WO2007119836A1 - Composition de résine colorée et encre pour jet d'encre comprenant celle-ci - Google Patents

Composition de résine colorée et encre pour jet d'encre comprenant celle-ci Download PDF

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Publication number
WO2007119836A1
WO2007119836A1 PCT/JP2007/058208 JP2007058208W WO2007119836A1 WO 2007119836 A1 WO2007119836 A1 WO 2007119836A1 JP 2007058208 W JP2007058208 W JP 2007058208W WO 2007119836 A1 WO2007119836 A1 WO 2007119836A1
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WIPO (PCT)
Prior art keywords
ink
group
pigment
parts
general formula
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PCT/JP2007/058208
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English (en)
Japanese (ja)
Inventor
Dai Inagaki
Tomonori Ikegami
Takayuki Nogami
Yoshikazu Tanaka
Tomoko Tachibana
Kazuhiro Jonai
Yasuo Iida
Daisuke Nishida
Original Assignee
Toyo Ink Mfg. Co., Ltd.
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Publication date
Application filed by Toyo Ink Mfg. Co., Ltd. filed Critical Toyo Ink Mfg. Co., Ltd.
Priority to KR1020087027406A priority Critical patent/KR101403290B1/ko
Publication of WO2007119836A1 publication Critical patent/WO2007119836A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02—Organic and inorganic ingredients
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/322—Pigment inks

Definitions

  • the present invention relates to a colored resin composition, an ink jet ink, and a method for producing the same.
  • the present invention relates to a printed matter using inkjet ink.
  • a liquid crystal display panel used in a thin television or the like includes a color filter substrate.
  • a color filter substrate is a substrate in which three or more kinds of fine stripe-shaped filter segments of different hues are arranged in parallel or intersecting on the surface of a transparent substrate such as glass. It consists of a series of mosaic-like filter segments arranged in a constant vertical and horizontal direction. From the viewpoint of productivity and low cost, it is advantageous to apply the inkjet method to color filter substrate applications.
  • the filter segment is formed by providing a black matrix on a transparent substrate in advance and filling an ink in an area divided by the black matrix by an ink jet method.
  • an ink composition it is required to disperse a pigment having a high concentration necessary for a color filter substrate. At the same time, it is required to have physical properties that can be stably discharged to a desired position on the substrate.
  • Japanese Patent Application Laid-Open No. 11-246773, Japanese Patent No. 2897575, Japanese Patent No. 3000852 or Japanese Patent No. 3127412 discloses a hot-melt type hot-melt inkjet ink. Speak. Excellent strength for fixing to non-permeable substrates Due to the characteristics of hot melt ink-jet inks, they were solidified on the substrate at the same time as printing. As a result, the prints were swelled with bad dot leveling, and the banding between dots, that is, the horizontal stripes generated in the scanning direction of the head, was prone to occur. Therefore, it was difficult and difficult to obtain the desired image quality.
  • JP 2004-182764 discloses a method for improving the fixing property and ejection stability to a non-permeable substrate by including a succinic acid metal salt in the ink.
  • the law is disclosed.
  • this method required annealing and fixing at a high temperature close to 600 ° C.
  • the transparency required for the ink is greatly reduced during printing.
  • This decrease in transparency causes a decrease in lightness just by color shift.
  • the decrease in lightness significantly reduces the color reproducibility, making it difficult to use as a printing application.
  • Japanese Patent Laid-Open No. 9-137094 discloses that ink having a specific soft spot or outflow start point is used to control the dot diameter to be small and to ensure friction resistance and density. .
  • this ink is printed on a non-permeable substrate, the dots do not maintain the desired diameter, the dot gain increases, and color mixing occurs.
  • active energy ray-curable ink is used to control the surface tension of the solvent and the surface tension of the radiation-curable reactive diluent, thereby improving the resistance and fineness. It is disclosed. However, in general, the active energy ray curable ink cures the liquid by a bridge. For this reason, if the irradiation timing after ejection is early, a graininess appears, and if the timing is late, color mixing occurs. Therefore, the printed material actually had a graininess from the viewpoint of quality and productivity. [0010] Inkjet ink force with controlled viscoelasticity is disclosed in JP-A-2000-186240.
  • Japanese Patent Application Laid-Open No. 11-84123 discloses a method that does not deteriorate dischargeability and in-pixel flatness with an ink having a low pigment concentration and solid content concentration. .
  • the film thickness was too thick when a coating with the required color density was formed.
  • the amount of ink to be filled in the area divided by the black matrix was increased, the ink overflowed beyond the black matrix, the ink mixed into the adjacent area, and the hue of the filter segment was damaged.
  • Japanese Patent Laid-Open No. 2003-66222 discloses a method for improving the in-pixel flatness by controlling the temperature and time during drying. However, the control of such a process could not solve the above problem.
  • JP 2004-339330, JP 2004-339331, JP 2004-339332, and JP 2004-339333 disclose that the color filter ink was evaluated by a rigid pendulum test. However, according to these inks, the smoothness of the printed matter was not sufficient only by focusing on heat resistance.
  • Patent Document 1 Japanese Patent Laid-Open No. 11 84123
  • Patent Document 2 Japanese Patent Laid-Open No. 2003-66222
  • Patent Document 3 Japanese Patent Laid-Open No. 11 246773
  • Patent Document 4 Japanese Patent No. 2897575
  • Patent Document 5 Japanese Patent No. 3000852
  • Patent Document 6 Japanese Patent No. 3127412
  • Patent Document 7 Japanese Patent Application Laid-Open No. 2004-182764
  • Patent Document 8 JP-A-9 137094
  • Patent Document 9 Special Publication 2004-522813
  • Patent Document 10 Japanese Patent Laid-Open No. 2000-18624
  • Patent Document 11 Japanese Patent Application Laid-Open No. 2004-339330
  • Patent Document 12 Japanese Patent Application Laid-Open No. 2004-339331
  • Patent Document 13 Japanese Patent Application Laid-Open No. 2004-339332
  • Patent Document 14 Japanese Patent Application Laid-Open No. 2004-339333
  • An embodiment of the present invention is a colored resin composition having excellent surface smoothness and in-pixel flatness.
  • a first embodiment of the present invention is a colored rosin composition containing a pigment, a pigment derivative, and a rosin carrier, and has a viscosity (however, shearing) at a solid content concentration of 20 wt% or more and less than 40 wt%. Only when the speed is 100 (lZs, the same shall apply hereinafter) is 3 to 200 (mPa's), and the TI value (however, the viscosity of shear rate 10 (lZs) r? A (mPa 's) is the ratio of the shear rate of 1000 (1 Zs) to the viscosity 7? b (mPa-s) (7? aZ b).
  • the same shall apply hereinafter.) is 1 to 2, and the solid content concentration
  • the present invention relates to a colored resin composition characterized by having a viscosity of 10 to 200 (mPa • s) and a TI value of 1 to 3 at 40 to 60% by weight.
  • the colored rosin composition described above is characterized in that a compound having a weight average molecular weight of 2000 to 10,000 is contained in an amount of 5% by weight or more based on the total solid content.
  • the compound having a weight average molecular weight of 2000 to 10000 preferably has at least one structure represented by the following general formulas (1) to (3).
  • R represents hydrogen or a methyl group
  • R represents an alkylene group
  • m is an integer of 1 to 20;
  • R ′ 1 is a tetravalent tetracarboxylic acid compound residue
  • R ′ 2 is a monoalcohol residue
  • R ′ 3 is a rataton residue
  • e is an integer of 2 or 3
  • f is an integer of 1 to 50.
  • G represents (4 e)
  • R '' is a hydrogen atom or a methyl group
  • X 1 is one COO, one CONH, one ⁇ , one OCO— or one CH ⁇ , and X 2
  • R al is a linear or branched alkylene group having 2 to 8 carbon atoms, or a cycloalkylene group having 3 to 8 carbon atoms, and ml is an integer of 1 to 50).
  • X 3 is a general formula:
  • R bl is a linear or branched alkylene group having 4 to 8 carbon atoms, or a cycloalkylene group having 4 to 8 carbon atoms, and m2 is 0 or an integer of 1 to 20). Is a group to be
  • Y 1 is the general formula (4):
  • One of eight to eight three is a combination of hydrogen atoms and the other two are COOH.
  • One of the forces A to A 3 is —COORC (where is the number of carbon atoms 1 to 18 And the other two are forces that are a combination of —COOH, or three of AA 3 —a COOH string and a combination, and k is 1 or 2)
  • a 5 to A 7 is a hydrogen atom and the other two are combinations of COOH, or one of A 5 to A 7 is —COOR d (where R d is carbon The other two are —COOH-combination forces or A 5 -A 7 —C OOH yarns and combinations,
  • R 2 is a direct bond, O—, —CO—, —COOCH CH OCO—, —SO—, — C (CF
  • the above colored resin composition containing an alkoxyalkyl group-containing melamine compound or an alkoxyalkyl group-containing benzoguanamine compound is also preferable.
  • the colored resin composition described above in which a pigment derivative and a resin carrier coating layer are formed on the pigment surface is also preferable.
  • An ink-jet ink can be obtained using the colored resin composition.
  • viscoelasticity is measured by a rigid pendulum test during heating at a rate of temperature increase of 5 ° CZ after coating on a printing substrate with a film thickness of 15 to 25 ⁇ m.
  • the present invention relates to an ink for ink jet, characterized in that the period in the entire temperature range of 100 to 170 ° C. is 0.6 to 0.9 seconds.
  • the ink-jet ink has a period in the whole temperature range of 100 to 170 ° C in a viscoelasticity measurement by a rigid pendulum test while the temperature is raised at a temperature rise rate of 5 ° CZ.
  • the printing substrate is preferably a non-permeable substrate, and the contact angle of the inkjet ink on the non-permeable substrate is preferably 10 to 30 °.
  • the printing substrate is preferably glass! /.
  • the ink-jet ink preferably contains 50 to 85% by weight of an organic solvent.
  • an organic solvent having a boiling point of 130 ° C to 300 ° C at normal pressure is used as the organic solvent.
  • a printed matter may be obtained by printing on a printing substrate using the inkjet ink.
  • the ink-jet ink is used in the measurement of viscoelasticity by a rigid pendulum test while the temperature is increased at a temperature increase rate of 5 ° CZ after the ink is discharged onto a printing substrate at 25 to 70 ° C by an ink jet discharge device.
  • the cycle in the entire temperature range of 100 to 170 ° C can be produced with a period of 0.6 to 0.9 seconds.
  • a colored resin composition having an effect of excellent dispersion stability and ejection stability during long-time continuous ejection is provided.
  • the colored resin composition excellent in surface smoothness and in-pixel flatness can be provided.
  • a composition can be provided. Further, it is possible to provide an ink jet ink having low viscosity and good ejection stability while maintaining resistance.
  • the printed matter achieves high-quality smoothness.
  • the granularity or fineness of printing ranging from low density to high density can be improved.
  • this ink-jet ink is made into a color filter by printing by the ink-jet method, the surface shape of the pixel on the power filter and the color unevenness occurring in the pixel can be remarkably improved. .
  • the ink yarn composition of the present invention as an inkjet ink, it is possible to produce a color filter, a knocker, or an outdoor sign board that is much more efficient than conventional methods. can do.
  • FIG. 1 A diagram showing a measurement result of a period by a rigid pendulum test of an example and a comparative example.
  • the colored rosin composition of the present invention includes a pigment, a pigment derivative, and a rosin carrier. Furthermore, it is preferable that the solid content contains 5% by weight or more of a compound having a weight average molecular weight of 2000 to 10,000.
  • the colored rosin composition of the present invention is characterized by satisfying the following viscosity physical properties I and ⁇ .
  • Viscosity (however, shear rate is 10
  • O (lZs) is 3 to 200 (mPa's), and the TI value (however, the viscosity ⁇ a (mPa-s) at a shear rate of 10 (lZs) and the shear rate of 1000 (lZs) ) Of the viscosity ⁇ b (mPa-s) (7? AZ b)) force ⁇ ⁇ 2.
  • Viscosity at a solid content concentration of 40% to 60% by weight (however, the shear rate is 10
  • the solid content of the ink composition (hereinafter sometimes referred to as solid content concentration) is preferably relative to the total weight of the ink composition. 3-6
  • the solid content is 3% by weight or more, the concentration of the ink film is appropriate and the resistance is excellent. If it is 60% by weight or less, the viscosity of the ink becomes moderate and the stability over time is excellent.
  • a composition that satisfies the above-mentioned viscosity physical properties I or II when the solvent is adjusted so that the solid content is 20% by weight or more and less than 40% by weight or 40% by weight or more and 60% by weight is disclosed. It is a bright colored rosin composition.
  • the TI value indicates thixotropy and is represented by the following relationship (i).
  • I. I. Value Viscosity measured at a rotor speed of 10 (1ZS) in a rheometer ⁇ Viscosity measured at a rotor speed of 1000 (1ZS) in a rheometer
  • the viscosity is 10 to 150 (111? & '3) brackets when the solid content concentration is 40 wt% or more and 60 wt% or less.
  • the value is 1 to 3, more preferably, the solid content concentration is 40 wt% or more and 60 wt% or less, the viscosity is 10: LOO (mPa's) and).
  • the value is 1 to 3 is there.
  • the colored resin composition of the present invention contains a pigment.
  • an organic pigment, an inorganic pigment, or carbon black can be used, and two or more kinds of pigments may be used in combination.
  • Examples of carbon black include acetylene black, channel black, and furnace black.
  • organic pigments examples include diketopyrrolopyrrole pigments, azo pigments such as azo, disazo, or polyazo, phthalocyanine pigments such as copper phthalocyanine, halogenated copper phthalocyanine, or metal-free phthalocyanine, and aminoanthraquinone.
