシルホスフィンオキシド部分が、リン原子を介して、オリゴマーまたはポリマー骨格に結合している重合開始剤が開示されている。また、特開2006-28514号公報には、開始用官能基を末端として少なくとも1個有する樹状重合体中心部を含んで成る高分子開始剤が開示されている。また、特開平6-80625号公報には、トリフェニルスルフォニウム塩単位系の高分子化合物が開示されている。
また、重合性化合物及び重合開始剤を含む組成のインクを用いて得られた硬化膜の場合、硬化膜中に未反応の重合性化合物、重合開始剤、及び重合開始剤残渣等の低分子量成分(分子量1000以下の成分)が残存することがあり、これらの低分子量成分が、種々の問題の一因となることがある。
例えば、硬化膜に残存した低分子量成分が、硬化膜中から外部へ移動する現象、いわゆるマイグレーションが発生することがある。硬化膜中からの低分子量成分のマイグレーションの量が多いと、硬化膜の臭気が強くなり、特に、インクを食品包装用等のパッケージ印刷に使用する場合には、内包物や周囲の食品に臭いが移るという問題が発生することがある。
一方、低分子量成分が硬化膜中に留まることもあり、低分子量成分が膜中に留まった場合には、硬化膜の膜物性に悪影響を及ぼすことがある。
したがって、低分子量成分のマイグレーションを抑制し、かつ、膜物性を損なわないインク組成物が求められている。
<1> 重合性基と活性エネルギー線の照射によりラジカルを発生する官能基とを有し、ウレタン結合及びウレア結合から選ばれる少なくとも1種の結合を含む三次元架橋構造を有するゲル粒子。
<4> 重合性モノマーを内包している<1>~<3>のいずれか1つに記載のゲル粒子。
<6> ゲル粒子の外部に、さらに重合性化合物を含有する<5>に記載の感光性組成物。
<8> ゲル粒子の外部に、さらに重合性化合物を含有する<7>に記載のインク組成物。
<10> さらに、ゲル化工程で得られたゲル粒子、水、及び着色剤を混合する混合工程を有する<9>に記載のゲル粒子の水分散物の製造方法。
本明細書において、「~」を用いて示された数値範囲は、「~」の前後に記載される数値をそれぞれ最小値及び最大値として含む範囲を示す。
本明細書において、(メタ)アクリレートとは、アクリレート及びメタクリレートの少なくとも一方を意味する。
本明細書では、紫外線を、「UV(Ultra Violet)光」ということがある。
本明細書では、LED(Light Emitting Diode)光源から生じた光を、「LED光」ということがある。
ゲル粒子は、重合性基と活性エネルギー線の照射によりラジカルを発生する官能基とを有し、ウレタン結合及びウレア結合から選ばれる少なくとも1種の結合を含む三次元架橋構造を有する。
ゲル粒子は、重合性基と活性エネルギー線の照射によりラジカルを発生する官能基とを有することで、ゲル粒子に活性エネルギー線を照射した際、活性エネルギー線の照射によりラジカルを発生する官能基からラジカルが発生する。これにより、互いに隣接しているゲル粒子間の、一方のゲル粒子に存在する重合性基と、他方のゲル粒子に存在する重合性基と、が容易に反応し、ゲル粒子間に架橋構造を形成する。そのため、ゲル粒子は、重合開始剤を用いることなく硬化膜を形成することができ、重合開始剤の未反応物及び重合開始剤残渣などに起因する低分子量成分が硬化膜中に残存することが少ない。すなわち、硬化膜における低分子量成分のマイグレーションの発生が抑制され、形成された膜の物性を損なうこともないと考えられる。
また、ゲル粒子が三次元架橋構造を有することで、ゲル粒子は耐溶剤性などの膜強度に優れた膜を形成しうると考えられる。
また、ゲル粒子は、活性エネルギー線の照射によりラジカルを発生する官能基を有するので、導入できる活性エネルギー線の照射によりラジカルを発生する官能基の選択の幅が広がり、ひいては、用いられる光源の選択の幅も広がる。そのため、従来よりも硬化感度を向上し得る。
しかしながら、アシルホスフィンオキシド化合物は、水に対する溶解性が低いため、従来は、水系の組成物には含有させることが難しかった。
ゲル粒子は、ゲル粒子の三次元構造に活性エネルギー線の照射によりラジカルを発生する官能基として、光に対する感度に優れるが水への溶解性が低いアシルホスフィンオキシド化合物等と同様の構造を官能基として導入することができ、独立成分としてアシルホスフィンオキシド化合物等の光重合開始剤を用いる必要がない。
活性エネルギー線の照射によりラジカルを発生する官能基がアシルホスフィンオキシド構造を有する基である場合、光に対する感度、特に、LED光に対する感度が向上する。
LED光の波長としては、355nm、365nm、385nm、395nm、又は405nmが好ましい。
本明細書において、「ゲル粒子が重合性基を有する」とは、ゲル粒子が、三次元架橋構造に含まれる重合性基、及び、三次元架橋構造に含まれない重合性基の少なくとも一方を有することを意味する。
即ち、ゲル粒子において、重合性基は、三次元架橋構造の一部として存在していてもよいし、三次元架橋構造以外の部分として存在していてもよい。
「重合性基が三次元架橋構造以外の部分として存在する」とは、ゲル粒子に、三次元架橋構造とは別に、重合性基を有するモノマー(以下、「重合性モノマー」ともいう。)が含まれていることを指す。
いずれの場合においても、重合性基は、ゲル粒子の表面部分(水との接触部分)に存在していることが好ましい。
「ゲル粒子が重合性基を有する」ことは、例えば、フーリエ変換赤外線分光測定(FT-IR)分析によって確認することができる。
ゲル粒子が有する重合性基、及び重合性基を有するモノマー(重合性モノマー)の詳細については、後述する。
「三次元架橋構造」とは、架橋によって形成された立体的な網目構造を指す。ゲル粒子は、粒子内で三次元架橋構造が形成されることにより形成されている。
即ち、本明細書中において、粒子が三次元架橋構造を有することと、粒子がゲル粒子であることとは同義である。
インク組成物から試料を採取する。採取した試料に対し、この試料中の全固形分に対して100質量倍のテトラヒドロフラン(THF)を加えて混合し、希釈液を調製する。得られた希釈液に対し、80000rpm、40分の条件の遠心分離を施す。遠心分離後に、残渣があるかどうかを目視で確認する。残渣がある場合、残渣を水で再分散させて再分散液を調製し、得られた再分散液について、湿式粒度分布測定装置(LA-910、(株)堀場製作所製)を用い、光散乱法によって粒度分布を測定する。
以上の操作によって粒度分布が確認できた場合を、インク組成物が三次元架橋構造を有するゲル粒子を含むと判断する。
ゲル粒子における三次元架橋構造は、3官能以上のイソシアネート化合物と水との反応により形成された生成物であることが好ましい。
また、ゲル粒子における三次元架橋構造は、活性エネルギー線の照射によりラジカルを発生する官能基を有する3官能以上のイソシアネート化合物と水との反応から形成された生成物であることがより好ましい。
3官能以上のイソシアネート化合物は、分子内に3つ以上のイソシアネート基を有する化合物であり、後述の方法により合成した化合物、及び公知の化合物を使用することができる。3官能以上のイソシアネート化合物としては、例えば、3官能以上の芳香族イソシアネート化合物、3官能以上の脂肪族イソシアネート化合物などが挙げられる。
公知の化合物としては例えば「ポリウレタン樹脂ハンドブック」(岩田敬治編、日刊工業新聞社発行(1987))に記載されている化合物が挙げられる。
一般式1中、nは3以上である。nは3~10が好ましく、3~8がより好ましく、3~6がさらに好ましい。
なお、「誘導された」とは、原料に上記の化合物を用い、原料に由来する構造を含むことを意味する。
これらの3官能以上のイソシアネート化合物は、複数の化合物が含まれる混合物であってもよく、以下に示す一般式2又は一般式3で表される化合物がこれら混合物の主成分であることが好ましく、他の成分を含んでいてもよい。
また、「活性水素基」とは、ヒドロキシル基、1級アミノ基、2級アミノ基、及びメルカプト基から選ばれる少なくとも1種の基を意味する。
アダクト型の3官能以上のイソシアネート化合物は、下記一般式2又は一般式3で表される化合物が好ましい。
一般式2及び一般式3中、Y1、Y2、Y3、Y4、及びY5はそれぞれ独立にO、S、又はNHを表し、O又はSが好ましく、Oがより好ましい。
一般式2及び一般式3中、Zは2価の有機基を表す。
一般に、分子中に3つ以上の活性水素基を有する化合物と反応させる2官能以上のイソシアネート化合物のモル数(分子数)は、分子中に3つ以上の活性水素基を有する化合物における活性水素基のモル数(活性水素基の当量数)に対し、0.6倍以上のモル数(分子数)の2官能以上のイソシアネート化合物が使用される。2官能以上のイソシアネート化合物のモル数は、上記の活性水素基のモル数の0.6倍~5倍が好ましく、0.6倍~3倍がよりに好ましく、0.8倍~2倍がさらに好ましい。
これらの2官能以上のイソシアネート化合物の中でも、下記(8-1)~(8-24)に示す構造の化合物が好ましい。
ビウレット型又はイソシアヌレート型の3官能以上のイソシアネート化合物は、下記一般式4又は一般式5で表される化合物が好ましい。
また、イソシアヌレート型の3官能以上のイソシアネート化合物としては、上市されている市販品を用いてもよく、例えば、D-127、D-170N、D-170HN、D-172N、D-177N(三井化学株式会社製)、スミジュールN3300、デスモジュール(登録商標)N3600、N3900、Z4470BA(住化バイエルウレタン)、コロネート(登録商標)HX、HK(日本ポリウレタン株式会社製)、デュラネート(登録商標)TPA-100、TKA-100、TSA-100、TSS-100、TLA-100、TSE-100(旭化成株式会社製)などが挙げられる。
ゲル粒子は、既述の3官能以上のイソシアネート化合物と、水又は2つ以上の活性水素基を有する化合物と、を反応させて製造されることが好ましい。
3官能以上のイソシアネート化合物と反応させる化合物としては、一般に水が使用される。3官能以上のイソシアネート化合物と水とが反応することで、ウレア結合を有する三次元架橋構造が形成される。
また、水以外に3官能以上のイソシアネート化合物と反応させる化合物として、2つ以上の活性水素基を有する化合物が挙げられ、2つ以上の活性水素基を有する化合物として、多官能アルコール、多官能フェノール、窒素原子上に水素原子を有する多官能アミン、又は多官能チオールも用いることができる。
多官能アミンの具体例としては、ジエチレントリアミン、テトラエチレンペンタミンなどが挙げられる。
多官能チオールの具体例としては、1,3-プロパンジチオール、1,2-エタンジチオールなどが挙げられる。
多官能フェノールの具体例としては、ビスフェノールAなどが挙げられる。
これらの化合物は1種を単独で使用してもよく、2種以上を併用してもよい。
ゲル粒子は、活性エネルギー線の照射によりラジカルを発生する官能基を有する。
活性エネルギー線の照射によりラジカルを発生する官能基は、ゲル粒子の表面に存在してもよいし、ゲル粒子の内部に存在してもよい。活性エネルギー線の照射によりラジカルを発生する官能基は、ゲル粒子の三次元架橋構造と共有結合により結合されていることが好ましい。活性エネルギー線の照射によりラジカルを発生する官能基は、三次元架橋構造と、1つの共有結合により結合していてもよく、2つ以上の共有結合により結合していてもよい。
