EP0755989B1 - Streichpigmentgemisch und Streichfarbe mit verbesserter Tiefdruckeignung - Google Patents
Streichpigmentgemisch und Streichfarbe mit verbesserter Tiefdruckeignung Download PDFInfo
- Publication number
- EP0755989B1 EP0755989B1 EP96111851A EP96111851A EP0755989B1 EP 0755989 B1 EP0755989 B1 EP 0755989B1 EP 96111851 A EP96111851 A EP 96111851A EP 96111851 A EP96111851 A EP 96111851A EP 0755989 B1 EP0755989 B1 EP 0755989B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- layered silicate
- coating
- finely divided
- activated
- acid
- 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 - Lifetime
Links
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/38—Coatings with pigments characterised by the pigments
- D21H19/40—Coatings with pigments characterised by the pigments siliceous, e.g. clays
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/38—Coatings with pigments characterised by the pigments
- D21H19/385—Oxides, hydroxides or carbonates
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/50—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by form
- D21H21/52—Additives of definite length or shape
Definitions
- the invention relates to a coating pigment mixture with improved Suitability for gravure printing as well as one made from it Coating color.
- LWC gravure formulations on the other hand, CaCO 3 is only around 10% - and this also limits the upper coating weight range.
- CaCO 3 is not suitable for gravure printing. It is believed that this is due to the rhombohedral structure of the CaCO 3 and the too rapid wettability by the gravure printing ink, which allow the ink to be removed too quickly.
- Talc / carbonate mixtures are an alternative gravure pigment e.g. in "Wochenblatt für Textilfabrikation” 17 (1991), pages 662-665. Talk is not, however a swellable layered silicate because its surface is hydrophobic is. Such mixtures result in poorly printable Papers; these papers can be because of the sliding properties of the talk does not feed well into printing presses. Also For this reason, paper stacks tend to slip easily.
- From CA-A-814 304 are surface-modified with organosilanes Pigments are known primarily as fillers for synthetic resin, paper, paints and varnishes, as well can be used as coating pigments.
- the surface modified Pigments e.g. layered silicates
- the surface modified Pigments are no longer swellable.
- printing papers which are on a cellulose-containing sheets a first and a second hydrophilic, contain water-absorbing and porous pigment layer, being the first layer of a non-smectitic Pigment, such as kaolin, calcium carbonate, talc or calcium sulfate, and the second layer of a swellable smectic Pigment exists.
- a non-smectitic Pigment such as kaolin, calcium carbonate, talc or calcium sulfate
- a swellable smectic Pigment exists.
- About the particle size of the smectite Pigments are not found.
- a CaCO 3 -talkum coating pigment slurry which consists of four cover-ground components: (a) 24-64% by weight CaCO 3 , (b) 5-48% by weight talc , (c) 20-40% by weight H 2 O and (d) an auxiliary combination of conventional grinding aids and dispersants, the pigment mixture having an average statistical particle diameter of 0.4-1.5 ⁇ m.
- the talc component is not swellable.
- EP-A-0 572 037 describes a coating pigment which can be fixed onto paper and cardboard essentially without a binding agent and which results in coating surfaces which can be printed by deep and offset printing.
- This pigment consists of at least 30% by weight of a swellable layered silicate and has a swelling volume of 5 to 30 ml (based on a suspension of 2 g in 100 ml of distilled water). Minerals from the smectite group, preferably bentonite or synthetic hectorite, are primarily used as swellable layered silicates.
- the remaining 70% by weight of the coating pigment can consist of conventional coating pigments, such as kaolin, CaCO 3 , etc. A summary of these coating pigments can be found in "Wochenblatt für Textilfabrikation" 6 (1994), pages 214-218.
- the gravure suitability of the coating color produced from this coating pigment leaves something to be desired, however, since it still has a relatively high viscosity even at low solids contents and can therefore only be processed on special coating units, such as film presses, "speedsizers", etc. and the coating weight at most 6 g / m 2 and side is limited.
- the invention is based, the gravure suitability of calcium carbonate-containing coating pigment mixtures.
- the invention thus relates to a coating pigment mixture with improved suitability for gravure printing, comprising a discrete mixture of (a) finely divided calcium carbonate and at least (b) 1 a finely divided swellable layered silicate and / or (b) 2 an acid-activated layered silicate with an average particle size of about 2 to 10 ⁇ m in a weight ratio of approximately 99.5: 0.5 to 80:20 (a / b 1 ) or 99: 1 to 70:30 (a / b 2 ).
