CN101278016B - Water-based ink for ink-jet recording - Google Patents
Water-based ink for ink-jet recording Download PDFInfo
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- CN101278016B CN101278016B CN2006800366045A CN200680036604A CN101278016B CN 101278016 B CN101278016 B CN 101278016B CN 2006800366045 A CN2006800366045 A CN 2006800366045A CN 200680036604 A CN200680036604 A CN 200680036604A CN 101278016 B CN101278016 B CN 101278016B
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Abstract
Disclosed are (1) an aqueous dispersion for inkjet recording, (2) an aqueous ink containing such an aqueous dispersion, and (3) a method for suppressing adhesion of agglomerates onto the inner surface of a nozzle of an inkjet head. The aqueous dispersion for inkjet recording contains a self-dispersible pigment (A) having a salt-forming group, and a polymer particle (B) having a constitutional unit derived from a salt-forming group-containing monomer and another constitutional unit derived from a silicone macromer, and the polymer particle (B) has the same salt-forming group as the self-dispersible pigment (A). This aqueous dispersion for inkjet recording is excellent in print density, marker resistance and ejection properties.
Description
Technical field
The present invention relates to water dispersion for ink-jet printing, contain the water-based ink for use in ink-jet recording of this water dispersion and in ink-jet recording, suppress the method that condensation product adheres to the nozzle internal surface.
Background technology
Ink-jet recording is from very tiny nozzle droplet of ink directly to be sprayed onto on the recording-member, and it is adhered to, thereby obtains the recording mode of writings and image.This ink-jet recording because have easy panchromaticization and cheapness, can use common paper as recording-member, and the product that are printed be noncontact etc. many advantages, so very universal.
Particularly, from weathering resistance and the water-proof viewpoint of improving printed matter, to use pigment be printing ink becomes main flow (for example, with reference to patent documentation 1 and 2) just gradually as the material of tinting material.
In patent documentation 1, to provide printing distinct, the weathering resistance excellence, the water color ink that printing state is good is a problem, a kind of water color ink is disclosed, this printing ink comprise color material and (i) have the macromonomer of polymerizability functional group, (ii) have the polymerizability unsaturated monomer of salt-forming group, (iii) can copolymerization the vinyl polymer particle that obtains of monomer copolymerization water dispersion and form, and macromonomer is silicone macromolecule monomer and/or the styrenic macromonomer that has polymerizability functional group at an end.
In patent documentation 2, so that the aqueous ink composition that shows excellent in water resistance, rub resistance and anti-mark and the water-based ink for use in ink-jet recording of printing excellence to be provided is problem, disclose a kind of aqueous ink composition, said composition contains aqueous medium, contains polymer particle A and/or the self-dispersion type pigment and the polymer particle B of dyestuff or pigment in water-insoluble polymer.
Though the performance of these printing ink makes moderate progress to a certain extent, also can't satisfy the demand.
Patent documentation 1:JP2001-254038A
Patent documentation 2:JP2001-329199A
Summary of the invention
The present invention relates to following (1)～(3).
(1) a kind of water dispersion for ink-jet printing, this water dispersion comprises: have the self-dispersion type pigment (A) and the polymer particle (B) of salt-forming group, this polymer particle (B) has the structural unit of the monomer (a) that comes self-contained salt-forming group and from the structural unit of silicone macromolecule monomer (b); And polymer particle (B) has and the identical salt-forming group of self-dispersion type pigment (A).
(2) contain the water-based ink for use in ink-jet recording of the water dispersion of above-mentioned (1).
(3) a kind of adherent method of nozzle internal surface that suppresses condensation product to ink-jet, this method is to suppress condensation product to the adherent method of nozzle internal surface in the ink-jet recording that uses polymer particle, wherein, be more than 80 ° at the water dispersion of this polymer particle of coating on the substrate and polymeric film that drying forms with respect to the contact angle of water.
Embodiment
The present invention relates to a kind of on common paper when printing satisfy the water dispersion for ink-jet printing of high printing concentration, anti-mark and ejection property excellence, water color ink and suppress the method that condensation product adheres to the nozzle internal surface of inkjet head.
Present inventors find to be mixed into the nozzle internal surface that pigment in the printing ink and polymer particle adhere to inkjet head, can cause obstruction at the top of this nozzle, reduce the ejection property, and the method for this problem that is resolved.
In addition, present inventors find that the condensation product that can suppress pigment or polymer particle in ink-jet recording adheres to the method for nozzle internal surface by the low polymer particle of the energy of blending surface in printing ink.
Just, the present invention relates to following (1)～(3).
(1) a kind of water dispersion for ink-jet printing, this water dispersion comprises: have the self-dispersion type pigment (A) and the polymer particle (B) of salt-forming group, this polymer particle (B) has the structural unit of the monomer (a) that comes self-contained salt-forming group and from the structural unit of silicone macromolecule monomer (b); And polymer particle (B) has and the identical salt-forming group of self-dispersion type pigment (A).
(2) contain the water-based ink for use in ink-jet recording of the water dispersion of above-mentioned (1).
(3) a kind of adherent method of nozzle internal surface that suppresses condensation product to ink-jet, this method is to suppress condensation product to the adherent method of nozzle internal surface in the ink-jet recording that uses polymer particle, wherein, be more than 80 ° at the water dispersion of this polymer particle of coating on the substrate and polymeric film that drying forms with respect to the contact angle of water.
Water dispersion for ink-jet printing of the present invention is to comprise the self-dispersion type pigment (A) with salt-forming group and the water dispersion of polymer particle (B), this polymer particle (B) has the structural unit of the monomer (a) that comes self-contained salt-forming group and from the structural unit of silicone macromolecule monomer (b), it is characterized in that: polymer particle (B) has and the identical salt-forming group of self-dispersion type pigment (A).
In addition, inhibition condensation product of the present invention is characterised in that to the adherent method of nozzle internal surface of ink-jet and uses following polymer particle: is more than 80 ° at the water dispersion of this polymer particle of coating on the substrate and polymeric film that drying forms with respect to the contact angle of water.Below, each integrant is described.
Pigment
From the adhesivity of printing concentration, anti-mark and the nozzle of the printed matter that improves gained, the viewpoint of ejection property, the polymer particle that uses among the present invention preferably uses together with pigment.
As pigment, can use any one of pigment dyestuff and mineral dye.In addition, they and pigment extender can also be used together as required.In pigment, preferably use so-called self-dispersion type pigment.
For color aqueous printing ink, preferred pigment dyestuff.As pigment dyestuff, can list for example azo pigment, diazo pigment, phthalocyanine pigment, quinoline a word used for translation ketone pigment, isoindolinone pigment, triazine dioxin pigment, perylene pigment, purple cyclic ketones (perinone) pigment, thioindigo color, anthraquinone pigment, quinophthalone pigment etc.
There is no particular limitation to tone, can use wounded look pigment such as organic red pigment, yellow organic pigment, blue pigment dyestuff, orange pigment dyestuff, yellow-green colour pigment dyestuff.
As the object lesson of preferred pigment dyestuff, can list the product that is selected from the various numberings more than a kind among C.I. Pigment Yellow 73, C.I. Pigment red, C.I. pigment violet, C.I. Pigment blue, the C.I. Pigment green.
As mineral dye, can list for example carbon black, metal oxide, metallic sulfide, metal chloride etc.Among them, particularly in black water printing ink, preferred carbon black.As carbon black, can list that furnace black, thermo-cracking are dim, acetylene black, channel black etc.
As pigment extender, can list silicon-dioxide, lime carbonate, talcum etc.
Self-dispersion type pigment
Described self-dispersion type pigment is meant as directly or by other atomic group being attached to the surface of pigment more than a kind in the anionic property hydrophilic group of salt-forming group or the cationic hydrophilic group, thereby also can be distributed to the pigment in the aqueous medium under the situation of not using tensio-active agent or resin.