  • Diaminodianthraquinone, anthrapyrimidine, furanthrone, anthanthrone, indanthrone, pyranthrone, or anthraquinone pigment such as violanthrone, quinacridone pigment, dioxazine pigment, perinone pigment, perylene pigment, thioindigo pigment, iso Examples thereof include indoline pigments, isoindolinone pigments, quinophthalone pigments, selenium pigments, and metal complex pigments.
  • inorganic pigments include titanium oxide, zinc white, zinc sulfide, white lead, calcium carbonate, precipitated barium sulfate, white carbon, alumina white, kaolin clay, talc, bentonite, black iron oxide, cadmium red, and red rose. , Molybdenum red, molybdate orange, chrome vermilion, yellow lead, cadmium yellow, yellow iron oxide, titanium yellow, acid chrome, viridian, titanium cobalt green, cobalt green, cobalt chrome green, Victoria green, ultramarine blue, bitumen , Cobalt blue, cerulean blue, cobalt silica blue, cobalt zinc silica blue, manganese violet, cobalt violet, etc. Can be mentioned.
  • pigments that can be used in the colored resin composition of the present invention are color indexes.
  • red coloring composition examples include C. I. Pigment Red 7, 9, 14, 41, 48: 1, 48.
  • Red pigments such as 200, 202, 208, 210, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 246, 254, 255, 264, 272 can be used.
  • a yellow pigment and a Z or orange pigment can be used in combination with the red coloring composition.
  • Yellow colored compositions include, for example, CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 8 6, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 11 5, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 1 39, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187,
  • orange pigments such as C. I. Pigment orange 36, 43, 51, 55, 59, 61 can be used, for example.
  • green pigments such as C. I. Pigment Green 7, 10, 36, 37 can be used.
  • a yellow pigment can be used in combination with the green coloring composition.
  • Blue coloring composition for example, CI Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64 or the like is used. be able to. Blue coloring compositions include, for example, C. I. Pigment Violet
  • the colored rosin composition of the present invention has the ability to contain one type of pigment alone, or can contain a mixture of two or more types.
  • the particle diameter of the pigment is preferably sufficiently small with respect to the wavelength of visible light in view of the absorption coefficient of visible light (spectrum suitability) and transparency.
  • the pigment should have an average primary particle size of SO. 01 ⁇ m or more and 0.3 ⁇ m or less, particularly 0.01 ⁇ m or more and 0.1 ⁇ m or less.
  • the primary particle diameter means the diameter of the smallest unit pigment particle, and is measured with an electron microscope.
  • the primary particle diameter of the pigment can be controlled within an appropriate range by using a known dispersing apparatus such as a sand mill, an adader, or a two roll.
  • the pigment is preferably contained in an amount of 1 to 30% by weight, more preferably 3 to 25% by weight, based on the total weight of the composition.
  • LV which is preferred to be contained in.
  • the ink film has a sufficient ink film concentration when used as an ink, and when it is 30% by weight or less, the viscosity does not increase and the stability over time is excellent.
  • the ink composition is excellent in film forming properties.
  • the colored resin composition of the present invention contains a pigment derivative.
  • the pigment derivative refers to a compound in which a specific substituent is introduced into the organic pigment residue described in the above color index.
  • Examples of the pigment derivative include those represented by the general formula (6):
  • G 1 is a chromogenic compound residue
  • E is a basic substituent, an acidic substituent, or a neutral substituent
  • q is an integer of 1 to 4
  • Examples of the basic substituent of the group E include substituents represented by the following general formula (7), general formula (8), general formula (9), and general formula (10). .
  • p represents an integer of 1 to 10.
  • R 33 and R 34 each independently represents an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted phenyl group, or R 33 and R 34 And together with a further nitrogen, oxygen or sulfur atom substituted, it may represent a heterocyclic ring.
  • Alkyl and alkenyl groups preferably have 1 to 10 carbon atoms! /.
  • R d R db each independently substituted !, may be an alkyl group, substituted,
  • R 35 and R 36 May be substituted with an alkyl group, an optionally substituted phenyl group, or a group containing additional nitrogen, oxygen or sulfur atoms together with R 35 and R 36 .
  • the carbon number of the alkyl group and the alkenyl group is preferably 1 to 10! /.
  • X represents —SO—, —CO—, —CH NHCOCH—, —CH— or a direct bond.
  • R 37 substituted !, may represent an alkyl group, may be substituted, may be a alkenyl group, or may be substituted, a phenyl group.
  • the alkyl group and alkenyl group preferably have 1 to 10 carbon atoms.
  • R 38 , R 39 , R 10 , R 11 each independently a hydrogen atom, an optionally substituted alkyl group, a substituted, an alkyl group, or a substituted group It represents a phenol group.
  • the alkyl group and the alkenyl group preferably have 1 to 5 carbon atoms.
  • X represents —SO—, —CO—, —CH NHCOCH—, —CH— or a direct bond.
  • Y — NR 12 — Z— NR 13 — or direct bond.
  • R 12 and R 13 are each independently a hydrogen atom, an optionally substituted alkyl group, a substituted V, a alkenyl group or a substituted !, may! / -Represents a ru group.
  • the alkyl group and the alkenyl group preferably have 1 to 5 carbon atoms.
  • Z represents an optionally substituted alkylene group, an optionally substituted alkylene group, or a substituted alkylene group.
  • the number of carbon atoms of the alkylene group and the alkene group is preferably 1-8.
  • P represents a substituent represented by the following general formula (11) or a substituent represented by the following general formula (12).
  • Q represents a hydroxyl group, an alkoxyl group, a substituent represented by the general formula (8) or a substituent represented by the general formula (9).
  • r represents an integer of l to 10.
  • R 14 and R 15 are each independently an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted phenyl group, or R 14 and R 15 And together with a further nitrogen, oxygen or sulfur atom substituted, it may represent a heterocyclic ring.
  • Alkyl and alkenyl groups preferably have 1 to 10 carbon atoms! /.
  • R: substituted ! may be an alkyl group, substituted, may be a alkenyl group or may be a phenyl group, which may be substituted.
  • the alkyl group and alkenyl group preferably have 1 to 10 carbon atoms.
  • R 17 , R 18 , R 19 , R 2 ° each independently a hydrogen atom, an optionally substituted alkyl group, a substituted, optionally a alkenyl group or substituted, Of course, it represents a phenol group.
  • the alkyl group and the alkenyl group preferably have 1 to 5 carbon atoms.
  • Examples of the acidic substituent or neutral substituent of the group E include substituents represented by the following general formula (13), general formula (14), and general formula (15).
  • M hydrogen atom, calcium atom, barium atom, strontium atom, manganese atom, Represents an aluminum atom.
  • R z R z R z R 4 represents a hydrogen atom or an alkyl group having 1 to 30 carbon atoms (provided that all except when a water atom).
  • A represents a hydrogen atom, a halogen atom, -NO, -NH or SO 2 H.
  • y represents an integer of 1 to 4.
  • Examples of the chromogenic compound residue G 1 include diketopyrrolopyrrole dyes, azo dyes such as azo, diazo, and polyazo, phthalocyanine dyes, diaminodianthraquinone, and anthrapyrimidine.
  • anthraquinone derivative anthraquinone having the above basic substituent, acidic substituent or neutral substituent can be used.
  • an alkyl group such as a methyl group or an ethyl group; an amino group; an alkylamino group such as a dimethylamino group, a jetylamino group or a dibutylamino group; a nitro group;
  • An alkoxy group such as a methoxy group, an ethoxy group or a butoxy group; a halogen such as chlorine; a phenyl group which may be substituted with a methyl group, a methoxy group, an amino group, a dimethylamino group or a hydroxyl group; or a methyl group or an ethyl group Group, a methoxy group, an ethoxy group, an amino group, a dimethylamino group, a
  • a derivative in which the above basic substituent, acidic substituent or neutral substituent is introduced into 1,3,5-triazine, which may have a substituent such as -luamino group, etc. can be used.
  • pigment derivatives containing a triazine ring and an anthraquinone group are more preferred.
  • a pigment derivative having a triazine ring and an anthraquinone group structure exhibits a higher adsorptivity to the pigment, provides a high dispersibility, and at the same time, causes a curing reaction of the thermoreactive compound more effectively and is resistant. We can expect further improvement.
  • the colored rosin composition of the present invention contains a rosin carrier.
  • the resin carrier is a non-reactive resin and is preferably a thermoplastic resin even at the reaction temperature of the thermoreactive compound described below.
  • Examples of the resin carrier include petroleum-based resin, maleic acid resin, nitrocellulose, cellulose acetate pettylate, cyclized rubber, salted rubber, alkyd resin, acrylic resin, and polyester resin. Fat, amino rosin, vinyl rosin, petital rosin and the like can be used.
  • the resin carrier one having a crosslinkable functional group may be used.
  • the crosslinkable functional group include a hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, and an alkoxyl group.
  • the resin having a crosslinkable functional group is preferably an acrylic resin having a hydroxyl group or a carboxyl group because the resin is slowly crosslinked by an esterification reaction.
  • An acrylic resin having a hydroxyl group or a carboxyl group is a resin obtained by copolymerizing a monomer having a hydroxyl group or a monomer having a carboxyl group with a hydroxyl group and a carboxyl group and / or an acrylic monomer. It is.
  • Monomers having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate.
  • Monomers having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, 2-carboxyethyl acrylate, ⁇ -carboxy-polypropylene monoacrylate. Examples thereof include rate, monohydroxyethyl phthalate phthalate, daltaconic acid, and tetrahydrophthalic acid.
  • acrylic monomer having no hydroxyl group or carboxyl group a monomer represented by the following general formula (16) may be used.
  • H 2 C C— C One O—— (R 42 — 0) .— R 43 (1 6)
  • R 41 and R 51 a hydrogen atom or a methyl group. It represents a C1-4 alkylene group having a carbon: [0112] R 42.
  • s represents an integer of l to 100.
  • Examples of the monomer represented by the general formula (16) include, for example, methoxypolyethyleneglycol monometatalylate, methoxypolyethyleneglycol monoatarylate, oxypolyethyleneglycol monoacrylate, otoxypolyethyleneglycolpolypropyleneglycol monomethacrylate.
  • Otoxypolyethylene glycol polypropylene glycol monoatylate Lauroxypolyethylene glycol monoatarylate, Lauroxypolyethylene glycol monoatallylate, Stearoxypolyethyleneglycol monometatalylate, Stearoxypolyethyleneglycol Polypropyleneglycolmonotalariate, Alyloxy Polyethylene glycol Polypropylene glycol monometatalylate, Aliro Xylon Polyethylene glycololate Polypropyleneglycolole monoate, ethylene glycol dimetatalylate, diethylene glycol dimetatalate, polyethylene glycol dimetatalate, polyethylene glycol diatalate, polypropylene glycol dimetatalylate, polypropylene glycol diatalate, polytetramethylene glycol dimethylate Tatari Rate
  • Polytetramethylene glycol ditalarate poly (ethylene glycol-tetramethylene glycol) dimetatalylate, poly (ethylene glycol-tetramethylene glycol) ditalylate, poly (propylene glycol monotetramethylene glycol) dimetatalylate, poly (Propylene glycol-tetramethylene glycol) diatalylate, polyethylene glycol monoole polypropylene glycololeate polyethylene glycol diatalylate, nonylphenoxypolyethyleneglycol monoacrylate, norphenoxypolyethyleneglycol polypropyleneglycolmonometatalylate, norphenoxypolypropylene Glyco-Lu polyethylene glycol monometatalylate, norphenoxypoly (ethylene Examples thereof include glycolene propylene glycol) monotalylate, phenol ethylene oxide modified acrylate, norphenol ethylene oxide modified acrylate, bisphenol F ethylene oxide modified diatalate, and the like. These are sold, for example
  • silyl monomer examples include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethyl hexyl (meth) acrylate, octyl (meth) acrylate, stearyl (meth) ) (Meth) acrylic acid alkyl esters such as acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, styrene, a- methyl styrene, butyl toluene, acetic acid Examples include bullets.
  • a monomer that is generally used for the synthesis of acrylic resins such as alkyl (meth) acrylate, in which part or all of the hydrogen atoms of the alkyl group are substituted with aromatic rings, heterocyclic rings, halogen atoms, etc. Can do.
  • the colored rosin composition of the present invention preferably contains a compound having a weight average molecular weight (Mw) of 2000 to 10,000 in a part of the rosin carrier. It is also a force capable of maintaining the relationship between the viscosity and the T.I. value of the colored resin composition of the present invention.
  • Mw weight average molecular weight
  • it is desirable to use a compound having a weight average molecular weight of Mw 2000 to 10,000 in order to obtain a colored resin composition having low viscosity and low thixotropy for the above reason!
  • a weight average molecular weight of Mw is required to obtain a colored rosin composition having low viscosity and low thixotropy.
  • a compound having a weight average molecular weight of 2000 to 10,000 may be used as long as the relationship between the viscosity and the TI value of the colored resin composition can be adjusted for the reasons described above. /.
  • the compound having a weight average molecular weight of 2000 to 10,000 may be a known compound, or may be the above resin carrier or the above thermoreactive compound. Furthermore, an oligomer or a resin having a function of pigment dispersion or dispersion stability is particularly preferable, and the following general formula is particularly preferable. It is a compound having the structure of (1) to (3).
  • R represents hydrogen or a methyl group.
  • R represents an alkylene group.
  • M is an integer of 1 to 20.
  • the compound having the structure represented by the general formula (1) is an oligomer or a resin having a phosphate group.
