CN1986659A - Water-based inks for ink-jet printing - Google Patents
Water-based inks for ink-jet printing Download PDFInfo
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- CN1986659A CN1986659A CNA2006101701396A CN200610170139A CN1986659A CN 1986659 A CN1986659 A CN 1986659A CN A2006101701396 A CNA2006101701396 A CN A2006101701396A CN 200610170139 A CN200610170139 A CN 200610170139A CN 1986659 A CN1986659 A CN 1986659A
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- Ink Jet Recording Methods And Recording Media Thereof (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Ink Jet (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
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 m<2>/g or (ii) the carbon black has a specific surface area of not less than 100 m<2>/g but less than 200 m<2>/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 literal or the record images mode of obtaining.This mode 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.
From the weathering resistance or the water-proof viewpoint of printed matter, using pigment in tinting material is that printing ink becomes main flow just gradually especially.(for example with reference to patent documentation 1～5).
Disclose a kind of water color ink that contains pigment in vinyl polymer in the patent documentation 1, wherein, in order to give high image density, the graftomer that will use macromonomer (macromer) is 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 the 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, it is scattered in water by the particle that contains sooty water-insoluble vinyl polymer and forms, this sooty DBP oil number 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 that contains sooty water-insoluble vinyl polymer particle, wherein, carbon black is below 5% at 950 ℃ volatile component, and the material one of at least inequality 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 1～6 sooty water dispersion forms.
But, also insufficient though 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] spy opens 2004-75820 number
[patent documentation 3] spy opens 2005-42005 number
[patent documentation 4] spy opens 2005-42098 number
[patent documentation 5] spy opens 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 sooty insoluble polymer particle, wherein, this sooty volatile component is that specific surface area is lower than 200m more than the 3 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 sooty insoluble polymer particle, 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.
Discoveries such as present inventor are in the water dispersion that contains sooty insoluble polymer particle, 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 a water dispersion for ink-jet printing, and it is the water dispersion that contains sooty insoluble polymer particle, and wherein, this sooty volatile component is that specific surface area is lower than 200m more than the 3 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.
Discoveries such as present inventor are in the water dispersion that contains sooty insoluble polymer particle, by set the relation of insoluble polymer amount, sooty amount and 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 a water dispersion for ink-jet printing, and it is the water dispersion that contains sooty insoluble polymer particle, 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, this sooty amount and specific surface area satisfies above-mentioned formula (1).
(carbon black)
Among the present invention, in printing ink, become stable particulate, and consider that from viewpoints such as photostabilization, water tolerance carbon black is comprised in the insoluble polymer particle in order to make carbon black.
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), cover the sooty polymer layer with suitable thickness owing to can give, so image color, drying property, photostabilization excellence.
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 preferably 200～500m especially
2/ g.
Consider from image color, the inhomogeneity viewpoint of image, the sooty volatile component 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 preferably 4～8% especially.If have the carbon black of the volatile component in this scope, then image color, image excellent in uniformity.
Sooty specific surface area (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 preferably 100m especially
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 preferably 100～180m especially
2The scope of/g.If have the carbon black of the specific surface area in this scope, then can give suitable thickness to covering the sooty polymer layer with less amount of polymers, and drying property, photostabilization excellence, image homogeneity (disguise) is also excellent simultaneously.
Consider that from the viewpoint of drying property, photostabilization, image color sooty DBP (Dibutyl phthalate) oil number of using among the present invention is preferably 40～400ml/100g, more preferably 40～300ml/100g is preferably 50～200ml/100g especially.
It is 1～8 that sooty pH value 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 preferably 250～500m especially
2/ g most preferably is 300～500m
2/ g.
Sooty specific surface area (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 preferably 110m especially
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 covering the sooty polymer layer with less amount of polymers, and drying property, photostabilization excellence, and image homogeneity (disguise) is also excellent.
Consider that from the viewpoint of printing concentration sooty DBP (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, be easy to remain in print surface because volume is big, thus the image color excellence, and contain the water-dispersion excellent in stability of sooty insoluble polymer particle.