活性エネルギー線の照射によりラジカルを発生する官能基は、発生した複数のラジカル種の全てが共有結合によりゲル粒子に結合している態様を「主鎖型」の官能基といい、発生した複数のラジカル種の一部が共有結合によりゲル粒子に結合している態様を「側鎖型」の官能基という。
ゲル粒子に活性エネルギー線の照射によりラジカルを発生する官能基と重合性基とが存在することで、開始種の伝播が進行しやすいため、高感度で、膜強度に優れた膜を形成できる。
Rで表される1価の基は、脂肪族基、芳香族基等の有機基、-H、-OH、-SH、-NH、-NH2、又は-L-R1などが挙げられ、-H、-OH、-SH、-NH、-NH2又は-L-R1であることが好ましい。R1は、1価の有機基を表し、-H、-OH、-SH、-NH、又は-NH2であることが好ましい。
Lで表される2価の有機基は、2価の脂肪族基、2価の芳香族基、2価の複素環基、-O-、-S-、-NH-、-CO-、-SO-、-SO2-又はそれらの組合せであることが好ましい。
ゲル粒子は、重合性基を有する。
ゲル粒子は、三次元架橋構造中に重合性基が導入されることにより重合性基を有していてもよく、重合性モノマーがゲル粒子の内部(三次元架橋構造の空隙)に含まれることにより重合性基を有していてもよい。また、その両方が併存してもよい。
ゲル粒子は、感度及び架橋性の観点から、ゲル粒子の表面に重合性基を有することが好ましい。
少なくとも1つの活性水素基と少なくとも1つの末端にエチレン不飽和結合とを有する化合物は下記構造式(a)で表すことができる。
L1LcmZn (a)
L1は、2価以上の脂肪族基、2価以上の芳香族基、2価以上の複素環基、-O-、-S-、-NH-、-N<、-CO-、-SO-、-SO2-又はそれらの組合せであることが好ましい。
m及びnは、それぞれ独立に、1~50であることが好ましく、2~20であることがより好ましく、3~10であることがさらに好ましく、3~5であることがとくに好ましい。
Lcで表される1価のエチレン性不飽和基としては、アリル基、ビニル基、アクリロイル基、メタクリロイル基、アクリルアミド基等を挙げることができる。
Zは、OH、SH、NH又はNH2であることが好ましく、OH又はNH2であることがより好ましく、OHであることがさらに好ましい。
ゲル粒子は、表面にさらに親水性基を有することが好ましい。
ゲル粒子は、その表面に親水性基を有することで、水媒体中への分散性がより向上する。そのため、ゲル粒子をインク組成物又は感光性組成物に適用した場合、インク組成物等におけるゲル粒子の分散性をより向上させることができる。
ゲル粒子において、親水性基は、三次元架橋構造の一部として存在していてもよいし、三次元架橋構造以外の部分として存在していてもよい。
ここで、「親水性基が三次元架橋構造の一部として存在する」とは、親水性基が三次元架橋構造の親水性基以外の部分と共有結合していることを指す。
また、「親水性基が三次元架橋構造以外の部分として存在する」とは、ゲル粒子に、三次元架橋構造とは別に、親水性基を有する有機化合物が含まれていることを指す。
上述のカルボン酸基の塩、スルホン酸基の塩、硫酸基の塩、ホスホン酸基の塩、及びリン酸基の塩は、ゲル粒子の製造過程で、中和によって形成された塩であってもよい。ゲル粒子がその表面に親水性基を有する場合、ゲル粒子は、親水性基を1種のみ有していてもよいし、2種以上有していてもよい。
親水性基を有する化合物としては、ポリエーテル構造を有する基を有する化合物、カルボン酸基を有する化合物、及びカルボン酸基の塩を有する化合物が好ましい。
これらのポリオキシアルキレン鎖を有する化合物の中でも、ポリエチレンオキシド、ポリプロピレンオキシド、ポリエチレンオキシド-ポリプロピレンオキシドブロック共重合体が好ましく、ポリエチレンオキシドがより好ましい。
また、ポリエーテル構造を有する基を有する化合物としては、ポリエチレンオキシドのモノエーテル体(モノエーテルとしては、例えば、モノメチルエーテル、モノエチルエーテル等が挙げられる)、ポリエチレンオキシドのモノエステル体(モノエステルとしては、例えば、モノ酢酸エステル、モノ(メタ)アクリル酸エステル等が挙げられる)も好ましい。
親水性基としてポリエーテル構造を有する基をゲル表面に導入する場合は、トリメチロールプロパン(TMP)とm-キシリレンジイソシアネート(XDI)とポリエチレングリコールモノメチルエーテル(EO)の付加物(例えば、三井化学株式会社製、タケネート(登録商標)D-116N)を用いることが好ましい。
親水性基としてカルボン酸基又はカルボン酸基の塩をゲル粒子の表面に導入する場合は、2,2-ビス(ヒドロキシメチル)プロピオン酸(DMPA)又は2,2-ビス(ヒドロキシメチル)プロピオン酸(DMPA)の塩とイソホロンジイソシアネート(IPDI)との反応物(カルボン酸基又はカルボン酸基の塩を含むイソシアネート化合物)を用いることが好ましい。カルボン酸基の塩としては、ナトリウム塩、カリウム塩、トリエチルアミン塩、ジメチルエタノールアミン塩が好ましく、ナトリウム塩又はトリエチルアミン塩がより好ましい。
ゲル粒子は、さらに重合性モノマーを内包していることが好ましい。
ゲル粒子が重合性モノマーを内包している態様は、膜の硬化感度及び膜の硬度を向上させる観点からみて有利である。
なお、ゲル粒子が、重合性モノマーを内包する場合、重合性モノマーの重合性基はゲル粒子が有する重合性基として機能する。
ゲル粒子が内包している重合性モノマー(以下、内包重合性モノマーともいう)としては、ラジカル重合可能なエチレン性不飽和結合を有する重合性モノマーから選択できる。
本明細書中において、例えば、「重合性モノマーがゲル粒子に内包されている」とは、重合性モノマーがゲル粒子の内部に含まれていることを意味する。ここでいう「ゲル粒子の内部」とは、三次元架橋構造の空隙を意味する。
ゲル粒子は、重合性モノマーの内包率(質量%)が、50質量%以上であることが好ましく、70質量%以上が更に好ましく、80質量%以上が更に好ましい。
水分散物に重合性モノマーが2種以上含まれる場合、少なくとも1種類の重合性モノマーの内包率が上記の範囲であることが好ましい。
ここで、重合性モノマーの内包率(質量%)とは、ゲル粒子の水分散物を調製した場合の水分散物中の重合性モノマーの全量に対する、ゲル粒子に内包されている重合性モノマーの量を意味し、以下のようにして求められた値を指す。なお、ゲル粒子の水分散物の製造方法は後述する。
以下の操作を、液温25℃の条件で行う。
以下の操作は、水分散物が顔料を含有していない場合にはこの水分散物をそのまま用いて行い、水分散物が顔料を含有している場合には、まず、遠心分離によって水分散物から顔料を除去し、顔料が除去された水分散物に対して行う。
まず、重合性モノマーの内包率(質量%)の測定対象であるゲル粒子の水分散物を調製し、調製した水分散物から、同質量の試料を2つ(以下、「試料1」及び「試料2」とする。)採取する。
試料1に対し、この試料1中の全固形分に対して100質量倍のテトラヒドロフラン(THF)を加えて混合し、希釈液を調製する。得られた希釈液に対し、80,000rpm(round per minute;以下同じ。)、40分の条件の遠心分離を施す。遠心分離によって生じた上澄み液(以下、「上澄み液1」とする。)を採取する。この操作により、試料1に含まれていた全ての重合性モノマーが、上澄み液1中に抽出されると考えられる。採取された上澄み液1中に含まれる重合性モノマーの質量を、液体クロマトグラフィー(例えば、Waters社の液体クロマトグラフィー装置)によって測定する。得られた重合性モノマーの質量を、「重合性モノマーの全量」とする。
また、試料2に対し、上記希釈液に施した遠心分離と同じ条件の遠心分離を施す。遠心分離によって生じた上澄み液(以下、「上澄み液2」とする。)を採取する。この操作により、試料2において、ゲル粒子に内包されていなかった(即ち、遊離していた)重合性モノマーが、上澄み液2中に抽出されると考えられる。採取された上澄み液2中に含まれる重合性モノマーの質量を、液体クロマトグラフィー(例えば、(株)Waters社の液体クロマトグラフィー装置)によって測定する。得られた重合性モノマーの質量を、「重合性モノマーの遊離量」とする。
上記「重合性モノマーの全量」及び上記「重合性モノマーの遊離量」に基づき、下記の式に従って、重合性モノマーの内包率(質量%)を求める。
重合性モノマーの内包率(質量%) = ((重合性モノマーの全量-重合性モノマーの遊離量)/重合性モノマーの全量)×100
内包重合性モノマーは、エチレン性不飽和基を有するモノマーが好ましい。
内包重合性モノマーは、1種単独で用いてもよく、2種以上を併用してもよい。
内包重合性モノマーは、(メタ)アクリレートモノマー、及びビニルエーテルモノマーの少なくとも一種であることが好ましく、(メタ)アクリレートモノマーがより好ましい。
その他、重合性モノマーとしては、NPGPODA(ネオペンチルグリコールプロピレンオキシド付加物ジアクリレート、サートマー社)、SR399E(ジペンタエリスリトールペンタアクリレート、サートマー社)、ATMM-3L(ペンタエリスリトールトリアクリレート、新中村化学工業(株))、A-DHP(ジペンタエリスリトールヘキサアクリレート、新中村化学工業(株))等の市販品を好適に用いることができる。
なお、重量平均分子量は、ゲルパーミエーションクロマトグラフィー(GPC)により測定できる。測定方法は後述のとおりである。
ゲル粒子の体積平均粒子径は、分散性の観点から0.01μm~10.0μmであることが好ましく、0.01μm~5μmであることがより好ましく、0.05μm~1μmであることがさらに好ましい。
ゲル粒子の体積平均粒子径は、光散乱法により測定することができる。なお、本明細書における体積平均粒子径は、湿式粒度分布測定装置LA-910((株)堀場製作所製)により測定された値が用いられる。
但し、分子量1,000以上の化合物については、上記の上澄み液1及び上澄み液2に含まれる化合物の質量を、ゲルパーミエーションクロマトグラフィー(GPC)によって測定し、それぞれ「化合物の全量」及び「化合物の遊離量」とし、化合物の内包率(質量%)を求める。
検量線は、東ソー(株)の「標準試料TSK standard,polystyrene」:「F-40」、「F-20」、「F-4」、「F-1」、「A-5000」、「A-2500」、「A-1000」、及び「n-プロピルベンゼン」の8サンプルから作製できる。
インク組成物は、重合性基と活性エネルギー線の照射によりラジカルを発生する官能基とを有し、ウレタン結合及びウレア結合から選ばれる少なくとも1種の結合を含む三次元架橋構造を有するゲル粒子と、水と、着色剤と、を含有する。
インク組成物は、既述の本発明の一実施形態のゲル粒子を含有するため、低分子量成分のマイグレーションの発生を抑制し、膜強度に優れた膜(例えば、画像)が得られる。
インク組成物は、インクジェット記録に好適に用いることができる。
なお、ゲル粒子の含有量は、粒子の内部(三次元架橋構造の空隙)に重合性モノマーなどの化合物を含む場合は、それらの化合物の質量も含めた値である。