  • the dispersibility of the pigment and the stability over time are improved, and the inkjet ink has a low viscosity.
  • the phosphate group is an alkali metal such as sodium, potassium or lithium, a polyvalent metal such as calcium, magnesium, aluminum or zinc, ammonia or ethylamine, dibutylamine, triethanolamine, ethylamine, propylamine or butylamine.
  • alkali metal such as sodium, potassium or lithium
  • a polyvalent metal such as calcium, magnesium, aluminum or zinc
  • Form salts with organic amines such as pentylamine, hexylamine, octylamine, dodecylamine, stearylamine, oleylamine, distearylamine, etc.
  • the phosphate group may be a monovalent phosphate group represented by the formula (17) or a divalent phosphate group represented by the formula (18).
  • the compound having the structure represented by the general formula (1) may include a resin containing a monomer having a phosphoric acid group represented by the following general formula (19) as a polymerization component.
  • Examples of the monomer having a phosphate group represented by the general formula (19) include ethylene glycol methacrylate phosphate, propylene glycolate methacrylate phosphate, ethylene glycol acrylate phosphate, and propylene glycol acrylate phosphate. Can be mentioned.
  • R 44 represents hydrogen or a methyl group.
  • R 45 represents an anoalkylene group.
  • u represents an integer of l to 20.
  • the above-mentioned monomer having a phosphate group can be used alone or in combination of two or more.
  • a monomer having a phosphate group may be used as a copolymer with another monomer.
  • the copolymerization ratio of the monomer having a phosphate group in the copolymer is preferably 0.1 to 30 parts by weight or less with respect to 100 parts by weight of all monomers, and 0.1 to 5 parts by weight or less. Is more preferable.
  • an oligomer or a resin having a phosphate group can be obtained by radical polymerization of a monomer having a phosphate group and a monomer having no phosphate group.
  • a monomer having no phosphoric acid group a monomer having a hydroxyl group, a monomer having a carboxyl group, a monomer having no hydroxyl group and a carboxyl group, as exemplified above, can be used.
  • the synthesis of the oligomer or resin having phosphoric acid groups is carried out in the presence of an initiator in an inert gas stream at 50 to 150 ° C for 2 to 10 hours. If necessary, it can be performed in the presence of a solvent.
  • Initiators include organic peroxides such as benzoyl peroxide, tamen hydroperoxide, t-butyl hydroperoxide, diisopropyl peroxycarbonate, di-t-butyl peroxide, t-butyl peroxybenzoate, 2 , 2'-azobisisobuty-mouth-tolyl and the like.
  • the initiator is preferably used in an amount of 1 to 20 parts by weight per 100 parts by weight of the monomer.
  • Solvents used for the synthesis of the functionalized rosin include acetate solvents such as ethyl cellulose sorb acetate and propylene glycol monomethyl ether acetate, ketone solvents such as cyclohexanone and methyl isobutyl ketone, and xylene. And ethylbenzene.
  • a resin containing the monomer represented by (21) as a polymerization component.
  • R 46 and R 48 represent a hydrogen atom or a methyl group
  • R 47 and R 49 represent an alkylene group having 1 to 4 carbon atoms
  • V and w represents an integer from 1 to L00.
  • the monomers represented by the general formula (20) and the general formula (21) include paracumylphenol ethylene oxide-modified acrylate, ethylene oxide-modified bisphenol A dimethacrylate, ethylene oxide-modified bisphenol A diaphthalate, propylene oxide.
  • the monomers represented by the general formula (20) and the general formula (21) may be one kind or two or more kinds. Can be used in combination with the monomer having a phosphate group.
  • a monomer represented by the general formula (19) is preferable.
  • the copolymerization ratio of the monomers represented by the general formula (20) and the general formula (21) in the copolymer is preferably 0.1 to 50 parts by weight with respect to 100 parts by weight of all monomers.
  • R ′ 1 is a tetravalent tetracarboxylic acid compound residue
  • R ′ 2 is a monoalcohol residue
  • R ′ 3 is a rataton residue
  • e is an integer of 2 or 3
  • f is an integer of 1 to 50.
  • G represents (4 e)
  • the dispersant represented by the general formula (2) may be synthesized using any production method as long as it has the structure represented by the general formula (2). There is no first step for producing a polyester having a hydroxyl group at one end by ring-opening polymerization of rataton using monoalcohol as an initiator, and polyester. It is preferable to produce from the hydroxyl group at one terminal of tellurium and the second step of reacting tetracarboxylic dianhydride.
  • the monoalcohol of the present invention may be any compound as long as it is a compound having one hydroxyl group.
  • a monoalcohol having an ethylenically unsaturated double bond may be used as the monoalcohol of the present invention.
  • it is suitable for use in an active energy ray-curable resin composition.
  • Examples of the ethylenically unsaturated double bond referred to in the present invention include a buyl group and a (meth) attalyloyl group.
  • a (meth) taroloyl group is preferred. These may be used alone or in combination, and different types of ethylenically unsaturated double bonds may be used in combination.
  • Monoalcohols having an ethylenically unsaturated double bond are classified according to the number of ethylenically unsaturated double bonds.
  • Monoalcohol with one ethylenically unsaturated double bond is classified according to the number of ethylenically unsaturated double bonds.
  • Monoalcohols with 3 ethylenically unsaturated double bonds include pentaerythritol triatalylate, and monoalcohols with 5 ethylenically unsaturated double bonds include dipentaerythritol pentaarate. I can get lost.
  • pentaerythritol triatalylate and dipentaerythritol pentaatalylate are obtained as a mixture with pentaerythritol tetraatalylate and dipentaerythritol hexaatalylate, respectively. It is necessary to determine the ratio of the monoalcohol compound by measuring the hydroxyl value.
  • an ethylenically unsaturated double bond having two or more is preferable because it becomes a dispersant having excellent curability when an active energy single-line curable resin composition is obtained.
  • alkylene oxide to be added examples include ethylene oxide, propylene oxide, 1,2-, 1,4-, 2,3- or 1,3-butylene oxide and combinations of two or more thereof.
  • the bond type may be random and either Z or block.
  • the addition number of alkylene oxide is usually 1 to 300, preferably 2 to 250, particularly preferably 5 to LOO in one molecule.
  • alkylene oxide can be performed by a known method, for example, at a temperature of 100 to 200 ° C. in the presence of an alkali catalyst.
  • Commercially available products include Nippon Oil & Fats 'Ox Series and Nippon Oil &Fats' Bremer Series.
  • Polyester having a hydroxyl group at one end can be obtained by ring-opening polymerization of rataton using monoalcohol as an initiator.
  • the ratatones used in the present invention are j8-butyrolatatanes, ⁇ -butyrolatatatons, ⁇ —norellolatatones, ⁇ —norellolatatones, ⁇ —force prolatatones, ⁇ —force prolatatones, alkyl-substituted ⁇ — Power Prolatathon.
  • ⁇ -valerolataton, ⁇ -force prolatatone, and alkyl-substituted ⁇ -one-prolatatone are preferably used in terms of ring-opening polymerization.
  • the ratatones of the present invention can be used without being limited to the above examples, and may be used alone or in combination of two or more. When two or more types are used in combination, the crystallinity is lowered and may become liquid at room temperature, which is preferable in terms of workability and compatibility with other resins.
  • Ring-opening polymerization can be carried out in a known manner, for example, by charging a reactor connected with a dehydrating tube and a condenser with monocol, rataton, and a polymerization catalyst in a nitrogen stream.
  • a reactor connected with a dehydrating tube and a condenser with monocol, rataton, and a polymerization catalyst in a nitrogen stream.
  • the reaction can be carried out under pressure using an autoclave.
  • the number of moles of ratatone added per mole of monoalcohol is 1 to 50 moles, preferably 3 to 20 moles, and most preferably 4 to 16 moles.
  • the added mole number is 1 mole or more, the effect as a dispersant can be sufficiently obtained, and when it is 50 moles or less, the molecular weight of the dispersant increases. Excellent dispersibility and fluidity.
  • Examples of the polymerization catalyst include tetramethylammonium chloride, tetraptylammonium chloride, tetramethylammonium bromide, tetraptylammonium bromide, tetramethylammonium chloride, tetraptylammonium chloride, benzyltrimethylammonium- Quaternary ammonium salts such as um chloride, benzyl trimethyl ammonium bromoide, benzyl trimethyl ammonium bromoide, tetramethyl phospho bromochloride, tetrabutyl phospho bromochloride, tetramethyl phospho bromo bromide, tetra butyl phospho bromo bromide, tetramethyl phospho -Muododo, Tetrabutylphosphomumuodo, Benzyltrimethylphosphomumuchloride, Benzyltrimethylphospho-mubromide, Benzyltrimethyl
  • a solvent-free or a suitable dehydrated organic solvent can also be used.
  • the solvent used in the reaction can be removed by an operation such as distillation or used as part of the product as it is.
  • the reaction temperature is 100 ° C to 220 ° C, preferably 110 ° C to 210 ° C.
  • the reaction rate is very slow at temperatures below 100 ° C.
  • side reactions other than the addition reaction of latatones for example, decomposition of latataton adducts into latatone monomers, formation of cyclic latatone dimers and trimers, etc. Is likely to occur.
  • Polymerization inhibitors used when using a monoalcohol having an ethylenically unsaturated double bond include hydroquinone, methylhydroquinone, and hydroquinone monomethyl.
  • Ether, p-benzoquinone, 2,4 dimethyl-6-t-butylphenol, phenothiazine and the like are preferable. These may be used alone or in combination in the range of 0.01% to 6%, preferably 0.05% to 1.0%.
  • the tetracarboxylic dianhydrides used in the second step include 1, 2, 3, 4 butane tetracarboxylic dianhydride, 1, 2, 3, 4 cyclobutane tetracarboxylic dianhydride, 1, 3 Dimethyl— 1, 2, 3, 4 Cyclobutanetetracarboxylic dianhydride, 1, 2, 3, 4 Cyclopentanetetracarboxylic dianhydride, 2, 3, 5 Tricarboxycyclopentylacetic acid dianhydride, 3, 5 , 6 Tricarboxynorbornane—2 Acetic dianhydride, 2, 3, 4, 5— Tetrahydrofurantetracarboxylic dianhydride, 5— (2,5-Dioxotetrahydrofural) —3-Methyl 3 cyclohexene mono 1, 2 dicarboxylic dianhydrides, aliphatic tetracarboxylic dianhydrides such as bicyclo [2, 2, 2] otato 7-en 2, 3,
  • the tetracarboxylic dianhydride used in the present invention is not limited to the compounds exemplified above, and any structure having two carboxylic acid anhydrides is acceptable. These can be used alone or in combination. Furthermore, what is preferably used in the present invention is an aromatic tetracarboxylic dianhydride from the viewpoint of lowering the viscosity of the pigment dispersion, more preferably a tetracarboxylic dianhydride having two or more aromatic rings. is there.
  • the reaction ratio in the second step is such that the number of moles of the hydroxyl group of the polyester having a hydroxyl group at one end is ⁇ H> and the number of moles of the anhydrous ring of the tetracarboxylic anhydride is ⁇ N>.
  • 0.5 ⁇ H> / ⁇ > ⁇ 1.2, more preferably 0.7 ⁇ H> / ⁇ N> ⁇ 1.1, most preferably ⁇ > ⁇ > 1 Is the case.
  • the remaining acid anhydride may be hydrolyzed with the required amount of water.
  • a catalyst in the second step does not work.
  • the catalyst include tertiary amine compounds such as triethylamine, triethylenediamine, ⁇ , ⁇ ⁇ ⁇ ⁇ dimethylbenzylamine, ⁇ -methylmorpholine, 1,8 diazabicyclo [5.4.0] -7 undecene. 1, 5— Diazabicyclo [4. 3. 0] — 5 Nonene and the like.
  • Both the first step and the second step may be performed without solvent, or an appropriate dehydrated organic solvent may be used.
  • the solvent used in the reaction can be used as a part of the product as it is removed by distillation or other operation.
  • the reaction temperature is 80 ° C to 180 ° C, preferably 90 ° C to 160 ° C. If the reaction temperature is 80 ° C or less, the reaction rate is slow. If the reaction temperature is 180 ° C or more, the force of half-esterification is generated again, and the cyclic anhydride may be formed again to terminate the reaction.
  • R '' 3 is a hydrogen atom or a methyl group
  • X 1 is one COO, one CONH, one O, one OCO— or one CH 2 O, and X 2
  • R al is a linear or branched alkylene group having 2 to 8 carbon atoms, or a cycloalkylene group having 3 to 8 carbon atoms, and ml is an integer of 1 to 50).
  • X 3 is a general formula:
  • R bl is a linear or branched alkylene group having 4 to 8 carbon atoms, or a cycloalkylene group having 4 to 8 carbon atoms, and m2 is 0 or an integer of 1 to 20). Is a group to be
  • Y 1 is the general formula (4):
  • a one is hydrogen atom among the Hache-eight 3, but the other two one of the force A to A 3 is a combination is COOH - COORC (where is 1 to 18 carbon atoms And the other two are forces that are combinations that are —COOH, or three of AA 3 are combinations of —COOH, and k is 1 or 2)
  • a force represented by the general formula (5) is a force represented by the general formula (5)
  • Alpha 5 ⁇ Alpha 7 is a hydrogen atom, or the other two are combined is COOH, one of Alpha 5 to? 7 is - COOR d (where, R d is carbon The other two are —COOH-combination forces or A 5 -A 7 —C OOH yarns and combinations,
  • R 2 is a direct bond, O—, —CO—, —COOCH CH OCO—, —SO—, — C (CF
  • the compound containing the structure represented by the above general formula (3) is generally contained in the vinyl polymer main chain.