The sooty volatile component 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 volatile components such as hydroxyl that then contains in carbon black or carboxyl is smaller, contains sooty insoluble polymer dispersion of particles excellent in stability.
Consider that from the viewpoint of dispersion stabilization it is 6～11 that sooty pH value 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 (with ASTM D1620-60 is benchmark) of heating after 7 minutes, specific surface area is to be the value of benchmark with ASTM D3037-81, the DBP oil number is to be the value of benchmark with ASTM D2414-65T, the value that pH is based on DIN ISO 787/9, use glass electrode that the pH of sooty aqueous suspension 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 sooty kind, 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 the 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,, can list MONARCH 1000 series, REGAL 400R series, the Mogul L of Cabot corporate system as the commercial sooty object lesson that can obtain; Special Black 500,350,250,100 series of Degusa corporate system, 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 of Cabot corporate system " MogulL ", 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 corporate 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,, can list MONARCH 280,460,800 series, ELFTEX8, VULCAN P, 9A32, the XC72 series of Cabot corporate system as the commercial sooty object lesson that can obtain; The NIPex 90,80,70,60,40,30 of Degusa corporate 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 corporate system " VULCAN 9A32 ", the DBP oil number is 114, volatile component is 1.5), (specific surface area is 145 for the trade(brand)name " NIPex 70 " of Degusa corporate system, 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 for 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 a word used for translation ketone 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, lime carbonate, talcum etc.
(insoluble polymer)
Consider that from obtaining 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 constituting the insoluble polymer particle can list water-insoluble vinyl polymer, water-insoluble esters polymer, water-insoluble polyurethane polymer etc.Wherein, consider, be preferably the water-insoluble vinyl polymer from the viewpoint of the stability of water dispersion.
Among the present invention, so-called " insoluble polymer " is meant at 105 ℃ down after 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 preferably following water-insoluble graftomer especially, it has at main chain and comprises 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 takes place 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 the spy to open the material etc. of record in the 24th row～this page the 8th hurdle, flat 9-286939 communique page 5 the 7th hurdle the 29th row.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 monomeric typical example of anionic property, 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, Ba Dousuan, 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 acid, (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, acrylic or methacrylic acid more preferably.
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 sooty insoluble polymer particulate, can list following macromonomer, promptly number-average molecular weight is 500～100000, is preferably 1000～10000 and have a monomer of polymerizability functional groups such as unsaturated group at an end.
In addition, (b) number-average molecular weight of composition can be measured as the gel permeation chromatography of solvent as the tetrahydrofuran (THF) that standard substance, use contain the acetic acid of 50 Bo mol by using polystyrene.
As the macromonomer of (b) composition, can list following (b-1) styrenic macromonomer, (b-2) (methyl) alkyl-acrylates macromonomer, (b-3) particularly 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 " is meant the macromonomer that has from the structural unit of 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 forms 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,, can obtain having the water-insoluble graftomer of the structural unit that comes from the styrenic macromonomer by making their copolymerization.
As other monomer, for example can list 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 the 60 weight %, more preferably more than the 70 weight %, is preferably especially more than the 90 weight %.
As commercial available styrenic macromonomer, the commodity that for example can list Toagosei Co., Ltd are called " AS-6 (S) ", " AN-6 (S) " and " HS-6 (S) " etc.
(b-2) (methyl) alkyl-acrylates macromonomer
So-called " (methyl) alkyl-acrylates macromonomer ", be meant the macromonomer with 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) vinylformic acid-2-hydroxyethyl ester, (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 monomeric structural unit of b-2, can obtain by making (methyl) alkyl-acrylates macromonomer generation copolymerization that has a polymerizability functional group at an end, for example can list 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 forms 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, for example can list 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 the 60 weight %, more preferably more than the 70 weight %, be preferably especially more than the 90 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 " is meant the macromonomer of the structural unit of (methyl) acrylate (b-3 monomer) that has self-contained aromatic nucleus.As (methyl) acrylate that contains aromatic nucleus, be preferably 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 preferably (methyl) benzyl acrylate especially.They can be distinguished use separately 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 preferably 2/1～10/1 especially.In addition, polymerizability functional group is set in side chain, contains and calculate its weight ratio.