ゲル粒子の全固形分量は、インク組成物の全固形分に対して、50質量%以上が好ましく、60質量%以上がより好ましく、70質量%以上がさらに好ましく、80質量%以上がさらに好ましく、85質量%以上が特に好ましい。ゲル粒子の全固形分量の上限は、インク組成物の全固形分に対して100質量%でもよく、インク組成物がゲル粒子以外の固形成分を含む場合、99質量%以下が好ましく、95質量%以下がより好ましい。
インク組成物は、着色剤の少なくとも1種を含有する。
着色剤としては、特に制限はなく、顔料、水溶性染料、分散染料等の公知の色材から任意に選択して使用することができる。中でも、着色剤は、耐候性に優れ、色再現性に富む点から、顔料を含むことがより好ましい。
顔料としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、公知の有機顔料及び無機顔料などが挙げられ、また、染料で染色した樹脂粒子、市販の顔料分散体や表面処理された顔料(例えば、顔料を分散媒として水、液状有機化合物や不溶性の樹脂等に分散させたもの、及び、樹脂や顔料誘導体等で顔料表面を処理したもの等)も挙げられる。
黄色顔料としては、C.I.ピグメントイエロー 1、2、3、4、5、10、65、73、74、75、97、98、111、116、130、167、205等のモノアゾ顔料、61、62、100、168、169、183、191、206、209、212等のモノアゾレーキ顔料、12、13、14、16、17、55、63、77、81、83、106、124、126、127、152、155、170、172、174、176、214、219等のジスアゾ顔料、24、99、108、193、199等のアントラキノン顔料、60等のモノアゾピラゾロン顔料、93、95、128、166等の縮合アゾ顔料、109、110、139、173、185等のイソインドリン顔料、120、151、154、175、180、181、194等のベンズイミダゾロン顔料、117、129、150、153等のアゾメチン金属錯体顔料、138等のキノフタロン顔料、213等のキノキサリン顔料が好ましい。
赤色顔料又はマゼンタ顔料としては、C.I.ピグメントレッド 193等のモノアゾレーキ顔料、38等のジスアゾ顔料、2、5、8、9、10、11、12、14、15、16、17、18、22、23、31、32、112、114、146、147、150、170、184、187、188、210、213、238、245、253、256、258、266、268、269等のナフトールAS顔料、3、4、6等のβ-ナフトール顔料、49、53、68等のβ-ナフトールレーキ顔料、237、239、247等のナフトールASレーキ顔料、41等のピラゾロン顔料、48、52、57、58、63、64:1、200等のBONAレーキ顔料、81:1、169、172等のキサンテンレーキ顔料、88、181、279等のチオインジゴ顔料、123、149、178、179、190、224等のペリレン顔料、144、166、214、220、221、242、262等の縮合アゾ顔料、168、177、182、226、263等のアントラキノン顔料、83等のアントラキノンレーキ顔料、171、175、176、185、208等のベンズイミダゾロン顔料、122、202(C.I.ピグメントバイオレット 19との混合物を含む)、207、209等のキナクリドン顔料、254、255、264、270、272等のジケトピロロピロール顔料、257、271等のアゾメチン金属錯体顔料が好ましい。
青色顔料又はシアン顔料としては、C.I.ピグメントブルー 25、26等のナフトールAS顔料、15、15:1、15:2、15:3、15:4、15:6、16、17:1、75、79等のフタロシアニン顔料、1、24:1、56、61、62等の染付けレーキ顔料、60等のアントラキノン系顔料、63等のインジゴ顔料、80等のジオキサジン顔料が好ましい。
緑色顔料としては、C.I.ピグメントグリーン 1、4等の染付けレーキ顔料、7、36等のフタロシアニン顔料、8等のアゾメチン金属錯体顔料が好ましい。
橙色顔料としては、C.I.ピグメントオレンジ 1等のモノアゾ顔料、2、3、5等のβ-ナフトール顔料、4、24、38、74等のナフトールAS顔料、13、34等のピラゾロン顔料、36、60、62、64、72等のベンズイミダゾロン顔料、15、16等のジスアゾ顔料、17、46等のβ-ナフトールレーキ顔料、19等のナフタレンスルホン酸レーキ顔料、43等のペリノン顔料、48、49等のキナクリドン顔料、51等のアントラキノン系顔料、61等のイソインドリノン顔料、66等のイソインドリン系顔料、68等のアゾメチン金属錯体顔料、71、73、81等のジケトピロロピロール顔料が好ましい。
褐色顔料としては、C.I.ピグメントブラウン 5等のBONAレーキ顔料、23、41、42等の縮合アゾ顔料、25、32等のベンズイミダゾロン顔料が好ましい。
紫色顔料としては、C.I.ピグメントバイオレット 1、2、3、27等の染付けレーキ顔料、13、17、25、50等のナフトールAS顔料、5:1等のアントラキノンレーキ顔料、19等のキナクリドン顔料、23、37等のジオキサジン顔料、29等のペリレン顔料、32等のベンズイミダゾロン顔料、38等のチオインジゴ顔料が好ましい。
黒色顔料としては、C.I.ピグメントブラック 1等のインダジン顔料、7であるカーボンブラック、10であるグラファイト、11であるマグネタイト、20等のアントラキノン顔料、31、32等のペリレン顔料が好ましい。
白色顔料としては、C.I.ピグメントホワイト 4である酸化亜鉛、6である酸化チタン、7である硫化亜鉛、12である酸化ジルコニウム(ジルコニウムホワイト)、18である炭酸カルシウム、19である酸化アルミニウム・酸化ケイ素(カオリンクレー)、21又は22である硫酸バリウム、23である水酸化アルミニウム(アルミナホワイト)、27である酸化ケイ素、28であるケイ酸カルシウムが好ましい。
白色顔料に使用される無機粒子は単体でもよいし、ケイ素、アルミニウム、ジルコニウム、チタン等の酸化物や有機金属化合物、有機化合物との複合粒子であってもよい。
なお、顔料粒子の体積平均粒子径及び粒径分布は、湿式粒度分布測定装置LA-910((株)堀場製作所製)等の市販の粒径測定装置を用いて、動的光散乱法により体積平均粒径を測定することにより求められるものである。
水溶性染料としては、例えば、酸性染料や直接染料が挙げられる。酸性染料、直接染料は、可溶化基として、酸性基をもつ構造となっている。酸性基としては、スルホン酸基及びその塩、カルボン酸基及びその塩、リン酸基及びその塩が挙げられる。酸性基の数はひとつでも複数でもよく、組み合わせでもよい。水溶性染料が含有する発色団の化学構造としては、アゾ系、フタロシアニン系、トリフェニルメタン系、キサンテン系、ピラゾロン系、ニトロ系、スチルベン系、キノリン系、メチン系、チアゾール系、キノンイミン系、インジゴイド系、ローダミン系、アントラキノン系、アンスラキノン系のものなどが挙げられる。
着色剤として顔料を用いる場合には、顔料粒子を調製する際に、必要に応じて顔料分散剤を用いてもよく、用いることのできる顔料分散剤としては、例えば、高級脂肪酸塩、アルキル硫酸塩、アルキルエステル硫酸塩、アルキルスルホン酸塩、スルホコハク酸塩、ナフタレンスルホン酸塩、アルキルリン酸塩、ポリオキシアルキレンアルキルエーテルリン酸塩、ポリオキシアルキレンアルキルフェニルエーテル、ポリオキシエチレンポリオキシプロピレングリコール、グリセリンエステル、ソルビタンエステル、ポリオキシエチレン脂肪酸アミド、アミンオキシド等の活性剤、又はスチレン、スチレン誘導体、ビニルナフタレン誘導体、アクリル酸、アクリル酸誘導体、マレイン酸、マレイン酸誘導体、イタコン酸、イタコン酸誘導体、フマル酸、フマル酸誘導体から選ばれた2種以上の単量体からなるブロック共重合体、ランダム共重合体及びこれらの塩を挙げることができる。
インク組成物には、ゲル粒子が有する活性エネルギー線の照射によりラジカルを発生する官能基の活性エネルギー線照射による分解を促進させるために増感剤を添加すること好ましい。増感剤は、特定の活性エネルギー線を吸収して電子励起状態となる。電子励起状態となった増感剤は、活性エネルギー線の照射によりラジカルを発生する官能基と接触して、電子移動、エネルギー移動、発熱などの作用を生じ、これにより活性エネルギー線の照射によりラジカルを発生する官能基の化学変化、即ち、分解、ラジカルの生成を促進させるものである。
上記の中でも、増感剤としては、LED光への適合性及び活性エネルギー線の照射によりラジカルを発生する官能基との反応性の観点から、チオキサントン、イソプロピルチオキサントン、及びベンゾフェノンから選ばれる少なくとも1種が好ましく、チオキサントン及びイソプロピルチオキサントンから選ばれる少なくとも1種がより好ましく、イソプロピルチオキサントンが更に好ましい。
インク組成物が増感剤を含有する場合、増感剤を1種単独で含有してもよく、又は、2種以上組み合わせて含有してもよい。
インク組成物が増感剤を含有する場合、増感剤の含有量は、インク組成物の全質量に対して、0.1質量%~25質量%であることが好ましい。
保存性を高める観点から重合禁止剤を添加してもよい。重合禁止剤としては、例えば、p-メトキシフェノール、ハイドロキノンやメトキシベンゾキノンなどのキノン類、フェノチアジン、カテコール類、アルキルフェノール類、アルキルビスフェノール類、ジメチルジチオカルバミン酸亜鉛、ジメチルジチオカルバミン酸銅、ジブチルジチオカルバミン酸銅、サリチル酸銅、チオジプロピオン酸エステル類、メルカプトベンズイミダゾール、ホスファイト類、などが挙げられ、p-メトキシフェノール、カテコール類、キノン類が好ましく、特にハイドロキノン、ベンゾキノン、p-メトキシフェノール、TEMPO、TEMPOL、クペロンAl、tris(N-nitroso-N-phenylhydroxylamine)aluminum salt等がより好ましい。
インク組成物には、得られる膜の耐候性向上、退色防止の観点から、紫外線吸収剤を用いてもよい。
紫外線吸収剤としては、公知の紫外線吸収剤、例えば、ベンゾトリアゾール系化合物、ベンゾフェノン系化合物、トリアジン系化合物、ベンズオキサゾール系化合物等が挙げられる。
インク組成物には、記録媒体との密着性を改良するため、以下の有機溶剤を添加してもよい。
・アルコール類(例えば、メタノール、エタノール、プロパノール、イソプロパノール、ブタノール、イソブタノール、セカンダリーブタノール、ターシャリーブタノール、ペンタノール、ヘキサノール、シクロヘキサノール、ベンジルアルコール等)、
・多価アルコール類(例えば、エチレングリコール、ジエチレングリコール、トリエチレングリコール、ポリエチレングリコール、プロピレングリコール、ジプロピレングリコール、ポリプロピレングリコール、ブチレングリコール、ヘキサンジオール、ペンタンジオール、グリセリン、ヘキサントリオール、チオジグリコール、2-メチルプロパンジオール等)、
・多価アルコールエーテル類(例えば、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノブチルエーテル、トリプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールジメチルエーテル、エチレングリコールモノメチルエーテルアセテート、トリエチレングリコールモノメチルエーテル、トリエチレングリコールモノエチルエーテル、トリエチレングリコールモノブチルエーテル、エチレングリコールモノフェニルエーテル、プロピレングリコールモノフェニルエーテル等)、