Here, as other atomic group, can to list carbonatoms be 1～24, be preferably carbonatoms is 1～12 alkylidene group, can have substituent phenylene maybe can have substituent naphthylidene etc.
As the anionic hydrophilic base,, just can use arbitrarily so long as make pigment particles can stably be distributed to the sufficiently high group of wetting ability of the such degree of aqueous medium.Its object lesson can list carboxyl (COOM
1), sulfonic group (SO
3M
1), phosphate (PO
3M
2 1) ,-SO
2NH
2,-SO
2NHCOR
1Or their dissociative ionic forms (COO
-,-SO
3 -,-PO
3 2-,-PO
3 -M
1) etc.
In the above-mentioned chemical formula, M
1Can be identical or different, be hydrogen atom; Basic metal such as lithium, sodium, potassium; Ammonium, monomethyl ammonium, dimethylammonio, trimethylammonium ammonium, single ethyl ammonium, diethyl ammonium, triethyl ammonium; Organic ammoniums such as single methanol-based ammonium, diformazan alcohol radical ammonium, three methanol-based ammoniums.
R
1Be that carbonatoms is 1～12 alkyl, can has substituent phenyl and maybe can have substituent naphthyl.
In these anionic property hydrophilic groups, preferred especially carboxyl (COOM
1), sulfonic group (SO
3M
1).
As the cationic hydrophilic group, can list ammonium, amino etc.Among them, the quaternary ammonium group shown in the preferred following formula (1),
(in the formula, R
2, R
3And R
4Represent hydrogen atom or R independently of one another
1(R
1The same), X represents halogen atoms such as fluorine atom, chlorine atom, removes the anionic property group after the deprotonation from carboxylic acid such as acetic acid, propionic acid, lactic acid, oxyacetic acid, glyconic acid, R-Glyceric acid or carbonatoms are 1～8 alkyl sulfuric ester) and following formula shown in group.
When pigment is made self-dispersion type pigment, the above-mentioned anionic property hydrophilic group or the cationic hydrophilic group of necessary amount can be chemically bonded to surface of pigments.As this method, can use the method for any known.Can list for example No. 5571311 specification sheets of United States Patent (USP), No. 5630868 specification sheets of United States Patent (USP), No. 5707432 specification sheets of United States Patent (USP), J.E.Johnson, ImagingScience and Technology ' s 50
ThAnnual Coference (1997); Yuan Yu, ImagingScience and Technology ' s 53th Annual Conference (2000), polyfile, the method for record in 1248 (1996) etc.
More specifically have: have the method that compounds such as tart acid import carboxyl like this by nitric acid, hydrogen peroxide, hypochlorous acid, chromic acid; Import the method for sulfo group by the thermolysis of persulfate compounds; Import the method for above-mentioned anionic property hydrophilic group etc. by diazenium compound, but be not limited to these methods with carboxyl, sulfo group, amino etc.
There is no particular limitation to the ratio that exists of anionic property hydrophilic group or cationic hydrophilic group, but with respect to every 1g self-dispersion type pigment, be preferably 50～5,000 μ mol/g, more preferably 100～3,000 μ mol/g.
In water dispersion and water color ink, from the viewpoint of the stability of this dispersion, the median size of self-dispersion type pigment is preferably 40～300nm, more preferably 50～200nm.In addition, median size can be by the laser particle analytical system ELS-8000 (cumulative analysis) of Otsuka Electronics Co., Ltd., in temperature is that the angle of 25 ℃, incident light and detector is 90 °, cumulative number is 100 times, and the specific refractory power (1.333) of input water is as carrying out under the condition of the specific refractory power of dispersion solvent.
As commercially available product, can list CAB-O-JET200, CAB-O-JET300 (Cabot corporate system) or BONJET CW-1, the BONJET CW-2 (Aqua-Black 162 (being about 800 μ mol/g) of system), East sea カ one ボ Application Co., Ltd. of オ リ エ Application ト chemical industry Co., Ltd. etc. as carboxyl from dispersed color (carbon black).
Self-dispersion type pigment can use a kind or mix more than 2 kinds and to use separately.
Polymer particle
In ink-vapor recording water dispersion of the present invention,, can improve printing concentration, anti-mark, but also can obtain excellent ejection by using polymer particle.
In addition, adhere in the method for internal surface of nozzle of ink-jet at inhibition condensation product of the present invention, for the polymkeric substance that uses in the polymer particle, importantly the contact angle of the film of this polymkeric substance and water is more than 80 °.
Contact angle can be measured by the method for embodiment record.From reducing and the affinity (wettability) of water color ink, the viewpoint of reduction surface energy, this contact angle is preferably more than 90 °, more preferably more than 95 °.There is no particular limitation for the upper limit, so long as promptly enough below 150 °.
On the other hand, in the nozzle of inkjet head, used thin slice, tackiness agent, polyimide resins such as this thin slice use polyetherimide etc., these resins expose in nozzle inner walls.At these resin surfaces, adhere to condensation product usually lentamente from printing ink.This condensation product is owing to dryings such as the polymkeric substance of nozzle edge portion or pigment produce, and their cohesions become membranaceous dirt settling, makes the direction of droplet of ink produce deviation, finally might produce in nozzle tip and stop up.
In the adherent method of inhibition condensation product of the present invention,, can suppress condensation product and adhere to the nozzle internal surface that forms by above-mentioned heat-resistant resin by using and the contact angle of water is a polymer particle more than 80 °.
" polymer particle " that uses among the present invention is in the solvent of external phase as water-medium, existing or not existing under the condition of tensio-active agent, can disperse to form the polymer particle of polymkeric substance emulsion.
In order to have given play to effect of the present invention, polymer particle be have self-contained salt-forming group monomer (a) structural unit and from the polymer particle of the structural unit of silicone macromolecule monomer (b), this polymer particle has the salt-forming group identical with self-dispersion type pigment.
Polymer particle is by having the structural unit from silicone macromolecule monomer (b), can suppress on the internal surface that polymer particle adheres to inkjet nozzle, and because this polymer particles has the salt-forming group identical with self-dispersion type pigment, so can think that polymer particle and self-dispersion type dispersing of pigments stability in the printing ink improve, ejection property and printing concentration improve.
Polymer particle has the salt-forming group identical with self-dispersion type pigment, and this salt-forming group can be all identical, but polymer particle in not damaging scope of the present invention, can also contain other salt-forming group except containing the salt-forming group identical with self-dispersion type pigment.
In the polymer particle, the viewpoint from the glossiness that improves printed matter is preferably (i) self-emulsifying polymer particle; From improving the viewpoint of anti-mark, be preferably the polymer particle that (ii) letex polymerization forms.
These polymer particles can use separately, also can mix back use more than 2 kinds.
(i) self-emulsifying polymer particle
(i) self-emulsifying polymer particle that uses among the present invention be meant in the salt-forming group that polymkeric substance is had and after, do not add tensio-active agent and directly put in the water, by mixing the particle of the insoluble polymer that becomes emulsified state (below, be called " (i) self-emulsifying polymkeric substance ").
The judgement of emulsified state is as follows: with the 30g insoluble polymer be dissolved into the solution that forms in the 70g organic solvent (for example, methylethylketone), can 100% this insoluble polymer of neutralization the neutralizing agent of salt-forming group (salt-forming group is if anionic property then is a sodium hydroxide; If cationic then is an acetic acid) and 200g water mixes, stirring (300rpm, 30 minutes, 25 ℃) after, from this mixing solutions, remove this organic solvent after, by Visual Confirmation emulsification or can dispersion state 1 week of stable existence carries out at least under 25 ℃.