In above-mentioned, consider from improving with sooty affinity and the viewpoint that improves storage stability, be preferably the styrenic macromonomer that has polymerizability functional group at an end.
(hydrophobic monomer (c))
Consider from improving 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 preferably (methyl) vinylformic acid (different) Lauryl Ester, (methyl) vinylformic acid (different) stearyl, (methyl) vinylformic acid (different) docosyl ester especially.
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 styrene monomers (c-1) such as vinylbenzene, 2-methyl styrene, Vinyl toluene; (methyl) acrylic acid aryl esters such as (methyl) benzyl acrylate, (methyl) vinylformic acid phenoxy ethyl, vinyl xylene, ethyl vinyl benzene, 4-vinyl biphenyl, 1, vinyl naphthalene, chlorostyrene etc. 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 is meant 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 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) and (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 to show the ejection reliability composition of the effect of the printing excellence that can suppress that also dislocation (slippage) takes place etc. continuously that improves water color ink.
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 to have also that substituent phenylene, carbonatoms are 1～30, preferred carbonatoms is 1～20 aliphatics alkylidene group, carbonatoms with aromatic nucleus is 7～30 alkylidene group and has the heterocyclic carbonatoms be 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 formed 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 7～30 alkyl or to have the heterocyclic carbonatoms be 4～30 alkyl.As R
5Preferred example can list 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 village chemical industry Co., Ltd. in making 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 weight %, more preferably 2～40 weight % are preferably 3～30 weight % especially, are preferably 5～20 weight % especially.
Consider that from the viewpoints such as dispersion stabilization of the dispersion that obtains (b) content of composition is preferably 1～50 weight %, more preferably 3～40 weight % are preferably 5～35 weight % especially.
Consider that from viewpoints such as water tolerance, photostabilization (c) content of composition is preferably 5～90 weight %, more preferably 5～80 weight %, more preferably 10～60 weight %.
Consider from viewpoints such as the prolonged preservation 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 weight %, more preferably 2～30 weight %, more preferably 5～25 weight %.
Consider that from viewpoints such as ejection reliability, dispersion stabilizations (e) content of composition is preferably 1～50 weight %, more preferably 2～30 weight %, more preferably 5～30 weight %.
Consider from viewpoints such as the stability water, water tolerance, (a) composition and (d) total content of composition be preferably 5～60 weight %, more preferably 7～50 weight %, more preferably 10～40 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 weight %, more preferably 7～50 weight %, more preferably 10～40 weight %.
Consider from the viewpoint of dispersion stabilization water and ejection reliability, as required, (a) composition, (d) composition and (e) total content of composition be preferably 5～60 weight %, more preferably 7～50 weight %, more preferably 10～40 weight %.
The insoluble polymer that constitutes insoluble polymer particle of the present invention can pass through 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, under the situation of solution polymerization process, be particularly suitable for obtaining effects such as high image density and high bleeding resistance.
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 the 50 weight %, more than the 5 weight %.As polar organic solvent, for example can list Fatty Alcohol(C12-C14 and C12-C18) such as butyl cellosolve; The fragrant same clan such as toluene, dimethylbenzene; Ketones such as methylethylketone, methyl-isobutyl copper; 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 two known polymerization starters such as organo-peroxide such as azo-compound, t-butyl peroxy octanoate, dibenzoyl base oxide such as (2, the 4-methyl pentane nitrile) of 2 '-azo.
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 known polymeric chain transfer agents such as 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 employed polymerization starter, monomer, solvent types etc.; Polymerization time is preferably 1～20 hour.In addition, polymerization atmosphere gas is preferably 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 known method such as desolvate is emanated out and generated.In addition, the polymkeric substance of gained can be removed unreacted monomer etc. by redeposition, membrane sepn, chromatography, extraction process etc. repeatedly and makes with extra care.
Consider that from viewpoints such as sooty dispersion stabilization, water tolerance, ejection reliabilities the weight-average molecular weight of the insoluble polymer that obtains is preferably 5000～500000, more preferably 8000～400000, be preferably 10000～300000 especially.