- the coating pigment mixture according to the invention can be dry Powder mixture or in the form of an aqueous dispersion.
- the weight ratio between finely divided calcium carbonate and finely divided swellable layered silicate or acid-activated layered silicate is approximately 99: 1 to 90:10 (a / b 1 ) or 97: 3 to 80:20 (a / b 2 ).
- the finely divided calcium carbonate (a) and the swellable layered silicate (b 1 ) or the acid-activated layered silicate (b 2 ) have an average particle size of approximately 3 to 7 ⁇ m, preferably approximately 5 ⁇ m.
- the average particle size (d50) is determined using a "Malvern Particle Sizer 2600 C "determined.
- the swellable layered silicate is preferably an alkali or alkaline earth layered silicate or an alkaline activated Layered silicate.
- a suitable layered silicate (b 1 ) or acid-activated layered silicate (b 2 ) is, for example, a smectitic layered silicate or is obtainable therefrom.
- Smectitic layered silicates are e.g. Bentonite, montmorillonite, Hectorite, saponite or nontronite. Are preferred from This series uses bentonite and montmorillonite. As also Synthetic layered silicates have been very suitable, especially synthetic hectorite.
- the Layer silicates swellability in the case of alkali layer silicates larger than that of the alkaline earth layer silicates.
- Swellable layered silicates can, for example, be the natural ones Alkali bentonites (e.g. Wyoming bentonite) can be used.
- the required swellability can also be caused by alkaline Activation of layered alkaline earth silicates (e.g.
- acid-activated layered silicates can advantageously be used, mineral acids such as hydrochloric acid and sulfuric acid preferably being used for the activation.
- Acid-activated bentonites are particularly preferred acid-activated sheet silicates.
- the invention also relates to a process for the preparation of the coating pigment mixture according to the invention, which is characterized in that either (A) in a dispersion of finely divided calcium carbonate (a) at least one finely divided swellable layered silicate (b 1 ) and / or an acid-activated layered silicate ( b 2 ) stir in; or (B) an aqueous dispersion of finely divided calcium carbonate (a) mixed with an aqueous dispersion of at least one finely divided swellable layered silicate (b 1 ) and / or an acidically activated swellable layered silicate (b 2 ).
- Process variant (A) is used in particular for the acid-activated layered silicates, these being added to the CaCO 3 dispersion (slurry) with vigorous stirring. If necessary, the solids content of the slurry must be somewhat reduced in order to maintain the flow properties.
- a similar procedure can be used with the swellable layered silicates; however, it proves more expedient here to disperse the layered silicate separately from the calcium carbonate with high shear and then to combine the aqueous dispersions.
- the layer silicates can of course just as well coating color production, e.g. dosed into the mixing chest become.
- the invention also relates to an aqueous coating slip with improved gravure suitability, containing the above coating pigment mixture described and, if appropriate, per se known coating color additives.
- the coating color preferably contains binders as further additives, Dispersants, retention aids, anti-foaming agents and / or thickeners.
- the invention further relates to a gravure printing paper, in particular an LWC gravure printing paper, which is coated with the coating pigment mixture described above or with a dewatered coating ink.
- the coating weight of the coating pigment mixture is preferably about 4 to 12 g / m 2 , in particular about 6 to 10 g / m 2 and side.
- the swellable layered silicates improve the running properties of the coating colors under high shear conditions, which means that synthetic thickeners can be dispensed with. This is important when reducing or avoiding the formation of beards or squeegees on the coating machine.
- Montmorilloniteteil raised to 90% by weight.
- This product was used in membrane filter presses thickened to a solids content of 40% by weight and in a twin-shaft mixer with 1% by weight (Example 1a), 3 % By weight (example 1b) and 5% by weight (example 1c) soda 5 min. activated to obtain a swellable sodium bentonite.
- the products were gently at 90 ° C to a water content of about 10 wt .-% dried and in a rotary rotor mill to an average particle size (d50; measured in "Malvern Particle Sizer 2600c ”) of about 5 ⁇ m.
- the alkaline-activated bentonite samples were dispersed in water at solids contents of 4-18% by weight and, after a maturing time of 6 hours, in amounts of 1 to 10% by weight of a coating carbonate slurry with an average particle size of 3.5 Am, ( measured in the "Malvern Particle Sizer 2600 C") or 90% ⁇ 2 ⁇ m (measured in the Sedigraph 5000) ("Hydrocarb 90" from Omya) added.