(self-emulsifying polymkeric substance)
As the self-emulsifying polymkeric substance, can list water-insoluble vinyl polymer, water-insoluble esters polymer, water-insoluble polyurethane polymer etc.Among them, be preferably the water-insoluble vinyl polymer.Here, described insoluble polymer is meant polymkeric substance at 105 ℃ down after dry 2 hours, when being dissolved in 25 ℃ the water of 100g, its meltage be 10g following, be preferably following, the following polymkeric substance of 1g more preferably of 5g.This meltage is according to the salt-forming group kind of insoluble polymer, be the salt-forming group of insoluble polymer is carried out in 100% with acetic acid or sodium hydroxide and the time meltage.
As the water-insoluble vinyl polymer, be preferably the water-insoluble vinyl polymer that the monomer mixture (following also abbreviate as " monomer mixture ") with (c) hydrophobic monomer that contains the monomer that (a) contain salt-forming group (below be also referred to as " (a) composition "), (b) silicone macromolecule monomer (below be also referred to as " (b) composition ") and use as required (below be also referred to as " (c) composition ") etc. forms by the solution polymerization process copolymerization.This water-insoluble vinyl polymer comprises structural unit from (a) composition, from the structural unit of (b) composition and as required and the structural unit that uses from (c) composition.
((a) contains the monomer of salt-forming group)
(a) monomer that contains salt-forming group uses from the viewpoint of the dispersion stabilization of the viewpoint that promotes self-emulsifying and the dispersion that improves gained.As salt-forming group, can list carboxyl, sulfonic group, phosphate, amino, ammonium etc.
As the monomer that contains salt-forming group, can list cationic monomer, anionic monomer etc.These monomeric examples can list the monomers put down in writing at row～the 8 hurdles, page 5 the 7th hurdle 24 of Japanese kokai publication hei 9-286939 communique 29 row etc.
As the representation example of cationic monomer, can list the monomer that contains unsaturated amine, the monomer that contains unsaturated ammonium salt etc.Among them, be preferably (methyl) vinylformic acid N, and N-dimethylamino ethyl ester, N-(N ', N '-dimethylaminopropyl) (methyl) acrylamide and vinyl pyrrolidone.
As the monomeric representation example of anionic property, can list unsaturated carboxylic acid monomer, unsaturated sulfonic acid monomer and unsaturated phosphorus acid monomer etc.
As unsaturated carboxylic acid monomer, can list vinylformic acid, methacrylic acid, Ba Dousuan, methylene-succinic acid, toxilic acid, fumaric acid, citraconic acid, 2-methacryloxy methylsuccinic acid etc.As the unsaturated sulfonic acid monomer, can list styrene sulfonic acid, 2-acrylamido-2-methyl propane sulfonic acid, (methyl) vinylformic acid 3-sulfo group propyl ester, two (3-sulfo group propyl group) itaconic ester etc.As unsaturated phosphorus acid monomer, can list vinyl phosphonate, vinyl phosphate, two (methacryloxyethyl) phosphoric acid ester, phenylbenzene-2-acryloxy ethyl phosphonic acid ester, phenylbenzene-2-methacryloxyethyl phosphoric acid ester, dibutyl-2-acryloxy ethyl phosphonic acid ester etc.
Viewpoint from dispersion stabilization, ejection stability in above-mentioned anionic monomer, is preferably unsaturated carboxylic acid monomer, acrylic or methacrylic acid more preferably.
((b) silicone macromolecule monomer)
(b) the silicone macromolecule monomer uses from the viewpoint that improves ejection stability.The silicone macromolecule monomer is preferably the silicone macromolecule monomer shown in the following formula (2).
X(Y)
qSi(R
5)
3-r(Z)
r (2)
(in the formula, X represents can the polymeric unsaturated group, Y represent divalent in conjunction with base, R
5Represent hydrogen atom, alkyl, aryl or alkoxyl group independently of one another, Z represents that number-average molecular weight is the residue of 1 valency siloxane polymer more than 500, and q represents 0 or 1, and r represents 1～3 integer.)
The monomeric number-average molecular weight of silicone macromolecule is preferably 500～100,000, more preferably 1,000～10,000, number-average molecular weight can be measured as the gel chromatography of solvent as the chloroform that reference material, use contain the dodecyl dimethyl amine of 1mmol/L by using polystyrene.
In formula (2),, can list CH as X
2=CH-base, CH
2=C (CH
3)-carbonatomss such as Ji are 2～6 1 valency unsaturated alkyl.
As Y, can list-the COO-base-COOC
aH
2a-Ji (a represents 1～5 integer), divalents such as phenylene are in conjunction with base, and be preferred-COOC
3H
6-.
As R
5, can list hydrogen atom; Carbonatoms such as methyl, ethyl is 1～5 alkyl; Carbonatomss such as phenyl are 6～20 aryl; Carbonatomss such as methoxyl group are 1～20 alkoxyl group etc., among them, are preferably methyl.Z preferably number-average molecular weight is 1 a valency residue of 500～5,000 dimethylsiloxane polymer.Q is 0 or 1, is preferably 1.R is 1～3 integer, is preferably 1.
As the representation example of (2) silicone macromolecule, can list the silicone macromolecule monomer shown in the following formula (2-1)～(2-4) etc.
CH
2＝CR
6-COOC
3H
6-[Si(R
7)
2-O]
b-Si(R
7)
3 (2-1)
(in the formula, R
6Expression hydrogen atom or methyl, R
7Represent that independently of one another hydrogen atom or carbonatoms are 1～5 low alkyl group, b represents 5～60 number).
CH
2＝CR
6-COO-[Si(R
7)
2-O]
b-Si(R
7)
3 (2-2)
(in the formula, R
6, R
7The same with b).
CH
2＝CR
6-Ph-[Si(R
7)
2-O]
b-Si(R
7)
3 (2-3)
(in the formula, Ph represents phenylene, R
6, R
7The same with b).
CH
2＝CR
6-COOC
3H
6-Si(OE)
3 (2-4)
(in the formula, R
6The same.E represents-[Si (R
7)
2-O]
c-Si (R
7)
3Base (R
7The same, c represents 0～65 number)).
Among them, be preferably the silicone macromolecule monomer shown in the formula (2-1), be preferably the silicone macromolecule monomer shown in the following formula (2-1a) especially.
CH
2＝C(CH
3)-COOC
3H
6-[Si(CH
3)
2-O]
d-CH
3 (2-1a)
(in the formula, d represents 8～40 number)
As the monomeric example of silicone macromolecule shown in the formula (2-1a), can list FM-0711, FM-0721, FM-0725, TM-0701 (Chisso Co., Ltd. makes, trade(brand)name) etc.
((c) hydrophobic monomer)
(c) hydrophobic monomer uses from improving viewpoints such as printing concentration, anti-mark.As hydrophobic monomer, can list (methyl) alkyl acrylate, contain the monomer of aryl etc.
As (methyl) alkyl acrylate, be preferably that to have carbonatoms be 1～22, be preferably carbonatoms and be (methyl) alkyl acrylate of 6～18 alkyl, can list (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) vinylformic acid (different) propyl ester, (methyl) vinylformic acid (XOR uncle) butyl ester, (methyl) vinylformic acid (different) pentyl ester, (methyl) cyclohexyl acrylate, (methyl) 2-EHA, (methyl) vinylformic acid (different) monooctyl ester, (methyl) vinylformic acid (different) ester in the last of the ten Heavenly stems, (methyl) vinylformic acid (different) dodecyl ester, (methyl) vinylformic acid (different) stearyl etc.
In addition, " (the XOR uncle) " described in this specification sheets and " (different) " are meant these two kinds of situations that exist and do not have these groups, when not having these groups, and expression " just "." (methyl) acrylate " represents acrylate and methacrylic ester in addition.