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, for example can list acid such as hydrochloric acid, acetic acid, propionic acid, phosphoric acid, sulfuric acid, lactic acid, succsinic acid, oxyacetic acid, glyconic acid, R-Glyceric acid, 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 preferably 50～150% especially.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 amine value (the HCLmg/g) * polymkeric substance of polymkeric substance] } * 100
Acid number or amine value can calculate from the structural unit of polymkeric substance, but also polymkeric substance can be dissolved in appropriate solvent (for example methylethylketone) back, utilize titrating method to try to achieve.
(manufacture method of water dispersion)
The water dispersion that contains sooty insoluble polymer particle (hereinafter referred to as " particle that contains CB ") 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, above-mentioned insoluble polymer is dissolved in the organic solvent, then, 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 weight %, and organic solvent is preferably 10～70 weight %, and insoluble polymer is preferably 2～40 weight %, and water is preferably 10～70 weight %.Have at insoluble polymer under 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 the 50 weight % and be solvent more than the 10 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 dibutyl ether, tetrahydrofuran (THF), diox etc.In these solvents, be preferably Virahol, acetone and methylethylketone, be preferably methylethylketone especially.These solvents can use separately or mix more than two kinds and use.
As neutralizing agent, according to the kind difference 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 shear-stress again and lead dispersion.
Mixture is being carried out when pre-dispersed, can use 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 main dispersive shear-stress, for example can list milling machines such as rolling mill, ball mill, kneader, extrusion machine, homogeneous phase valve formula or chamber formula 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 the 0.1 weight %, more preferably below the 0.01 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.Seldom measure not stop up the nozzle of printer for oversize particle not being existed or existing, 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 sooty insoluble polymer is scattered in based in the solvent of water and form.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.For example comprise: in insoluble polymer, contain the sooty particle shape, in insoluble polymer, be dispersed with the sooty particle shape equably, expose sooty particle shape 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 preferably 50～200nm especially.Median size is measured with measuring method described later.
The water dispersion of insoluble polymer particle can directly use as the water color ink that with water is main solvent, but also can be added on common humectants 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 sooty content is preferably 1～30 weight % in water dispersion of the present invention and the water color ink, more preferably 2～20 weight %, more preferably 2～15 weight %.In addition, consider from viewpoints such as image color, drying property and photostabilization, the ratio of insoluble polymer and sooty amount, promptly 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, 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 weight %, more preferably 1～15 weight % from the viewpoint of image color and ejection reliability.
In water dispersion of the present invention and the water color ink, the content of water is preferably 30～90 weight %, more preferably 40～80 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 weight % (solid state component) of water dispersion of the present invention is preferably 1～12mPas, and more preferably 1～9mPas is preferably 2～8mPas especially.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 preferably 2.4～12mPas especially.
Embodiment
In following Production Example, embodiment and comparative example, if not special record, then " part " and " % " is " weight part " and " 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) shown in the table 1, and carry out sufficient nitrogen replacement with weight part, obtained mixing solutions.
On the other hand, in dropping funnel, add 160.4 parts of dropping monomer (representing) solution shown in the table 1, carry out sufficient nitrogen replacement, obtained mixing solutions with weight part.
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 down at 75 ℃, to in 5 parts of methylethylketones, dissolve 0.3 part of polymerization starter (2 then, 2 '-azo two (2, the 4-methyl pentane nitrile)) solution that forms joins in this mixing solutions, again 75 ℃ of following slakings 3 hours, 85 ℃ of following slakings 2 hours, thereby obtained polymers soln.
The part of resulting polymers soln 105 ℃ of following drying under reduced pressure 2 hours, is removed and desolvated, separate thus.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 each monomeric numeric representation effective constituent in the table.