  • the carboxyl group-containing unit (G) represented by the formula (3) is included in an amount of 0.3 or more and 3.0 or less on average per molecule of the bull polymer, its chemical structure and production method are There is no particular limitation.
  • a pigment dispersant has a structure of a part that adsorbs to a pigment and a part that has a high affinity for a solvent that is a dispersion medium, and the performance of the dispersant is determined by the balance of these two functional parts.
  • both the ability of the dispersant to adsorb to the pigment and the affinity to the solvent as the dispersion medium are very important.
  • Y 1 represented by the general formula (4) or the general formula (5) is directly bonded to the ring-constituting carbon atom of the aromatic ring.
  • the compound containing the structure represented by the general formula (3) exhibits high dispersibility, fluidity, and storage stability.
  • the compound having the structure represented by the general formula (3) (hereinafter referred to as the vinyl dispersant (a)) is represented by the general formula (3) with respect to one molecule of the vinyl polymer. It is preferable to contain an average of 0.3 to 3.0 carboxyl group-containing units (G). More preferably, it is 0.35 or more and 2.0 or less, and most preferably 0.4 or more and 1.5 or less. 0. When 3 or more, there are many sites adsorbing to the pigment, and the dispersion ability is excellent. When the number is 3.0 or less, the portion adsorbed on the pigment is moderate and the dispersibility is excellent.
  • G carboxyl group-containing units
  • X 1 is preferably C OO from the viewpoint of lowering the viscosity of the pigment dispersion and storage stability.
  • R al is preferably a hydrocarbon group having 1 to 4 carbon atoms (for example, a methylene group, an ethylene group, a linear or branched propylene group, or a linear or branched butylene group).
  • the ml is preferably from 1 to 10, more preferably from 1 to 3.
  • R bl is preferably a pentamethylene group.
  • m2 is preferably 0 to 5, more preferably 0 to 3.
  • Y 1 is preferably a group represented by general formula (4), and more preferably, in general formula (4), all of Ai A 3 are COOH and k is 1.
  • Y 1 can also be a group represented by the general formula (5).
  • R 2 is -COOCH CH OCO, or the formula: [Chemical 28]
  • [0176] is preferably a group represented by One of A 5 to A 7 is one COOR d (where R d is a straight-chain or branched alkyl group having 6 to 10 carbon atoms) and the other two are —COOH Preferred to be a combination.
  • the vinyl dispersant (a) used in the present invention includes the carboxyl group-containing unit (G) represented by the general formula (3) and the general formula (4j):
  • R 4 represents a hydrogen atom or a methyl group
  • X 4 is one COO, one CONH, one O, one OCO— or one CH 2 O, and X 5
  • R 5 represents a hydrogen atom or a methyl group
  • R 6 is an aromatic group, or —CO—X 7 —R 7 (where X 7 is —O— or —NH—, R 7 is a hydrogen atom or a straight chain having 1 to 18 carbon atoms) Or R 7 may have an aromatic group as a substituent. ]
  • Examples thereof include a block copolymer or a random copolymer consisting of each structural unit with the main chain structural unit (K).
  • the above-mentioned bule-based dispersant (a) that is preferably used in the present invention includes the general formula (4a), that is, the copolymer represented by the general formula (4b).
  • G is a carboxyl group-containing unit represented by the general formula (3)
  • J is a hydroxyl group-containing unit represented by the general formula (4j)
  • K is the general formula It is a main chain constituent unit represented by the formula (4k).
  • pi is 0.3 or more and 3.0 or less, preferably 0.35 or more and 2.0 or less, and more preferably 0.4 or more and 1.5 or less.
  • p2 is 0 or more and 180 or less, preferably 0.05 or more and 50 or less.
  • p3 is 6 or more and 250 or less, preferably 10 or more and 100 or less.
  • the carboxyl group-containing unit (G), the hydroxyl group-containing unit CO, and the main chain constituent unit ( ⁇ ) are present in a block copolymerization format or a random copolymerization format, respectively. can do.
  • the carboxyl group-containing unit (G), the hydroxyl group-containing unit CF 3), and the main chain structural unit ( ⁇ ) can each be present in plural in the general formula (4a). In this case, each unit can be the same or different from each other.
  • the main chain structural unit (K) can include structural units having two or more structures.
  • X 4 is preferably one COO—.
  • R a 2 is preferably a hydrocarbon group having 1 to 4 carbon atoms (for example, a methylene group, an ethylene group, a linear or branched propylene group, or a linear or branched butylene group). That's right.
  • m3 is preferably 1 to 10, more preferably 1 to 3.
  • R M is preferably a pentamethylene group.
  • m4 is preferably 0 to 5, more preferably 0 to 3.
  • R 5 is a methylol group
  • R 6 is —CO—O—CH.
  • the vinyl dispersant (a) used in the present invention represented by the general formula (4b) or the general formula (4a) is the main chain constituent unit (K), wherein R 5 is a methyl group.
  • R 6 includes a main chain structural unit (K2), which is —CO—O—R 7 (wherein R 7 is a linear or branched alkyl group having 2 to 10 carbon atoms).
  • the main chain structural unit (K2) coexists with the main chain structural unit (K1) in the beer-based dispersant (a).
  • R 5 is a methyl group as the main chain structural unit (K).
  • R 6 is an aromatic group (particularly a phenyl group), the main chain structural unit (K3) alone, or the main chain structural unit (K1) and Z or the main chain structural unit ( It is preferable to include it together with K2).
  • a main chain structural unit (K4) in which R 5 is a hydrogen atom and R 6 is a carboxyl group the main chain structural unit (K1), a main chain structural unit ( K2), and Z or main chain structural unit ( ⁇ 3) can also be included.
  • the ratio [K1ZK2) is, for example, 0.01 to 100, preferably 0.1 to 10.
  • the ratio [ ⁇ 3 ⁇ ( ⁇ 1 + ⁇ 2)] is, for example, It can be from 0.01 to 10 and preferably from 0.05 to 2.
  • the ratio [ ⁇ 4 ⁇ ] is, for example, 0 to 0.1, preferably 0 to 0.01. Can be.
  • the end of the main chain of the vinyl-based dispersant (a) represented by the general formula (4b) is a known polymerization method of an ethylenically unsaturated monomer, or a structure considered in the polymerization process, for example, polymerization. It may have a chemical structure derived from an initiator, a chain transfer agent, a solvent, or an ethylenically unsaturated monomer.
  • a main chain structural unit (K) in which R 6 is a carboxyl group (-COOH) is converted into a main chain structural unit ( It can be included as at least a part of K).
  • the amount of the carboxyl group-containing main chain structural unit (K) is the amount of the carboxyl group-containing unit (G).
  • the number is preferably 0 to 4 times, more preferably 0 to 2 times the number.
  • the vinyl dispersant (a) used in the present invention can be prepared by the production method used in the present invention. According to the production method used in the present invention, which will be described later, not only the vinyl dispersant (a) but also all the bule dispersants (A) having a wide structure including the bull dispersant (a). Can be manufactured. That is, in the production method used in the present invention to be described later, the beer-based dispersant (a) used in the present invention can be prepared by selecting a specific starting material.
  • Examples of the method for producing the vinyl dispersant (A) used in the present invention include the following production methods 1 to 3.
  • M3 tricarboxylic acid anhydride
  • M4 a tetracarboxylic acid anhydride
  • (B) It comprises a step of copolymerizing the ethylenically unsaturated monomer and another ethylenically unsaturated monomer.
  • any monomer having a hydroxyl group and having an ethylenically unsaturated double bond may be used.
  • a (meth) acrylate monomer having a hydroxyl group for example, 2 hydroxyethyl (meth) acrylate, 2 (or 3) -hydroxypropyl (meth) acrylate, 2 (or 3 or 4) -hydroxybutyl (meth) acrylate and hydroxyalkyl (meth) acrylate, such as cyclohexane dimethanol mono (meth) acrylate, or (meth) acrylamide monomers having a hydroxyl group, such as N- (2-hydroxyethyl) (meth) acrylamide, N- (2-hydroxypropyl) (meth) acrylamide, N- (2-hydroxybutyl) (meth) N- (hydroxyalkyl) (meth) acrylamide, such as acrylamide, or a butyl ether monomer having a hydroxyl group, such as 2-hydroxyethyl vinyl ether, 2 (or 3) hydroxypropyl vinyl ether, 2 (or 3 or 4 )
  • hydroxyalkyl (meth) acrylate N- (hydroxyalkyl) (meth) acrylamide, hydroxyalkyl butyl ether or hydroxyalkyl allyl ether.
  • the ethylenically unsaturated monomer obtained can also be used as the ethylenically unsaturated monomer (h) having a hydroxyl group in the production method used in the present invention.
  • alkylene oxide to be added include ethylene oxide, propylene oxide, 1, 2 1, 4 2, 3 or 1, 3 butylene oxide, and combinations of two or more thereof.
  • the bond type may be random and either Z or block.
  • the added ratataton includes ⁇ -noratolatataton, ⁇ -force prolatathone, ⁇ -force prolatatatone substituted with an alkyl group having 16 carbon atoms, and a combination of two or more of these. Can be mentioned. You may add both alkylene oxide and rataton.
  • Examples of the tricarboxylic acid anhydride (M3) include aliphatic tricarboxylic acid anhydrides, aromatic tricarboxylic acid anhydrides, and polycyclic tricarboxylic acid anhydrides.
  • Aliphatic tricarboxylic acid anhydrides include, for example, 3 carboxymethyldaltaric acid anhydrous, 1, 2, 4 butanetricarboxylic acid 1, 2 anhydride, cis propene-1, 2, 3 tricarboxylic acid 1 , 2 anhydride, 1,3,4-cyclopentanetricarboxylic acid anhydride, and the like.
  • aromatic tricarboxylic acid examples include benzenetricarboxylic acid anhydride (1, 2, 3-benzenetricarboxylic acid anhydride, trimellitic acid anhydride (1, 2, 4 benzenetricarboxylic acid anhydride), etc.), Naphthalene tricarboxylic acid anhydride (1, 2, 4 naphthalene tricarboxylic acid anhydride, 1, 4, 5 naphthalene tricarboxylic acid anhydride, 2, 3, 6 naphthalene tricarboxylic acid anhydride, 1, 2, 8 naphthalene tricarboxylic acid anhydride 3, 4, 4 'monobenzophenone tricarboxylic acid anhydride, 3, 4, 4, biphenyl ether tricarboxylic acid anhydride, 3, 4, 4, biphenyl tricarboxylic acid anhydride, 2, 3 1, 2, -biphenyl tricarboxylic acid anhydride, 3, 4, 4, -
  • a tetracarboxylic dianhydride having two acid anhydrides per molecule in a tetracarboxylic acid anhydride (M4) described later is 1 molecule.
  • a tetracarboxylic anhydride monoester monoanhydride obtained by ring-opening one of the acid anhydrides with an alcohol having 1 to 18 carbon atoms or a cycloalcohol having 5 to 18 carbon atoms is also used in the production method of the present invention.
  • an aliphatic tetracarboxylic acid monoester monoanhydride is an aliphatic tricarboxylic acid anhydride
  • an aromatic tetracarboxylic acid monoester monoanhydride is an aromatic tricarboxylic acid anhydride
  • a polycyclic tetracarboxylic acid anhydride The monoester monoanhydride is described as a polycyclic tricarboxylic anhydride. Specific examples of these tetracarboxylic acid anhydride monoester monoanhydrides are obvious to those skilled in the art from the tetracarboxylic acid anhydrides described below.
  • Examples of the alcohol having 1 to 18 carbon atoms or the cycloalcohol having 5 to 18 carbon atoms include methanol, ethanol, linear or branched propanol, Linear or branched butanol, linear or branched pentanol or cyclopentanol, linear or branched hexanol or cyclohexanol, linear or branched heptanol or cycloto Ptanol, linear or branched octanol or cyclooctanol, linear or branched nonanol or cyclononanol, linear or branched decanol or cyclodecanol, linear or Branched dodecanol or cyclododecanol, linear or branched myristyl alcohol or cyclomyristyl alcohol, linear or branched cetyl alcohol or cyclocetyl alcohol, linear or branched stearyl alcohol or And Los ste
  • Examples of the tetracarboxylic acid anhydride (M4) include aliphatic tetracarboxylic acid anhydrides, aromatic tetracarboxylic acid anhydrides, and polycyclic tetracarboxylic acid anhydrides.
  • Examples of the aliphatic tetracarboxylic acid anhydride include 1, 2, 3, 4 butanetetracarboxylic acid anhydride, 1, 2, 3, 4-cyclobutanetetracarboxylic acid anhydride, 1,3 dimethyl- 1 , 2, 3, 4-cyclobutanetetracarboxylic anhydride, 1, 2, 3, 4 cyclopentanetetracarboxylic anhydride, 2, 3, 5 tricarboxycyclopentylacetic anhydride, 3, 5, 6 tricarboxynorbornane 2 Acetic anhydride, 2, 3, 4, 5—tetrahydrofuran tetra-rubberic anhydride, 5- (2,5 dioxotetrahydrofural) -3-methyl-3 cyclohexene mono 1,2 dicarboxylic anhydride, Bicyclo [2, 2, 2] -otato 7-en 2, 3, 5, 6-tetracarboxylic anhydride.