As the monomer that contains aryl, be preferably can have contain heteroatomic substituent, to have carbonatoms be 6～22, be preferably the vinyl monomer that carbonatoms is 6～12 aryl, can list styrene monomer (c-1 composition) for example, contain (methyl) acrylate (c-2 composition) of aryl.
As styrene monomer (c-1 composition), can list vinylbenzene, 2-methyl styrene, Vinyl toluene, ethyl vinyl toluene, vinyl naphthalene, chlorostyrene etc., be preferably vinylbenzene and 2-methyl styrene especially.
Can list as (methyl) acrylate (c-2 composition) that contains aryl: can have and contain heteroatomic substituently and to have carbonatoms be 7～22, be preferably 7～18, more preferably 7～12 aralkyl, perhaps carbonatoms is 6～22, is preferably (methyl) acrylate of 6～18, more preferably 6～12 aryl etc.As containing heteroatomic substituting group, can list halogen atom, ester group, ether, hydroxyl etc.More specifically, can list for example (methyl) benzyl acrylate, (methyl) vinylformic acid phenoxy ethyl, vinylformic acid 2-hydroxyl-3-phenoxy group propyl ester, 2-methacryloxyethyl-2-hydroxypropyl phthalic ester etc., be preferably (methyl) benzyl acrylate especially.
From improving the viewpoint of printing concentration and anti-mark, (c) (c-1) composition in the composition or (c-2) content of composition be preferably 10～100 weight %, 20～80 weight % more preferably.
In (c) composition, from improving the viewpoint of printing concentration and anti-mark, be preferably styrene monomer (c-1) composition, be preferably vinylbenzene and 2-methyl styrene especially, also preferably will (c-1) composition and (c-2) composition and usefulness.
(monomer of (d) hydroxyl)
In order to improve dispersion stabilization, in monomer mixture, can further contain the monomer (below be also referred to as " (d) composition ") of (d) hydroxyl.(d) composition shows and improves dispersion stabilization and improve the such excellent effect of anti-mark in the short period of time when printing.
As (d) composition, for example can list (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) vinylformic acid 3-hydroxypropyl acrylate, (n is 2～30 to polyoxyethylene glycol, and n represents the average addition mole number of oxyalkylene group.(methyl) acrylate, polypropylene glycol (n is 2～30) (methyl) acrylate, poly-(ethylene glycol (n is 1～15) propylene glycol (n is 1～15)) (methyl) acrylate etc. down together).Wherein, be preferably (methyl) vinylformic acid 2-hydroxyl ethyl ester, polyethylene glycol monomethacrylate, polypropylene glycol methacrylic ester.
In monomer mixture, can further contain (e) with the monomer shown in the following formula (3) (below be also referred to as " (e) composition ").(e) continuous printing also can suppress to produce " slippage (slippage, ヨ レ) " such excellent effect even composition shows the ejection stability that improves water color ink.
CH
2＝C(R
8)COO(R
9O)
pR
10 (3)
(in the formula, R
8Expression hydrogen atom or carbonatoms are 1～5 low alkyl group, R
9It is 1～30 divalent alkyl that expression can have heteroatomic carbonatoms, R
10Expression can have the alkyl that heteroatomic carbonatoms is 1～30 1 valency, and p represents average addition mole number, is 1～60, is preferably 1～30 number.)
Here, as heteroatoms, can list for example nitrogen-atoms, Sauerstoffatom, halogen atom and sulphur atom.
As R
8Suitable example, can list methyl, ethyl, (different) propyl group etc.
As R
9The suitable example of O base, can list oxyethylene group, oxidation (different) propenyl, oxidation 1,4-butenyl, oxidation 1,7-heptenyl, oxidation 1,6-hexenyl or be 2～7 oxyalkylene group by the carbonatoms that is combined to form more than 2 kinds of these oxyalkylene groups.
As R
10Suitable example, can to list carbonatoms be 1～30, be preferably carbonatoms is that 1～20 aliphatic alkyl, the carbonatoms with aromatic ring are 7～30 alkyl and to have the heterocyclic carbonatoms be 4～30 alkyl.
Object lesson as (e) composition, can list methoxy poly (ethylene glycol) (1～30, the value of p in the expression following formula (3), (methyl) acrylate down together), methoxyl group poly-1,4-butyleneglycol (1～30) (methyl) acrylate, oxyethyl group polyoxyethylene glycol (1～30) (methyl) acrylate, octyloxy polyoxyethylene glycol (1～30) (methyl) acrylate, polyoxyethylene glycol (1～30) (methyl) acrylate 2-ethylhexyl ether, (different) propoxy-polyoxyethylene glycol (1～30) (methyl) acrylate, butoxy polyoxyethylene glycol (1～30) (methyl) acrylate, methoxyl group polypropylene glycol (1～30) (methyl) acrylate, methoxyl group (copolymerization of ethylene glycol propylene glycol) (1～30, wherein ethylene glycol partly is 1～29) (methyl) acrylate etc.Among them, be preferably octyloxy polyoxyethylene glycol (1～30) (methyl) acrylate, polyoxyethylene glycol (1～30) (methyl) acrylate 2-ethylhexyl ether.
As can commercial (d), the object lesson of (e) composition that obtains, can enumerate polyfunctional acrylate's monomer (NK Ester) M-40G, M-90G, M-230G, the EH-4G of village chemical industry Co., Ltd. in making new advances, the Blenmer Series P E-90 of NOF Corp, PE-200, PE-350, PME-100, PME-200, PME-400, PME-1000, PP-500, PP-800, PP-1000, AP-150, AP-400, AP-550, AP-800,50PEP-300,50POEP-800B etc.
Above-mentioned (a)～(e) composition can be distinguished use separately or will mix the back more than 2 kinds and use.
(content of each composition in the monomer mixture)
When the water-insoluble vinyl polymer is made, the content of above-mentioned (a)～(e) composition in monomer mixture (as the content of dosis neutralisata not, down with.) or insoluble polymer in the content from the structural unit of (a)～(e) composition as follows.
From the viewpoint of the dispersion stabilization of the polymer particle of self-emulsifying, gained, (a) content of composition is preferably 3～40 weight %, and more preferably 5～30 weight % are preferably 5～20 weight % especially.
From the viewpoint of ejection property, (b) content of composition is preferably 10～90 weight %, and more preferably 15～80 weight % are preferably 22～70 weight % especially, most preferably are 25～65 weight %.
From the viewpoint of printing concentration, anti-mark, (c) content of composition is preferably 5～80 weight %, more preferably 10～60 weight %, be preferably 15～50 weight % especially.
From the dispersion stabilization of polymer particle, the viewpoint of anti-mark, (d) content of composition is preferably 5～40 weight %, more preferably 7～20 weight %.
From spraying viewpoints such as stability, (e) content of composition is preferably 5～50 weight %, more preferably 10～40 weight %.
From the dispersion stabilization of polymer particle, water-proof viewpoint, the total content of [(a) composition+(d) composition] is preferably 6～60 weight %, more preferably 10～50 weight %.
From the viewpoint of the dispersion stabilization of polymer particle, ejection stability, the total content of [(a) composition+(e) composition] is preferably 6～75 weight %, more preferably 13～50 weight %.
In addition, from the viewpoint of the dispersion stabilization of polymer particle, ejection stability, the total content of [(a) composition of composition+(d)+(e) composition] is preferably 6～60 weight %, more preferably 7～50 weight %.
From viewpoints such as prolonged preservation stability, ejection property, the weight ratio of (a) and (b), (c) composition [(a)/[(b)+(c)]] is preferably 0.01～0.5, and more preferably 0.03～0.3, more preferably 0.05～0.2.