[table 1]
| Production Example 1 | Production Example 2 | ||
| Initial charge monomer solution (weight part) | (a) methacrylic acid | 3 | 3 |
| (b) vinylbenzene macromonomer *1 | 2 | 2 | |
| (c) vinylbenzene | 10 | 2 | |
| (c) methacrylic acid stearyl ester | 10 | ||
| (d) polypropylene glycol monomethacrylate *2 | 3 | ||
| (e) octyloxy polyethylene glycol monomethacrylate *3 | 5 | ||
| Methylethylketone | 20 | 20 | |
| 2 mercapto ethanol | 0.1 | 0.1 | |
| Drip monomer solution (weight part) | (a) methacrylic acid | 12 | 12 |
| (b) vinylbenzene macromonomer *1 | 8 | 8 | |
| (c) vinylbenzene | 40 | 8 | |
| (c) methacrylic acid stearyl ester | 40 | ||
| (d) polypropylene glycol monomethacrylate *2 | 12 | ||
| (e) octyloxy polyethylene glycol monomethacrylate *3 | 20 | ||
| Methylethylketone | 80 | 80 | |
| 2 mercapto ethanol | 0.1 | 0.1 | |
| 2,2 '-azo two (2, the 4-methyl pentane nitrile) | 0.3 | 0.3 | |
| The weight-average molecular weight of resulting polymkeric substance | 38000 | 51000 | |
*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 a 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 75 parts of carbon blacks again, [(CB amount * CB specific surface area)/insoluble polymer amount] is adjusted into 435, add an amount of methylethylketone again, ion exchanged water is to form mobile and fully to stir, used three roller roller mills (Noritake of Co., Ltd. system, commodity are called " NR-84A ") then 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 the median size of the particle of the resulting CB of containing according to following method.This results are shown in table 2.
10 parts of 25 parts of water dispersions, glycerine, 2-{2-(2-butoxy oxyethyl group) oxyethyl group with the above-mentioned particle that contains CB that obtains } 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 ") 0.5 part and ion exchanged water mix for 57.5 parts, with the mixed solution that obtains membrane filter (Sartorius corporate 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 the carbon black shown in the table 2 again, add an amount of methylethylketone, ion exchanged water again to form mobile and to stir fully, used three roller roller mills (Noritake of Co., Ltd. system, commodity are called " NR-84A ") then mixing 2 hours.Use the method identical to handle the mixing thing that obtains, obtained to contain the water dispersion of the particle of CB with embodiment 1.And then, use the method identical to obtain water color ink with embodiment 1.
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
-3Weight %
[measurement of CB specific surface area] is benchmark with ASTM D3037-81
[measurement of DBP oil number] is benchmark with ASTM D2414-65T
[measurement of volatile component]
In the residual quantity (with ASTM D1620-60 is benchmark) of heating after 7 minutes under 950 ℃.
Estimate the rerum natura of the water color ink that obtains 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), upward print 100 at common paper P paper (Fuji Xerox Co., Ltd. system) with 2000 literal/Zhang Lianxu, printing comprises the test file of literal, whole image (solid images) and gage line (ruled-lines) then, estimate following three projects: (i) form clearly and clearly literal of lines, (ii) uniform whole image, and the gage line that does not (iii) 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
Go up whole image of printing at the common paper P paper identical, recycled writing paper G100, C2 (Fuji Xerox Co., Ltd. system) with above-mentioned (1), place after 1 day, use optical concentration meter SpectrroEye (Gretag-Macbeth corporate system) to measure 10 places arbitrarily, obtain mean value.
(3) image homogeneity (disguise)
At the common paper P paper identical with above-mentioned (1), recycled writing paper G100, C2 last printing whole image identical with above-mentioned (2), 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 an irregular colour even a little.
