CN1986659B - Water-based inks for ink-jet printing - Google Patents
Water-based inks for ink-jet printing Download PDFInfo
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- CN1986659B CN1986659B CN2006101701396A CN200610170139A CN1986659B CN 1986659 B CN1986659 B CN 1986659B CN 2006101701396 A CN2006101701396 A CN 2006101701396A CN 200610170139 A CN200610170139 A CN 200610170139A CN 1986659 B CN1986659 B CN 1986659B
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Abstract
The present invention relates to (i) a water dispersion for ink-jet printing which satisfies not only a high image density but also excellent dryness and high lighter-fastness or (ii) a water dispersion for ink-jet printing which are excellent in image uniformity, high lighter-fastness and dryness, and a water-based ink containing the water dispersion. There are provided a water dispersion for ink-jet printing including particles of a water-insoluble polymer containing carbon black in which (i) the carbon black contains volatile components in an amount of 3% by weight or more and has a specific surface area of less than 200 m2/g or (ii) the carbon black has a specific surface area of not less than 100 m2/g but less than 200 m2/g, and an amount of the water-insoluble polymer, an amount of the carbon black (CB) and the specific surface area of CB satisfy the relationship represented by the following formula (1).
Description
Technical field
The present invention relates to the water dispersion that uses in water-based ink for use in ink-jet recording and this printing ink.
Background technology
Thereby ink-jet recording is from very tiny nozzle droplet of ink directly to be sprayed onto recording-member to make it adhere to the recording mode that obtains literal or image.This mode because have easy panchromaticization and cheapness, can use common paper as recording-member, and the product that are printed are many advantages such as non-contacting, so very universal.
Special in the weathering resistance of printed matter or the viewpoint of water tolerance, using pigment in tinting material is that printing ink becomes main flow just gradually.(for example with reference to patent documentation 1～5).
Disclose a kind of water color ink that in vinyl polymer, contains pigment in the patent documentation 1, wherein, in order to give high image density, will use the graftomer of macromonomer (macromer) as vinyl polymer.
Disclose a kind of printing ink in the patent documentation 2, it is included in acrylic acid or the like organic high molecular compound that side chain has the cationic group, has acrylic acid or the like organic high molecular compound and the acidic carbon black of anionic property group at side chain.
A kind of printing ink is disclosed in the patent documentation 3, its particle by the water-insoluble vinyl polymer that contains carbon black is scattered in water and forms, the DBP oil number of this carbon black is more than the 100ml/100g, and this polymkeric substance is the water-insoluble vinyl polymer with salt-forming group.
A kind of spray ink Printing record use printing ink is disclosed in the patent documentation 4, it comprises the water dispersion of the water-insoluble vinyl polymer particle that contains carbon black, wherein, carbon black is below 5% at 950 ℃ volatile component, and one of at least not identical material that contains two or more primary particle sizes, specific surface area and DBP absorbed dose is as carbon black.
A kind of water color ink is disclosed in the patent documentation 5, in the polymer particle of the insoluble polymer that it has been neutralized by base by acidic group at the acid number with 60～200KOHmg/g and 30～80mol%, use that to contain pH be that the water dispersion of 1～6 carbon black forms.
But, also insufficient although these water color inks have improved image color etc. to a certain extent, require further to improve performance.
[patent documentation 1] is international to be disclosed No. 00/39226
[patent documentation 2] JP 2004-75820 number
[patent documentation 3] JP 2005-42005 number
[patent documentation 4] JP 2005-42098 number
[patent documentation 5] JP 2003-231831 number
Summary of the invention
The present invention relates to following [1]～[4].
[1] water dispersion for ink-jet printing, it is the water dispersion that contains the insoluble polymer particle of carbon black, wherein, the volatile component of this carbon black is that specific surface area is lower than 200m more than 3 % by weight
2/ g; The amount of the amount of polymers of this insoluble polymer and this carbon black (CB) and the relation of specific surface area satisfy following formula (1):
(CB amount * CB specific surface area)/insoluble polymer amount=50～600 (m
2/ g) (1).
[2] water-based ink for use in ink-jet recording, it contains the water dispersion of above-mentioned [1].
[3] water dispersion for ink-jet printing, it is the water dispersion that contains the insoluble polymer particle of carbon black, wherein, the specific surface area of this carbon black (CB) is 100m
2/ g is above and be lower than 200m
2/ g; The amount of the amount of polymers of this insoluble polymer and this carbon black (CB) and the relation of specific surface area satisfy above-mentioned formula (1).
[4] water-based ink for use in ink-jet recording, it contains the water dispersion of above-mentioned [3].
Embodiment
The present invention relates to satisfy image color, and the water dispersion that uses in the water-based ink for use in ink-jet recording of drying property and photostabilization (lighter-fastness) excellence and this printing ink.
The discoveries such as present inventor are in the water dispersion of the insoluble polymer particle that contains carbon black, by set insoluble polymer amount, volatile component amounts of carbon black how and the relation of specific surface area according to the mode that satisfies specific relational expression, image color be can satisfy, and excellent drying property and photostabilization given.
That is, the 1st scheme of the present invention is water dispersion for ink-jet printing, and it is the water dispersion that contains the insoluble polymer particle of carbon black, and wherein, the volatile component of this carbon black is that specific surface area is lower than 200m more than 3 % by weight
2/ g, the amount of the amount of polymers of this insoluble polymer, this carbon black (CB) and the relation of specific surface area satisfy following formula (1):
(CB amount * CB specific surface area)/insoluble polymer amount=50～600 (m
2/ g) (1).
In addition, the present invention relates to the water dispersion that uses in the water-based ink for use in ink-jet recording of image homogeneity, photostabilization and drying property excellence and this printing ink.
The discoveries such as present inventor are in the water dispersion of the insoluble polymer particle that contains carbon black, by set the amount of insoluble polymer amount, carbon black and the relation of specific surface area according to the mode that satisfies specific relational expression, then can give image homogeneity, photostabilization and drying property.
That is, the 2nd scheme of the present invention is water dispersion for ink-jet printing, and it is the water dispersion that contains the insoluble polymer particle of carbon black, and wherein the specific surface area of carbon black (CB) is 100m
2/ g is above and be lower than 200m
2/ g, the relation of the amount of polymers of this insoluble polymer, the amount of this carbon black and specific surface area satisfies above-mentioned formula (1).
(carbon black)
Among the present invention, in printing ink, become stable particulate in order to make carbon black, and consider that from viewpoints such as photostabilization, water tolerance carbon black is comprised in the insoluble polymer particle.
The relation of the amount of polymers of insoluble polymer, the amount of CB and specific surface area satisfies above-mentioned formula (1).Above-mentioned formula (1) is the inverse of the amount of polymers of CB per unit area, and value is little to show that then the amount of polymers of CB per unit area is many.In the scope that satisfies formula (1) and since can give cover carbon black polymer layer with suitable thickness, so image color, drying property, excellent in light-resistance.
The situation of the 1st scheme
Consider that from image color, drying property, sunproof viewpoint (CB amount * CB specific surface area)/insoluble polymer amount is 50～600m
2/ g, more preferably 100～500m
2/ g is particularly preferably 200～500m
2/ g.
Consider from image color, the inhomogeneity viewpoint of image, the volatile component of carbon black is more than 3%, preferred more than 4%, consider from dispersion stabilization, conservatory viewpoint, on be limited to below 20%, be preferably below 10%, more preferably below 8%, be preferably 3～20%, more preferably 3～10%, be particularly preferably 4～8%.If have the carbon black of the volatile component in this scope, then image color, image excellent in uniformity.
The specific surface area of carbon black (BET method) is lower than 200m
2/ g is preferably 190m
2Below/the g, 180m more preferably
2Below/the g.Lower limit is preferably 50m
2More than/the g, 70m more preferably
2More than/the g, be particularly preferably 100m
2More than/the g, be preferably 50m
2/ g is above and be lower than 200m
2The scope of/g, more preferably 70～190m
2The scope of/g is particularly preferably 100～180m
2The scope of/g.If have the carbon black of the specific surface area in this scope, then can give suitable thickness to the polymer layer that covers carbon black with less amount of polymers, and drying property, excellent in light-resistance, image homogeneity (disguise) is also excellent simultaneously.