・アミン類(例えば、エタノールアミン、ジエタノールアミン、トリエタノールアミン、N-メチルジエタノールアミン、N-エチルジエタノールアミン、モルホリン、N-エチルモルホリン、エチレンジアミン、ジエチレンジアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ポリエチレンイミン、ペンタメチルジエチレントリアミン、テトラメチルプロピレンジアミン等)、
・アミド類(例えば、ホルムアミド、N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミド等)、
・複素環類(例えば、2-ピロリドン、N-メチル-2-ピロリドン、シクロヘキシルピロリドン、2-オキサゾリドン、1,3-ジメチル-2-イミダゾリジノン、γ-ブチロラクトン等)、
・スルホキシド類(例えば、ジメチルスルホキシド等)、
・スルホン類(例えば、スルホラン等)、
・その他(尿素、アセトニトリル、アセトン等)
インク組成物には、界面活性剤を添加してもよい。なお、インク組成物に用いられる界面活性剤は、ゲル粒子製造時に用いられる界面活性剤とは区別される。
界面活性剤としては、特開昭62-173463号公報、同62-183457号の各公報に記載されたものが挙げられる。例えば、ポリオキシエチレンアルキルエーテル類、ポリオキシエチレンアルキルアリルエーテル類、アセチレングリコール類、ポリオキシエチレン・ポリオキシプロピレンブロックコポリマー類、シロキサン類等のノニオン性界面活性剤、が挙げられる。
なお、界面活性剤の代わりに有機フルオロ化合物を用いてもよい。
有機フルオロ化合物は、疎水性であることが好ましい。有機フルオロ化合物としては、例えば、フッ素系界面活性剤、オイル状フッ素系化合物(例、フッ素油)及び固体状フッ素化合物樹脂(例、四フッ化エチレン樹脂)が含まれ、特公昭57-9053号公報(第8~17欄)、特開昭62-135826号の各公報に記載されたものが挙げられる。
インク組成物がゲル粒子の外部に重合性化合物を含有するとは、インク組成物がゲル粒子に内包されない重合性化合物を含有することを意味する。水溶性樹脂、水分散性樹脂等をゲル粒子の外部に含有する場合も同様である。
インク組成物は、ゲル粒子の外部に重合性化合物を含有することが好ましい。
インク組成物が、ゲル粒子の外部に重合性化合物を含有することでゲル粒子同士の架橋効率を向上させることができ、より膜強度の高い膜を形成することができる。さらに、露光照度の低い(例えば、40mJ/cm2~70mJ/cm2)活性エネルギー線(光)に対しても高効率で架橋が進行する。
これらの中でも、上記重合性化合物としては、エチレン性不飽和基を有する化合物が好ましく、(メタ)アクリロイル基を有する化合物が特に好ましい。さらに、上記重合性化合物としては、水溶性又は水分散性の重合性化合物であることが好ましい。
「水溶性」とは、105℃で2時間乾燥させた場合に、25℃の蒸留水100gに対する溶解量が1gを超える性質を意味する。
また、「水分散性」とは、水不溶性であり、かつ、水中に分散される性質を指す。ここで、「水不溶性」とは、105℃で2時間乾燥させた場合に、25℃の蒸留水100gに対する溶解量が1g以下である性質を意味する。
一般式(b)中、複数のR3はそれぞれ独立に、水素原子又はメチル基を表し、複数のL2はそれぞれ独立に、炭素原子数1~8のアルキレン基を表し、複数のk及びpはそれぞれ独立に、0又は1を表し、複数のmはそれぞれ独立に、0~8の整数を表し、但し、k及びpの少なくとも1つは1である。
一般式(c)中、複数のR4はそれぞれ独立に、水素原子又はメチル基を表し、複数のnはそれぞれ独立に、1~8の整数を表し、lは0又は1の整数を表す。
一般式(d)中、Z1はポリオールのヒドロキシル基から水素原子をq個除いた残基を表し、qは3~6の整数を表し、複数のR5はそれぞれ独立に、水素原子又はメチル基を表し、複数のL3はそれぞれ独立に炭素原子数1~8のアルキレン基を表す。
上記水溶性樹脂又は水分散性樹脂の構造については、特に制限はなく、任意の構造であればよい。上記水溶性樹脂又は水分散性樹脂の構造としては、例えば、鎖状構造、枝分かれ(分岐)構造、星型構造、架橋構造、網状構造等の構造が挙げられる。
水溶性樹脂における「水溶性」は、前述した「水溶性重合性化合物」における「水溶性」と同義であり、また、水分散性樹脂における「水分散性」は、前述した「水分散性重合性化合物」における「水分散性」と同義である。
水溶性樹脂又は水分散性樹脂としては、カルボキシ基、カルボキシ基の塩、スルホ基、スルホ基の塩、硫酸基、硫酸基の塩、ホスホン酸基、ホスホン酸基の塩、リン酸基、リン酸基の塩、アンモニウム塩基、水酸基、カルボン酸アミド基、及びアルキレンオキシ基から選ばれる官能基を有する樹脂であることが好ましい。
上述した塩の対カチオンとしては、ナトリウム、カリウム等のアルカリ金属カチオン、カルシウム、マグネシウム等のアルカリ土類金属カチオン、アンモニウムカチオン、又はホスホニウムカチオンが好ましく、アルカリ金属カチオンが特に好ましい。
アンモニウム塩基のアンモニウム基に含まれるアルキル基としては、メチル基又はエチル基が好ましい。
また、アンモニウム塩基の対アニオンとしては、塩素、臭素等のハロゲンアニオン、硫酸アニオン、硝酸アニオン、リン酸アニオン、スルホン酸アニオン、カルボン酸アニオン、又は炭酸アニオンが好ましく、ハロゲンアニオン、スルホン酸アニオン、又はカルボン酸アニオンが特に好ましい。
カルボン酸アミド基の窒素原子上の置換基としては、炭素数8以下のアルキル基が好ましく、炭素数6以下のアルキル基が特に好ましい。
アルキレンオキシ基を有する樹脂は、アルキレンオキシ基の繰り返しからなるアルキレンオキシ鎖を有することが好ましい。アルキレンオキシ鎖に含まれるアルキレンオキシ基の数は、2以上が好ましく、4以上が特に好ましい。
インク組成物は、インク組成物を25℃~50℃とした場合に、粘度が、3mPa・s~15mPa・sであることが好ましく、3mPa・s~13mPa・sであることがより好ましい。特に、インク組成物として、25℃におけるインク組成物の粘度が50mPa・s以下であることが好ましい。インク組成物の粘度が上記の範囲であると、インクジェット記録に適用した場合に高い吐出安定性を実現することができる。インクジェット記録に適用した場合のインク組成物の粘度変動は、液滴サイズの変化及び液滴吐出速度の変化に対して大きな影響を与え、ひいては画質劣化を引き起こす。したがって、吐出時のインク組成物の温度はできるだけ一定に保つことが必要である。よって、インク組成物の温度の制御幅は、好ましくは設定温度の±5℃、より好ましくは設定温度の±2℃、さらに好ましくは設定温度±1℃とすることが適当である。
なお、インク組成物の粘度は、粘度計:VISCOMETER TV-22(東機産業(株)製)を用いる。
感光性組成物は、重合性基と活性エネルギー線の照射によりラジカルを発生する官能基とを有し、ウレタン結合及びウレア結合から選ばれる少なくとも1種の結合を含む三次元架橋構造を有するゲル粒子と、水と、を含有する。
感光性組成物におけるゲル粒子及び水は、既述のインク組成物において用いたものと同じものを用いることができる。
感光性組成物は、既述の本発明の一実施形態のゲル粒子を含有するため、低分子量成分のマイグレーションの発生を抑制し、膜強度に優れた膜が得られる。
また、感光性組成物は、膜強度の観点から、ゲル粒子の外部にさらに重合性化合物を含有することが好ましい。
ゲル粒子の水分散物の製造方法は、上記の構成を有しているゲル粒子と水とを含むゲル粒子の水分散物を製造できればよく、特に限定されるものではない。
ゲル粒子の水分散物を製造する方法としては、ゲル粒子の水分散物を得やすいという観点から、以下で説明する、本実施形態のゲル粒子の水分散物の製造方法が好ましい。
油相成分としては、ゲル粒子の水分散物をより製造しやすいという観点から、油相成分A、油相成分B、及び油相成分Dが好ましい。
本実施形態の製造方法は、必要に応じ、その他の工程を有していてもよい。
本実施形態の製造方法によれば、上述したゲル粒子の水分散物を容易に製造することができる。
なお、各工程で用いる成分の具体例、及び好ましい態様については、上述のゲル粒子の項に記載したとおりであるため、ここでは説明を省略する。
乳化工程は、油相成分A、油相成分B、油相成分C、及び油相成分Dから選ばれるいずれかの油相成分と、水を含む水相成分と、を混合し、乳化させて乳化物を得る工程である。
乳化工程において、油相成分として、活性エネルギー線の照射によりラジカルを発生する官能基を有する3官能以上のイソシアネート化合物、重合性モノマー、及び有機溶媒を含む油相成分A、活性エネルギー線の照射によりラジカルを発生する官能基を有する3官能以上のイソシアネート化合物、重合性基を有する3官能以上のイソシアネート化合物、及び有機溶媒を含む油相成分B、重合性基と活性エネルギー線の照射によりラジカルを発生する官能基とを有する3官能以上のイソシアネート化合物、重合性モノマー、及び有機溶媒を含む油相成分C、並びに、活性エネルギー線の照射によりラジカルを発生する官能基を有する3官能以上のイソシアネート化合物、重合性基を有する3官能以上のイソシアネート化合物、重合性モノマー、及び有機溶媒を含む油相成分Dから選ばれるいずれかの油相成分を使用することで、最終的に、少なくとも表面、又は、表面及び表面付近に重合性基と活性エネルギー線の照射によりラジカルを発生する官能基とを有するゲル粒子を得ることができる。
油相成分A、油相成分C、及び油相成分Dが含む重合性モノマー、並びに、油相成分B、油相成分C及び油相成分Dが含む重合性基を有する3官能以上のイソシアネート化合物が、ゲル粒子の表面、又は、表面及び表面付近に存在する重合性基となると考えられる。
他の成分としては、例えば、上述の親水性基を有する化合物が挙げられる。
油相成分が上述の親水性基を有する化合物を含むことで、表面に親水性基を有するゲル粒子を得ることができる。
油相成分が、親水性基を有する化合物として、カルボキシ基、スルホ基、硫酸基、ホスホン酸基、及びリン酸基から選ばれる少なくとも1種の親水性基を有する化合物を含む場合、水相成分は、中和剤を含んでいてもよい。
油相成分が親水性基を有する化合物を含み、かつ、水相成分が中和剤を含むと、油相成分と水相成分との混合によって、カルボキシ基等の親水性基が中和され、カルボキシ基等の塩が形成される。この形成される塩も、ゲル粒子の親水性基として機能する。これらの塩は、ゲル粒子を水中に分散させる効果に特に優れる。
中和剤としては、例えば、水酸化ナトリウム等が挙げられる。
具体的には、多官能アルコール(例えば、プロピレングリコール、グリセリン、トリメチロールプロパン等)、多官能アミン(例えば、ビス(ヘキサメチレン)トリアミン、エチレンジアミン、ジエチレントリアミン等)、多官能チオール(例えば、ペンタエリスリトールテトラ(3-メルカプトプロピオナート)等)などの化合物が挙げられ、多官能アルコールが特に好ましい。
これらの化合物は、1種単独で用いてもよいし、2種以上併用してもよい。これらの化合物は、その溶解性等に応じて、油相成分及び/又は水相成分に添加される。