*: there is irregular colour to spare (blank is arranged)
(4) color is oozed profit
To the common paper P paper identical, recycled writing paper G100, the C2 identical with above-mentioned (2) with above-mentioned (1), made following pattern, promptly 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
Go up whole image of printing 20mm * 20mm size at the common paper P paper identical, photochrome precision work paper (Fuji Xerox Co., Ltd. system) with above-mentioned (1), 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 again (load area is the load of 43mm * 30mm) from the top, whole imaging surface moved, measure the pollution condition of the paper that is stacked.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 corporate 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: promptly 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]
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| The manufacturing of polymkeric substance | Production Example 1 | Production Example 1 | Production Example 1 | Production Example 2 | Production Example 1 | Production Example 1 | Production Example 2 | Production Example 2 |
| The kind of carbon black (CB) *1 | CB-1 | CB-2 | CB-3 | CB-2 | CB-4 | CB-5 | CB-6 | CB-7 |
| Amount of polymers (g) | 25 | 25 | 25 | 25 | 25 | 25 | 20 | 20 |
| CB measures (g) | 75 | 75 | 75 | 46.4 | 75 | 100 | 80 | 80 |
| CB specific surface area (m 2/g) | 65 | 138 | 96 | 138 | 150 | 370 | 94 | 260 |
| Volatile component (weight %) | 3.5 | 4.5 | 3.5 | 4.5 | 5.0 | 1.8 | 1.0 | 5.0 |
| DBP oil number (ml/100g) | 45 | 60 | 69 | 60 | 150 | 77 | 71 | 160 |
| (CB amount * CB specific surface area)/amount of polymers | 195 | 414 | 288 | 256 | 450 | 1480 | 376 | 1040 |
| The median size (nm) that contains the particle of CB | 78 | 116 | 134 | 115 | 118 | 119 | 86 | - |
| The ejection reliability | ○ | ○ | ○ | ○ | ○ | × | ○ | Do not disperse |
| Image color | 1.17 | 1.34 | 1.32 | 1.32 | 1.41 | 1.11 | 1.09 | |
| The image homogeneity | ○ | ○ | ○ | ○ | ○ | ○ | × | |
| Color is oozed profit | ○ | ○ | ○ | ○ | ○ | × | △ | |
| Drying property | ○ | ○ | ○ | ○ | ○ | × | ○ | |
| Photostabilization | ○ | ○ | ○ | ○ | ○ | △ | △ |
*The 1:CB-1:Degusa corporate system, Special Black350 (specific surface area is 65, and the DBP oil number is 45, and volatile component is 3.5)
The CB-2:Cabot corporate system, Mogul L (specific surface area is 138, and the DBP oil number is 60, and volatile component is 4.5)
The CB-3:Cabot corporate system, Regal 400R (specific surface area is 96, and the DBP oil number is 69, and volatile component is 3.5)
The CB-4:Degusa corporate system, Color Black S160 (specific surface area is 150, and the DBP oil number is 150, and volatile component is 5.0)
CB-5: Mitsubishi chemical Co., Ltd's system, #2600 (specific surface area is 370, and the DBP oil number is 77, and volatile component is 1.8)
The CB-6:Cabot corporate system, Regal 330R (specific surface area is 94, and the DBP oil number is 71, and volatile component is 1.0)
The CB-7:Degusa corporate system, FW18 (specific surface area is 260, and the DBP oil number is 160, and volatile component is 5.0)
[table 3]
| Embodiment 6 | Embodiment 7 | Embodiment 8 | Comparative example 4 | Comparative example 5 | Comparative example 6 | Comparative example 3 | |
| The manufacturing of polymkeric substance | Production Example 1 | Production Example 2 | Production Example 2 | Production Example 1 | Production Example 1 | Production Example 2 | Production Example 2 |
| The kind of carbon black (CB) *2 | CB-1 | CB-2 | CB-3 | CB-4 | CB-5 | CB-6 | CB-7 |
| Amount of polymers (g) | 25 | 25 | 25 | 20 | 20 | 25 | 20 |
| CB measures (g) | 75 | 75 | 75 | 80 | 80 | 100 | 80 |
| (CB amount * CB specific surface area)/amount of polymers | 435 | 345 | 426 | 376 | 880 | 1480 | 1040 |
| CB specific surface area (m 2/g) | 145 | 115 | 142 | 94 | 220 | 370 | 260 |
| DBP oil number (ml/100g) | 123 | 114 | 130 | 71 | 110 | 77 | 160 |
| The median size (nm) that contains the particle of CB | 156 | 154 | 153 | 86 | 110 | 119 | - |
| The ejection reliability | ○ | ○ | ○ | ○ | ○ | × | Do not disperse |
| Image color | 1.37 | 1.36 | 1.40 | 1.09 | 1.35 | 1.11 | |