Consider that from the viewpoint of drying property, photostabilization, image color the DBP of the carbon black that uses among the present invention (Dibutyl phthalate) oil number is preferably 40～400ml/100g, more preferably 40～300ml/100g is particularly preferably 50～200ml/100g.
It is 1～8 that the pH value of carbon black is preferably pH, and more preferably pH is 2～6, and more preferably pH is 2.5～5, and its average primary particle diameter is preferably 10～40nm, more preferably 10～30nm, more preferably 10～20nm.
The situation of the 2nd scheme
Consider that from image color, drying property, sunproof viewpoint (CB amount * CB specific surface area)/insoluble polymer amount is 50～600m
2/ g is preferably 100～500m
2/ g, more preferably 200～500m
2/ g is particularly preferably 250～500m
2/ g most preferably is 300～500m
2/ g.
The specific surface area of carbon black (BET method) is lower than 200m
2/ g is preferably 190m
2Below/the g, 180m more preferably
2Below/the g.Lower limit is preferably 100m
2More than/the g, 105m more preferably
2More than/the g, be particularly preferably 110m
2More than/the g, be preferably 100～190m
2The scope of/g, more preferably 110～180m
2The scope of/g.If have the carbon black of the specific surface area in this scope, then can give suitable thickness to the polymer layer that covers carbon black with less amount of polymers, and drying property, excellent in light-resistance, and image homogeneity (disguise) is also excellent.
Consider that from the viewpoint of printing concentration the DBP of carbon black (Dibutyl phthalate) oil number is preferably 80～400ml/100g, more preferably 85～300ml/100g, more preferably 90～200ml/100g.If have the carbon black of the oil number in this scope, then because volume is large, be easy to remain in print surface, so image color is excellent, and contain the dispersion stability excellence of the insoluble polymer particle of carbon black.
The volatile component of carbon black is preferably and is lower than 3%, more preferably below 2.5%.Lower limit is preferably more than 0.1%.If carbon black has the volatile component in this scope, the content of the volatile components such as the hydroxyl that then contains in carbon black or carboxyl is smaller, contains the insoluble polymer dispersion of particles excellent in stability of carbon black.
Consider that from the viewpoint of dispersion stabilization it is 6～11 that the pH value of carbon black is preferably pH, more preferably pH is 7～10, and more preferably pH is 8～9.5, and its average primary particle diameter is preferably 10～40nm, more preferably 10～30nm, more preferably 10～20nm.
In the measurement of above-mentioned various characteristics, volatile component is 950 ℃, the residual quantity (take ASTM D1620-60 as benchmark) of heating after 7 minutes, specific surface area is the value take ASTM D3037-81 as benchmark, the DBP oil number is the value take ASTM D2414-65T as benchmark, the value that pH is based on DIN ISO 787/9, use glass electrode that the pH of the aqueous suspension of carbon black is measured.Average primary particle diameter is the mean diameter (number average bead diameter of 100 particles) of measuring and calculating with electron microscope, when having major diameter and minor axis, measures major diameter.
As the kind of carbon black, can enumerate that furnace black (comprising dark furnace black, middle look furnace black), thermolamp are black, acetylene black, thermally oxidized black etc.Also can utilize gas phase or the surface-modification method such as liquid phase oxidation or Cement Composite Treated by Plasma of oxygenants such as using ozone, nitric acid, hydrogen peroxide, oxynitride that carbon black is carried out oxide treatment.
In the 1st scheme of the present invention, as the object lesson of the commercial carbon black that can obtain, can list MONARCH 1000 series, REGAL 400R series, the Mogul L of Cabot company system; The Special Black 500,350,250 of Degusa company system, 100 series, Color Black FW1, S170, S160,5,4,150T, 140U, U, V series; The #2350 of Mitsubishi chemical Co., Ltd's system, #2200B, #1000, #970 series etc.
In the above-mentioned commercially available carbon black, particularly preferably be: (specific surface area is 138 to the trade(brand)name " MogulL " of Cabot company system, the DBP oil number is 66, volatile component is 4.5), " REGAL400R " (specific surface area is 96, the DBP oil number is 69, volatile component is 3.5), (specific surface area is 200 for the trade(brand)name " Color Black S170 " of Degusa company system, the DBP oil number is 150, volatile component is 5.0), " Color Black S160 " (specific surface area is 150, oil number is 150, and volatile component is 5.0).
In the 2nd scheme of the present invention, as the object lesson of the commercial carbon black that can obtain, can list MONARCH 280,460,800 series, ELFTEX8, VULCAN P, 9A32, the XC72 series of Cabot company system; The NIPex 90,80,70,60,40,30 of Degusa company system, Printex 3, L6, L, P series; The #750B of Mitsubishi chemical Co., Ltd's system, #650B, #540, #30, #20, #10, #5, MA600, #3030B, #3040B, #3050B, #3350B; TOKABLACK SAF-HS, N234, IISAF-HS, HAF-HS, the N351 of Tokai Carbon Co., Ltd. system; Raven 2000,1500,1250,1200,1190,1170, the 890H of Colombian Co., Ltd. system, C series etc.
In above-mentioned commercially available carbon black, particularly preferably be: (specific surface area is 140 to the trade(brand)name of Cabot company system " VULCAN 9A32 ", the DBP oil number is 114, volatile component is 1.5), (specific surface area is 145 to the trade(brand)name of Degusa company system " NIPex 70 ", the DBP oil number is 123, volatile component is 1.2), " NIPex 60 " (specific surface area is 115, the DBP oil number is 114, volatile component is 1.0), (specific surface area is 142 to the trade(brand)name " SAF-HS " of Tokai Carbon Co., Ltd. system, the DBP oil number is 130, and volatile component is 0.4).
Above-mentioned carbon black can use separately or be used in combination more than two kinds.
Among the present invention, also can in water-insoluble vinyl polymer particle, contain carbon black mineral dye or pigment dyestuff in addition.In addition, also can as required they and pigment extender also be used.Mineral dye as beyond the carbon black can list metal oxide, metallic sulfide, metal chloride etc.As pigment dyestuff, can list azo pigment, disazo pigment, phthalocyanine pigment, quinoline Azone pigment, isoindolinone pigment, triazine dioxin pigment, perylene pigment, purple cyclic ketones (perinone) pigment, thioindigo pigment, anthraquinone pigment, quinophthalone pigment etc.As pigment extender, can list silicon-dioxide, calcium carbonate, talcum etc.
(insoluble polymer)
Consider that from obtaining the viewpoints such as excellent ejection reliability, image color water dispersion of the present invention uses is in water color ink carbon black to be included in the insoluble polymer particle and the water dispersion that forms.
Insoluble polymer as consisting of the insoluble polymer particle can list water-insoluble vinyl polymer, water-insoluble esters polymer, water-insoluble polyurethane polymer etc.Wherein, consider from the viewpoint of the stability of water dispersion, be preferably the water-insoluble vinyl polymer.
Among the present invention, so-called " insoluble polymer " refers at 105 ℃ after lower dry 2 hours, in the time of in making its water 100g that is dissolved in 25 ℃, its meltage be 10g following, be preferably following, the following polymkeric substance of 1g more preferably of 5g.When insoluble polymer has salt-forming group, according to the difference of its kind, above-mentioned meltage be the salt-forming group of insoluble polymer has been carried out in 100% with acetic acid or sodium hydroxide and the time meltage.
Consider that from the viewpoint that realizes enough image colors insoluble polymer is preferably the water-insoluble graftomer that contains the structural unit that comes from macromonomer (b).Insoluble polymer is particularly preferably following water-insoluble graftomer, it has at main chain and comprises the structural unit that comes from the monomer (a) that contains salt-forming group and the polymkeric substance that comes from the structural unit of hydrophobic monomer (c), has the structural unit that comes from macromonomer (b) at side chain.