(manufacturing of insoluble polymer)
The insoluble polymer that is used to form (i) self-emulsifying polymkeric substance can pass through known polymerization processs such as solution polymerization process, mass polymerization, makes the monomer mixture copolymerization and makes.In these polymerization processs, the preferred solution polymerization.
As the solvent that uses in the solution polymerization process, there is no particular limitation, is preferably polar organic solvent.When polar organic solvent has the water Combination, can also mix with water and use.As polar organic solvent, can list carbonatomss such as methyl alcohol, ethanol, propyl alcohol for example and be 1～3 Fatty Alcohol(C12-C14 and C12-C18); Ketone such as acetone, methylethylketone; Ester classes such as ethyl acetate etc.Among them, be preferably methyl alcohol, ethanol, acetone, methylethylketone or they more than a kind and the mixed solvent of water.
When polymerization; can use 2; 2 '-Diisopropyl azodicarboxylate, 2,2 '-azo two azo-compound or known radical polymerization initiators such as organo-peroxide such as tert-butyl hydroperoxide octanoate, dibenzoyl superoxide such as (2, the 4-methyl pentane nitrile).With respect to per 1 mole of monomer mixture, the consumption of radical polymerization initiator is preferably 0.001～5 mole, more preferably 0.01～2 mole.When polymerization, can further add known polymeric chain transfer agents such as thio-alcohols such as octyl mercaptan, 2 mercapto ethanol, thiuram disulfides.
The polymerizing condition of monomer mixture cannot treat different things as the same according to the difference of employed radical polymerization initiator, monomer, solvent types etc. and different.Common is, polymerization temperature is preferably 30～100 ℃, and more preferably 50～80 ℃, polymerization time is preferably 1～20 hour.In addition, polymerization atmosphere is preferably inertness atmosphere such as nitrogen atmosphere, argon gas.
After polyreaction finishes, can pass through known method such as precipitation, solvent distillation once more, from reaction soln, isolate the polymkeric substance of generation separately.In addition, the polymkeric substance of gained precipitates once more by repeating, and perhaps removes unreacted monomer by membrane sepn, chromatography, extraction process etc. and makes with extra care.
From the viewpoint of printing concentration, anti-mark, ejection property, the weight-average molecular weight of the insoluble polymer of gained is preferably 5,000～500,000, and more preferably 10,000～400,000, be preferably 10,000～300,000 especially.
In addition, the weight-average molecular weight of polymkeric substance can use polystyrene to measure as reference material by using the dimethyl formamide of lithiumbromide that dissolving contains the phosphoric acid of 60mmol/L and 50mmol/L as the gel chromatography of solvent.
(manufacturing of (i) self-emulsifying polymer particle)
From above-mentioned insoluble polymer manufacturing (i) the self-emulsifying polymer beads period of the day from 11 p.m. to 1 a.m, preferably obtain by following operation (1) and (2) form with water dispersion.
Operation (1): the operation that will contain the mixture stirring of insoluble polymer, organic solvent, neutralizing agent and aqueous medium;
Operation (2): the operation of removing above-mentioned organic solvent.
In above-mentioned operation (1), above-mentioned insoluble polymer is dissolved in the organic solvent, then add the aqueous medium that contains neutralizing agent and mix, stir, obtain the dispersion of oil-in-water-type.Like this,, can not need powerful shearing force, and storage stability more obtains the water dispersion of fine (i) self-emulsifying polymer particle of particle diameter in the highland by in containing the aqueous medium of neutralizing agent, adding insoluble polymer.The stirring means of this mixture has no particular limits.
In mixture, organic solvent is preferably 10～70 weight %, and insoluble polymer is preferably 2～40 weight %, and aqueous medium is preferably 10～70 weight %.
There is no particular limitation to the degree of neutralization of insoluble polymer.Usually, preferably the liquid property of the water dispersion that will finally obtain is adjusted into slightly acidic～weakly alkaline, and for example pH is 4～10.
In above-mentioned operation (2), from the dispersion that above-mentioned operation (1) obtains, heat up in a steamer organic solvent by ordinary methods such as underpressure distillation and form water-based system, can obtain the water dispersion of (i) self-emulsifying polymer particle thus.Organic solvent in the water dispersion of gained is removed on substantially, and the amount of organic solvent is generally below the 0.1 weight %, is preferably below the 0.01 weight %.
Viewpoint from the storage stability of water dispersion, the D50 of the water dispersion of (i) self-emulsifying polymer particle of gained is (in the frequency distribution of scattering strength, the value of the accumulation 50% of calculating from the small-particle side) is preferably below the 500nm, more preferably below the 300nm, be preferably below the 200nm especially.In addition, from the easy degree of making, its lower limit is preferably more than the 10nm.
In addition, from reducing the viewpoint of oversize particle with the storage stability that improves dispersion, the D90 of this water dispersion (in the frequency distribution of scattering strength, the value of the accumulation 90% of calculating from the small particle size side) is preferably below the 2000nm, more preferably below the 1000nm, be preferably below the 500nm especially.In addition, from the easy degree of making, its lower limit is preferably more than the 20nm.
In addition, D50 and D90 can measure under same condition by the laser particle analytical system ELS-8000 (cumulative analysis) of above-mentioned Otsuka Electronics Co., Ltd..
The (ii) polymer particle that forms of letex polymerization
The polymer particle that the (ii) letex polymerization of using among the present invention forms is meant the particle of the polymkeric substance that uses tensio-active agent and/or reactive surfactant that monomer mixture is carried out letex polymerization and obtain (below, be called " letex polymerization polymkeric substance ").Monomer mixture preferably contains above-mentioned (a) composition and (b) composition and (c) composition of use as required.
Therefore, this letex polymerization polymkeric substance preferably contains from the structural unit of above-mentioned (a) composition, from structural unit of (b) composition and the structural unit from (c) composition that uses as required, can also contain above-mentioned (d) composition, (e) composition further.
As the polymerization starter of letex polymerization, can use known polymerization starter, can list for example inorganic peroxides such as hydrogen peroxide, Potassium Persulphate, ammonium persulphate; Organo-peroxides such as cumene hydroperoxide, diisopropyl benzene hydrogen peroxide, p-menthane hydroperoxide; Organic class superoxide such as azo-initiator such as Diisopropyl azodicarboxylate, p-methoxy-phenyl diazonium mercaptonaphthalene; Perhaps in organic class initiator such as azo-initiators such as Diisopropyl azodicarboxylate, anisole diazonium mercaptonaphthalene or superoxide, oxygenant and the oxidation-reduction polymerization starter that obtains with reductive agent such as sodium bisulfite, Sulfothiorine, ferrous sulfate, sugar etc.
As the tensio-active agent that letex polymerization is used, there is no particular limitation, is preferably anionic surfactant's (for example, the ammonium salt of Sodium dodecylbenzene sulfonate, sodium laurate, Voranol EP 2001 sulfuric ester etc.); Nonionic surfactant (for example, Voranol EP 2001, polyxyethylated ester, polyoxyethylene sorbitan aliphatic ester, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl amine, polyoxyethylene alkylamide etc.).They can separately or mix use more than 2 kinds.
Viewpoint from the anti-mark that improves water dispersion and water color ink, perhaps, preferably in letex polymerization, use reactive surfactant from making the contact angle of water on film forming polymeric film (film) be more than 80 °, suppress the viewpoint that condensation product generates, improves the ejection of water dispersion and water color ink.
Reactive surfactant be intramolecularly have more than 1 can radical polymerization the tensio-active agent of unsaturated double-bond.Reactive surfactant has excellent monomer emulsifying property, can stably make excellent water dispersion, consequently can improve anti-mark and ejection property.