| The image homogeneity | ○ | ○ | ○ | × | ○ | ○ | |
| Color is oozed profit | ○ | ○ | ○ | △ | × | × | |
| Drying property | ○ | ○ | ○ | ○ | × | × | |
| Photostabilization | ○ | ○ | ○ | △ | × | △ |
*The 2:CB-1:Degusa corporate system, NIPex 70 (specific surface area is 145, and the DBP oil number is 123, and volatile component is 1.2)
The CB-2:Degusa corporate system, NIPex 60 (specific surface area is 115, and the DBP oil number is 114, and volatile component is 1.0)
CB-3:Tokai Carbon Co., Ltd. system, SAF-HG (specific surface area is 142, and the DBP oil number is 130, and volatile component is 0.4)
The CB-4:Cabot corporate system, Regal 330R (specific surface area is 94, and the DBP oil number is 71, and volatile component is 1.0)
The CB-5:Cabot corporate system, M880 (specific surface area is 220, and the DBP oil number is 110, and volatile component is 1.5)
CB-6: Mitsubishi chemical Co., Ltd's system, #2600 (specific surface area is 370, and the DBP oil number is 77, and volatile component is 1.8)
The CB-7:Degusa corporate system, FW18 (specific surface area is 260, and the DBP oil number is 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 photostabilization excellence.
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 excellence.
Therefore, the water color ink of the 1st scheme of the present invention and the 2nd scheme can be applicable to that the print speed of carrying out with ink-jet recording is in the high speed printing more than 80/minute.
Claims (10)
1. water dispersion for ink-jet printing, it is the water dispersion that contains sooty insoluble polymer particle, wherein, this sooty volatile component is that specific surface area is lower than 200m more than the 3 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. the water dispersion for ink-jet printing of claim 1 record, wherein, the sooty specific surface area is 50m
2More than/the g.
3. the water dispersion for ink-jet printing of claim 1 record, wherein, sooty DBP oil number is 40～400ml/100g.
4. water dispersion for ink-jet printing, it is the water dispersion that contains sooty insoluble polymer particle, 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 following formula (1):
(CB amount * CB specific surface area)/insoluble polymer amount=50～600 (m
2/ g) (1).
5. the water dispersion for ink-jet printing of claim 4 record, wherein, the sooty volatile component is lower than 3%.
6. the water dispersion for ink-jet printing of claim 4 record, wherein, sooty DBP oil number is 80～400ml/100g.
Claim 1 or 4 the record water dispersion for ink-jet printing, wherein, insoluble polymer is the water-insoluble graftomer that contains the structural unit that comes from macromonomer (b).
Claim 1 or 4 the record water dispersion for ink-jet printing, wherein, 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.
9. the ink-vapor recording pigment water dispersion of claim 8 record, wherein 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.
10. water-based ink for use in ink-jet recording, it contains the water dispersions of claim 1 or 4 records.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005370376A JP4845506B2 (en) | 2005-12-22 | 2005-12-22 | Water-based ink for inkjet recording |
| JP370373/2005 | 2005-12-22 | ||
| JP370376/2005 | 2005-12-22 | ||
| JP2005370373A JP2007169505A (en) | 2005-12-22 | 2005-12-22 | Water-based ink for ink-jet recording |
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| CN1986659A true CN1986659A (en) | 2007-06-27 |
| CN1986659B CN1986659B (en) | 2013-03-13 |
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| 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 |
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| JP3779107B2 (en) * | 1999-10-28 | 2006-05-24 | 花王株式会社 | Water-based ink for inkjet recording |
| 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 |
| JP4284988B2 (en) * | 2002-12-12 | 2009-06-24 | コニカミノルタホールディングス株式会社 | Aqueous dispersion, ink jet ink and image forming 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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| JP4845506B2 (en) | 2011-12-28 |
| CN1986659B (en) | 2013-03-13 |
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