As such water-insoluble graftomer, be preferably that copolymerization occurs the monomer mixture that makes the monomer (a) that contains salt-forming group (below be sometimes referred to as " (a) composition "), macromonomer (b) (below be sometimes referred to as " (b) composition ") and hydrophobic monomer (c) (below be sometimes referred to as " (c) composition ") (below be sometimes referred to as " monomer mixture ") and the water-insoluble vinyl polymer that forms.
(monomer (a) that contains salt-forming group)
Above-mentioned (a) composition is to consider and the material of use from the viewpoints such as dispersion stabilization that improve resulting dispersion, can list cationic monomer, anionic property monomer etc.Particularly, can use material of putting down in writing in Unexamined Patent 9-286939 communique page 5 the 7th hurdle the 24th row～this page the 8th hurdle the 29th row etc.As salt-forming group, can list carboxyl, sulfonic group, phosphate, amino, ammonium etc.
Typical example as cationic monomer, can list the monomer that contains unsaturated amine, the monomer that contains unsaturated ammonium salt etc., in these monomers, preferred (methyl) vinylformic acid-N, N-dimethylamino ethyl ester, N-(N ', N '-dimethylaminopropyl) (methyl) acrylamide.
As the typical example of anionic property monomer, can list unsaturated carboxylic acid monomer, unsaturated sulfonic acid monomer, unsaturated phosphorus acid monomer etc.
As unsaturated carboxylic acid monomer, can list vinylformic acid, methacrylic acid, β-crotonic acid, methylene-succinic acid, toxilic acid, fumaric acid, citraconic acid, 2-methacryloxy methylsuccinic acid etc.
As the unsaturated sulfonic acid monomer, can list styryl sulfonic acid, 2-acrylamide-2-methyl propane sulfonic, (methyl) vinylformic acid-3-sulfo group propyl ester, two (3-sulfo group propyl group)-itaconic esters 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.
From viewpoints such as dispersion stabilization, ejection reliabilities, in above-mentioned anionic property monomer, be preferably unsaturated carboxylic acid monomer, more preferably acrylic or methacrylic acid.
Above-mentioned (a) composition can use separately respectively or be used in combination more than two kinds.
(macromonomer (b))
Above-mentioned (b) composition is to consider and the material that uses from the viewpoints such as dispersion stabilization that raising contains the insoluble polymer particulate of carbon black, can list following macromonomer, namely number-average molecular weight is 500～100000, is preferably 1000～10000 and have a monomer of the polymerizability functional groups such as unsaturated group at an end.
In addition, (b) number-average molecular weight of composition can be by measuring as the gel permeation chromatography of solvent as the tetrahydrofuran (THF) that standard substance, usefulness contain 50 mM/ls acetic acid with polystyrene.
As the macromonomer of (b) composition, can list particularly following (b-1) styrenic macromonomer, (b-2) (methyl) alkyl-acrylates macromonomer, (b-3) and contain (methyl) esters of acrylic acid macromonomer of aromatic nucleus and (b-4) silicone macromonomer etc.
(b-1) styrenic macromonomer
So-called " styrenic macromonomer " refers to have the macromonomer from the structural unit of the styrene monomers (being called " b-1 monomer ") such as vinylbenzene, alpha-methyl styrene, Vinyl toluene.Be preferably vinylbenzene in the styrenic macromonomer.
For the styrenic macromonomer, for example can list at an end and have the styrene homopolymers of polymerizability functional group and have the multipolymer that is formed by vinylbenzene and other monomer copolymerization of polymerizability functional group at an end.Be preferably acryloxy or methacryloxy a terminal polymerizability functional group that exists, by making their copolymerization, can obtain having the water-insoluble graftomer of the structural unit that comes from the styrenic macromonomer.
As other monomer, such as listing vinyl cyanide, (methyl) described later alkyl acrylate (b-2 monomer) and (methyl) acrylic ester monomer (b-3 monomer) that contains aromatic nucleus except vinylbenzene etc.
Consider that from sunproof viewpoint the content of the structural unit that comes from styrene monomer in the side chain or in the styrenic macromonomer is preferably more than 60 % by weight, more preferably more than 70 % by weight, is particularly preferably more than 90 % by weight.
As commercial available styrenic macromonomer, such as the commodity that can list Toagosei Co., Ltd " AS-6 (S) " by name, " AN-6 (S) " and " HS-6 (S) " etc.
(b-2) (methyl) alkyl-acrylates macromonomer
So-called " (methyl) alkyl-acrylates macromonomer ", refer to have the macromonomer of following structural unit, described structural unit is 1～22 from having the carbonatoms that also can have hydroxyl, be preferably (methyl) acrylate (being called the b-2 monomer) that carbonatoms is 1～18 alkyl.
As (methyl) acrylate, particularly, can list (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) vinylformic acid (different) propyl ester, (methyl) 2-hydroxyethyl acrylate, (methyl) vinylformic acid (XOR uncle) butyl ester, (methyl) ethyl acrylate, (methyl) vinylformic acid (different) monooctyl ester, (methyl) vinylformic acid (different) ester in the last of the ten Heavenly stems, (methyl) vinylformic acid (different) stearyl etc.
For the side chain that contains from the structural unit of b-2 monomer, can obtain by making (methyl) alkyl-acrylates macromonomer generation copolymerization that has a polymerizability functional group at an end, such as listing methyl methacrylate class macromonomer, butyl acrylate class macromonomer, Propenoic acid, 2-methyl, isobutyl ester class macromonomer, lauryl methacrylate(LMA) class macromonomer etc.
For (methyl) alkyl-acrylates macromonomer, can list an end have polymerizability functional group (methyl) alkyl acrylate homopolymer and have the multipolymer that is formed by (methyl) alkyl acrylate and other monomer copolymerization of polymerizability functional group at an end, polymerizability functional group is preferably acryloxy or methacryloxy.As other monomer, such as listing above-mentioned styrene monomer (b-1 monomer), (methyl) acrylic ester monomer (b-3 monomer) that contains aromatic nucleus except vinylbenzene described later etc.
Consider from sunproof viewpoint, in the side chain or the content of the structural unit that comes from (methyl) acrylate in (methyl) alkyl-acrylates macromonomer maximum, be preferably more than 60 % by weight, more preferably more than 70 % by weight, be particularly preferably more than 90 % by weight.
(b-3) contain (methyl) esters of acrylic acid macromonomer of aromatic nucleus
So-called " (methyl) esters of acrylic acid macromonomer that contains aromatic nucleus " refers to have the macromonomer of structural unit of (methyl) acrylate (b-3 monomer) of self-contained aromatic nucleus.As (methyl) acrylate that contains aromatic nucleus, be preferably the monomer by following formula (2) expression.
CH
2＝CR
1COOR
2(2)
(in the formula, R
1Expression hydrogen atom or methyl, R
2It is that 7～22 aralkyl or carbonatoms are 6～22 aryl that expression also can have substituent, carbonatoms.)
Particularly, can list (methyl) benzyl acrylate, (methyl) phenyl acrylate, (methyl) vinylformic acid 2-phenyl chlorocarbonate, (methyl) vinylformic acid phenoxy ethyl, vinylformic acid-1-naphthalene ester, (methyl) vinylformic acid-2-naphthalene ester, (methyl) vinylformic acid phthalic imidine methyl esters, (methyl) vinylformic acid p-nitrophenyl ester, (methyl) vinylformic acid-2-hydroxyl-3-phenoxy group propyl ester, 2-hydroxypropyl phthalic acid-2-methacryloxy ethyl ester, phthalic acid-2-acryloxy ethyl ester etc.Wherein, be particularly preferably (methyl) benzyl acrylate.They can be distinguished separately use or mix more than two kinds and use.
