CA1150213A - Continuous method of producing aqueous phthalocyanine pigment dispersions - Google Patents
Continuous method of producing aqueous phthalocyanine pigment dispersionsInfo
- Publication number
- CA1150213A CA1150213A CA000350659A CA350659A CA1150213A CA 1150213 A CA1150213 A CA 1150213A CA 000350659 A CA000350659 A CA 000350659A CA 350659 A CA350659 A CA 350659A CA 1150213 A CA1150213 A CA 1150213A
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- CA
- Canada
- Prior art keywords
- pigment
- water
- crude
- surfactant
- dispersed
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0001—Post-treatment of organic pigments or dyes
- C09B67/0022—Wet grinding of pigments
- C09B67/0023—Wet grinding of pigments of phthalocyanines
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0025—Crystal modifications; Special X-ray patterns
- C09B67/0026—Crystal modifications; Special X-ray patterns of phthalocyanine pigments
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
Abstract of the Disclosure A continuous method for producing an aqueous dispersion of phthalocyanine blue pigment is disclosed.
The method involves the following two steps:
(A) mixing in water a phthalocyanine crude pigment at about 10 to 50%
by weight with from about 12 to 30%
by weight of surfactant and (B) continuously pumping the blend of (A) through at least two shot mills in series in which the shot grinding media range in size from 0.1 to 1.5 mm.
diameter and grinding the blend until the particle size of the crude is re-duced to where the dispersion has suitable pigment tinctorial strength for use in inks and coatings.
The aqueous dispersion of blue pigment produced by this method is especially useful in inks and coatings.
The method involves the following two steps:
(A) mixing in water a phthalocyanine crude pigment at about 10 to 50%
by weight with from about 12 to 30%
by weight of surfactant and (B) continuously pumping the blend of (A) through at least two shot mills in series in which the shot grinding media range in size from 0.1 to 1.5 mm.
diameter and grinding the blend until the particle size of the crude is re-duced to where the dispersion has suitable pigment tinctorial strength for use in inks and coatings.
The aqueous dispersion of blue pigment produced by this method is especially useful in inks and coatings.
Description
~5~3Z13 CONTI~UOUS ~lETEIOD OF Pr~ODUCING AQUEOUS
PHT~lr-LOCYANINE PIGMI~NT DISPERSIONS
Background of the Invention Field of the Invention This invention relates to a continuous process for the manufacture of phthalocyanine pigment dispersions of primarily beta crystal structure and more particularly to a continuous process for the manufacture of phthalocyanine blue pigment in an aqueous dispersion. The aqueous phthalo-cyanine blue pigment dispersion may be used directly in water-based printing inks and coatings and may be used directly in oil-based inks whex~ the associated t~ter can be tolerated. The dispersion may also be used in oil-based printing inks by flushing the aqueous pigment into a water-immiscible printing ink vehicle.
Description of the Prior Art The manufacture of phthalocyanine crude pigments usually results in the formation of a product of relatively large crystal size or one containing impurities and has been referred to in the art as phthalo crude-. This crude requires some form of particle size reduction and/or purification to be useful as a pigment having the tinctorial strength and intensity necessary for use in compositions such as inks, paints, etc.
`''' ' '' ' `, ` '~ ~..
.... , .. ., . . . , _ . . . .. . ... . . . . . . .. ... . ... . . . . . . . . . . . .
~V~3 Various methods have been proposed by thc prior art to reduce the particle si e and improve the purity of the phthalo crude.
One such method relates to the mîlling of the ph~halo crude in an organic liquid as exem~lified in U. S.
Patents 2,556,726; 2,556,727; 2,55G,728; and 2,908~690.
The use of an aqueous medium for milling phthalo crude is also kno~ and is disclosed in U. S. Patent~2,999,862.
This patent, however, relates to the use of water as the ex-clusive grinding assistant and results in a flocculated puri-fied product. U. S. Patent 3,775,149 relates to the prepara-tion of phthalocyanine pigments and is specifically concerned with the milling of phthalo crude in aqueous suspension, in the presence of a surfactant, to give a filterable paste of phtha]ocyanine which is predominantly of the beta-pigment form.
This method, however, also results in flocculated product where the pig.ment is purified when recovered as a presscake Or in dry form. Thus, flocculation of the piyment has been a desirable feature according to these prior art processes and has provided a means Eor purifying the pigment. However, the resultant presscaXe or dry form of the pigment must then be redispersed for use in products such as inks, paints, etc.
h7e have now found that beta phthalocyanine pigment can be pro-duced by a continuous method in aqueous suspension form that can then be used directly in water-based products such as inks and can be directly used in oil-based products where small amounts or watcr can be tolerated or flushed into oil-based ~.~.5C~Z13 products such as oil-basod inks. This aqueous pigment dispersion according to the invention thus eliminates two steps in the use of phthalo blue pigment, i.e., filtering the flocculated pigment and redispersion for an end use.