  • aromatic tetracarboxylic anhydride examples include pyromellitic anhydride, ethylene glycol ditrimellitic anhydride ester, propylene glycol ditrimellitic anhydride ester, butylene glycol ditrimellitic anhydride ester, 3, 3 ', 4, 4, monobenzophenone tetracarboxylic anhydride, 3, 3', 4, 4'-biphenylsulfone tetracarboxylic anhydride, 1, 4, 5, 8 naphthalene tetracarboxylic anhydride, 2 , 3, 6, 7 Naphthalene tetracarboxylic acid anhydride, 3, 3 ', 4, 4, -biphenyl ether tetracarboxylic acid anhydride, 3, 3', 4, 4'-dimethyldiphenylsilane tetracarboxylic acid anhydride 3,3 ', 4,4'-tetrafluorosilane tetracarboxylic acid
  • polycyclic tetracarboxylic acid anhydrides examples include 3,4-dicarboxy 1,2,3,4-tetrahydro-1 naphthalene succinic anhydride, 3,4 dicarboxy 1,2,3,4-tetrahydro 6- And methyl-1-naphthalene succinic anhydride.
  • the tetracarboxylic acid anhydride may be either a monoanhydride or a dianhydride. Of the above, it is preferable to use an aromatic tricarboxylic acid anhydride or an aromatic tetracarboxylic acid anhydride, more preferably trimellitic acid anhydride, pyromellitic acid anhydride, 2, 3, 6 naphthalenetricarboxylic acid. An acid anhydride, 2, 3, 6, 7 naphthalenetetracarboxylic acid anhydride is preferable, and trimellitic acid anhydride is more preferable.
  • step A of reacting the ethylenically unsaturated monomer (h) having a hydroxyl group with a tricarboxylic acid anhydride (M3) or a tetracarboxylic acid anhydride (M4) is performed.
  • This step A is preferably carried out at 80 ° C. to 150 ° C. by adding a polymerization inhibitor while allowing dry air to flow into the reaction apparatus so that the monomer is not thermally polymerized. More preferably, it is 90 ° C to 130 ° C.
  • the polymerization inhibitor include hydroquinone, hydrated quinone monomethyl ether, and methylhydroquinone.
  • the reaction ratio is "ethylenically unsaturated monomer having a hydroxyl group (h)".
  • the number of moles of Z tricarboxylic acid anhydride (M3) ” is preferably 0.8 or more and 10 or less. More preferably, it is 0.9 or more and 5 or less, and further preferably 0.95 or more and 2 or less. If it is less than 0.8, the tricarboxylic acid anhydride (M3) remains, which is not preferable.
  • the reaction ratio is "ethylenically unsaturated monomer having a hydroxyl group (h).
  • the number of moles of Z tetracarboxylic anhydride (M4) ” is preferably 0.9 or more and 1.1 or less. More preferably 1. If it is less than 0.9, a large amount of tetracarboxylic acid anhydride (M4) remains, which is not preferable. 1.
  • the catalyst is preferably a tertiary amine compound such as triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, 1,8-diazabicyclo [5.4.0] -7 Wundesen, 1, 5—Diazabicyclo [4. 3. 0] —5-Nonene and the like.
  • a tertiary amine compound such as triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, 1,8-diazabicyclo [5.4.0] -7 Wundesen, 1, 5—Diazabicyclo [4. 3. 0] —5-Nonene and the like.
  • step Aa can facilitate removal of the unwanted tetracarboxylic anhydride (M4).
  • step B is carried out in which the ethylenically unsaturated monomer synthesized in step A is copolymerized with another ethylenically unsaturated monomer.
  • ethylenically unsaturated monomers used in Step A include alkyl (meth) atalylate having 1 to 18 carbon atoms which may be substituted with an aromatic group, and having 1 to 18 carbon atoms.
  • alkyl (meth) atalylate having 1 to 18 carbon atoms which may be substituted with an aromatic group, and having 1 to 18 carbon atoms.
  • N—Alkyl (meth) acrylamide, ethylenically unsaturated monomer having styrene and hydroxyl group (h) (including those remaining in Step A)
  • the selected ethylenically unsaturated monomer is copolymerized. It is preferable.
  • Examples of unsubstituted alkyl (meth) acrylate include methyl (meth) acrylate and ethyl (meth ) Atalylate, linear or branched propyl (meth) acrylate, linear or branched butyl (meth) acrylate, linear or branched pentyl (meth) acrylate, cyclopentyl (meta ) Atarylate, linear or branched hexyl (meth) acrylate, cyclohexyl (meth) acrylate, linear or branched heptyl (meth) acrylate, cycloheptyl (meta ) Atalylate, linear or branched octyl (meth) acrylate, cyclooctyl (meth) acrylate, linear or branched nor (meth) acrylate, cyclononyl (meth) acrylate, linear -Like or branched decy
  • Non-substituted N-alkyl (meth) acrylamides include N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, linear or branched N-propyl (meth) atyramide, linear or branched N-butyl (meth) acrylamide, linear or branched N-pentyl (meth) acrylamide, N-cyclopentyl (meth) acrylamide, linear or branched N-hexyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, linear or branched N-heptyl (meth) acrylamide, N-cycloheptyl (meth) acrylamide, linear or branched N-octyl (meth) acrylic N-cyclooctyl (meth) acrylamide, linear or branched N-nor (meth) acrylamide, N-cyclooctyl (meth) acrylamide
  • alkyl (meth) acrylates substituted with aromatic rings examples include N benzyl (meth) acrylamide.
  • (meth) acrylate refers to meta acrylate or acrylate
  • (meth) acrylamide refers to methacrylamide or acrylamide.
  • step B polymerization is preferably carried out at 50 ° C to 150 ° C using a polymerization initiator while the reaction vessel is purged with nitrogen.
  • Polymerization initiators include alkyl peroxides, t-butyl hydride oral peroxide, tamen hydroperoxide, p methane hydroperoxide, nob til peroxide, lauryl peroxide, 3, 5, 5-trimethylhexanoyl peroxide.
  • a chain transfer agent may be used.
  • Chain transfer agents include methyl thioglycolate, octyl thioglycolate, methoxybutyl thioglycolate, ethylene glycol bisthioglycolate, butanediol bisthioglycolate, hexanediol bisthioglycolate, trimethylolpropane tristiglycoglycol.
  • Step B it is preferable to use a solvent.
  • Solvents include acetates such as ethyl acetate, propyl acetate, butyl acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, and ketones such as acetone, methyl ethyl ketone, cyclohexanone, and methyl isobutyl ketone.
  • Aromatic hydrocarbons such as xylene, toluene and ethylbenzene can be used.
  • step Aa the acid anhydride remaining after step B can be ring-opened with water or an alcohol having 1 to 18 carbon atoms (step Bb).
  • the number of moles of water to be reacted or the alcohol having 1 to 18 carbon atoms is 0.9 to 5 times (preferably 1 to the number of moles of the remaining acid anhydride. It is preferably 2 times or less). Less than 9 times, many highly reactive anhydride rings remain, and if it exceeds 5 times, water or alcohol with 1 to 18 carbon atoms remains, either way, when it is applied to ink or paint, May be a problem.
  • reaction step Aa or step Bb is preferably carried out at 80 to 150 ° C.
  • Step C of copolymerizing the ethylenically unsaturated monomer (h) having a hydroxyl group with another ethylenically unsaturated monomer is performed.
  • Other ethylenically unsaturated monomers may be substituted with the aromatic ring exemplified in Step B of Production Method 1, and may be an alkyl (meth) acrylate having 1 to 18 carbon atoms or aromatic. It may be substituted with a ring !, or! / ⁇ N-alkyl (meth) acrylamide having 1 to 18 carbon atoms, and styrene power are preferably copolymerized.
  • the copolymerization ratio between the ethylenically unsaturated monomer having a hydroxyl group (h) and another ethylenically unsaturated monomer is at least 0.3 to 177 on average per molecule after polymerization. Of the hydroxyl group.
  • Step D is performed in which the hydroxyl group of the copolymer obtained in Step C is reacted with a tricarboxylic acid anhydride (M3) or a tetracarboxylic acid anhydride (M4).
  • M3 tricarboxylic acid anhydride
  • M4 tetracarboxylic acid anhydride
  • step D it is preferable to carry out at 80 ° C to 150 ° C while flowing nitrogen or dry air into the reaction vessel.
  • the catalyst exemplified in Step A of Production Method 1 can also be used.
  • Step D of Production Method 2 tricarboxylic acid anhydride (M3) or tetracarboxylic acid anhydride
  • tricarboxylic acid anhydride (M3) is preferably used.
  • tetracarboxylic anhydride (M4) gelling may occur.
  • tetracarboxylic anhydride (M4) is used and an anhydrous ring remains, the ring can be opened with water or an alcohol having 1 to 18 carbon atoms by the same method as in Step Bb of Production Method 1 ( Process Dd).
  • an ethylenically unsaturated monomer (h) having a hydroxyl group is copolymerized with another ethylenically unsaturated monomer, and a tricarboxylic acid anhydride (M3 ) Or tetracarboxylic anhydride (M4).
  • the reaction is preferably carried out at 80 ° C to 150 ° C with nitrogen flowing into the reaction vessel.
  • the catalyst for the reaction between the hydroxyl group and the acid anhydride is the one shown in Step A of Production Method 1, polymerization start
  • the polymerization conditions such as the type of agent, the type of chain transfer agent, the type and amount of solvent, and the reaction temperature are preferably those shown in Step B of Production Method 1.
  • ethylenically unsaturated monomers used in production method 3 are the same as the compounds used in step C of production method 2.
  • gelation may occur when tetracarboxylic dianhydride is used.
  • tetracarboxylic dianhydride When tetracarboxylic dianhydride is used and an anhydrous ring remains, it can be ring-opened with water or an alcohol having 1 to 18 carbon atoms by the same method as step Bb in production method 1 (process) Ee).
  • the vinyl dispersant (A) used in the present invention can be produced.
  • production method 2 is preferred because it is easy to control the number of carboxyl group-containing units (G) in one molecule of the dispersant.
  • the number average molecular weight of the copolymer obtained in Step C of Production Method 2 can be measured in advance, and the tricarboxylic acid anhydride ( The amount with which M3) or tetracarboxylic anhydride (M4) is reacted can be determined.
  • the number average molecular weight of the copolymer obtained in step C is measured, and when the measured value force S [X] is It is sufficient to react 0.3 mol or more and 3.0 mol or less of tricarboxylic acid anhydride (M3) or tetracarboxylic acid anhydride (M4) with respect to X] g.
  • M3 tricarboxylic acid anhydride
  • M4 tetracarboxylic acid anhydride
  • the tricarboxylic acid anhydride (M3) or the tetracarboxylic acid anhydride (M4) is selected as an aromatic tricarbon rubon.
  • An acid anhydride or an aromatic tetracarboxylic acid anhydride is preferred.
  • aromatic tricarboxylic acid anhydrides are more preferable, and trimellitic acid anhydride, pyromellitic acid anhydrous, 2, 3, 6-naphthalene tricarboxylic acid anhydride, 2, 3, 6, 7-Naphthalenetetracarboxylic acid anhydride is preferred and most preferred is trimellitic acid anhydride.
  • the number of unsubstituted carbon atoms which may have a branch as another ethylenically unsaturated monomer It is preferable that 1 to 12 alkyl (meth) acrylate, benzyl (meth) acrylate and an ethylenically unsaturated monomer (h) having a hydroxyl group if necessary are copolymerized. Furthermore, it may have a branch in one molecule of the vinyl dispersant (A)! 1 1 to 50 unsubstituted alkyl (meth) acrylate with 1 to 12 carbon atoms, benzyl (meth) attaly It is preferred that 1 to 50 rates are copolymerized.
  • the butyl dispersant (A) used in the present invention can be copolymerized with various ethylenically unsaturated monomers other than those exemplified so far as long as the dispersibility is not hindered.
  • ethylenically unsaturated monomers having thermally crosslinkable groups such as isocyanato groups, blocked isocyanato groups, alkoxysilyl groups, 3- to 5-membered cyclic ether groups, and ethylenic monomers having carboxyl groups
  • thermally crosslinkable groups such as isocyanato groups, blocked isocyanato groups, alkoxysilyl groups, 3- to 5-membered cyclic ether groups, and ethylenic monomers having carboxyl groups
  • An unsaturated monomer is mentioned.
  • Monomers such as methacrylic acid and acrylic acid are tricarboxylic anhydride (M3) or tetracarboxylic acid anhydrous (M4) present in the bule dispersant (A) in any of production methods 1 to 3.
  • M3 or M4 present in the bule dispersant (A) in any of production methods 1 to 3.
  • M3 or M4 present in the bule dispersant (A) in any of production methods 1 to 3.
  • a use range of 0 to 4 times, more preferably 0 to 2 times the number of moles is preferable.
  • the bull dispersant (a) can be prepared by the production method used in the present invention.
  • the colored resin composition of the present invention is obtained using the vinyl dispersant (A) [or in particular the vinyl dispersant (a)] and the pigment (P).
  • the vinyl dispersant (A) or particularly the vinyl dispersant (a)]
  • a colored resin composition excellent in dispersibility, fluidity and storage stability is obtained.
  • the colored resin composition of the present invention preferably further contains a heat-reactive compound.
  • the heat-reactive compound that can be used in the ink composition of the present invention is a force that is non-reactive at room temperature, for example, at a temperature of 100 ° C or higher (preferably 150 ° C or higher). It is a compound that exhibits a reaction, a polymerization reaction, a polycondensation reaction, or a polyaddition reaction.
  • the molecular weight of the heat-reactive compound that can be used in the ink composition of the present invention is not particularly limited, and is preferably from about 2,000 to about 2,000, more preferably from about 100 to 1,000.