The side chain that comprises the structural unit that comes from (methyl) acrylate that contains aromatic nucleus can obtain by making (methyl) esters of acrylic acid macromonomer generation copolymerization that contains aromatic nucleus that has a polymerizability functional group at an end.
For (methyl) esters of acrylic acid macromonomer that contains aromatic nucleus, can list at an end and have (methyl) Voncoat R 3310 that contains aromatic nucleus of polymerizability functional group and have the multipolymer that is formed by (methyl) acrylate that contains aromatic nucleus and other monomer copolymerization of polymerizability functional group at an end, polymerizability functional group is preferably acryloxy or methacryloxy.As other monomer, can list above-mentioned styrene monomer (b-1 monomer), (methyl) esters of acrylic acid (b-2 monomer) etc.
In side chain or contain in (methyl) esters of acrylic acid macromonomer of aromatic nucleus, the content of structural unit that comes from (methyl) acrylate that contains aromatic nucleus is maximum.
(b-4) silicone macromonomer
The water-insoluble graftomer that uses among the present invention also can have the organopolysiloxane chain as side chain.This side chain for example be preferably can by following formula (3) expression, make at an end and have the silicone macromonomer generation copolymerization of polymerizability functional group and obtain.
CH
2＝C(CH
3)-COOC
3H
6-[Si(CH
3)
2O]
t-Si(CH
3)
3(3)
(in the formula, t represents 8～40 number)
When employed polymkeric substance is the water-insoluble graftomer among the present invention, consider that from the viewpoint that improves photostabilization and storage stability the weight ratio of [main chain/side chain] is preferably 1/1～20/1, more preferably 3/2～15/1, be particularly preferably 2/1～10/1.In addition, polymerizability functional group is set as in side chain, contains and calculate its weight ratio.
In above-mentioned, from improving and the affinity of carbon black and the viewpoint consideration that improves storage stability, be preferably the styrenic macromonomer that has polymerizability functional group at an end.
(hydrophobic monomer (c))
Consider from improving the viewpoints such as water tolerance, photostabilization, can use the hydrophobic monomer of above-mentioned (c) composition, can list (methyl) alkyl acrylate, alkyl (methyl) acrylamide, contain the monomer of aromatic nucleus etc.
As (methyl) alkyl acrylate, can enumerate (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) vinylformic acid (different) propyl diester, (methyl) vinylformic acid (XOR uncle) butyl ester, (methyl) vinylformic acid (different) amyl group ester, (methyl) cyclohexyl acrylate, (methyl) 2-ethylhexyl acrylate, (methyl) vinylformic acid (different) octyl group ester, (methyl) vinylformic acid (different) decyl ester, (methyl) vinylformic acid (different) dodecyl ester, (methyl) vinylformic acid (different) cetyl ester, (methyl) vinylformic acid (different) stearyl, (methyl) vinylformic acid (different) docosyl ester etc. has (methyl) acrylate that carbonatoms is 1～30 alkyl.Wherein, consider from the viewpoint of dispersion stabilization, (methyl) acrylate that preferably have carbonatoms and be 8～30, preferred carbonatoms is 12～22 chain alkyl is particularly preferably (methyl) vinylformic acid (different) Lauryl Ester, (methyl) vinylformic acid (different) stearyl, (methyl) vinylformic acid (different) docosyl ester.
As alkyl (methyl) acrylamide, can list dimethyl (methyl) acrylamide, diethyl (methyl) acrylamide, dibutyl (methyl) acrylamide, the tertiary butyl (methyl) acrylamide, octyl group (methyl) acrylamide, dodecyl (methyl) acrylamide etc. and have (methyl) acrylamide that carbonatoms is 1～22 alkyl.
As the monomer that contains aromatic nucleus, can preferably list the styrene monomers (c-1) such as vinylbenzene, 2--vinyl toluene, Vinyl toluene; (methyl) acrylic acid aryl ester, vinyl xylene, ethyl vinyl benzene, 4-vinyl biphenyl, 1，1-diphenylethylene, vinyl naphthalene, the chlorostyrenes etc. such as (methyl) benzyl acrylate, (methyl) vinylformic acid phenoxy ethyl contain the vinyl monomer (c-2) that carbonatoms is 6～22 aromatic series base.
In addition, " (XOR uncle) " and " (different) " described in this specification sheets refers to comprise that these groups exist and non-existent both of these case, when these groups do not exist, and expression " just ".In addition, " (methyl) acrylate " expression comprises the both of these case of acrylate and methacrylic ester.
As (c) composition, consider preferably have carbonatoms and be (methyl) acrylate of 8～30 chain alkyl and/or contain the monomer of aromatic nucleus from improving the viewpoints such as image color, photostabilization.
Above-mentioned (c) composition can use separately respectively or be used in combination more than two kinds.
In the present invention, the monomer mixture that contains above-mentioned (a), (b), (c) each composition preferably further contains the monomer (d) (below be sometimes referred to as " (d) composition ") of hydroxyl.
(d) composition is the material that improves dispersion stabilization.As (d) composition, for example can list (methyl) vinylformic acid-2-hydroxyl ethyl ester, (methyl) vinylformic acid-3-hydroxypropyl acrylate, (n=2～30, n represents the average addition mole number of oxyalkylene group to polyoxyethylene glycol.Below identical) (methyl) acrylate, (polypropylene glycol (n=2～30) methyl) acrylate, poly-(ethylene glycol (n=1～15)/propylene glycol (n=1～15)) (methyl) acrylate etc.Wherein, be preferably (methyl) vinylformic acid-2-hydroxyl ethyl ester, polyethylene glycol monomethacrylate, polypropylene glycol methacrylic ester.
Above-mentioned monomer mixture can also contain by the monomer (e) of following formula (4) expression (below be sometimes referred to as " (e) composition ").
CH
2＝C(R
3)COO(R
4O)
p-R
5(4)
(in the formula, R
3Expression hydrogen atom or carbonatoms are 1～5 alkyl, R
4It is 1～30 bivalent hydrocarbon radical that expression also can have heteroatomic carbonatoms, R
5It is 1～30 monovalence alkyl that expression also can have heteroatomic carbonatoms, and p represents average addition mole number, and it is 1～60, be preferably 1～30 number.)
(e) even composition is the composition that can show the effect of the excellence that the ejection reliability continuous printing that improves water color ink can suppress that also dislocation (slippage) occurs etc.
In formula (4), as R
4And R
5In the heteroatoms that also can have, for example can list nitrogen-atoms, Sauerstoffatom, halogen atom or sulphur atom.
As with R
4Or R
5The typical example of group of expression can list carbonatoms and be 6～30 aromatic series base, carbonatoms and be 3～30 heterocyclic radical, carbonatoms and be 1～30 alkylidene group, and these groups also can have substituting group.These groups also can be used in combination more than two kinds.As substituting group, can list aromatic series base, heterocyclic radical, alkyl, halogen atom, amino etc.
As above-mentioned R
4, preferably list carbonatoms and be 1～24 can have also that substituent phenylene, carbonatoms are 1～30, preferred carbonatoms is 1～20 aliphatics alkylidene group, carbonatoms with aromatic nucleus is that 7～30 alkylidene group and the carbonatoms with heterocycle are 4～30 alkylidene group.As R
4The particularly preferred object lesson of O base can list the inferior heptyl of oxyethylene group, oxidation (different) propenyl, oxybutylene, oxidation, oxidation hexylidene or is 2～7 oxyalkylene group or oxidation phenylene by more than one carbonatomss that form in these oxyalkylene groups.
As R
5, the carbonatoms that can list phenyl, carbonatoms and be 1～30, preferably also can have a side chain is that 1～20 aliphatic alkyl, the carbonatoms with aromatic nucleus are that 7～30 alkyl or the carbonatoms with heterocycle are 4～30 alkyl.As R
5Preferred example can list the carbonatomss such as methyl, ethyl, (different) propyl group, (different) butyl, (different) amyl group, (different) hexyl and be 1～12 alkyl, phenyl etc.