Summary of the Invention The present invention relates to a two-step continuous method of converting crude phthalocyanine to a dispersed form which is useful in inXs and coatings, said method comprising (A) premixing phthalo crude with from about 12 to about 30% by weight of surfactant, based on pigment, and an amount of water , sufficient to reduce the crude concentra-tion to 10 to 50% by weight, based on the total mixture, said premixing being ac-complished by agitation to break loose crude agglomerates and obtain a uniform blend of the ingredients without appre-ciably reducing the particle size of the crude and (B) continuously pumping the blend of (A) through at least two shot mills in series containing between 50 and 90% by volumP
of a grinding media that has a size in the range of from about 0.1 to 1.5 mm.
diameter and then grinding until the ~150Z13 particle size has been reduced to where the pigment dispersion has suitable tinctorial strength for use in inks and coatings.
Detailed_Description of the Invention The present invention provides a continuous method of producing aqueous phthalocyanine blue pigment dispersion. The method comprises ~A) premixing phthalo crude with from about 12 to 30% by weight of surfactant based on pigment and an amount of water suffi-cient to reduce the crude concentration to 10 to 50% by weight, based on the total mixture, said premixing being accomplished ~y agitation to break down loose crude agglomerates and obtain a uniform blend of the crude without ap-preciably reducing the particle size of the crude, and (B) continuou~ly pumping the blend of (A) through at least two shot mills in series containing between 50 and 9~0 by volume of a grinding media that has a size of from about 0.1 to 1.5 mm. diameter and then yrinding until the particle siæ~
has been reduced to pigment particle size.
Z~3 By phthalo crude we mean phthalocyanine crude pig-ments obtained commercially by various syntheses and include the copper-, cobalt-, zinc-, nickel-, and cadmium-phthalo-cyanines as well as metal-free phthalocyanine. Especially preferred is copper phthalocyanine because of its known com-mercial value in inks and coatings. The phthalo crude typically has a particle size wherein at least 8~/o of the crude particles have a size greater than 1 micrometer. After conversion of the crude according to the method of this invention, it has been found that at least 95% of the pigment particles have a size less than 1 micrometer, and this size is referred to herein as pigment particle size. The particle size measure-ments are conveniently made by using a Sedigraph 500 Particle Size ~nalyzer. By pigment particle size we mean that the particle size of the crude has been reduced to where the dispersion of phthalocyanine pigment has the tinctorial strength suitable for use in inks and coatings.
Tinctorial strength is conveniently measured by comparing the color of one pigment (the batch), mixed with a specified amount of white base, with the color of another pigment ~the standard) mixed with an equal amount Gf the same white base. The amounts of standard and batch pigments are the same in the two tints, but they will appear to be different if ther~ is a difference in strength. If the color of the Z~ 3 batch tint appears -to have b~en produced by a larger amount of pigmellt than the color o:E the~ standard tint, the batch is considered to be stronger t~lan t~le standard. Utilizing such proccdures, it has be2n found that the tinctorial strength of the crude is very small or essenti.ally ~.ero whereas that of the piyment dispersion according to this invention is much stronger (on the order oF 100 times~ than that oI the crude.
In a preferred embodiment, the present invention relates to a method of converting a crude copper pht}lalocyanine pigment having at least 80% of the particle sizes of greater i than 1 micro~eter to a dispersed form which is useful in inl~s and coatings, said method comprising (A) premixing crude pigment, with 12 to 30%, by w2ight of surfactant and an amoun-. of ~ater sufficient to reduce the pigment concentration to 10 to 50%, by weight, -5(a)-1~5~3Z~3 based on total m~ture, said prelni~irlg being acccmplished by agitation to brea~ down loose pi~merlt agcJlomerates and obtain a uniform blend of the in-gredients ~ithout appreciably reducing the particle size of the piymen~, and ~) continuously pumping the blend ~f (A) through at least two shot mills in series containing between 50 and 9 by volume of a grindin~ media that has a particle size in the range of 0~1 to 1.5 mm. diameter, and then grincing until the dispersion has suitable tinctorial strength for use in inks and coatings.
The surfactants useful in the present method all rust have an HLB value o~ greater than 8 and include water-soluble, non-ionic, cationic, and anionic types. However, only certain compounds in each class will be effective dis-persants. In order to be effective a sur~actant according to this invention must meet the followin~ criteria:
(~) The concentration of the surfactant relative to the crude pigment must ; be such that the total surace of the crude is covered in a mol~omolecular layer of surfactant in the dispersed - sta~e, and (s) The sur:Eactant musl be water-solu~le or dispclsible up to the rcquired concentration le~el.
The n~n-ionic surfactanLs can generally be described as ethylene oxide adducts and can be represented by the follo~ing formulas: -I. R-o(cEI2cEI2o)n-H
~herein n = 3 to 10 R is selected from 1) an alkyl ~roup containing 10-22 carbon atoms , or
PHT~lr-LOCYANINE PIGMI~NT DISPERSIONS
Background of the Invention Field of the Invention This invention relates to a continuous process for the manufacture of phthalocyanine pigment dispersions of primarily beta crystal structure and more particularly to a continuous process for the manufacture of phthalocyanine blue pigment in an aqueous dispersion. The aqueous phthalo-cyanine blue pigment dispersion may be used directly in water-based printing inks and coatings and may be used directly in oil-based inks whex~ the associated t~ter can be tolerated. The dispersion may also be used in oil-based printing inks by flushing the aqueous pigment into a water-immiscible printing ink vehicle.