  • thermally reactive compound for example, a melamine compound, a benzoguanamine compound, an epoxy compound, a phenol compound, a blocked isocyanate compound, an acrylate monomer, or a silane coupling agent is used. Can do.
  • Examples of the melamine compound include those having an imino group, a methylol group, and a cage or an alkoxymethyl group, and a melamine compound containing only an alkoxymethyl group is particularly preferable.
  • Specific examples of the alkoxyalkyl group-containing melamine compound include hexamethoxymethylol melamine, hexasuboxymethylol melamine, and the like.
  • Specific examples of commercially available melamine compounds include the following. However, it is not necessarily limited to these. Sanwa Chemical Co., Ltd.-Power rack MW—30M, MW—30, MW—22, MS—21, MX—45, MX—500, MX—520, MX—43, MX—302, Nippon Cytex Industry Cymel 300, 301, 303, 350, 28 5, 232, 235, 236, 238, Mycoe 506, 508.
  • Examples of the benzoguanamine compound include those having an imino group, a methylol group, and an alkoxymethyl group, and an alkoxyalkyl group-containing benzoguanamine compound is particularly preferable.
  • Specific examples of commercial products of the benzoguanamine compound include Sanwa Chemical Co., Ltd.-Power Rack BX-4000, SB-401, Nippon Cytex Industry Co., Ltd. Cymel 11 23, and the like.
  • Examples of the epoxy compound include bisphenol fluorenediglycidyl ether, biscresol fluorenediglycidyl ether, bisphenoxyethanol fluorenediglycidyl ether, neopentylglycol diglycidyl ether, and 1,6-hexanediol diester.
  • phenolic compound for example, both a novolac type phenolic compound obtained by reacting phenols and aldehydes in the presence of an acidic catalyst, and a resol type phenolic compound obtained by reacting in the presence of a basic catalyst are used. be able to.
  • phenols include orthocresol, paracresol, paraphenolphenol, paraanolphenol, 2,3 xylenol, phenol, methacresol, 3,5-xylenol, resorcinol, catechol, hydroquinone, bisphenolanol A, bisphenolanol. F, bisphenol nore B, bisphenol E, bisphenol H, bisphenol S and the like.
  • aldehydes include formaldehyde and acetoaldehyde. Phenolics and aldehydes may be used alone or in combination of two or more.
  • Blocked isocyanate compounds include, for example, hexamethylene diisocyanate, isophorone diisocyanate, toluidine isocyanate, diphenylenomethane 4, 4 ' Diisocyanates such as sulfonate, diphenol-methane 2,4'-diisocyanate, bis (4-isocyanate cyclohexyl) methane, tetramethylenoxylylene diisocyanate, isocyanurates of these diisocyanates, trimethylolpropane adduct Examples include a type, a pyruret type, a prepolymer having an isocyanate residue (a diisocyanate and a low polymer obtained from a polyol force), and an uretdione having an isocyanate residue.
  • Examples of the blocking agent used in the blocked isocyanate compound include phenol (dissociation temperature of 180 ° C or higher), ⁇ -one-prolactam (dissociation temperature of 160 to 180 ° C), oxime (dissociation temperature of 130 to 160 ° C), or active methylene (100 to 120 ° C). Also, one type can be used alone, or two or more types can be used in combination.
  • Examples of the acrylate monomer include methyl (meth) acrylate, ethyl (meth) acrylate, cyclohexyl (meth) acrylate, ⁇ -carboxyethyl (meth) acrylate, polyethylene glycol.
  • Acid ester and methacrylate ester (meth) acrylic acid, styrene, butyl acetate, hydroxyethyl butyl ether, ethylene glycol dibutyl ether, pentaerythritol tribule ether, (meth) acrylamide, N hydroxymethyl (meth) acrylamide, N butylformamide, acrylonitrile and the like.
  • a polymerization initiator can be used for the purpose of further improving curability.
  • a thermal polymerization initiator may be used for the purpose of improving curability during heating.
  • an organic peroxide initiator examples include azo initiators.
  • silane coupling agent examples include vinyl silanes such as vinyl tris (/ 3-methoxyethoxy) silane, vinyl ethoxy silane, and vinyl trimethoxy silane; ⁇ — (meth) acryl silanes such as methacryloxy propyl trimethoxy silane ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, mono (3,4-epoxycyclohexyl) methyltrimethoxysilane, 13- (3,4-epoxycyclohexyl) ethyltriethoxysilane , J8 — (3,4-epoxycyclohexyl) methyltriethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropinoletriethoxysilane, and other epoxy silanes; ⁇ - ⁇ (aminoethyl ) ⁇ -Amin
  • an alkoxyalkylated melamine and an alkoxyalkyl group-containing benzoguanamine compound are particularly preferable.
  • These heat-reactive compounds are preferably contained in the colored resin composition in an amount of 1 wt% to 40 wt%.
  • the content of these heat-reactive compounds is 1% by weight or more, the heat resistance and chemical resistance are excellent.
  • the content is 40% or less, the storage stability is excellent with no increase in viscosity.
  • the colored resin composition may contain an organic solvent for the purpose of promoting adsorption with the pigment, the pigment derivative, and the resin, and reducing the viscosity of the composition.
  • organic solvent for example, aromatic hydrocarbons, alcohols, esters, ethers, ketons, glycol ethers, alicyclic hydrocarbons, aliphatic hydrocarbons, etc. may be used. I'll do it.
  • a coating layer of a pigment derivative and a resin carrier is formed on the surface of the pigment.
  • the coating treatment of the pigment may be performed by previously mixing the pigment, the organic solvent, the pigment derivative, the resin carrier, and the like so as to be uniform, and then kneading using a disperser. it can. It is preferable to adjust the blending amount of the solvent according to the mechanical properties of the mixture.
  • the dispersing machine used for the coating treatment of the pigment include an ader, a roll mill, a ball mill, a bunnery mixer, a roller mill, and a stone mill. A two-roll mill is preferable because it can be mixed and kneaded in one apparatus. .
  • the blending amount of the raw material when coating the pigment is 1 to 30 parts by weight of the pigment derivative, 100% by weight of the pigment-type dispersant, and the binder resin (hereinafter referred to as the resin component). ) It is preferably in the range of 20 to 200 parts by weight and 4 to 200 parts by weight of solvent. If the amount of pigment derivative is less than 1 part by weight, the anchor effect will be small, so the effect of reducing the viscosity of the ink will be small. If it exceeds 30 parts by weight, the pigment derivative will be excessive and unadsorbed pigment derivative. The inks thicken because they aggregate together.
  • the blending amount of the resin component is less than 20 parts by weight, the pigment surface cannot be sufficiently covered, and the dispersion stability of the pigment is lowered, and when it exceeds 200 parts by weight, it does not adsorb to the pigment.
  • the viscosity of the ink increases due to the free oil component.
  • the amount of the solvent is less than 4 parts by weight, the initial viscosity of the pigment derivative and the resin component may not be sufficiently applied to the pigment, and the pigment may not be sufficiently coated, so that the viscosity of the ink may not be stable.
  • the amount exceeds 200 parts by weight it is difficult to coat the pigment.
  • the coating treatment of the pigment is performed by the following two-stage process.
  • the first step is a tipping process in which wetting and adsorption of the resin component to the pigment proceeds by passing the composition containing the pigment, resin component, solvent, etc. about 20 times through two rolls. . In this process, about 80% by weight of the blended solvent is volatilized.
  • the second step is a coating treatment step of forming a coating layer on the surface of the pigment particles by continuously heating and kneading the kneaded product in which the resin component is adsorbed to the pigment by chip formation. If the kneaded product has a high viscosity and cannot be kneaded, add an appropriate amount of solvent to aid kneading.
  • the resin component has a crosslinkable functional group
  • the resin component is cross-linked in the coating treatment step, and the resin is partially cut.
  • This reaction is a mechanochemical reaction, resulting from excessive mechanical pressure and grinding, and even heating, with only pigments and oil components.
  • the cross-linking reaction of the resin component is unlikely to occur.
  • the heating temperature is preferably in the range of 80 ° C ⁇ 120 ° C. If the temperature is lower than 80 ° C, the resin component may not be sufficiently bridged. If the temperature exceeds 120 ° C, deterioration of the resin component may occur.
  • the excess oil component that does not adsorb on the pigment surface affects physical properties such as the viscosity of the ink, it is preferably removed by washing or filtration.
  • the coated pigment may be dried after washing if it does not agglomerate after drying.
  • the solvent used during the coating treatment is a solvent that can be used as a liquid medium for inkjet ink, it is dried. There is no need.
  • the colored rosin composition of the present invention can be produced by using the above-mentioned pigment, the above-mentioned heat-reactive compound, the above-mentioned organic solvent, and, if necessary, the above-mentioned binder rosin and Z or a pigment derivative. And then dispersed until the desired average particle size becomes a particle size distribution.
  • the raw materials for the colored resin composition may be mixed and dispersed all at once, or may be mixed and dispersed separately in consideration of the characteristics and economics of each raw material.
  • the ink composition can be prepared by adding a liquid medium for dilution to the ink stock solution and stirring uniformly.
  • a sand mill, a bead mill, an agitator mill, a dyno mill, a cobol mill, or the like is suitable.
  • the viscosity can be adjusted by changing the ratio of various resin components and pigments.
  • the ink composition for ink jet recording is preferably filtered by a filter or a centrifugal method for the purpose of removing coarse particles and foreign matters after being dispersed by a disperser.
  • a surfactant-type dispersant In producing a colored resin composition, a surfactant-type dispersant, an anthraquinone derivative, and a Z or triazine derivative can be further used.
  • the surfactant type pigment dispersing agent include naphthalenesulfonic acid formalin condensate salt, aromatic sulfonic acid formalin condensate, polyoxyethylene alkyl phosphate ester, polyoxyethylene urea ether, or stearylamine acetate. Can be mentioned.
  • An inkjet ink using the colored resin composition is also an embodiment of the present invention. In the inkjet ink of the present invention, an organic solvent known as technical common sense in the field of inkjet can be used.
  • an organic solvent used in an ink composition for ink jet recording has a high solubility in a resin and has a small swelling effect on a printer member in contact with the ink when ink is ejected from the ink jet printer. It is preferable that the viscosity of the solvent is as low as possible.
  • the organic solvent is selected from the viewpoints of solubility in rosin, swelling action on the printer member, viscosity, and drying property of the ink in the nozzle, alcohol solvent, glycol solvent, ester solvent, and Z or ketone solvent.
  • One kind of solvent can be used alone, or two or more kinds can be mixed and used.
  • Examples of the alcohol solvent include hexanol, heptanol, octanol, nonanol, decanol, undenoyl, cyclohexanol, benzyl alcohol, and amyl alcohol.
  • glycol solvent examples include ethylene glycol monomethyl ether, ethylene glycol monoethanolinoateolene, ethyleneglycololemonoisopropinoreatenore, ethyleneglycololebutinoreatenore, ethyleneglycololemonore Hexinoreethenore, methoxymethoxyethanol, diethylene glycol monomethyl ether, diethyleneglycol monoethylenoleatenore, diethyleneglycolenolemonobutenoleatenore, diethyleneglycolenomonomonoethylenate acetate, diethyleneglycolenoremonoethino Reethenorea cetate, diethylene glycol monobutyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether , Propylene glycol mono-mono methino ethenore, propylene glycol mono methino ethenore, propylene glycol mono met
  • ester solvent examples include ethyl acetate, lactate propane, and butyl lactate.
  • ketone solvent examples include cyclohexanone, ethyl amyl ketone, diacetone alcohol, diisoptyl ketone, isophorone, methylcyclohexanone, and acetophenone.
  • the ink-jet ink of the present invention may contain various additives as long as the above viscosity conditions are satisfied.
  • a surfactant can be included in order to control the wettability of the ink to the substrate.
  • Surfactants include those that are ionic, cationic, amphoteric, or nonionic, and a suitable one may be selected.
  • the viscosity of the inkjet ink of the present invention is preferably 2 mPa's or more and 40 mPa's or less, more preferably 3 mPa's or more and 30 mPa's or less, and further preferably 4 mPa's or more and 20 mPa's or less. It is. If the viscosity is 40 mPa's or less, stable and continuous discharge is possible.
  • the average dispersed particle size of the inkjet ink of the present invention is preferably 5 nm or more and 200 nm or less, more preferably lOnm or more and 150 nm or less. If the average dispersed particle size is 200 nm or less, stable ejection that makes the head less susceptible to clogging is possible. When the average dispersed particle size is 5 nm or more, reaggregation is difficult to occur and the stability over time is excellent.
  • the surface tension of the inkjet ink of the present invention is preferably from 20 mNZm to 40 mNZm, more preferably from 24 mNZm to 35 mNZm.
  • the surface tension force is less than OmNZm, the colored resin composition can be stably ejected from the head, and when the surface tension is more than 20 mN Zm, the ink forms droplets reliably.
  • the inkjet ink of the present invention is excellent in ejection stability because it has a high pigment concentration and low viscosity, and has a higher pigment content than ordinary inkjet inks, so that the ejection amount can be reduced.
  • the colored resin composition of the present invention and the inkjet ink using the colored resin composition of the present invention are suitable for the production of color filter substrates that require high productivity and quality.
  • the inkjet ink of the present invention has a high concentration of pigment dispersed therein, the paper in which ink penetrates in the depth direction, the blasting that spreads in the lateral direction, glass, and metal Even so, the print density can be increased. Furthermore, since the discharge amount can be suppressed, it is possible to prevent the ink from flowing out and mixing due to exceeding the ink receiving amount of the receiving layer, and avoiding the force that the dot shape is not a perfect circle. Inkjet printing can be used for limited applications.