一般に、乳化分散に用いる界面活性剤は、比較的長鎖の疎水基を有する界面活性剤が優れているとされている。例えば、界面活性剤としては、「界面活性剤便覧」(西一郎他、産業図書発行(1980))に記載の界面活性剤、具体的には、アルキル硫酸塩、アルキルスルホン酸、アルキルベンゼンスルホン酸等のアルカリ金属塩が好ましく、アルキル硫酸エステル塩がより好ましい。
アルキル硫酸エステル塩のアルキル鎖長は、分散安定性の観点から、12以上が好ましく、16以上がより好ましい。
界面活性剤としては、高分子型界面活性剤であるナフタレンスルホン酸ナトリウムホルマリン縮合物などの芳香族スルホン酸ホルマリン縮合物のナトリウム塩及びポリカルボン酸塩、並びに反応性界面活性剤であるポリオキシエチレン-1-(アリルオキシメチル)アルキルエーテル硫酸塩及びポリオキシエチレンノニルプロペニルフェニルエーテル硫酸塩も挙げられる。
高分子型界面活性剤及び反応性界面活性剤は、マイグレーションの抑制の観点から特に好適に用いることができる。
界面活性剤は、油相成分又は水相成分の何れに添加してもよいが、通常、有機溶媒に対する溶解度が低いため、水相成分に添加する。
界面活性剤の量は、油相成分の全固形分量に対して0.1質量%~5質量%が好ましく、0.5質量%~3質量%がより好ましい。
油相成分中における活性エネルギー線の照射によりラジカルを発生する官能基を有する3官能以上のイソシアネート化合物の量は、特に限定されず、例えば、全固形分量に対して0.1質量%~25質量%であることが好ましい。
油相成分中における重合性基を有する3官能以上のイソシアネート化合物の量は、特に限定されず、例えば、全固形分量に対して10質量%~70質量%であることが好ましい。
油相成分中における重合性基と活性エネルギー線の照射によりラジカルを発生する官能基とを有する3官能以上のイソシアネート化合物の量は、特に限定されず、例えば、全固形分量に対して0.1質量%~25質量%であることが好ましい。
油相成分が重合性モノマーを含む場合、油相成分中における重合性モノマーの量は、特に限定されず、例えば、全固形分量に対して0.1質量%~75質量%であることが好ましい。
有機溶媒の量は、特に限定されず、油相成分中に含まれる成分の種類、量等により、適宜、選択される。
水の量は、特に限定されず、油相成分中に含まれる成分の種類、量等により、適宜、選択される。
油相成分と水相成分との混合の方法としては、特に限定されず、例えば、攪拌による混合が挙げられる。
乳化における分散機の回転数は、例えば、5000rpm~20000rpmであり、好ましくは10000rpm~15000rpmである。
乳化における回転時間は、例えば、1分間~120分間であり、好ましくは3分間~60分間であり、より好ましくは3分間~30分間であり、更に好ましくは5分間~15分間である。
ゲル化工程は、上記乳化物を加熱してゲル化させる工程である。
ゲル化工程では、上記乳化物の加熱によって、3官能以上のイソシアネート化合物と水とが反応し、イソシアネート基同士が架橋することで、ウレタン結合及びウレア結合から選ばれる少なくとも一方を含む三次元架橋構造と、重合性基及び活性エネルギー線の照射によりラジカルを発生する官能基と、を有するゲル粒子を含有する分散液を得ることができる。
ゲル化工程における加熱時間(反応時間)は、6時間~50時間が好ましく、12時間~40時間がより好ましく、15時間~35時間が更に好ましい。
ゲル化工程は、乳化物から有機溶媒を留去する工程を含むことが好ましい。
混合工程は、ゲル化工程で得られたゲル粒子、水、及び着色剤を混合する工程を有してもよい。ゲル粒子、水、及び着色剤を混合する方法は特に制限されない。また、ゲル粒子は分散液の状態で用いてもよい。
着色剤は、既述のゲル粒子の水分散物に含有される着色剤として説明したとおりである。
その他の工程としては、その他の成分を添加する工程が挙げられる。
添加されるその他の成分については、ゲル粒子の水分散物に含有され得るその他の成分として既に説明したとおりである。
画像形成方法は、既述のインク組成物を記録媒体上に付与するインク付与工程と、記録媒体上に付与されたインク組成物に活性エネルギー線を照射する照射工程と、を含む。これらの工程を行うことで、記録媒体上に定着したインク組成物による膜(例えば、画像)が形成される。
以下、画像形成方法における、インク付与工程について説明する。
インク付与工程は、インク組成物を記録媒体上に付与する工程であれば限定されない。
インク供給系は、例えば、インク組成物を含む元タンク、供給配管、インクジェットヘッド直前のインク供給タンク、フィルター、ピエゾ型のインクジェットヘッドからなる。ピエゾ型のインクジェットヘッドは、好ましくは1pl~100pl、より好ましくは8pl~30plのマルチサイズドットを、好ましくは320dpi×320dpi~4000dpi×4000dpi(dot per inch)、より好ましくは400dpi×400dpi~1600dpi×1600dpi、さらに好ましくは720dpi×720dpiの解像度で吐出できるよう駆動することができる。なお、dpiとは、2.54cm(1inch)当たりのドット数を表す。
温度コントロールの方法としては、特に制約はないが、例えば、温度センサーを各配管部位に複数設け、インク組成物の流量、環境温度に応じた加熱制御をすることが好ましい。温度センサーは、インク供給タンク及びインクジェットヘッドのノズル付近に設けることができる。また、加熱するヘッドユニットは、装置本体を外気からの温度の影響を受けないよう、熱的に遮断若しくは断熱されていることが好ましい。加熱に要するプリンタ立上げ時間を短縮するため、又は熱エネルギーのロスを低減するために、他部位との断熱を行うとともに、加熱ユニット全体の熱容量を小さくすることが好ましい。
中でも、インク組成物は密着性に優れるため、記録媒体として非吸収性記録媒体に対して好適に使用することができ、ポリ塩化ビニル、ポリエチレンテレフタレート、ポリエチレン等のプラスチック基材が好ましく、ポリ塩化ビニル樹脂基材がより好ましく、ポリ塩化ビニル樹脂シート又はフィルムがさらに好ましい。
以下、画像形成方法における、照射工程について説明する。
照射工程は、記録媒体上に付与されたインク組成物に活性エネルギー線を照射する工程であれば限定されない。
インク組成物に活性エネルギー線を照射することで、インク組成物中のゲル粒子の架橋反応が進行し、画像を定着させ、画像の膜強度等を向上させることが可能となる。
なお、増感剤を併用しない場合は、例えば、200nm~310nmであることが好ましく200nm~280nmがより好ましい。
また、上記で例示された光源の、半導体紫外発光デバイスへの置き換えは、産業的にも環境的にも非常に有用である。
半導体紫外発光デバイスの中でも、LED(Light Emitting Diode)(好ましくはUV-LED)、LD(Laser Diode)(好ましくはUV-LD)は小型、高寿命、高効率、及び低コストであり、光源として期待されている。
光源としては、メタルハライドランプ、超高圧水銀ランプ、高圧水銀ランプ、中圧水銀ランプ、低圧水銀ランプ、LED、又は青紫レーザーが好ましい。
これらの中でも、増感剤を併用する場合は、波長365nm、405nm、若しくは436nmの光照射が可能な超高圧水銀ランプ、波長365nm、405nm、若しくは436nmの光照射が可能な高圧水銀ランプ、又は、波長355nm、365nm、385nm、395nm、若しくは405nmの光照射が可能なLEDがより好ましく、波長355nm、365nm、385nm、395nm、若しくは405nmの光照射が可能なLEDが最も好ましい。
例えば、350nm~450nmに吸収波長を有する、一般式Jで表されるモノアシルホスフィンオキシド構造、一般式Kで表されるビスアシルホスフィンオキシド構造、及び一般式Lで表されるビスアシルホスフィンオキシド構造から選ばれる少なくとも1種の構造を含む基を有するゲル粒子とチオキサントン化合物等の増感剤とを併用する場合には、光源としては、特に、LEDが好ましい。
また、一般式Jで表されるモノアシルホスフィンオキシド構造、一般式Kで表されるビスアシルホスフィンオキシド構造、及び一般式Lで表されるビスアシルホスフィンオキシド構造から選ばれる少なくとも1種の構造を含む基を有するゲル粒子とチオキサントン化合物等の増感剤とを併用する場合には、紫外線よりも波長の長い380nm~450nmにピーク波長を有する活性エネルギー線(光)も好ましく用いることができる。
一般式Jで表されるモノアシルホスフィンオキシド構造、一般式Kで表されるビスアシルホスフィンオキシド構造、及び一般式Lで表されるビスアシルホスフィンオキシド構造から選ばれる少なくとも1種の構造を含む基を有するゲル粒子と増感剤とを併用しない場合には、メタルハライドランプ、中圧水銀ランプ、又は低圧水銀ランプが好ましい。
照射条件並びに基本的な照射方法は、特開昭60-132767号公報に開示されている照射条件及び照射方法を本発明の一実施形態においても同様に適用することができる。具体的には、インクの吐出装置を含むヘッドユニットの両側に光源を設け、いわゆるシャトル方式でヘッドユニットと光源を走査する方式や、駆動を伴わない別光源によって行われ、駆動を伴わない別光源によって行われる方式が好ましい。活性エネルギー線の照射は、インク着弾、加熱乾燥後、一定時間(例えば、0.01秒間~120秒間、好ましくは、0.01秒間~60秒間)をおいて行われることになる。
画像形成方法は、必要によりインク付与工程後であって照射工程前に、更に加熱乾燥工程を有してもよい。
加熱乾燥工程において、記録媒体上に吐出されたインク組成物は、加熱手段により、水及び必要に応じて併用される水溶性有機溶剤が蒸発されることにより画像が定着されることが好ましい。
加熱手段としては、水及び必要に応じて併用される水溶性有機溶剤を乾燥させることができればよく、限定されないが、ヒートドラム、温風、赤外線ランプ、熱オーブン、ヒート版加熱などを使用することができる。
加熱温度は、40℃以上が好ましく、40℃~150℃程度がより好ましく、40℃~80℃程度が更に好ましい。なお、乾燥/加熱時間は、用いるインク組成物の組成及び印刷速度を加味して適宜設定することができる。
三口フラスコにトリメチロールプロパン(TMP)10g、ヘキサメチレンジイソシアネート(HDI)50.14g、酢酸エチル(AcOEt)111.69gを加え、50℃に加熱し、TOYOCAT-RX21(東ソー株式会社製、反応型触媒)を0.172g添加し、6時間反応させ、NCO103を得た。
三口フラスコにペンタエリスリトールエチレンオキシド20g、イソホロンジイソシアネート(IPDI)71.16g、酢酸エチル(AcOEt)169.3gを加え、50℃に加熱し、そこにTOYOCAT-RX21(東ソー株式会社製、反応型触媒)を0.26g添加し、6時間反応させ、NCO109を得た。
三口フラスコにINT-1 22.17g、NCO103(固形分35質量%)171.84g、酢酸エチル(AcOEt)41.16gを加え、50℃に加熱し、そこにTOYOCAT-RX21(東ソー株式会社製、反応型触媒)を0.236g添加し、6時間反応させ、INT-NCO1(活性エネルギー線によりラジカルを発生する官能基が導入された3官能以上のイソシアネート化合物)を得た。