- the viscosity of the blend slurry was adjusted to about 200 mPa.s by adding water.
- a gravure binder (DL 1010® from DOW, 5 parts per 100 parts of pigment) was then metered into the slurries, and the coating color thus obtained was applied to an LWC base paper (containing wood, using a hand knife at application weights of 6-7 g / m 2 , 45g / m 2 ) doctored.
- the coated papers were satin-finished in a laboratory calender and printed with black gravure ink from Kast and Ehinger GmbH in the "LTG" pressure device from Testa Color, a laboratory gravure printing machine for rolls and formats with a mileage of around 100 m / min. The pressure was assessed visually based on the halftone area.
- the gray scale produced by printing technology (well depth 0.8 mm with a screen density of 70 dots / cm 2 ) was assessed according to cloudiness (calm / uneven print image) and missing screen dots (missing dots).
- the bentonite stock slurry could be produced with a solids content of 18, 8 or 5% by weight.
- the blend ratios with CaCO 3 were between 90/10 (example la) and 98/2 (example lc), the solids content of the coating colors and the viscosities being adjusted accordingly.
- the results of the gravure test were better for all blends than for an uncut CaCO 3 coating color. It was found that the printability was a function of the amount of bentonite added and the higher degree of alkaline activation of the bentonites.
- Brookfield viscosities (spindles 2 and 3, 100 rpm) were determined.
- example Bentonite slurry% solid Blends Hydrocarb 90 / Bentonite Coating color Pressure assessment Solid% Brookf.Vis. mPa.s comparison - 100/0 66.3 270 + - 1a 18th 90/10 58.2 255 ++ 95/5 62.0 310 + 97/3 64.5 290 + 1b 8th 95/5 57.5 295 ++ 97/3 62.4 325 ++ 1c 5 96/4 56.5 310 ++ 98/2 62.5 295 +
- Bavarian calcium bentonite was slurried as in Example 1 and cleaned up using hydrocyclones.
- the hydrocyclone inlet was with 40 wt .-% (based on bentonite) Hydrochloric acid (30%) added and activated at 95 to 98 ° C for 10 h.
- the acid-activated bentonite thus obtained was still filtered hot, washed free of chloride and gentle at 80 ° C dried to a solids content of about 7% by weight.
- the product was placed on a medium sized rotor mill Diameter (d50; Malvern Particle Sizer 2600 c of about Grind 5 ⁇ m.
- the acid activated bentonite became a Hydrocarb® 90 slurry metered in amounts of 5-25 wt .-%, and the slurry was applied to a coating color as in Example 1 processed.
- the Hydrocarb® 90 slurry was each mixed with 5% by weight of synthetic hectorite (from Süd-Chemie AG) (average particle size 4.5 ⁇ m) and, as in Example 1, processed and examined for a coating color.
- the results are shown in Table III. Here, too, a better printing result could be achieved than without the addition.
- Example Layered silicate Coating color Pressure assessment Solid% Brookf.Vis. mPa.s 3rd Hectorite 59.6 305 ++
- the coating colors were rheologically characterized and coated with an application weight of 7.9 to 8.4 g / m 2 in the "Dixon Coater" on LWC base paper of 36 g / m 2 .