  • the ink-jet ink of the present invention is a viscoelasticity measurement by a rigid pendulum test during heating at a temperature rising rate of 5 ° CZ after coating on a printing substrate with a film thickness of 15 to 25 ⁇ m.
  • the period in the whole temperature range of 100 to 170 ° C is 0.6 to 0.9 seconds.
  • the rigid pendulum test used in the present invention was conducted with a rigid pendulum viscoelasticity measuring instrument (RPT-3000W type: AandD).
  • RPT-3000W type: AandD This device is a measurement device suitable for grasping the viscoelastic behavior of a sample that cannot be formed into a film because the viscosity and crosslinkability at the time of drying or crosslinking can be evaluated in the state of the coating film. .
  • the amount of contact with the coating film also affects the measurement.
  • the coating amount in the present invention was measured using a bar coater No. 15 to 20, coated to a film thickness of 15 to 25 ⁇ m, placed in an undried state and loaded with a pendulum.
  • the film thickness is preferably 20 m. This is because the accuracy of measurement is increased.
  • the temperature increase was performed from room temperature at a temperature increase rate of 5 ° CZ.
  • an impermeable base material is preferably used in order to directly measure the properties of the ink.
  • coating on glass or a metal plate is preferable from the viewpoint of heat resistance.
  • glass can be suitably used because it has a smooth surface and can be prepared in any size.
  • the ink was applied to the glass that had been dimensioned on the stage and was covered, and the willow was determined.
  • the temperature was set based on the temperature at which the ink dries.
  • solvent-type ink-jet ink a solvent with a boiling point of 100 ° C or higher, preferably 130 ° C or higher, and 150 ° C or higher is used depending on the application in order to prevent drying in the head. For this reason, 100-170 ° C was selected as the measurement range.
  • solvents used in inkjet inks have a low viscosity, and from the viewpoint of drying workability after printing, solvents having a boiling point of 300 ° C or lower, preferably 250 ° C or lower, are selected.
  • the film is dried within the range of 100 to 170 ° C. under the conditions of the rigid pendulum test in the present invention.
  • the period measured in the present invention shows the elastic characteristics of the object to be measured, and when the absolute value of this period is small, it is considered mechanically equivalent to having a strong panel constant. Therefore, it is understood that the elasticity of the object to be measured is strong and that the degree of crosslinking is strong depending on the object to be measured, which is a measure of the ease of deformation.
  • the cycle in the whole temperature range of 100 to 170 ° C is 0.6 to 0.9 seconds.
  • this period is 0.6 seconds or more, the deformability by heating during drying is good, the smoothness is excellent, and the color unevenness is improved.
  • the period is 0.9 seconds or less, moderate resistance to deformation is generated in the ink, so the printing result is excellent in fineness that the ink does not flow excessively and the dot does not diffuse more than necessary. It becomes.
  • the drying speed of the solvent also has an effect. If a solvent of 150 ° C or higher is used, the drying speed can be reduced, and a smoother surface can be obtained. Further, in order to obtain sufficient fluidity during drying, when the T ⁇ value at the solid content concentration of 40% by weight to 60% by weight is 1 to 3, more preferably 1 to 2, further smoothness is obtained. It can be used as a display with good quality.
  • the present invention makes it possible to control the fluidity of dots by controlling the period around the drying temperature.
  • a printed matter having excellent smoothness and fineness that can be provided by controlling the cycle and the fluidity of dots is also an aspect of the present invention.
  • a method for producing an ink for an ink jet characterized in that the period in the entire temperature range of 100 to 170 ° C. is controlled to 0.6 to 0.9 seconds, is also an aspect of the present invention.
  • the ink-jet ink of the present invention and the printed material are used after the discharge, by controlling the viscoelasticity of the ink at the time of drying or during drying, in order to achieve both smoothness and fineness of the printed material.
  • Ink power set above In the drying process the fluidity is lost due to the volatilization of the solvent in the drying process, and at the same time, the fluidity is improved by heating the raw materials such as pigment dispersion, resin, and additives. It is characterized by controlling viscoelasticity in conflicting phenomena.
  • the above measurement conditions do not limit the temperature in the drying process after printing the ink of the present invention with an ink jet apparatus, but are printed on a glass substrate and dried as a color filter application. In some cases, it is preferable to have a step of drying the solvent at 80 to 190 ° C.
  • any method may be used to control the viscosity and elasticity of the drying step as long as the period in the entire temperature range of 100 to 170 ° C is 0.6 to 0.9 seconds. .
  • the selection of raw materials in the ink composition, the control of rheology by the selection of the dispersion method, and the control of ink wettability are preferred.
  • the temperature increase range was 100 to 170 ° C. If the period is 0.6 to 0.9 seconds, it can be used as a raw material of the present invention.
  • a binder resin or a flow imparting agent is added.
  • the raw material in the ink composition is preferably 0.1 to 50% by weight.
  • the residence time can be calculated by the following equation (1), such as the vessel volume used, the bead particle size, and the filling rate.
  • Residence time (min) (Bessel capacity Bead filling volume + Bead packing X Porosity) X Dispersion time (min) Z Dispersed ink amount
  • the residence time is preferably in the range of 5 to 45 minutes. More preferably, if it is 10 to 35 minutes, more fluid dispersion can be achieved.
  • the contact angle of the ink on the non-permeable substrate is preferably 10 to 30 °.
  • the CA-X contact angle type made by Kyowa Interface Chemical Co., Ltd. was used for the measurement of the contact angle.
  • the ink was filled in a syringe, dropped on a slide glass (manufactured by Matsunami Glass Co., Ltd., S-2215 type), and the contact angle after 10 seconds was calculated by the 0Z2 method.
  • the dots that are ejected and land on the substrate do not spread and have excellent definition.
  • the ink below 30 ° has good wettability to the base material, and excellent adhesion and adhesion.
  • the contact angle is more preferably 10 ° to 20 °. This is because, after ink landing, it does not spread extremely and has the property of spreading as needed when overheated, and printing with excellent fineness can be performed.
  • the organic solvent blended in the present invention is preferably 50 to 85% by weight in the ink-jet ink. If it is 50% by weight or more, the viscosity for printing with an ink jet apparatus becomes appropriate, and it is not necessary to heat the ink to an unnecessarily high temperature. If it is 85% by weight or less, it can be used for color filter applications due to the shortening of printing time. In this case, in order to obtain the required chromaticity, color mixing due to ink leakage from the black matrix can be prevented by printing with a small droplet amount.
  • the boiling point of the organic solvent is preferably 130 ° C or higher. This is related to the system requirements at the time of printing. When the boiling point of the solvent is 130 ° C or higher, the nozzle clogging due to ink drying can be reduced, and high productivity can be obtained. In addition, when high impact accuracy is required, such as for color filter applications, when the boiling point of the organic solvent is 170 ° C to 250 ° C, the nozzle by drying or the impact accuracy is improved. Preferred from.
  • Solvents that can be used in the present invention are as described above. Solvents that can be suitably used include carbitol acetate, butyl carbitol acetate, propylene having a boiling point of 130 ° C or higher.
  • solvents that can be used in combination include, for example, cyclohexanone, 1-methoxy-2-propylenoacetate, diethylene glycol dimethyl ether, ethylbenzene, ethylene glycol jetyl ether, xylene, methyl-n-amyl ketone, propylene glycol monomethyl ether.
  • carbitol acetate, butyl carbitol acetate, and polypropylene glycol monomethyl ether acetate as the main agent are preferable from the viewpoint of dispersion stability of the pigment.
  • the organic solvent having a boiling point of 130 ° C to 300 ° C is preferably 75% by weight or more in consideration of printing stability, which is preferably 50% by weight or more in the total solvent. Even better It is particularly preferably 95% by weight or more. This is because if it is less than 50% by weight, the desired drying property cannot be controlled.
  • the above-mentioned heat-reactive compound can be used.
  • the aforementioned pigments and pigment derivatives can be used as colorants.
  • the colored rosin composition described in Embodiment 1 of the present invention is used.
  • rosin can be contained.
  • the resin can be used during salt milling or as a pigment surface treatment raw material. Further, it can also be used as a dispersed resin during pigment dispersion.
  • a dispersion method in the case of dispersion can be freely selected to satisfy the present invention, such as a sand mill, a homogenizer, a ball mill, a paint shaker, and ultrasonic dispersion.
  • the raw materials and the dispersion method for dispersion described above have a great influence on the viscoelasticity of the ink, so that sufficient selection is required.
  • Additives such as a surfactant, an antihalation agent, an antistatic agent, a leveling agent, and an antifoaming agent can be appropriately mixed and used in the ink.
  • rosin may be added as a binder.
  • the fluidity during drying can be controlled by its Tg, molecular weight and skeleton.
  • raw materials having an unsaturated bond such as monofunctional or polyfunctional monomers, oligomers, and prepolymers, oils, leveling agents, and the like can be appropriately contained.
  • an epoxy monomer or a monomer having an oxetane ring can be used in order to impart various resistances. These also enable cross-linking with active energy rays.
  • energy rays such as ultraviolet rays
  • an initiator according to the reaction can also be used.
  • the cycle is finally in the entire temperature range of 100 to 170 ° C. and the period is 0.6 to 0.9 seconds, one or more of these may be selected. These may be used alone or in combination.
  • the printing substrate used in the present invention is not limited, but in order to express the effects of the invention greatly, A non-permeable substrate is particularly preferable.
  • a highly transparent substrate with a relatively high Tg such as polycarbonate, polymethyl methacrylate (PMMA), norbornene-based rosin, and polyethylene naphthalate (PEN). It is preferable.
  • PMMA polymethyl methacrylate
  • PEN polyethylene naphthalate
  • it since it is possible to perform fine printing on glass where dots are likely to spread, regardless of the presence or absence of surface treatment, it can be used more suitably.
  • the inkjet ink of the present invention can be ejected at an ink set temperature of 25 to 70 ° C by an inkjet ejection device.
  • a known inkjet discharge device may be selected.
  • the ink temperature set by the inkjet discharge device is a set temperature for adjusting the temperature around the inkjet head. This is because the temperature of the inkjet ink is adjusted by heating the periphery of the inkjet head.
  • the heating method of the head is generally heating by a circulating water bath or a band heater, but is not limited thereto.
  • the dot is prevented from flowing unnecessarily and is set to a desired position by increasing the viscosity because the temperature of the dot decreases during or after ejection. it can.
  • the reason for heating and discharging the ink is not limited to these.
  • the ink-jet ink of the present invention can obtain a sufficient effect even at around room temperature, but heating to about 25 ° C to 70 ° C is preferable because the above effect can be expected. If it is higher than 70 ° C, the adhesive and other parts around the head may be dissolved, and in many cases it cannot be used. In addition, the strength of the ink design In order to design ink when printing at a temperature higher than 70 ° C, an ink design with a remarkably low vapor pressure should be used to avoid clogging due to drying at the head. Therefore, as a result of having to make the drying process very hot, the heat resistance and the ink stability point can be used. The base material and the ink raw material are extremely limited, so that the practical use is difficult.
  • the temperature of the discharge device is more preferably 25 ° C to 50 ° C in view of the stability of the ink.
  • the ink-jet ink of the present invention is preferably used for color filter applications. .
  • the ink-jet method is a method of forming by ejecting ink-jet ink by an ink-jet ejection device in a region divided by the black matrix of the substrate on which the black matrix is formed.
  • the black matrix can be etched by applying a radical polymerization type black resist, exposing, developing and patterning, printing using black ink, or metal deposition. It can be formed on the substrate by an evaporation method or the like.
  • Red pigment C. I. Pigment Red 254 ("Ilga for RED B-CFJ" manufactured by Ciba Specialty Chemicals)
  • Green pigment C. I. Pigment Green 36 ("Rionol Darin 6YK” manufactured by Toyo Ink Co., Ltd.)
  • Yellow pigment C. I. Pigment Yellow 138 ("Lionogen Ero 1010" manufactured by Toyo Ink Co., Ltd.)
  • Magenta pigment C. I. Pigment Red 122 (“Rionogen Magenta 5750” manufactured by Toyo Ink Co., Ltd.)
  • Cyan pigment CI Pigment Blue 15: 3 ("Rionol Bull” (FG-7351J)
  • BuCBAc Diethylene glycol monobutyl ether acetate
  • a reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer is charged with 62.6 parts of 1 dodecanol, 287.4 parts of ⁇ -strength prolatatone, and 0.1 part of monobutyltin (IV) oxide as a catalyst. After substituting with nitrogen gas, the mixture was heated and stirred at 120 ° C for 4 hours. After confirming that 98% had reacted by solid content measurement, 36.6 parts of pyromellitic anhydride was added and reacted at 120 ° C. for 2 hours. By measuring the acid value, it was confirmed that 98% or more of the acid anhydride had been half-esterified, and the reaction was completed to obtain a dispersant (S1). The obtained dispersant was a light yellow waxy solid at ordinary temperature, the weight average molecular weight (Mw) was 4000, and the acid value was 49 mgKOHZg.
  • the obtained dispersant was a light yellow waxy solid at room temperature, the weight average molecular weight (Mw) was 14400, and the acid value was 12 mgKOHZg.
  • Step C of Production Example 1 a vinyl resin intermediate (C1) having a number average molecular weight (Mn) of 3800, a weight average molecular weight (Mw) of 6900, and an average number of hydroxyl groups in one molecule of 3.5 was obtained.
  • Mn number average molecular weight
  • Mw weight average molecular weight
  • Step C of Production Example 1 a vinyl resin intermediate (C2) having a number average molecular weight (Mn) of 7000, a weight average molecular weight (Mw) of 13800, and an average number of hydroxyl groups in one molecule of 3.5 was obtained.