三口フラスコにINT-5 16.71g、NCO103(固形分35質量%)171.84g、酢酸エチル(AcOEt)41.16gを加え、50℃に加熱し、そこにTOYOCAT-RX21(東ソー株式会社製、反応型触媒)を0.236g添加し、6時間反応させ、INT-NCO9(活性エネルギー線によりラジカルを発生する官能基が導入された3官能以上のイソシアネート化合物)を得た。
三口フラスコにINT-5 20g、NCO109(固形分35質量%)206.42g、酢酸エチル37.13gを加え、50℃に加熱し、そこにTOYOCAT-RX21(東ソー株式会社製、反応型触媒)を0.318g添加し、6時間反応させ、INT-NCO11(活性エネルギー線によりラジカルを発生する官能基が導入された3官能以上のイソシアネート化合物)を得た。
三口フラスコにトリメチロールプロパン(TMP)10g、イソホロンジイソシアネート(IPDI)66.27g、酢酸エチル(AcOEt)185.2gを加え、50℃に加熱し、そこにTOYOCAT-RX21(東ソー株式会社製、反応型触媒)を0.285g添加し、3時間反応させた。反応後、そこにブレンマーAP-400(日油株式会社製)23.43g、加えてさらに50℃、6時間反応させ、INT-NCO28(重合性基と活性エネルギー線によりラジカルを発生する官能基とが導入された3官能以上のイソシアネート化合物)を得た。
三口フラスコにトリメチロールプロパン(TMP)10g、m-キシリレンジイソシアネート(XDI)56.11g、酢酸エチル(AcOEt)132.2gを加え、50℃に加熱し、そこにTOYOCAT-RX21(東ソー株式会社製、反応型触媒)を0.04g添加し、3時間反応させた。そこにポリエチレングリコールモノメチルエーテル(EO)(アルドリッチ社製、数平均分子量(Mn)=5000)を66.1g添加し、さらに4時間反応させ、親水性基を導入したイソシアネート化合物1(ポリエーテル構造を有する基を含むイソシアネート化合物、固形分50質量%)を得た。
三口フラスコに2,2-ビス(ヒドロキシメチル)プロピオン酸(DMPA)45g、イソホロンジイソシアネート(IPDI)223.72g、酢酸エチル(AcOEt)499.05gを加え、50℃に加熱し、そこにTOYOCAT-RX21(東ソー株式会社製、反応型触媒)を0.7677g添加し、3時間反応させ親水性基を導入したイソシアネート化合物2(カルボン酸基を含むイソシアネート化合物、固形分35質量%)を得た。
(実施例1)
<乳化工程>
-油相成分の作製-
イソシアネート化合物INT-NCO1(固形分35質量%)20g(活性エネルギー線によりラジカルを発生する官能基が導入された3官能以上のイソシアネート化合物)、親水基を導入したイソシアネート化合物1(固形分50質量%)3.2g、ジペンタエリスリトールペンタアクリレート(サートマー製、SR-399E)7g(内包重合性化合物)を酢酸エチル12g中に溶解させて、油相成分を得た。
ラベリンFP(第一工業製薬株式会社製)0.32g(界面活性剤)を蒸留水50gに溶解させて、水相成分を得た。
油相成分に水相成分を添加、混合し、得られた混合物を、ホモジナイザーを用いて12000rpmで10分間乳化させて乳化物を得た。
得られた乳化物を、蒸留水25gに添加し、室温で30分攪拌後、50℃で3時間攪拌し、酢酸エチルを留去した。
その後、さらに50℃で24時間攪拌し、得られたゲル粒子の分散液の固形分濃度を20質量%になるように蒸留水を用いて希釈し、ゲル粒子1の分散液(ゲル粒子の水分散物)を得た。光散乱法により測定したゲル粒子の体積平均粒子径は0.15μmであった。なお、体積平均粒子径の測定には、湿式粒度分布測定装置LA-910((株)堀場製作所製)を用いた。
上記にて得られたゲル粒子1の分散液を用い、下記のインク組成物1になるように各成分を混合してインク組成物を調製した。
・ゲル粒子1の分散液・・・82部
・フッ素系界面活性剤(DuPont社製、Capstone FS-31、固形分25質量%)・・・0.3部
・インク(Pro-jet Cyan APD1000(FUJIFILMImaging Colorants社製)着色剤濃度14質量%)・・・13部
・2-メチルプロパンジオール・・・4.7部
上記で作製したインク組成物をRK PRINT COAT INSTRUMENTS社製 Kハンドコーター KハンドコーターのNo.2バーを用いて基材(塩化ビニル(PVC)シート(エイブリィ・デニソン社製、AVERY 400 GLOSS WHITE PERMANENT))に12μmの厚みで塗布した。塗布後、塗膜を60℃で3分間乾燥することで水分を除去し、インク組成物評価用試料を得た。
得られた試料について、以下の評価を行った。評価結果は下記表6に示す。
露光光源としてオゾンレスメタルハライドランプMAN250Lを搭載し、コンベアスピード9.0m/分、露光強度2.0W/cm2に設定した実験用UVミニコンベア装置CSOT((株)ジーエス・ユアサパワーサプライ製)により、活性エネルギー線を上記で得られたインク組成物評価用試料に照射し、試料を硬化させた。記録媒体への密着性は、硬化塗膜を用いてISO2409(クロスカット法)により下記の基準で評価した。
なお、下記基準0~5における格子の剥がれを示す「%」は、1mm間隔で直角に切り込まれて形成された25の格子数に対し、剥がれが観察された格子数の割合を百分率で示したものである。
格子の剥がれた割合(%)=〔(剥がれの生じた格子数)/(全格子数)〕×100
0:カット縁が滑らかであり、全ての格子に剥がれがない。
1:カットの交点において塗膜に小さな剥がれが観察される。剥がれが観察された箇所は、全格子数の5%以下である。
2:塗膜のカット部の縁に沿った部分、及びカット交点の少なくともいずれかにおいて剥がれが観察される。剥がれが観察された箇所は、全格子数の5%を超え、15%以下である。
3:塗膜のカット部の縁に沿って、部分的もしくは全面的に剥がれが観察されるか、又は、格子の種々の部分で部分的もしくは全面的な剥がれが観察される。剥がれが観察された箇所は、全格子数の15%を超え、35%以下である。
4:塗膜のカット部の縁に沿って、部分的もしくは全面的な剥がれが観察されるか、又は、格子の種々の部分で部分的もしくは全面的な剥がれが観察される。剥がれが観察された箇所は、全格子数の35%を超え、65%以下である。
5:剥がれが観察された箇所が、全格子数の65%を超える。
上記評価において、0~1が実用上許容されるレベルであると評価した。
上記で得られたインク組成物評価用試料をDeep UVランプ(ウシオ電機株式会社製、SP-7)で1000mJ/cm2のエネルギーとなる条件で露光した。露光後の試料表面の定着度合いを触診にて評価した。べたつきが残る場合は、べたつきが無くなるまで露光を繰り返し、べたつきがなくなるまでの露光量により定着性を評価した。
A:1回の露光でべたつきが無くなる。
B:2回~3回の露光でべたつきが無くなる。
C:4回~5回の露光でべたつきが無くなる。
D:6回以上露光してもべたつきが無くならない。
上記で得られたインク組成物評価用試料をDeep UVランプ(ウシオ電機株式会社製、SP-7)で8000mJ/cm2のエネルギーとなる条件で露光した。8000mJ/cm2のエネルギー条件で露光した印画物の表面を、イソプロピルアルコールを含浸した綿棒にてこすり、以下の基準に従い目視で評価した。
A:10回以上こすっても、画像に変化が認められなかった。
B:5回~9回のこすりで、画像の濃度が低下した。
C:2回~4回のこすりで、画像の濃度が低下した。
D:1回こすっただけで、画像の濃度が著しく低下した。
上記で得られたインク組成物評価用試料をDeep UVランプ(ウシオ電機株式会社製、SP-7)で8000mJ/cm2のエネルギーとなる条件で露光した。8000mJ/cm2のエネルギー条件で露光した印画物の表面を、水を含浸した綿棒にてこすり、以下の基準に従い目視で評価した。
A:10回以上こすっても、画像に変化が認められなかった。
B:5回~9回のこすりで、画像の濃度が低下した。
C:2回~4回のこすりで、画像の濃度が低下した。
D:1回こすっただけで、画像の濃度が著しく低下した。
インク組成物をRK PRINT COAT INSTRUMENTS社製 Kハンドコーター KハンドコーターのNo.2バーを用いて、アルミプレートに12μmの厚みで塗布した。塗布後、塗膜を60℃で3分間乾燥し、水分を除去した。この塗膜の表面を、水を含浸したスポンジでこすった。
スポンジでこする前の塗膜及びこすった後の塗膜のそれぞれについて、フーリエ変換赤外線分光測定(FT-IR)を実施し、得られた結果から、下記式に基づき、ゲル粒子の残存率を算出した。
ゲル粒子の残存率 = (スポンジでこすった後の塗膜におけるゲル粒子由来のピークの強度/スポンジでこする前の塗膜におけるゲル粒子由来のピークの強度)×100
ここで、ゲル粒子由来のピークとは、1700cm-1のピークである。
得られたゲル粒子の残存率に基づき、下記の評価基準に従い、インク組成物の再分散性を評価した。
A:ゲル粒子の残存率が1%以下である。
B:ゲル粒子の残存率が1%を超えて5%以下である。
C:ゲル粒子の残存率が5%を超えて10%以下である。
D:ゲル粒子の残存率が10%を超える。
インクジェットプリンタ(ローランド ディー.ジー.社製、SP-300V)を用いて、ヘッドから30分間吐出して、停止し、5分間経過した後、再び吐出することで記録媒体(エイブリィ・デニソン社製、AVERY 400 GLOSS WHITE PERMANENT)上にベタ画像及び細線を記録した。得られた画像(5cm×5cm)を観察し、下記の評価基準に従って目視により評価した。
A:ドット抜けの発生が認められず、良好な画質の画像が得られた。
B:ドット抜けの発生がわずかに認められたが、実用上画質に支障を来さない程度であった。
C:ドット抜けの発生があり、実用上画質に支障を来たす。
D:吐出ができなかった。
得られたインク組成物を容器に密封し、60℃で2週間経時させたのち、上記の吐出性
評価と同様の評価を実施し、同様の基準で評価した。
インクジェットプリンタ(ローランド ディー.ジー.社製、SP-300V)を用いて、記録媒体(エイブリィ・デニソン社製、AVERY 400 GLOSS WHITE PERMANENT)上にベタ画像(0.01m2以上)を形成した。ベタ画像が形成された記録媒体を、0.01m2の大きさに切り取り、画像形成面に水:エタノール=70:30混合液10mLを滴下した。滴下後の記録媒体を、水-エタノール混合液が揮発しないように、ガラス密閉容器に入れ、40℃で10日間放置した。10日後、水-エタノール混合液中に含有されるベタ画像から溶出した溶出成分の全溶出量(オーバーオールマイグレーション量:OML)を測定し、下記の評価基準に従って、評価を行った。なお、全容出量の測定は、10日間放置後に、水-エタノール混合液を揮発させ、残存成分の質量を測定することにより行った。
A:溶出量が10ppb以下である。
B:溶出量が10ppbを超え、50ppb以下である。
C:溶出量が50ppbを超え、100ppb以下である。
D:溶出量が100ppbを超え、2000ppb以下である。
E:溶出量が2000ppbを超える。
上記にて得られたゲル粒子1の分散液を用い、下記の感光性組成物になるように各成分を混合して感光性組成物を調製した。
・ゲル粒子1の分散液・・・81部