Object lesson as (e) composition, can list methoxy poly (ethylene glycol) (p in the above-mentioned formula (4) is 1～30) (methyl) acrylate, methoxyl group poly-1,4-butyleneglycol (p=1～30) (methyl) acrylate, oxyethyl group polyoxyethylene glycol (p=1～30) (methyl) acrylate, isopropoxy polyoxyethylene glycol (p=1～30) (methyl) acrylate, butoxy polyoxyethylene glycol (p=1～30) (methyl) acrylate, octyloxy polyoxyethylene glycol (p=1～30) (methyl) acrylate, methoxyl group polypropylene glycol (p=1～30) (methyl) acrylate, methoxyl group (ethylene glycol/propylene glycol copolymerization) (p=1～30, wherein ethylene glycol partly is 1～29) (methyl) acrylate etc.Wherein, be preferably methoxy poly (ethylene glycol) (p=2～20) (methyl) acrylate, octyloxy polyoxyethylene glycol (p=2～20) (methyl) acrylate.
As the object lesson of commercial (d) that can obtain, (e) composition, can enumerate polyfunctional acrylate's monomer (NK ester) M-40G, M-90G, M-230G, the BLEMMER series of NOF Corp, PE-90, 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, the 50POEP-800B etc. of the middle village chemical industry Co., Ltd. that makes new advances.
Above-mentioned (d) composition and (e) composition can use separately respectively or be used in combination more than two kinds.
When the manufacturing of insoluble polymer, the content from the structural unit of (a)～(e) composition in the content of above-mentioned (a)～(e) composition in monomer mixture (as the content of dosis neutralisata not, below identical) or the insoluble polymer is as follows.
Consider that from the viewpoints such as dispersion stabilization of the dispersion that obtains (a) content of composition is preferably 1～50 % by weight, more preferably 2～40 % by weight are particularly preferably 3～30 % by weight, are particularly preferably 5～20 % by weight.
Consider that from the viewpoints such as dispersion stabilization of the dispersion that obtains (b) content of composition is preferably 1～50 % by weight, more preferably 3～40 % by weight are particularly preferably 5～35 % by weight.
Consider that from viewpoints such as water tolerance, photostabilization (c) content of composition is preferably 5～90 % by weight, more preferably 5～80 % by weight, more preferably 10～60 % by weight.
Consider from viewpoints such as the long-term storing stability of the water color ink that obtains, ejection reliabilities, (a) content of composition and (b) composition and (c) weight ratio of the total content of composition ((a)/[(b)+(c)]) be preferably 0.01～1, more preferably 0.02～0.7, more preferably 0.05～0.5.
Consider that from the viewpoint of redispersibility, dispersion stabilization (d) content of composition is preferably 1～40 % by weight, more preferably 2～30 % by weight, more preferably 5～25 % by weight.
Consider that from viewpoints such as ejection reliability, dispersion stabilizations (e) content of composition is preferably 1～50 % by weight, more preferably 2～30 % by weight, more preferably 5～30 % by weight.
Consider from viewpoints such as the stability water, water tolerance, (a) composition and (d) total content of composition be preferably 5～60 % by weight, more preferably 7～50 % by weight, more preferably 10～40 % by weight.
In addition, consider from the dispersion stabilization water, viewpoint such as ejection reliability etc., (a) composition and (e) total content of composition be preferably 5～75 % by weight, more preferably 7～50 % by weight, more preferably 10～40 % by weight.
Consider from the viewpoint of the dispersion stabilization water and ejection reliability, as required, (a) composition, (d) composition and (e) total content of composition be preferably 5～60 % by weight, more preferably 7～50 % by weight, more preferably 10～40 % by weight.
The insoluble polymer that consists of insoluble polymer particle of the present invention can pass through the known polymerization processs such as mass polymerization, solution polymerization process, suspension polymerization, emulsion polymerization method, make above-mentioned monomer mixture copolymerization and make, in these polymerization processs, in the situation of solution polymerization process, be particularly suitable for obtaining high image density and high bleeding resistance texts.
As employed solvent in the solution polymerization process, be preferably the polar organic solvent high with the affinity of insoluble polymer, be preferably the solubleness in water under 20 ℃ and be the solvent below 50 % by weight, more than 5 % by weight.As polar organic solvent, such as listing the Fatty Alcohol(C12-C14 and C12-C18) such as butyl cellosolve; The fragrant same clan such as toluene, dimethylbenzene; The ketones such as methylethylketone, methyl-isobutyl copper; The ester classes such as vinyl acetic monomer etc.Wherein, be preferably methylethylketone, methyl iso-butyl ketone (MIBK), toluene, dimethylbenzene, butyl cellosolve or in them more than a kind with the mixed solvent of water.
When polymerization, can use 2,2 '-azobis isobutyronitrile, 2, the known polymerization starters such as organo-peroxide such as the two azo-compounds such as (2,4-methyl pentane nitriles) of 2 '-azo, t-butyl peroxy octanoate, dibenzoyl base oxide.
With respect to per 1 mole monomer mixture, the consumption of polymerization starter is preferably 0.001～5 mole, more preferably 0.01～2 mole.
During polymerization, can further add the known polymerizable chain transfer agents such as the thio-alcohols such as octyl mercaptan, 2 mercapto ethanol, thiuram disulfide class.
And different, usually, polymerization temperature is 30～100 ℃ to the polymerizing condition of monomer mixture, is preferably 50～80 ℃ according to the kind of employed polymerization starter, monomer, solvent etc.; Polymerization time is preferably 1～20 hour.In addition, polymerization atmosphere gas is preferably the inert atmosphere gases such as nitrogen atmosphere gas, argon.
After polyreaction finishes, can by from the reaction soln redeposition, heat up in a steamer the polymkeric substance that the known method such as desolventizing is emanated out and generated.In addition, the polymkeric substance of gained can be removed unreacted monomer etc. by repeatedly redeposition, membrane sepn, chromatography, extraction process etc. and makes with extra care.
Consider that from viewpoints such as the dispersion stabilization of carbon black, water tolerance, ejection reliabilities the weight-average molecular weight of the insoluble polymer that obtains is preferably 5000～500000, more preferably 8000～400000, be particularly preferably 10000～300000.
In addition, the weight-average molecular weight of polymkeric substance can by with polystyrene as reference material, used the chloroform of the dodecyl-dimethyl amine that contains 1mmol/L to measure weight-average molecular weight as the gel permeation chromatography of solvent.
Under above-mentioned insoluble polymer has situation from the salt-forming group of the monomer that contains salt-forming group (a), neutralize with neutralizing agent, as neutralizing agent, can select according to the kind of the salt-forming group in the polymkeric substance, can use acid or alkali, such as listing the acid such as hydrochloric acid, acetic acid, propionic acid, phosphoric acid, sulfuric acid, lactic acid, succsinic acid, oxyacetic acid, glyconic acid, R-Glyceric acid, the alkali such as lithium hydroxide, sodium hydroxide, potassium hydroxide, ammonia, methylamine, dimethylamine, Trimethylamine 99, ethamine, diethylamine, triethylamine, trolamine, Tributylamine.
The degree of neutralization of salt-forming group is preferably 10～200%, and more preferably 20～180%, be particularly preferably 50～150%.Wherein, when salt-forming group was the anionic property group, degree of neutralization can be tried to achieve according to following formula.
{ [equivalent of the weight of neutralizing agent (g)/neutralizing agent]/[weight (g)/(56 * 1000) of the acid number of polymkeric substance (KOHmg/g) * polymkeric substance] } * 100
When salt-forming group was the cationic group, degree of neutralization can be tried to achieve by following formula.
{ [equivalent of the weight of neutralizing agent (g)/neutralizing agent]/[weight (g)/(36.5 * 1000) of the amine value (HCLmg/g) of polymkeric substance * polymkeric substance] } * 100
Acid number or amine value can calculate from the structural unit of polymkeric substance, but after also polymkeric substance can being dissolved in suitable solvent (for example methylethylketone), utilize the method for titration to try to achieve.