Landscapes
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Paper (AREA)
- Paints Or Removers (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Description
- +++
- sehr gutes, ruhiges Bildbild mit wenig "missing dots"
- - --
- unruhiges Druckbild, mit vielen "missings dots"
Beispiel | Bentonit-Slurry % Feststoff | Verschnitte Hydrocarb 90/Bentonit | Streichfarbe | Druckbeurteilung | |
Feststoff % | Brookf.Vis. mPa.s | ||||
Vergleich | - | 100/0 | 66,3 | 270 | +- |
1a | 18 | 90/10 | 58,2 | 255 | ++ |
95/5 | 62,0 | 310 | + | ||
97/3 | 64,5 | 290 | + | ||
1b | 8 | 95/5 | 57,5 | 295 | ++ |
97/3 | 62,4 | 325 | ++ | ||
1c | 5 | 96/4 | 56,5 | 310 | ++ |
98/2 | 62,5 | 295 | + |
Beispiel | Verschnitte Hydrocarb 90/Bentonit | Streichfarbe | Druckbeurteilung | |
Feststoff % | Brookf.Vis. mPa.s | |||
2a | 75/25 | 54,6 | 318 | +++ |
2b | 85/15 | 59,2 | 295 | +++ |
2c | 90/10 | 61,5 | 332 | ++ |
2d | 95/5 | 64,5 | 320 | ++ |
Beispiel | Schichtsilicat | Streichfarbe | Druckbeurteilung | |
Feststoff % | Brookf.Vis. mPa.s | |||
3 | Hectorit | 59,6 | 305 | ++ |
Beispiel | 4a | 4b | 4c |
TiefdruckkaolinTeile | 80 | 80 | 80 |
"Hydrocarb 90" Teile | 20 | 20 | 20 |
Bentonit von Beispiel 1c Teile | - | 1 | 2 |
Tiefdrucklatex Teile | 4,5 | 4,5 | 4,5 |
synth. VerdickerTeile | 1,0 | 0,6 | - |
Beispiel | 4a | 4b | 4c |
Feststoffgehalt Gew.-% | 50,4 | 50,3 | 50,3 |
pH-Wert | 8 | 8,2 | 8,2 |
Brookfield 100 U/min mPa.s | 2070 | 1330 | 650 |
Wasserrückhaltevermögen (Warren) sec. | 38 | 24 | 17 |
Streichgeschwindigkeit m/min | 100 | 100 | 100 |
Strichgewicht g/m2 | 7,9 | 8,2 | 8,4 |
Glätte (Bekk)) sec | 1460 | 1520 | 1550 |
Glanz (75°) % | 46,7 | 47,9 | 52,4 |
Weißgrad (Elrepho R457) % | 71,2 | 70,6 | 70,7 |
Opazität % | 90,0 | 89,6 | 89,7 |
Bedruckbarkeit | +- | + | ++ |
Beispiel | Viskosität Pa.s | ||
Scherrate 1/sec | 4a | 4b | 4c |
100 000 | 0,18 | 0,12 | 0,10 |
200 000 | 0,10 | 0,09 | 0,08 |
400 000 | 0,08 | 0,07 | 0,04 |
600 000 | 0,06 | 0,05 | 0,02 |
800 000 | 0,06 | 0,04 | 0,02 |
1 000 000 | 0,055 | 0,038 | 0,015 |
2 000 000 | 0,03 | 0,01 | 0,006 |
Claims (11)
- Streichpigmentgemisch mit verbesserter Tiefdruckeignung, enthaltend diskrete Teilchen aus (a) feinteiligem Calciumcarbonat und mindestens (b)1 einem feinteiligen quellfähigen Schichtsilicat und/oder (b)2 einem sauer aktivierten Schichtsilicat mit einer mittleren Teilchengröße von etwa 2 bis 10 µm in einem Gewichtsverhältnis von etwa 99,5:0,5 bis 80:20 (a/b1) bzw. 99:1 bis 70:30 (a/b2).
- Streichpigmentgemisch nach Anspruch 1, dadurch gekennzeichnet, daß das Gewichtsverhältnis zwischen feinteiligem Calciumcarbonat und feinteiligen Schichtsilicat bzw. sauer aktiviertem quellfähigem Schichtsilicat etwa 99:1 bis 90:10 (a/b1) bzw. 97:3 bis 80:20 (a/b2) beträgt.
- Streichpigmentgemisch nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß das feinteilige Calciumcarbonat (a) und das quellfähige Schichtsilicat (b1) bzw. das sauer aktivierte Schichtsilicat (b2) eine mittlere Teilchengröße von etwa 3 bis 7 µm, vorzugsweise von etwa 5 µm, haben.
- Streichpigmentgemisch nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß das quellfähige Schichtsilicat ein Alkali-oder Erdalkali-Schichtsilicat oder ein alkalisch aktiviertes Schichtsilicat darstellt.
- Streichpigmentgemisch nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß das quellfähige Schichtsilicat (b1) bzw. das sauer aktivierte Schichtsilicat (b2) ein smektitisches Schichtsilicat darstellt bzw. daraus erhältlich ist.
- Verfahren für die Herstellung des Streichpigmentgemisches nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß man entweder (A) in eine Dispersion von feinteiligem Calciumcarbonat (a) mindestens ein feinteiliges quellfähiges Schichtsilicat (b1) und/oder ein sauer aktiviertes Schichtsilicat (b2) einrührt; oder (B) eine wäßrige Dispersion von feinteiligem Calciumcarbonat (a) mit einer wäßrigen Dispersion mindestens eines feinteiligen quellfähigen Schichtsilicats (b1) und/oder eines sauer aktivierten Schichtsilicats (b2) vermischt.