As reactive surfactant, be preferably that to have at least 1 carbonatoms be 8～30, be preferably the hydrophobic group such as alkyl, alkenyl of 12～22 straight or branched, and the anionic property or the nonionic surfactant of hydrophilic radical such as at least 1 ionic group, oxyalkylene group.
As alkyl, can list octyl group, 2-ethylhexyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, docosyl etc.
As alkenyl, can list oleyl, octenyl etc.
As ionic group, can list cationic group (ammonium etc.) and anionic property group, be preferably the group of anionic property, more preferably anionic property group or its alkali correctives such as carboxyl, sulfonic group, sulfate, phosphate.It is identical with above-mentioned neutralizing agent to be used for neutral alkali.
The preferred carbonatoms of oxyalkylene group is 1～4, and the mean polymerisation degree of repeating unit is preferably 1～100, more preferably 4～80, be preferably 4～50 especially.Wherein be preferably oxyethylene group and/or oxypropylene group especially.
When using oxyalkylene group more than 2 kinds, for example oxyethylene group and oxypropylene group, can be any one of block type, random, interactive etc.There is no particular limitation to the end of oxyalkylene group, except hydroxyl, can make alkoxyl groups such as methoxyl group, oxyethyl group.
When the polymer particle that forms when letex polymerization had from the monomeric structural unit of anionic property, from the viewpoint of the cohesion stability of polymer particle, reactive surfactant was preferably the tensio-active agent with anionic property group and/or oxyalkylene group; When the structural unit that has from cationic monomer, from the coherent viewpoint of polymer particle, reactive surfactant is preferably the tensio-active agent with cationic group and/or oxyalkylene group.
As the object lesson of reactive surfactant, can list for example (for example, ラ テ system Le S-120P, the S-180A of Kao Corp's manufacturing of the sulfosuccinic ester class shown in following formula (4), (5); The エ レ ミ ノ one Le JS-2 that Sanyo Chemical Industries Co., Ltd. makes etc.) and the alkyl phenolic group ethers shown in the general formula (6) (for example, Di-ichi Kogyo Seiyaku Co., Ltd. make ア Network ア ロ Application HS-10, RN-20 etc.).
(in the formula, M
2Expression Na, K or NH
4, R
11The expression carbonatoms is 8～18 alkyl).
(in the formula, M
2And R
11Identical with formula (4)).
(in the formula, X represents H, SO
3Na, SO
3K or SO
3NH
4, R
11Identical with formula (4), n represents 1～200, is preferably 1～50 integer).
In these reactive surfactants,, be preferably the have following formula tensio-active agent of anionic property group of (4) and (5) from the viewpoint of the operability of letex polymerization.These reactive surfactants can separately or mix above use the in 2.
With respect to the ethylenically unsaturated monomer beyond the reactive surfactant of 100 weight parts, the consumption of reactive surfactant is generally 0.1～10 weight part, is preferably 0.1～5 weight part, more preferably 0.1～3 weight part.When this consumption is 0.1 weight part when above, the having good stability of polymer particles, the dispersion stabilization of polymkeric substance improves; When this consumption is 10 weight parts when following, anti-mark is good.
(each composition or from the content of the structural unit of each composition)
The content of (a)～(e) composition in the above-mentioned monomer mixture is (as the content of dosis neutralisata not, down with) or (ii) the content in the letex polymerization polymkeric substance from the structural unit of (a)～(e) composition be, except (a) composition, the situation with above-mentioned self-emulsifying polymkeric substance in the purpose of using and suitable scope is identical.From the viewpoint of dispersion stabilization, the content of (a) composition in the monomer mixture or be preferably 0.3～10 weight % from the content of the structural unit of (a) composition, more preferably 0.5～5 weight % is preferably 0.5～3 weight % especially.
The solids component amount of the polymer particle of gained is preferably 1～80%, from stability and blended viewpoint, is preferably 10～70%.
(the (ii) manufacturing of the polymer particle that forms of letex polymerization)
(ii) the polymer particle that forms of letex polymerization is by known emulsion polymerisation process manufacturing.
Good from the system film, as to improve anti-mark viewpoint, the second-order transition temperature of letex polymerization polymkeric substance is preferably below 50 ℃, more preferably below 30 ℃.In addition, from improving overlay film intensity, improving the viewpoint of anti-mark, second-order transition temperature is preferably more than-70 ℃, more preferably-40 ℃ more than.
In water dispersion and water color ink, (ii) the D50 of the water dispersion of the polymer particle that forms of letex polymerization is (in the frequency distribution of scattering strength, calculate the value of accumulation 50% from the small-particle side) so long as printing ink is stably existed when preserving, just there is no particular limitation, the D50 that the measuring method (25 ℃) of laser particle analytical system ELS-8000 (cumulative analysis) by above-mentioned Otsuka Electronics Co., Ltd. obtains is preferably 5～300nm, more preferably 30～200nm.
Water dispersion, water color ink
The polymer particle that uses among the present invention preferably contains in water dispersion or water color ink and uses.Water color ink be contain water dispersion, be the printing ink of main medium with water.
Water dispersion of the present invention, water color ink can obtain by pigment (self-dispersion type pigment), polymer particles and water are mixed.The blended order can be random order.The content of the pigment in water dispersion for ink-jet printing of the present invention and the water color ink (self-dispersion type pigment), polymer particle and water is as follows.
From the viewpoint of the stability of water dispersion and printing ink, printing concentration, ejection property, the content of pigment (self-dispersion type pigment) is preferably 1～15 weight %, and more preferably 2～10 weight % are preferably 2～8 weight % especially.
From the method for the stability of water dispersion and printing ink, anti-mark, inhibition condensation product, the viewpoint of ejection property, the content of polymer particle is preferably 0.5～15 weight %, and more preferably 1～12 weight % is preferably 2～10 weight % especially.
From the viewpoint of printing concentration, anti-mark, ejection property, the weight ratio of [pigment (self-dispersion type pigment)/polymer particle] is preferably 20/80～90/10, and more preferably 30/70～80/30.
The content of the water in water dispersion, the water color ink is preferably 30～90 weight %, more preferably 40～80 weight %.
In water color ink of the present invention, can add additives such as wetting agent, dispersion agent, defrother, mould inhibitor, sequestrant as required.In addition, the pH value of water color ink is preferably 4～10.
The preferred surface tension of water dispersion of the present invention and water color ink (20 ℃) is: as water dispersion, be preferably 30～65mN/m, more preferably 35～60mN/m; As water color ink, be preferably 25～50mN/m, more preferably 27～45mN/m.
Good for the viscosity when forming water color ink, the viscosity the when solids component of water dispersion is 10 weight % (20 ℃) is preferably 2～6mPas, more preferably 2～5mPas.In addition, in order to keep good ejection, the viscosity of water color ink (20 ℃) is preferably 2～12mPas, more preferably 2.5～10mPas.
Ink-jet recording
There is no particular limitation for ink-jet recording of the present invention, can adopt any of piezoelectricity mode, hot mode, but be particularly suitable for the piezoelectricity mode.
Even water color ink of the present invention is in the high speed ink-jetting style, ejection property is also excellent.
In the adherent method of inhibition condensation product of the present invention, because use and the contact angle of water be more than 80 °, be preferably more than 90 °, the polymer particle more than 95 ° more preferably, so even print speed is a high speed, also can suppress effectively on the internal surface of nozzle that condensation product adheres to inkjet head.
Therefore, the method according to this invention, the emission direction of droplet of ink is fixed, the straight ahead raising, ejection property is good.
In addition, adhere to the nozzle internal surface even suppose condensation product, also can be owing to printing ink self remove the dirt settling of nozzle internal surface from cleanliness (solvability of bur), the deviation of position thereby the spray that suppresses droplet of ink falls, can obtain " slippage " (slippage, the thin informal voucher in whole when printing) and few good printing word, the image of " omission " (lack, whole thick informal voucher when printing).