(manufacture method of water dispersion)
The water dispersion that contains the insoluble polymer particle (hereinafter referred to as " particle that contains CB ") of carbon black preferably obtains by following operation (1) and (2).
Operation (1): will contain insoluble polymer, organic solvent, carbon black, water and as required and the mixture of the neutralizing agent that uses carries out the operation of dispersion treatment;
Operation (2): the operation of removing above-mentioned organic solvent.
In operation (1), preferred way is: at first, then above-mentioned insoluble polymer is dissolved in the organic solvent,, with carbon black, water, as required and the neutralizing agent that uses, tensio-active agent etc. join and mix in the above-mentioned organic solvent, obtain the dispersion of oil-in-water-type.In mixture, carbon black is preferably 5～50 % by weight, and organic solvent is preferably 10～70 % by weight, and insoluble polymer is preferably 2～40 % by weight, and water is preferably 10～70 % by weight.Have at insoluble polymer in the situation of salt-forming group, preferably use neutralizing agent, but also can neutralize to insoluble polymer with neutralizing agent in advance.There is no particular limitation for degree of neutralization.Usually, the liquid property of the water dispersion that finally obtains is for neutral, and for example, pH is preferably 4～10.Also can determine pH according to the desirable degree of neutralization of above-mentioned insoluble polymer.
As organic solvent, preferably list alcoholic solvent, ketones solvent and ether solvent, preferably be below 50 % by weight and be solvent more than 10 % by weight in the solubleness in water under 20 ℃.
As alcoholic solvent, can list ethanol, Virahol, various butanols, Pyranton etc.; As ketones solvent, can list acetone, methylethylketone, metacetone, methyl iso-butyl ketone (MIBK) etc.; As ether solvent, can list two dibutyl ether, tetrahydrofuran (THF), diox etc.In these solvents, be preferably Virahol, acetone and methylethylketone, be particularly preferably methylethylketone.These solvents can use separately or mix more than two kinds and use.
As neutralizing agent, different according to the kind of the salt-forming group in the insoluble polymer, can use acid or alkali, also can use above-mentioned neutralizing agent.
There is no particular limitation for the dispersing method of mixture in the above-mentioned operation (1).Preferably behind pre-dispersed carrying out, apply again shear-stress and lead dispersion.
Mixture is being carried out when pre-dispersed, can use the mixed stirring devices commonly used such as anchor fluke stirring rake.Among mixed whipping appts, be preferably the high-speed stirring mixing apparatus.
As the device that applies the main shear-stress that disperses, such as listing the milling machines such as rolling mill, ball mill, kneader, extrusion machine, homogeneous phase valve formula or chamber type high-pressure homogenizer etc.
In above-mentioned operation (2), by from the dispersion of above-mentioned operation (1) gained, heating up in a steamer organic solvent and become water-based, thereby can obtain having the water dispersion of the particle that contains CB of desirable median size.Can remove organic solvent contained in the water dispersion by common methods such as underpressure distillation.Organic solvent in the resulting water dispersion that comprises the particle that contains CB is substantially removed, and the amount of organic solvent is preferably below 0.1 % by weight, more preferably below 0.01 % by weight.In addition, in order to obtain to have the particle that contains CB of desirable particle diameter, also can carry out centrifugation and classification to this water dispersion.Preferably by the resulting water dispersion that comprises the particle that contains CB is filtered to remove oversize particle.For oversize particle not being existed or having the nozzle of seldom measuring not stop up printer, the particle diameter of filter membrane is preferably 0.45～10 μ m, more preferably 0.8～5 μ m.
The water dispersion that contains the particle of CB is that the solid state component that will contain the insoluble polymer of carbon black is scattered in take water and forms in main solvent.Here, there is no particular limitation to the form of the particle that contains CB, so long as at least by carbon black and insoluble polymer and the particle that forms is just passable.Such as comprising: in insoluble polymer, contain the particle shape of carbon black, in insoluble polymer, be dispersed with equably carbon black particle shape, expose particle shape of carbon black etc. at the particle surface of insoluble polymer.
From viewpoints such as the obstruction that prevents printer nozzle, dispersion stabilizations, the average primary particle diameter that contains the particle of CB is preferably 10～500nm, and more preferably 30～300nm is particularly preferably 50～200nm.Median size is measured with measuring method described later.
The water dispersion of insoluble polymer particle can directly use as the water color ink take water as main solvent, but also can be added on wetting agent commonly used in the water-based ink for use in ink-jet recording, permeate agent, dispersion agent, viscosity modifier, defoamer, mould inhibitor, rust-preventive agent etc.
Consider that from viewpoints such as dispersion stabilization, image colors the content of carbon black is preferably 1～30 % by weight in water dispersion of the present invention and the water color ink, more preferably 2～20 % by weight, more preferably 2～15 % by weight.In addition, consider from viewpoints such as image color, drying property and photostabilization, the ratio of the amount of insoluble polymer and carbon black, namely the weight ratio of [carbon black/insoluble polymer] is preferably 50/50～90/10, and more preferably 50/50～78/22, more preferably 55/45～75/25.
In addition, consider from the viewpoint of image color and ejection reliability, wish the content (solid state component) that contains the particle of CB in water dispersion and the water color ink is regulated, make it be preferably 0.5～30 % by weight, more preferably 1～15 % by weight.
In water dispersion of the present invention and the water color ink, the content of water is preferably 30～90 % by weight, more preferably 40～80 % by weight.
Preferred surface tension (20 ℃) for water dispersion of the present invention and water color ink as water dispersion, is preferably 30～72mN/m, more preferably 40～72mN/m; As water color ink, be preferably 25～50mN/m, more preferably 27～45mN/m.
In order to form the water color ink with preferred viscosity, the viscosity (20 ℃) of 20 % by weight (solid state component) of water dispersion of the present invention is preferably 1～12mPas, and more preferably 1～9mPas is particularly preferably 2～8mPas.In addition, in order to keep good ejection reliability, the viscosity of water color ink (20 ℃) is preferably 2～20mPas, and more preferably 2.2～15mPas is particularly preferably 2.4～12mPas.
Embodiment
In following Production Example, embodiment and comparative example, if not special record, then " part " and " % " is " weight part " and " % by weight ".
Production Example 1 and 2 (preparation of polymers soln)
In reaction vessel, mix after adding 40.1 parts of initial charge monomer solutions (representing with weight part) shown in the table 1, and carry out sufficient nitrogen replacement, obtained mixing solutions.
On the other hand, in dropping funnel, add 160.4 parts of dropping monomer (representing with the weight part) solution shown in the table 1, carry out sufficient nitrogen replacement, obtained mixing solutions.
Under nitrogen atmosphere, on one side the interior mixing solutions of stirring reaction container, be warmed up to 75 ℃ on one side, in 3 hours, the mixing solutions in the dropping funnel is added drop-wise in the reaction vessel lentamente.After dripping end, the liquid temperature of this mixing solutions was kept 2 hours under 75 ℃, then will in 5 parts of methylethylketones, dissolve 0.3 part of polymerization starter (2,2 '-azo two (2, the 4-methyl pentane nitrile)) solution that forms joins in this mixing solutions, again 75 ℃ of lower slakings 3 hours, 85 ℃ of lower slakings 2 hours, thereby obtained polymers soln.
105 ℃ of lower drying under reduced pressure 2 hours, desolventizing was separated thus with the part of resulting polymers soln.By with polystyrene as reference material, used the chloroform of the dodecyl-dimethyl amine that contains 1mmol/L to measure weight-average molecular weight as the gel permeation chromatography of solvent.
The results are shown in table 1.In addition, the weight part of the numeric representation effective constituent of each monomer in the table.