・フッ素系界面活性剤(DuPont社製、Capstone FS-31)・・・0.3部
・水・・・全体を100部とした残部
上記で作製した感光性組成物をRK PRINT COAT INSTRUMENTS社製 Kハンドコーター KハンドコーターのNo.2バーを用いて基材(トリアセチルセルロース(TAC)フィルム、富士フイルム株式会社製)に12μmの厚みで塗布した。塗布後、塗膜を60℃で3分間乾燥し水分を除去し、感光性組成物評価用試料を得た。
得られた感光性組成物評価用試料について、以下の評価を行った。評価結果は下記表6に示す。
露光光源としてオゾンレスメタルハライドランプMAN250Lを搭載し、コンベアスピード9.0m/分、露光強度2.0W/cm2に設定した実験用UVミニコンベア装置CSOT((株)ジーエス・ユアサパワーサプライ製)により、活性エネルギー線を感光性組成物評価用試料に照射し、試料を硬化させた。記録媒体への密着性は、硬化塗膜を用いてISO2409(クロスカット法)により下記の基準で評価した。
なお、下記基準0~5における格子の剥がれを示す「%」は、1mm間隔で直角に切り込まれて形成された25の格子数に対し、剥がれが観察された格子数の割合を百分率で示したものである。
格子の剥がれた割合(%)=〔(剥がれの生じた格子数)/(全格子数)〕×100
0:カット縁が滑らかであり、全ての格子に剥がれがない。
1:カットの交点において塗膜に小さな剥がれが観察される。剥がれが観察された箇所は、全格子数の5%以下である。
2:塗膜のカット部の縁に沿った部分、及びカット交点の少なくともいずれかにおいて剥がれが観察される。剥がれが観察された箇所は、全格子数の5%を超え、15%以下である。
3:塗膜のカット部の縁に沿って、部分的もしくは全面的に剥がれが観察されるか、又は、格子の種々の部分で部分的もしくは全面的な剥がれが観察される。剥がれが観察された箇所は、全格子数の15%を超え、35%以下である。
4:塗膜のカット部の縁に沿って、部分的もしくは全面的な剥がれが観察されるか、又は、格子の種々の部分で部分的もしくは全面的な剥がれが観察される。剥がれが観察された箇所は、全格子数の35%を超え、65%以下である。
5:剥がれが観察された箇所が、全格子数の65%を超える。
上記評価において、0~1が実用上許容されるレベルであると評価した。
密着性評価に用いたものと同様に作製したインク硬化膜について、JIS K5600-5-4(1999年)に基づき、鉛筆硬度試験を行った。感光性組成物において、硬度の許容範囲はHB以上であり、H以上であることが好ましい。評価結果がB以下である印刷物は印刷物の取り扱い時に傷が生じる可能性があり好ましくない。
なお、鉛筆は三菱鉛筆(株)製のUNI(登録商標)を使用した。
実施例2~実施例33は、以下に示す方法でゲル粒子を作製し、実施例1と同様にして、作製されたゲル粒子の分散液を用いてインク組成物及び感光性組成物を調製し、各種評価を行った。評価結果は、下記表6に示す。
実施例1で用いた3官能以上のイソシアネート化合物(INT-NCO1)を、下記表5に示す、活性エネルギー線によりラジカルを発生する官能基が導入された3官能以上のイソシアネート化合物(INT-NCO)に変更した以外は、実施例1と同様にして、ゲル粒子2~ゲル粒子16の分散液を作製した。
<乳化工程>
-油相成分の作製-
イソシアネート化合物INT-NCO20(固形分35質量%)15.46g(活性エネルギー線によりラジカルを発生する官能基が導入された3官能以上のイソシアネート化合物)、INT-NCO27(固形分35質量%)4.54g(活性エネルギー線によりラジカルを発生する官能基が導入された3官能以上のイソシアネート化合物)、親水基を導入したイソシアネート化合物1(固形分50質量%)3.2g、ジペンタエリスリトールペンタアクリレート(サートマー製、SR-399E)7g(内包重合性モノマー)を酢酸エチル12g中に溶解させて、油相成分を得た。
-水相成分の作製-
ラベリンFP(第一工業製薬株式会社製)0.32g(界面活性剤)を蒸留水50gに溶解させて、水相成分を得た。
油相成分に水相成分を添加、混合し、得られた混合物を、ホモジナイザーを用いて12000rpmで10分間乳化させて乳化物を得た。
得られた乳化物を、蒸留水25gに添加し、室温で30分攪拌後、50℃で3時間攪拌し、酢酸エチルを留去した。
その後、さらに50℃で24時間攪拌し、得られたゲル粒子の分散液の固形分濃度を20質量%になるように蒸留水を用いて希釈し、ゲル粒子17の分散液を得た。光散乱法により測定したゲル粒子の体積平均粒子径は0.15μmであった。
<乳化工程>
-油相成分の作製-
イソシアネート化合物INT-NCO9(固形分35質量%)22.34g(活性エネルギーによりラジカルを発生する官能基が導入された3官能以上のイソシアネート化合物)、親水性基を導入したイソシアネート化合物2 2.28g、ジペンタエリスリトールペンタアクリレート(サートマー製、SR-399E)7g(内包重合性モノマー)を酢酸エチル12g中に溶解させて、油相成分を得た。
ラベリンFP(第一工業製薬株式会社製)0.32g(界面活性剤)、水酸化ナトリウム0.035gを蒸留水50gに溶解させて、水相成分を得た。
油相成分に水相成分を添加、混合し、得られた混合物を、ホモジナイザーを用いて12000rpmで10分間乳化させて乳化物を得た。
得られた乳化物を、蒸留水25gに添加し、室温で30分攪拌後、50℃で3時間攪拌し、酢酸エチルを留去した。
その後、さらに50℃で24時間攪拌し、得られたゲル粒子の分散液の固形分濃度を20質量%になるように蒸留水を用いて希釈し、ゲル粒子18の分散液を得た。光散乱法により測定したゲル粒子の体積平均粒子径は0.15μmであった。
実施例18で用いた3官能以上のイソシアネート化合物(INT-NCO9)を、下記表5に示す活性エネルギー線によりラジカルを発生する官能基が導入された3官能以上のイソシアネート化合物(INT-NCO)に変更した以外は、実施例18と同様にして、ゲル粒子19~ゲル粒子21の分散液を作製した。
<乳化工程>
-油相成分の作製-
イソシアネート化合物INT-NCO9(固形分35質量%)17.3g(活性エネルギー線によりラジカルを発生する官能基が導入された3官能以上のイソシアネート化合物)、親水基を導入したイソシアネート化合物1(固形分50質量%)3.5g、親水性基を導入したイソシアネート化合物2 2.28g、ジペンタエリスリトールペンタアクリレート(サートマー製、SR-399E)7g(内包重合性モノマー)を酢酸エチル12g中に溶解させて、油相成分を得た。
ラベリンFP(第一工業製薬株式会社製)0.4g(界面活性剤)、水酸化ナトリウム0.035gを蒸留水50gに溶解させて、水相成分を得た。
油相成分に水相成分を添加、混合し、得られた混合物を、ホモジナイザーを用いて12000rpmで10分間乳化させて乳化物を得た。
得られた乳化物を、蒸留水25gに添加し、室温で30分攪拌後、50℃で3時間攪拌し、酢酸エチルを留去した。
その後、さらに50℃、24時間攪拌し、得られたゲル粒子の分散液の固形分濃度を20質量%になるように蒸留水を用いて希釈し、ゲル粒子22の分散液を得た。光散乱法により測定したゲル粒子の体積平均粒子径は0.15μmであった。
実施例22で用いた3官能以上のイソシアネート化合物(INT-NCO9)を、下記表5に示す活性エネルギー線によりラジカルを発生する官能基が導入された3官能以上のイソシアネート化合物(INT-NCO)に変更した以外は、実施例22と同様にして、ゲル粒子23~ゲル粒子25の分散液を作製した。
<乳化工程>
-油相成分の作製-
イソシアネート化合物INT-NCO11(固形分35質量%)20g(活性エネルギー線によりラジカルを発生する官能基が導入された3官能以上のイソシアネート化合物)、親水基を導入したイソシアネート化合物1(固形分50質量%)3.2g、ネオペンチルグリコールプロピレンオキシド付加物ジアクリレート(サートマー製、SR9003、NPGPODA)7g(内包重合性モノマー)を酢酸エチル12g中に溶解させて、油相成分を得た。
ラベリンFP(第一工業製薬株式会社製)0.32g(界面活性剤)を蒸留水50gに溶解させて、水相成分を得た。
油相成分に水相成分を添加、混合し、得られた混合物を、ホモジナイザーを用いて12000rpmで10分間乳化させて乳化物を得た。
得られた乳化物を、蒸留水25gに添加し、室温で30分攪拌後、50℃で3時間攪拌し、酢酸エチルを留去した。
その後、さらに50℃24時間攪拌し、得られたゲル粒子の分散液の固形分濃度を20質量%になるように蒸留水を用いて希釈し、ゲル粒子26の分散液を得た。光散乱法により測定したゲル粒子の体積平均粒子径は0.15μmであった。
実施例26で用いた内包重合性モノマー(NPGPODA)を、下記表5に示す内包重合性モノマーに変更した以外は、実施例26と同様にして、ゲル粒子27~ゲル粒子30の分散液を作製した。
<乳化工程>
-油相成分の作製-
イソシアネート化合物INT-NCO1(固形分35質量%)20g(活性エネルギーによりラジカルを発生する官能基が導入された3官能以上のイソシアネート化合物)、親水基を導入したイソシアネート化合物1(固形分50質量%)3.2g、INT-NCO28(固形分35質量%)20g(重合性基と活性エネルギーによりラジカルを発生する官能基とが導入された3官能以上のイソシアネート化合物)を酢酸エチル2g中に溶解させて、油相成分を得た。
ラベリンFP(第一工業製薬株式会社製)0.32g(界面活性剤)を蒸留水50gに溶解させて、水相成分を得た。
油相成分に水相成分を添加、混合し、得られた混合物を、ホモジナイザーを用いて12000rpmで10分間乳化させて乳化物を得た。
得られた乳化物を、蒸留水25gに添加し、室温で30分攪拌後、50℃で3時間攪拌し、酢酸エチルを留去した。
その後、さらに50℃24時間攪拌し、得られたゲル粒子の分散液の固形分濃度を20質量%になるように蒸留水を用いて希釈し、ゲル粒子31の分散液を得た。光散乱法により測定したゲル粒子の体積平均粒子径は0.15μmであった。
<乳化工程>
-油相成分の作製-
イソシアネート化合物INT-NCO1(固形分35質量%)22.34g(活性エネルギーによりラジカルを発生する官能基が導入された3官能以上のイソシアネート化合物)、親水性基を導入したイソシアネート化合物2 2.28g、INT-NCO28(固形分35質量%)20g(重合性基と活性エネルギーによりラジカルを発生する官能基とが導入された3官能以上のイソシアネート化合物)を酢酸エチル2g中に溶解させて、油相成分を得た。
ラベリンFP(第一工業製薬株式会社製)0.32g(界面活性剤)、水酸化ナトリウム0.035gを蒸留水50gに溶解させて、水相成分を得た。
油相成分に水相成分を添加、混合し、得られた混合物を、ホモジナイザーを用いて12000rpmで10分間乳化させて乳化物を得た。
得られた乳化物を、蒸留水25gに添加し、室温で30分攪拌後、50℃で3時間攪拌し、酢酸エチルを留去した。
その後、さらに50℃で24時間攪拌し、得られたゲル粒子の分散液の固形分濃度を20質量%になるように蒸留水を用いて希釈し、ゲル粒子32の分散液を得た。光散乱法により測定したゲル粒子の体積平均粒子径は0.15μmであった。
<乳化工程>
-油相成分の作製-