Embodiment
In following Production Example, embodiment and comparative example, if not special record, " part " and " % " is " weight part " and " weight % ".
Production Example 1 (using reactive surfactant to make the polymer particle that letex polymerization forms)
In beaker, add the silicone macromolecule monomer (trade(brand)name: FM-0711 of (a) vinylformic acid/(b), Chisso Co., Ltd. makes)/(c) vinylbenzene/(c) monomer mixture 100g and 10g reactive surfactant ラ テ Le system S-180A (Kao Corp's manufacturing of 2-ethylhexyl acrylate=2/29/49/20, trade(brand)name, the sulfosuccinic ester class, effective constituent 50%), 0.5g Potassium Persulphate, 50g water, stir with homo-mixer, prepare uniform milky white solution.
Then, in having the glass reaction vessel of agitator, thermometer, reflux exchanger, nitrogen ingress pipe, add 300g ion exchanged water, the above-mentioned ラ テ of 2.3g Le system S-180A, 0.1g Potassium Persulphate, behind the nitrogen replacement, in hot water bath, temperature is warmed up to 70 ℃.In 2 hours to wherein adding above-mentioned milky white solution, afterwards, 80 ℃ aging 2 hours down, obtain the solids component amount and be 29% polymer particle.The measurement result of the D50 of the polymer particle of gained is 90nm.
In addition, the mensuration of D50 uses laser particle analytical system (Otsuka Electronics Co., Ltd. to make article number: ELS-8000), measure down at 25 ℃.
Production Example 2 (manufacturing of self-emulsifying polymer particle)
In reaction vessel, add 20 parts of methylethylketones, 0.01 portion of polymeric chain transfer agent (2 mercapto ethanol) and (a) silicone macromolecule monomer (trade(brand)name: FM-0711 of methacrylic acid/(b), Chisso Co., Ltd. makes)/(c) 10% in 200 parts of the monomer mixtures of butyl acrylate=10/60/30, fully carry out nitrogen replacement, obtain mixing solutions.
In addition, it is remaining 90% to add above-mentioned monomer mixture in dropping funnel, adds 0.27 portion of above-mentioned polymeric chain transfer agent, 60 parts of methylethylketones and 1.2 parts of radical polymerization initiators (2,2 '-azo two (2, the 4-methyl pentane nitrile) also mixes, fully carry out nitrogen replacement, obtain mixing solutions.
Under nitrogen atmosphere, on one side the interior mixing solutions of stirring reaction container, be warmed up to 65 ℃ on one side, the mixed solution in 3 hours in the slow addition funnel.After drip finishing, 65 ℃ place 2 hours down after, add the solution that 0.3 part of above-mentioned radical polymerization initiator is dissolved in 5 parts of methylethylketones and forms, again 65 ℃ aging 2 hours down, 70 ℃ aging 2 hours down, obtain polymers soln.Then, adding the methylethylketone of specified amount in this polymers soln, is 50% polymers soln by stirring, obtaining solid component concentration.The weight-average molecular weight of the polymkeric substance of gained is about 30,000.
In the polymers soln of 30 parts of gained, add 40 parts of methylethylketones and 30 parts of acetone, after stirring, add dropping funnel, in 30 minutes, be added drop-wise in the reaction vessel of ion exchanged water of the aqueous sodium hydroxide solution that adds in advance and be mixed with 4.3 parts 5mol/L, 1.2 parts 25% ammoniacal liquor and 217.5 parts, neutralize.And then stirred 30 minutes, obtain emulsifying composition.The emulsifying composition of gained is removed organic solvent, ammonia and a part of water under decompression, 60 ℃, be that the strainer (Japanese Port one Le company make) of 5 μ m filters by mean pore size then, remove oversize particle, obtain the solids component amount and be 20% the water dispersion that contains polymer particle.The D50 of the polymer particle of gained is 48nm.
Production Example 3 (using reactive surfactant to make the polymer particle that letex polymerization forms)
Except the monomer mixture that uses 2-ethylhexyl acrylate=2/49/49 of the vinylbenzene of (a) vinylformic acid/(c)/(c) and Production Example 1 similarly obtain polymer particle.The D50 of the polymer particle of gained is 120nm by measuring with Production Example 1 same method.
Production Example 4 (manufacturing of self-emulsifying polymer particle)
Except the monomer mixture that uses butyl acrylate=10/90 of (a) methacrylic acid/(c) and Production Example 2 similarly obtain polymer particle.The D50 of the polymer particle of gained is 35nm by measuring with Production Example 1 same method.
Embodiment 1～3 and comparative example 1～4
With self dispersible carbon black water dispersion (the pigment solids composition is 7 parts), the water dispersion (the polymer particle solids component is 3 parts), glycerine (5 parts), 2-Pyrrolidone (5 parts), Virahol (2 parts), ア セ チ レ ノ one Le EH (river is ground Off ア イ Application ケ ミ カ Le Co., Ltd. and made) (1 part) and the water (residual content) that contain the polymer particle that Production Example 1～3 obtains is that 100 parts mode is mixed stirring down at 25 ℃ with total amount, the preparation dispersion liquid, the strainer of this dispersion liquid by 0.8 micron filtered, obtain water color ink.
(1) condensation product of water color ink of estimating gained by following method is at the adhesivity of the internal surface of nozzle, (2) ejection property, (3) printing concentration and (4) anti-mark.In addition, also measure the water contact angle of the polymeric film that the water dispersion film forming of the polymer particle that uses in embodiment and the comparative example obtains.The result is as shown in table 1.
In addition, the self dispersible carbon black in the table 1 is water dispersion, and it is as follows to abridge.
CW-2:Orient chemical industry Co., Ltd. makes, trade(brand)name: BONJET CW-2, solid component concentration 15% (salt-forming group: carboxyl)
The commodity that Cab:Cabot Speciality Chemicals Inc company makes Cab-O-Jet200 by name, solid component concentration is 20% (salt-forming group: sulfonic group)
(1) water contact angle of polymeric film
The following mensuration of the water contact angle of polymeric film: (solids component is 20 weight %, 1g) is applied to slide (20cm with the water dispersion of polymer particle
2) last (0.01g/cm
2), be under 50% the environment at 25 ℃, relative humidity, place and made its drying in 24 hours, on even film forming film, drip 1 pure water, the contact angle meter " CA-D " that uses consonance interface science Co., Ltd. to make, under 25 ℃, the environment of relative humidity 50%, measure the contact angle of this film and pure water.As slide, can use foliated glass (trade(brand)name: water ス ラ イ De グ ラ ス, manufacturing company: loose unrestrained nitre Industrial Co., Ltd, model: S7224, specification: プ レ Network リ Application (degreasing washing back) isolates wide 26mm * long 76mm, thick 1.2～1.5mm).As long as the polymer-coated amount of per unit area is as implied above, just can regulate solids component and glue spread.
(2) condensation product is to the tack of nozzle internal surface
Use Kapton (about 20cm
2) (ユ one ピ レ Star Network ス 25S, Ube Industries, Ltd make) as mimic nozzle interior starting material, be coated with printing ink (about 1g) equably after, under 25 ℃, the condition of relative humidity 50%, place drying and made its drying in 24 hours.It is had in adding dipping washed gently with pure water after 1 hour in 25 ℃ the beaker of identical printing ink, measure the revolution mark of printing ink.
[metewand]
Zero: residual printing ink is less than 10% of coated face
△: residual ink be coated face more than 10% but be less than 50%
*: residual printing ink is more than 50% of coated face
(3) ejection property
(Seiko Epson Co., Ltd. makes to use commercially available ink-jet printer, model: EM-930C, the piezoelectricity mode), go up with whole printing of fine pattern (high speed printing pattern) at high-quality dedicated paper (manufacturing of XERON Co., Ltd.), after the drying, estimate with visual by following benchmark.