Description of the Prior Art The manufacture of phthalocyanine crude pigments usually results in the formation of a product of relatively large crystal size or one containing impurities and has been referred to in the art as phthalo crude-. This crude requires some form of particle size reduction and/or purification to be useful as a pigment having the tinctorial strength and intensity necessary for use in compositions such as inks, paints, etc.
`''' ' '' ' `, ` '~ ~..
.... , .. ., . . . , _ . . . .. . ... . . . . . . .. ... . ... . . . . . . . . . . . .
~V~3 Various methods have been proposed by thc prior art to reduce the particle si e and improve the purity of the phthalo crude.
One such method relates to the mîlling of the ph~halo crude in an organic liquid as exem~lified in U. S.
Patents 2,556,726; 2,556,727; 2,55G,728; and 2,908~690.
The use of an aqueous medium for milling phthalo crude is also kno~ and is disclosed in U. S. Patent~2,999,862.
This patent, however, relates to the use of water as the ex-clusive grinding assistant and results in a flocculated puri-fied product. U. S. Patent 3,775,149 relates to the prepara-tion of phthalocyanine pigments and is specifically concerned with the milling of phthalo crude in aqueous suspension, in the presence of a surfactant, to give a filterable paste of phtha]ocyanine which is predominantly of the beta-pigment form.
This method, however, also results in flocculated product where the pig.ment is purified when recovered as a presscake Or in dry form. Thus, flocculation of the piyment has been a desirable feature according to these prior art processes and has provided a means Eor purifying the pigment. However, the resultant presscaXe or dry form of the pigment must then be redispersed for use in products such as inks, paints, etc.
h7e have now found that beta phthalocyanine pigment can be pro-duced by a continuous method in aqueous suspension form that can then be used directly in water-based products such as inks and can be directly used in oil-based products where small amounts or watcr can be tolerated or flushed into oil-based ~.~.5C~Z13 products such as oil-basod inks. This aqueous pigment dispersion according to the invention thus eliminates two steps in the use of phthalo blue pigment, i.e., filtering the flocculated pigment and redispersion for an end use.
Summary of the Invention The present invention relates to a two-step continuous method of converting crude phthalocyanine to a dispersed form which is useful in inXs and coatings, said method comprising (A) premixing phthalo crude with from about 12 to about 30% by weight of surfactant, based on pigment, and an amount of water , sufficient to reduce the crude concentra-tion to 10 to 50% by weight, based on the total mixture, said premixing being ac-complished by agitation to break loose crude agglomerates and obtain a uniform blend of the ingredients without appre-ciably reducing the particle size of the crude and (B) continuously pumping the blend of (A) through at least two shot mills in series containing between 50 and 90% by volumP
of a grinding media that has a size in the range of from about 0.1 to 1.5 mm.
diameter and then grinding until the ~150Z13 particle size has been reduced to where the pigment dispersion has suitable tinctorial strength for use in inks and coatings.
Detailed_Description of the Invention The present invention provides a continuous method of producing aqueous phthalocyanine blue pigment dispersion. The method comprises ~A) premixing phthalo crude with from about 12 to 30% by weight of surfactant based on pigment and an amount of water suffi-cient to reduce the crude concentration to 10 to 50% by weight, based on the total mixture, said premixing being accomplished ~y agitation to break down loose crude agglomerates and obtain a uniform blend of the crude without ap-preciably reducing the particle size of the crude, and (B) continuou~ly pumping the blend of (A) through at least two shot mills in series containing between 50 and 9~0 by volume of a grinding media that has a size of from about 0.1 to 1.5 mm. diameter and then yrinding until the particle siæ~
has been reduced to pigment particle size.
Z~3 By phthalo crude we mean phthalocyanine crude pig-ments obtained commercially by various syntheses and include the copper-, cobalt-, zinc-, nickel-, and cadmium-phthalo-cyanines as well as metal-free phthalocyanine. Especially preferred is copper phthalocyanine because of its known com-mercial value in inks and coatings. The phthalo crude typically has a particle size wherein at least 8~/o of the crude particles have a size greater than 1 micrometer. After conversion of the crude according to the method of this invention, it has been found that at least 95% of the pigment particles have a size less than 1 micrometer, and this size is referred to herein as pigment particle size. The particle size measure-ments are conveniently made by using a Sedigraph 500 Particle Size ~nalyzer. By pigment particle size we mean that the particle size of the crude has been reduced to where the dispersion of phthalocyanine pigment has the tinctorial strength suitable for use in inks and coatings.
Tinctorial strength is conveniently measured by comparing the color of one pigment (the batch), mixed with a specified amount of white base, with the color of another pigment ~the standard) mixed with an equal amount Gf the same white base. The amounts of standard and batch pigments are the same in the two tints, but they will appear to be different if ther~ is a difference in strength. If the color of the Z~ 3 batch tint appears -to have b~en produced by a larger amount of pigmellt than the color o:E the~ standard tint, the batch is considered to be stronger t~lan t~le standard. Utilizing such proccdures, it has be2n found that the tinctorial strength of the crude is very small or essenti.ally ~.ero whereas that of the piyment dispersion according to this invention is much stronger (on the order oF 100 times~ than that oI the crude.