[table 1]
*1: Toagosei Co., Ltd's system, trade(brand)name: AS-6S, number-average molecular weight: 6000
*2: NOF Corp, trade(brand)name: PP500
(the average addition mole number of propylene oxide=9, end is hydrogen atom)
*3: Xin Zhong village chemical industry Co., Ltd., exploitation product
(the average addition mole number of ethylene oxide=4, end is the 2-ethylhexyl)
Embodiment 1 (containing the water dispersion of particle of CB and the manufacturing of water color ink)
25 parts in the polymkeric substance that will carry out drying under reduced pressure to the polymers soln that is obtained by Production Example 1 and obtain is dissolved in 25 parts of the methylethylketones, and be 65% neutralizing agent (5N aqueous sodium hydroxide solution) to wherein adding with respect to acid number, salt-forming group is neutralized, add again 75 parts of carbon blacks, [(CB amount * CB specific surface area)/insoluble polymer amount] is adjusted into 435, add again an amount of methylethylketone, ion exchanged water is to form mobile and fully to stir, then used three roller roller mills (Noritake of Co., Ltd. system, commodity are called " NR-84A ") mixing 2 hours.
The cream of gained is stuck with paste in the ion exchanged water that drops into 250 parts, after fully stirring, used vaporizer to heat up in a steamer methylethylketone and water, thereby obtained the water dispersion that the solid state component amount is 20% the particle that contains CB.Obtain by the following method the median size of the particle of the resulting CB of containing.This results are shown in table 2.
With 25 parts of the water dispersions of the particle that contains CB obtained above, 10 parts of glycerine, 2-{2-(2-butoxy oxyethyl group) oxyethyl group } 5 parts of ethanol, 2 parts of hexylene glycols, acetylenediol (acetylene glycol) EO affixture (n=10) (Kawaken Fine Chemical Co., Ltd., commodity are called " ACETYLENOL E100 ") 57.5 parts of 0.5 part and ion exchanged waters mix, with the mixed solution that obtains membrane filter (the Sartorius company system with 1.2 μ m, commodity are called " Minisart ") filter, thus obtained water color ink.
Embodiment 2-5 and comparative example 1～3 (containing the water dispersion of particle of CB and the manufacturing of water color ink)
The polymer dissolution that to carry out drying under reduced pressure to the polymers soln that is obtained by Production Example 1 or 2 and obtain is in the methylethylketone of same amount, and be 65% neutralizing agent (5N aqueous sodium hydroxide solution) to wherein adding with respect to acid number, salt-forming group is neutralized, add again the carbon black shown in the table 2, add again an amount of methylethylketone, ion exchanged water to form mobile and to stir fully, then used three roller roller mills (Noritake of Co., Ltd. system, commodity are called " NR-84A ") mixing 2 hours.Use the method identical with embodiment 1 to process the mixing thing that obtains, obtained to contain the water dispersion of the particle of CB.And then, use the method identical with embodiment 1 to obtain water color ink.
Embodiment 6～8 and comparative example 4～6 (containing the water dispersion of particle of CB and the manufacturing of water color ink)
Obtained water color ink with the method identical with embodiment 2～5 and comparative example 1～3.
[measurement of median size]
The laser particle analytical system ELS-8000 of Shi Yong Otsuka Electronics Co., Ltd. (cumulative analysis, cumulant analysis) measures under the following conditions.
Temperature: 25 ℃
The angle of incident light and detector: 90 °
Cumulative frequency: 200 times
The specific refractory power of dispersion solvent: the specific refractory power of water (1.333)
Measure concentration: about 5 * 10
-3% by weight
[measurement of CB specific surface area] is take ASTM D3037-81 as benchmark
[measurement of DBP oil number] is take ASTM D2414-65T as benchmark
[measurement of volatile component]
In the residual quantity (take ASTM D1620-60 as benchmark) of 950 ℃ of lower heating after 7 minutes.
Estimate the physical property of the water color ink that is obtained by each embodiment and each comparative example based on following method.This results are shown in table 2 and table 3.
(1) ejection reliability
Use the ink-jet printer (production number: EM-930C of commercially available Seiko Epson Co., Ltd., the piezoelectricity mode), upper with 100 of 2000 a literal/continuous printing at common paper P paper (Fuji Xerox Co., Ltd. system), then printing comprises literal, the test file of whole image (solid images) and gage line (ruled-lines), estimate following three projects: (i) form lines clearly and literal clearly, (ii) uniform whole image, and the gage line that (iii) does not have dislocation, and estimate according to following judging criterion.
[judging criterion]
Zero: three project all satisfies (no problem)
△: three projects roughly satisfy (no problem in the practicality)
*: one is not satisfied (problem is arranged in the practicality) more than the project
(2) image color
Print whole image at the common paper P paper identical with above-mentioned (1), recycled writing paper G100, C2 (Fuji Xerox Co., Ltd. system), place after 1 day, use optical concentration meter SpectrroEye (Gretag-Macbeth company system) to measure arbitrarily 10 places, obtain mean value.
(3) image homogeneity (disguise)
At the common paper P paper identical with above-mentioned (1), whole image of recycled writing paper G100, the C2 identical with above-mentioned (2) printing, whether irregular colour is even carries out sensory evaluation to having, and estimates according to following judging criterion.
[judging criterion]
Zero: do not have irregular colour to spare (not coming off)
△: have a little an irregular colour even.
*: there is irregular colour to spare (blank is arranged)
(4) color is oozed profit
To the common paper P paper identical with above-mentioned (1), recycled writing paper G100, the C2 identical with above-mentioned (2), made following pattern, namely at the back side of having printed the literal of 10 points with the 1st liquid composition, printed the 2nd liquid composition, the profit of oozing to word segment is carried out sensory evaluation, and estimates according to following judging criterion.
[judging criterion]
Zero: Chinese character, hiragana reproduce all no problemly.
△: the part Chinese character can not reproduce, and is not preferred in the practicality.
*: can not debate and read Chinese character, hiragana.
(5) drying property
Whole image in the common paper P paper identical with above-mentioned (1), photochrome precision work paper (Fuji Xerox Co., Ltd. system) printing 20mm * 20mm size, above the printed images after per 10 seconds after just printing finishes, after 30 seconds, after 60 seconds, stack the back side of other common paper P paper, apply 490g (load area is the load of 43mm * 30mm) from the top again, whole imaging surface moved, measure the pollution condition of the paper that stacks.Estimate according to following judging criterion.
[judging criterion]
Zero: print comes off hardly, does not have blackening on every side.
△: print comes off hardly, and a blackening is arranged on every side a little, but practical no problem.
*: print is come off by friction, becomes very black on every side, points also quite dirty.
(6) photostabilization
Use printer and paper same as described above, carry out test printing, after 6 hours, with commercially available e-Pointer (Zebra company system, commodity are called " BEAM LINER S BM-151 ") the test pattern image planes are coated with retouch, the pollution level of the printed sample that detects by an unaided eye is estimated photostabilization according to following judging criterion.
[judging criterion]
Zero: namely use e-Pointer to be coated with and retouch also generation hangover stains such as (rubbed staines).
△: be coated with a little a bit hangover when retouching with e-Pointer, but practical no problem.
*: be coated with e-Pointer and produce hangover when retouching, very dirty.