  • Mn number average molecular weight
  • Mw weight average molecular weight
  • a resin dispersant (A2) having an average number of (G) of 1.0 was obtained.
  • the solid content ratio in the rosin type dispersant (A2) was 50%.
  • the kneaded product was formed into a sheet and cooled to room temperature, and then coarsely pulverized to obtain 167 parts of a coated pigment.
  • 167 parts of coated pigment and 476 parts of solvent (CBAc) are mixed in a mixer, and further dispersed in a sand mill for 4 hours.
  • 40 parts of melamine resin (MX-43) and 66 parts of solvent (CBAc) was mixed in a mixer.
  • pressure filtration was performed with a membrane filter to obtain an ink composition for ink jet recording having a pigment concentration (PC) of 13% and a solid content concentration of 28%.
  • PC pigment concentration
  • the kneaded product was formed into a sheet shape, cooled to room temperature, and coarsely pulverized with force to obtain 167 parts of a coated pigment.
  • 167 parts of coated pigment and 476 parts of solvent (CB Ac) are mixed in a mixer, and further dispersed in a sand mill for 4 hours.
  • 40 parts of melamine resin (MX-43) and solvent (CBAc) 66 Part into a mixer did.
  • pressure filtration was performed with a membrane filter to obtain an ink composition for inkjet recording having a pigment concentration (PC) of 13% and a solid content concentration of 28%.
  • PC pigment concentration
  • An inkjet ink having a pigment concentration of 13% and a solid content concentration of 28% was obtained in the same manner as in Example 2, except that 100 parts of the resin (R1) was used instead of 100 parts of the resin (R2).
  • Example 2 100 parts of resin (A1) was used instead of 100 parts of resin (R2), and 40 parts of benzoguanamine resin (Yukalac SB-401) was used instead of 40 parts of melamine resin (MX-43). In the same manner as described above, an inkjet ink having a pigment concentration of 13% and a solid content concentration of 28% was obtained.
  • An inkjet ink having a pigment concentration of 13% and a solid content concentration of 28% was obtained in the same manner as in Example 1, except that 133 parts of the resin (R2) was used instead of 133 parts of the resin (R1).
  • the kneaded product was formed into a sheet shape, cooled to room temperature, and coarsely pulverized with force to obtain 167 parts of a coated pigment.
  • 167 parts of the coated pigment and 476 parts of the solvent (C BAc) are mixed in a mixer, and further dispersed in a sand mill for 4 hours.
  • pressure filtration was performed with a membrane filter to obtain an ink composition for ink jet recording having a pigment concentration (PC) of 13% and a solid content concentration of 28%.
  • PC pigment concentration
  • An inkjet ink having a pigment concentration of 13% and a solid content concentration of 28% was obtained in the same manner as in Example 1, except that 133 parts of the resin (R3) was used instead of 133 parts of the resin (R1).
  • An inkjet ink having a pigment concentration of 13% and a solid content concentration of 28% was obtained in the same manner as in Example 2, except that 33 parts of the resin (S2) was used instead of 33 parts of the resin (S1).
  • An inkjet ink having a pigment concentration of 13% and a solid content concentration of 28% was obtained in the same manner as in Example 2, except that 33 parts of the resin (S3) was used instead of 33 parts of the resin (S1).
  • An inkjet ink having a pigment concentration of 13% and a solid content concentration of 28% was obtained in the same manner as in Example 1, except that 133 parts of the resin (A1) was used instead of 133 parts of the resin (R1).
  • An inkjet ink having a pigment concentration of 13% and a solid content concentration of 28% was obtained in the same manner as in Example 2, except that 100 parts of the resin (A1) was used instead of 100 parts of the resin (R2).
  • An inkjet ink having a pigment concentration of 13% and a solid content concentration of 28% was obtained in the same manner as in Example 1, except that 133 parts of the resin (A2) was used instead of 133 parts of the resin (R1).
  • the kneaded product was formed into a sheet shape, cooled to room temperature, and coarsely pulverized to obtain a coated pigment.
  • the mixture was further placed in a sand mill and dispersed for 4 hours.
  • 40 parts of melamine resin (MX-43) and 66 parts of solvent (CBAc) were placed in a mixer and mixed.
  • pressure filtration was performed with a membrane filter to obtain an ink composition for ink jet recording having a pigment concentration (PC) of 16.7% and a solid content concentration of 32%.
  • PC pigment concentration
  • Example 8 75 parts of the resin (A1) is replaced with 75 parts of the resin (A2), and 25 parts of the resin (S1) is further replaced with 25 parts of the resin (S2).
  • the kneaded product was formed into a sheet shape, cooled to room temperature, and coarsely pulverized with force to obtain 167 parts of a coated pigment.
  • 167 parts of the coated pigment and 267 parts of the solvent (CBAc) are mixed in a mixer, further placed in a sand mill and dispersed for 4 hours.
  • 40 parts of melamine resin (MX-43) and 53 parts of solvent (CBAc) was mixed in the mixer.
  • pressure filtration was performed with a membrane filter to obtain an ink composition for ink jet recording having a pigment concentration (PC) of 15.4% and a solid content concentration of 32%.
  • PC pigment concentration
  • Example 9 100 parts of the resin (A1) is replaced with 100 parts of the resin (A2), and 33 parts of the resin (S1) is further replaced with 33 parts of the resin (S2).
  • An ink jet ink having a pigment concentration of 15.4% and a solid content concentration of 32% was obtained.
  • the kneaded product was formed into a sheet shape, cooled to room temperature, and coarsely pulverized with force to obtain 167 parts of a coated pigment.
  • 167 parts of the coated pigment and 552 parts of the solvent (CBAc) are mixed in a mixer, further placed in a sand mill and dispersed for 4 hours, and further 40 parts of melamine resin (MX-43) and solvent (CBAc) 60
  • MX-43 melamine resin
  • CBAc solvent
  • Example 10 except that 100 parts of the resin (A1) is replaced with 100 parts of the resin (A2), and 33 parts of the resin (S1) is replaced with 33 parts of the resin (S2).
  • An ink jet ink having a pigment concentration of 12% and a solid content concentration of 25% was obtained.
  • the ink was dropped on the glass plate, and 1 minute after the dropping, the glass plate was placed on a hot plate heated to 90 ° C. After 5 minutes, the ink table was dried using a non-contact 3D surface profilometer. The surface roughness (Ra) was observed. O: Ra ⁇ 200nm
  • the surface smoothness when the ink of the present invention was dried was remarkably excellent.
  • the inks of Comparative Examples 1 to 9, which are outside the scope of the present invention, that is, Comparative Examples 1 to 9, have ink viscosity outside the scope of the present invention, of which Comparative Examples 1 and 3 to 9 are TI values.
  • the surface smoothness was inferior in all cases.
  • Pigment Dispersion A was prepared with the following composition. This pigment dispersion A was charged with a pigment and a dispersant in an organic solvent and stirred with a high-speed mixer or the like until uniform, and the resulting mill base was produced with a horizontal sand mill with a residence time of 20 minutes.
  • Pigment Dispersion B was prepared with the following composition.
  • Pigment Dispersion C was prepared with the following composition.
  • Pigment Dispersion D was prepared with a residence time of 5 minutes, and Pigment Dispersion E with a residence time of 75 minutes.
  • Pigment Dispersion F was prepared with the following composition.
  • Pigment Dispersion G was prepared when the residence time was 5 minutes
  • Pigment Dispersion H was prepared when the residence time was 75 minutes.
  • Dispersion H was prepared by replacing the solvent of pigment dispersion C with propylene glycol monomethyl ether acetate. Similarly, a dispersion in which butyl acetate is replaced
  • Example 15 and Comparative Example 11 and FIG. 6 the measurement results of the period in the entire temperature range of 100 to 170 ° C. are shown. As in Example 15, the period at 100 to 170 ° C is within 0.6 to 0.9 seconds and V, and as in Comparative Example 11, it is not! It was described in 9. [0375] [Measurement of contact angle]
  • the head having a piezo element was heated to 35 ° C. and discharged onto a glass substrate.
  • the discharged printed material was dried at 120 ° C. for 10 minutes.
  • the printed matter after drying was evaluated under the following conditions, and the results are shown in Table 9.
  • smoothness of solid image (hereinafter referred to as smoothness)
  • fineness (Character fineness (hereinafter referred to as fineness)]
  • a black matrix was prepared as follows.
  • cyclohexanone was added to prepare an acrylic resin solution.
  • the weight average molecular weight of the acrylic resin was 40000.
  • Carbon black (Dedasa “Print ex 55”) 9.3 parts, Dispersant (Generiki “Solce Purse 20000”) 2 parts, Acrylic resin solution 24 parts and Cyclohexanone 40 parts
  • a carbon black dispersion was prepared by mixing and dispersing for 5 hours in a sand mill using glass beads having a diameter of 1 mm.
  • the photosensitive black composition was applied to a 10 cm ⁇ 10 cm glass substrate by spin coating, and then dried at 70 ° C. for 15 minutes to form a coating film having a dry film thickness of 2 / zm. After that, using an ultrahigh pressure mercury lamp, UV light was exposed to 200 mjZcm 2 through a photomask. Next, after spray-developing the unexposed area using an aqueous sodium carbonate solution, the unexposed area was removed by washing with ion-exchanged water, and post-beta was performed at 230 ° C for 30 minutes.
  • A Surface roughness or distortion is not observed in the pixel.
  • ⁇ Slight surface roughness is observed.
  • Examples 4, 8, 10-23 are 100-170.
  • the period was 0.6 to 0.9 seconds.
  • the evaluation results showed that the smoothness was good and the fineness was more than a practical level.
  • evaluations conducted in a black matrix showed an extremely smooth surface shape in Examples 4, 8, and 10, and the T. I. value seems to be low.
  • the surface shape in the black matrix also contributes to the improvement of smoothness by using a solvent having a high boiling point.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Inks, Pencil-Leads, Or Crayons (AREA)
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Abstract

Composition de résine colorée présentant un lissé de surface et un à-plat excellents dans chaque pixel ; et une encre pour jet d'encre comprenant la composition de résine colorée. La composition de résine colorée comprend un pigment, un dérivé de pigment et un véhicule résineux. Elle est caractérisée en ce que la composition de résine colorée, lorsque sa concentration en solides est de 20 à 40 % en poids, 40 % non compris, présente une viscosité (si le taux de cisaillement est limité à 100 (1/s) ; il en va de même ci-après) de 3 à 200 (mPa s) et un T.I. (qui est le rapport de la viscosité, ηa, (mPa s) à un taux de cisaillement de 10 (1/s) à la viscosité, ηb, (mPa s) à un taux de cisaillement de 1 000 (1/s) (ηa/ηb) ; il en va de même ci-après) de 1 à 2. Elle est en outre caractérisée en ce que la composition, lorsqu'elle présente une concentration en solides de 40 à 60 % en poids, a une viscosité de 10 à 200 (mPa s) et un T.I. de 1 à 3.
PCT/JP2007/058208 2006-04-13 2007-04-13 Composition de résine colorée et encre pour jet d'encre comprenant celle-ci WO2007119836A1 (fr)

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JP2008266534A (ja) * 2007-04-25 2008-11-06 Toyo Ink Mfg Co Ltd 印刷用着色組成物、及びカラーフィルタ基板
WO2009116442A1 (fr) * 2008-03-17 2009-09-24 富士フイルム株式会社 Composition dans laquelle est dispersé un pigment, composition photosensible colorée, composition photodurcissable, filtre coloré, élément d'affichage à cristaux liquides et élément de capture d'image solide
JP2009227839A (ja) * 2008-03-24 2009-10-08 Fujifilm Corp 顔料分散組成物、光硬化性組成物、カラーフィルタ、液晶表示装置、および固体撮像素子
JP2009256572A (ja) * 2008-03-17 2009-11-05 Fujifilm Corp 顔料分散組成物、着色感光性組成物、カラーフィルタ、液晶表示素子、及び固体撮像素子
JP2010254746A (ja) * 2009-04-22 2010-11-11 Toyo Ink Mfg Co Ltd 印刷インキ、およびカラーフィルタ基板
JP2011123369A (ja) * 2009-12-11 2011-06-23 Fujifilm Corp ウエハレベルレンズ用黒色硬化性組成物、ウエハレベルレンズ、及びカメラモジュール
JP2012224781A (ja) * 2011-04-21 2012-11-15 Riso Kagaku Corp 非水系顔料インク
JP2014529765A (ja) * 2012-07-25 2014-11-13 エルジー・ケム・リミテッド 相変化インクを用いたフレキシブルカラーフィルタ基板及びその製造方法

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JPH06157736A (ja) * 1992-11-26 1994-06-07 Toyobo Co Ltd 末端変性共重合ポリエステル及びその製造方法
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JP2005206783A (ja) * 2003-10-31 2005-08-04 Canon Inc 化合物、その高分子化合物、該高分子化合物を用いた組成物、記録材料、画像形成方法及び装置
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008266534A (ja) * 2007-04-25 2008-11-06 Toyo Ink Mfg Co Ltd 印刷用着色組成物、及びカラーフィルタ基板
WO2009116442A1 (fr) * 2008-03-17 2009-09-24 富士フイルム株式会社 Composition dans laquelle est dispersé un pigment, composition photosensible colorée, composition photodurcissable, filtre coloré, élément d'affichage à cristaux liquides et élément de capture d'image solide
JP2009256572A (ja) * 2008-03-17 2009-11-05 Fujifilm Corp 顔料分散組成物、着色感光性組成物、カラーフィルタ、液晶表示素子、及び固体撮像素子
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