In a preferred embodiment, the present invention relates to a method of converting a crude copper pht}lalocyanine pigment having at least 80% of the particle sizes of greater i than 1 micro~eter to a dispersed form which is useful in inl~s and coatings, said method comprising (A) premixing crude pigment, with 12 to 30%, by w2ight of surfactant and an amoun-. of ~ater sufficient to reduce the pigment concentration to 10 to 50%, by weight, -5(a)-1~5~3Z~3 based on total m~ture, said prelni~irlg being acccmplished by agitation to brea~ down loose pi~merlt agcJlomerates and obtain a uniform blend of the in-gredients ~ithout appreciably reducing the particle size of the piymen~, and ~) continuously pumping the blend ~f (A) through at least two shot mills in series containing between 50 and 9 by volume of a grindin~ media that has a particle size in the range of 0~1 to 1.5 mm. diameter, and then grincing until the dispersion has suitable tinctorial strength for use in inks and coatings.
The surfactants useful in the present method all rust have an HLB value o~ greater than 8 and include water-soluble, non-ionic, cationic, and anionic types. However, only certain compounds in each class will be effective dis-persants. In order to be effective a sur~actant according to this invention must meet the followin~ criteria:
(~) The concentration of the surfactant relative to the crude pigment must ; be such that the total surace of the crude is covered in a mol~omolecular layer of surfactant in the dispersed - sta~e, and (s) The sur:Eactant musl be water-solu~le or dispclsible up to the rcquired concentration le~el.
The n~n-ionic surfactanLs can generally be described as ethylene oxide adducts and can be represented by the follo~ing formulas: -I. R-o(cEI2cEI2o)n-H
~herein n = 3 to 10 R is selected from 1) an alkyl ~roup containing 10-22 carbon atoms , or
- 2) an alkyl phenol group containing 8-18 carbon atoms.
', ' ' ' ' . . , . '' ' ' IT~ R- ~ ~ (cH2cEI2o)n-H
~.~herein n = 3 to 10 and R is an - alk~l group containing 8 to 18 carbon atoms.
III. R-R' `C--O(CE~2CH20)n-EI
R is an alX~l group containing 12 to 22 carbon atoins.
I Useful cationic surfactants are quaternary .¦ ammonium salts and specific amines and can be represented by the following formulas:
.
Z~.3 ~1 X ~ A~V C~t.~
R4- N - R2 R2, R3 and R~ are alkyl groups con-I taining from 1 to 12 carbon atoms, R3 Rl is an alkyl group containing 8-22 carbon atoms, X = Cl , Br~, I , &
II. Rl X Primar~,_Secondary or Tertia_y ¦ Amines + .
I Rl is a group containing at least R3 8 carbon atoms, +
R2 and R3 can be H or alkyl groups containing from 1 to 22 carbon atoms.
III. Ethoxylated Primary Amines r-- ~CH2cH2o)n ~ n & m = 1 to 10 R - ~ R consists of an alkyl I (CH2CR20)m H gxoup containing 8-22 carbon atoms.
IV. - Ethy~l~t~d ~nil~-- o r- (CH2CEI20)n H R consists of a - ~ ~C - N group containing I (CH2CH20) H from 7 to 21 m carbon atoms.
V. Ethoxylated Fatty secondary Amides ~-- (CH2CH20) H R is a group con-R - N n tainin~ 8 to 20 - L CH3 carbon atoms.
. .
VI. Substituted Quaternized Fthoxylated Amines .
Rl _ N+_ (CH2CH 0) H R is a group co~-2 n taining 8 to 20 R carbon a~oms.
VII. EthoXYlated Fatty seconaarY
Amine i C ~ CH3 R is a group containing 8 to 20 carbon atoms ~L5~Z~.3 , , _.
The anionic surfactants can generally be describPd as acid salts and can be repres~nted by the follo~iny formulas:
I. Fatky Acid Salts (R - COO )M~ R is an alkyl group containing 12 to 22 carbon atoms.
M+ = ~a, K, M~I4 or substituted ammonium.
II. Sulfonates ~R-S03 )M+ R is an alkyl group containing 12 to 22 carbon atoms.
M+ = ~a, K, NH4 or substituted ammonium.
.
III. . Sulfates - R - OS03 M+ R is an al~yl group containing 12 to 22 carbon atoms.
M~ = Na, K, NH4 or substituted ammonium.
IV. Sulfosuccinates M 03S - CEI - CooR M = ~a, K, NH4 or substituted - I ammonium.
- CH2 R is a group containing from 1 4 to ~2 carbon atoms~.
CooR
V. R' - ~ -S03 M M = Na., ~, ~H4 or su~stituted ammonium.
R is an alkyl group containing 8 to 18 carbon atoms.
~15~Z13 speci:~iC surfactants that h~ve been found suita'ol~
include the follo~ling:
_rfactant Type Trade M~e Chemical N~me I. Non-Ionic a) Triton X-114 Octyl phenoxy polyetho.;yethanol b) Triton N-101 Nonyl phenoxy polyeth~xyethanol II. Anionic a) Aerosol~ T 75 Sodium dioctyl sulfosuccinate - b) Aerosol TR-70 Sodium Bis (Tridecyl! s~lfosuccinat c) A~monium Tallate Ammonium Tallate I~I. Cationic a) Ethomeen~C-15 Polyoxyethylene cocoamine b) Ethom2en 0-15 Polyoxyethyl~ne oleylamine Typical useful surfactant concentration levels have been found to be from about 12 to 30% by ~leight based-on the crude phthalocyanine. This concentration level of surfactant is a critical aspect of the invention and has been found to result in a shorter grinding time ~up to 15%~ as well as the grinding of crude to a much smaller particle size without flocculation of the pigment in the aqueous solution.