イソシアネート化合物MI-NCO9(固形分35質量%)17.3g(活性エネルギー線によりラジカルを発生する官能基が導入された3官能以上のイソシアネート化合物)、親水基を導入したイソシアネート化合物1(固形分50質量%)3.5g、親水性基を導入したイソシアネート化合物2 4.56g、ジペンタエリスリトールペンタアクリレート(サートマー製、SR-399E)7g(内包重合性モノマー)を酢酸エチル12g中に溶解させて、油相成分を得た。
水酸化ナトリウム0.07gを蒸留水50gに溶解させて、水相成分を得た。
油相成分に水相成分を添加、混合し、得られた混合物を、ホモジナイザーを用いて12000rpmで10分間乳化させて乳化物を得た。
得られた乳化物を、蒸留水25gに添加し、室温で30分攪拌後、50℃で3時間攪拌し、酢酸エチルを留去した。
その後、さらに50℃、24時間攪拌し、得られたゲル粒子の分散液の固形分濃度を20質量%になるように蒸留水を用いて希釈し、ゲル粒子33の分散液を得た。光散乱法により測定したゲル粒子の体積平均粒子径は0.15μmであった。
上記にて得られた実施例1~33のゲル粒子の分散液中が、実際にゲル粒子を含むかどうかを、以下の方法により確認した。なお、以下の操作は、液温25℃の条件で行った。
上記にて得られたゲル粒子の分散液から試料を採取した。採取した試料に対し、この試料中の全固形分(本実施例では粒子)の100質量倍のテトラヒドロフラン(THF)を加えて混合し、ゲル粒子の分散液の希釈液を調製した。得られた希釈液に対して、遠心分離(80000rpm、40分間)を施した。遠心分離後、目視によって残渣の有無を確認し、残渣が確認された場合には、この残渣に水を加え、スターラーを用いて1時間攪拌することにより、残渣を水で再分散させて再分散液を得た。得られた再分散液について、湿式粒度分布測定装置(LA-910、(株)堀場製作所製)を用い、光散乱法によって、粒度分布を測定した。以上の操作により粒度分布が確認された場合を、分散液がゲル粒子を含むと判断した。
その結果、全てのゲル粒子の分散液がゲル粒子を含むことが確認された。
また、以上の結果とフーリエ変換赤外線分光測定(FT-IR)分析の結果とから、全てのゲル粒子の分散液が、重合性基を有するゲル粒子を含むこと(すなわち、ゲル粒子が、実際に重合性基を有するゲル粒子であること)が確認された。
上記にて得られた実施例1~33のゲル粒子の分散液のうち、作製に重合性モノマーを用いたゲル粒子の分散液について、重合性モノマーの内包率(%)を測定することにより、ゲル粒子に重合性モノマーが内包されているか否かを確認した。詳細を以下に示す。なお、以下の操作は、液温25℃の条件で行った。
上記ゲル粒子の分散液から、同質量の試料を2つ(以下、「試料1A」及び「試料2A」とする。)採取した。
試料1Aに対し、この試料1A中の全固形分に対して100質量倍のテトラヒドロフラン(THF)を加えて混合し、希釈液を調製した。得られた希釈液に対し、80,000rpm、40分の条件の遠心分離を施した。遠心分離によって生じた上澄み液(以下、「上澄み液1A」とする。)を採取した。採取された上澄み液1A中に含まれる重合性モノマーの質量を、Waters社の液体クロマトグラフィー装置「Waters2695」によって測定した。得られた重合性モノマーの質量を、「重合性モノマーの全量」とした。
また、試料2Aに対し、上記希釈液に施した遠心分離と同じ条件の遠心分離を施した。遠心分離によって生じた上澄み液(以下、「上澄み液2A」とする。)を採取した。採取された上澄み液2A中に含まれる重合性モノマーの質量を、上記液体クロマトグラフィー装置によって測定した。得られた重合性モノマーの質量を、「重合性モノマーの遊離量」とした。
上記「重合性モノマーの全量」及び上記「重合性モノマーの遊離量」に基づき、下記の式に従って、重合性モノマーの内包率(質量%)を求めた。
油相成分として、NCO103(固形分35質量%)20g(3官能以上のイソシアネート化合物)、トリメチロールプロパンとキシレンジイソシアネートとポリエチレングリコールモノメチルエーテルの付加物(三井化学株式会社製、タケネート(登録商標)D-116N酢酸エチル50質量%溶液、親水性基を導入したイソシアネート化合物3)3.2g、ジペンタエリスリトールペンタアクリレート(サートマー製、SR-399E)7g(内包重合性モノマー)、Irgacure(登録商標)819(BASF製)1g(内包光重合開始剤)を酢酸エチル12g中に溶解させた。
水相成分としてラベリンFP(第一工業製薬株式会社製)0.32gを蒸留水50gに溶解させた。
油相成分に水相成分を添加、混合し、ホモジナイザーを用いて12000rpmで10分間乳化した。
得られた乳化物を、蒸留水25gに添加し、室温で30分攪拌後、50℃で3時間攪拌し、酢酸エチルを留去した。
その後、さらに50℃で24時間攪拌し、得られた粒子の分散液の固形分濃度を20質量%になるように蒸留水を用いて希釈し、比較粒子1の分散液を得た。光散乱法により測定した粒子の体積平均粒子径は0.15μmであった。なお、体積平均粒子径の測定には、湿式粒度分布測定装置LA-910((株)堀場製作所製)を用いた。
なお、比較粒子1の分散液において、比較粒子1は活性エネルギー線の照射によりラジカルを発生する官能基を有していない。
比較例1で用いた内包光重合開始剤(Irgacure(登録商標)819)を、下記表5に示す内包光重合開始剤に変更した以外は、比較例1と同様にして、比較粒子2~比較粒子5の分散液を作製した。
比較粒子2~比較粒子5の分散液において、比較粒子2~比較粒子5は、いずれも活性エネルギー線の照射によりラジカルを発生する官能基を有していない。
これらのことから、実施例は、マイグレーションの発生を抑制し、膜強度に優れた膜が得られることがわかる。
〔LEDを用いたインク組成物の評価〕
実施例11及び17のインク組成物について、LEDを用いた評価を行った。
詳細には、上記の密着性評価A、密着性評価B及び鉛筆硬度の評価において、露光光源(オゾンレスメタルハライドランプMAN250L)を、実験用385nmUV-LED照射器(CCS(株)製)に変更し、露光エネルギーを300mJ/cm2に変更したこと以外は、同様の操作を行った。
結果を表7に示す。
〔インク組成物の調製〕
上記実施例4のゲル粒子の分散液を用いて、下記に示すシアンインク組成物になるように各成分を混合してシアンインク組成物を調製した。
・ゲル粒子4分散液・・・75部
・SR9035(サートマー社製、エトキシ化トリメチロールプロパントリアクリレート、重合性化合物)・・・10部
・インク(Pro-jet Cyan APD1000(FUJIFILM Imaging Colorants社製)着色剤濃度 14質量%)・・・10部
・フッ素系界面活性剤(DuPont社製、Capstone FS-31、固形分25質量%)・・・0.3部
・2-メチルプロパンジオール・・・4.7部
実施例36のシアンインク組成物で用いたSR9035(重合性化合物)を、下記表8に示す重合性化合物に変更した以外は、実施例36と同様にして各実施例のシアンインク組成物を作製した。
実施例36~実施例40のシアンインク組成物で用いたゲル粒子4を上記ゲル粒子23に変更した以外は、実施例36~実施例40と同様にして各実施例のシアンインク組成物を作製した。
上記で得られた実施例36~実施例45の各シアンインク組成物をRK PRINT COAT INSTRUMENTS社製 Kハンドコーター KハンドコーターのNo.2バーを用いて基材(塩化ビニルシート(エイブリィ・デニソン社製、AVERY 400 GLOSS WHITE PERMANENT))に12μmの厚みで塗布した。塗布後、塗膜を60℃で3分間水分を乾燥し、インク組成物評価用試料を得た。
得られた試料について、上記と同様の方法で密着性評価A、定着性評価、耐溶剤性評価、耐水性評価、及び鉛筆硬度の評価を行った。評価結果は下記表9に示す。
また、上記で得られた実施例36~実施例45のシアンインク組成物について上記と同様の方法で再分散性評価、及び保存安定性評価を行い、さらに下記の方法で吐出性の評価を行った。評価結果は下記表9に示す。
上記で得られた実施例36~実施例45のシアンインク組成物をインクジェットプリンタ(ローランド ディー.ジー.社製、SP-300V)を用いて、ヘッドから30分間吐出して、停止し、5分間経過した後、再び吐出することで記録媒体(エイブリィ・デニソン社製、AVERY 400 GLOSS WHITE PERMANENT)上にベタ画像及び細線を記録した。得られた画像(5cm×5cm)を観察し、下記の評価基準に従って目視により評価した。
A:ドット抜けの発生が認められず、良好な画質の画像が得られた。
B:ドット抜けの発生がわずかに認められたが、実用上画質に支障を来さない程度であった。
C:ドット抜けの発生があり、実用上画質に支障を来たす。
D:吐出ができなかった。
本明細書に記載された全ての文献、特許出願、及び技術規格は、個々の文献、特許出願、及び技術規格が参照により取り込まれることが具体的かつ個々に記された場合と同程度に、本明細書に参照により取り込まれる。
Claims (11)
- 重合性基と活性エネルギー線の照射によりラジカルを発生する官能基とを有し、ウレタン結合及びウレア結合から選ばれる少なくとも1種の結合を含む三次元架橋構造を有するゲル粒子。
- 表面にさらに親水性基を有する請求項1又は請求項2に記載のゲル粒子。
- 重合性モノマーを内包している請求項1~請求項3のいずれか1項に記載のゲル粒子。
- 請求項1~請求項4のいずれか1項に記載のゲル粒子と、水と、を含有する感光性組成物。
- ゲル粒子の外部に、さらに重合性化合物を含有する請求項5に記載の感光性組成物。
- 請求項1~請求項4のいずれか1項に記載のゲル粒子と、水と、着色剤と、を含有するインク組成物。
- ゲル粒子の外部に、さらに重合性化合物を含有する請求項7に記載のインク組成物。
- 活性エネルギー線の照射によりラジカルを発生する官能基を有する3官能以上のイソシアネート化合物、重合性モノマー、及び有機溶媒を含む油相成分、活性エネルギー線の照射によりラジカルを発生する官能基を有する3官能以上のイソシアネート化合物、重合性基を有する3官能以上のイソシアネート化合物、及び有機溶媒を含む油相成分、重合性基と活性エネルギー線の照射によりラジカルを発生する官能基とを有する3官能以上のイソシアネート化合物、重合性モノマー、及び有機溶媒を含む油相成分、並びに、活性エネルギー線の照射によりラジカルを発生する官能基を有する3官能以上のイソシアネート化合物、重合性基を有する3官能以上のイソシアネート化合物、重合性モノマー、及び有機溶媒を含む油相成分から選ばれるいずれかの油相成分と、水を含む水相成分と、を混合し、乳化させて乳化物を得る乳化工程と、
前記乳化物を加熱してゲル化させるゲル化工程と、
を有するゲル粒子の水分散物の製造方法。 - さらに、前記ゲル化工程で得られたゲル粒子、水、及び着色剤を混合する混合工程を有する請求項9に記載のゲル粒子の水分散物の製造方法。
- 請求項7又は請求項8に記載のインク組成物を記録媒体上に付与するインク付与工程と、
前記記録媒体上に付与されたインク組成物に活性エネルギー線を照射する照射工程と、
を含む画像形成方法。
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