[table 2]
*1:CB-1:Degusa company system, Special Black350 (specific surface area is that 65, DBP oil number is 45, and volatile component is 3.5)
CB-2:Cabot company system, Mogul L (specific surface area is that 138, DBP oil number is 60, and volatile component is 4.5)
CB-3:Cabot company system, Regal 400R (specific surface area is that 96, DBP oil number is 69, and volatile component is 3.5)
CB-4:Degusa company system, Color Black S160 (specific surface area is that 150, DBP oil number is 150, and volatile component is 5.0)
CB-5: Mitsubishi chemical Co., Ltd's system, #2600 (specific surface area is that 370, DBP oil number is 77, and volatile component is 1.8)
CB-6:Cabot company system, Regal 330R (specific surface area is that 94, DBP oil number is 71, and volatile component is 1.0)
CB-7:Degusa company system, FW18 (specific surface area is that 260, DBP oil number is 160, and volatile component is 5.0)
[table 3]
*2:CB-1:Degusa company system, NIPex 70 (specific surface area is that 145, DBP oil number is 123, and volatile component is 1.2)
CB-2:Degusa company system, NIPex 60 (specific surface area is that 115, DBP oil number is 114, and volatile component is 1.0)
CB-3:Tokai Carbon Co., Ltd. system, SAF-HS (specific surface area is that 142, DBP oil number is 130, and volatile component is 0.4)
CB-4:Cabot company system, Regal 330R (specific surface area is that 94, DBP oil number is 71, and volatile component is 1.0)
CB-5:Cabot company system, M880 (specific surface area is that 220, DBP oil number is 110, and volatile component is 1.5)
CB-6: Mitsubishi chemical Co., Ltd's system, #2600 (specific surface area is that 370, DBP oil number is 77, and volatile component is 1.8)
CB-7:Degusa company system, FW18 (specific surface area is 260, DBP oil number 160, and volatile component is 5.0)
The water color ink that contains water dispersion for ink-jet printing of the 1st scheme of the present invention can satisfy image color, and drying property and excellent in light-resistance.
The image homogeneity of the water color ink that contains water dispersion for ink-jet printing of the 2nd scheme of the present invention, photostabilization and drying property are excellent.
Therefore, the water color ink of the 1st scheme of the present invention and the 2nd scheme print speed that can be applicable to carry out with ink-jet recording is in the high speed printing more than 80/minute.
Claims (6)
1. water dispersion for ink-jet printing, it is the water dispersion that contains the insoluble polymer particle of carbon black, and wherein, the volatile component of this carbon black is 4～8 % by weight, and specific surface area is 100～180m
2/ g, the DBP oil number is 50～200ml/100g;
Described insoluble polymer is to make the monomer mixture generation copolymerization that comprises the monomer (a), macromonomer (b) and the hydrophobic monomer (c) that contain salt-forming group and the water-insoluble vinyl polymer that forms,
Described macromonomer (b) is selected from styrenic macromonomer, (methyl) alkyl-acrylates macromonomer, contains (methyl) esters of acrylic acid macromonomer and the silicone macromonomer of aromatic nucleus,
Described hydrophobic monomer (c) is that to have carbonatoms be (methyl) alkyl acrylate of 8～30 chain alkyl and/or the monomer that contains aromatic nucleus,
The amount of polymers of this insoluble polymer and this carbon black are that the amount of CB and the relation of specific surface area satisfy following formula (1):
(CB amount * CB specific surface area)/insoluble polymer amount=200～500m
2/ g(1).
2. the water dispersion for ink-jet printing of claim 1 record, wherein, the volatile component of described carbon black is 5.0 % by weight, specific surface area is 150m
2/ g, the DBP oil number is 150ml/100g.
3. water dispersion for ink-jet printing, it is the water dispersion that contains the insoluble polymer particle of carbon black, and wherein, the volatile component of this carbon black is that 0.1 % by weight is above and be lower than 3 % by weight, and specific surface area is 110～180m
2/ g, the DBP oil number is 90～200ml/100g;
Described insoluble polymer is to make the monomer mixture generation copolymerization that comprises the monomer (a), macromonomer (b) and the hydrophobic monomer (c) that contain salt-forming group and the water-insoluble vinyl polymer that forms,
Described macromonomer (b) is selected from styrenic macromonomer, (methyl) alkyl-acrylates macromonomer, contains (methyl) esters of acrylic acid macromonomer and the silicone macromonomer of aromatic nucleus,
Described hydrophobic monomer (c) is that to have carbonatoms be (methyl) alkyl acrylate of 8～30 chain alkyl and/or the monomer that contains aromatic nucleus,
The amount of polymers of this insoluble polymer and this carbon black are that the amount of CB and the relation of specific surface area satisfy following formula (1):
(CB amount * CB specific surface area)/insoluble polymer amount=300～500m
2/ g(1).
4. the water dispersion for ink-jet printing of claim 3 record, wherein, the volatile component of described carbon black is 1.2 % by weight, specific surface area is 145m
2/ g, the DBP oil number is 123ml/100g.
5. the water dispersion for ink-jet printing of claim 3 record, wherein, the volatile component of described carbon black is 0.4 % by weight, specific surface area is 142m
2/ g, the DBP oil number is 130ml/100g.
6. water-based ink for use in ink-jet recording, it contains the water dispersions of claim 1 or 3 records.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP370376/2005 | 2005-12-22 | ||
| JP2005370373A JP2007169505A (en) | 2005-12-22 | 2005-12-22 | Water-based ink for ink-jet recording |
| JP370373/2005 | 2005-12-22 | ||
| JP2005370376A JP4845506B2 (en) | 2005-12-22 | 2005-12-22 | Water-based ink for inkjet recording |
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| Publication Number | Publication Date |
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| CN1986659A CN1986659A (en) | 2007-06-27 |
| CN1986659B true CN1986659B (en) | 2013-03-13 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN2006101701396A Active CN1986659B (en) | 2005-12-22 | 2006-12-22 | Water-based inks for ink-jet printing |
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| Country | Link |
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| JP (1) | JP4845506B2 (en) |
| CN (1) | CN1986659B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5286874B2 (en) * | 2007-09-14 | 2013-09-11 | 株式会社リコー | Ink for recording, ink cartridge, ink jet recording method, ink jet recording apparatus, and ink recorded matter |
| JP2009084494A (en) * | 2007-10-01 | 2009-04-23 | Fujifilm Corp | Aqueous colorant dispersion, method of producing aqueous colorant dispersion, and aqueous ink for inkjet recording |
| JP5166846B2 (en) * | 2007-12-12 | 2013-03-21 | 花王株式会社 | Water-based ink for inkjet recording |
| JP4668305B2 (en) | 2008-02-29 | 2011-04-13 | 富士フイルム株式会社 | Water-based colorant dispersion, method for producing water-based colorant dispersion, and water-based ink for inkjet recording |
| JP5523724B2 (en) | 2009-03-19 | 2014-06-18 | 富士フイルム株式会社 | Method for producing pigment dispersion and water-based ink for ink jet recording |
| JP2011157450A (en) * | 2010-01-29 | 2011-08-18 | Mitsubishi Chemicals Corp | Aqueous pigment dispersion liquid and recording liquid |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1243623A1 (en) * | 1999-10-28 | 2002-09-25 | Kao Corporation | Water-based ink for ink-jet recording |
| US20040116553A1 (en) * | 2002-12-12 | 2004-06-17 | Masaki Nakamura | Aqueous dispersion, ink for ink-jet printing, and image forming method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5253694B2 (en) * | 2000-02-02 | 2013-07-31 | 三菱化学株式会社 | Inkjet recording fluid |
| JP2003213180A (en) * | 2002-01-28 | 2003-07-30 | Seiko Epson Corp | Ink set for inkjet recording and inkjet recording method |
| JP4708731B2 (en) * | 2003-05-27 | 2011-06-22 | キヤノン株式会社 | Set of liquid composition, liquid application method and liquid application apparatus using the same |
| JP2005133008A (en) * | 2003-10-31 | 2005-05-26 | Canon Inc | Method of producing block polymer |
| JP2006342268A (en) * | 2005-06-09 | 2006-12-21 | Canon Inc | Block polymer compound, composition including the same, recording material, image-recording method and image-recording device |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1243623A1 (en) * | 1999-10-28 | 2002-09-25 | Kao Corporation | Water-based ink for ink-jet recording |
| US20040116553A1 (en) * | 2002-12-12 | 2004-06-17 | Masaki Nakamura | Aqueous dispersion, ink for ink-jet printing, and image forming method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1986659A (en) | 2007-06-27 |
| JP2007169506A (en) | 2007-07-05 |
| JP4845506B2 (en) | 2011-12-28 |
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