It is very important that flocculation not take place ac-cording to the present dispersion method of pigment pro~uc-tion and the surfactant selection and concentration are therefore critical aspects of the present ~ethod.
- ~ ~rA~e~
The process according to the invention is pre-ferably run at a temperature from about 5 to ~0C. and ~Jill work perfectly adeguately at room -temperature. In fact, however, all grinding operations result in generation of heat, so that cooling is necessary if the mix is to be kept at am-bient temperature; the temperature may be allowed to rise somewhat, for example to 80C., so as to save expense on cooling, without detrimental effect, bu-t we prefer that the temperature of grinding should not in any case rise to above 9 ~C .
The blending of the crude (Step ~) in the present me_hod ma~ be accomplished in any type reaction vessel or shot mill. The blend LS agitated to produce a homogeneous composition. Preferably, the blend is then pumped through at least iwo pressurized shot mills in series capable of retaining gr r~ing media made from glass, steel, ceramics, etc., in the size range of from ~.1 to 1.5 mm diameter.
The rate at which the blend is fed into the shot mills can be varied between 50 and 1000 lb/hour and most pre~erably .. . .
in the range of 100 to 250 lb/hour. The blend is passed through at least two shot mills in series to achieve the tinctorial color value of pigment suitable for commercial use~
However, it will be appreciated that the residence time in the shot mil]!s will determine the particle size of the pig-ment but one, or more than two shot mills in series, can also 2~3 be used in the grinding step. Xt has been found that the use of at least t~;o shot mills provides the optimum conditions of time and po~r usage for the Eormation of pigmGn-t disperslon having the tinctorial color value desired in commercial use.
The aqueous pigment dispersions prepared in accor-dance with the present invention may be used for coloring a variety of compositions such as, for example, paper, plas-tics, fibers and especially water-basea inks and paints. rrhe aqueous pigment dispersions may also be used in oil-based inks and paints by flushing the aqueous dispersion into the desired oil-based product or by direct addition when the associated water can be tolerated.
~ ypically, inks prepared in accordance with this invention contain a pigment ~Jhich is dispersed in a resin solution. The inks may contain other conventional ink in-gredien.s. ~or instance, ethyl cellulose, wax compounds, pigment we.ting agents, reactive hydrocarbon resins, e~c., may be added for their kno~n effects.
The invention will next be illustrated in terms of speci~ic examples. In these examples, as well as in the other parts of the present application, all amounts and pro-portions are expressed as parts by weight unless otherwise indicated.
3Zl~
Descri~tion of the Preferred E~nbodi~nts Example I
Prcparation of Phthalo slue Aqueous Dispersion The following materials were charged to a 150 gallon tank: `
a) w~ter 260 lbs.
b~ Triton X-114 60 lbs.
c) crude Cu-Phthalo Blue 300 lbs~
These materials were then blended in the tank until a homogeneous dispersion was obtained and a further charge of 130 lbs. of water added to reduce the viscosi-ty of the mixture to one more suitable for shot milling. The mixture was continuously pumped through two shot mills (Drais mills) in series at a rat~e of 150 lbs/hr. ~ach Drais mill contained steel sho, o~ mm. diameter. ~rinding ~as continued for 30 minutes a~ter which the aqueous dispersion was found to possess superior blue color properties and the pigment concen-tration was 4~3 by weight. Grinding was completed at 150 lbs/h and the resulting aqueous dispersion of phthalo blue pigment was used directly in an aqueous flexo ink formul~tion.
~L5¢3Z~3 Example II
. The follo~in~ surfactants are used in place of the - Triton X-114 of Example I and the same procedure followed.
a) Triton N-101 b) Aerosol OT-75 c) Aerosol TR-70 d) Ethomeen C-15 e) Ethomeen 0-15 f) Ammonium Tallate .
Excellent aqueous blue pigment dispersions are ; formed usin~ the Method of Exan~ple I with each of the six surfactants.
Z~3 Example III
Preparation of Blue Flush ~ase The following were added to a 500 gallon Dough mixer:
Component Parts 80~ Acetic Acid Solution 1.24 Water 11.80 Pigment Dispersion (of Ex. I) 26.95 Reactive HC Resin 10.70 Mixing took place for 35 minutes after which the water was decanted and a vacuum applied. To the above mixture the following mixture was then added:
Component Parts Reactive HC Resin 2.85 Alkyd varnish 3.85 Antioxidant .38 Magie 500 oil 1.54 Mixing again took place for 30 minutes after which the mixture was useful as a blue flush base for oil-based inks.
Z~3 Example IV
The follo~ing components were added to a Dough mixer:
Component Parts HC resin varnish 30.00 alkyd resin 25.00 520 Magie oil 2.00 emulsifier 2.40 ~ lixing took place for 5 minutes until the mixture was uni~orm. The pi~ment dispersion of Example I was then added at 9.00 parts and mixing continued for 10 minutes .
after which 10.0 parts water and 10.0 parts 520 Magie oil were added and mixing continued for 10 minutes.