In addition, described " slippage " brought thin informal voucher into though be meant the nozzle that does not spray.Described " omission " is meant the not nozzle of ejection, brought thick informal voucher into.
[metewand]
Zero: do not have slippage, omission
△: slippage is arranged
*: slippage, omission are arranged
(4) printing concentration
Use above-mentioned printer, carry out whole printing at PPC on recycled writing paper (Japan processing papermaking Co., Ltd. make), at room temperature, seasoning is after 24 hours, (Gretag-Macbeth company makes, article number: RD918) measure its optical concentration to use the Macbeth densitometer.
[metewand]
Zero: printing concentration is more than 1.40
△: printing concentration is more than 1.35 but less than 1.40
*: printing concentration is less than 1.35
(anti-mark)
Use above-mentioned printer, in PPC recycled writing paper (Japan processing papermaking Co., Ltd. makes) this printing of enterprising style of writing, (ゼ Block ラ Co., Ltd. makes with commercially available aqueous fluorescent pen after 3 minutes, after 10 minutes in visual observation, trade(brand)name: the pollution level of the printing sample when describing オ プ テ Star Network ス 1), estimate according to following benchmark.
[metewand]
◎: promptly use e-Pointer to describe, also hangover does not wait stain.
Zero: describe to produce hangover with e-Pointer, but practical no problem level.
△: describe to produce hangover with e-Pointer, contaminated.
*: describe with e-Pointer, produce hangover at whole, stain is very showy.
Can know that from the result shown in the table 1 the aqueous inkjet printing ink that embodiment obtains is on being printed onto common paper the time, high printing concentration, anti-mark excellence, and also ejection property is also excellent.
Can know in addition,, can suppress the adhesion of condensation product according to embodiments of the invention, ejection property excellence, in the time of on being printed onto common paper, high printing concentration, anti-mark (particularly after 10 minutes) excellence.
In addition, the printing ink that embodiment 2 and 3 obtains commercially available dedicated paper (photography paper＜gloss〉SeikoEpson Co., Ltd. makes trade(brand)name: when KA450PSK) going up printing, the glossiness of printed matter is also excellent.
When the water color ink that contains water dispersion for ink-jet printing of the present invention prints on common paper, high printing concentration, anti-mark excellence, and ejection property excellence.
That is to say, in water color ink of the present invention, owing to be mixed into the internal surface that pigment in the printing ink and polymer particle seldom stick to inkjet nozzle, even suppose adhesion is arranged, also can by self remove the dirt settling of nozzle internal surface from cleanliness (solvability of dirt settling), therefore can prevent the generation of " slippage " and " omission " that the obstruction because of the nozzle top causes.
In addition, according to the adherent method of inhibition condensation product of the present invention, can suppress the nozzle internal surface that condensation product adheres to inkjet head, so the straight ahead raising of the droplet of ink of ejection, ejection property is good.
In addition, even if condensation product adheres to the nozzle internal surface, also can be owing to printing ink self remove the dirt settling of nozzle internal surface from cleanliness (dirt settling solvability), suppress the deviation of the drippage position of droplet of ink, thereby obtain " slippage " and " omission " few good printing word, image.
Claims (9)
1. water dispersion for ink-jet printing, this water dispersion comprises: have the self-dispersion type pigment (A) and the polymer particle (B) of salt-forming group, this polymer particle (B) be have self-contained salt-forming group monomer (a) structural unit and from the polymer particle structural unit of silicone macromolecule monomer (b), that self-emulsifying polymer particle and/or letex polymerization form; And polymer particle (B) has and the identical salt-forming group of self-dispersion type pigment (A).
2. water dispersion for ink-jet printing according to claim 1, wherein, self-dispersion type pigment (A) is carbon black.
3. water dispersion for ink-jet printing according to claim 1 and 2, wherein, salt-forming group is a carboxyl.
4. water dispersion for ink-jet printing according to claim 1 and 2, wherein, the containing ratio from the structural unit of silicone macromolecule monomer (b) of polymer particle (B) is 15～80 weight %.
5. water dispersion for ink-jet printing according to claim 1 and 2, wherein, self-dispersion type pigment (A) is 20/80～90/10 with the weight ratio of polymer particle (B).
6. water-based ink for use in ink-jet recording, this printing ink contains each described water dispersion in the claim 1～5.
7. one kind is suppressed condensation product to the adherent method of inkjet nozzle internal surface, this method is to suppress condensation product to the adherent method of nozzle internal surface in the ink-jet recording that uses polymer particle, wherein, polymer particle be have self-contained salt-forming group monomer (a) structural unit and from the polymer particle structural unit of silicone macromolecule monomer (b), that self-emulsifying polymer particle and/or letex polymerization form; Is more than 80 ° at the water dispersion of this polymer particle of coating on the substrate and polymeric film that drying forms with respect to the contact angle of water.
8. the adherent method of inhibition condensation product according to claim 7, wherein, polymer particle and pigment use together.
9. according to claim 7 or the adherent method of 8 described inhibition condensation products, wherein, polymer particle contains the structural unit of 15～80 weight % from silicone macromolecule monomer (b).
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
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| JP253425/2005 | 2005-09-01 | ||
| JP2005253427 | 2005-09-01 | ||
| JP2005253425A JP2007063463A (en) | 2005-09-01 | 2005-09-01 | Water-based ink for ink-jet recording |
| JP253427/2005 | 2005-09-01 | ||
| PCT/JP2006/317115 WO2007026768A1 (en) | 2005-09-01 | 2006-08-30 | Aqueous ink for inkjet recording |
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| CN101278016B true CN101278016B (en) | 2011-01-19 |
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| JP2008255170A (en) * | 2007-04-02 | 2008-10-23 | Kao Corp | Water-based ink for inkjet recording |
| JP2008284874A (en) * | 2007-04-20 | 2008-11-27 | Ricoh Co Ltd | Ink media set and ink cartridge, ink recording object, ink-jet recording method, and ink-jet recording device |
| JP5232443B2 (en) * | 2007-11-05 | 2013-07-10 | 花王株式会社 | Water-based ink for inkjet recording |
| JP4780118B2 (en) | 2008-02-07 | 2011-09-28 | 富士ゼロックス株式会社 | Method for producing display particles |
| JP5500854B2 (en) * | 2009-04-01 | 2014-05-21 | 富士フイルム株式会社 | Inkjet recording method and inkjet recorded matter |
| CA2776194C (en) * | 2009-09-30 | 2016-03-29 | Dai Nippon Printing Co., Ltd. | Ink composition |
| JP5902393B2 (en) * | 2011-03-03 | 2016-04-13 | ブラザー工業株式会社 | Droplet discharge head inspection method, droplet discharge head manufacturing method, and inspection liquid |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2000191967A (en) * | 1998-12-28 | 2000-07-11 | Kao Corp | Aqueous ink for ink-jet printing |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH1112512A (en) * | 1997-06-20 | 1999-01-19 | Toyo Ink Mfg Co Ltd | Ink jet printing liquid |
| JP3779107B2 (en) * | 1999-10-28 | 2006-05-24 | 花王株式会社 | Water-based ink for inkjet recording |
| JP2002020673A (en) * | 2000-04-10 | 2002-01-23 | Seiko Epson Corp | Method for manufacturing pigment dispersion, pigment dispersion obtained thereby, ink jet recording ink using the same, and recording method and recorded matter therewith |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2000191967A (en) * | 1998-12-28 | 2000-07-11 | Kao Corp | Aqueous ink for ink-jet printing |
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| CN101278016A (en) | 2008-10-01 |
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