- Verfahren nach Anspruch 6, dadurch gekennzeichnet, daß man das Dispersionsgemisch (A) oder die Dispersion des feinteiligen quellfähigen Schichtsilicats (b1) und/oder des sauer aktivierten Schichtsilicats (b2) einer hochscherenden Dispergierbehandlung unterzieht.
- Wäßrige Streichfarbe mit verbesserter Tiefdruckeignung, enthaltend ein Streichpigmentgemisch nach einem der Ansprüche 1 bis 5 bzw. hergestellt nach Anspruch 6 oder 7 sowie gegebenenfalls an sich bekannte Streichfarbenzusätze.
- Streichfarbe nach Anspruch 8, dadurch gekennzeichnet, daß sie als weitere Zusätze Bindemittel, Dispergiermittel, Retentionsmittel Schaumverhütungsmittel und/oder Verdickungsmittel enthält.
- Tiefdruckpapier, das mit einem Streichpigmentgemisch nach einem der Ansprüche 1 bis 5 bzw. mit einer entwässerten Streichfarbe nach Anspruch 8 oder 9 beschichtet ist.
- Tiefdruckpapier, nach Anspruch 10, dadurch gekennzeichnet, daß das Streichgewicht des Streichpigmentgemischs etwa 4 bis 12 g/m2, vorzugsweise etwa 6 bis 10 g/m2 und Seite beträgt.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19527161 | 1995-07-25 | ||
DE19527161A DE19527161A1 (de) | 1995-07-25 | 1995-07-25 | Pigmentgemisch und Streichfarbe mit verbesserter Tiefdruckeignung |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0755989A2 EP0755989A2 (de) | 1997-01-29 |
EP0755989A3 EP0755989A3 (de) | 1999-05-12 |
EP0755989B1 true EP0755989B1 (de) | 2001-05-23 |
Family
ID=7767750
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP96111851A Expired - Lifetime EP0755989B1 (de) | 1995-07-25 | 1996-07-23 | Streichpigmentgemisch und Streichfarbe mit verbesserter Tiefdruckeignung |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP0755989B1 (de) |
AT (1) | ATE201432T1 (de) |
DE (2) | DE19527161A1 (de) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10042455A1 (de) * | 2000-08-29 | 2002-03-14 | Sued Chemie Ag | Verbesserte quellfähige Schichtsilicate |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA814304A (en) * | 1969-06-03 | J. M. Huber Corporation | Surface modified pigments | |
FR2249139B1 (de) * | 1973-10-24 | 1976-10-01 | Lafarge Sa | |
US4725318A (en) * | 1985-02-19 | 1988-02-16 | Maruo Calcium Company, Limited | Filler for paper-making and neutral paper-making process by the use thereof |
GB8808552D0 (en) * | 1988-04-12 | 1988-05-11 | Ecc Int Ltd | Paper coating |
DE4202598C1 (de) * | 1992-01-30 | 1993-09-02 | Stora Feldmuehle Ag, 4000 Duesseldorf, De | |
DE4217779A1 (de) * | 1992-05-29 | 1993-12-02 | Sued Chemie Ag | Streichpigment |
ES2159286T3 (es) * | 1992-12-23 | 2001-10-01 | Imerys Minerals Ltd | Procedimiento para el tratamiento de suspensiones de desperdicios. |
DE4312463C1 (de) * | 1993-04-16 | 1994-07-28 | Pluss Stauffer Ag | CaCO¶3¶ -Talkum-Streichpigmentslurry, Verfahren zu seiner Herstellung und seine Verwendung |
-
1995
- 1995-07-25 DE DE19527161A patent/DE19527161A1/de not_active Withdrawn
-
1996
- 1996-07-23 EP EP96111851A patent/EP0755989B1/de not_active Expired - Lifetime
- 1996-07-23 AT AT96111851T patent/ATE201432T1/de not_active IP Right Cessation
- 1996-07-23 DE DE59606935T patent/DE59606935D1/de not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
EP0755989A3 (de) | 1999-05-12 |
DE19527161A1 (de) | 1997-01-30 |
ATE201432T1 (de) | 2001-06-15 |
EP0755989A2 (de) | 1997-01-29 |
DE59606935D1 (de) | 2001-06-28 |
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