The resultant ink composition was found to be a superior oil-b~sed inX.
', ' ' ' ' . . , . '' ' ' IT~ R- ~ ~ (cH2cEI2o)n-H
~.~herein n = 3 to 10 and R is an - alk~l group containing 8 to 18 carbon atoms.
III. R-R' `C--O(CE~2CH20)n-EI
R is an alX~l group containing 12 to 22 carbon atoins.
I Useful cationic surfactants are quaternary .¦ ammonium salts and specific amines and can be represented by the following formulas:
.
Z~.3 ~1 X ~ A~V C~t.~
R4- N - R2 R2, R3 and R~ are alkyl groups con-I taining from 1 to 12 carbon atoms, R3 Rl is an alkyl group containing 8-22 carbon atoms, X = Cl , Br~, I , &
II. Rl X Primar~,_Secondary or Tertia_y ¦ Amines + .
I Rl is a group containing at least R3 8 carbon atoms, +
R2 and R3 can be H or alkyl groups containing from 1 to 22 carbon atoms.
III. Ethoxylated Primary Amines r-- ~CH2cH2o)n ~ n & m = 1 to 10 R - ~ R consists of an alkyl I (CH2CR20)m H gxoup containing 8-22 carbon atoms.
IV. - Ethy~l~t~d ~nil~-- o r- (CH2CEI20)n H R consists of a - ~ ~C - N group containing I (CH2CH20) H from 7 to 21 m carbon atoms.
V. Ethoxylated Fatty secondary Amides ~-- (CH2CH20) H R is a group con-R - N n tainin~ 8 to 20 - L CH3 carbon atoms.
. .
VI. Substituted Quaternized Fthoxylated Amines .
Rl _ N+_ (CH2CH 0) H R is a group co~-2 n taining 8 to 20 R carbon a~oms.
VII. EthoXYlated Fatty seconaarY
Amine i C ~ CH3 R is a group containing 8 to 20 carbon atoms ~L5~Z~.3 , , _.
The anionic surfactants can generally be describPd as acid salts and can be repres~nted by the follo~iny formulas:
I. Fatky Acid Salts (R - COO )M~ R is an alkyl group containing 12 to 22 carbon atoms.
M+ = ~a, K, M~I4 or substituted ammonium.
II. Sulfonates ~R-S03 )M+ R is an alkyl group containing 12 to 22 carbon atoms.
M+ = ~a, K, NH4 or substituted ammonium.
.
III. . Sulfates - R - OS03 M+ R is an al~yl group containing 12 to 22 carbon atoms.
M~ = Na, K, NH4 or substituted ammonium.
IV. Sulfosuccinates M 03S - CEI - CooR M = ~a, K, NH4 or substituted - I ammonium.
- CH2 R is a group containing from 1 4 to ~2 carbon atoms~.
CooR
V. R' - ~ -S03 M M = Na., ~, ~H4 or su~stituted ammonium.
R is an alkyl group containing 8 to 18 carbon atoms.
~15~Z13 speci:~iC surfactants that h~ve been found suita'ol~
include the follo~ling:
_rfactant Type Trade M~e Chemical N~me I. Non-Ionic a) Triton X-114 Octyl phenoxy polyetho.;yethanol b) Triton N-101 Nonyl phenoxy polyeth~xyethanol II. Anionic a) Aerosol~ T 75 Sodium dioctyl sulfosuccinate - b) Aerosol TR-70 Sodium Bis (Tridecyl! s~lfosuccinat c) A~monium Tallate Ammonium Tallate I~I. Cationic a) Ethomeen~C-15 Polyoxyethylene cocoamine b) Ethom2en 0-15 Polyoxyethyl~ne oleylamine Typical useful surfactant concentration levels have been found to be from about 12 to 30% by ~leight based-on the crude phthalocyanine. This concentration level of surfactant is a critical aspect of the invention and has been found to result in a shorter grinding time ~up to 15%~ as well as the grinding of crude to a much smaller particle size without flocculation of the pigment in the aqueous solution.
It is very important that flocculation not take place ac-cording to the present dispersion method of pigment pro~uc-tion and the surfactant selection and concentration are therefore critical aspects of the present ~ethod.
- ~ ~rA~e~
The process according to the invention is pre-ferably run at a temperature from about 5 to ~0C. and ~Jill work perfectly adeguately at room -temperature. In fact, however, all grinding operations result in generation of heat, so that cooling is necessary if the mix is to be kept at am-bient temperature; the temperature may be allowed to rise somewhat, for example to 80C., so as to save expense on cooling, without detrimental effect, bu-t we prefer that the temperature of grinding should not in any case rise to above 9 ~C .
The blending of the crude (Step ~) in the present me_hod ma~ be accomplished in any type reaction vessel or shot mill. The blend LS agitated to produce a homogeneous composition. Preferably, the blend is then pumped through at least iwo pressurized shot mills in series capable of retaining gr r~ing media made from glass, steel, ceramics, etc., in the size range of from ~.1 to 1.5 mm diameter.
The rate at which the blend is fed into the shot mills can be varied between 50 and 1000 lb/hour and most pre~erably .. . .
in the range of 100 to 250 lb/hour. The blend is passed through at least two shot mills in series to achieve the tinctorial color value of pigment suitable for commercial use~
However, it will be appreciated that the residence time in the shot mil]!s will determine the particle size of the pig-ment but one, or more than two shot mills in series, can also 2~3 be used in the grinding step. Xt has been found that the use of at least t~;o shot mills provides the optimum conditions of time and po~r usage for the Eormation of pigmGn-t disperslon having the tinctorial color value desired in commercial use.
The aqueous pigment dispersions prepared in accor-dance with the present invention may be used for coloring a variety of compositions such as, for example, paper, plas-tics, fibers and especially water-basea inks and paints. rrhe aqueous pigment dispersions may also be used in oil-based inks and paints by flushing the aqueous dispersion into the desired oil-based product or by direct addition when the associated water can be tolerated.
~ ypically, inks prepared in accordance with this invention contain a pigment ~Jhich is dispersed in a resin solution. The inks may contain other conventional ink in-gredien.s. ~or instance, ethyl cellulose, wax compounds, pigment we.ting agents, reactive hydrocarbon resins, e~c., may be added for their kno~n effects.
The invention will next be illustrated in terms of speci~ic examples. In these examples, as well as in the other parts of the present application, all amounts and pro-portions are expressed as parts by weight unless otherwise indicated.
3Zl~
Descri~tion of the Preferred E~nbodi~nts Example I
Prcparation of Phthalo slue Aqueous Dispersion The following materials were charged to a 150 gallon tank: `
a) w~ter 260 lbs.
b~ Triton X-114 60 lbs.
c) crude Cu-Phthalo Blue 300 lbs~
These materials were then blended in the tank until a homogeneous dispersion was obtained and a further charge of 130 lbs. of water added to reduce the viscosi-ty of the mixture to one more suitable for shot milling. The mixture was continuously pumped through two shot mills (Drais mills) in series at a rat~e of 150 lbs/hr. ~ach Drais mill contained steel sho, o~ mm. diameter. ~rinding ~as continued for 30 minutes a~ter which the aqueous dispersion was found to possess superior blue color properties and the pigment concen-tration was 4~3 by weight. Grinding was completed at 150 lbs/h and the resulting aqueous dispersion of phthalo blue pigment was used directly in an aqueous flexo ink formul~tion.
~L5¢3Z~3 Example II
. The follo~in~ surfactants are used in place of the - Triton X-114 of Example I and the same procedure followed.
a) Triton N-101 b) Aerosol OT-75 c) Aerosol TR-70 d) Ethomeen C-15 e) Ethomeen 0-15 f) Ammonium Tallate .
Excellent aqueous blue pigment dispersions are ; formed usin~ the Method of Exan~ple I with each of the six surfactants.
Z~3 Example III
Preparation of Blue Flush ~ase The following were added to a 500 gallon Dough mixer:
Component Parts 80~ Acetic Acid Solution 1.24 Water 11.80 Pigment Dispersion (of Ex. I) 26.95 Reactive HC Resin 10.70 Mixing took place for 35 minutes after which the water was decanted and a vacuum applied. To the above mixture the following mixture was then added:
Component Parts Reactive HC Resin 2.85 Alkyd varnish 3.85 Antioxidant .38 Magie 500 oil 1.54 Mixing again took place for 30 minutes after which the mixture was useful as a blue flush base for oil-based inks.
Z~3 Example IV
The follo~ing components were added to a Dough mixer:
Component Parts HC resin varnish 30.00 alkyd resin 25.00 520 Magie oil 2.00 emulsifier 2.40 ~ lixing took place for 5 minutes until the mixture was uni~orm. The pi~ment dispersion of Example I was then added at 9.00 parts and mixing continued for 10 minutes .
after which 10.0 parts water and 10.0 parts 520 Magie oil were added and mixing continued for 10 minutes.
The resultant ink composition was found to be a superior oil-b~sed inX.
Claims (14)
1. The method of converting a phthalocyanine crude wherein at least 80% of the crude particles have a size greater than 1 micrometer to a dispersed form which is useful in inks and coatings, said method comprising (A) premixing phthalo crude with from about 12 to 30% by weight of surfactant based on pigment and an amount of water suffi-cient to reduce the crude concentration to 10 to 50% by weight, based on the total mixture, said premixing being accomplished by agitation to break down loose crude agglomerates and obtain a uniform blena of the crude without ap-preciably reducing the particle size of the crude, and (B) continuously pumping the blend of (A) throuyh at least two shot mills in series containing between 50 and 90% by volume of a grinding media that has a size of from about 0.1 to 1.5 mm. diameter and then grinding until the particle size has been reduced to pigment particle size.
2. The method of claim 1 in which the grinding in the shot mill is carried out at a temperature of 5 to 80°C.
3. The method of claim 1 in which the surfactant is a water-soluble non-ionic surfactant.
4. The method of claim 3 in which the water-soluble non-ionic surfactant is an ethylene oxide adduct.
5. The method of claim 1 in which the surfactant is a water-soluble cationic surfactant.
6. The method of claim 5 in which the water-soluble cationic surfactant is a quarternary ammonium salt.
7. The method of claim 1 in which the surfactant is a water-soluble anionic surfactant.
8. The method of claim 7 in which the water-soluble anionic surfactant is an acid salt.
9. The method of claim 1 wherein the crude phthalo-cyanine pigment is selected from copper, cobalt, zinc, nickel, cadmium and metal-free phthalocyanine.
10. A water-based printing ink comprising dispersed phthalocyanine blue pigment in an aqueous solution of water-soluble resin wherein the pigment is dispersed by the method of claim 1.
11. A printing ink comprising phthalocyanine blue pigment dispersed in a water immiscible vehicle made by flushing the aqueous pigment dispersion of claim 1 into a water-immiscible printing ink vehicle.
12. The method of converting a crude copper phthalocyanine pigment wherein at least 80% of the crude has a size greater than 1 micrometer to a dispersed form which is useful in inks and coatings, said method comprising (A) premixing crude pigment, with 12 to 30%, by weight of surfactant and an amount of water sufficient to reduce the pigment concentration to 10 to 50%, by weight, based on total mixture, said premixing being accomplished by agitation to break down loose pigment agglomerates and obtain a uniform blend of the in-gredients without appreciably reducing the particle size of the pigment, and (B) continuously pumping the blend of (A) through at least two shot mills in series containing between 50 and 90%
by volume of a grinding media that has a particle size in the range of 0.1 to 1.5 mm. diameter, and then grinding until the dispersion has suitable tinctorial strength for use in inks and coatings.
by volume of a grinding media that has a particle size in the range of 0.1 to 1.5 mm. diameter, and then grinding until the dispersion has suitable tinctorial strength for use in inks and coatings.
13. A water-based printing ink comprising copper phthalo-cyanine blue pigment dispersed in an aqueous solution of water-soluble resin wherein the pigment is dispersed by the method of claim 12.
14. A printing ink comprising copper phthalocyanine blue pigment dispersed in a water-immiscible vehicle made by flushing the aqueous pigment dispersion of claim 12 into a water-immiscible printing ink vehicle.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US3336279A | 1979-04-26 | 1979-04-26 | |
| US033,362 | 1979-04-26 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1150213A true CA1150213A (en) | 1983-07-19 |
Family
ID=21869984
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000350659A Expired CA1150213A (en) | 1979-04-26 | 1980-04-25 | Continuous method of producing aqueous phthalocyanine pigment dispersions |
Country Status (4)
| Country | Link |
|---|---|
| CA (1) | CA1150213A (en) |
| DE (1) | DE3016052A1 (en) |
| GB (1) | GB2051108B (en) |
| IT (1) | IT1130125B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5800607A (en) * | 1995-07-06 | 1998-09-01 | Hoechst Aktiengesellschaft | Process for the preparation of liquid pigment preparations |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4548968A (en) * | 1983-04-06 | 1985-10-22 | Ciba Geigy Corporation | Manufacture of resin extended pigments |
| US4478968A (en) * | 1983-04-06 | 1984-10-23 | Ciba-Geigy Corporation | Manufacture of resin extended pigments |
| US4522654A (en) * | 1983-12-23 | 1985-06-11 | Inmont Corporation | Continuous method of producing phthalocyanine pigment dispersions in organic solvent |
| USH564H (en) | 1986-04-28 | 1989-01-03 | Basf Corporation | Pigment milling process |
| EP1557448B1 (en) * | 2004-01-26 | 2011-06-08 | Dainichiseika Color & Chemicals Mfg. Co., Ltd. | Wet grinding process using microbeads |
| ATE485343T1 (en) | 2004-06-16 | 2010-11-15 | Colour Ltd | METHOD FOR PRODUCING BETA COPPER PHTHALOCYANINE BLUE PIGMENTS AND USE THEREOF |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2556727A (en) * | 1949-03-05 | 1951-06-12 | Du Pont | Process of finishing phthalocyanine pigments |
| US2556726A (en) * | 1949-03-05 | 1951-06-12 | Du Pont | Copper-phthalocyanine in pigmentary beta form and a process of making the same |
| US2556728A (en) * | 1949-03-05 | 1951-06-12 | Du Pont | Process of producing tinctorially stable phthalocyanine coloring matters |
| US2908690A (en) * | 1955-11-29 | 1959-10-13 | Du Pont | Production of phthalocyanine pigments |
| US2999862A (en) * | 1958-08-15 | 1961-09-12 | Sandoz Ltd | Process for converting crude copper phthalocyanine into finely divided beta-form |
| GB1362180A (en) * | 1970-11-20 | 1974-07-30 | Ciba Geigy Uk Ltd | Preparation of pigments |
-
1980
- 1980-04-25 CA CA000350659A patent/CA1150213A/en not_active Expired
- 1980-04-25 DE DE19803016052 patent/DE3016052A1/en active Granted
- 1980-04-28 GB GB8013980A patent/GB2051108B/en not_active Expired
- 1980-04-28 IT IT67672/80A patent/IT1130125B/en active
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5800607A (en) * | 1995-07-06 | 1998-09-01 | Hoechst Aktiengesellschaft | Process for the preparation of liquid pigment preparations |
Also Published As
| Publication number | Publication date |
|---|---|
| IT8067672A0 (en) | 1980-04-28 |
| GB2051108B (en) | 1983-08-24 |
| IT1130125B (en) | 1986-06-11 |
| DE3016052C2 (en) | 1989-11-16 |
| DE3016052A1 (en) | 1980-11-06 |
| GB2051108A (en) | 1981-01-14 |
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